WO2021060537A1 - Fluorine-containing compound, fluorine-containing compound-containing composition, coating solution, article, and method for producing article - Google Patents

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

Info

Publication number
WO2021060537A1
WO2021060537A1 PCT/JP2020/036461 JP2020036461W WO2021060537A1 WO 2021060537 A1 WO2021060537 A1 WO 2021060537A1 JP 2020036461 W JP2020036461 W JP 2020036461W WO 2021060537 A1 WO2021060537 A1 WO 2021060537A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
fluorine
compound
atom
same
Prior art date
Application number
PCT/JP2020/036461
Other languages
French (fr)
Japanese (ja)
Inventor
勇佑 冨依
元志 青山
健二 石関
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to JP2021548465A priority Critical patent/JPWO2021060537A1/ja
Priority to CN202080058932.5A priority patent/CN114258412A/en
Publication of WO2021060537A1 publication Critical patent/WO2021060537A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C08G65/3346—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur having sulfur bound to carbon and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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 compound, a fluorine-containing compound-containing composition, a coating liquid, an article, and a method for producing the article.
  • the water- and oil-repellent layer is also required to have durability such as abrasion resistance and weather resistance.
  • a fluorine-containing compound capable of forming a water- and oil-repellent layer having excellent durability a fluorine-containing compound into which a hydrolyzable silyl group has been introduced has been studied.
  • a hydrolyzable silyl group is used as a surface treatment agent capable of forming a coating film having excellent water and oil repellency and removal of oil and fat stains and excellent deterioration resistance even under high temperature conditions in the presence of an acid catalyst.
  • a surface treatment agent containing one or two specific fluoroether compounds is disclosed.
  • Patent Document 1 a surface treatment agent in which the specific fluorine-containing ether compound is combined with a fluorine-containing ether compound having three hydrolyzable silyl groups is disclosed.
  • the hydrolyzable silyl group binds to the surface of the article to form a durable water- and oil-repellent layer.
  • a fluorine-containing compound capable of forming a water- and oil-repellent layer having excellent durability, a fluorine-containing compound-containing composition and a coating liquid, and a surface having excellent durability and maintaining water-repellent and oil-repellent properties and fingerprint removing properties for a long period of time
  • An object of the present invention is to provide an article having a layer and a method for producing the same.
  • the present invention provides a fluorine-containing compound having the following constitutions [1] to [13] and a method for producing the same, a fluorine-containing compound-containing composition, a coating liquid, an article, and a method for producing the same.
  • a fluorine-containing compound-containing composition having the following constitutions [1] to [13] and a method for producing the same, a fluorine-containing compound-containing composition, a coating liquid, an article, and a method for producing the same.
  • a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom are bonded to *.
  • Q 1 represents a hydrogen atom or a fluorine atom
  • a plurality of Q 1 is may be the same or different and R 1 is a linear or branched fluoroalkylene group, and when there are a plurality of R 1, they may be the same or different.
  • L is a hydrolyzable group or a hydroxyl group, and when there are a plurality of L, the L may be the same or different.
  • R 10 is a hydrogen atom or a monovalent hydrocarbon group, and when there are a plurality of them, R 10 may be the same or different.
  • n is an integer greater than or equal to 0 and m is an integer greater than or equal to 1
  • p is an integer of 1 to 3.
  • Q 1 represents a hydrogen atom or a fluorine atom
  • a plurality of Q 1 is may be the same or different and R 1 is a linear or branched fluoroalkylene group, and when there are a plurality of R 1, they may be the same or different.
  • A is a (q + 1) -valent organic group
  • L is a hydrolyzable group or a hydroxyl group, and when there are a plurality of L, the L may be the same or different.
  • R 10 is a hydrogen atom or a monovalent hydrocarbon group, and when there are a plurality of them, R 10 may be the same or different.
  • n is an integer greater than or equal to 0 and m is an integer greater than or equal to 1
  • p is an integer from 1 to 3 and q is an integer of 1 or more, and the sum of q is 4 or more.
  • A is a (q + 1) -valent organic group, and a plurality of A's may be the same or different.
  • L is a hydrolyzable group or a hydroxyl group, and a plurality of Ls may be the same or different.
  • R 10 is a hydrogen atom or a monovalent hydrocarbon group, and a plurality of R 10s may be the same or different.
  • n is an integer of 0 or more, and a plurality of n may be the same or different.
  • m is an integer of 1 or more, and a plurality of m may be the same or different.
  • p is an integer of 1 to 3, and a plurality of ps may be the same or different.
  • q is an integer of 1 to 3, the sum of q is 4 or more, and a plurality of qs may be the same or different.
  • r is an integer of 3 or more.
  • Q 3 is a hydrogen atom or a fluorine atom.
  • C in the formula (X-6) is a carbon atom constituting an aromatic ring, one of the bonds possessed by the carbon atom is a single bond, and the remaining bond (the bond with a wavy line) is It constitutes an aromatic ring.
  • the fluorine-containing compound according to any one of [2] to [4].
  • R f5 is a fluoroalkylene group having 5 carbon atoms.
  • R f6 is a fluoroalkylene group having 6 carbon atoms and has 6 carbon atoms.
  • m1, m2, m3, m4, m5, and m6 represent integers of 0 or 1, respectively, and m1 + m2 + m3 + m4 + m5 + m6 are integers of 1 to 200.
  • a fluorine-containing compound-containing composition containing the fluorine-containing compound according to any one of the above [1] to [6] and another fluorine-containing compound.
  • a coating liquid containing the fluorine-containing compound according to any one of [1] to [6] or the fluorine-containing compound-containing composition of [7] and a liquid medium.
  • the base layer contains an oxide containing silicon
  • An article in which the water- and oil-repellent layer contains a condensate of any of the fluorine-containing compounds [1] to [6].
  • the oxide is one selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten.
  • the article of [9] containing the above elements.
  • the oxide is one selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten.
  • the article of [11] containing the above elements.
  • the fluorine-containing compound according to any one of [1] to [6], the fluorine-containing compound-containing composition of [7], or the coating solution of [8] is used to repel by a dry coating method or a wet coating method. A method of manufacturing an article that forms a water-repellent layer.
  • a fluorine-containing compound capable of forming a water- and oil-repellent layer having excellent durability, a fluorine-containing compound-containing composition and a coating liquid, and a surface having excellent durability and maintaining water-repellent and oil-repellent properties and fingerprint repellent properties for a long period of time.
  • An article having a layer and a method for producing the same can be provided.
  • the partial structure represented by the formula (1) may be referred to as a partial structure (1).
  • the compound represented by the formula (4) may be referred to as a compound (4).
  • the term "perfluoroalkyl group” means a group in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms.
  • the fluoroalkyl group means an alkyl group having one or more fluorine atoms, and includes a perfluoroalkyl group. The same applies to the fluoroalkylene group.
  • the fluorine-containing compound of the present invention (hereinafter, also referred to as the present compound) has three or more partial structures represented by the following formula (1) and four or more partial structures represented by the following formula (2).
  • a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom are bonded to *.
  • Q 1 represents a hydrogen atom or a fluorine atom
  • a plurality of Q 1 is may be the same or different and R 1 is a linear or branched fluoroalkylene group, and a plurality of R 1s may be the same or different.
  • L is a hydrolyzable group or a hydroxyl group, and a plurality of Ls may be the same or different.
  • R 10 is a hydrogen atom or a monovalent hydrocarbon group, and a plurality of R 10s may be the same or different.
  • n is an integer of 0 or more
  • m is an integer of 1 or more
  • p is an integer of 1 to 3.
  • the partial structure (2) of this compound undergoes a dehydration condensation reaction to form a chemical bond with the surface of the substrate, as will be described later.
  • the partial structure (1) is a fluoropolyether chain, which exhibits water and oil repellency and oil and fat stain removing properties. Since this compound can form four or more bonding points with the surface of the base material, a highly durable water- and oil-repellent layer is formed. Further, three or more partial structures (1) are arranged on the outer surface side of the water-repellent oil-repellent layer, exhibit excellent water-repellent oil-repellent property and oil-fat stain removing property, and prevent chemicals such as alkali from entering the bonding point. It is presumed to suppress it. As a result, it is considered that the resistance to various chemicals is also excellent. From these facts, this compound makes it possible to form a water-repellent and oil-repellent layer having excellent durability.
  • the partial structure (1) represents a fluoropolyether chain. Since this compound has three or more fluoropolyether chains, it is excellent in water repellency, oil repellency, oil stain removal property, and the like.
  • the tertiary or quaternary atom constitutes a linking group described later alone or together with other atoms as necessary, and a plurality of partial structures (1) and the like are linked.
  • the same tertiary or quaternary atom may be bonded to the * of the plurality of partial structures (1), or different tertiary or quaternary atoms may be bonded.
  • ⁇ C (Q 1) 2 ⁇ Q 1 in the n partial structures (1) is a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different.
  • Q 1 may be all hydrogen atoms, and at least one may be a fluorine atom. That is, ⁇ C (Q 1 ) 2 ⁇ n may be an alkylene group or a fluoroalkylene group.
  • a fluoroalkylene group is preferable, and a perfluoroalkylene group is more preferable, from the viewpoint of water repellency and oil repellency and oil stain removal property.
  • n may be 0 or may be an integer of 1 or more. When n is 0, the partial structure (1) has the structure of the following equation (1-1).
  • each reference numeral in the equation (1-1) is the same as that in the equation (1).
  • n is an integer of 1 or more
  • the n represents the number of carbon atoms of ⁇ C (Q 1 ) 2 ⁇ n.
  • the n is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
  • n -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- and the like can be mentioned.
  • R 1 O of the partial structure (1) represents an oxyfluoroalkylene group, and R 1 is a fluoroalkylene group having a linear, branched or ring structure. Since the partial structure (1) has a repeating unit of an oxyfluoroalkylene group, this compound is excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removal property. From the viewpoint of being excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removing property, (R 1 O) m is preferably a structure represented by the following formula (R-1).
  • R f1 is a fluoroalkylene group having 1 carbon atom.
  • R f2 is a fluoroalkylene group having 2 carbon atoms.
  • R f3 is a fluoroalkylene group having 3 carbon atoms.
  • R f4 is a fluoroalkylene group having 4 carbon atoms.
  • R f5 is a fluoroalkylene group having 5 carbon atoms.
  • R f6 is a fluoroalkylene group having 6 carbon atoms and has 6 carbon atoms.
  • m1, m2, m3, m4, m5, and m6 represent integers of 0 or 1, respectively, and m1 + m2 + m3 + m4 + m5 + m6 are integers of 1 to 200.
  • the bonding order of (R f1 O) to (R f6 O) in the formula (R-1) is arbitrary.
  • M1 to m6 of the formula (R-1) represent the number of (R f1 O) to (R f6 O), respectively, and do not represent the arrangement.
  • (R f5 O) m5 is, (R f5 O)
  • the number of stands that the m5 amino, (R f5 O) does not represent a block arrangement of m5.
  • the description order of (R f1 O) to (R f6 O) does not represent the binding order of each unit.
  • R f1 examples include -CF 2- and -CHF-.
  • R f2 are, -CF 2 CF 2 -, - CHFCF 2 -, - CHFCHF -, - CH 2 CF 2 -, - CH 2 CHF- , and the like.
  • R f3 is, -CF 2 CF 2 CF 2 - , - CF 2 CHFCF 2 -, - CF 2 CH 2 CF 2 -, - CHFCF 2 CF 2 -, - CHFCHFCF 2 -, - CHFCHFCHF -, - CHFCH 2 CF 2 -, - CHFCH 2 CF 2 -, - CH 2 CF 2 CF 2 -, - CH 2 CHFCF 2 -, - CH 2 CH 2 CF 2 -, - CH 2 CF 2 CHF -, - CH 2 CHFCHF -, -CH 2 CH 2 CHF-, -CF (CF 3 ) -CF 2- , -CF (CHF 2 ) -CF 2- , -CF (CH 2 F) -CF 2- , -CF (CH 3 ) -CF 2- , -CF (CF 3 ) -CHF-, -CF (CHF 2 ) -CH 2-
  • R f4 examples include -CF 2 CF 2 CF 2 CF 2- , -CHFCF 2 CF 2 CF 2- , -CH 2 CF 2 CF 2 CF 2- , -CF 2 CHFCF 2 CF 2- , -CHFCHFCF.
  • R f5 include -CF 2 CF 2 CF 2 CF 2 CF 2- , -CHFCF 2 CF 2 CF 2- , -CH 2 CHFCF 2 CF 2 CF 2- , -CF 2 CHFCF 2 CF 2 CF 2- , -CHFCHFCF 2 CF 2 CF 2- , -CH 2 CHFCF 2 CF 2 CF 2- , -CF 2 CH 2 CF 2 CF 2 CF 2- , -CHFCH 2 CF 2 CF 2 CF 2- , -CH 2 CH 2 CF 2 CF 2 CF 2- , -CF 2 CF 2 CHFCF 2 CF 2- , -CHFCF 2 CHFCF 2 CF 2- , -CHFCF 2 CHFCF 2 CF 2- , -CH 2 CHFCF 2 CF 2- , -CH 2 CHFCF 2 CF 2- , -CH 2 CHFCF 2 CF 2- , -CH 2 CHFCF 2 CF 2- , -CH 2
  • R f6 are, -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -, - CF 2 CF 2 CHFCHFCF 2 CF 2 -, - CHFCF 2 CF 2 CF 2 CF 2 -, - CHFCHFCHFCHFCHFCHF- , -CHFCF 2 CF 2 CF 2 CH 2- , -CH 2 CF 2 CF 2 CF 2 CH 2- , -cycloC 6 F 10-, and the like.
  • -cycloC 4 F 6- means a perfluorocyclobutane diyl group, and specific examples thereof include a perfluorocyclobutane-1,2-diyl group.
  • -CycloC 5 F 8 - means a perfluoro cyclopentane-diyl group, and specific examples thereof include perfluoro cyclopentane-1,3-diyl group.
  • -CycloC 6 F 10- means a perfluorocyclohexanediyl group, and specific examples thereof include a perfluorocyclohexane-1,4-diyl group.
  • (R 1 O) m is any of the following formulas (R-2) to (R-4).
  • R f3 O) m3 (R-4) the reference numerals of the formulas (R-2) to (R-4) are the same as those of the formula (R-1).
  • the bonding order of (R f1 O) and (R f2 O) and (R f2 O) and (R f4 O) is arbitrary.
  • (R f1 O) and (R f2 O) may be arranged alternately, (R f1 O) and (R f2 O) may be arranged in blocks, respectively, or may be random.
  • m1 is preferably 1 to 30, more preferably 1 to 20.
  • m2 is preferably 1 to 30, more preferably 1 to 20.
  • m3 is preferably 1 to 30, more preferably 1 to 20.
  • m4 is preferably 1 to 30, more preferably 1 to 20.
  • m3 is preferably 1 to 30, more preferably 1 to 20.
  • m2 / m1 is preferably 0.1 to 10, more preferably 0.2 to 5.0, from the viewpoint of further excellent abrasion resistance and fingerprint stain removal property of the surface layer. 0.2 to 2.0 is more preferable, 0.2 to 1.5 is particularly preferable, and 0.2 to 0.85 is most preferable.
  • the ratio of fluorine atoms in the partial structure (1) [ ⁇ number of fluorine atoms / (number of fluorine atoms + number of hydrogen atoms) ⁇ x 100 (%)] is excellent in water and oil repellency and fingerprint removal. , 40% or more is preferable, 50% or more is more preferable, and 60% or more is further preferable.
  • the total molecular weight of the partial structure (1) portion is preferably 200 to 30,000, more preferably 600 to 25,000, and further 1,000 to 20,000 from the viewpoint of wear resistance. preferable.
  • L in the partial structure (2) is a hydrolyzable group or a hydroxyl group.
  • L When L is a hydroxyl group, it constitutes a silanol (Si—OH) group together with a Si atom.
  • the hydrolyzable group is a group that becomes a hydroxyl group by a hydrolyzing reaction.
  • the silanol group further reacts between 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). Since this compound has four or more partial structures (2), it has excellent wear durability.
  • the partial structure (2) is preferably 4 to 20, more preferably 4 to 15.
  • L as a hydrolyzable group examples include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an isocyanate group (-NCO) and the like.
  • alkoxy group an alkoxy group having 1 to 4 carbon atoms is preferable.
  • acyl group an acyl group having 1 to 6 carbon atoms is preferable.
  • acyloxy group an acyloxy group having 1 to 6 carbon atoms is preferable.
  • L an alkoxy group or a halogen atom having 1 to 4 carbon atoms is preferable from the viewpoint of ease of production of this compound.
  • halogen atom a chlorine atom is particularly preferable.
  • an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgassing at the time of coating and the storage stability of this compound is excellent, and an ethoxy group is used when long-term storage stability of this compound is required. It is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.
  • R 10 is a hydrogen atom or a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group and the like.
  • the monovalent hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms. If the carbon number of R 10 is within this range, the compound easily produced.
  • p is preferably 2 or 3, and more preferably 3.
  • the presence of a plurality of L in one hydrolyzable silyl group further improves the adhesion to the substrate.
  • -Si (OCH 3 ) 3 As the partial structure (2), -Si (OCH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si (OCH 2 CH 3 ) 3 , -SiCl 3 , -Si (OCOCH 3 ) 3 , -Si ( NCO) 3 is preferable.
  • -Si (OCH 3 ) 3 is particularly preferable from the viewpoint of ease of handling in industrial manufacturing.
  • the position of the partial structure (2) in the present compound may be, for example, the partial structure (2) may be directly bonded to the linking group X described later, or the partial structure (2) may be directly bonded or via an organic group. It may be combined with (R 1 O) m ⁇ of the partial structure (1). From the viewpoint of the durability of the water- and oil-repellent layer and the water- and oil-repellent properties, the partial structure (2) is bonded to (R 1 O) m-of the partial structure (1) directly or via an organic group. Is preferable.
  • this compound preferably has three or more partial structures represented by the following formula (3).
  • A is an organic group having a (q + 1) valence
  • q is an integer of 1 or more
  • *, Q 1 , R 1 , L, R 10 , n, p are the above formulas (1) or (2). Is similar to.
  • A is a q + 1 valent linear or branched linking group.
  • A is at least one kind of branch point selected from the group consisting of C, N, Si, ring structure and q + 1 valent organopolysiloxane residue (hereinafter referred to as “branch point P”). ) Is preferable.
  • a specific branched chain is bound to the branch point P.
  • the specific branched chain means a chain having a partial structure (1) or a partial structure (2) in the chain.
  • the ring structure is a 3- to 8-membered aliphatic ring and a 3- to 8-membered aromatic ring because it is easy to produce this compound and the surface layer is more 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.
  • Examples of the q + 1-valent organopolysiloxane residue include the following groups.
  • R 5 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. Carbon atoms in the alkyl group and alkoxy group for R 5 is preferably 1 to 10, 1 is particularly preferred.
  • Organic group A includes alkylene group, fluoroalkylene group, hydroxyalkylene group, alkoxyalkylene group, carbonyl group, amide bond, ether bond, thioether bond, urea bond, urethane bond, carbonate bond, ester bond, -SO 2 NR 6-. , -Si (R 6) 2 - , - OSi (R 6) 2 -, - Si (CH 3) 2 -Ph-Si (CH 3) 2 - and 1 selected from divalent organopolysiloxane residue It may have a group containing more than a species (hereinafter, also referred to as bond B).
  • R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Ph is a phenylene group.
  • the number of carbon atoms of the alkyl group of R 6 is preferably 1 to 3 and particularly preferably 1 to 2 from the viewpoint that the present compound can be easily produced.
  • each bond or group constituting the organic group A may have any end arranged on the partial structure (1) side.
  • the carbon atom may be arranged on the partial structure (1) side and the nitrogen atom may be arranged on the partial structure (2) side, or the carbon atom may be arranged on the partial structure (2) side and nitrogen. Atoms may be arranged on the partial structure (1) side. The same applies to other bonds and groups.
  • 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.
  • the organic group A is a hydrocarbon group, -C (O) NR 6- , -C (O)-, -C (O) OR 6- , -NR 6- and -O because it is easy to produce this compound. It is preferable to have at least one bond selected from the group consisting of ⁇ , and the hydrocarbon group, ⁇ C (O) NR 6 ⁇ , ⁇ C (O) is further excellent in light resistance and chemical resistance of the surface layer. )-Or -C (O) O- is particularly preferred.
  • the organic group A a combination of two or more divalent hydrocarbon groups and one or more branch points P, or two or more hydrocarbon groups and one or more branch points P and one or more bonds.
  • the combination with B 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.
  • the organic group A is preferably a group represented by any of the following formulas (A1) to (A9) from the viewpoint of excellent water and oil repellency, abrasion resistance, and fingerprint stain removal property.
  • a 1 represents a single bond, an alkylene group, or a carbon of an alkylene group having 2 or more carbon atoms - -C between carbon atoms (O) NR 8 -, - C (O) OR 8 -, - C (O) -, -OC (O) O -, - NR 8 C (O) O -, - NHC (O) NR 8 -, - O -, - NHR 8 -, - NR 8 2 - or SO 2 NR 8 - group with , and the in the formulas, if a 1 is present 2 or more, 2 or more of a 1 may be different even in the same.
  • the hydrogen atom of the alkylene group may be substituted with a fluorine atom.
  • the carbon number of A 1 is preferably 1 to 8.
  • the carbon of the alkylene group having two or more alkylene groups having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O-, an alkylene group -C at the end on the side not connected to the Si of the (O) NR 8 -, - C (O) -, - NR 8 - or a group having O-, or carbon number of 2 or more alkylene group of a carbon - between carbon atoms -C (O) NR 8 to -, - C (O) - , - NR 8 - or O- the have and -C to the end on the side not connected to the Si (O) NR 8 -, - C (O) -, -NR 8 -or O-, and if two or more Q 22s are present in each formula, the two or more Q 22s may be the same or different.
  • Q 23 is an alkylene group, or a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O- , the two of Q 23 may be the same or different.
  • Q 24, when atom in Z 1 to Q 24 is attached is a carbon atom, a Q 22, when atoms in Z 1 to Q 24 is attached is a nitrogen atom, a Q 23, in each formula, Q 24 If is present 2 or more, two or more Q 24 may be different even in the same.
  • Q 25 is an alkylene group, or a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O- , In each equation, when two or more Q 25s are present, the two or more Q 25s may be the same or different.
  • Q 26 is an alkylene group, or a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having the O- ..
  • R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • Q 27 is a single bond or an alkylene group.
  • Q 28 represents an alkylene group, or a carbon atom of the alkylene group having 2 or more carbon atoms - a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms.
  • R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • Z 1 is a group having a (1 + h2) valent ring structure having a carbon atom or nitrogen atom to which A 1 is directly bonded and a carbon atom or nitrogen atom to which Q 24 is directly bonded.
  • R e1 is a hydrogen atom or an alkyl group, and when two or more Re1s are present in each formula, two or more Re1s may be the same or different.
  • Re2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
  • Re3 is an alkyl group.
  • Re4 is a hydrogen atom or an alkyl group, and a hydrogen atom is preferable because it is easy to produce a compound.
  • the two or more Re 4s may be the same or different.
  • Re5 is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable from the viewpoint that a compound can be easily produced.
  • d2 is an integer of 0 to 3, preferably 1 or 2.
  • d4 is an integer of 0 to 3, preferably 2 or 3. 2 to 5 are preferable for d2 + d4.
  • e2 is 2 or 3.
  • h2 is an integer of 1 or more (preferably 2 or 3).
  • i2 is 2 or 3.
  • i3 is 2 or 3.
  • i4 is 1 or more (an integer of 1 to 10 is preferable, and an integer of 1 to 6 is particularly preferable).
  • i5 is an integer of 2 to 7.
  • the carbon number of the alkylene group of Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , and Q 28 makes it easy to manufacture this compound, and the abrasion resistance, light resistance, and light resistance of the water- and oil-repellent layer. From the viewpoint of further excellent chemical properties, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable. However, when a specific bond is formed between carbon atoms, the lower limit of the number of carbon atoms of the alkylene group is 2.
  • Examples of the ring structure in Z 1 include the above-mentioned ring structure, and the preferred form is also the same. Since A 1 and Q 24 are directly bonded to the ring structure in Z 1 , for example, an alkylene group is linked to the ring structure, and A 1 and Q 24 are not linked to the alkylene group.
  • Z a is a (i5 + 1) -valent organopolysiloxane residue, and the above-mentioned group is preferable.
  • organic group A a group represented by any of the following formulas (A11) to (A19) can be mentioned.
  • G 1 is a group represented by the following (G1), wherein (A11) ⁇ formula (A19), if G 1 is present 2 or more, 2 or more in G 1 is optionally substituted by one or more identical May be good.
  • the codes other than G 1 are the same as the codes in the formulas (A1) to (A9).
  • -Si (R 9 ) 3-r1 (-Q 30- ) r1 formula (G1) However, in the equation (G1), the Si side is connected to Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 , and the Q 30 side is connected to the partial structure (2).
  • R 9 is an alkyl group.
  • the carbon of the alkylene group, having two or more alkylene groups having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O-, or ( OSi (R 10) 2) a pp -O-, 2 or more Q 3 are may be the same or different.
  • r1 is 2 or 3.
  • R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • R 10 is an alkyl group, a phenyl group or an alkoxy group, and the two R 10s may be the same or different.
  • pp is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSI (R 10 ) 2 ) may be the same or different.
  • the alkylene group of Q 30 are that the compound easily produced, and, rub resistance water- and oil-repellent layer, from the viewpoint of light resistance and chemical resistance are further excellent, preferably 1-10, 1-6 Is more preferable, and 1 to 4 are particularly preferable.
  • the lower limit of the number of carbon atoms of the alkylene group is 2.
  • the number of carbon atoms of the alkyl group of R 9 is preferably 1 to 10, more preferably 1 to 6, further 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 10 is preferably 1 to 10, more preferably 1 to 6, further 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 10 is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of excellent storage stability of the present compound.
  • the pp is preferably 0 or 1.
  • the structure of the following formula can be mentioned.
  • L 1 in the formula indicates a partial structure (1)
  • L 2 indicates a partial structure (2), and does not constitute a linking group A.
  • this compound is preferably a fluorine-containing compound represented by the following formula (4).
  • X [- ⁇ C (Q 1 ) 2 ⁇ n- O- (R 1 O) m- A ⁇ -SiL p R 10 (3-p) ⁇ q ] r
  • X is an r-valent connection having one or more atoms selected from a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, and a tertiary nitrogen atom.
  • the linking group X connects r substructures (1), and may have any structure as long as the object is achieved.
  • the linking group X is a hydrocarbon group which may have a hetero atom or the hydrogen atom may be substituted with a fluorine atom, and is a [- ⁇ C (Q 1 ) 2 ⁇ of the partial structure (1).
  • n ] can be mentioned as an element bonded to a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, and a tertiary nitrogen atom.
  • an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom is preferable from the viewpoint of the stability of the present compound.
  • r may be 3 or more, preferably 3 to 20 from the viewpoint of durability and water and oil repellency, and more preferably 3 to 10.
  • the X has one or more partial structures selected from the following formulas (X-1) to the following formulas (X-6).
  • the linking group X is provided with a branch having a chemically stable structure.
  • Q 3 is a hydrogen atom or a fluorine atom.
  • C in the formula (X-6) is a carbon atom constituting an aromatic ring, one of the bonds possessed by the carbon atom is a single bond, and the remaining bond (the bond with a wavy line) is It constitutes an aromatic ring.
  • C in the formula (X-1) represents a tertiary carbon atom
  • C in the formula (X-2) represents a quaternary carbon atom
  • Si in the formula (X-3) represents a tertiary silicon atom
  • Si in the formula (X-4) represents a quaternary silicon atom
  • N in the formula (X-5) represents a tertiary silicon atom
  • each of these atoms has a single bond.
  • C in the formula (X-6) is a carbon atom constituting an aromatic ring, one of the bond hands possessed by the carbon atom is a single bond, and the remaining bond hands (bond hands in which wavy lines are described) are described. ) Consists of an aromatic ring.
  • the partial structure (X-1) to the partial structure (X-5) may independently form a branch point.
  • the partial structure (X-6) may form a branch point together with other elements constituting the aromatic ring.
  • the benzene ring can be regarded as a structure in which six partial structures (X-6) are connected, and constitutes a branch point of six branches.
  • the partial structures (X-1) to (X-5) may independently constitute the linking group X, and may directly or via the linking group with the other substructures (X-1) to (X-6). It may be combined. By connecting a plurality of partial structures (X-1) to (X-6), a connecting group X having a large number of branches is obtained.
  • the single bonds of the partial structure (X-1) to the partial structure (X-6) are independently bonded to the * of the partial structure (1), either directly or via a linking group, or another partial structure (X-1). )-(X-6), or with other substituents.
  • the linking group here include an alkylene group which may have an ether bond in the carbon chain and may be substituted with a fluorine atom.
  • substituents include alkyl groups, fluorine atoms, hydroxyl groups, and the like, which may have an ether bond in the carbon chain and may be substituted with a fluorine atom.
  • the aromatic ring formed by the partial structure (X-6) may be a carbon ring or a heterocycle.
  • Examples of the carbon ring include naphthalene, indene, anthracene, and fluorene, in addition to the benzene ring.
  • Examples of the heterocycle include furan, thiophene, pyrrole, and pyridine.
  • the linking group X is the above formula (X-1) to (X-5) or the following formulas (X-11) to (X-25) from the viewpoint of durability and water repellency and oil repellency of the present compound. Is preferable.
  • Q 3 are a hydrogen atom or a fluorine atom
  • a plurality of Q 3 are may be the same or different and R 2 is an alkylene group that may have a single bond or an ether bond in the carbon chain, or may be substituted with a fluorine atom.
  • linking group X A preferable specific example of the linking group X is shown below.
  • L 1 in the formula indicates the partial structure (1) and does not constitute the connecting group X.
  • the plurality of present compounds may exist as one kind of single compound, or may exist as two or more kinds of compounds.
  • the molecular weight of this compound is preferably 500 to 100,000, particularly preferably 1000 to 20,000.
  • the molecular weight distribution (Mw / Mn) of the compounds is preferably 1.0 to 2.0, particularly preferably 1.0 to 1.3.
  • R 1 , L 2 and m are as described above
  • R 3 is a fluoroalkylene group having 1 to 6 carbon atoms
  • R 4 is a linear or branched fluoroalkylene group, which is preferable. Is a fluoroalkylene group having 1 to 6 carbon atoms, and R 3 and R 4 form a part of the organic group A in the formula (4).
  • R 12 is a fluoroalkylene group having 1 to 5 carbon atoms
  • "R 12- CH 2- O" in the following formula is one "R 1 " of (R 1 O) m in the formula (4). It constitutes "O".
  • the compound represented by the formula (4) can be produced, for example, by hydrosilylating a precursor represented by the formula (4A) and a compound represented by the formula (5A) below.
  • A' has an ethylenically unsaturated bond at the terminal, and after the introduction of the hydrolyzable silyl group, it is an organic group corresponding to A of the formula (4)
  • X, Q 1 , R 1 , L, R 10 , n, m, r, and p are the same as in the equation (4).
  • the compound represented by the formula (4) can be produced, for example, by subjecting a precursor represented by the formula (4B) below and a compound represented by the formula (5B) to an amidation reaction.
  • a "is an organic group having a structure in which" A "-C ( O) -NH-R b " corresponds to the organic group A in the formula (4) after synthesis, and Ra is an alkyl group or a fluoroalkyl group.
  • R b is an alkylene group or a fluoroalkylene group
  • X, Q 1 , R 1 , L, R 10 , n, m, r, and p are the same as in the formula (4).
  • 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 that are unavoidable 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.
  • a compound that is less likely to deteriorate the properties 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.
  • Examples of the by-product fluorine-containing compound include unreacted fluorine-containing compounds at the time of synthesis of this compound.
  • the purification step for removing the by-product fluorine-containing compound 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 fluoropolymers described in Japanese Patent No. 28747115, Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097, Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 2000-327772, Fluorinated siloxane described in Japanese Patent Publication No. 2002-506887, Organic silicone compounds described in Japanese Patent Publication No. 2008-534696, Fluorinated modified hydrogen-containing polymer described in Japanese Patent No. 4138936, Compounds described in U.S.
  • 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 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, lubricity, and appearance.
  • the coating liquid of the present invention 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 present compound or the present composition, and may contain impurities such as by-products produced in the manufacturing process of the present 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.
  • an organic solvent is preferable.
  • the organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or both solvents.
  • fluorinated organic solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.
  • 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 CHFC CHFCF 3 (manufactured by The Chemours Company, Bertrel® XF) and the like.
  • 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, for example, CF 3 CH 2 OCF 2 CF 2 H (AGC, Asahiclean® AE-3000), C 4 F 9 OCH 3 (3M, Novec® 7100), Examples include C 4 F 9 OC 2 H 5 (3M, Novec® 7200), C 2 F 5 CF (OCH 3 ) C 3 F 7 (3M, Novec® 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.
  • the non-fluorine-based organic solvent a compound consisting of only hydrogen atoms and carbon atoms and a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms are preferable, and hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, 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, and preferably 85 to 99.99% by mass. It is particularly preferable to contain 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 in 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 water- and oil-repellent layer 22 in this order.
  • the base layer contains an oxide containing silicon, and the water- and oil-repellent 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 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 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 water-repellent oil-repellent layer is further improved.
  • As the surface treatment a corona discharge treatment or a plasma treatment is preferable because the wear resistance of the water-repellent oil-repellent layer is further excellent.
  • 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 water- and oil-repellent layer having excellent wear durability. Is formed.
  • 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.
  • the content of silicon oxide is the balance obtained by subtracting the total content of other elements (in the case of oxide, the amount converted to oxide) from the mass of the underlying layer.
  • the oxides in the base layer are further composed of alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel and chromium. , Molybdenum, and 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 base layer 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 of these elements is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and even 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 sum of boron and phosphorus relative to the molar concentration of silicon in terms of wear resistance of the water and oil repellent layer.
  • the molar concentration ratio is preferably 0.003 to 9, preferably 0.003 to 2, and even more preferably 0.003 to 0.5.
  • the base layer contains alkaline earth metal elements
  • the total content of these is the total molar concentration of alkaline earth metal elements with respect to the molar concentration of silicon in terms of the abrasion resistance of the water- and oil-repellent layer.
  • the ratio 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 water-repellent oil-repellent layer is 0.1 to 0.3 nm is 2.0 ⁇ 10 19 atoms / cm 3. The above is preferable.
  • 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, 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 becomes 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 of 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 during 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 vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.
  • Evaporation methods for the vaporized material include a resistance heating method in which the vaporized material is melted and evaporated on a refractory metal resistance heating boat, an electron beam is applied to the vaporized material, and the vaporized material is directly heated to melt the surface.
  • the refractory 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 gun method is preferred.
  • a molten granule or a sintered body is preferable because it is difficult to scatter even if an air flow is generated.
  • the water- and oil-repellent layer on the base layer contains the condensate of the present compound.
  • a silanol group Si—OH
  • Si—OH silanol group
  • 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.
  • the water-repellent and oil-repellent layer may contain a condensate of a fluorine-containing compound other than this compound. That is, the water- and oil-repellent layer contains a fluorine-containing compound having a reactive silyl group in a state in which a part or all of the reactive silyl groups of the fluorine-containing compound is condensed.
  • the thickness of the water-repellent and oil-repellent layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the water- and oil-repellent layer is equal to or greater than the lower limit of the above range, the effect of the water- and oil-repellent layer can be sufficiently obtained. When the thickness of the water-repellent and oil-repellent layer is equal to or less than the upper limit of the above range, the utilization efficiency is high.
  • the thickness of the water-repellent oil-repellent layer is the thickness obtained by the X-ray diffractometer for thin film analysis.
  • the thickness of the water-repellent and oil-repellent layer can be calculated from the vibration cycle of the interference pattern by obtaining the interference pattern of 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 water-repellent oil-repellent layer 22 in this order.
  • the base material contains an oxide containing silicon
  • the water- and oil-repellent layer contains the condensate of the present compound.
  • the base material has the composition of the base layer in the first article
  • the water and oil repellent layer is excellent in abrasion durability even if the water and oil repellent 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 water-repellent and oil-repellent layer is the same as that of the first article, the description thereof is omitted here.
  • the method for producing an article according to the present invention is a method of forming a water-repellent oil-repellent 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 methods such as vacuum deposition, CVD, and sputtering.
  • 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 the present 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 the present compound can be produced by impregnating a metal porous body with a solution of the present compound, drying the mixture, and removing the 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 carried out.
  • the operation include heating, humidification, and light irradiation.
  • a hydrolyzable group is hydrolyzed, a hydroxyl group 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 2, Example 3, Example 4, Example 5, Example 8, Example 9, and Example 10 are examples, and Examples 1, 6, and 7 are comparative examples.
  • AC in the the CCl 2 FCClF 2 R-113, CClF 2 CF 2 CCl 2 CF 2 CF 3 a R-419, CF 3 CH 2 OCF 2 CF a 2 H AE-3000, C 6 F 13 H or less -2000, CF 3 CF 2 CHCl 2 is referred to as AK-225.
  • the crude solution obtained here was dissolved in AK-225, washed with saturated aqueous sodium hydrogen carbonate, and the organic phase was recovered. Further, magnesium sulfate was added to the recovered organic phase and the mixture was stirred. Then, magnesium sulfate was removed, and AK-225 was distilled off with an evaporator to obtain a liquid compound (1-1) (52.8 g) at room temperature.
  • the internal temperature was lowered to 25 ° C., and then a vacuum pump was installed in the cooling pipe to keep the inside of the system under reduced pressure, the solvent and reaction by-products were distilled off, and a liquid product (13.3 g) was obtained at room temperature. It was. As a result of analyzing the product, the formation of the following compound (1-3) was confirmed.
  • the ratio of the number of -COF groups in the product to the total number of ester bonds in compound (1-2) was 99 mol% or more.
  • fluorine gas diluted to 10% with nitrogen gas (hereinafter referred to as 10% fluorine gas) was blown into the autoclave at a flow rate of 24.8 L / hour for 1 hour.
  • 10% fluorine gas fluorine gas diluted to 10% with nitrogen gas
  • 12 mL of R-113 was injected while blowing 10% fluorine gas into the autoclave at the same flow rate.
  • the internal temperature was changed to 40 ° C.
  • Ts is a tosyl group.
  • the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 ⁇ m to obtain 5.4 g of the following compound IV.
  • the number average molecular weight of the product was 8620.
  • Example 8 Synthesis of compound VIII (Synthesis Example 8-1) 10 g of the compound (1-4), 50 g of 1,3-bistrifluorobenzene, and 5 g of a 2.0 M ammonia-methanol solution were placed in a 100 cc pressure resistant reactor, and the mixture was stirred at room temperature. Then, the solvent was distilled off to obtain 9.8 g of the following compound (8-1).
  • the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 ⁇ m to obtain 1.2 g of the following compound VIII.
  • the number average molecular weight of the product was 4550.
  • the surface treatment of the base material was performed using each of the compounds obtained in Examples 1 to 10 to obtain an article having a water-repellent and oil-repellent layer.
  • the surface treatment method the following dry coating method and wet coating method were used for each example. Chemically tempered glass was used as the base material.
  • the obtained article was evaluated by the following method. The results are shown in Tables 1 and 2.
  • Dry coating was performed using a vacuum vapor deposition apparatus (VTR-350M, manufactured by ULVAC, Inc.) (vacuum vapor deposition method).
  • VTR-350M vacuum vapor deposition apparatus
  • the 0.5g of the compound obtained in Example 1-7 was charged into a molybdenum boat in the vacuum evaporation apparatus was evacuated in the vacuum evaporation apparatus below 1 ⁇ 10- 3 Pa.
  • 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 vacuum vapor deposition apparatus
  • the shutter was closed to complete the film formation on the surface of the base material.
  • the base material on which the compound was deposited was heat-treated at 200 ° C. for 30 minutes and washed with AK-225 to obtain an article having a water-repellent and oil-repellent layer on the surface of the base material.
  • ⁇ Initial contact angle> For the water- and oil-repellent layer, the initial water contact angle and the initial n-hexadecane contact angle were measured by the above-mentioned measuring method. The evaluation criteria are as follows. Initial water contact angle: ⁇ (excellent): 113 degrees or more. ⁇ (Good): 105 degrees or more and less than 113 degrees. ⁇ (possible): 100 degrees or more and less than 105 degrees. ⁇ (impossible): Less than 100 degrees.
  • ⁇ Abrasion resistance> For the water- and oil-repellent layer, a felt (dimensions: 10 mm ⁇ 10 mm ⁇ 50 mm) was reciprocated at a load of 9.8 N and a speed of 80 rpm using a felt wear tester. The contact angle of water in the water-repellent and oil-repellent layer was measured every 1,000 round trips. The smaller the decrease in the contact angle of water after wear, the smaller the decrease in performance due to wear, and the better the wear resistance.
  • ⁇ Alkali resistance> The articles of Examples 1 to 7 were impregnated with an aqueous sodium hydroxide solution having a pH of 13 for 2 hours. After washing and drying the article with water, the water contact angle of the water-repellent and oil-repellent layer was measured. Water contact angle after alkaline immersion: ⁇ (excellent): 113 degrees or more. ⁇ (Good): 105 degrees or more and less than 113 degrees. ⁇ (possible): 100 degrees or more and less than 105 degrees. ⁇ (impossible): Less than 100 degrees.
  • the coating liquid 1 for forming a silicon oxide layer was dried at 150 ° C., and the organic solvent and water were removed to obtain a silicon oxide powder.
  • the content of sodium with respect to Si contained in the silicon oxide powder was measured by ICP emission spectroscopic analysis (SPS5520 manufactured by Hitachi High-Tech Science Co., Ltd.).
  • a coating liquid 1 for forming a silicon oxide layer was applied to the corona discharge-treated surface of the glass substrate by a spin coating method under the conditions of a rotation speed of 3,000 rpm and a rotation time of 20 seconds to form a wet film.
  • the wet film was fired under the conditions of firing temperature: 550 ° C. and firing time: 30 minutes to produce a glass substrate with a silicon oxide layer having a silicon oxide layer having a thickness of about 10 nm.
  • the base material was changed from the chemically strengthened glass to the above-mentioned glass base material with a silicon oxide layer, and the compounds obtained in the above-mentioned Example 1, Example 2, Example 4, Example 5 and Example 10 were used.
  • the surface treatment of the base material was performed using the above dry coating method and wet coating method, respectively.
  • the obtained article was evaluated by the method described above. The results are shown in Table 2.
  • both compounds I and II showed higher wear durability than those of the normal SiO 2 layer.
  • the degree of durability improvement when the Na-containing Si-oxide layer was used was higher than that of I. It is considered that this is because the number of hydrolyzable silyl groups bonded to the base material increases due to the effect of the Na-containing Si layer.
  • Articles provided with a water- and oil-repellent layer containing this compound include, for example, optical articles, touch panels, antireflection films, antireflection glass, SiO 2 treated glass, tempered glass, which are used as part of the following product parts. It is useful as sapphire glass, quartz substrate, mold metal, etc.

Abstract

Provided are: a fluorine-containing compound capable of forming a water- and oil-repellent layer having excellent durability; a fluorine-containing compound-containing composition and coating liquid; an article provided with a surface layer that has excellent durability and can maintain water- and oil-repellency and fingerprint removal property for a long period of time; and a method for producing same. This fluorine-containing compound has at least three moiety structures represented by formula (1), and at least four moiety structures represented by formula (2).　(1): *-{C(Q1)2}n-O-(R1O)m- (2): -SiLpR10 (3-p) (where, each symbol in the formulae is as disclosed in the specification).

Description

含フッ素化合物、含フッ素化合物含有組成物、コーティング液、物品、及び物品の製造方法Fluorine-containing compound, fluorine-containing compound-containing composition, coating liquid, article, and method for producing the article
　本発明は、含フッ素化合物、含フッ素化合物含有組成物、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 compound, a fluorine-containing compound-containing composition, a coating liquid, an article, and a method for producing the article.
　従来より各技術分野において、物品の表面に撥水性を付与することが求められている。眼鏡レンズ、ウェアラブル端末、タッチパネルディスプレイ等の表面は、指紋など皮脂汚れが付着しやすいため、撥水撥油層を設けることが望まれている。基材の表面に撥水撥油性を付与すると、物品表面の汚れを拭き取りやすくなり、汚れの除去性が向上する。さらに近年では、各種物品の光学面のみならず、例えばスマートフォン等小型機器の筐体の指紋除去性も求められている。 Conventionally, in each technical field, it has been required to impart water repellency to the surface of an article. Since sebum stains such as fingerprints are likely to adhere to the surfaces of spectacle lenses, wearable terminals, touch panel displays, etc., it is desired to provide a water- and oil-repellent layer. By imparting water and oil repellency to the surface of the base material, it becomes easier to wipe off dirt on the surface of the article, and the dirt removal property is improved. Further, in recent years, not only the optical surface of various articles but also the fingerprint removal property of the housing of a small device such as a smartphone is required.
　撥水撥油層には、耐摩耗性や耐候性といった耐久性も求められている。耐久性に優れた撥水撥油層を形成し得る含フッ素化合物として、加水分解性シリル基が導入された含フッ素化合物が検討されている。
　例えば特許文献１では、撥水撥油性、油脂汚れの除去性に優れ、酸触媒の存在かつ高温条件下においても劣化耐性に優れた塗膜を形成できる表面処理剤として、加水分解性シリル基を１又は２個有する特定の含フッ素エーテル化合物を含む表面処理剤が開示されている。当該特許文献１の実施例では当該特定の含フッ素エーテル化合物に、加水分解性シリル基を３個有する含フッ素エーテル化合物を組み合わせた表面処理剤が開示されている。加水分解性シリル基が物品表面と結合することで耐久性を有する撥水撥油層が形成される。 The water- and oil-repellent layer is also required to have durability such as abrasion resistance and weather resistance. As a fluorine-containing compound capable of forming a water- and oil-repellent layer having excellent durability, a fluorine-containing compound into which a hydrolyzable silyl group has been introduced has been studied.
For example, in Patent Document 1, a hydrolyzable silyl group is used as a surface treatment agent capable of forming a coating film having excellent water and oil repellency and removal of oil and fat stains and excellent deterioration resistance even under high temperature conditions in the presence of an acid catalyst. A surface treatment agent containing one or two specific fluoroether compounds is disclosed. In the examples of Patent Document 1, a surface treatment agent in which the specific fluorine-containing ether compound is combined with a fluorine-containing ether compound having three hydrolyzable silyl groups is disclosed. The hydrolyzable silyl group binds to the surface of the article to form a durable water- and oil-repellent layer.
国際公開第２００９／００８３８０号International Publication No. 2009/0083380
　特許文献１に記載の含フッ素エーテル化合物よりも、更なる耐久性が得られる含フッ素化合物が求められている。 There is a demand for a fluorine-containing compound that can obtain further durability than the fluorine-containing ether compound described in Patent Document 1.
　本発明は、耐久性に優れた撥水撥油層を形成可能な含フッ素化合物、含フッ素化合物含有組成物及びコーティング液、耐久性に優れ、撥水撥油性及び指紋除去性が長期間維持できる表面層を備えた物品及びその製造方法の提供を目的とする。 INDUSTRIAL APPLICABILITY According to the present invention, a fluorine-containing compound capable of forming a water- and oil-repellent layer having excellent durability, a fluorine-containing compound-containing composition and a coating liquid, and a surface having excellent durability and maintaining water-repellent and oil-repellent properties and fingerprint removing properties for a long period of time An object of the present invention is to provide an article having a layer and a method for producing the same.
　本発明は、以下［１］～［１３］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）で表される部分構造を３つ以上、
　下式（２）で表される部分構造を４つ以上有する、含フッ素化合物。
　　＊－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－　　　　（１）
　　－ＳｉＬｐＲ１０ （３－ｐ）　　　　　　　　　　　　　　（２）
　ただし、
　＊には、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、
　Ｑ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよく、
　Ｒ１は、直鎖又は分岐を有するフルオロアルキレン基であって、複数ある場合のＲ１は同一であっても異なっていてもよく、
　Ｌは加水分解性基又は水酸基であって、複数ある場合のＬは同一であっても異なっていてもよく、
　Ｒ１０は水素原子又は１価の炭化水素基であって、複数ある場合のＲ１０は同一であっても異なっていてもよく、
　ｎは０以上の整数であり、
　ｍは１以上の整数であり、
　ｐは１～３の整数である。 The present invention provides a fluorine-containing compound having the following constitutions [1] to [13] and a method for producing the same, a fluorine-containing compound-containing composition, a coating liquid, an article, and a method for producing the same.
[1] Three or more partial structures represented by the following equation (1),
A fluorine-containing compound having four or more partial structures represented by the following formula (2).
*-{C (Q 1 ) 2 } n- O- (R 1 O) m- (1)
-SiL p R 10 (3-p) (2)
However,
A tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom are bonded to *.
Q 1 represents a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different and
R 1 is a linear or branched fluoroalkylene group, and when there are a plurality of R 1, they may be the same or different.
L is a hydrolyzable group or a hydroxyl group, and when there are a plurality of L, the L may be the same or different.
R 10 is a hydrogen atom or a monovalent hydrocarbon group, and when there are a plurality of them, R 10 may be the same or different.
n is an integer greater than or equal to 0 and
m is an integer greater than or equal to 1
p is an integer of 1 to 3.
　［２］下式（３）で表される部分構造を３つ以上有する、［１］の含フッ素化合物。
　　＊－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ｛－ＳｉＬｐＲ１０ （３－ｐ）｝ｑ　　　　（３）
　ただし、
　＊には、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、
　Ｑ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよく、
　Ｒ１は、直鎖又は分岐を有するフルオロアルキレン基であって、複数ある場合のＲ１は同一であっても異なっていてもよく、
　Ａは（ｑ＋１）価の有機基であり、
　Ｌは加水分解性基又は水酸基であって、複数ある場合のＬは同一であっても異なっていてもよく、
　Ｒ１０は水素原子又は１価の炭化水素基であって、複数ある場合のＲ１０は同一であっても異なっていてもよく、
　ｎは０以上の整数であり、
　ｍは１以上の整数であり、
　ｐは１～３の整数であり、
　ｑは１以上の整数であり、ｑの総和は４以上である。 [2] The fluorine-containing compound of [1] having three or more partial structures represented by the following formula (3).
*-{C (Q 1 ) 2 } n- O- (R 1 O) m- A {-SiL p R 10 (3-p) } q (3)
However,
A tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom are bonded to *.
Q 1 represents a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different and
R 1 is a linear or branched fluoroalkylene group, and when there are a plurality of R 1, they may be the same or different.
A is a (q + 1) -valent organic group,
L is a hydrolyzable group or a hydroxyl group, and when there are a plurality of L, the L may be the same or different.
R 10 is a hydrogen atom or a monovalent hydrocarbon group, and when there are a plurality of them, R 10 may be the same or different.
n is an integer greater than or equal to 0 and
m is an integer greater than or equal to 1
p is an integer from 1 to 3 and
q is an integer of 1 or more, and the sum of q is 4 or more.
　［３］下式（４）で表される、［１］又は［２］の含フッ素化合物。
　　Ｘ［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ｛－ＳｉＬｐＲ１０ （３－ｐ）｝ｑ］ｒ　　　　（４）
　ただし、
　Ｘは、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、及び３級窒素原子より選択される原子を１個以上有するｒ価の連結基であり、
　［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－］のＸ側には、Ｘにおける３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、
　Ｑ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよく、
　Ｒ１は、直鎖又は分岐を有するフルオロアルキレン基であって、複数あるＲ１は同一であっても異なっていてもよく、
　Ａは（ｑ＋１）価の有機基であって、複数あるＡは同一であっても異なっていてもよく、
　Ｌは加水分解性基又は水酸基であって、複数あるＬは同一であっても異なっていてもよく、
　Ｒ１０は水素原子又は１価の炭化水素基であって、複数あるＲ１０は同一であっても異なっていてもよく、
　ｎは０以上の整数であり、複数あるｎは同一であっても異なっていてもよく、
　ｍは１以上の整数であり、複数あるｍは同一であっても異なっていてもよく、
　ｐは１～３の整数であり、複数あるｐは同一であっても異なっていてもよく、
　ｑは１～３の整数であり、ｑの総和は４以上であり、複数あるｑは同一であっても異なっていてもよく、
　ｒは３以上の整数である。 [3] The fluorine-containing compound of [1] or [2] represented by the following formula (4).
X [-{C (Q 1 ) 2 } n- O- (R 1 O) m- A {-SiL p R 10 (3-p) } q ] r (4)
However,
X is an r-valent connection having one or more atoms selected from a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, and a tertiary nitrogen atom. Is the basis and
On the X side of [-{C (Q 1 ) 2 } n- O-], there are a tertiary carbon atom in X, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, and a quaternary silicon atom. , Or a tertiary nitrogen atom is bonded,
Q 1 represents a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different and
R 1 is a linear or branched fluoroalkylene group, and a plurality of R 1s may be the same or different.
A is a (q + 1) -valent organic group, and a plurality of A's may be the same or different.
L is a hydrolyzable group or a hydroxyl group, and a plurality of Ls may be the same or different.
R 10 is a hydrogen atom or a monovalent hydrocarbon group, and a plurality of R 10s may be the same or different.
n is an integer of 0 or more, and a plurality of n may be the same or different.
m is an integer of 1 or more, and a plurality of m may be the same or different.
p is an integer of 1 to 3, and a plurality of ps may be the same or different.
q is an integer of 1 to 3, the sum of q is 4 or more, and a plurality of qs may be the same or different.
r is an integer of 3 or more.
　［４］前記Ｘが下式（Ｘ－１）～下式（Ｘ－６）より選択される１種以上の部分構造を有する、［３］の含フッ素化合物。 [4] The fluorine-containing compound of [3], wherein the X has one or more partial structures selected from the following formulas (X-1) to (X-6).
Figure JPOXMLDOC01-appb-C000002
 　ただし、Ｑ３は、水素原子又はフッ素原子である。式（Ｘ－６）中のＣは芳香環を構成する炭素原子であり、当該炭素原子が有する結合手の１つは単結合であり、残りの結合手（波線が記載された結合手）は芳香環を構成する。
Figure JPOXMLDOC01-appb-C000002
 However, Q 3 is a hydrogen atom or a fluorine atom. C in the formula (X-6) is a carbon atom constituting an aromatic ring, one of the bonds possessed by the carbon atom is a single bond, and the remaining bond (the bond with a wavy line) is It constitutes an aromatic ring.
　［５］前記Ａが、アルキレン基、フルオロアルキレン基、カルボニル基、アミド結合、エーテル結合、エステル結合、ウレア結合、ウレタン結合及びカーボネート結合より選択される１種以上を含む（ｑ＋１）価の有機基である、［２］～［４］いずれかの含フッ素化合物。 [5] The (q + 1) -valent organic group in which the A contains one or more selected from an alkylene group, a fluoroalkylene group, a carbonyl group, an amide bond, an ether bond, an ester bond, a urea bond, a urethane bond and a carbonate bond. The fluorine-containing compound according to any one of [2] to [4].
　［６］前記（Ｒ１Ｏ）が、下式（Ｒ－１）で表される、［１］～［５］いずれかの含フッ素化合物。
　　［（Ｒｆ１Ｏ）ｍ１（Ｒｆ２Ｏ）ｍ２（Ｒｆ３Ｏ）ｍ３（Ｒｆ４Ｏ）ｍ４（Ｒｆ５Ｏ）ｍ５（Ｒｆ６Ｏ）ｍ６］　　　　　　　　　　　　　　　　（Ｒ－１）
　ただし、
　Ｒｆ１は、炭素数１のフルオロアルキレン基であり、
　Ｒｆ２は、炭素数２のフルオロアルキレン基であり、
　Ｒｆ３は、炭素数３のフルオロアルキレン基であり、
　Ｒｆ４は、炭素数４のフルオロアルキレン基であり、
　Ｒｆ５は、炭素数５のフルオロアルキレン基であり、
　Ｒｆ６は、炭素数６のフルオロアルキレン基であり、
　ｍ１、ｍ２、ｍ３、ｍ４、ｍ５、ｍ６は、それぞれ、０又は１以上の整数を表しｍ１＋ｍ２＋ｍ３＋ｍ４＋ｍ５＋ｍ６は１～２００の整数である。 [6] The fluorine-containing compound according to any one of [1] to [5], wherein (R 1 O) is represented by the following formula (R-1).
[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ] (R-1)
However,
R f1 is a fluoroalkylene group having 1 carbon atom.
R f2 is a fluoroalkylene group having 2 carbon atoms.
R f3 is a fluoroalkylene group having 3 carbon atoms.
R f4 is a fluoroalkylene group having 4 carbon atoms.
R f5 is a fluoroalkylene group having 5 carbon atoms.
R f6 is a fluoroalkylene group having 6 carbon atoms and has 6 carbon atoms.
m1, m2, m3, m4, m5, and m6 represent integers of 0 or 1, respectively, and m1 + m2 + m3 + m4 + m5 + m6 are integers of 1 to 200.
　［７］前記［１］～［６］いずれかの含フッ素化合物と、他の含フッ素化合物とを含む、含フッ素化合物含有組成物。
　［８］前記［１］～［６］いずれかの含フッ素化合物、又は［７］の含フッ素化合物含有組成物と、液状媒体とを含有する、コーティング液。
　［９］基材と、下地層と、撥水撥油層とをこの順で有する物品であって、
　前記下地層がケイ素を含む酸化物を含有し、
　前記撥水撥油層が、［１］～［６］いずれかの含フッ素化合物の縮合体を含有する、物品。
　［１０］前記酸化物が、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、［９］の物品。
　［１１］基材と、撥水撥油層とをこの順で有する物品であって、
　前記基材がケイ素を含む酸化物を含有し、前記撥水撥油層が、［１］～［６］いずれかの含フッ素化合物の縮合体を含有する、物品。
　［１２］前記酸化物が、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、［１１］の物品。
　［１３］前記［１］～［６］いずれかの含フッ素化合物、［７］の含フッ素化合物含有組成物、又は［８］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、撥水撥油層を形成する、物品の製造方法。 [7] A fluorine-containing compound-containing composition containing the fluorine-containing compound according to any one of the above [1] to [6] and another fluorine-containing compound.
[8] A coating liquid containing the fluorine-containing compound according to any one of [1] to [6] or the fluorine-containing compound-containing composition of [7] and a liquid medium.
[9] An article having a base material, a base layer, and a water- and oil-repellent layer in this order.
The base layer contains an oxide containing silicon,
An article in which the water- and oil-repellent layer contains a condensate of any of the fluorine-containing compounds [1] to [6].
[10] The oxide is one selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. The article of [9] containing the above elements.
[11] An article having a base material and a water- and oil-repellent layer in this order.
An article in which the base material contains an oxide containing silicon, and the water-repellent oil-repellent layer contains a condensate of a fluorine-containing compound according to any one of [1] to [6].
[12] The oxide is one selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. The article of [11] containing the above elements.
[13] The fluorine-containing compound according to any one of [1] to [6], the fluorine-containing compound-containing composition of [7], or the coating solution of [8] is used to repel by a dry coating method or a wet coating method. A method of manufacturing an article that forms a water-repellent layer.
　本発明により、耐久性に優れた撥水撥油層を形成可能な含フッ素化合物、含フッ素化合物含有組成物及びコーティング液、耐久性に優れ、撥水撥油性及び指紋除去性が長期間維持できる表面層を備えた物品及びその製造方法を提供できる。 According to the present invention, a fluorine-containing compound capable of forming a water- and oil-repellent layer having excellent durability, a fluorine-containing compound-containing composition and a coating liquid, and a surface having excellent durability and maintaining water-repellent and oil-repellent properties and fingerprint repellent properties for a long period of time. An article having a layer and a method for producing the same can be 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）で表される部分構造を、部分構造（１）と称することがある。また、式（４）で表される化合物を、化合物（４）と称することがある。他の式についてもこれに準ずる。
　本明細書においてペルフルオロアルキル基とは、アルキル基の水素原子が全てフッ素原子で置換された基を意味する。また、本明細書においてフルオロアルキル基とは、１個以上のフッ素原子を有するアルキル基を意味し、ペルフルオロアルキル基を含むものとする。フルオロアルキレン基もこれに準ずる。 In the present specification, the partial structure represented by the formula (1) may be referred to as a partial structure (1). Further, the compound represented by the formula (4) may be referred to as a compound (4). The same applies to other formulas.
As used herein, the term "perfluoroalkyl group" means a group in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms. Further, in the present specification, the fluoroalkyl group means an alkyl group having one or more fluorine atoms, and includes a perfluoroalkyl group. The same applies to the fluoroalkylene group.
［含フッ素化合物］
　本発明の含フッ素化合物（以下、本化合物ともいう。）は、下式（１）で表される部分構造を３つ以上、下式（２）で表される部分構造を４つ以上有する。
　　＊－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－　　　　（１）
　　－ＳｉＬｐＲ１０ （３－ｐ）　　　　　　　　　　　　　　（２）
　ただし、
　＊には、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、
　Ｑ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよく、
　Ｒ１は、直鎖又は分岐を有するフルオロアルキレン基であって、複数あるＲ１は同一であっても異なっていてもよく、
　Ｌは加水分解性基又は水酸基であって、複数あるＬは同一であっても異なっていてもよく、
　Ｒ１０は水素原子又は１価の炭化水素基であって、複数あるＲ１０は同一であっても異なっていてもよく、
　ｎは０以上の整数であり、ｍは１以上の整数であり、ｐは１～３の整数である。 [Fluorine-containing compound]
The fluorine-containing compound of the present invention (hereinafter, also referred to as the present compound) has three or more partial structures represented by the following formula (1) and four or more partial structures represented by the following formula (2).
*-{C (Q 1 ) 2 } n- O- (R 1 O) m- (1)
-SiL p R 10 (3-p) (2)
However,
A tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom are bonded to *.
Q 1 represents a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different and
R 1 is a linear or branched fluoroalkylene group, and a plurality of R 1s may be the same or different.
L is a hydrolyzable group or a hydroxyl group, and a plurality of Ls may be the same or different.
R 10 is a hydrogen atom or a monovalent hydrocarbon group, and a plurality of R 10s may be the same or different.
n is an integer of 0 or more, m is an integer of 1 or more, and p is an integer of 1 to 3.
　本化合物が有する部分構造（２）は、後述する通り、脱水縮合反応して基材表面と化学結合を形成する。また部分構造（１）はフルオロポリエーテル鎖であり撥水撥油性や油脂汚れ除去性を発揮する。本化合物は基材表面と４点以上の結合点を形成し得るため、耐久性の高い撥水撥油層が形成される。また３つ以上の部分構造（１）は撥水撥油層の外面側に配置されて、優れた撥水撥油性や油脂汚れ除去性を示すとともに、前記結合点へのアルカリ等の薬品の侵入を抑制するものと推定される。その結果、各種薬品に対する耐性にも優れていると考えられる。これらのことから、本化合物により、耐久性に優れた撥水撥油層が形成可能となる。 The partial structure (2) of this compound undergoes a dehydration condensation reaction to form a chemical bond with the surface of the substrate, as will be described later. Further, the partial structure (1) is a fluoropolyether chain, which exhibits water and oil repellency and oil and fat stain removing properties. Since this compound can form four or more bonding points with the surface of the base material, a highly durable water- and oil-repellent layer is formed. Further, three or more partial structures (1) are arranged on the outer surface side of the water-repellent oil-repellent layer, exhibit excellent water-repellent oil-repellent property and oil-fat stain removing property, and prevent chemicals such as alkali from entering the bonding point. It is presumed to suppress it. As a result, it is considered that the resistance to various chemicals is also excellent. From these facts, this compound makes it possible to form a water-repellent and oil-repellent layer having excellent durability.
　部分構造（１）は、フルオロポリエーテル鎖を表す。本化合物は３つ以上のフルオロポリエーテル鎖を有するため、撥水撥油性、油脂汚れ除去性などに優れている。
　部分構造（１）の＊側には、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子（以下、これらを３級又は４級原子ということがある）が結合している。当該３級又は４級原子は、単独で又は必要に応じて他の原子とともに後述する連結基を構成し、複数ある部分構造（１）などを連結している。複数ある部分構造（１）の＊には、同一の３級又は４級原子が結合していてもよく、また、異なる３級又は４級原子が結合していてもよい。 The partial structure (1) represents a fluoropolyether chain. Since this compound has three or more fluoropolyether chains, it is excellent in water repellency, oil repellency, oil stain removal property, and the like.
On the * side of the partial structure (1), a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom (hereinafter referred to as these) (Sometimes called a tertiary or quaternary atom) is bonded. The tertiary or quaternary atom constitutes a linking group described later alone or together with other atoms as necessary, and a plurality of partial structures (1) and the like are linked. The same tertiary or quaternary atom may be bonded to the * of the plurality of partial structures (1), or different tertiary or quaternary atoms may be bonded.
　部分構造（１）の｛Ｃ（Ｑ１）２｝ｎにおけるＱ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよい。ここでのＱ１はすべて水素原子であってもよく、少なくとも１つがフッ素原子であってもよい。即ち、｛Ｃ（Ｑ１）２｝ｎは、アルキレン基であってもよく、フルオロアルキレン基であってもよい。撥水撥油性、油脂汚れ除去性の点から、フルオロアルキレン基が好ましく、ペルフルオロアルキレン基がより好ましい。ｎは０であってもよく、１以上の整数であってもよい。
　ｎが０の場合、部分構造（１）は下式（１－１）の構造となる。
　　＊－Ｏ－（Ｒ１Ｏ）ｍ－　　　　　　　　　　（１－１）
　ただし、式（１－１）中の各符号は、式（１）と同様である。
　また、ｎが１以上の整数の場合、当該ｎは｛Ｃ（Ｑ１）２｝ｎの炭素数を表す。ｎが１以上の場合、当該ｎは１～３０が好ましく、１～２０がより好ましく、１～１５がさらに好ましい。
　｛Ｃ（Ｑ１）２｝ｎの具体例としては、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－等が挙げられる。 {C (Q 1) 2} Q 1 in the n partial structures (1) is a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different. Here, Q 1 may be all hydrogen atoms, and at least one may be a fluorine atom. That is, {C (Q 1 ) 2 } n may be an alkylene group or a fluoroalkylene group. A fluoroalkylene group is preferable, and a perfluoroalkylene group is more preferable, from the viewpoint of water repellency and oil repellency and oil stain removal property. n may be 0 or may be an integer of 1 or more.
When n is 0, the partial structure (1) has the structure of the following equation (1-1).
* -O- (R 1 O) m- (1-1)
However, each reference numeral in the equation (1-1) is the same as that in the equation (1).
When n is an integer of 1 or more, the n represents the number of carbon atoms of {C (Q 1 ) 2 } n. When n is 1 or more, the n is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
{C (Q 1) 2} Examples of n are, -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- and the like can be mentioned.
　部分構造（１）の（Ｒ１Ｏ）はオキシフルオロアルキレン基を表し、Ｒ１は、直鎖、分岐又は環構造を有するフルオロアルキレン基である。部分構造（１）がオキシフルオロアルキレン基の繰り返し単位を有することにより、本化合物は撥水撥油性、耐摩耗性、指紋汚れ除去性に優れている。
　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、（Ｒ１Ｏ）ｍは、中でも、下式（Ｒ－１）で表される構造が好ましい。
　［（Ｒｆ１Ｏ）ｍ１（Ｒｆ２Ｏ）ｍ２（Ｒｆ３Ｏ）ｍ３（Ｒｆ４Ｏ）ｍ４（Ｒｆ５Ｏ）ｍ５（Ｒｆ６Ｏ）ｍ６］　　　式（Ｒ－１）
　ただし、
　Ｒｆ１は、炭素数１のフルオロアルキレン基であり、
　Ｒｆ２は、炭素数２のフルオロアルキレン基であり、
　Ｒｆ３は、炭素数３のフルオロアルキレン基であり、
　Ｒｆ４は、炭素数４のフルオロアルキレン基であり、
　Ｒｆ５は、炭素数５のフルオロアルキレン基であり、
　Ｒｆ６は、炭素数６のフルオロアルキレン基であり、
　ｍ１、ｍ２、ｍ３、ｍ４、ｍ５、ｍ６は、それぞれ、０又は１以上の整数を表しｍ１＋ｍ２＋ｍ３＋ｍ４＋ｍ５＋ｍ６は１～２００の整数である。
　なお、式（Ｒ－１）における（Ｒｆ１Ｏ）～（Ｒｆ６Ｏ）の結合順序は任意である。式（Ｒ－１）のｍ１～ｍ６は、それぞれ、（Ｒｆ１Ｏ）～（Ｒｆ６Ｏ）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、（Ｒｆ５Ｏ）ｍ５は、（Ｒｆ５Ｏ）の数がｍ５個であることを表し、（Ｒｆ５Ｏ）ｍ５のブロック配置構造を表すものではない。同様に、（Ｒｆ１Ｏ）～（Ｒｆ６Ｏ）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。 (R 1 O) of the partial structure (1) represents an oxyfluoroalkylene group, and R 1 is a fluoroalkylene group having a linear, branched or ring structure. Since the partial structure (1) has a repeating unit of an oxyfluoroalkylene group, this compound is excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removal property.
From the viewpoint of being excellent in water repellency, oil repellency, abrasion resistance, and fingerprint stain removing property, (R 1 O) m is preferably a structure represented by the following formula (R-1).
[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ] Equation (R-1)
However,
R f1 is a fluoroalkylene group having 1 carbon atom.
R f2 is a fluoroalkylene group having 2 carbon atoms.
R f3 is a fluoroalkylene group having 3 carbon atoms.
R f4 is a fluoroalkylene group having 4 carbon atoms.
R f5 is a fluoroalkylene group having 5 carbon atoms.
R f6 is a fluoroalkylene group having 6 carbon atoms and has 6 carbon atoms.
m1, m2, m3, m4, m5, and m6 represent integers of 0 or 1, respectively, and m1 + m2 + m3 + m4 + m5 + m6 are integers of 1 to 200.
The bonding order of (R f1 O) to (R f6 O) in the formula (R-1) is arbitrary. M1 to m6 of the formula (R-1) represent the number of (R f1 O) to (R f6 O), respectively, and do not represent the arrangement. For example, (R f5 O) m5 is, (R f5 O) The number of stands that the m5 amino, (R f5 O) does not represent a block arrangement of m5. Similarly, the description order of (R f1 O) to (R f6 O) does not represent the binding order of each unit.
　Ｒｆ１の具体例としては、－ＣＦ２－、－ＣＨＦ－が挙げられる。
　Ｒｆ２の具体例としては、－ＣＦ２ＣＦ２－、－ＣＨＦＣＦ２－、－ＣＨＦＣＨＦ－、－ＣＨ２ＣＦ２－、－ＣＨ２ＣＨＦ－などが挙げられる。
　Ｒｆ３の具体例としては、－ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦＣＦ２－、－ＣＦ２ＣＨ２ＣＦ２－、－ＣＨＦＣＦ２ＣＦ２－、－ＣＨＦＣＨＦＣＦ２－、－ＣＨＦＣＨＦＣＨＦ－、－ＣＨＦＣＨ２ＣＦ２－、－ＣＨＦＣＨ２ＣＦ２－、－ＣＨ２ＣＦ２ＣＦ２－、－ＣＨ２ＣＨＦＣＦ２－、－ＣＨ２ＣＨ２ＣＦ２－、－ＣＨ２ＣＦ２ＣＨＦ－、－ＣＨ２ＣＨＦＣＨＦ－、－ＣＨ２ＣＨ２ＣＨＦ－、－ＣＦ（ＣＦ３）－ＣＦ２－、－ＣＦ（ＣＨＦ２）－ＣＦ２－、－ＣＦ（ＣＨ２Ｆ）－ＣＦ２－、－ＣＦ（ＣＨ３）－ＣＦ２－、－ＣＦ（ＣＦ３）－ＣＨＦ－、－ＣＦ（ＣＨＦ２）－ＣＨＦ－、－ＣＦ（ＣＨ２Ｆ）－ＣＨＦ－、－ＣＦ（ＣＨ３）－ＣＨＦ－、－ＣＦ（ＣＦ３）－ＣＨ２－、－ＣＦ（ＣＨＦ２）－ＣＨ２－、－ＣＦ（ＣＨ２Ｆ）－ＣＨ２－、－ＣＦ（ＣＨ３）－ＣＨ２－、－ＣＨ（ＣＦ３）－ＣＦ２－、－ＣＨ（ＣＨＦ２）－ＣＦ２－、－ＣＨ（ＣＨ２Ｆ）－ＣＦ２－、－ＣＨ（ＣＨ３）－ＣＦ２－、－ＣＨ（ＣＦ３）－ＣＨＦ－、－ＣＨ（ＣＨＦ２）－ＣＨＦ－、－ＣＨ（ＣＨ２Ｆ）－ＣＨＦ－、－ＣＨ（ＣＨ３）－ＣＨＦ－、－ＣＨ（ＣＦ３）－ＣＨ２－、－ＣＨ（ＣＨＦ２）－ＣＨ２－、－ＣＨ（ＣＨ２Ｆ）－ＣＨ２－などが挙げられる。
　Ｒｆ４の具体例としては、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＨＦＣＦ２ＣＦ２ＣＦ２－、－ＣＨ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＨＦＣＨＦＣＦ２ＣＦ２－、－ＣＨ２ＣＨＦＣＦ２ＣＦ２－、－ＣＦ２ＣＨ２ＣＦ２ＣＦ２－、－ＣＨＦＣＨ２ＣＦ２ＣＦ２－、－ＣＨ２ＣＨ２ＣＦ２ＣＦ２－、－ＣＨＦＣＦ２ＣＨＦＣＦ２－、－ＣＨ２ＣＦ２ＣＨＦＣＦ２－、－ＣＦ２ＣＨＦＣＨＦＣＦ２－、－ＣＨＦＣＨＦＣＨＦＣＦ２－、－ＣＨ２ＣＨＦＣＨＦＣＦ２－、－ＣＦ２ＣＨ２ＣＨＦＣＦ２－、－ＣＨＦＣＨ２ＣＨＦＣＦ２－、－ＣＨ２ＣＨ２ＣＨＦＣＦ２－、－ＣＦ２ＣＨ２ＣＨ２ＣＦ２－、－ＣＨＦＣＨ２ＣＨ２ＣＦ２－、－ＣＨ２ＣＨ２ＣＨ２ＣＦ２－、－ＣＨＦＣＨ２ＣＨ２ＣＨＦ－、－ＣＨ２ＣＨ２ＣＨ２ＣＨＦ－、－ｃｙｃｌｏＣ４Ｆ６－などが挙げられる。
　Ｒｆ５の具体例としては、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＨＦＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＨ２ＣＨＦＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨＦＣＦ２ＣＦ２ＣＦ２－、－ＣＨＦＣＨＦＣＦ２ＣＦ２ＣＦ２－、－ＣＨ２ＣＨＦＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＨ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＨＦＣＨ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＨ２ＣＨ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＨＦＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＨ２ＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＨＦＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＨ２ＣＦ２ＣＨＦＣＦ２ＣＦ２－、－ＣＨ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２－、－ｃｙｃｌｏＣ５Ｆ８－などが挙げられる。
　Ｒｆ６の具体例としては、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＨＦＣＨＦＣＦ２ＣＦ２－、－ＣＨＦＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＨＦＣＨＦＣＨＦＣＨＦＣＨＦＣＨＦ－、－ＣＨＦＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２－、－ＣＨ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＨ２－、－ｃｙｃｌｏＣ６Ｆ１０－などが挙げられる。
　ここで、－ｃｙｃｌｏＣ４Ｆ６－は、ペルフルオロシクロブタンジイル基を意味し、その具体例としては、ペルフルオロシクロブタン－１，２－ジイル基が挙げられる。－ｃｙｃｌｏＣ５Ｆ８－は、ペルフルオロシクロペンタンジイル基を意味し、その具体例としては、ペルフルオロシクロペンタン－１，３－ジイル基が挙げられる。－ｃｙｃｌｏＣ６Ｆ１０－は、ペルフルオロシクロヘキサンジイル基を意味し、その具体例としては、ペルフルオロシクロヘキサン－１，４－ジイル基が挙げられる。 Specific examples of R f1 include -CF 2- and -CHF-.
Specific examples of R f2 are, -CF 2 CF 2 -, - CHFCF 2 -, - CHFCHF -, - CH 2 CF 2 -, - CH 2 CHF- , and the like.
Specific examples of R f3 is, -CF 2 CF 2 CF 2 - , - CF 2 CHFCF 2 -, - CF 2 CH 2 CF 2 -, - CHFCF 2 CF 2 -, - CHFCHFCF 2 -, - CHFCHFCHF -, - CHFCH 2 CF 2 -, - CHFCH 2 CF 2 -, - CH 2 CF 2 CF 2 -, - CH 2 CHFCF 2 -, - CH 2 CH 2 CF 2 -, - CH 2 CF 2 CHF -, - CH 2 CHFCHF -, -CH 2 CH 2 CHF-, -CF (CF 3 ) -CF 2- , -CF (CHF 2 ) -CF 2- , -CF (CH 2 F) -CF 2- , -CF (CH 3 ) -CF 2- , -CF (CF 3 ) -CHF-, -CF (CHF 2 ) -CHF-, -CF (CH 2 F) -CHF-, -CF (CH 3 ) -CHF-, -CF (CF) 3 ) -CH 2- , -CF (CHF 2 ) -CH 2- , -CF (CH 2 F) -CH 2- , -CF (CH 3 ) -CH 2- , -CH (CF 3 ) -CF 2 -, -CH (CHF 2 ) -CF 2- , -CH (CH 2 F) -CF 2- , -CH (CH 3 ) -CF 2- , -CH (CF 3 ) -CHF-, -CH (CHF) 2) -CHF -, - CH ( CH 2 F) -CHF -, - CH (CH 3) -CHF -, - CH (CF 3) -CH 2 -, - CH (CHF 2) -CH 2 -, - CH (CH 2 F) -CH 2- and the like can be mentioned.
Specific examples of R f4 include -CF 2 CF 2 CF 2 CF 2- , -CHFCF 2 CF 2 CF 2- , -CH 2 CF 2 CF 2 CF 2- , -CF 2 CHFCF 2 CF 2- , -CHFCHFCF. 2 CF 2- , -CH 2 CHFCF 2 CF 2- , -CF 2 CH 2 CF 2 CF 2- , -CHFCH 2 CF 2 CF 2- , -CH 2 CH 2 CF 2 CF 2- , -CHFCF 2 CHFCF 2 -, - CH 2 CF 2 CHFCF 2 -, - CF 2 CHFCHFCF 2 -, - CHFCHFCHFCF 2 -, - CH 2 CHFCHFCF 2 -, - CF 2 CH 2 CHFCF 2 -, - CHFCH 2 CHFCF 2 -, - CH 2 CH 2 CHFCF 2- , -CF 2 CH 2 CH 2 CF 2- , -CHFCH 2 CH 2 CF 2- , -CH 2 CH 2 CH 2 CF 2- , -CHFCH 2 CH 2 CHF-, -CH 2 CH 2 CH 2 CHF-, -cycloC 4 F 6- and the like can be mentioned.
Specific examples of R f5 include -CF 2 CF 2 CF 2 CF 2 CF 2- , -CHFCF 2 CF 2 CF 2 CF 2- , -CH 2 CHFCF 2 CF 2 CF 2- , -CF 2 CHFCF 2 CF 2 CF 2- , -CHFCHFCF 2 CF 2 CF 2- , -CH 2 CHFCF 2 CF 2 CF 2- , -CF 2 CH 2 CF 2 CF 2 CF 2- , -CHFCH 2 CF 2 CF 2 CF 2- , -CH 2 CH 2 CF 2 CF 2 CF 2- , -CF 2 CF 2 CHFCF 2 CF 2- , -CHFCF 2 CHFCF 2 CF 2- , -CH 2 CF 2 CHFCF 2 CF 2- , -CF 2 CF 2 CHFCF 2 CF 2 -, - CHFCF 2 CHFCF 2 CF 2 -, - CH 2 CF 2 CHFCF 2 CF 2 -, - CH 2 CF 2 CF 2 CF 2 CH 2 -, - cycloC 5 F 8 - , and the like.
Specific examples of R f6 are, -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 -, - CF 2 CF 2 CHFCHFCF 2 CF 2 -, - CHFCF 2 CF 2 CF 2 CF 2 CF 2 -, - CHFCHFCHFCHFCHFCHF- , -CHFCF 2 CF 2 CF 2 CF 2 CH 2- , -CH 2 CF 2 CF 2 CF 2 CF 2 CH 2- , -cycloC 6 F 10-, and the like.
Here, -cycloC 4 F 6- means a perfluorocyclobutane diyl group, and specific examples thereof include a perfluorocyclobutane-1,2-diyl group. -CycloC 5 F 8 - means a perfluoro cyclopentane-diyl group, and specific examples thereof include perfluoro cyclopentane-1,3-diyl group. -CycloC 6 F 10- means a perfluorocyclohexanediyl group, and specific examples thereof include a perfluorocyclohexane-1,4-diyl group.
　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、中でも（Ｒ１Ｏ）ｍが下式（Ｒ－２）～下式（Ｒ－４）のいずれかとなるものが好ましい。
　　（Ｒｆ１Ｏ）ｍ１－（Ｒｆ２Ｏ）ｍ２　　　　　　　　　（Ｒ－２）
　　（Ｒｆ２Ｏ）ｍ２－（Ｒｆ４Ｏ）ｍ４　　　　　　　　　（Ｒ－３）
　　（Ｒｆ３Ｏ）ｍ３　　　　　　　　　　　　　　　　　（Ｒ－４）
　ただし、式（Ｒ－２）～式（Ｒ－４）の各符号は、前記式（Ｒ－１）と同様である。 From the viewpoint of being excellent in water and oil repellency, abrasion resistance, and fingerprint stain removing property, it is preferable that (R 1 O) m is any of the following formulas (R-2) to (R-4).
(R f1 O) m1- (R f2 O) m2 (R-2)
(R f2 O) m2- (R f4 O) m4 (R-3)
(R f3 O) m3 (R-4)
However, the reference numerals of the formulas (R-2) to (R-4) are the same as those of the formula (R-1).
　上式（Ｒ－２）及び式（Ｒ－３）において、（Ｒｆ１Ｏ）と（Ｒｆ２Ｏ）、（Ｒｆ２Ｏ）と（Ｒｆ４Ｏ）の結合順序は各々任意である。例えば（Ｒｆ１Ｏ）と（Ｒｆ２Ｏ）が交互に配置されてもよく、（Ｒｆ１Ｏ）と（Ｒｆ２Ｏ）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（Ｒ－３）においても同様である。
　式（Ｒ－２）において、ｍ１は１～３０が好ましく、１～２０がより好ましい。またｍ２は１～３０が好ましく、１～２０がより好ましい。
　式（Ｒ－３）において、ｍ３は１～３０が好ましく、１～２０がより好ましい。またｍ４は１～３０が好ましく、１～２０がより好ましい。
　式（Ｒ－４）において、ｍ３は１～３０が好ましく、１～２０がより好ましい。
　特に式（Ｒ－２）において、ｍ２／ｍ１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、０．１～１０が好ましく、０．２～５．０がより好ましく、０．２～２．０がさらに好ましく、０．２～１．５が特に好ましく、０．２～０．８５が最も好ましい。 In the above equations (R-2) and (R-3), the bonding order of (R f1 O) and (R f2 O) and (R f2 O) and (R f4 O) is arbitrary. For example, (R f1 O) and (R f2 O) may be arranged alternately, (R f1 O) and (R f2 O) may be arranged in blocks, respectively, or may be random. The same applies to the formula (R-3).
In the formula (R-2), m1 is preferably 1 to 30, more preferably 1 to 20. Further, m2 is preferably 1 to 30, more preferably 1 to 20.
In the formula (R-3), m3 is preferably 1 to 30, more preferably 1 to 20. Further, m4 is preferably 1 to 30, more preferably 1 to 20.
In the formula (R-4), m3 is preferably 1 to 30, more preferably 1 to 20.
In particular, in the formula (R-2), m2 / m1 is preferably 0.1 to 10, more preferably 0.2 to 5.0, from the viewpoint of further excellent abrasion resistance and fingerprint stain removal property of the surface layer. 0.2 to 2.0 is more preferable, 0.2 to 1.5 is particularly preferable, and 0.2 to 0.85 is most preferable.
　本化合物において部分構造（１）中のフッ素原子の割合［｛フッ素原子数／（フッ素原子数＋水素原子数）｝×１００（％）］は、撥水撥油性及び指紋除去性に優れる点から、４０％以上が好ましく、５０％以上がより好ましく、６０％以上が更に好ましい。 In this compound, the ratio of fluorine atoms in the partial structure (1) [{number of fluorine atoms / (number of fluorine atoms + number of hydrogen atoms)} x 100 (%)] is excellent in water and oil repellency and fingerprint removal. , 40% or more is preferable, 50% or more is more preferable, and 60% or more is further preferable.
　また、本化合物において部分構造（１）部分の合計の分子量は、耐摩耗性の点から、２００～３０，０００が好ましく、６００～２５，０００がより好ましく、１，０００～２０，０００が更に好ましい。 Further, in this compound, the total molecular weight of the partial structure (1) portion is preferably 200 to 30,000, more preferably 600 to 25,000, and further 1,000 to 20,000 from the viewpoint of wear resistance. preferable.
　部分構造（２）のＬは加水分解性基又は水酸基である。Ｌが水酸基の場合、Ｓｉ原子と共にシラノール（Ｓｉ－ＯＨ）基を構成する。また、加水分解性基は加水分解反応によって水酸基となる基である。シラノール基は、さらに分子間で反応してＳｉ－Ｏ－Ｓｉ結合を形成する。また、シラノール基は、基材の表面の水酸基（基材－ＯＨ）と脱水縮合反応して、化学結合（基材－Ｏ－Ｓｉ）を形成する。
　本化合物は部分構造（２）を４つ以上有するため、摩耗耐久性に優れている。本化合物においては、部分構造（２）が４～２０が好ましく、４～１５がより好ましい。 L in the partial structure (2) is a hydrolyzable group or a hydroxyl group. When L is a hydroxyl group, it constitutes a silanol (Si—OH) group together with a Si atom. The hydrolyzable group is a group that becomes a hydroxyl group by a hydrolyzing reaction. The silanol group further reacts between 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).
Since this compound has four or more partial structures (2), it has excellent wear durability. In this compound, the partial structure (2) is preferably 4 to 20, more preferably 4 to 15.
　加水分解性基であるＬとしては、アルコキシ基、アリールオキシ基、ハロゲン原子、アシル基、アシルオキシ基、イソシアナート基（－ＮＣＯ）等が挙げられる。アルコキシ基としては、炭素数１～４のアルコキシ基が好ましい。アシル基としては、炭素数１～６のアシル基が好ましい。アシルオキシ基としては、炭素数１～６のアシルオキシ基が好ましい。
　Ｌとしては、本化合物の製造のしやすさの点から、炭素数１～４のアルコキシ基又はハロゲン原子が好ましい。ハロゲン原子としては、塩素原子が特に好ましい。Ｌ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、塗布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。 Examples of L as a hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an isocyanate group (-NCO) and the like. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the acyl group, an acyl group having 1 to 6 carbon atoms is preferable. As the acyloxy group, an acyloxy group having 1 to 6 carbon atoms is preferable.
As L, an alkoxy group or a halogen atom having 1 to 4 carbon atoms is preferable from the viewpoint of ease of production of this compound. As the halogen atom, a chlorine atom is particularly preferable. As L, an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgassing at the time of coating and the storage stability of this compound is excellent, and an ethoxy group is used when long-term storage stability of this compound is required. It is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.
　Ｒ１０は、水素原子又は１価の炭化水素基である。１価の炭化水素基としては、アルキル基、シクロアルキル基、アルケニル基、アリル基等が挙げられる。１価の炭化水素基の炭素数は、１～６が好ましく、１～３がより好ましく、１～２が特に好ましい。Ｒ１０の炭素数がこの範囲であれば、本化合物を製造しやすい。
　ｐは、２又は３が好ましく、３がより好ましい。１つの加水分解性シリル基にＬが複数存在することによって、基材との密着性がより向上する。 R 10 is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an allyl group and the like. The monovalent hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms. If the carbon number of R 10 is within this range, the compound easily produced.
p is preferably 2 or 3, and more preferably 3. The presence of a plurality of L in one hydrolyzable silyl group further improves the adhesion to the substrate.
　部分構造（２）としては、－Ｓｉ（ＯＣＨ３）３、－ＳｉＣＨ３（ＯＣＨ３）２、－Ｓｉ（ＯＣＨ２ＣＨ３）３、－ＳｉＣｌ３、－Ｓｉ（ＯＣＯＣＨ３）３、－Ｓｉ（ＮＣＯ）３が好ましい。工業的な製造における取扱いやすさの点から、－Ｓｉ（ＯＣＨ３）３が特に好ましい。 As the partial structure (2), -Si (OCH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si (OCH 2 CH 3 ) 3 , -SiCl 3 , -Si (OCOCH 3 ) 3 , -Si ( NCO) 3 is preferable. -Si (OCH 3 ) 3 is particularly preferable from the viewpoint of ease of handling in industrial manufacturing.
　本化合物内における部分構造（２）の位置は、例えば、部分構造（２）が後述する連結基Ｘに直接結合していてもよく、また部分構造（２）が直接又は有機基を介して、部分構造（１）の（Ｒ１Ｏ）ｍ－と結合していてもよい。撥水撥油層の耐久性や撥水撥油性の点から、中でも、部分構造（２）が直接又は有機基を介して部分構造（１）の（Ｒ１Ｏ）ｍ－と結合していることが好ましい。 The position of the partial structure (2) in the present compound may be, for example, the partial structure (2) may be directly bonded to the linking group X described later, or the partial structure (2) may be directly bonded or via an organic group. It may be combined with (R 1 O) m − of the partial structure (1). From the viewpoint of the durability of the water- and oil-repellent layer and the water- and oil-repellent properties, the partial structure (2) is bonded to (R 1 O) m-of the partial structure (1) directly or via an organic group. Is preferable.
　本化合物は耐久性及び撥水撥油性の点から、中でも下式（３）で表される部分構造を３つ以上有することが好ましい。
　　＊－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ｛－ＳｉＬｐＲ１０ （３－ｐ）｝ｑ　　　　（３）
　ただし、Ａは（ｑ＋１）価の有機基であり、ｑは１以上の整数であり、＊、Ｑ１、Ｒ１、Ｌ、Ｒ１０、ｎ、ｐは前記式（１）又は式（２）と同様である。 From the viewpoint of durability and water / oil repellency, this compound preferably has three or more partial structures represented by the following formula (3).
*-{C (Q 1 ) 2 } n- O- (R 1 O) m- A {-SiL p R 10 (3-p) } q (3)
However, A is an organic group having a (q + 1) valence, q is an integer of 1 or more, and *, Q 1 , R 1 , L, R 10 , n, p are the above formulas (1) or (2). Is similar to.
　Ａは、ｑ＋１価の直鎖状又は分岐状の連結基である。Ａは、ｑ＋１が３以上のとき、Ｃ、Ｎ、Ｓｉ、環構造及びｑ＋１価のオルガノポリシロキサン残基からなる群から選ばれる少なくとも１種の分岐点（以下、「分岐点Ｐ」と記す。）を有することが好ましい。なお分岐点Ｐには特定分岐鎖が結合する。ここで特定分岐鎖とは、部分構造（１）又は部分構造（２）をその鎖内に有する鎖をいう。 A is a q + 1 valent linear or branched linking group. When q + 1 is 3 or more, A is at least one kind of branch point selected from the group consisting of C, N, Si, ring structure and q + 1 valent organopolysiloxane residue (hereinafter referred to as “branch point P”). ) Is preferable. A specific branched chain is bound to the branch point P. Here, the specific branched chain means a chain having a partial structure (1) or a partial structure (2) in the chain.
　環構造としては、本化合物を製造しやすい点、及び表面層の耐摩擦性、耐光性及び耐薬品性がさらに優れる点から、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。 The ring structure is a 3- to 8-membered aliphatic ring and a 3- to 8-membered aromatic ring because it is easy to produce this compound and the surface layer is more 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 (an etheric oxygen atom may be contained 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-C000003
Figure JPOXMLDOC01-appb-C000003
　ｑ＋１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 q + 1-valent organopolysiloxane residue include the following groups. However, R 5 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. Carbon atoms in the alkyl group and alkoxy group for R 5 is preferably 1 to 10, 1 is particularly preferred.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　有機基Ａは、アルキレン基、フルオロアルキレン基、ヒドロキシアルキレン基、アルコキシアルキレン基、カルボニル基、アミド結合、エーテル結合、チオエーテル結合、ウレア結合、ウレタン結合、カーボネート結合、エステル結合、－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より選択される１種以上を含む基（以下、結合Ｂともいう）を有していてもよい。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。また、有機基Ａを構成する各結合又は基は、いずれの末端が部分構造（１）側に配置されていてもよい。例えば、アミド結合は、炭素原子が部分構造（１）側に配置され、窒素原子が部分構造（２）側に配置されていてもよく、炭素原子が部分構造（２）側に配置され、窒素原子が部分構造（１）側に配置されていてもよい。他の結合や基についても同様である。 Organic group A includes alkylene group, fluoroalkylene group, hydroxyalkylene group, alkoxyalkylene group, carbonyl group, amide bond, ether bond, thioether bond, urea bond, urethane bond, carbonate bond, ester bond, -SO 2 NR 6-. , -Si (R 6) 2 - , - OSi (R 6) 2 -, - Si (CH 3) 2 -Ph-Si (CH 3) 2 - and 1 selected from divalent organopolysiloxane residue It may have a group containing more than a species (hereinafter, also referred to as bond B). However, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Ph is a phenylene group. The number of carbon atoms of the alkyl group of R 6 is preferably 1 to 3 and particularly preferably 1 to 2 from the viewpoint that the present compound can be easily produced. Further, each bond or group constituting the organic group A may have any end arranged on the partial structure (1) side. For example, in the amide bond, the carbon atom may be arranged on the partial structure (1) side and the nitrogen atom may be arranged on the partial structure (2) side, or the carbon atom may be arranged on the partial structure (2) side and nitrogen. Atoms may be arranged on the partial structure (1) side. The same applies to other bonds and groups.
　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-C000005
Figure JPOXMLDOC01-appb-C000005
　有機基Ａは、本化合物を製造しやすい点から、炭化水素基、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、－Ｃ（Ｏ）ＯＲ６－、－ＮＲ６－及び－Ｏ－からなる群から選ばれる少なくとも１種の結合を有することが好ましく、表面層の耐光性及び耐薬品性がさらに優れる点から、炭化水素基、－Ｃ（Ｏ）ＮＲ６－、－Ｃ（Ｏ）－、又は、－Ｃ（Ｏ）Ｏ－を有することが特に好ましい。 The organic group A is a hydrocarbon group, -C (O) NR 6- , -C (O)-, -C (O) OR 6- , -NR 6- and -O because it is easy to produce this compound. It is preferable to have at least one bond selected from the group consisting of −, and the hydrocarbon group, −C (O) NR 6 −, −C (O) is further excellent in light resistance and chemical resistance of the surface layer. )-Or -C (O) O- is particularly preferred.
　有機基Ａ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Ｐ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Ｐと１個以上の結合Ｂ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 the organic group A, a combination of two or more divalent hydrocarbon groups and one or more branch points P, or two or more hydrocarbon groups and one or more branch points P and one or more bonds. The combination with B 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.
　撥水撥油性、耐摩擦性、指紋汚れ除去性に優れる点から、有機基Ａは、下式（Ａ１）～（Ａ９）のいずれかで表される基であることが好ましい。 The organic group A is preferably a group represented by any of the following formulas (A1) to (A9) from the viewpoint of excellent water and oil repellency, abrasion resistance, and fingerprint stain removal property.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　－Ａ１－Ｃ（Ｒｅ２）３－ｅ２（－Ｑ２２）ｅ２　　　（Ａ２）
　－Ａ１－Ｎ（－Ｑ２３）２　　　　　（Ａ３）
　－Ａ１－Ｚ１（－Ｑ２４）ｈ２　　　　（Ａ４）
　－Ａ１－Ｓｉ（Ｒｅ３）３－ｉ２（－Ｑ２５）ｉ２　（Ａ５）
　－Ａ１－Ｑ２６－　　　　　（Ａ６）
　－Ａ１－ＣＨ（－Ｑ２２－）－Ｓｉ（Ｒｅ３）３－ｉ３（－Ｑ２５－）ｉ３　　　（Ａ７）
　－Ａ１－［ＣＨ２Ｃ（Ｒｅ４）（－Ｑ２７－）］ｉ４－Ｒｅ５　　　（Ａ８）
　－Ａ１－Ｚａ（－Ｑ２８－）ｉ５　　　（Ａ９）
　ただし、式（Ａ１）～式（Ａ９）においては、Ａ１側が部分構造（１）に接続し、Ｑ２２、Ｑ２３、Ｑ２４、Ｑ２５、Ｑ２６、Ｑ２７及びＱ２８側が部分構造（２）に接続する。 -A 1- C (R e2 ) 3-e2 (-Q 22 ) e2 (A2)
-A 1 -N (-Q 23 ) 2 (A3)
-A 1 -Z 1 (-Q 24 ) h2 (A4)
-A 1- Si (R e3 ) 3-i2 (-Q 25 ) i2 (A5)
-A 1 -Q 26 - (A6)
-A 1 -CH (-Q 22 -) - Si (R e3) 3-i3 (-Q 25 -) i3 (A7)
-A 1 - [CH 2 C ( R e4) (- Q 27 -)] i4 -R e5 (A8)
-A 1 -Z a (-Q 28 - ) i5 (A9)
However, in the formula (A1) ~ formula (A9), A 1 side is connected to the substructure (1), Q 22, Q 23, Q 24, Q 25, Q 26, Q 27 and Q 28 side substructure ( Connect to 2).
　Ａ１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）ＮＲ８－、－Ｃ（Ｏ）ＯＲ８－、－Ｃ（Ｏ）－、－ＯＣ（Ｏ）Ｏ－、－ＮＲ８Ｃ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＲ８－、－Ｏ－、－ＮＨＲ８－、－ＮＲ８ ２－又はＳＯ２ＮＲ８－を有する基であり、各式中、Ａ１が２以上存在する場合、２以上のＡ１は同一であっても異なっていてもよい。アルキレン基の水素原子は、フッ素原子に置換されていてもよい。Ａ１の炭素数は１～８が好ましい。 A 1 represents a single bond, an alkylene group, or a carbon of an alkylene group having 2 or more carbon atoms - -C between carbon atoms (O) NR 8 -, - C (O) OR 8 -, - C (O) -, -OC (O) O -, - NR 8 C (O) O -, - NHC (O) NR 8 -, - O -, - NHR 8 -, - NR 8 2 - or SO 2 NR 8 - group with , and the in the formulas, if a 1 is present 2 or more, 2 or more of a 1 may be different even in the same. The hydrogen atom of the alkylene group may be substituted with a fluorine atom. The carbon number of A 1 is preferably 1 to 8.
　Ｑ２２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）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－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）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－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）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－を有しかつＳｉに接続しない側の末端に－Ｃ（Ｏ）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－を有する基であり、各式中、Ｑ２２が２以上存在する場合、２以上のＱ２２は同一であっても異なっていてもよい。
　Ｑ２３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）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－を有する基であり、２個のＱ２３は同一であっても異なっていてもよい。
　Ｑ２４は、Ｑ２４が結合するＺ１における原子が炭素原子の場合、Ｑ２２であり、Ｑ２４が結合するＺ１における原子が窒素原子の場合、Ｑ２３であり、各式中、Ｑ２４が２以上存在する場合、２以上のＱ２４は同一であっても異なっていてもよい。
　Ｑ２５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）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－を有する基であり、各式中、Ｑ２５が２以上存在する場合、２以上のＱ２５は同一であっても異なっていてもよい。
　Ｑ２６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）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－を有する基である。
　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。
　Ｑ２７は、単結合又はアルキレン基である。
　Ｑ２８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原子－炭素原子間にエーテル性酸素原子もしくは２価のオルガノポリシロキサン残基を有する基である。 Q 22, the carbon of the alkylene group, having two or more alkylene groups having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O-, an alkylene group -C at the end on the side not connected to the Si of the (O) NR 8 -, - C (O) -, - NR 8 - or a group having O-, or carbon number of 2 or more alkylene group of a carbon - between carbon atoms -C (O) NR 8 to -, - C (O) - , - NR 8 - or O- the have and -C to the end on the side not connected to the Si (O) NR 8 -, - C (O) -, -NR 8 -or O-, and if two or more Q 22s are present in each formula, the two or more Q 22s may be the same or different.
Q 23 is an alkylene group, or a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O- , the two of Q 23 may be the same or different.
Q 24, when atom in Z 1 to Q 24 is attached is a carbon atom, a Q 22, when atoms in Z 1 to Q 24 is attached is a nitrogen atom, a Q 23, in each formula, Q 24 If is present 2 or more, two or more Q 24 may be different even in the same.
Q 25 is an alkylene group, or a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O- , In each equation, when two or more Q 25s are present, the two or more Q 25s may be the same or different.
Q 26 is an alkylene group, or a carbon number of 2 or more alkylene group having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having the O- ..
R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
Q 27 is a single bond or an alkylene group.
Q 28 represents an alkylene group, or a carbon atom of the alkylene group having 2 or more carbon atoms - a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms.
　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。
　Ｚ１は、Ａ１が直接結合する炭素原子又は窒素原子を有しかつＱ２４が直接結合する炭素原子又は窒素原子を有する（１＋ｈ２）価の環構造を有する基である。
　Ｒｅ１は、水素原子又はアルキル基であり、各式中、Ｒｅ１が２以上存在する場合、２以上のＲｅ１は同一であっても異なっていてもよい。
　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る。
　Ｒｅ３は、アルキル基である。
　Ｒｅ４は、水素原子又はアルキル基であり、化合物を製造しやすい点から、水素原子が好ましい。各式中、Ｒｅ４を２以上存在する場合、２以上のＲｅ４は同一であっても異なっていてもよい。
　Ｒｅ５は、水素原子又はハロゲン原子であり、化合物を製造しやすい点から、水素原子が好ましい。 R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
Z 1 is a group having a (1 + h2) valent ring structure having a carbon atom or nitrogen atom to which A 1 is directly bonded and a carbon atom or nitrogen atom to which Q 24 is directly bonded.
R e1 is a hydrogen atom or an alkyl group, and when two or more Re1s are present in each formula, two or more Re1s may be the same or different.
Re2 is a hydrogen atom, a hydroxyl group, an alkyl group or an acyloxy group.
Re3 is an alkyl group.
Re4 is a hydrogen atom or an alkyl group, and a hydrogen atom is preferable because it is easy to produce a compound. When two or more Re 4s are present in each equation, the two or more Re 4s may be the same or different.
Re5 is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable from the viewpoint that a compound can be easily produced.
　ｄ２は、０～３の整数であり、１又は２が好ましい。ｄ４は、０～３の整数であり、２又は３が好ましい。ｄ２＋ｄ４は２～５が好ましい。ｅ２は２又は３である。
　ｈ２は、１以上の整数（２又は３が好ましい）である。
　ｉ２は、２又は３である。
　ｉ３は、２又は３である。
　ｉ４は、１以上（１～１０の整数が好ましく、１～６の整数が特に好ましい）である。
　ｉ５は、２～７の整数である。 d2 is an integer of 0 to 3, preferably 1 or 2. d4 is an integer of 0 to 3, preferably 2 or 3. 2 to 5 are preferable for d2 + d4. e2 is 2 or 3.
h2 is an integer of 1 or more (preferably 2 or 3).
i2 is 2 or 3.
i3 is 2 or 3.
i4 is 1 or more (an integer of 1 to 10 is preferable, and an integer of 1 to 6 is particularly preferable).
i5 is an integer of 2 to 7.
　Ｑ２２、Ｑ２３、Ｑ２４、Ｑ２５、Ｑ２６、Ｑ２７、Ｑ２８のアルキレン基の炭素数は、本化合物を製造しやすい点、及び撥水撥油層の耐摩擦性、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。 The carbon number of the alkylene group of Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 , and Q 28 makes it easy to manufacture this compound, and the abrasion resistance, light resistance, and light resistance of the water- and oil-repellent layer. From the viewpoint of further excellent chemical properties, 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is particularly preferable. However, when a specific bond is formed between carbon atoms, the lower limit of the number of carbon atoms of the alkylene group is 2.
　Ｚ１における環構造としては、上述した環構造が挙げられ、好ましい形態も同様である。なお、Ｚ１における環構造にはＡ１やＱ２４が直接結合するため、環構造にたとえばアルキレン基が連結して、そのアルキレン基にＡ１やＱ２４が連結することはない。
　Ｚａは、（ｉ５＋１）価のオルガノポリシロキサン残基であり、前述の基が好ましい。 Examples of the ring structure in Z 1 include the above-mentioned ring structure, and the preferred form is also the same. Since A 1 and Q 24 are directly bonded to the ring structure in Z 1 , for example, an alkylene group is linked to the ring structure, and A 1 and Q 24 are not linked to the alkylene group.
Z a is a (i5 + 1) -valent organopolysiloxane residue, and the above-mentioned group is preferable.
　有機基Ａの好ましい他の形態として、下式（Ａ１１）～（Ａ１９）のいずれかで表される基が挙げられる。 As another preferable form of the organic group A, a group represented by any of the following formulas (A11) to (A19) can be mentioned.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　－Ａ１－Ｃ（Ｒｅ２）３－ｅ２（－Ｑ２２－Ｇ１）ｅ２　　　（Ａ１２）
　－Ａ１－Ｎ（－Ｑ２３－Ｇ１）２　　　（Ａ１３）
　－Ａ１－Ｚ１（－Ｑ２４－Ｇ１）ｈ２　（Ａ１４）
　－Ａ１－Ｓｉ（Ｒｅ３）３－ｉ２（－Ｑ２５－Ｇ１）ｉ２　（Ａ１５）
　－Ａ１－Ｑ２６－Ｇ１　　　（Ａ１６）
　－Ａ１－ＣＨ（－Ｑ２２－）－Ｓｉ（Ｒｅ３）３－ｉ３（－Ｑ２５－Ｇ１）ｉ３　（Ａ１７）
　－Ａ１－［ＣＨ２Ｃ（Ｒｅ４）（－Ｑ２７－Ｇ１）］ｉ４－Ｒｅ５　　　（Ａ１８）
　－Ａ１－Ｚａ（－Ｑ２８－Ｇ１）ｉ５　　　（Ａ１９）
　ただし、式（Ａ１１）～式（Ａ１９）においては、Ａ１側が部分構造（１）に接続し、Ｇ１側が部分構造（２）に接続する。 -A 1- C (R e2 ) 3-e2 (-Q 22 -G 1 ) e2 (A12)
-A 1- N (-Q 23- G 1 ) 2 (A13)
-A 1- Z 1 (-Q 24- G 1 ) h2 (A14)
-A 1- Si (R e3 ) 3-i2 (-Q 25- G 1 ) i2 (A15)
-A 1- Q 26- G 1 (A16)
-A 1 -CH (-Q 22 -) - Si (R e3) 3-i3 (-Q 25 -G 1) i3 (A17)
-A 1- [CH 2 C (R e4 ) (-Q 27- G 1 )] i4- R e5 (A18)
-A 1- Z a (-Q 28- G 1 ) i5 (A19)
However, in the formula (A11) ~ formula (A19), A 1 side is connected to the substructure (1), G 1 side is connected to the substructure (2).
　Ｇ１は、下記（Ｇ１）で表される基であり、式（Ａ１１）～式（Ａ１９）中、Ｇ１が２以上存在する場合、２以上のＧ１は同一であっても異なっていてもよい。Ｇ１以外の符号は、式（Ａ１）～式（Ａ９）における符号と同じである。
　－Ｓｉ（Ｒ９）３－ｒ１（－Ｑ３０－）ｒ１　式（Ｇ１）
　ただし、式（Ｇ１）においては、Ｓｉ側がＱ２２、Ｑ２３、Ｑ２４、Ｑ２５、Ｑ２６、Ｑ２７及びＱ２８に接続し、Ｑ３０側が部分構造（２）に接続する。Ｒ９は、アルキル基である。Ｑ３０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）ＮＲ８－、－Ｃ（Ｏ）－、－ＮＲ８－又はＯ－を有する基、又は（ＯＳｉ（Ｒ１０）２）ｐｐ－Ｏ－であり、２以上のＱ３は同一であっても異なっていてもよい。ｒ１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。Ｒ１０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Ｒ１０は同一であっても異なっていてもよい。ｐｐは、０～５の整数であり、ｐが２以上の場合、２以上の（ＯＳｉ（Ｒ１０）２）は同一であっても異なっていてもよい。 G 1 is a group represented by the following (G1), wherein (A11) ~ formula (A19), if G 1 is present 2 or more, 2 or more in G 1 is optionally substituted by one or more identical May be good. The codes other than G 1 are the same as the codes in the formulas (A1) to (A9).
-Si (R 9 ) 3-r1 (-Q 30- ) r1 formula (G1)
However, in the equation (G1), the Si side is connected to Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 , and the Q 30 side is connected to the partial structure (2). R 9 is an alkyl group. Q 30, the carbon of the alkylene group, having two or more alkylene groups having a carbon - -C between carbon atoms (O) NR 8 -, - C (O) -, - NR 8 - or a group having O-, or ( OSi (R 10) 2) a pp -O-, 2 or more Q 3 are may be the same or different. r1 is 2 or 3. R 8 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R 10 is an alkyl group, a phenyl group or an alkoxy group, and the two R 10s may be the same or different. pp is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSI (R 10 ) 2 ) may be the same or different.
　Ｑ３０のアルキレン基の炭素数は、本化合物を製造しやすい点、ならびに、撥水撥油層の耐摩擦性、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。
　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、１～１０が好ましく、１～６がより好ましく、１～３がさらに好ましく、１～２が特に好ましい。
　Ｒ１０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、１～１０が好ましく、１～６がより好ましく、１～３がさらに好ましく、１～２が特に好ましい。
　Ｒ１０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、１～１０が好ましく、１～６がより好ましく、１～３がさらに好ましく、１～２が特に好ましい。
　ｐｐは、０又は１が好ましい。 The alkylene group of Q 30 are that the compound easily produced, and, rub resistance water- and oil-repellent layer, from the viewpoint of light resistance and chemical resistance are further excellent, preferably 1-10, 1-6 Is more preferable, and 1 to 4 are particularly preferable. However, when a specific bond is formed between carbon atoms, the lower limit of the number of carbon atoms of the alkylene group is 2.
The number of carbon atoms of the alkyl group of R 9 is preferably 1 to 10, more preferably 1 to 6, further 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 10 is preferably 1 to 10, more preferably 1 to 6, further 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 10 is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of excellent storage stability of the present compound.
The pp is preferably 0 or 1.
　有機基Ａの好ましい具体例として、たとえば、下式の構造が挙げられる。但し、Ｑ４は各々独立に水素原子又はフッ素原子であり、ｎ１＝１～６の整数である。また、式中のＬ１は部分構造（１）を、Ｌ２は部分構造（２）を示すものであり、連結基Ａを構成するものではない。 As a preferable specific example of the organic group A, for example, the structure of the following formula can be mentioned. However, Q 4 is independently a hydrogen atom or a fluorine atom, and is an integer of n1 = 1 to 6. Further, L 1 in the formula indicates a partial structure (1), and L 2 indicates a partial structure (2), and does not constitute a linking group A.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　本化合物は中でも、下式（４）で表される含フッ素化合物であることが好ましい。
　　Ｘ［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ｛－ＳｉＬｐＲ１０ （３－ｐ）｝ｑ］ｒ　　　　（４）
　ただし、
　Ｘは、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、及び３級窒素原子より選択される原子を１個以上有するｒ価の連結基であり、
　［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－］のＸ側には、Ｘにおける３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、ｒは３以上の整数である。
　Ｑ１、Ｒ１、Ａ、Ｌ、Ｒ１０、ｎ、ｍ、ｐ、ｑは前記式（３）と同様である。 Among them, this compound is preferably a fluorine-containing compound represented by the following formula (4).
X [-{C (Q 1 ) 2 } n- O- (R 1 O) m- A {-SiL p R 10 (3-p) } q ] r (4)
However,
X is an r-valent connection having one or more atoms selected from a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, and a tertiary nitrogen atom. Is the basis and
On the X side of [-{C (Q 1 ) 2 } n- O-], there are a tertiary carbon atom in X, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, and a quaternary silicon atom. , Or a tertiary nitrogen atom is bonded, and r is an integer of 3 or more.
Q 1 , R 1 , A, L, R 10 , n, m, p, q are the same as in the above formula (3).
　上記連結基Ｘはｒ個の部分構造（１）を連結するものであり、目的を達成する範囲で任意の構造とすることができる。連結基Ｘは、ヘテロ原子を有していてもよく、水素原子がフッ素原子に置換されていてもよい炭化水素基であって、部分構造（１）の［－｛Ｃ（Ｑ１）２｝ｎ］と結合する元素が、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、及び３級窒素原子であるものが挙げられる。
　Ｘに含まれるヘテロ原子としては、本化合物の安定性の点から、酸素原子、窒素原子、硫黄原子又はケイ素原子が好ましい。ｒは３以上であればよく、耐久性及び撥水撥油性の点から３～２０が好ましく、３～１０がより好ましい。 The linking group X connects r substructures (1), and may have any structure as long as the object is achieved. The linking group X is a hydrocarbon group which may have a hetero atom or the hydrogen atom may be substituted with a fluorine atom, and is a [-{C (Q 1 ) 2 } of the partial structure (1). n ] can be mentioned as an element bonded to a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, and a tertiary nitrogen atom.
As the hetero atom contained in X, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom is preferable from the viewpoint of the stability of the present compound. r may be 3 or more, preferably 3 to 20 from the viewpoint of durability and water and oil repellency, and more preferably 3 to 10.
　中でも、前記Ｘが下式（Ｘ－１）～下式（Ｘ－６）より選択される１種以上の部分構造を有することが好ましい。部分構造（Ｘ－１）～部分構造（Ｘ－６）のいずれかを有することにより、連結基Ｘに化学的に安定な構造の分岐が設けられる。 Above all, it is preferable that the X has one or more partial structures selected from the following formulas (X-1) to the following formulas (X-6). By having any one of the partial structure (X-1) to the partial structure (X-6), the linking group X is provided with a branch having a chemically stable structure.
Figure JPOXMLDOC01-appb-C000014
 　ただし、Ｑ３は、水素原子又はフッ素原子である。式（Ｘ－６）中のＣは芳香環を構成する炭素原子であり、当該炭素原子が有する結合手の１つは単結合であり、残りの結合手（波線が記載された結合手）は芳香環を構成する。
Figure JPOXMLDOC01-appb-C000014
 However, Q 3 is a hydrogen atom or a fluorine atom. C in the formula (X-6) is a carbon atom constituting an aromatic ring, one of the bonds possessed by the carbon atom is a single bond, and the remaining bond (the bond with a wavy line) is It constitutes an aromatic ring.
　式（Ｘ－１）中のＣは３級炭素原子を表し、式（Ｘ－２）中のＣは４級炭素原子を表し、式（Ｘ－３）中のＳｉは３級ケイ素原子を表し、式（Ｘ－４）中のＳｉは４級ケイ素原子を表し、式（Ｘ－５）中のＮは３級ケイ素原子を表し、これらの原子が有する結合手は各々単結合である。また、式（Ｘ－６）中のＣは芳香環を構成する炭素原子であり、当該炭素原子が有する結合手の１つは単結合であり、残りの結合手（波線が記載された結合手）は芳香環を構成する。 C in the formula (X-1) represents a tertiary carbon atom, C in the formula (X-2) represents a quaternary carbon atom, and Si in the formula (X-3) represents a tertiary silicon atom. , Si in the formula (X-4) represents a quaternary silicon atom, N in the formula (X-5) represents a tertiary silicon atom, and each of these atoms has a single bond. Further, C in the formula (X-6) is a carbon atom constituting an aromatic ring, one of the bond hands possessed by the carbon atom is a single bond, and the remaining bond hands (bond hands in which wavy lines are described) are described. ) Consists of an aromatic ring.
　部分構造（Ｘ－１）～部分構造（Ｘ－５）は、単独で分岐点を構成し得る。また、部分構造（Ｘ－６）は、芳香環を構成する他の元素とともに分岐点を構成し得る。例えば、ベンゼン環は、部分構造（Ｘ－６）が６個連結した構造とみることができ、６分岐の分岐点を構成する。
　部分構造（Ｘ－１）～（Ｘ－５）は、単独で連結基Ｘを構成してもよく、他の部分構造（Ｘ－１）～（Ｘ－６）と直接又は連結基を介して結合していてもよい。複数の部分構造（Ｘ－１）～（Ｘ－６）が連結することで、分岐数の大きい連結基Ｘとなる。 The partial structure (X-1) to the partial structure (X-5) may independently form a branch point. In addition, the partial structure (X-6) may form a branch point together with other elements constituting the aromatic ring. For example, the benzene ring can be regarded as a structure in which six partial structures (X-6) are connected, and constitutes a branch point of six branches.
The partial structures (X-1) to (X-5) may independently constitute the linking group X, and may directly or via the linking group with the other substructures (X-1) to (X-6). It may be combined. By connecting a plurality of partial structures (X-1) to (X-6), a connecting group X having a large number of branches is obtained.
　部分構造（Ｘ－１）～部分構造（Ｘ－６）の単結合は、各々独立に、部分構造（１）の＊と結合する、直接又は連結基を介して他の部分構造（Ｘ－１）～（Ｘ－６）に結合する、又は他の置換基と結合する。ここでの連結基としては、炭素鎖中にエーテル結合を有していてもよく、フッ素原子で置換されていてもよいアルキレン基などが挙げられる。また他の置換基としては、炭素鎖中にエーテル結合を有していてもよく、フッ素原子で置換されていてもよいアルキル基、フッ素原子、水酸基などが挙げられる。
　部分構造（Ｘ－６）が構成する芳香環は、炭素環であっても複素環であってもよい。当該炭素環としては、ベンゼン環の他、ナフタレン、インデン、アントラセン、フルオレンなどが挙げられる。また、複素環としては、フラン、チオフェン、ピロール、ピリジンなどが挙げられる。 The single bonds of the partial structure (X-1) to the partial structure (X-6) are independently bonded to the * of the partial structure (1), either directly or via a linking group, or another partial structure (X-1). )-(X-6), or with other substituents. Examples of the linking group here include an alkylene group which may have an ether bond in the carbon chain and may be substituted with a fluorine atom. Examples of other substituents include alkyl groups, fluorine atoms, hydroxyl groups, and the like, which may have an ether bond in the carbon chain and may be substituted with a fluorine atom.
The aromatic ring formed by the partial structure (X-6) may be a carbon ring or a heterocycle. Examples of the carbon ring include naphthalene, indene, anthracene, and fluorene, in addition to the benzene ring. Examples of the heterocycle include furan, thiophene, pyrrole, and pyridine.
　連結基Ｘは、本化合物の耐久性及び撥水撥油性の点から、前記式（Ｘ－１）～（Ｘ－５）、又は、下記式（Ｘ－１１）～（Ｘ－２５）であることが好ましい。 The linking group X is the above formula (X-1) to (X-5) or the following formulas (X-11) to (X-25) from the viewpoint of durability and water repellency and oil repellency of the present compound. Is preferable.
Figure JPOXMLDOC01-appb-C000015
 　ただし、
　Ｑ３は、水素原子又はフッ素原子であって、複数あるＱ３は同一であっても異なっていてもよく、
　Ｒ２は単結合、又は、炭素鎖中にエーテル結合を有していてもよく、フッ素原子で置換されていてもよいアルキレン基である。
Figure JPOXMLDOC01-appb-C000015
 However,
Q 3 are a hydrogen atom or a fluorine atom, a plurality of Q 3 are may be the same or different and
R 2 is an alkylene group that may have a single bond or an ether bond in the carbon chain, or may be substituted with a fluorine atom.
　連結基Ｘの好ましい具体例を以下に示す。 A preferable specific example of the linking group X is shown below.
Figure JPOXMLDOC01-appb-C000016
 　なお、式中のＬ１は部分構造（１）を示すものであり、連結基Ｘを構成するものではない。
Figure JPOXMLDOC01-appb-C000016
 Note that L 1 in the formula indicates the partial structure (1) and does not constitute the connecting group X.
　複数ある本化合物は、１種類の単一化合物として存在してもよく、２種以上の化合物で存在してもよい。
　本化合物の分子量は５００～１００，０００が好ましく、１０００～２０，０００が特に好ましい。また本化合物が２種以上の化合物の混合物からなる場合、化合物の分子量分布（Ｍｗ／Ｍｎ）は１．０～２．０が好ましく、１．０～１．３が特に好ましい。分子量及び分子量分布が該範囲にある場合には、粘度が低く、蒸発成分が少なく、溶媒に溶解した際の均一性に優れる利点がある。本化合物の分子量及び分子量分布は、ゲルパーミエーションクロマトグラフィにより測定でき、測定条件は、後述する実施例中に記載した条件が採用できる。
　本化合物の具体例としては、下記化合物が挙げられる。なお下式中のＲ１、Ｌ２及びｍは前述のとおりであり、Ｒ３は炭素数１～６のフルオロアルキレン基であり、Ｒ４は直鎖又は分岐を有するフルオロアルキレン基であって好ましくは炭素数１～６のフルオロアルキレン基であり、Ｒ３及びＲ４は式（４）における有機基Ａの一部を構成する。また、Ｒ１２は炭素数１～５のフルオロアルキレン基であって、下式中の「Ｒ１２－ＣＨ２－Ｏ」は、式（４）における（Ｒ１Ｏ）ｍの一つの「Ｒ１Ｏ」を構成する。 The plurality of present compounds may exist as one kind of single compound, or may exist as two or more kinds of compounds.
The molecular weight of this compound is preferably 500 to 100,000, particularly preferably 1000 to 20,000. When the present compound is composed of a mixture of two or more kinds of compounds, the molecular weight distribution (Mw / Mn) of the compounds is preferably 1.0 to 2.0, particularly preferably 1.0 to 1.3. When the molecular weight and the molecular weight distribution are in the above range, there are advantages that the viscosity is low, the evaporation component is small, and the uniformity when dissolved in a solvent is excellent. The molecular weight and molecular weight distribution of this compound can be measured by gel permeation chromatography, and the measurement conditions can be the conditions described in Examples described later.
Specific examples of this compound include the following compounds. In the following formula, R 1 , L 2 and m are as described above, R 3 is a fluoroalkylene group having 1 to 6 carbon atoms, and R 4 is a linear or branched fluoroalkylene group, which is preferable. Is a fluoroalkylene group having 1 to 6 carbon atoms, and R 3 and R 4 form a part of the organic group A in the formula (4). Further, R 12 is a fluoroalkylene group having 1 to 5 carbon atoms, and "R 12- CH 2- O" in the following formula is one "R 1 " of (R 1 O) m in the formula (4). It constitutes "O".
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
 　　
　　　　
Figure JPOXMLDOC01-appb-C000019
 　　
　　　　
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（４）で表される化合物は、例えば、下式（４Ａ）で表される前駆体と下式（５Ａ）で表される化合物とをヒドロシリル化反応させることにより製造できる。
　　Ｘ［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ’］ｒ　（４Ａ）
　　ＨＳｉＬｐＲ１０ （３－ｐ）　　　　　　　　　　　　　　（５Ａ）
　ただし、Ａ’は末端にエチレン性不飽和結合を有し、加水分解性シリル基の導入後には、式（４）のＡに相当する有機基であり、Ｘ、Ｑ１、Ｒ１、Ｌ、Ｒ１０、ｎ、ｍ、ｒ、ｐは式（４）と同様である。 The compound represented by the formula (4) can be produced, for example, by hydrosilylating a precursor represented by the formula (4A) and a compound represented by the formula (5A) below.
X [-{C (Q 1 ) 2 } n- O- (R 1 O) m- A'] r (4A)
HSiL p R 10 (3-p) (5A)
However, A'has an ethylenically unsaturated bond at the terminal, and after the introduction of the hydrolyzable silyl group, it is an organic group corresponding to A of the formula (4), and X, Q 1 , R 1 , L, R 10 , n, m, r, and p are the same as in the equation (4).
　また、式（４）で表される化合物は、例えば、下式（４Ｂ）で表される前駆体と下式（５Ｂ）で表される化合物とをアミド化反応させることにより製造できる。
　　Ｘ［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ”｛－Ｃ（＝Ｏ）ＯＲａ｝ｑ］ｒ　（４Ｂ）
　　Ｈ２ＮＲｂＳｉＬｐＲ１０ （３－ｐ）　　　　　　　　　　　　　　（５Ｂ）
　ただし、Ａ”は合成後「Ａ”－Ｃ（＝Ｏ）－ＮＨ－Ｒｂ」が式（４）における有機基Ａに相当する構造の有機基であり、Ｒａはアルキル基又はフルオロアルキル基であり、Ｒｂはアルキレン基又はフルオロアルキレン基であり、Ｘ、Ｑ１、Ｒ１、Ｌ、Ｒ１０、ｎ、ｍ、ｒ、ｐは式（４）と同様である。 Further, the compound represented by the formula (4) can be produced, for example, by subjecting a precursor represented by the formula (4B) below and a compound represented by the formula (5B) to an amidation reaction.
X [-{C (Q 1 ) 2 } n- O- (R 1 O) m- A "{-C (= O) OR a } q ] r (4B)
H 2 NR b SiL p R 10 (3-p) (5B)
However, A "is an organic group having a structure in which" A "-C (= O) -NH-R b " corresponds to the organic group A in the formula (4) after synthesis, and Ra is an alkyl group or a fluoroalkyl group. R b is an alkylene group or a fluoroalkylene group, and X, Q 1 , R 1 , L, R 10 , n, m, r, and p are the same as in the formula (4).
［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 that are unavoidable 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。
　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.
As the other fluorine-containing compound, a compound that is less likely to deteriorate the properties 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未反応の含フッ素化合物等が挙げられる。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 unreacted fluorine-containing compounds at the time of synthesis of this compound. When the present composition contains a by-product fluorine-containing compound, the purification step for removing the by-product fluorine-containing compound 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号公報に記載のパーフルオロポリエーテル変性アミノシラン、
　日本特表２００２－５０６８８７号公報に記載のフッ素化シロキサン、
　日本特表２００８－５３４６９６号公報に記載の有機シリコーン化合物、
　日本特許第４１３８９３６号公報に記載のフッ素化変性水素含有重合体、
　米国特許出願公開第２０１０／０１２９６７２号明細書、国際公開第２０１４／１２６０６４号、日本特開２０１４－０７０１６３号公報に記載の化合物、
　国際公開第２０１１／０６００４７号、国際公開第２０１１／０５９４３０号に記載のオルガノシリコン化合物、
　国際公開第２０１２／０６４６４９号に記載の含フッ素オルガノシラン化合物、
　日本特開２０１２－７２２７２号公報に記載のフルオロオキシアルキレン基含有ポリマー、
　国際公開第２０１３／０４２７３２号、国際公開第２０１３／１２１９８４号、国際公開第２０１３／１２１９８５号、国際公開第２０１３／１２１９８６号、国際公開第２０１４／１６３００４号、日本特開２０１４－０８０４７３号公報、国際公開第２０１５／０８７９０２号、国際公開第２０１７／０３８８３０号、国際公開第２０１７／０３８８３２号、国際公開第２０１７／１８７７７５号に記載の含フッ素エーテル化合物、
　日本特開２０１４－２１８６３９号公報、国際公開第２０１７／０２２４３７号、国際公開第２０１８／０７９７４３号、国際公開第２０１８／１４３４３３号に記載のパーフルオロ（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２０１９／０４４４７９号、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 fluoropolymers described in Japanese Patent No. 28747115,
Organosilicon compounds described in Japanese Patent Application Laid-Open No. 2000-144097,
Perfluoropolyether-modified aminosilane described in Japanese Patent Application Laid-Open No. 2000-327772,
Fluorinated siloxane described in Japanese Patent Publication No. 2002-506887,
Organic silicone compounds 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, and Japanese Patent Application Laid-Open No. 2014-0701163,
The organosilicon compounds described in International Publication No. 2011/060047 and International Publication No. 2011/059430,
Fluorine-containing organosilane compound according to International Publication No. 2012/064694,
Fluoroxyalkylene group-containing polymer described in Japanese Patent Application Laid-Open No. 2012-722272,
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. 2014-080473, International Fluorine-containing ether compounds according to Publication No. 2015/087902, International Publication No. 2017/038830, International Publication No. 2017/038832, International Publication No. 2017/187775,
Perfluoro (poly) ether-containing silane compounds according to Japanese Patent Application Laid-Open No. 2014-218369, 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 Application 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. 2016-222859. / 216630, International Publication No. 2019/039226, International Publication No. 2019/039341, International Publication No. 2019/039186, International Publication No. 2019/0444979, Japanese Patent Application Laid-Open No. 2019-44158, International Publication No. 2019 / The fluoroether compound according to No. 044479 and International Publication No. 2019/163282.
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 Inc., and Daikin Industries, Ltd. Includes Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, and the like.
　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、潤滑性、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 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, lubricity, 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 present compound or the present composition, and may contain impurities such as by-products produced in the manufacturing process of the present 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 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 CHFC CHFCF 3 (manufactured by The Chemours Company, Bertrel® 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. Commercially available products include, for example, CF 3 CH 2 OCF 2 CF 2 H (AGC, Asahiclean® AE-3000), C 4 F 9 OCH 3 (3M, Novec® 7100), Examples include C 4 F 9 OC 2 H 5 (3M, Novec® 7200), C 2 F 5 CF (OCH 3 ) C 3 F 7 (3M, Novec® 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 of only hydrogen atoms and carbon atoms and a compound consisting of only hydrogen atoms, carbon atoms and oxygen atoms are preferable, and hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, 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, and preferably 85 to 99.99% by mass. It is particularly preferable to contain 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 in 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、撥水撥油層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、前記撥水撥油層が、前記本化合物の縮合体を含有する。 [Goods]
FIG. 1 is a schematic cross-sectional view showing an example of the article of the present invention. The first article of the present invention is an article 20 having a base material 12, a base layer 14, and a water- and oil-repellent layer 22 in this order.
The base layer contains an oxide containing silicon, and the water- and oil-repellent 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 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、撥水撥油層の耐摩耗性がさらに向上する。表面処理としては、撥水撥油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 water-repellent oil-repellent layer is further improved. As the surface treatment, a corona discharge treatment or a plasma treatment is preferable because the wear resistance of the water-repellent oil-repellent 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撥水撥油層が形成される。 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 water- and oil-repellent layer having excellent wear durability. Is formed.
　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 base layer, and the mechanical properties of the base layer are sufficiently ensured. The content of silicon oxide is the balance obtained by subtracting the total content of other elements (in the case of oxide, the amount converted to oxide) from the mass of the underlying layer.
　撥水撥油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 water- and oil-repellent layer, the oxides in the base layer are further composed of alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel and chromium. , Molybdenum, and 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、撥水撥油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、撥水撥油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 base layer 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 of these elements is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and even 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 underlying layer contains one or more selected from boron and phosphorus, the total content of these is the sum of boron and phosphorus relative to the molar concentration of silicon in terms of wear resistance of the water and oil repellent layer. The molar concentration ratio is preferably 0.003 to 9, preferably 0.003 to 2, and even more preferably 0.003 to 0.5.
When the base layer contains alkaline earth metal elements, the total content of these is the total molar concentration of alkaline earth metal elements with respect to the molar concentration of silicon in terms of the abrasion resistance of the water- and oil-repellent layer. The ratio 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、前記撥水撥油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 water-repellent oil-repellent layer is 0.1 to 0.3 nm is 2.0 × 10 19 atoms / cm 3. The above is preferable. 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、分光エリプソメータ、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, 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 becomes 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 of 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ートの温度）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ート上で蒸着材料を溶融し、蒸発させる抵抗加熱法、電子ビームを蒸着材料に照射し、蒸着材料を直接加熱して表面を溶融し、蒸発させる電子銃法等が挙げられる。蒸着材料の蒸発方法としては、局所的に加熱できるため高融点物質も蒸発できる点、電子ビームが当たっていないところは低温であるため容器との反応や不純物の混入のおそれがない点から、電子銃法が好ましい。電子銃法に用いる蒸着材料としては、気流が生じても飛散しにくい点から、溶融粒状体又は焼結体が好ましい。 Examples of the method for forming the base layer 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 during 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 vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.
Evaporation methods for the vaporized material include a resistance heating method in which the vaporized material is melted and evaporated on a refractory metal resistance heating boat, an electron beam is applied to the vaporized material, and the vaporized material is directly heated to melt the surface. However, there is an electron gun method that evaporates. As a method of evaporating the vaporized material, since it can be heated locally, the refractory 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 gun method is preferred. 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.
　下地層上の撥水撥油層は、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、撥水撥油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、撥水撥油層は、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 water- and oil-repellent 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 hydrolyzing 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 water-repellent and oil-repellent layer may contain a condensate of a fluorine-containing compound other than this compound. That is, the water- and oil-repellent layer contains a fluorine-containing compound having a reactive silyl group in a state in which a part or all of the reactive silyl groups of the fluorine-containing compound is condensed.
　撥水撥油層の厚さは、１～１００ｎｍが好ましく、１～５０ｎｍが特に好ましい。撥水撥油層の厚さが前記範囲の下限値以上であれば、撥水撥油層による効果が充分に得られる。撥水撥油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。
　撥水撥油層の厚さは、薄膜解析用Ｘ線回折計で得られた厚さである。撥水撥油層の厚さは、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 water-repellent and oil-repellent layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the water- and oil-repellent layer is equal to or greater than the lower limit of the above range, the effect of the water- and oil-repellent layer can be sufficiently obtained. When the thickness of the water-repellent and oil-repellent layer is equal to or less than the upper limit of the above range, the utilization efficiency is high.
The thickness of the water-repellent oil-repellent layer is the thickness obtained by the X-ray diffractometer for thin film analysis. The thickness of the water-repellent and oil-repellent layer can be calculated from the vibration cycle of the interference pattern by obtaining the interference pattern of 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、撥水撥油層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、
　前記撥水撥油層が、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 water-repellent oil-repellent layer 22 in this order.
The base material contains an oxide containing silicon,
The water- and oil-repellent 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、基材に直接撥水撥油層を形成しても撥水撥油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、撥水撥油層の構成も前記第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 water and oil repellent layer is excellent in abrasion durability even if the water and oil repellent 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 water-repellent and oil-repellent 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撥水撥油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 water-repellent oil-repellent 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 methods such as vacuum deposition, CVD, and sputtering. 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 the present 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 the present compound can be produced by impregnating a metal porous body with a solution of the present compound, drying the mixture, and removing the 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。 If necessary, in order to improve the abrasion resistance of the surface layer, an operation for promoting the reaction between the present compound and the substrate may be carried out. 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 a water-containing atmosphere, a hydrolyzable group is hydrolyzed, a hydroxyl group 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２、例３、例４、例５、例８、例９及び例１０が実施例であり、例１、例６、及び例７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 2, Example 3, Example 4, Example 5, Example 8, Example 9, and Example 10 are examples, and Examples 1, 6, and 7 are comparative examples. Also, AC in the the CCl 2 FCClF 2 R-113, CClF 2 CF 2 CCl 2 CF 2 CF 3 a R-419, CF 3 CH 2 OCF 2 CF a 2 H AE-3000, C 6 F 13 H or less -2000, CF 3 CF 2 CHCl 2 is referred to as AK-225.
［例１］化合物Ｉの合成
（合成例１－１）
　フラスコにポリオキシエチレングリセロールエーテル（日本油脂製、ユニオックスＧ１２００、下式中ａ１＋ａ２＋ａ３の平均は２７）１０ｇをいれ、そこにＦＣＯＣＦ（ＣＦ３）ＯＣＦ２ＣＦ（ＣＦ３）Ｏ（ＣＦ２）２ＣＦ３（３４．３ｇ）を、内温を１０℃以下に保ちながら滴下した。滴下終了後、２５℃で撹拌して、粗液を回収した。さらに粗液を減圧ろ過し、その後、回収液を真空乾燥機で乾燥した。ここで得た粗液をＡＫ－２２５に溶解し、飽和重曹水で水洗し、有機相を回収した。さらに、回収した有機相に硫酸マグネシウムを加え撹拌を行った。その後、硫酸マグネシウムを除去し、エバポレータでＡＫ－２２５を留去し、室温で液体の化合物（１－１）（５２．８ｇ）を得た。 [Example 1] Synthesis of Compound I (Synthesis Example 1-1)
Put 10 g of polyoxyethylene glycerol ether (manufactured by NOF Corporation, Uniox G1200, average of a1 + a2 + a3 in the following formula is 27) in a flask, and put FCOCF (CF 3 ) OCF 2 CF (CF 3 ) O (CF 2 ) 2 CF there. 3 (34.3 g) was added dropwise while maintaining the internal temperature at 10 ° C. or lower. After completion of the dropping, the mixture was stirred at 25 ° C. to recover the crude liquid. Further, the crude liquid was filtered under reduced pressure, and then the recovered liquid was dried in a vacuum dryer. The crude solution obtained here was dissolved in AK-225, washed with saturated aqueous sodium hydrogen carbonate, and the organic phase was recovered. Further, magnesium sulfate was added to the recovered organic phase and the mixture was stirred. Then, magnesium sulfate was removed, and AK-225 was distilled off with an evaporator to obtain a liquid compound (1-1) (52.8 g) at room temperature.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（合成例１－２）
　５００ｍＬのハステロイ製オートクレーブに、Ｒ－１１３（３１２ｇ）を加えて撹拌し、２５℃に保った。オートクレーブガス出口には、０℃に保持した冷却器、ＮａＦペレット充填層、及び－１０℃に保持した冷却器を直列に設置した。－１０℃に保持した冷却器からは、凝集した液をオートクレーブに戻すための液体返送ラインを設置した。窒素ガスを１時間吹き込んだ後、窒素ガスで２０％に希釈したフッ素ガス（以下、２０％フッ素ガスと記す。）を、流速１６．９７Ｌ／時間で１時間吹き込んだ。
　つぎに、２０％フッ素ガスを同じ流速で吹き込みながら、合成例１－１で得た化合物（１－１）（１５ｇ）をＲ－１１３（２００ｇ）に溶解した溶液を注入した。
　つぎに、２０％フッ素ガスを同じ流速で吹き込みながら、Ｒ－１１３溶液を６ｍＬ注入した。さらに、窒素ガスを１時間吹き込んだ。
　反応終了後、粗液を回収し、溶媒を真空乾燥にて留去して、室温で液体の生成物（２１．４ｇ）を得た。該生成物を分析した結果は、合成例１－１で得た化合物（１－１）中の水素原子の実質的に全て（９９．９モル％以上）がフッ素原子に置換された下記化合物（１－２）であることを確認した。 (Synthesis Example 1-2)
R-113 (312 g) was added to a 500 mL Hastelloy autoclave, and the mixture was stirred and kept at 25 ° C. At the autoclave gas outlet, a cooler kept at 0 ° C., a NaF pellet filling layer, and a cooler kept at −10 ° C. were installed in series. From the cooler kept at -10 ° C, a liquid return line was installed to return the agglomerated liquid to the autoclave. After blowing nitrogen gas for 1 hour, fluorine gas diluted to 20% with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown at a flow rate of 16.97 L / hour for 1 hour.
Next, while blowing 20% fluorine gas at the same flow rate, a solution in which the compound (1-1) (15 g) obtained in Synthesis Example 1-1 was dissolved in R-113 (200 g) was injected.
Next, 6 mL of R-113 solution was injected while blowing 20% fluorine gas at the same flow rate. Further, nitrogen gas was blown in for 1 hour.
After completion of the reaction, the crude liquid was recovered and the solvent was distilled off by vacuum drying to obtain a liquid product (21.4 g) at room temperature. As a result of analyzing the product, the following compound (99.9 mol% or more) in which substantially all (99.9 mol% or more) of hydrogen atoms in the compound (1-1) obtained in Synthesis Example 1-1 were replaced with fluorine atoms ( It was confirmed that it was 1-2).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（合成例１－３）
　スターラーチップを投入した５０ｍＬの丸底フラスコを充分に窒素置換した。該丸底フラスコに１，１，３，４－テトラクロロヘキサフルオロブタン（２５ｇ）、ＫＦ（０．２０ｇ）及び、合成例１－２で得た化合物（１－２）（２０ｇ）を加えて激しく撹拌し、１２０℃に保った。丸底フラスコ出口には、２０℃に保持した冷却器、及びドライアイス－エタノール冷却管を直列に設置し、窒素シールを行った。
　内温を２５℃まで下げ、続いて冷却管に真空ポンプを設置して系内を減圧に保ち、溶媒及び反応副性物を留去し、室温で液体の生成物（１３．３ｇ）を得た。
　生成物を分析した結果、下記化合物（１－３）の生成を確認した。化合物（１－２）中のエステル結合の総数に対する、生成物中の－ＣＯＦ基数の割合は９９モル％以上であった。 (Synthesis Example 1-3)
A 50 mL round-bottom flask containing a stirrer tip was sufficiently nitrogen-substituted. To the round bottom flask, 1,1,3,4-tetrachlorohexafluorobutane (25 g), KF (0.20 g), and the compound (1-2) (20 g) obtained in Synthesis Example 1-2 were added. It was stirred vigorously and kept at 120 ° C. At the outlet of the round-bottom flask, a cooler maintained at 20 ° C. and a dry ice-ethanol cooling tube were installed in series, and nitrogen sealing was performed.
The internal temperature was lowered to 25 ° C., and then a vacuum pump was installed in the cooling pipe to keep the inside of the system under reduced pressure, the solvent and reaction by-products were distilled off, and a liquid product (13.3 g) was obtained at room temperature. It was.
As a result of analyzing the product, the formation of the following compound (1-3) was confirmed. The ratio of the number of -COF groups in the product to the total number of ester bonds in compound (1-2) was 99 mol% or more.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（合成例１－４）
　合成例１－３で得た化合物（１－３）が入った丸底フラスコにＫＦ（０．９ｇ）、Ｒ－１１３（５．０ｇ）を投入し、内温を２５℃に保ちながら激しく撹拌した。さらに、メタノール（０．５ｇ）を、内温を２５℃以上に保ちながらゆっくりと滴下した。
　撹拌を停止し、粗液を加圧ろ過器にてろ過し、ＫＦを除去した。続いて、エバポレータにてＲ－１１３、及び過剰のメタノールを完全に除去した。シリカゲルカラム後、溶媒を留去し、室温で液状の生成物（１３．５ｇ）を得た。
　生成物を分析した結果、下記化合物（１－４）の生成を確認した。化合物（１－３）中の－ＣＯＦ基の全てがメチルエステル化されていた。 (Synthesis Example 1-4)
Put KF (0.9 g) and R-113 (5.0 g) into a round-bottom flask containing the compound (1-3) obtained in Synthesis Example 1-3, and stir vigorously while keeping the internal temperature at 25 ° C. did. Further, methanol (0.5 g) was slowly added dropwise while maintaining the internal temperature at 25 ° C. or higher.
Stirring was stopped and the crude liquid was filtered through a pressure filter to remove KF. Subsequently, R-113 and excess methanol were completely removed by an evaporator. After the silica gel column, the solvent was distilled off to obtain a liquid product (13.5 g) at room temperature.
As a result of analyzing the product, the formation of the following compound (1-4) was confirmed. All of the -COF groups in compound (1-3) were methyl esterified.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（合成例１－５）
　ＷＯ２００９／００８３８０の例２の合成を参考に　１００ｍＬの丸底フラスコ内に、合成例１－４で得た化合物（１－４）の１０ｇ、下記ＡＰＳの２．０ｇを入れ、２５℃で２時間撹拌した。反応終了後、未反応のＡＰＳ及び副生したメタノールを減圧留去し、室温で液体の化合物の１１．４ｇを得た。
　ＮＨ２ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３　：ＡＰＳ (Synthesis Example 1-5)
With reference to the synthesis of Example 2 of WO2009 / 0083380, 10 g of the compound (1-4) obtained in Synthesis Example 1-4 and 2.0 g of the following APS were placed in a 100 mL round-bottom flask at 25 ° C. for 2 hours. Stirred. After completion of the reaction, unreacted APS and by-produced methanol were distilled off under reduced pressure to obtain 11.4 g of a liquid compound at room temperature.
NH 2 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 : APS
　該化合物のＮＭＲ分析の結果、化合物（１－４）中の－ＣＦ２Ｃ（Ｏ）ＯＣＨ３の９８．０モル％が－ＣＦ２Ｃ（Ｏ）ＮＨＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３に変換され、－（ＯＣＦ２Ｏ）－単位が存在しない化合物であることを確認した。すなわち、下記化合物Ｉが主たる生成物であった。化合物Ｉの数平均分子量は４１５０であった。 As a result of NMR analysis of the compound, 98.0 mol% of -CF 2 C (O) OCH 3 in compound (1-4) was -CF 2 C (O) NHCH 2 CH 2 CH 2 Si (OCH 3 ). It was converted to 3 and it was confirmed that the compound had no-(OCF 2 O) -unit. That is, the following compound I was the main product. The number average molecular weight of Compound I was 4150.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
［例２］化合物ＩＩの合成
（合成例２－１）
　フラスコ内に、下式で表されるポリオキシエチレンポリグリセリルエーテル（ＳＣ－Ｅ１５００；式中のｂ１＋ｂ２＋ｂ３＋ｂ４の平均は３０）の２０ｇ、ＡＣ－２０００の２０ｇ、ＮａＦの５．７ｇ、及びピリジンの１．６ｇを入れ、内温を１０℃以下に保ちながら激しく撹拌し、窒素をバブリングさせた。フラスコ内に、下記（ＨＦＰＯ）３の１３４．１ｇを、内温を５℃以下に保ちながら滴下した。滴下終了後、５０℃にて撹拌し、２５℃にて撹拌して、粗液を回収した。粗液を減圧濾過した後、回収液を真空乾燥機で乾燥し、粗液を得た。粗液をＡＣ－２０００に溶解し、飽和重曹水で水洗し、有機相を回収した。有機相に硫酸マグネシウムを加え、撹拌した後、加圧濾過して硫酸マグネシウムを除去し、回収液からエバポレータにてＡＣ－２０００を留去し、室温で液体である化合物の４５．７ｇを得た。該化合物のＮＭＲ分析の結果、下記化合物（２－１）であることを確認した。 [Example 2] Synthesis of Compound II (Synthesis Example 2-1)
In the flask, 20 g of polyoxyethylene polyglyceryl ether (SC-E1500; the average of b1 + b2 + b3 + b4 in the formula is 30) represented by the following formula, 20 g of AC-2000, 5.7 g of NaF, and 1.6 g of pyridine. Was vigorously stirred while keeping the internal temperature below 10 ° C., and nitrogen was bubbled. 134.1 g of the following (HFPO) 3 was added dropwise to the flask while keeping the internal temperature at 5 ° C. or lower. After completion of the dropping, the mixture was stirred at 50 ° C. and 25 ° C. to recover the crude liquid. After the crude liquid was filtered under reduced pressure, the recovered liquid was dried in a vacuum dryer to obtain a crude liquid. The crude solution was dissolved in AC-2000, washed with saturated aqueous sodium hydrogen carbonate, and the organic phase was recovered. Magnesium sulfate was added to the organic phase, and after stirring, magnesium sulfate was removed by pressure filtration, and AC-2000 was distilled off from the recovered solution with an evaporator to obtain 45.7 g of a compound that was liquid at room temperature. .. As a result of NMR analysis of the compound, it was confirmed that it was the following compound (2-1).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（合成例２－２）
　３０００ｍＬのハステロイ製オートクレーブ内に、Ｒ－１１３の１５６０ｇを入れて撹拌し、２５℃に保った。オートクレーブガス出口には、０℃に保持した冷却器、ＮａＦペレット充填層、及び－１０℃に保持した冷却器を直列に設置した。また、－１０℃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ための液体返送ラインを設置した。
　オートクレーブ内に窒素ガスを１時間吹き込んだ後、窒素ガスで１０％に希釈したフッ素ガス（以下、１０％フッ素ガスと記す。）を、流速２４．８Ｌ／時間で１時間吹き込んだ。つぎに、オートクレーブ内に１０％フッ素ガスを同じ流速で吹き込みながら、化合物（２－１）の３０．１ｇをＲ－１１３の１３５０ｇに溶解した溶液を注入した。つぎに、オートクレーブ内に１０％フッ素ガスを同じ流速で吹き込みながら、Ｒ－１１３の１２ｍＬを注入した。この際、内温を４０℃に変更した。つづけて、ベンゼンを１質量％溶解したＲ－１１３溶液の６ｍＬを注入した。さらに、フッ素ガスを１時間吹き込んだ後、窒素ガスを１時間吹き込んだ。
　反応終了後、溶媒を真空乾燥にて留去し、室温で液体の化合物の４９．８ｇを得た。該化合物のＮＭＲ分析の結果、化合物（２－１）の水素原子の総数の９９．９％がフッ素原子に置換された、下記化合物（２－２）が主たる成分であることを確認した。 (Synthesis Example 2-2)
In a 3000 mL Hastelloy autoclave, 1560 g of R-113 was placed and stirred, and kept at 25 ° C. At the autoclave gas outlet, a cooler kept at 0 ° C., a NaF pellet filling layer, and a cooler kept at −10 ° C. were installed in series. In addition, a liquid return line was installed to return the agglomerated liquid from the cooler kept at −10 ° C. to the autoclave.
After blowing nitrogen gas into the autoclave for 1 hour, fluorine gas diluted to 10% with nitrogen gas (hereinafter referred to as 10% fluorine gas) was blown into the autoclave at a flow rate of 24.8 L / hour for 1 hour. Next, while blowing 10% fluorine gas into the autoclave at the same flow rate, a solution in which 30.1 g of compound (2-1) was dissolved in 1350 g of R-113 was injected. Next, 12 mL of R-113 was injected while blowing 10% fluorine gas into the autoclave at the same flow rate. At this time, the internal temperature was changed to 40 ° C. Subsequently, 6 mL of an R-113 solution in which 1% by mass of benzene was dissolved was injected. Further, after blowing fluorine gas for 1 hour, nitrogen gas was blown for 1 hour.
After completion of the reaction, the solvent was evaporated by vacuum drying to obtain 49.8 g of a liquid compound at room temperature. As a result of NMR analysis of the compound, it was confirmed that the following compound (2-2) was the main component, in which 99.9% of the total number of hydrogen atoms of the compound (2-1) was replaced with fluorine atoms.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
（合成例２－３）
　化合物（２－２）の４０ｇが入ったナスフラスコ内に、ＡＣ－２０００の４０．０ｇを入れ、内温を２５℃に保ちながら激しく撹拌した。ナスフラスコ内に、エタノールの３．２ｇを、内温を２５℃以上に保ちながらゆっくりと滴下した。
　８時間後、撹拌を停止し、粗液を加圧濾過し、ＫＦを除去した。つづいて、回収液からエバポレータにてＡＣ－２０００及び過剰のエタノールを完全に除去した。シリカゲルカラム後、溶媒を留去し、室温で液状の化合物の２７．９ｇを得た。該化合物のＮＭＲ分析の結果、化合物（２－２）の酸フルオリドの総数がエステル化された、下記化合物（２－３）が主たる生成物であることを確認した。 (Synthesis Example 2-3)
40.0 g of AC-2000 was placed in an eggplant flask containing 40 g of compound (2-2), and the mixture was vigorously stirred while maintaining the internal temperature at 25 ° C. 3.2 g of ethanol was slowly added dropwise to the eggplant flask while keeping the internal temperature at 25 ° C. or higher.
After 8 hours, stirring was stopped and the crude liquid was pressure filtered to remove KF. Subsequently, AC-2000 and excess ethanol were completely removed from the recovered solution by an evaporator. After the silica gel column, the solvent was distilled off to obtain 27.9 g of a compound liquid at room temperature. As a result of NMR analysis of the compound, it was confirmed that the following compound (2-3), in which the total number of acid fluorides of the compound (2-2) was esterified, was the main product.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
（合成例２－４）
　１００ｍＬの丸底フラスコ内に、化合物（２－３）の５ｇ、ＡＰＳの１．２ｇを入れ、２５℃で撹拌した。反応終了後、未反応のＡＰＳ及び副生したエタノールを減圧留去し、室温で液体の化合物の５．９ｇを得た。
　該化合物のＮＭＲ分析の結果、化合物（２－３）中の－ＣＦ２Ｃ（Ｏ）ＯＣＨ２ＣＨ３の９５．０モル％が－ＣＦ２Ｃ（Ｏ）ＮＨＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３に変換され、－（ＯＣＦ２Ｏ）－単位が存在しない化合物であることを確認した。すなわち、下記化合物ＩＩが主たる生成物であった。化合物ＩＩの数平均分子量は４７００であった。 (Synthesis Example 2-4)
In a 100 mL round bottom flask, 5 g of compound (2-3) and 1.2 g of APS were placed and stirred at 25 ° C. After completion of the reaction, unreacted APS and by-produced ethanol were distilled off under reduced pressure to obtain 5.9 g of a liquid compound at room temperature.
As a result of NMR analysis of the compound, 95.0 mol% of -CF 2 C (O) OCH 2 CH 3 in compound (2-3) was -CF 2 C (O) NHCH 2 CH 2 CH 2 Si (OCH). 3 ) It was converted to 3 and it was confirmed that the compound had no-(OCF 2 O) -unit. That is, the following compound II was the main product. The number average molecular weight of Compound II was 4700.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
［例３］化合物ＩＩＩの合成
（合成例３－１）
　前記合成例１－４の方法で得た化合物（１－４）の１０ｇとＡＣ－２０００の１５０ｇとテトラヒドロフランの１５０ｇを混ぜ、ボラン・テトラヒドロフラン錯体の３．１ｇを窒素気流下で加え、２５℃で撹拌した。溶媒をエバポレータで留去し、残存物に２ｍｏｌ／Ｌの塩酸を加えて、ＡＣ－２０００で抽出し、抽出物を濃縮して粗生成物（１１．９５ｇ）を得た。粗生成物をシリカゲルカラムで精製した。１Ｈ－ＮＭＲ、及び１９Ｆ－ＮＭＲによって下記化合物（３－１）８．８ｇ生成を確認した。 [Example 3] Synthesis of Compound III (Synthesis Example 3-1)
10 g of compound (1-4) obtained by the method of Synthesis Example 1-4, 150 g of AC-2000 and 150 g of tetrahydrofuran are mixed, 3.1 g of borane-tetrahydrofuran complex is added under a nitrogen stream, and the temperature is 25 ° C. Stirred. The solvent was distilled off with an evaporator, 2 mol / L hydrochloric acid was added to the residue, and the mixture was extracted with AC-2000, and the extract was concentrated to obtain a crude product (11.95 g). The crude product was purified on a silica gel column. The production of 8.8 g of the following compound (3-1) was confirmed by 1 1 H-NMR and 19 F-NMR.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
（合成例３－２）
　１００ｍＬの２つ口ナスフラスコに、化合物（３－１）の８．０ｇ、１，３－ビス（トリフルオロメチル）ベンゼンの８．０ｇ、ＣＦ３ＳＯ２Ｃｌの１．２ｇ及びトリエチルアミンの０．７ｇを入れ、窒素雰囲気下、２５℃で撹拌した。反応終了後、ＡＣ－２０００を加え、水及び飽和食塩水で洗浄し、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、化合物（３－２）の８．８ｇを得た。 (Synthesis Example 3-2)
In a 100 mL two-necked eggplant flask, 8.0 g of compound (3-1), 8.0 g of 1,3-bis (trifluoromethyl) benzene , 1.2 g of CF 3 SO 2 Cl and 0. of triethylamine. 7 g was added, and the mixture was stirred at 25 ° C. under a nitrogen atmosphere. After completion of the reaction, AC-2000 was added, and the mixture was washed with water and saturated brine, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 8.8 g of compound (3-2).
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
（合成例３－３）
　５０ｍＬのナスフラスコ内に、化合物（３－２）の８．５ｇ、１，３－ビス（トリフルオロメチル）ベンゼンの８．５ｇ、ＨＮ（ＣＨ２ＣＨ＝ＣＨ２）２の３．２ｇ、及びトリエチルアミンの０．７ｇを入れ、窒素雰囲気下、９０℃で撹拌した。反応終了後、ＡＫ－２２５を加え、水及び飽和食塩水で洗浄し、有機相を回収した後、エバポレータで濃縮した。その後、シリカゲルカラムを実施した後、溶媒を留去し、化合物（３－３）の７．９ｇを得た。 (Synthesis Example 3-3)
In a 50 mL eggplant flask, 8.5 g of compound (3-2), 8.5 g of 1,3-bis (trifluoromethyl) benzene, 3.2 g of HN (CH 2 CH = CH 2 ) 2, and 0.7 g of triethylamine was added, and the mixture was stirred at 90 ° C. under a nitrogen atmosphere. After completion of the reaction, AK-225 was added, the mixture was washed with water and saturated brine, the organic phase was recovered, and the mixture was concentrated with an evaporator. Then, after carrying out the silica gel column, the solvent was distilled off to obtain 7.9 g of the compound (3-3).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
（合成例３－４）
　１００ｍＬのＰＦＡ製ナスフラスコに、化合物（３－３）の５．０ｇ、１，３－ビス（トリフルオロメチル）ベンゼン（東京化成工業社製）の５ｇ、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％）の０．５ｇ、ＨＳｉ（ＯＣＨ３）３の１．７ｇ、及びジメチルスルホキシドの０．１ｇを入れ、４０℃で撹拌した。反応終了後、溶媒等を減圧留去し、孔径０．２μｍのメンブランフィルタでろ過し、化合物（３－３）の２つアリル基がヒドロシリル化された化合物ＩＩＩの５．４ｇを得た。化合物ＩＩＩの数平均分子量は４０５０であった。 (Synthesis Example 3-4)
In a 100 mL PFA eggplant flask, 5.0 g of compound (3-3), 5 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.), platinum / 1,3-divinyl-1, Add 0.5 g of xylene solution (platinum content: 2%) of 1,3,3-tetramethyldisiloxane complex, 1.7 g of HSi (OCH 3 ) 3 , and 0.1 g of dimethyl sulfoxide at 40 ° C. Was stirred with. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm to obtain 5.4 g of compound III in which the two allyl groups of compound (3-3) were hydrosilylated. The number average molecular weight of Compound III was 4050.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
［例４］化合物ＩＶの合成
（合成例４－１）
　５００ｍＬのフラスコに、エリスリトールの１０．０ｇと、トリエチルアミンの６６．９ｇと、Ｎ，Ｎ－ジメチル－４－アミノピリジンの０．９ｇと、ジクロロメタン（ＣＨ２Ｃｌ２）の１５０ｇを入れ、０℃で１０分間撹拌した。次いで、ジクロロメタン１５０ｇに溶解させた塩化パラトルエンスルホニル６３．０ｇをゆっくりと添加した。窒素シールを行い、０℃で撹拌した。ジエチルエーテルで抽出し、減圧濃縮した。その後、シリカゲルカラムを実施した後、溶媒を留去し、下記化合物（４－１）３６．５ｇを得た。 [Example 4] Synthesis of compound IV (Synthesis Example 4-1)
In a 500 mL flask, put 10.0 g of erythritol, 66.9 g of triethylamine, 0.9 g of N, N-dimethyl-4-aminopyridine, and 150 g of dichloromethane (CH 2 Cl 2 ) at 0 ° C. The mixture was stirred for 10 minutes. Then, 63.0 g of paratoluenesulfonyl chloride dissolved in 150 g of dichloromethane was slowly added. Nitrogen seal was performed and the mixture was stirred at 0 ° C. It was extracted with diethyl ether and concentrated under reduced pressure. Then, after carrying out a silica gel column, the solvent was distilled off to obtain 36.5 g of the following compound (4-1).
Figure JPOXMLDOC01-appb-C000038
 　ただし、Ｔｓはトシル基である。
Figure JPOXMLDOC01-appb-C000038
 However, Ts is a tosyl group.
（合成例４－２）
　５００ｍＬフラスコに化合物（４－１）の１０．０ｇと、下記化合物４ａの１１３．２ｇと、Ｃｓ２ＣＯ３の２．２ｇと、１，３－ビストリフルオロメチルベンゼンの２００ｇを入れ、窒素シールを行い、７０℃で撹拌した。２ＮのＨＣｌで反応を停止し、ＡＣ－２０００で抽出し、減圧濃縮した。その後、シリカゲルカラムを実施した後、溶媒を留去し、下記化合物（４－２）３８．４ｇを得た。 (Synthesis Example 4-2)
In a 500 mL flask, put 10.0 g of compound (4-1), 113.2 g of the following compound 4a , 2.2 g of Cs 2 CO 3 , and 200 g of 1,3-bistrifluoromethylbenzene, and seal with nitrogen. And stirred at 70 ° C. The reaction was stopped with 2N HCl, extracted with AC-2000 and concentrated under reduced pressure. Then, after carrying out a silica gel column, the solvent was distilled off to obtain 38.4 g of the following compound (4-2).
Figure JPOXMLDOC01-appb-C000039
 　ただし、ｐは平均が７．２であり、ｑは平均が９．２である。
Figure JPOXMLDOC01-appb-C000039
 However, p has an average of 7.2, and q has an average of 9.2.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
（合成例４－３）
　還流冷却器を接続した２００ｍＬのナスフラスコに、前記化合物（４－２）の２０．２ｇ、ＮａＦ粉末５．１ｇ、ＡＣ－２０００の４０．４ｇを入れ、下記（ＨＦＰＯ）２の１９．５ｇを加えた。窒素雰囲気下、４０℃で撹拌した後、２５℃で終夜撹拌した。加圧ろ過器でＮａＦ粉末を除去した後、過剰の（ＨＦＰＯ）２とＡＣ－２０００を減圧留去した。シリカゲルクロマトグラフィで高極性の不純物を除去し、下記化合物（４－３）の２３．１ｇを得た。 (Synthesis Example 4-3)
In a 200 mL eggplant flask connected to a reflux condenser, 20.2 g of the compound (4-2), 5.1 g of NaF powder, and 40.4 g of AC-2000 were placed, and 19.5 g of the following (HFPO) 2 was added. added. After stirring at 40 ° C. under a nitrogen atmosphere, the mixture was stirred at 25 ° C. overnight. After removing the NaF powder with a pressure filter, excess (HFPO) 2 and AC-2000 were distilled off under reduced pressure. Highly polar impurities were removed by silica gel chromatography to obtain 23.1 g of the following compound (4-3).
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
（合成例４－４）
　オートクレーブ（ニッケル製、内容積５００ｍＬ）を用意し、オートクレーブのガス出口に、０℃に保持した冷却器、ＮａＦペレット充填層、及び－１０℃に保持した冷却器を直列に設置した。また－１０℃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Ｒ－４１９の２５０ｇを投入し、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。次いで、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、前記化合物（４－３）の２０ｇをＲ－４１９の８０ｇに溶解した溶液を注入した。
　次いで、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、Ｒ－４１９中に０．０１５ｇ／ｍＬのベンゼンを含むベンゼン溶液１５ｍＬ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１０ｍＬを、４０℃を保持しながら注入し、注入口を閉めた。同様の操作をさらに３回繰り返した。ベンゼンの注入総量は０．８２ｇであった。
　さらに、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。次いで、オートクレーブ内の圧力を大気圧にして、窒素ガスを１時間吹き込んだ。オートクレーブの内容物をエバポレータで濃縮し、下記化合物（４－４）の２０．９ｇを得た。 (Synthesis Example 4-4)
An autoclave (made of nickel, internal volume 500 mL) was prepared, and a cooler held at 0 ° C., a NaF pellet-filled layer, and a cooler held at −10 ° C. were installed in series at the gas outlet of the autoclave. In addition, a liquid return line was installed to return the aggregated liquid from the cooler kept at -10 ° C to the autoclave.
250 g of R-419 was put into an autoclave, and the mixture was 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. Then, while blowing 20% fluorine gas at the same flow rate, a solution in which 20 g of the compound (4-3) was dissolved in 80 g of R-419 was injected into the autoclave.
Next, the internal pressure of the autoclave was pressurized to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow velocity. 15 mL of a benzene solution containing 0.015 g / mL benzene in R-419 was injected into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution injection port of the autoclave was closed. After stirring, 10 mL of the benzene solution was injected again while maintaining 40 ° C., and the injection port was closed. The same operation was repeated three more times. The total amount of benzene injected was 0.82 g.
Further, stirring was continued while blowing 20% fluorine gas at the same flow rate. Next, the pressure in the autoclave was adjusted to atmospheric pressure, and nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated with an evaporator to obtain 20.9 g of the following compound (4-4).
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
（合成例４－５）
　５０ｍＬのナスフラスコに、前記化合物４－４の１５．０ｇ、ＮａＦの０．７ｇ、及びＡＣ－２０００の１５ｇを入れた。窒素雰囲気下、メタノールの０．６ｇを加え、５０℃で撹拌した後、２５℃で撹拌した。加圧ろ過器でＮａＦを除去した後、反応混合物をエバポレータで濃縮し、下記化合物（４－５）の１２．６ｇを得た。 (Synthesis Example 4-5)
In a 50 mL eggplant flask, 15.0 g of the compound 4-4, 0.7 g of NaF, and 15 g of AC-2000 were placed. Under a nitrogen atmosphere, 0.6 g of methanol was added, and the mixture was stirred at 50 ° C. and then at 25 ° C. After removing NaF with a pressure filter, the reaction mixture was concentrated with an evaporator to obtain 12.6 g of the following compound (4-5).
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
（合成例４－６）
　２００ｍＬの３つ口ナスフラスコ内にて、塩化リチウムの０．１８ｇをエタノールの１８．５ｇに溶解させた。これに化合物（４－５）の１２．５ｇを加えて氷浴で冷却しながら、水素化ホウ素ナトリウムの１．９ｇをエタノールの４５ｇに溶解した溶液をゆっくり滴下した。氷浴を取り外し、２５℃までゆっくり昇温しながら撹拌を続けた。２５℃で撹拌後、液性が酸性になるまで塩酸水溶液を滴下した。ＡＣ－２０００の３０ｍＬを添加し、水と飽和食塩水で洗浄し、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（４－６）の１１．４ｇを得た。 (Synthesis Example 4-6)
In a 200 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 18.5 g of ethanol. To this, 12.5 g of compound (4-5) was added, and while cooling in an ice bath, a solution of 1.9 g of sodium borohydride dissolved in 45 g of ethanol was slowly added dropwise. The ice bath was removed and stirring was continued while slowly raising the temperature to 25 ° C. After stirring at 25 ° C., an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic. 30 mL of AC-2000 was added, washed with water and saturated brine, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 11.4 g of the following compound (4-6).
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
（合成例４－７）
　１００ｍＬの２つ口ナスフラスコに、前記化合物（４－６）の１０．０ｇ、硫酸水素テトラブチルアンモニウムの０．５ｇ、ＢｒＣＨ２ＣＨ＝ＣＨ２の０．７ｇ及び２０％水酸化カリウム水溶液の０．３ｇを加え６０℃で８時間撹拌した。反応終了後、ＡＣ－２０００を加え、希塩酸水溶液で洗浄し、有機相を回収した。回収した有機相をシリカゲルカラムに通し、回収した溶液をエバポレータで濃縮し、化合物（４－７）の１０．１ｇを得た。 (Synthesis Example 4-7)
In a 100 mL two-necked eggplant flask, 10.0 g of the compound (4-6), 0.5 g of tetrabutylammonium hydrogen sulfate , 0.7 g of BrCH 2 CH = CH 2 , and 0 of a 20% potassium hydroxide aqueous solution. .3 g was added and the mixture was stirred at 60 ° C. for 8 hours. After completion of the reaction, AC-2000 was added, and the mixture was washed with a dilute aqueous hydrochloric acid solution to recover the organic phase. The recovered organic phase was passed through a silica gel column, and the recovered solution was concentrated with an evaporator to obtain 10.1 g of compound (4-7).
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（合成例４－８）
　還流冷却器、温度計及び撹拌器を取り付けた１００ｍＬの４つ口フラスコに、前記化合物（４－７）の８．５ｇ、１，３－ビス（トリフルオロメチル）ベンゼンの８．５ｇ、トリアセトキシメチルシランの０．１２ｇ、トリクロロシランの０．９３ｇを仕込み、窒素気流化、５℃で撹拌した。続いて、１，３－ジビニル－１，１，３，３－テトラメチルジシクロキサンのＰｔ錯体を２％含むキシレン溶液を０．１ｍＬ加えた後、６０℃まで昇温させ、この温度にて撹拌した。その後、減圧下で揮発分を留去することにより、下記化合物（４－８）を得た。 (Synthesis Example 4-8)
In a 100 mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 8.5 g of the compound (4-7), 8.5 g of 1,3-bis (trifluoromethyl) benzene, and triacetoxy. 0.12 g of methylsilane and 0.93 g of trichlorosilane were charged, and the mixture was made into a nitrogen stream and stirred at 5 ° C. Subsequently, 0.1 mL of a xylene solution containing 2% of the Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldicycloxane was added, and then the temperature was raised to 60 ° C. at this temperature. Stirred. Then, the volatile matter was distilled off under reduced pressure to obtain the following compound (4-8).
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
（合成例４－９）
　還流冷却器、温度計及び撹拌器を取り付けた１００ｍＬの４つ口フラスコに、前記化合物（４－８）の７．０ｇ、１，３－ビス（トリフルオロメチル）ベンゼンの２０ｇを仕込み、窒素気流下、５℃で撹拌した。続いて、アリルマグネシウムブロマイドを１ｍｏｌ／Ｌ含むジエチルエーテル溶液を１１．４ｍＬ加えた後、２５℃まで昇温させ、この温度にて撹拌した。その後、５℃まで冷却し、メタノールを５ｍＬ加えた後、２５℃まで昇温させて不溶物をろ過した。続いて、減圧下で揮発分を留去した後、不揮発分をＡＣ－２０００で希釈し、メタノールで洗浄し、減圧下で揮発分を留去した。続いて、シリカゲルカラム（溶離液：ＡＣ－２０００）を実施した後、溶媒を留去し、下記化合物（４－９）の７．０ｇを得た。 (Synthesis Example 4-9)
7.0 g of the compound (4-8) and 20 g of 1,3-bis (trifluoromethyl) benzene were charged into a 100 mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and a nitrogen stream was charged. Below, it was stirred at 5 ° C. Subsequently, 11.4 mL of a diethyl ether solution containing 1 mol / L of allyl magnesium bromide was added, the temperature was raised to 25 ° C., and the mixture was stirred at this temperature. Then, the mixture was cooled to 5 ° C., 5 mL of methanol was added, the temperature was raised to 25 ° C., and the insoluble material was filtered. Subsequently, after distilling off the volatile matter under reduced pressure, the non-volatile matter was diluted with AC-2000, washed with methanol, and the volatile matter was distilled off under reduced pressure. Subsequently, a silica gel column (eluent: AC-2000) was carried out, and then the solvent was distilled off to obtain 7.0 g of the following compound (4-9).
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
（合成例４－１０）
　１００ｍＬのＰＦＡ製ナスフラスコに、前記化合物（４－９）の５．２ｇ、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％）の０．２６ｇ、ＨＳｉ（ＯＣＨ３）３の１．１７ｇ、ジメチルスルホキシドの０．０２５ｇ及び１，３－ビス（トリフルオロメチル）ベンゼンの２．１ｇを入れ、４０℃で撹拌した。反応終了後、溶媒等を減圧留去し、孔径０．２μｍのメンブランフィルタでろ過し、下記化合物ＩＶの５．４ｇを得た。生成物の数平均分子量は８６２０であった。 (Synthesis Example 4-10)
In a 100 mL PFA eggplant flask, 5.2 g of the compound (4-9) and a xylene solution of platinum / 1,3-divinyl 1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). ), 1.17 g of HSi (OCH 3 ) 3 , 0.025 g of dimethyl sulfoxide and 2.1 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm to obtain 5.4 g of the following compound IV. The number average molecular weight of the product was 8620.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
［例５］化合物Ｖの合成
（合成例５－１）
　３００ｍＬのＰＦＡ製ナスフラスコに炭酸カリウム２１．３ｇ、エリスリトールを５ｇ、及び２１．５ｇのＡＥ－３０００を加えた。１２０℃にて混合物を撹拌しながら、４２．９ｇのＣＦ２＝ＣＦＯ－ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＯＨをゆっくり添加し、加熱撹拌した。反応混合物を冷却した後、ＡＥ－３０００を１００ｇ、２Ｎ塩酸水溶液を４５ｇ加え、反応を停止させた。水及び飽和食塩水で洗浄し、有機相を回収した後、回収した有機層をエバポレータで濃縮し、化合物（５－１）の３２．６ｇを得た。 [Example 5] Synthesis of compound V (Synthesis Example 5-1)
To a 300 mL PFA eggplant flask, 21.3 g of potassium carbonate, 5 g of erythritol, and 21.5 g of AE-3000 were added. While stirring the mixture at 120 ° C., 42.9 g of CF 2 = CFO-CF 2 CF 2 CF 2 CH 2 OH was slowly added, and the mixture was heated and stirred. After cooling the reaction mixture, 100 g of AE-3000 and 45 g of a 2N aqueous hydrochloric acid solution were added to stop the reaction. After washing with water and saturated brine and recovering the organic phase, the recovered organic layer was concentrated with an evaporator to obtain 32.6 g of compound (5-1).
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
（合成例５－２）
　還流冷却器を接続した２００ｍＬのナスフラスコに、合成例５－１で得た化合物（５－１）の２０ｇ、炭酸カリウムの１７．７ｇを加えた。窒素雰囲気下、１００℃に加熱しながら、ＣＦ２＝ＣＦＯ－ＣＦ２ＣＦ２ＣＦ２ＣＨ２ＯＨを滴下した。１２０℃に昇温し保ったまま更に撹拌した後、塩酸水溶液を加えて、過剰の炭酸カリウムを処理し、水とＡＥ－３０００を加えて分液処理を行った。水洗後、有機相を回収し、エバポレータで濃縮することによって、高粘度のオリゴマーを得た。再び、ＡＥ－３０００で希釈し、シリカゲルカラムクロマトグラフィに展開して分取した。各フラクションについて、単位数ｍ１１、ｍ１２、ｍ１３及びｍ１４の平均値を１９Ｆ－ＮＭＲの積分値から求めた。下式中、ｍ１１、ｍ１２、ｍ１３及びｍ１４の平均値が３～５のフラクションを合わせた化合物（５－２）の２８．３ｇを得た。 (Synthesis Example 5-2)
To a 200 mL eggplant flask to which a reflux condenser was connected, 20 g of the compound (5-1) obtained in Synthesis Example 5-1 and 17.7 g of potassium carbonate were added. CF 2 = CFO-CF 2 CF 2 CF 2 CH 2 OH was added dropwise under a nitrogen atmosphere while heating at 100 ° C. After further stirring while keeping the temperature at 120 ° C., an aqueous hydrochloric acid solution was added to treat excess potassium carbonate, and water and AE-3000 were added to carry out a liquid separation treatment. After washing with water, the organic phase was recovered and concentrated with an evaporator to obtain a highly viscous oligomer. It was diluted again with AE-3000, developed by silica gel column chromatography, and collected. For each fraction, the average value of the units m11, m12, m13 and m14 was obtained from the integrated value of 19 F-NMR. In the following formula, 28.3 g of compound (5-2) was obtained by combining fractions having an average value of m11, m12, m13 and m14 of 3 to 5.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
（合成例５－３）
　還流冷却器を接続した１００ｍＬのナスフラスコに、合成例５－２で得た化合物（５－２１）の２０．５ｇ、ＮａＦ粉末の４．３ｇ、ＡＣ－２０００の４１ｇを取り入れ、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＦの９．８２ｇを加えた。窒素雰囲気下、４０℃で２４時間撹拌した後、２５℃で撹拌した。加圧ろ過器でＮａＦ粉末を除去した後、過剰のＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＦとＡＣ－２０００を減圧留去した。シリカゲルクロマトグラフィで高極性の不純物を除去し、下式中、ｍ１１＋ｍ１２＋ｍ１３＋ｍ１４の平均値が２０である、化合物（５－３）の２４．２ｇを得た。 (Synthesis Example 5-3)
20.5 g of the compound (5-21) obtained in Synthesis Example 5-2, 4.3 g of NaF powder, and 41 g of AC-2000 were taken into a 100 mL eggplant flask to which a reflux condenser was connected, and CF 3 CF 2 CF 2 OCF (CF 3 ) COF was added in an amount of 9.82 g. After stirring at 40 ° C. for 24 hours under a nitrogen atmosphere, the mixture was stirred at 25 ° C. After removing the NaF powder with a pressure filter, excess CF 3 CF 2 CF 2 OCF (CF 3 ) COF and AC-2000 were distilled off under reduced pressure. Highly polar impurities were removed by silica gel chromatography to obtain 24.2 g of compound (5-3) having an average value of m11 + m12 + m13 + m14 of 20 in the following formula.
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
（合成例５－４）
　オートクレーブ（ニッケル製、内容積５００ｍＬ）を用意し、オートクレーブのガス出口に、０℃に保持した冷却器、ＮａＦペレット充填層、及び－１０℃に保持した冷却器を直列に設置した。また－１０℃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Ｒ－１１３の３１２ｇを投入し、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。次いで、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、合成例５－３で得た化合物（５－３）の２０．２ｇをＲ－１１３の８４ｇに溶解した溶液を注入した。
　次いで、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、Ｒ－１１３中に０．０１５ｇ／ｍＬのベンゼンを含むベンゼン溶液の９ｍＬ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。１５分撹拌した後、再びベンゼン溶液の６ｍＬを、４０℃を保持しながら注入し、注入口を閉めた。同様の操作をさらに３回繰り返した。ベンゼンの注入総量は０．３５ｇであった。
　さらに、２０％フッ素ガスを同じ流速で吹き込みながら、１時間撹拌を続けた。次いで、オートクレーブ内の圧力を大気圧にして、窒素ガスを１時間吹き込んだ。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（５－４）の２２．３ｇを得た。 (Synthesis Example 5-4)
An autoclave (made of nickel, internal volume 500 mL) was prepared, and a cooler held at 0 ° C., a NaF pellet-filled layer, and a cooler held at −10 ° C. were installed in series at the gas outlet of the autoclave. In addition, a liquid return line was installed to return the aggregated liquid from the cooler kept at -10 ° C to the autoclave.
312 g of R-113 was put into 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. Then, while blowing 20% fluorine gas at the same flow rate, a solution prepared by dissolving 20.2 g of the compound (5-3) obtained in Synthesis Example 5-3 in 84 g of R-113 was injected into the autoclave.
Next, the internal pressure of the autoclave was pressurized to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow velocity. 9 mL of a benzene solution containing 0.015 g / mL benzene in R-113 was injected into the autoclave while heating from 25 ° C. to 40 ° C., and the benzene solution injection port of the autoclave was closed. After stirring for 15 minutes, 6 mL of the benzene solution was injected again while maintaining 40 ° C., and the injection port was closed. The same operation was repeated three more times. The total amount of benzene injected was 0.35 g.
Further, stirring was continued for 1 hour while blowing 20% fluorine gas at the same flow rate. Next, the pressure in the autoclave was adjusted to atmospheric pressure, and nitrogen gas was blown in for 1 hour. The contents of the autoclave were concentrated on an evaporator to give 22.3 g of compound (5-4).
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
（合成例５－５）
　１００ｍＬのナスフラスコに、例５－４で得た化合物（５－４）の１５．０ｇ、ＮａＦ０．８ｇ、及びＡＣ－２０００の１５ｇを入れた。窒素雰囲気下、メタノールの０．６ｇを加え、５０℃で撹拌した後、２５℃で撹拌した。加圧ろ過器でＮａＦを除去した後、反応混合物をエバポレータで濃縮し、化合物（５－５）の１２．２ｇを得た。 (Synthesis Example 5-5)
In a 100 mL eggplant flask, 15.0 g of the compound (5-4) obtained in Example 5-4, 0.8 g of NaF, and 15 g of AC-2000 were placed. Under a nitrogen atmosphere, 0.6 g of methanol was added, and the mixture was stirred at 50 ° C. and then at 25 ° C. After removing NaF with a pressure filter, the reaction mixture was concentrated with an evaporator to obtain 12.2 g of compound (5-5).
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
（合成例５－６）
　５０ｍＬのナスフラスコに、合成例５－５で得た化合物（５－５）の１０．０ｇ及びＨ２Ｎ－ＣＨ２－Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３の１．１ｇを入れ撹拌した。ＮＭＲから、化合物（５－５）がすべて化合物（５－６）に変換していることを確認した。また、副生物であるメタノールが生成していた。得られた溶液をＡＥ－３０００の９．０ｇで希釈し、シリカゲルカラムクロマトグラフィで精製し、化合物（５－６）の８．４ｇを得た。 (Synthesis Example 5-6)
In a 50 mL eggplant flask, 10.0 g of the compound (5-5) obtained in Synthesis Example 5-5 and 1.1 g of H 2 N-CH 2- C (CH 2 CH = CH 2 ) 3 were placed and stirred. .. From NMR, it was confirmed that all the compound (5-5) was converted to the compound (5-6). In addition, methanol, which is a by-product, was produced. The obtained solution was diluted with 9.0 g of AE-3000 and purified by silica gel column chromatography to obtain 8.4 g of compound (5-6).
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
（合成例５－７）
　５０ｍＬのＰＦＡ製容器に、化合物（５－６）の５．５ｇ、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％）の０．５５ｇ、ＨＳｉ（ＯＣＨ３）３の１．４ｇ、ジメチルスルホキシドの０．０３ｇ及び１，３－ビス（トリフルオロメチル）ベンゼンの５．５ｇを入れ、４０℃で４時間撹拌した。反応終了後、溶媒等を減圧留去し、メンブランフィルタでろ過し、化合物（５－６）の３つのアリル基がヒドロシリル化された化合物Ｖ及び化合物（５－６）の３つのアリル基の一部又は全部がインナーオレフィン（－ＣＨ＝ＣＨＣＨ３）に異性化した副生物からなる組成物の５．３ｇを得た。化合物Ｖの数平均分子量は７６３０であった。 (Synthesis Example 5-7)
In a 50 mL PFA container, 5.5 g of compound (5-6) and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%) 0.55 g of HSi (OCH 3 ) , 1.4 g of HSi (OCH 3) 3 , 0.03 g of dimethyl sulfoxide and 5.5 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. for 4 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, filtered through a membrane filter, and one of the three allyl groups of compound V and compound (5-6) in which the three allyl groups of compound (5-6) were hydrosilylated. 5.3 g of a composition composed of by-products in part or all of which were isomerized to inner olefin (-CH = CHCH 3) was obtained. The number average molecular weight of Compound V was 7630.
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
［例６］化合物ＶＩの合成
　１００ｍＬの丸底フラスコ内に、ＣＦ３Ｏ［ＣＦ２ＣＦ２Ｏ］ａＣＦ２Ｃ（Ｏ）ＯＣＨ２ＣＨ３の３３．１ｇ、ＮＨ２ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３の３．７ｇを入れ、室温で撹拌し、下式で表される化合物ＶＩ（数平均分子量１１００）を得た。
　ＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）ｎＣＦ２Ｃ（Ｏ）ＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３） [Example 6] Synthesis of compound VI In a 100 mL round-bottom flask, 33.1 g of CF 3 O [CF 2 CF 2 O] a CF 2 C (O) OCH 2 CH 3 and NH 2 CH 2 CH 2 CH 2 3.7 g of Si (OCH 3 ) 3 was added and stirred at room temperature to obtain compound VI (number average molecular weight 1100) represented by the following formula.
CF 3 O (CF 2 CF 2 O) n CF 2 C (O) NH (CH 2 ) 3 Si (OCH 3 )
［例７］化合物ＶＩＩの合成
　国際公開第２０１４／１２６０６４号パンフレットの化合物（ｉｉ－２）の合成方法により、下式で表される化合物ＶＩＩ（数平均分子量４９３０）を得た。
　ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２Ｏ（ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２Ｏ）１３ＣＦ２ＣＦ２ＣＦ２Ｃ（Ｏ）ＮＨＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３ [Example 7] Synthesis of compound VII Compound VII (number average molecular weight 4930) represented by the following formula was obtained by the method for synthesizing compound (ii-2) in Pamphlet International Publication No. 2014/126064.
CF 3 CF 2 OCF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) 13 CF 2 CF 2 CF 2 C (O) NHCH 2 CH 2 CH 2 Si (OCH 3 ) 3
［例８］化合物ＶＩＩＩの合成
（合成例８－１）
　１００ｃｃの耐圧反応器に前記化合物（１－４）を１０ｇ、１，３－ビストリフルオロベンゼンを５０ｇ、２．０Ｍアンモニア－メタノール溶液を５ｇ入れ、室温で攪拌した。その後、溶媒を留去し、下記化合物（８－１）を９．８ｇ得た。 [Example 8] Synthesis of compound VIII (Synthesis Example 8-1)
10 g of the compound (1-4), 50 g of 1,3-bistrifluorobenzene, and 5 g of a 2.0 M ammonia-methanol solution were placed in a 100 cc pressure resistant reactor, and the mixture was stirred at room temperature. Then, the solvent was distilled off to obtain 9.8 g of the following compound (8-1).
Figure JPOXMLDOC01-appb-C000057
 　ただし、ｍ１５＋ｍ１６＋ｍ１７の平均は２７である。
Figure JPOXMLDOC01-appb-C000057
 However, the average of m15 + m16 + m17 is 27.
（合成例８－２）
　３００ｃｃのナスフラスコに化合物（８－１）を９ｇ、ＡＣ－６０００を４５ｇ、ジエチルエーテルを１８ｇ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０．７ｇゆっくり加え、室温で２０時間攪拌した。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、目的の化合物（８－２）を５．２ｇで得た。 (Synthesis Example 8-2)
9 g of compound (8-1), 45 g of AC-6000 and 18 g of diethyl ether were added to a 300 cc eggplant flask, and the mixture was stirred under an ice bath. Then, 0.7 g of lithium aluminum hydride was slowly added, and the mixture was stirred at room temperature for 20 hours. Then, 0.3 cc of a saturated aqueous solution of sodium sulfate was added, and the precipitated solid was removed by Celite filtration. The obtained filtrate was concentrated and then purified by silica gel column chromatography to obtain 5.2 g of the target compound (8-2).
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
（合成例８－３）
　５０ｃｃのナスフラスコにＨＯ（Ｃ＝Ｏ）ＣＨ（ＣＨ２ＣＨ＝ＣＨ２）２の０．９ｇ、ジクロロメタンの１０ｍＬ、オキサリルクロリドの０．９ｍＬ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０．１ｇを添加した。その後室温で攪拌後、濃縮し、Ｃｌ（Ｃ＝Ｏ）ＣＨ（ＣＨ２ＣＨ＝ＣＨ２）２の０．９ｇを得た。
　別途５０ｃｃのナスフラスコに化合物（８－２）の５ｇ、トリエチルアミンの１．４ｍＬを加え、上記Ｃｌ（Ｃ＝Ｏ）ＣＨ（ＣＨ２ＣＨ＝ＣＨ２）２と１，３－ビストリフルオロメチルベンゼン２０ｍＬを添加した。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、化合物（８－３）を１．７ｇ得た。 (Synthesis Example 8-3)
To a 50 cc eggplant flask, 0.9 g of HO (C = O) CH (CH 2 CH = CH 2 ) 2 , 10 mL of dichloromethane, and 0.9 mL of oxalyl chloride were added and stirred under ice-cooling, and then DMF (N, 0.1 g of N-dimethylformamide) was added. Then, the mixture was stirred at room temperature and concentrated to obtain 0.9 g of Cl (C = O) CH (CH 2 CH = CH 2 ) 2.
Separately, add 5 g of compound (8-2) and 1.4 mL of triethylamine to a 50 cc eggplant flask, and add Cl (C = O) CH (CH 2 CH = CH 2 ) 2 and 1,3-bistrifluoromethylbenzene 20 mL. Was added. The mixture was stirred and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 1.7 g of compound (8-3).
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
（合成例８－４）
　１００ｍＬのＰＦＡ製ナスフラスコに、前記化合物（８－３）の１ｇ、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％）の０．０５ｇ、ＨＳｉ（ＯＣＨ３）３の０．６４ｇ、ジメチルスルホキシドの０．０１ｇ及び１，３－ビス（トリフルオロメチル）ベンゼンの０．４ｇを入れ、４０℃で１０時間撹拌した。反応終了後、溶媒等を減圧留去し、孔径０．２μｍのメンブランフィルタでろ過し、下記化合物ＶＩＩＩの１．２ｇを得た。生成物の数平均分子量は４５５０であった。 (Synthesis Example 8-4)
In a 100 mL PFA eggplant flask, 1 g of the compound (8-3) and a xylene solution of platinum / 1,3-divinyl 1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). 0.05 g, 0.64 g of HSi (OCH 3 ) 3 , 0.01 g of dimethyl sulfoxide and 0.4 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. for 10 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure, and the mixture was filtered through a membrane filter having a pore size of 0.2 μm to obtain 1.2 g of the following compound VIII. The number average molecular weight of the product was 4550.
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
［例９］化合物ＩＸの合成
（合成例９－１）
　２００ｃｃのナスフラスコにＨＯ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３の１．３ｇ、ジクロロメタンの１０ｍＬ、オキサリルクロリドの１．３ｍＬ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０．１３ｇを添加した。その後室温で攪拌後、濃縮し、Ｃｌ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を得た。
　別途５０ｃｃのナスフラスコに化合物（４－６）の５ｇ、ＡＣ－６０００を１０ｇ、トリエチルアミンを１ｇ、Ｎ，Ｎ－ジメチル－４－アミノピリジンを１．３ｇ加え、上記Ｃｌ（Ｃ＝Ｏ）Ｃ（ＣＨ２ＣＨ＝ＣＨ２）３を加えて攪拌した。得られた反応液をシリカゲルカラムクロマトグラフィで精製し、化合物（９－１）を１．３ｇ得た。 [Example 9] Synthesis of compound IX (Synthesis Example 9-1)
To a 200 cc eggplant flask, add 1.3 g of HO (C = O) C (CH 2 CH = CH 2 ) 3 , 10 mL of dichloromethane, and 1.3 mL of oxalyl chloride, and stir under ice-cooling, and then DMF (N, 0.13 g of N-dimethylformamide) was added. Then, the mixture was stirred at room temperature and concentrated to obtain Cl (C = O) C (CH 2 CH = CH 2 ) 3.
Separately, 5 g of compound (4-6), 10 g of AC-6000, 1 g of triethylamine, and 1.3 g of N, N-dimethyl-4-aminopyridine were added to a 50 cc eggplant flask, and the above Cl (C = O) C ( CH 2 CH = CH 2 ) 3 was added and stirred. The obtained reaction solution was purified by silica gel column chromatography to obtain 1.3 g of compound (9-1).
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
（合成例９－２）
　１００ｍＬのＰＦＡ製ナスフラスコに、前記化合物（９－１）の１ｇ、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％）の０．８ｇ、ＨＳｉ（ＯＣＨ３）３の０．４ｇ、ジメチルスルホキシドの０．００５ｇ及び１，３－ビス（トリフルオロメチル）ベンゼンの０．５ｇを入れ、４０℃で撹拌した。反応終了後、溶媒等を減圧留去し、メンブランフィルタでろ過し、下記化合物ＩＸの１．２ｇを得た。生成物の数平均分子量は９１９０であった。 (Synthesis Example 9-2)
In a 100 mL PFA eggplant flask, 1 g of the compound (9-1) and a xylene solution (platinum content: 2%) of platinum / 1,3-divinyl 1,1,3,3-tetramethyldisiloxane complex. 0.8 g, 0.4 g of HSi (OCH 3 ) 3 , 0.005 g of dimethyl sulfoxide and 0.5 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter to obtain 1.2 g of the following compound IX. The number average molecular weight of the product was 9190.
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
［例１０］化合物Ｘの合成
（合成例１０－１）
　ＤｉｅｔｈｙｌＤｉａｌｌｙｌｍａｌｏｎａｔｅ（６０．０ｇ）、塩化リチウム（２３．７ｇ）、水（６．５ｇ）、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（１０－１）を３９．５ｇ得た。 [Example 10] Synthesis of compound X (Synthesis Example 10-1)
Diethyl Dialylmalonate (60.0 g), lithium chloride (23.7 g), water (6.5 g) 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 (10-1).
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
（合成例１０－２）
　ＴＨＦ（２６０ｍＬ）、ジイソプロピルアミン（２９．８ｍＬ）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）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（１０－１）（３９．５ｇ）をＴＨＦ溶液に加え、撹拌した後、臭化アリル（２４．１ｍＬ）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（１０－２）を４５．０ｇ得た。 (Synthesis Example 10-2)
After adding THF (260 mL) and diisopropylamine (29.8 mL), the solution was cooled to −78 ° C. An n-butyllithium hexane solution (2.76 M, 96.6 mL) 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 (10-1) (39.5 g) was added to a THF solution, stirred, and then allyl bromide (24.1 mL) 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 (10-2).
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
（合成例１０－３）
　上記化合物（１０－２）（４５．０ｇ）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）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（１０－３）を３１．３ｇ得た。 (Synthesis Example 10-3)
The above compound (10-2) (45.0 g) was dissolved in THF (620 mL) and cooled to 0 ° C. A THF solution of lithium aluminum hydride (104 mL) was added and 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 (10-3).
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
（合成例１０－４）
　アセトニトリル（３８０ｍＬ）、前記化合物（１０－３）（３１．３ｇ）、トリフェニルホスフィン（６４．３ｇ）、四塩化炭素（３３．９ｇ）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、蒸留によって、下記化合物（１０－４）を２８．２ｇ得た。 (Synthesis Example 10-4)
Acetonitrile (380 mL), the compound (10-3) (31.3 g), triphenylphosphine (64.3 g) and carbon tetrachloride (33.9 g) 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 (10-4) was obtained by distillation.
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
（合成例１０－５）
　マグネシウム（２．３６ｇ）にＴＨＦ（３５ｍＬ）、ヨウ素（０．１８０ｇ）を加えて、室温で撹拌した。前記化合物（１０－４）（１４．０ｇ）のＴＨＦ（３５ｍＬ）溶液を加え、加熱還流することで、下記化合物（１０－５）の溶液（０．８０Ｍ）を調製した。 (Synthesis Example 10-5)
THF (35 mL) and iodine (0.180 g) were added to magnesium (2.36 g), and the mixture was stirred at room temperature. A solution (0.80M) of the following compound (10-5) was prepared by adding a solution of the compound (10-4) (14.0 g) in THF (35 mL) and heating under reflux.
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
（合成例１０－６）
　１－ブロモ－４－クロロブタン（２．９ｇ）、１－フェニル－１－プロピン（０．２０ｇ）、ＣｕＣｌ２（０．０５ｇ）を加え０℃で撹拌した。前記化合物（１０－５）（０．８０Ｍ，２４．０ｍＬ）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、蒸留によって、下記化合物（１０－６）を３．４５ｇ得た。 (Synthesis Example 10-6)
1-Bromo-4-chlorobutane (2.9 g), 1-phenyl-1-propyne (0.20 g) and CuCl 2 (0.05 g) were added, and the mixture was stirred at 0 ° C. The compound (10-5) (0.80 M, 24.0 mL) 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 (10-6) was obtained in an amount of 3.45 g by distillation.
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
（合成例１０－７）
　マグネシウム（０．１７ｇ）にＴＨＦ（２．６ｍＬ）、ヨウ素（１４．０ｍｇ）を加えて、室温で撹拌した。前記化合物（１０－６）（１．４１ｇ）のＴＨＦ（２．６ｍＬ）溶液を加え、熱還流することで、下記化合物（１０－７）の溶液（０．７４Ｍ）を調製した。 (Synthesis Example 10-7)
THF (2.6 mL) and iodine (14.0 mg) were added to magnesium (0.17 g), and the mixture was stirred at room temperature. A solution (0.74M) of the following compound (10-7) was prepared by adding a solution of the compound (10-6) (1.41 g) in THF (2.6 mL) and subjecting to thermal reflux.
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
（合成例１０－８）
　２００ｍＬの３つ口ナスフラスコ内にて、塩化リチウムの０．１８ｇをエタノールの１８．５ｇに溶解させた。これに上記化合物（５－５）の１０ｇを加えて氷浴で冷却しながら、水素化ホウ素ナトリウムの２．９ｇをＴＨＦの１５０ｇに溶解した溶液をゆっくり滴下した。氷浴を取り外し、２５℃までゆっくり昇温しながら撹拌を続けた。２５℃で撹拌後、液性が酸性になるまで塩酸水溶液を滴下した。ＡＣ－２０００の１５０ｍＬを添加し、水と飽和食塩水で洗浄し、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（１０－８）の９．２ｇを得た。 (Synthesis Example 10-8)
In a 200 mL three-necked eggplant flask, 0.18 g of lithium chloride was dissolved in 18.5 g of ethanol. To this, 10 g of the above compound (5-5) was added, and while cooling in an ice bath, a solution in which 2.9 g of sodium borohydride was dissolved in 150 g of THF was slowly added dropwise. The ice bath was removed and stirring was continued while slowly raising the temperature to 25 ° C. After stirring at 25 ° C., an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic. 150 mL of AC-2000 was added, washed with water and saturated brine, and the organic phase was recovered. The recovered organic phase was concentrated with an evaporator to obtain 9.2 g of the following compound (10-8).
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
（合成例１０－９）
　前記化合物（１０－８）の９ｇ、２，６－ルチジンの３ｇ、１，３－ビスフルオロメチルベンゼンの４５ｇ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の３．９ｇ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（１０－９）を６．８ｇ得た。 (Synthesis Example 10-9)
9 g of the compound (10-8), 3 g of 2,6-lutidine, and 45 g of 1,3-bisfluoromethylbenzene were added, and the mixture was stirred at 0 ° C. After adding 3.9 g of trifluoromethanesulfonic anhydride, 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 (10-9).
Figure JPOXMLDOC01-appb-C000071
 　ただし、ＯＴｆはトリフラート：－Ｏ－Ｓ（＝Ｏ）２（－ＣＦ３）である。
Figure JPOXMLDOC01-appb-C000071
 However, OTf is triflate: -OS (= O) 2 (-CF 3 ).
（合成例１０－１０）
　ＣｕＣｌ２の０．１４４ｇ、１－フェニル－１－プロピンの０．３１ｇ、１，３－ビストリフルオロメチルベンゼン１９０ｇ、前記化合物（１０－９）の９．５ｇを加えた後、前記化合物（１０－７）の１７．７ｇ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（１０－１０）を０．９ｇ得た。 (Synthesis Example 10-10)
After adding 0.144 g of CuCl 2 , 0.31 g of 1-phenyl-1-propyne, 190 g of 1,3-bistrifluoromethylbenzene, and 9.5 g of the compound (10-9), the compound (10-) 17.7 g of 7) was added. After stirring at room temperature, the mixture was 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 0.9 g of the following compound (10-10).
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
（合成例１０－１１）
　１００ｍＬのＰＦＡ製ナスフラスコに、前記化合物（１０－１０）の１ｇ、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％）の０．０５ｇ、ＨＳｉ（ＯＣＨ３）３の０．６４ｇ、ジメチルスルホキシドの０．０１ｇ及び１，３－ビス（トリフルオロメチル）ベンゼンの０．４ｇを入れ、４０℃で撹拌した。反応終了後、溶媒等を減圧留去し、メンブランフィルタでろ過し、下記化合物Ｘの０．７ｇを得た。生成物の数平均分子量は８９４０であった。 (Synthesis Example 10-11)
In a 100 mL PFA eggplant flask, 1 g of the compound (10-10) and a xylene solution of platinum / 1,3-divinyl 1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%). 0.05 g, 0.64 g of HSi (OCH 3 ) 3 , 0.01 g of dimethyl sulfoxide and 0.4 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter to obtain 0.7 g of the following compound X. The number average molecular weight of the product was 8940.
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
［物品の製造及び評価］
　例１～１０で得た各化合物を用いて基材の表面処理を行い、撥水撥油層を有する物品を得た。表面処理方法として、各例について下記のドライコーティング法及びウェットコーティング法をそれぞれ用いた。基材としては化学強化ガラスを用いた。得られた物品について、下記の方法で評価した。結果を表１～２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 10 to obtain an article having a water-repellent and oil-repellent layer. As the surface treatment method, the following dry coating method and wet coating method were used for each example. Chemically tempered glass was used as the base material. The obtained article was evaluated by the following method. The results are shown in Tables 1 and 2.
（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１～７で得た各化合物の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、ＡＫ－２２５にて洗浄することによって、基材の表面に撥水撥油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). The 0.5g of the compound obtained in Example 1-7 was charged into a molybdenum boat in the vacuum evaporation apparatus was evacuated in the vacuum evaporation apparatus below 1 × 10- 3 Pa. 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 base material. The base material on which the compound was deposited was heat-treated at 200 ° C. for 30 minutes and washed with AK-225 to obtain an article having a water-repellent and oil-repellent layer on the surface of the base material.
（ウェットコーティング法）
　例１～１０で得た各化合物と、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、ＡＫ－２２５にて洗浄することによって、基材の表面に撥水撥油層を有する物品を得た。 (Wet coating method)
Each compound obtained in Examples 1 to 10 and C 4 F 9 OC 2 H 5 (manufactured by 3M, Novec® 7200) as a liquid medium are mixed and coated with a solid content concentration of 0.05%. The liquid was prepared. The base material was dipped in the coating liquid, left for 30 minutes, and then the base material was pulled up (dip coating method). The coating film was dried at 200 ° C. for 30 minutes and washed with AK-225 to obtain an article having a water-repellent and oil-repellent layer on the surface of the base material.
（評価方法）
＜接触角の測定方法＞
　撥水撥油層の表面に置いた、約２μＬの蒸留水又はｎ－ヘキサデカンの接触角を、接触角測定装置（協和界面科学社製、ＤＭ－５００）を用いて測定した。表面層の表面における異なる５箇所で測定を行い、その平均値を算出した。接触角の算出には２θ法を用いた。 (Evaluation methods)
<Measurement method of contact angle>
The contact angle of about 2 μL of distilled water or n-hexadecane placed on the surface of the water-repellent oil-repellent layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were performed at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.
＜初期接触角＞
　撥水撥油層について、初期水接触角及び初期ｎ－ヘキサデカン接触角を前記測定方法で測定した。評価基準は下記のとおりである。
初期水接触角：
　◎（優）　：１１３度以上。
　○（良）　：１０５度以上１１３度未満。
　△（可）　：１００度以上１０５度未満。
　×（不可）：１００度未満。
初期ｎ－ヘキサデカン接触角：
　◎（優）　：６６度以上。
　○（良）　：６３度以上６６度未満。
　△（可）　：６０度以上６３度未満。
　×（不可）：６０度未満。 <Initial contact angle>
For the water- and oil-repellent layer, the initial water contact angle and the initial n-hexadecane contact angle were measured by the above-mentioned measuring method. The evaluation criteria are as follows.
Initial water contact angle:
◎ (excellent): 113 degrees or more.
○ (Good): 105 degrees or more and less than 113 degrees.
Δ (possible): 100 degrees or more and less than 105 degrees.
× (impossible): Less than 100 degrees.
Initial n-hexadecane contact angle:
◎ (excellent): 66 degrees or more.
○ (Good): 63 degrees or more and less than 66 degrees.
Δ (possible): 60 degrees or more and less than 63 degrees.
× (impossible): Less than 60 degrees.
＜耐摩擦性＞
　撥水撥油層について、フェルト摩耗試験機を用い、フェルト（寸法：１０ｍｍ×１０ｍｍ×５０ｍｍ）を荷重：９．８Ｎ、速度：８０ｒｐｍで往復させた。往復１，０００回ごとに、撥水撥油層の水の接触角を測定した。摩耗後の水の接触角の低下が小さいほど摩耗による性能の低下が小さく、耐摩耗性に優れる。
水接触角１００度維持回数：
　◎（優）　：１０，０００回以上
　○（良）　：５，０００回以上１０，０００回未満
　△（可）　：３，０００回以上５，０００回未満
　×（不可）：３，０００回未満。 <Abrasion resistance>
For the water- and oil-repellent layer, a felt (dimensions: 10 mm × 10 mm × 50 mm) was reciprocated at a load of 9.8 N and a speed of 80 rpm using a felt wear tester. The contact angle of water in the water-repellent and oil-repellent layer was measured every 1,000 round trips. The smaller the decrease in the contact angle of water after wear, the smaller the decrease in performance due to wear, and the better the wear resistance.
Water contact angle maintained at 100 degrees Number of times:
◎ (excellent): 10,000 times or more ○ (good): 5,000 times or more and less than 10,000 times △ (possible): 3,000 times or more and less than 5,000 times × (impossible): less than 3,000 times ..
＜耐アルカリ性＞
　例１～７の物品をｐＨ１３の水酸化ナトリウム水溶液に２時間含侵した。物品を水洗乾燥した後、撥水撥油層の水接触角を測定した。
アルカリ浸漬後の水接触角：
　◎（優）　：１１３度以上。
　○（良）　：１０５度以上１１３度未満。
　△（可）　：１００度以上１０５度未満。
　×（不可）：１００度未満。 <Alkali resistance>
The articles of Examples 1 to 7 were impregnated with an aqueous sodium hydroxide solution having a pH of 13 for 2 hours. After washing and drying the article with water, the water contact angle of the water-repellent and oil-repellent layer was measured.
Water contact angle after alkaline immersion:
◎ (excellent): 113 degrees or more.
○ (Good): 105 degrees or more and less than 113 degrees.
Δ (possible): 100 degrees or more and less than 105 degrees.
× (impossible): Less than 100 degrees.
＜油脂汚れ除去性＞
　撥水撥油層表面に、オレイン酸で人工的に油脂汚れを付着させた後、一定荷重でセルロース製不織布（旭化成社製、ペンコットＭ－３）で拭き取り、油脂汚れの取れやすさを目視で判定した。判定基準は下記の通りである。
油脂汚れ除去性判定基準：
　○（良）　：油脂汚れを完全に拭き取ることができる。
　△（可）　：油脂汚れのふき取り跡が残る。
　×（不可）：油脂汚れをふき取ることができない。 <Removability of oil and fat stains>
After artificially adhering oil and fat stains to the surface of the water and oil repellent layer with oleic acid, wipe it off with a cellulose non-woven fabric (Pencot M-3, manufactured by Asahi Kasei Corporation) with a constant load, and visually judge the ease of removing the oil and fat stains. did. The judgment criteria are as follows.
Criteria for removing oil stains:
○ (Good): Oil stains can be completely wiped off.
△ (Yes): A trace of oil and fat stains remains.
× (impossible): Oil stains cannot be wiped off.
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000074
　化合物ＩからＶのように分子中に存在するフルオロアルキレン基の分子量が大きく、また加水分解性シリル基の数が多いほど耐摩耗性が向上する傾向にあることが分かった。これは基材に結合するフッ素量が多いこと、また分子中における基材と結合点が増加することに起因するためと考えられる。耐アルカリ性については化合物ＩＶの様に分子内にアルカリに影響を受けにくいユニットを持つものほど、耐アルカリ性に優れることが示唆された。 It was found that the larger the molecular weight of the fluoroalkylene groups present in the molecule, such as compounds I to V, and the larger the number of hydrolyzable silyl groups, the better the wear resistance tends to be. It is considered that this is because the amount of fluorine bonded to the base material is large and the number of bonding points with the base material in the molecule increases. Regarding the alkali resistance, it was suggested that the one having a unit in the molecule that is not easily affected by alkali, such as compound IV, is superior in alkali resistance.
［製造例：酸化ケイ素層付きガラス基材の製造］
　５質量％のケイ酸ナトリウム水溶液（昭和化学社製３号ケイ酸ナトリウム溶液）の２０ｇに、陽イオン交換樹脂（三菱化学社製ＳＫ１Ｂ）の１２ｇを加え、１０分間撹拌した。ろ過で陽イオン交換樹脂を除去し、ケイ酸水溶液を得た。イソプロピルアルコールの４．７５ｇにケイ酸水溶液の０．２５ｇを加え、酸化ケイ素層形成用コーティング液１（固形分濃度（ＳｉＯ２換算）：０．２５質量％）を得た。
　酸化ケイ素層形成用コーティング液１について下記測定を行った結果、Ｓｉに対してナトリウムを３００ｐｐｍ有する酸化ケイ素粉末が得られることを確認した。
（測定方法）
　酸化ケイ素層形成用コーティング液１を１５０℃で乾燥し、有機溶媒と水とを除去して、酸化ケイ素粉末を得た。酸化ケイ素粉末に含まれるＳｉに対するナトリウムの含有量をＩＣＰ発光分光分析（日立ハイテクサイエンス社製ＳＰＳ５５２０）で測定した。 [Manufacturing example: Manufacture of glass substrate with silicon oxide layer]
To 20 g of a 5 mass% sodium silicate aqueous solution (Showa Kagaku Co., Ltd. No. 3 sodium silicate solution), 12 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd. SK1B) was added, and the mixture was stirred for 10 minutes. The cation exchange resin was removed by filtration to obtain an aqueous silicic acid solution. 0.25 g of an aqueous silicic acid solution was added to 4.75 g of isopropyl alcohol to obtain a coating liquid 1 for forming a silicon oxide layer (solid content concentration (SiO 2 equivalent): 0.25% by mass).
As a result of the following measurement of the coating liquid 1 for forming a silicon oxide layer, it was confirmed that a silicon oxide powder having 300 ppm of sodium with respect to Si could be obtained.
(Measuring method)
The coating liquid 1 for forming a silicon oxide layer was dried at 150 ° C., and the organic solvent and water were removed to obtain a silicon oxide powder. The content of sodium with respect to Si contained in the silicon oxide powder was measured by ICP emission spectroscopic analysis (SPS5520 manufactured by Hitachi High-Tech Science Co., Ltd.).
　ガラス基材（ＡＧＣ社製Ｄｒａｇｏｎｔｒａｉｌ（登録商標））の一方の表面を、高周波電源（春日電機社製ＣＧ１０２Ａ）を用いて８０Ｖ、３．５Ａの条件下でコロナ放電処理した。
　ガラス基材のコロナ放電処理した面に酸化ケイ素層形成用コーティング液１を、スピンコート法によって回転数：３，０００ｒｐｍ、回転時間：２０秒間の条件にて塗布し、ウェット膜を形成した。ウェット膜を、焼成温度：５５０℃、焼成時間：３０分間の条件にて焼成し、厚さ約１０ｎｍの酸化ケイ素層を有する酸化ケイ素層付きガラス基材を製造した。 One surface of a glass substrate (Dragonrail (registered trademark) manufactured by AGC) was subjected to corona discharge treatment under the conditions of 80 V and 3.5 A using a high frequency power supply (CG102A manufactured by Kasuga Electric Works Ltd.).
A coating liquid 1 for forming a silicon oxide layer was applied to the corona discharge-treated surface of the glass substrate by a spin coating method under the conditions of a rotation speed of 3,000 rpm and a rotation time of 20 seconds to form a wet film. The wet film was fired under the conditions of firing temperature: 550 ° C. and firing time: 30 minutes to produce a glass substrate with a silicon oxide layer having a silicon oxide layer having a thickness of about 10 nm.
　上記物品の製造及び評価において、基材を化学強化ガラスから、上記酸化ケイ素層付きガラス基材に変更し、上記例１、例２、例４、例５及び例１０で得た化合物を用い、上記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、基材の表面処理を行った。得られた物品について前述の方法で評価を行った。結果を表２に示す。 In the production and evaluation of the above-mentioned article, the base material was changed from the chemically strengthened glass to the above-mentioned glass base material with a silicon oxide layer, and the compounds obtained in the above-mentioned Example 1, Example 2, Example 4, Example 5 and Example 10 were used. The surface treatment of the base material was performed using the above dry coating method and wet coating method, respectively. The obtained article was evaluated by the method described above. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000075
 　なお、表中の「ａ×１０＾ｂ」は「ａ×１０ｂ」を表す。
Figure JPOXMLDOC01-appb-T000075
 In addition, "a × 10 ^ b" in the table represents "a × 10 b ".
　含Ｎａ酸化Ｓｉ層の際、通常のＳｉＯ２層のものに比べ、化合物Ｉ、ＩＩはともに高い摩耗耐久性を示した。特に化合物ＩＩにおいては含Ｎａ酸化Ｓｉ層にした際の耐久性向上具合はＩより高い結果を示した。これは含Ｎａ酸化Ｓｉ層の効果で基材と結合する加水分解性シリル基の数が増えるためと考えられる。 In the case of the Na-containing Si oxide layer, both compounds I and II showed higher wear durability than those of the normal SiO 2 layer. In particular, in Compound II, the degree of durability improvement when the Na-containing Si-oxide layer was used was higher than that of I. It is considered that this is because the number of hydrolyzable silyl groups bonded to the base material increases due to the effect of the Na-containing Si layer.
　本化合物を含む撥水撥油層を備えた物品は、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、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 provided with a water- and oil-repellent layer containing this compound include, for example, optical articles, touch panels, antireflection films, antireflection glass, SiO 2 treated glass, tempered glass, which are used as part of the following product parts. It is useful as sapphire glass, quartz substrate, mold metal, etc.
Products: Car navigation systems, mobile phones, digital cameras, digital video cameras, mobile information terminals (PDA), 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、２０１９年９月２７日に出願された日本出願特願２０１９－１７７６６２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. 2019-177662 filed on September 27, 2019, 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：撥水撥油層 10: Base material with base layer, 12: Base material, 14: Base layer,
20: Article, 22: Water- and oil-repellent layer

Claims (13)

  1. 　下式（１）で表される部分構造を３つ以上、
    　下式（２）で表される部分構造を４つ以上有する、含フッ素化合物。
    　　＊－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－　　　　　　（１）
    　　－ＳｉＬｐＲ１０ （３－ｐ）　　　　　　　　　　　　　　（２）
    　ただし、
    　＊には、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、
    　Ｑ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよく、
    　Ｒ１は、直鎖又は分岐を有するフルオロアルキレン基であって、複数ある場合のＲ１は同一であっても異なっていてもよく、
    　Ｌは加水分解性基又は水酸基であって、複数ある場合のＬは同一であっても異なっていてもよく、
    　Ｒ１０は水素原子又は１価の炭化水素基であって、複数ある場合のＲ１０は同一であっても異なっていてもよく、
    　ｎは０以上の整数であり、
    　ｍは１以上の整数であり、
    　ｐは１～３の整数である。     Three or more partial structures represented by the following formula (1),
    A fluorine-containing compound having four or more partial structures represented by the following formula (2).
    *-{C (Q 1 ) 2 } n- O- (R 1 O) m- (1)
    -SiL p R 10 (3-p) (2)
    However,
    A tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom are bonded to *.
    Q 1 represents a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different and
    R 1 is a linear or branched fluoroalkylene group, and when there are a plurality of R 1, they may be the same or different.
    L is a hydrolyzable group or a hydroxyl group, and when there are a plurality of L, the L may be the same or different.
    R 10 is a hydrogen atom or a monovalent hydrocarbon group, and when there are a plurality of them, R 10 may be the same or different.
    n is an integer greater than or equal to 0 and
    m is an integer greater than or equal to 1
    p is an integer of 1 to 3.
  2. 　下式（３）で表される部分構造を３つ以上有する、請求項１に記載の含フッ素化合物。
    　　＊－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ｛－ＳｉＬｐＲ１０ （３－ｐ）｝ｑ　　　　（３）
    　ただし、
    　＊には、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、
    　Ｑ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよく、
    　Ｒ１は、直鎖又は分岐を有するフルオロアルキレン基であって、複数ある場合のＲ１は同一であっても異なっていてもよく、
    　Ａは（ｑ＋１）価の有機基であり、
    　Ｌは加水分解性基又は水酸基であって、複数ある場合のＬは同一であっても異なっていてもよく、
    　Ｒ１０は水素原子又は１価の炭化水素基であって、複数ある場合のＲ１０は同一であっても異なっていてもよく、
    　ｎは０以上の整数であり、
    　ｍは１以上の整数であり、
    　ｐは１～３の整数であり、
    　ｑは１以上の整数であり、ｑの総和は４以上である。     The fluorine-containing compound according to claim 1, which has three or more partial structures represented by the following formula (3).
    *-{C (Q 1 ) 2 } n- O- (R 1 O) m- A {-SiL p R 10 (3-p) } q (3)
    However,
    A tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, or a tertiary nitrogen atom are bonded to *.
    Q 1 represents a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different and
    R 1 is a linear or branched fluoroalkylene group, and when there are a plurality of R 1, they may be the same or different.
    A is a (q + 1) -valent organic group,
    L is a hydrolyzable group or a hydroxyl group, and when there are a plurality of L, the L may be the same or different.
    R 10 is a hydrogen atom or a monovalent hydrocarbon group, and when there are a plurality of them, R 10 may be the same or different.
    n is an integer greater than or equal to 0 and
    m is an integer greater than or equal to 1
    p is an integer from 1 to 3 and
    q is an integer of 1 or more, and the sum of q is 4 or more.
  3. 　下式（４）で表される、請求項１又は２に記載の含フッ素化合物。
    　　Ｘ［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－（Ｒ１Ｏ）ｍ－Ａ｛－ＳｉＬｐＲ１０ （３－ｐ）｝ｑ］ｒ　　　　（４）
    　ただし、
    　Ｘは、３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、及び３級窒素原子より選択される原子を１個以上有するｒ価の連結基であり、
    　［－｛Ｃ（Ｑ１）２｝ｎ－Ｏ－］のＸ側には、Ｘにおける３級炭素原子、４級炭素原子、芳香環を構成する炭素原子、３級ケイ素原子、４級ケイ素原子、又は、３級窒素原子が結合し、
    　Ｑ１は、水素原子又はフッ素原子であって、複数あるＱ１は同一であっても異なっていてもよく、
    　Ｒ１は、直鎖又は分岐を有するフルオロアルキレン基であって、複数あるＲ１は同一であっても異なっていてもよく、
    　Ａは（ｑ＋１）価の有機基であって、複数あるＡは同一であっても異なっていてもよく、
    　Ｌは加水分解性基又は水酸基であって、複数あるＬは同一であっても異なっていてもよく、
    　Ｒ１０は水素原子又は１価の炭化水素基であって、複数あるＲ１０は同一であっても異なっていてもよく、
    　ｎは０以上の整数であり、複数あるｎは同一であっても異なっていてもよく、
    　ｍは１以上の整数であり、複数あるｍは同一であっても異なっていてもよく、
    　ｐは１～３の整数であり、複数あるｐは同一であっても異なっていてもよく、
    　ｑは１～３の整数であり、ｑの総和は４以上であり、複数あるｑは同一であっても異なっていてもよく、
    　ｒは３以上の整数である。     The fluorine-containing compound according to claim 1 or 2, which is represented by the following formula (4).
    X [-{C (Q 1 ) 2 } n- O- (R 1 O) m- A {-SiL p R 10 (3-p) } q ] r (4)
    However,
    X is an r-valent connection having one or more atoms selected from a tertiary carbon atom, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, a quaternary silicon atom, and a tertiary nitrogen atom. Is the basis and
    On the X side of [-{C (Q 1 ) 2 } n- O-], there are a tertiary carbon atom in X, a quaternary carbon atom, a carbon atom constituting an aromatic ring, a tertiary silicon atom, and a quaternary silicon atom. , Or a tertiary nitrogen atom is bonded,
    Q 1 represents a hydrogen atom or a fluorine atom, a plurality of Q 1 is may be the same or different and
    R 1 is a linear or branched fluoroalkylene group, and a plurality of R 1s may be the same or different.
    A is a (q + 1) -valent organic group, and a plurality of A's may be the same or different.
    L is a hydrolyzable group or a hydroxyl group, and a plurality of Ls may be the same or different.
    R 10 is a hydrogen atom or a monovalent hydrocarbon group, and a plurality of R 10s may be the same or different.
    n is an integer of 0 or more, and a plurality of n may be the same or different.
    m is an integer of 1 or more, and a plurality of m may be the same or different.
    p is an integer of 1 to 3, and a plurality of ps may be the same or different.
    q is an integer of 1 to 3, the sum of q is 4 or more, and a plurality of qs may be the same or different.
    r is an integer of 3 or more.
  4. 　前記Ｘが下式（Ｘ－１）～下式（Ｘ－６）より選択される１種以上の部分構造を有する、請求項３に記載の含フッ素化合物。
    Figure JPOXMLDOC01-appb-C000001
     　ただし、Ｑ３は、水素原子又はフッ素原子である。式（Ｘ－６）中のＣは芳香環を構成する炭素原子であり、当該炭素原子が有する結合手の１つは単結合であり、残りの結合手（波線が記載された結合手）は芳香環を構成する。     The fluorine-containing compound according to claim 3, wherein X has one or more partial structures selected from the following formulas (X-1) to (X-6).
    Figure JPOXMLDOC01-appb-C000001
     However, Q 3 is a hydrogen atom or a fluorine atom. C in the formula (X-6) is a carbon atom constituting an aromatic ring, one of the bonds possessed by the carbon atom is a single bond, and the remaining bond (the bond with a wavy line) is It constitutes an aromatic ring.
  5. 　前記Ａが、アルキレン基、フルオロアルキレン基、カルボニル基、アミド結合、エーテル結合、ウレア結合、ウレタン結合及びカーボネート結合より選択される１種以上を含む（ｑ＋１）価の有機基である、請求項２～４のいずれか一項に記載の含フッ素化合物。 2. Claim 2 is a (q + 1) -valent organic group containing at least one selected from an alkylene group, a fluoroalkylene group, a carbonyl group, an amide bond, an ether bond, a urea bond, a urethane bond and a carbonate bond. The fluorine-containing compound according to any one of 4 to 4.
  6. 　前記（Ｒ１Ｏ）が、下式（Ｒ－１）で表される、請求項１～５のいずれか一項に記載の含フッ素化合物。
    　　［（Ｒｆ１Ｏ）ｍ１（Ｒｆ２Ｏ）ｍ２（Ｒｆ３Ｏ）ｍ３（Ｒｆ４Ｏ）ｍ４（Ｒｆ５Ｏ）ｍ５（Ｒｆ６Ｏ）ｍ６］　　　　　　　　　　　　　　（Ｒ－１）
    　ただし、
    　Ｒｆ１は、炭素数１のフルオロアルキレン基であり、
    　Ｒｆ２は、炭素数２のフルオロアルキレン基であり、
    　Ｒｆ３は、炭素数３のフルオロアルキレン基であり、
    　Ｒｆ４は、炭素数４のフルオロアルキレン基であり、
    　Ｒｆ５は、炭素数５のフルオロアルキレン基であり、
    　Ｒｆ６は、炭素数６のフルオロアルキレン基であり、
    　ｍ１、ｍ２、ｍ３、ｍ４、ｍ５、ｍ６は、それぞれ、０又は１以上の整数を表しｍ１＋ｍ２＋ｍ３＋ｍ４＋ｍ５＋ｍ６は１～２００の整数である。     The fluorine-containing compound according to any one of claims 1 to 5, wherein (R 1 O) is represented by the following formula (R-1).
    [(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ] (R-1)
    However,
    R f1 is a fluoroalkylene group having 1 carbon atom.
    R f2 is a fluoroalkylene group having 2 carbon atoms.
    R f3 is a fluoroalkylene group having 3 carbon atoms.
    R f4 is a fluoroalkylene group having 4 carbon atoms.
    R f5 is a fluoroalkylene group having 5 carbon atoms.
    R f6 is a fluoroalkylene group having 6 carbon atoms and has 6 carbon atoms.
    m1, m2, m3, m4, m5, and m6 represent integers of 0 or 1, respectively, and m1 + m2 + m3 + m4 + m5 + m6 are integers of 1 to 200.
  7. 　請求項１～６のいずれか一項に記載の含フッ素化合物と、他の含フッ素化合物とを含む、含フッ素化合物含有組成物。 A fluorinated compound-containing composition containing the fluorinated compound according to any one of claims 1 to 6 and another fluorinated compound.
  8. 　請求項１～６のいずれか一項に記載の含フッ素化合物、又は請求項７に記載の含フッ素化合物含有組成物と、液状媒体とを含有する、コーティング液。 A coating liquid containing the fluorine-containing compound according to any one of claims 1 to 6 or the fluorine-containing compound-containing composition according to claim 7 and a liquid medium.
  9. 　基材と、下地層と、撥水撥油層とをこの順で有する物品であって、
    　前記下地層がケイ素を含む酸化物を含有し、
    　前記撥水撥油層が、請求項１～６のいずれか一項に記載の含フッ素化合物の縮合体を含有する、物品。     An article having a base material, a base layer, and a water- and oil-repellent layer in this order.
    The base layer contains an oxide containing silicon,
    An article in which the water- and oil-repellent layer contains a condensate of the fluorine-containing compound according to any one of claims 1 to 6.
  10. 　前記酸化物が、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、
    　請求項９に記載の物品。     The oxide is one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. Contains,
    The article according to claim 9.
  11. 　基材と、撥水撥油層とをこの順で有する物品であって、
    　前記基材がケイ素を含む酸化物を含有し、
    　前記撥水撥油層が、請求項１～６のいずれか一項に記載の含フッ素化合物の縮合体を含有する、物品。     An article having a base material and a water- and oil-repellent layer in this order.
    The base material contains an oxide containing silicon,
    An article in which the water- and oil-repellent layer contains a condensate of the fluorine-containing compound according to any one of claims 1 to 6.
  12. 　前記酸化物が、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、
    　請求項１１に記載の物品。     The oxide is one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. Contains,
    The article according to claim 11.
  13. 　請求項１～６のいずれか一項に記載の含フッ素化合物、請求項７に記載の含フッ素化合物含有組成物、又は請求項８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、撥水撥油層を形成する、物品の製造方法。 Using the fluorine-containing compound according to any one of claims 1 to 6, the fluorine-containing compound-containing composition according to claim 7, or the coating liquid according to claim 8, by a dry coating method or a wet coating method. A method for manufacturing an article, which forms a water-repellent and oil-repellent layer.
PCT/JP2020/036461 2019-09-27 2020-09-25 Fluorine-containing compound, fluorine-containing compound-containing composition, coating solution, article, and method for producing article WO2021060537A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021548465A JPWO2021060537A1 (en) 2019-09-27 2020-09-25
CN202080058932.5A CN114258412A (en) 2019-09-27 2020-09-25 Fluorine-containing compound, composition containing fluorine-containing compound, coating liquid, article, and method for producing article

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019177662 2019-09-27
JP2019-177662 2019-09-27

Publications (1)

Publication Number Publication Date
WO2021060537A1 true WO2021060537A1 (en) 2021-04-01

Family

ID=75164988

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/036461 WO2021060537A1 (en) 2019-09-27 2020-09-25 Fluorine-containing compound, fluorine-containing compound-containing composition, coating solution, article, and method for producing article

Country Status (3)

Country Link
JP (1) JPWO2021060537A1 (en)
CN (1) CN114258412A (en)
WO (1) WO2021060537A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074874A1 (en) * 2021-10-29 2023-05-04 Ａｇｃ株式会社 Compound, composition, surface treatment agent, coating liquid, article, and method for manufacturing article
WO2024038866A1 (en) * 2022-08-18 2024-02-22 Ａｇｃ株式会社 Compound, composition, surface treatment agent, coating liquid, article, and method for producing article

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05238781A (en) * 1991-11-29 1993-09-17 Ppg Ind Inc Glass article having durable water repellent surface
WO2009101986A1 (en) * 2008-02-12 2009-08-20 Fujifilm Corporation Fluorine-containing polyfunctional silicon compound and method for producing fluorine-containing polyfunctional silicon compound
JP2009191101A (en) * 2008-02-12 2009-08-27 Fujifilm Corp Surface treatment agent composition containing fluorine-containing polyfunctional silicon compound
WO2018235778A1 (en) * 2017-06-21 2018-12-27 Ａｇｃ株式会社 Article having water- and oil-repellent layer formed thereon, and method for manufacturing same
WO2019163282A1 (en) * 2017-12-27 2019-08-29 Ａｇｃ株式会社 Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article and production method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4857528B2 (en) * 2004-06-11 2012-01-18 旭硝子株式会社 Silane coupling group-containing fluorine-containing ether compound, solution composition, coating film and article
WO2006011387A1 (en) * 2004-07-27 2006-02-02 Asahi Glass Company, Limited Lubricant solution for magnetic recording medium containing fluorine-containing polyether compound as lubricant
WO2011065312A1 (en) * 2009-11-26 2011-06-03 旭硝子株式会社 Ether compound, lubricant containing same, and composition for lubricant containing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05238781A (en) * 1991-11-29 1993-09-17 Ppg Ind Inc Glass article having durable water repellent surface
WO2009101986A1 (en) * 2008-02-12 2009-08-20 Fujifilm Corporation Fluorine-containing polyfunctional silicon compound and method for producing fluorine-containing polyfunctional silicon compound
JP2009191101A (en) * 2008-02-12 2009-08-27 Fujifilm Corp Surface treatment agent composition containing fluorine-containing polyfunctional silicon compound
WO2018235778A1 (en) * 2017-06-21 2018-12-27 Ａｇｃ株式会社 Article having water- and oil-repellent layer formed thereon, and method for manufacturing same
WO2019163282A1 (en) * 2017-12-27 2019-08-29 Ａｇｃ株式会社 Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article and production method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074874A1 (en) * 2021-10-29 2023-05-04 Ａｇｃ株式会社 Compound, composition, surface treatment agent, coating liquid, article, and method for manufacturing article
WO2024038866A1 (en) * 2022-08-18 2024-02-22 Ａｇｃ株式会社 Compound, composition, surface treatment agent, coating liquid, article, and method for producing article

Also Published As

Publication number Publication date
CN114258412A (en) 2022-03-29
JPWO2021060537A1 (en) 2021-04-01

Similar Documents

Publication Publication Date Title
JP5235026B2 (en) Fluorooxyalkylene group-containing polymer composition, surface treatment agent containing the composition, and article surface-treated with the surface treatment agent
CN111032732B (en) Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing same
JP5431724B2 (en) Fluorinated organosilicon coating material
WO2021131960A1 (en) Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, and manufacturing method for article
JP7180665B2 (en) Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing the same
WO2021060537A1 (en) Fluorine-containing compound, fluorine-containing compound-containing composition, coating solution, article, and method for producing article
CN113165346B (en) Fluorine-containing ether compound, composition, and article
CN113165345B (en) Fluorochemical, fluorochemical-containing composition, coating liquid, article, and method for producing same
US20210230735A1 (en) Substrate with water-and-oil repellent layer, vapor deposition material, and method for producing substrate with water-and-oil repellent layer
US20230256469A1 (en) Substrate with water and oil repellent layer, and method for producing substrate with water and oil repellent layer
WO2022186269A1 (en) Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, method for producing article, and compound
JP7428142B2 (en) Vapor deposition material, and method for producing a base material with a base layer and a base material with a water- and oil-repellent layer using the same
JP7415951B2 (en) Substrate with water- and oil-repellent layer, vapor deposition material, and manufacturing method of substrate with water- and oil-repellent layer
JP2021172842A (en) Substrate with water and oil repellent layer, vapor deposition material, and manufacturing method of substrate with water and oil repellent layer
JP6635229B2 (en) Method for producing fluorine-containing ether compound and method for producing article
WO2020100759A1 (en) Substrate with water repellent oil repellent layer, vapor deposition material, and method for producing substrate with water repellent oil repellent layer
WO2021161905A1 (en) Fluoroether compound, fluoroether composition, coating fluid, article, and method for producing article
JPWO2020137990A1 (en) A method for manufacturing a vapor-deposited material, a base material with a base layer, and a method for manufacturing a base material with a water-repellent and oil-repellent layer.
JPWO2020137993A1 (en) A method for manufacturing a vapor-deposited material, a base material with a base layer, and a method for manufacturing a base material with a water-repellent and oil-repellent layer.
WO2022039172A1 (en) Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing article
WO2021251396A1 (en) Fluoroether compound, production method therefor, compound and production method therefor, fluoroether composition, coating fluid, and article and production method therefor
WO2023074874A1 (en) Compound, composition, surface treatment agent, coating liquid, article, and method for manufacturing article
WO2024038873A1 (en) Compound, composition, surface treatment agent, coating liquid, article, and method for producing article
WO2022059623A1 (en) Composition, substrate with surface layer, method for producing substrate with surface layer, compound, and method for producing compound
WO2022186198A1 (en) Composition, base material with surface layer and method for producing base material with surface layer

Legal Events

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

Ref document number: 20867618

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021548465

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20867618

Country of ref document: EP

Kind code of ref document: A1