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WO2024203923A1 - Composé, composition, agent de traitement de surface, article et procédé de production d'article - Google Patents

Composé, composition, agent de traitement de surface, article et procédé de production d'article Download PDF

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WO2024203923A1
WO2024203923A1 PCT/JP2024/011434 JP2024011434W WO2024203923A1 WO 2024203923 A1 WO2024203923 A1 WO 2024203923A1 JP 2024011434 W JP2024011434 W JP 2024011434W WO 2024203923 A1 WO2024203923 A1 WO 2024203923A1
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group
compound
carbon atoms
article
surface layer
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Japanese (ja)
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英一郎 安樂
汐織 川上
貴史 川上
博信 阪口
啓吾 松浦
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—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
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a compound, a composition, a surface treatment agent, an article, and a method for manufacturing an article.
  • Fluorine-containing ether compounds having fluorine atoms have excellent properties such as a low refractive index, a low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency, and are used in a wide variety of fields, such as electric and electronic materials, semiconductor materials, optical materials, and surface treatment agents.
  • a fluorine-containing ether compound having a perfluoropolyether chain and a hydrolyzable silyl group can form a surface layer on the surface of a substrate that exhibits high lubricity, water- and oil-repellency, etc., and is therefore suitable for use as a surface treatment agent.
  • a surface treatment agent containing a fluorine-containing ether compound is used as a surface treatment agent in applications requiring a long-term maintenance of the performance of preventing the water- and oil-repellency from decreasing even when the surface layer is repeatedly rubbed with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability), for example, as a surface treatment agent for members constituting the surface of a touch panel that is touched by fingers, eyeglass lenses, and displays of wearable terminals.
  • it may be required to have a non-slip property (slip resistance).
  • Patent Document 1 discloses the formation of a surface layer obtained by using a specific fluorine-containing ether compound in order to make the surface of an electronic device non-slip.
  • glass-coated housings are sometimes used for mobile devices such as smartphones and tablet terminals, and the above-mentioned surface treatment agent is sometimes used on the housing side.
  • the use of wireless chargers as chargers for mobile phones is increasing.
  • the surface layer formed by the current surface treatment agent may be slippery, and there is a risk of the mobile device slipping off when it is operated or placed on a desk or wireless charger.
  • the performance requirements for a surface layer formed using a fluorinated ether compound are increasing, and not only excellent abrasion resistance and fingerprint stain removability but also excellent slip resistance are required.
  • the present inventors referring to the surface treatment agent described in Patent Document 1, evaluated a surface layer formed using a surface treatment agent containing a fluorinated ether compound and found that at least the slip resistance does not reach the level required in recent years and there is room for improvement.
  • the present invention aims to provide a compound, composition, surface treatment agent, article having a surface layer formed from the compound, etc., capable of forming a surface layer having excellent abrasion resistance, fingerprint stain removability, and slip resistance, and a method for manufacturing the article.
  • Another aim is to provide a novel compound that can be used to manufacture the compound.
  • R f1 is a group represented by the following formula (2): X-L-Y-...(2) however, X represents an aliphatic hydrocarbon ring group which may have a substituent, an aromatic ring group which may have a substituent, or a chain hydrocarbon group having 3 or more carbon atoms;
  • L is a single bond, an alkylene group which may have a substituent, *-P(R L1 )-R L2 -**, or -Si(R L3 ) 2 -,
  • R L1 is an alkyl group or a phenyl group
  • R L2 is an alkylene group, and the two R L3s are each independently an alkyl group or a phenyl group, * is the bonding position to X in formula (2), and ** is the bonding position to Y in formula (2), and when L is an alkylene group which may have a substituent, X is an aliphatic hydrocarbon ring group which may have a substituent, an aromatic ring
  • [6] The compound according to [5], wherein Y is -O-.
  • [7] The compound according to any one of [1] to [6], wherein the organic group in R f1 contains a ring structure.
  • [8] A composition comprising the compound according to any one of [1] to [7] and another fluorine-containing compound.
  • a surface treatment agent comprising the compound according to any one of [1] to [7] or the composition according to [8].
  • the surface treatment agent according to [9] which is an antifouling coating agent or a waterproof coating agent.
  • the surface treatment agent according to [9] or [10] further comprising a liquid medium.
  • [12] An article having a surface layer formed on a surface of a substrate using the compound according to any one of [1] to [7] or the composition according to [8]. [13] The article according to [12], having the above-mentioned surface layer on a surface of a member constituting a surface of a touch panel that is touched by a finger. [14] The article according to [12] or [13], which is an optical member. [15] A method for producing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent according to any one of [9] to [11]. [16] A method for producing an article, comprising forming a surface layer by a wet coating method using the surface treatment agent according to any one of [9] to [11].
  • the present invention provides a compound, composition, surface treatment agent, and article having a surface layer formed from the compound, etc., capable of forming a surface layer that is excellent in abrasion resistance, fingerprint stain removability, and slip resistance, as well as a method for manufacturing the article. It also provides a novel compound that can be used to manufacture the compound.
  • FIG. 1 is a schematic cross-sectional view showing an example of an article of the present invention.
  • fluoroalkyl group is a general term that includes perfluoroalkyl groups and partial fluoroalkyl groups.
  • perfluoroalkyl group refers to a group in which all hydrogen atoms of an alkyl group are replaced with fluorine atoms.
  • partial fluoroalkyl group refers to an alkyl group in which one or more hydrogen atoms are replaced with fluorine atoms and which has one or more hydrogen atoms.
  • a fluoroalkyl group is an alkyl group that has one or more fluorine atoms.
  • fluoroalkylene groups are an alkyl group that has one or more fluorine atoms.
  • reactive silyl group is a general term for a hydrolyzable silyl group and a silanol group (Si-OH), and the term “hydrolyzable silyl group” refers to a group that can form a silanol group by hydrolysis.
  • organic group refers to a hydrocarbon group which may have a substituent and which may have a heteroatom or other bond in the carbon chain.
  • hydrocarbon group refers to an aliphatic hydrocarbon group (such as a straight-chain alkylene group, a branched alkylene group, or a cycloalkylene group), an aromatic hydrocarbon group (such as a phenylene group), or a group consisting of a combination thereof.
  • Me may represent a methyl group.
  • surface layer refers to a layer formed on the surface of a substrate. The use of "to” indicating a range of numerical values means that the numerical values before and after it are included as the lower limit and upper limit.
  • the order of bonds in each divalent group is not limited unless otherwise specified. For example, when L 1 described later is a group represented by -C(O)N(R 26 )-, the left bond may be bonded to the R 1 side of formula (1), or the right bond may be bonded to the R 1 side of formula (1).
  • R f1 is an organic group containing a ring structure or a chain hydrocarbon group having 3 or more carbon atoms and containing no fluorine atoms
  • R f2 is a single bond or a fluoroalkylene group having 1 to 6 carbon atoms
  • R f3 is a fluoroalkylene group having 1 to 6 carbon atoms
  • R 1 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms and an etheric oxygen atom
  • L1 is a single bond or a 1+x1 valent group
  • R2 is an alkylene group or an alkylene group having an etheric oxygen atom
  • T1 is a reactive group
  • y1 is an integer of 2 or more
  • x1 is an integer from 1 to 10
  • compound 1 has a structure of "fluoropolyether chain"-"linking group"-"reactive group disposed on the surface of a substrate", and an organic group containing a ring structure or a chain-like hydrocarbon group having 3 or more carbon atoms and no fluorine atom (hereinafter also referred to as a "specific organic group”) is disposed at the end of the fluoropolyether chain.
  • an organic group containing a ring structure or a chain-like hydrocarbon group having 3 or more carbon atoms and no fluorine atom hereinafter also referred to as a "specific organic group”
  • the reactive group of compound 1 is likely to be arranged on the substrate side, and the reactive group is strongly chemically bonded to the substrate, so that the resulting surface layer has excellent abrasion resistance.
  • a specific organic group is likely to be arranged on the surface of the surface layer opposite to the substrate, and the specific organic group has an intermolecular interaction, so that the resulting surface layer has excellent abrasion resistance compared to a fluoroalkyl group.
  • fluoropolyether chains having specific organic groups at their terminals are arranged on the surface of the surface layer opposite the substrate, and the resulting surface layer is therefore excellent in fingerprint stain removal properties and in water and oil repellency.
  • the compound 1 since the compound 1 has a specific organic group at the end of the fluoropolyether chain, it is presumed that the movement of the fluoropolyether chain on the surface is restricted compared to a fluorine-containing ether compound whose end is a fluoroalkyl group. As a result, the surface layer formed by the compound 1 has a high friction coefficient. For these reasons, the article having the surface layer obtained by using the compound 1 has excellent fingerprint stain removability and abrasion resistance, and also has excellent slip resistance.
  • R f1 is an organic group containing a ring structure or a chain hydrocarbon group having 3 or more carbon atoms and containing no fluorine atoms.
  • R f1 examples include an aliphatic hydrocarbon ring, an aromatic ring, and a heterocycle. In terms of obtaining better effects of the present invention, it is preferable that R f1 contains at least one ring selected from the group consisting of an aliphatic hydrocarbon ring and an aromatic ring.
  • aliphatic hydrocarbon ring examples include monocyclic aliphatic hydrocarbons such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane; polycyclic aliphatic hydrocarbons such as 4-cyclohexylcyclohexane and decahydronaphthalene; aliphatic hydrocarbons having a bridged ring structure such as bicyclopentane, norbornane, norbornene, and adamantane; and aliphatic hydrocarbons having a spiro ring structure such as spiro[3.4]octane.
  • monocyclic aliphatic hydrocarbons such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane
  • polycyclic aliphatic hydrocarbons such as 4-cyclohexylcyclohexane and de
  • aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, and anthracene, and aromatic heterocycles such as furan, pyrrole, thiophene, pyridine, triazine, triazole, pyrazole, thiazole, and benzothiazole.
  • aromatic heterocycle examples include pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, dioxane, quinuclidine, and crown ether.
  • the aliphatic hydrocarbon ring, aromatic ring and heterocyclic ring may have a substituent, and specific examples of the substituent are as described below.
  • the chain hydrocarbon group in R f1 may be saturated or unsaturated, but is preferably saturated (that is, a straight-chain alkyl group) in terms of obtaining better effects of the present invention.
  • the chain hydrocarbon group in R f1 has 3 or more carbon atoms, and from the viewpoint of better abrasion resistance and slip resistance, it is preferably 8 or more, and more preferably 16 or more.
  • the number of carbon atoms in the chain hydrocarbon group in R f1 is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less, in terms of better antifouling performance.
  • the organic group in R f1 preferably contains a ring structure in that the slip resistance is more excellent.
  • R f1 is preferably a group represented by the following formula (2). X-L-Y-...(2)
  • X represents an aliphatic hydrocarbon ring group which may have a substituent, an aromatic ring group which may have a substituent, or a chain hydrocarbon group having 3 or more carbon atoms;
  • L is a single bond, an alkylene group which may have a substituent, *-P(R L1 )-R L2 -**, or -Si(R L3 ) 2 -,
  • R L1 is an alkyl group or a phenyl group
  • R L2 is an alkylene group, and the two R L3s are each independently an alkyl group or a phenyl group, * is the bonding position to X in formula (2), and ** is the bonding position to Y in formula (2), and when L is an alkylene group which may have a substituent,
  • X is an aliphatic hydrocarbon ring group which may have a substituent, or an aromatic ring group which may have a substituent
  • Y is -O-, -NR 11 C
  • the number of carbon atoms in the alkyl group for R 11 is 1 to 6, and preferably 1 to 4.
  • the alkyl group may be linear or may have a branched or cyclic structure.
  • aliphatic hydrocarbon ring group and aromatic ring group in X are the same as the aliphatic hydrocarbon ring and aromatic ring explained in Rf1 , and preferred embodiments are also the same.
  • chain hydrocarbon group having 3 or more carbon atoms in X are the same as those explained in relation to R f1 , and preferred embodiments are also the same.
  • substituents that the aliphatic hydrocarbon ring group and aromatic ring group in X may have include an alkyl group (preferably having 1 to 20 carbon atoms), an alkoxy group (preferably having 1 to 3 carbon atoms), -N(R X1 ) 2 , a phenyl group, a phenoxy group, and a pyridyl group, and these groups may further have a substituent.
  • Two R X1 are each independently a hydrogen atom, an alkyl group, or a phenyl group.
  • the number of carbon atoms in the alkylene group which may have a substituent in L is, from the viewpoints of abrasion resistance, slip resistance, and stain resistance, preferably 1 to 30, more preferably 3 to 25, and even more preferably 6 to 20.
  • the carbon atoms contained in the substituent are not included in the number of carbon atoms in the alkylene group.
  • the alkylene group for L has 3 or more carbon atoms and may have a substituent
  • the alkylene group may be linear or may have a branched or cyclic structure.
  • a linear alkylene group or a branched alkylene group is preferable.
  • a specific example of a substituent that the alkylene group in L may have is a phenyl group.
  • R L1 is an alkyl group or a phenyl group.
  • the alkyl group in R 1 L1 may be linear or may have a branched or cyclic structure.
  • the alkyl group in R 1 L1 preferably has 1 to 3 carbon atoms.
  • the alkylene group in R 1 L2 may be linear or may have a branched or cyclic structure.
  • the alkylene group in R 1 L2 preferably has 1 to 6 carbon atoms.
  • each of the two R L3s is independently an alkyl group or a phenyl group.
  • the alkyl group in R 1 L3 may be linear or may have a branched or cyclic structure.
  • the alkyl group in R 1 L3 preferably has 1 to 6 carbon atoms.
  • L is preferably a single bond or an alkylene group which may have a substituent, since this provides a better effect of the present invention.
  • Y is preferably --O-- or --NR 11 C( ⁇ O)-- in that the effects of the present invention are more excellent, and more preferably --O-- in that abrasion resistance is particularly excellent.
  • R f2 may be a single bond.
  • R f1 is bonded to the terminal oxygen atom of (OR f3 ) y1 .
  • R f2 may be a fluoroalkylene group having 1 to 6 carbon atoms.
  • the fluoroalkylene group having 3 to 6 carbon atoms may be linear or may have a branched or cyclic structure.
  • the number of carbon atoms in R f2 is preferably 1 to 3 from the viewpoint of ease of synthesis.
  • fluoroalkyl group for R f2 examples include -CF 2 -, -CHF-, -CF 2 CF 2 -, -CF 2 CHF-, -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CHFCHF-, -CF 2 CF(CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CF 2 CF(CF 3 )-CF 2 -, -CF 2 C(CF 3 ) 2 -CF 2 -, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, and -CF 2 CF 2 CF 2 CF 2 CF 2 - is an example.
  • (OR f3 ) y1 represents a fluoropolyether chain and y1 is an integer of 2 or more.
  • the fluoropolyether chain in (OR f3 ) y1 preferably has a structure represented by the following formula (G1).
  • G f1 is a fluoroalkylene group having 1 carbon atom
  • G f2 is a fluoroalkylene group having 2 carbon atoms
  • G f3 is a fluoroalkylene group having 3 carbon atoms
  • G f4 is a fluoroalkylene group having 4 carbon atoms
  • G f5 is a fluoroalkylene group having 5 carbon atoms
  • G f6 is a fluoroalkylene group having 6 carbon atoms
  • m1, m2, m3, m4, m5, and m6 each independently represent 0 or an integer of 1 or more
  • m1+m2+m3+m4+m5+m6 is an integer of 2 to 200.
  • the bonding order of (OG f1 ) to (OG f6 ) in formula (G1) is arbitrary.
  • m1 to m6 in formula (G1) respectively represent the number of (OG f1 ) to (OG f6 ), and do not represent the arrangement.
  • (OG f5 ) m5 represents that the number of (OG f5 ) is m5, and does not represent the block arrangement structure of (OG f5 ) m5 .
  • the order of (OG f1 ) to (OG f6 ) does not represent the bonding order of each unit.
  • the fluoroalkylene group having 3 to 6 carbon atoms may be linear or may have a branched or cyclic structure.
  • G f1 include --CF 2 -- and --CHF--.
  • G f2 include -CF 2 CF 2 -, -CHFCF 2 -, -CHFCHF-, -CH 2 CF 2 -, and -CH 2 CHF-.
  • G f3 examples include -CF 2 CF 2 CF 2 -, -CF 2 CH 2 CF 2 -, -CHFCF 2 CF 2 - , -CHFCHFCF 2 -, -CHFCHFCHF- , -CHFCH 2 CF 2 - , -C H2CF2CF2- , -CH2CHFCF2-, -CH2CH2CF2- , -CH2CF2CHF- , -CH2CH2CHF-, -CH2CH2CHF-, -CH2CH2CHF-, -CF( CF3 ) -CF2- , -CF2 ) -CF 2 -, -CF ( CH 2 F ) -CF 2 -, -CF( CH3 ) -CF2- , -CF( CF3 )-CHF-, -CF( CHF2 )-CHF-, -CF(CH2F)-CHF-, -CF( CH3
  • G f4 include -CF 2 CF 2 CF 2 CF 2 -, -CHFCF 2 CF 2 CF 2 -, -CH 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CHFCHF 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 -, -CHFCHFCF 2 -, -CH 2 CHFCF 2 -, -CF 2 CHFCF 2 -, -CHFCH 2 CHFCF 2 -, -CH 2 CH 2 CHFCF 2 -, -CF 2 CH 2 CF 2 -, -CHFCH 2 CHFCF 2
  • G f5 examples 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 -, -CHFCH FCF2CF2CF2- , -CF2CH2CF2CF2CF2- , -CHFCH2CF2CF2CF2- , -CH2CH2CF2CF2CF2- , -CF2CF2CHFCF2CF2 - , -CHFCF 2 Examples thereof include CHFCF 2 CF 2 --, --CH 2 CF 2 CHFCF 2 CF 2 --, --CH 2 CF 2 CF 2 CH 2 --, and --cycloC 5 F 8 --.
  • Gf6 examples include -CF2CF2CF2CF2CF2CF2CF2- , -CF2CF2CHFCHFCF2CF2CF2- , -CHFCF2CF2CF2CF2CF2CF2CF2- , -CHFCHFCHFCHFCHFCHF- , -CHFCF2CF2CF2CF2CF2CF2CH2- , -CH2CF2CF2CF2CF2CH2- , -CH2CF2CF2CF2CF2CF2CH2- , and -cycloC6F10- .
  • -cycloC 4 F 6 - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group
  • -cycloC 5 F 8 - means a perfluorocyclopentanediyl group, a specific example of which is a perfluorocyclopentane-1,3-diyl group
  • -cycloC 6 F 10 - means a perfluorocyclohexanediyl group, a specific example of which is a perfluorocyclohexane-1,4-diyl group.
  • OR f2 y1 preferably has a structure represented by any one of the following formulae (G2) to (G4).
  • the order of bonding between (OG f1 ) and (OG f2 ), between (OG f2 ) and (OG f4 ) is arbitrary.
  • (OG f1 ) and (OG f2 ) may be arranged alternately, (OG f1 ) and (OG f2 ) may be arranged in blocks, or may be arranged randomly.
  • m1+m2 is 2 or more.
  • m1 is preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.
  • m2 is preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.
  • m2+m4 is 2 or more.
  • m2 is preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.
  • m4 is preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.
  • m3 is 2 or more, preferably 2 to 50, and more preferably 2 to 30.
  • the fluoropolyether chain (OR f3 ) y1 may have a hydrogen atom.
  • the proportion of fluorine atoms in (OR f3 ) y1 is preferably 60% or more, more preferably 80% or more, and even more preferably substantially 100%, that is, a perfluoropolyether chain. If the proportion of fluorine atoms is 60% or more, the amount of fluorine in the fluoropolyether chain increases, and the slipperiness and fingerprint removability are further improved.
  • the proportion of fluorine atoms here is a value calculated by the following formula (I).
  • Formula (I): Percentage of fluorine atoms (%) (number of fluorine atoms)/ ⁇ (number of fluorine atoms)+(number of hydrogen atoms) ⁇ 100
  • R1 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or an alkylene group having an etheric oxygen atom having 1 to 20 carbon atoms.
  • Rf3 located at the end of ( ORf3 ) y1 is directly bonded to L1 .
  • R 1 is a fluoroalkylene group having 3 to 20 carbon atoms
  • the fluoroalkylene group may be linear or may have a branched or cyclic structure.
  • the alkylene group may be linear or may have a branched or cyclic structure.
  • R1 is an alkylene group having 3 to 20 carbon atoms and an etheric oxygen atom
  • the alkylene group may be linear or may have a branched or cyclic structure.
  • the etheric oxygen atom may be located at the terminal of the alkylene group or between carbon atoms.
  • R 1 is a fluoroalkylene group, an alkylene group, or an alkylene group having an etheric oxygen atom
  • R 1 has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.
  • L 1 is a single bond or a 1+x1 valent group.
  • the 1+x1 valent group may have a heteroatom such as N, O, S, or Si, and may have a branch point.
  • R1 and R2 in formula (1) are directly bonded.
  • ( ORf3 ) y1 and R2 in compound 1 are directly bonded.
  • L 1 When L 1 is a trivalent or higher group, L 1 has at least one branch point (hereinafter referred to as “branch point P 1 ”) selected from the group consisting of C, N, Si, a ring structure, and a (1+x1)-valent organopolysiloxane residue.
  • branch point P 1 branch point selected from the group consisting of C, N, Si, a ring structure, and a (1+x1)-valent organopolysiloxane residue.
  • the branch point P1 When N is the branch point P1 , the branch point P1 is expressed, for example, as *-N(-**) 2 , where * is a bond on the R1 side, and ** is a bond on the R2 side.
  • the branch point P1 When C is the branch point P1 , the branch point P1 is represented, for example, by *-C(-**) 3 or * -CR29 (-**) 2 , where * and ** are the same as when N is the branch point P1 , and R29 is a monovalent group such as a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxy group.
  • the branch point P1 is expressed, for example, as *-Si(-**) 3 or *-SiR 29 (-**) 2.
  • * and ** are the same as when N is the branch point P1
  • R 29 is the same as when C is the branch point P1 .
  • the ring structure constituting the branch point P1 from the viewpoint of ease of synthesis and of providing a surface layer with better abrasion resistance, light resistance and chemical resistance, it is preferable to use one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle and a condensed ring consisting of two or more of these rings, and a ring structure shown in the following formula is more preferable.
  • the ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group ( ⁇ O).
  • a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group ( ⁇ O).
  • organopolysiloxane residues constituting branch point P1 include the following groups.
  • R 25 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 25 is preferably 1 to 10, and more preferably 1. Multiple R 25s may be the same or different.
  • the divalent or higher L 1 may have at least one bond (hereinafter referred to as "bond B 1 ") selected from the group consisting of -C(O)N(R 26 )-, -C(O)O-, -C(O)-, -C(OH)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)N(R 26 )-, -SO 2 N(R 26 )-, -N(R 26 )SO 2 -, -Si(R 26 ) 2 - , -OSi(R 26 ) 2 -, -Si(CH 3 ) 2 -Ph-Si(CH 3 ) 2 -, and a divalent organopolysiloxane residue.
  • bond B 1 selected from the group consisting of -C(O)N(R 26 )-, -C(O)-
  • R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. From the viewpoint of ease of production of compound 1, the number of carbon atoms of the alkyl group of R 26 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. When there are multiple R 26 , the multiple R 26 may be the same or different from each other.
  • R 27 is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 27 is preferably 1 to 10, and more preferably 1.
  • a plurality of R 27s may be the same or different.
  • bond B1 from the viewpoint of ease of synthesis, at least one bond selected from the group consisting of -C(O)NR 26 -, -N(R 26 )C(O)-, -C(O)- and -NR 26 - is preferable, and from the viewpoint of further improving the light resistance and chemical resistance of the surface layer, -C(O)NR 26 -, -N(R 26 )C(O)- or -C(O)- is more preferable.
  • L 1 having a valence of two or more include one or more bonds B 1 (for example, *-B 1 -**, *-B 1 -R 28 -B 1 -**).
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 1 side
  • ** is a bond on the R 2 side.
  • the atoms adjacent to R 1 and R 2 are each a constituent element of the bond B 1 or the branch point P 1.
  • trivalent or higher L 1 include one or more branch points P 1 (for example, ⁇ *-P 1 (-**) x1 ⁇ ), a combination of one or more branch points P 1 and one or more bonds B 1 (for example, ⁇ *-B 1 -R 28 -P 1 (-**) x1 ⁇ , ⁇ *-B 1 -R 28 -P 1 (-R 28 -B 1 -**) x1 ⁇ ).
  • R28 is a single bond or a divalent organic group
  • * is a bond on the R1 side
  • ** is a bond on the R2 side.
  • Examples of the divalent organic group in R 28 include divalent aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups, etc.) and divalent aromatic hydrocarbon groups (phenylene groups, etc.), which may have a bond B1 between carbon atoms of the hydrocarbon group having 2 or more carbon atoms.
  • the number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
  • E6 -E 1 -CH(-E 22 -)-Si(R E3 ) 3-e5 (-E 25 -) e5 ...Formula (E7)
  • E 1 , E 2 or E 3 is connected to R 1 in the formula (1)
  • E 22 , E 23 , E 24 , E 25 or E 26 is connected to R Connect to 2 .
  • E 1 is a single bond, -B 5 -, -B 6 -R 40 -, or -B 6 -R 40 -B 5 -
  • R 40 is an alkylene group or a cyclic group having 2 or more carbon atoms.
  • B 5 is a group having —C(O)NR E6 —, —C(O)—, —NR E6 — or —O— between carbon atoms of an alkylene group; E6 -, -C(O)-, -NR E6 - or -O-, B 6 is -C(O)NR E6 -, -C(O)- or -NR E6 -; E 2 is a single bond or -B 6 -R 40 -; E3 is E1 when the atom in Z1 to which E3 is bonded is a carbon atom, and is E2 when the atom in Z1 to which E3 is bonded is a nitrogen atom; E 11 is a single bond, —O—, an alkylene group, or —C(O)NR E6 —, —C(O)—, or —NR E6 — between carbon atoms of an alkylene group having 2 or more carbon atoms.
  • E 22 is a single bond, -B 5 -, -R 40 -B 6 - or -B 5 -R 40 -B 6 -, and when there are two or more E 22 , the two or more E 22 are the same. may be different, E 23 is a single bond or -R 40 -B 6 -, and two E 23 's may be the same or different; E 24 is E 22 when the atom in Z 1 to which E 24 is bonded is a carbon atom, and is E 23 when the atom in Z 1 to which E 24 is bonded is a nitrogen atom; E 24 has 2 or more.
  • E 24 may be the same or different
  • E 25 is a single bond or -R 40 -B 6 -, and when two or more E 25's are present, the two or more E 25 's may be the same or different
  • E 26 is a single bond or -R 40 -B 6 -
  • Z1 is a group having a (e4+1)-valent ring structure having a carbon atom or nitrogen atom to which E3 is directly bonded and a carbon atom or nitrogen atom to which E24 is directly bonded
  • R E1 is a hydrogen atom or an alkyl group, and when there are two or more R E1s , the two or more R E1s may be the same or different
  • R E2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group, and when there are two or more R E2 s , the two or more R E2 s may be the same or different
  • R E3 is an alkyl group, and when
  • the number of carbon atoms in the alkylene group of R 40 is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4, from the viewpoints of ease of production of compound 1 and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer.
  • the lower limit of the number of carbon atoms in the alkylene group is 2.
  • Examples of the ring structure in Z 1 include the ring structures described above, and the preferred embodiments are also the same. Since E 24 is directly bonded to the ring structure in Z 1 , for example, an alkylene group is not bonded to the ring structure and E 24 is not bonded to the alkylene group.
  • the number of carbon atoms in the alkyl group of R E1 , R E2 or R E3 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of ease of production of compound 1.
  • the number of carbon atoms in the alkyl group portion of the acyloxy group of R E2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of compound 1.
  • e4 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, in terms of ease of production of compound 1 and further superior abrasion resistance and fingerprint stain removability of the surface layer.
  • L 1 include groups represented by any one of the following formulae (E11) to (E17).
  • E 1 , E 2 or E 3 is connected to R 1 in formula (1), and E 22 , E 23 , E 24 , E 25 or E 26 is connected to R 2.
  • E G is the following formula (E G ), and two or more E Gs in L 1 may be the same or different.
  • the symbols other than G are the same as the symbols in formulas (E1) to (E7).
  • the Si side is connected to E 22 , E 23 , E 24 , E 25 or E 26 , and the E 3 side is connected to R 2.
  • R 23 is an alkyl group.
  • E 3 is a single bond or -R 45 -B 6 -
  • R 45 is an alkylene group, or a group having -C(O)NR 46 -, -C(O)-, -NR 46 - or -O- between carbon atoms of an alkylene group having 2 or more carbon atoms, or -(OSi(R 24 ) 2 ) p -O-, and two or more E 3s may be the same or different.
  • k is 2 or 3.
  • R 46 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 24 is an alkyl group, a phenyl group or an alkoxy group, and two R 24s may be the same or different.
  • p is an integer of 0 to 5, and when p is 2 or greater, the two or more (OSi(R 24 ) 2 ) may be the same or different.
  • the number of carbon atoms in the alkylene group of E3 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4, from the viewpoints of ease of production of compound 1 and of further improving the abrasion resistance, light resistance, and chemical resistance of the surface layer.
  • the lower limit of the number of carbon atoms in the alkylene group is 2.
  • the number of carbon atoms in the alkyl group of R 23 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
  • the number of carbon atoms in the alkyl group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
  • the number of carbon atoms in the alkoxy group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, in terms of excellent storage stability of compound 1.
  • p is preferably 0 or 1.
  • R2 is an alkylene group or an alkylene group having an etheric oxygen atom.
  • the atom bonded to L 1 may be an ethereal oxygen atom, or an ethereal oxygen atom may be present between carbon atoms.
  • the plurality of R2 may be the same or different.
  • the R2 is preferably a group represented by the following formula (H1).
  • R g11 is an alkylene group having 1 to 12 carbon atoms, and when there are multiple R g11 , the multiple R g11 may be the same or different from each other, R g12 is an alkylene group having 1 to 12 carbon atoms; a4 is 0 or 1; a5 is an integer of 0 or more, * is a bond bonded to L1 , ** is a bond binding to T1 .
  • a4 When a4 is 0, the atom having the bond * is a carbon atom, and when a4 is 1, the atom having the bond * is an oxygen atom.
  • a4 may be either 0 or 1, and may be appropriately selected from the viewpoint of ease of synthesis, etc.
  • a5 is the number of repetitions of R g11 O, and is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1, from the standpoint of durability as a surface layer, etc.
  • the alkylene group of R g11 may be a linear or branched alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.
  • the alkylene group is preferably a linear alkylene group.
  • the alkylene group of R g12 may be a linear or branched alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms.
  • the alkylene group is preferably a linear alkylene group.
  • --R 1 -L 1 (-R 2 -T 1 ) x1 can be represented by the following formula (RL-1). *-R 43 -(OR 44 ) y3 -T 1 ...Formula (RL-1) however, R 43 is a single bond or an alkylene group having 1 to 6 carbon atoms; R 44 is an alkylene group having 1 to 6 carbon atoms, and when there are a plurality of R 44s , the plurality of R 44s may be the same or different from each other, y3 is an integer equal to or greater than 0; * represents a bond bonded to R f3 at the end of (OR f3 ) y1 in formula (1).
  • compound 1 When R 43 is a single bond, compound 1 has a structure in which the terminal O of (OR 44 ) y3 is directly bonded to the terminal R f3 of (OR f3 ) y1 in formula (1). When y3 is 0, compound 1 has a structure in which R43 is directly bonded to T1 .
  • T 1 is a reactive group, and due to the reactivity of T 1 , compound 1 exhibits various functions.
  • the functions include a function of improving adhesion to a substrate surface, a function of imparting photocurability or thermosetting property to compound 1, a function of imparting acidity/alkalinity to compound 1, a function of adjusting the solubility of compound 1 in a specific solvent, and a function as a precursor when synthesizing other compounds.
  • R 10 is a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted fluoroalkyl group having 1 to 6 carbon atoms, or an optionally substituted aryl group;
  • Ar is an optionally substituted aryl group,
  • X2 is an alkali metal ion or an ammonium ion;
  • X3 is a halide ion;
  • X4 is a halogen atom;
  • R a1 is a hydrolyzable group or a hydroxyl group;
  • R a11 is a hydrocarbon group;
  • z1 is an integer from 1 to 3,
  • the plurality of R 10 , R a1 or R a11 may be the same or different.
  • the fluoroalkyl group in R 10 has 1 to 6 carbon atoms, preferably 3 to 6 carbon atoms.
  • the fluoroalkyl group may have other substituents.
  • Compound 1 having a fluoroalkyl group as T is a compound with a high fluorine content, and is excellent in various properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency.
  • substituent that the fluoroalkyl group may have include halogen atoms such as chlorine atoms, and the same as those exemplified as the functionality-imparting group T described below.
  • the aryl group in Ar and R 10 includes a phenyl group, a naphthyl group, etc., and may further have a substituent.
  • substituents that the aryl group may have include a halogen atom such as a fluorine atom or a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and the same as those exemplified as the functionality-imparting group T.
  • the alkyl group in R 10 has 1 to 6 carbon atoms, and preferably 3 to 6 carbon atoms.
  • the alkyl group may have another substituent. Examples of the substituent that the alkyl group may have include a halogen atom such as a chlorine atom, and the same as those exemplified as the functionality-imparting group T described later.
  • Examples of counter ions of the quaternary ammonium group include halide ions.
  • Examples of counter ions of the carboxylate, sulfonate, and phosphate include alkali metal ions and ammonium ions.
  • a compound 1 having a group having a carbon-carbon double bond as the reactive group T1 can be combined with a photoinitiator or the like to prepare a photocurable composition, and a cured coating film obtained from the composition has both water and oil repellency and hard coat properties.
  • Examples of the group having a carbon-carbon double bond include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, an acryloyloxy group, a methacryloyloxy group, an olefin, and the like.
  • compound 1 having an isocyanate group, an epoxy group, a glycidyl group, an oxetanyl group, or a mercapto group as the reactive group T1 can be combined with an epoxy curing agent to prepare a thermosetting or photocurable composition, and the cured coating film obtained from the composition has both water and oil repellency and hard coat properties.
  • the amide bond, ester bond, ether bond, thioether bond, siloxane bond, and urea bond in the reactive group T1 are bonds that connect the alkyl group, fluoroalkyl group, aryl group, heteroaryl group, and the like contained in T1 .
  • Other functionality-imparting groups may be further provided via these bonds.
  • a hydroxy group, an amino group, or a group having a carbon-carbon double bond is preferred from the viewpoints of synthesis, chemical stability, adhesion to a substrate, etc.
  • the groups having a carbon-carbon double bond an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an olefin is preferred.
  • T1 is preferably a group having a reactive silyl group.
  • a group having a reactive silyl group a group represented by -SiR a1 z1 R a11 3-z1 is preferable.
  • R a1 is a hydrolyzable group or a hydroxyl group
  • R a11 is a hydrocarbon group
  • z1 is an integer from 1 to 3
  • the plurality of R a1 or R a11 may be the same or different.
  • R a1 When R a1 is a hydroxyl group, it constitutes a silanol (Si-OH) group together with the Si atom.
  • the hydrolyzable group is a group that becomes a hydroxyl group by hydrolysis.
  • the silanol group further reacts with other molecules to form a Si-O-Si bond.
  • the silanol group also undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si).
  • T 1 By having one or more T 1 , compound 1 has excellent abrasion resistance after the formation of the surface layer.
  • Examples of the hydrolyzable group for R a1 include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group (-NCO).
  • the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
  • the acyl group is preferably an acyl group having 1 to 6 carbon atoms.
  • the acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
  • R a1 is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom.
  • the alkoxy group in R a1 is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoints of excellent storage stability of compound 1 and suppression of outgassing during the reaction, more preferably an ethoxy group from the viewpoint of long-term storage stability, and more preferably a methoxy group from the viewpoint of shortening the hydrolysis reaction time.
  • halogen atom a chlorine atom is particularly preferable.
  • R a11 is a hydrocarbon group.
  • the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group. From the viewpoint of ease of synthesis, an alkyl group is preferable. From the viewpoint of ease of synthesis, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.
  • the number z1 of R a1 may be from 1 to 3, and from the viewpoint of adhesion to the substrate, it is preferably 2 or 3, and more preferably 3.
  • Specific examples of --SiR a1 z1 R a11 3-z1 include --Si(OCH 3 ) 3 , --SiCH 3 (OCH 3 ) 2 , --Si(OCH 2 CH 3 ) 3 , --SiCl 3 , --Si(OCOCH 3 ) 3 , and --Si(NCO) 3. From the viewpoint of ease of handling in production, --Si(OCH 3 ) 3 is preferred.
  • the number x1 of T1 in one molecule of compound 1 may be 1 to 10, and from the viewpoints of ease of synthesis and ease of handling of compound 1, x1 is preferably 1 to 6, and more preferably 1 to 3. When there are two or more T1s in one molecule of compound 1, the T1s may have the same structure or different structures.
  • T1 does not have a reactive silyl group
  • R a represents an alkyl group, a fluoroalkyl group, or an aryl group which may have a substituent
  • R b represents a fluoroalkyl group or an aryl group which may have a substituent
  • R represents an alkyl group having 1 to 6 carbon atoms which may have a substituent or a fluoroalkyl group having 1 to 6 carbon atoms which may have a substituent
  • L represents an aryl group which may have a substituent or a fluoroaryl group which may have a substituent
  • c represents an integer of 0 to 3
  • * represents a bond.
  • the plurality of R's and the plurality of L's may be the same or different.
  • L 1 -(R 2 -T 1 ) x1 include groups represented by the following formulae.
  • compound 1 examples include compounds represented by the following formula: In the formula, n and m are each independently an integer of 1 or greater.
  • the method for producing compound 1 is not particularly limited, but will be described below with a specific example.
  • An example of a method for adding R f1 to the fluoropolyether chain (OR f3 ) y1 is a method of reacting a compound represented by the following formula (3) with a compound represented by the following formula (4).
  • R f31 is a group containing a ring structure or a chain hydrocarbon group having 3 or more carbon atoms and not containing a fluorine atom
  • D1 is a group containing a group capable of reacting with D2 and not containing a fluorine atom
  • D2 is a group containing a group capable of reacting with D1 and not containing a fluorine atom
  • D 3 is —R 1 -L 1 -(R 2 -T 1 ) x1 or a group into which —R 1 -L 1 -(R 2 -T 1 ) x1 can be introduced by a subsequent operation
  • R f31 , D 1 and D 2 are groups which become R f1 in formula (1) after the reaction; The other symbols are the same as those in formula (1) above.
  • the combination of D1 and D2 is not particularly limited, and examples thereof include a combination of an amino group and an alkyloxycarbonyl group.
  • D1 and D2 are not particularly limited, and examples thereof include a combination of an amino group and an alkyloxycarbonyl group.
  • Another example of the method for adding R f1 to the fluoropolyether chain (OR f3 ) y1 is a method of reacting a compound represented by the following formula (5) with a compound represented by the following formula (6).
  • D4 is a group containing a group capable of reacting with D5 and not containing a fluorine atom
  • D5 is a group containing a group capable of reacting with D4
  • R f31 and D 4 are groups which become R f1 in formula (1) after the reaction
  • D5 is a group which becomes R f1 in formula (1) after the reaction
  • the combination of D4 and D5 is not particularly limited, and examples thereof include a combination of a hydroxyl group and a fluorine-containing olefin.
  • composition contains compound 1 and a fluorine-containing compound other than compound 1 (hereinafter also referred to as “another fluorine-containing compound”). Note that the composition does not contain a liquid medium described later.
  • fluorine-containing compounds include both compounds that are unavoidably included and compounds that are used in combination depending on the application, etc.
  • fluorine-containing compounds that can be used in combination with compound 1 include known fluorine-containing ether compounds and fluorine-containing oils.
  • fluorine-containing oils examples include polytetrafluoroethylene (PTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and polychlorotrifluoroethylene (PCTFE).
  • PTFE polytetrafluoroethylene
  • ECTFE ethylene-chlorotrifluoroethylene copolymer
  • PVDF polyvinylidene fluoride
  • PVF polyvinyl fluoride
  • PCTFE polychlorotrifluoroethylene
  • Examples of known fluorine-containing ether compounds include fluorine-containing ether compounds commercially available as surface treatment agents. When the present composition contains a known fluorine-containing ether compound, new effects such as compensating for the properties of compound 1 may be exhibited.
  • Examples of known fluorine-containing ether compounds include those described in the following documents: Perfluoropolyether-modified aminosilanes described in Japanese Patent Laid-Open No. 11-029585; Silicon-containing organic fluorine-containing polymers as described in Japanese Patent No.
  • examples of commercially available compounds include the KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., the SURECO AF series such as SURECO (registered trademark) 2101S manufactured by AGC, and OPTOOL (registered trademark) DSX, OPTOOL (registered trademark) AES, OPTOOL (registered trademark) UF503, OPTOOL (registered trademark) UD509, OPTOOL (registered trademark) UD120, etc. manufactured by Daikin Industries, Ltd.
  • the content ratio may be adjusted appropriately depending on the application, etc.
  • the content ratio of compound 1 in this composition is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 25 to 75 mass%.
  • Compounds that are inevitably contained include fluorine-containing compounds that are by-produced in the manufacturing process of compound 1 (hereinafter also referred to as "by-product fluorine-containing compounds").
  • by-product fluorine-containing compounds include unreacted compounds and fluorine-containing compounds in which a portion of the allyl group is isomerized to an inner olefin during hydrosilylation in the manufacture of compound 1.
  • the by-product fluorine-containing compound can be removed by purification. Furthermore, the by-product fluorine-containing compound may be contained in the present composition to the extent that the properties of compound 1 can be fully exhibited. This can simplify the purification process of the by-product fluorine-containing compound.
  • the content of compound 1 in the composition is preferably 60% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, and even more preferably 80% by mass or more and less than 100% by mass.
  • the content of by-product fluorine-containing compounds is preferably more than 0% by mass or more and less than 40% by mass, more preferably more than 0% by mass or more and less than 30% by mass, and even more preferably more than 0% by mass or more and less than 20% by mass.
  • the initial water and oil repellency, abrasion resistance, fingerprint stain removability, light resistance, and chemical resistance of the surface layer will be even more excellent.
  • compounds that are inevitably contained include additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups.
  • acid catalysts include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid.
  • basic catalysts include sodium hydroxide, potassium hydroxide, and ammonia. The content of these in the composition is preferably 0 to 9.999 mass%, and more preferably 0 to 0.99 mass%.
  • the surface treatment agent of the present invention contains Compound 1 or the present composition.
  • the present surface treatment agent is preferably used as a surface treatment agent for applications requiring long-term maintenance of the performance in which the water- and oil-repellency are not likely to decrease even when the surface layer is repeatedly rubbed with fingers (abrasion resistance) and the performance in which fingerprints attached to the surface layer can be easily removed by wiping (fingerprint stain removability), for example, for members constituting the surfaces of touch panels that are touched by fingers, eyeglass lenses, and displays of wearable devices.
  • the present surface treatment agent has excellent slip resistance, it can be suitably used for glass-coated housings of mobile devices such as smartphones and tablet terminals.
  • the present surface treatment agent is also suitable for use as an antifouling coating agent or a waterproof coating agent.
  • the present surface treatment agent may further contain a liquid medium.
  • the present surface treatment agent containing a liquid medium may be referred to as a coating liquid.
  • the coating liquid may be in a liquid state, and may be a solution or a dispersion.
  • the coating liquid may contain the compound 1, and may contain impurities such as by-products generated in the manufacturing process of the compound 1.
  • the concentration of Compound 1 in the coating liquid is preferably from 0.001 to 40% by mass, more preferably from 0.01 to 20% by mass, and even more preferably from 0.1 to 10% by mass.
  • the liquid medium is preferably an organic solvent.
  • the organic solvent may be a fluorine-containing organic solvent, a non-fluorine-containing organic solvent, or may contain both.
  • Specific examples of the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and hydrofluoroolefins (HFOs).
  • the fluorinated alkane is preferably a compound having a carbon number of 4 to 8.
  • fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
  • the fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms.
  • fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine.
  • fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
  • a specific example of HFO is 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) (manufactured by AGC, Amorea (registered trademark) AS-300).
  • non-fluorinated organic solvent a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferable, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and glycol organic solvents.
  • hydrocarbon organic solvents include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, bicyclohexyl, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.
  • alcohol-based organic solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol,
  • ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and 3,3,5-trimethylcyclohexanone, and isophorone.
  • ether-based organic solvents include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.
  • ester-based organic solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl acetate, propylene glycol dimethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Ether acetate, cyclohex
  • glycol-based organic solvents include ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropyl
  • organic solvents include chlorine-based organic solvents, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds.
  • chlorine-based organic solvents include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane.
  • Nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
  • Sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.
  • Siloxane compounds include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.
  • the coating liquid preferably contains 75 to 99.999% by mass of the liquid medium, more preferably 85 to 99.99% by mass, and even more preferably 90 to 99.9% by mass.
  • the coating liquid may contain other components in addition to the compound 1 and the liquid medium, as long as the effects of the present disclosure are not impaired.
  • other components include known additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups.
  • the content of other components in the coating liquid is preferably 10% by mass or less, and more preferably 1% by mass or less.
  • the total concentration of compound 1 and other components in the coating liquid (hereinafter also referred to as "solid content concentration”) is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, further preferably 0.01 to 10 mass%, and particularly preferably 0.01 to 1 mass%.
  • 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.
  • the article of the present invention (hereinafter also referred to as “the present article”) has a surface layer formed from Compound 1 or the present composition on the surface of a substrate.
  • Fig. 1 is a schematic cross-sectional view showing a first article, which is an example of the present article.
  • the first article is an article 20 having a substrate 12, an underlayer 14, and a surface layer 22 in this order, in which the underlayer 14 contains an oxide containing silicon, and the surface layer 22 contains a condensate of compound 1.
  • the material and shape of the substrate 12 may be appropriately selected depending on the application of the article 20.
  • Examples of the material of the substrate 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof.
  • the glass may be chemically strengthened.
  • examples of the substrate 12 that is required to be water- and oil-repellent include substrates for touch panels, substrates for displays, and substrates that constitute the housings of electronic devices.
  • the touch panel substrate and the display substrate have light-transmitting properties.
  • the term "light-transmitting properties" means that the normal incidence visible light transmittance in accordance with JIS R3106:1998 (ISO 9050:1990) is 25% or more.
  • the material of the touch panel substrate is preferably glass or a transparent resin.
  • the substrate 12 may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc. on the surface on which the undercoat layer 14 is provided.
  • a surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc.
  • the surface that has been subjected to the surface treatment has better adhesion between the substrate 12 and the undercoat layer 14, and as a result, the abrasion resistance of the surface layer 22 is further improved.
  • a corona discharge treatment or a plasma treatment is preferable since it provides the surface layer 22 with further excellent abrasion resistance.
  • the underlayer 14 is an oxide containing at least silicon, i.e., a layer containing silicon oxide, and may further contain other elements.
  • T1 of the compound 1 undergoes dehydration condensation, forming a Si-O-Si bond between the underlayer 14 and the underlayer 14, forming a surface layer 22 with superior abrasion resistance.
  • the content of silicon oxide in the underlayer 14 is preferably 65 mass % or more, more preferably 80 mass % or more, even more preferably 85 mass % or more, and particularly preferably 90 mass % or more.
  • the content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxide) from the mass of underlayer 14 .
  • the oxide in the underlayer 14 further contains 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. By containing these elements, the bond between the underlayer 14 and the compound 1 is strengthened, improving the abrasion resistance.
  • the total content of these elements relative to silicon oxide is preferably 10 to 1100 ppm by mass, more preferably 50 to 1100 ppm by mass, even more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass.
  • the total content thereof is preferably 10 to 2500 ppm by mass, more preferably 15 to 2000 ppm by mass, and even more preferably 20 to 1000 ppm by mass.
  • the total content of the alkali metal elements is preferably 0.05 to 15 mass %, more preferably 0.1 to 13 mass %, and further preferably 1.0 to 10 mass %.
  • the alkali metal element include lithium, sodium, potassium, rubidium, and cesium.
  • the underlayer 14 contains a platinum group element the total content of the platinum group elements is preferably from 0.02 to 800 ppm by mass, more preferably from 0.04 to 600 ppm by mass, and even more preferably from 0.7 to 200 ppm by mass.
  • the platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium.
  • the total content of these elements is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, in terms of the abrasion resistance of the surface layer 22.
  • the total content of these elements expressed as the ratio of the molar concentration of the total alkaline earth metal elements to the molar concentration of silicon, is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2, from the viewpoint of the abrasion resistance of the surface layer 22.
  • alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.
  • the undercoat layer 14 is preferably a silicon oxide layer containing alkali metal atoms. It is particularly preferable that the average concentration of alkali metal atoms in the silicon oxide layer in a region 0.1 to 0.3 nm deep from the surface in contact with the surface layer 22 is 2.0 ⁇ 10 19 atoms/cm 3 or more. On the other hand, from the viewpoint of sufficiently ensuring the mechanical properties of the silicon oxide layer, it is preferable that the average concentration of alkali metal atoms is 4.0 ⁇ 10 22 atoms/cm 3 or less.
  • the thickness of the underlayer 14 is preferably 1 to 200 nm, and particularly preferably 2 to 20 nm. If the thickness of the underlayer 14 is equal to or greater than the lower limit of the above range, the effect of improving the adhesiveness of the underlayer 14 is easily obtained. If the thickness of the underlayer 14 is equal to or less than the upper limit of the above range, the abrasion resistance of the underlayer 14 itself is increased.
  • Methods for measuring the thickness of the underlayer 14 include a method of observing a cross section of the underlayer 14 with an electron microscope (SEM, TEM, etc.), and a method using an optical interference film thickness gauge, a spectroscopic ellipsometer, a step gauge, or the like.
  • a specific example of a method for forming the underlayer 14 is a method in which a deposition material having a desired composition for the underlayer 14 is deposited on the surface of the substrate 12 .
  • An example of the deposition method is a vacuum deposition method in which a deposition material is evaporated in a vacuum chamber and attached to the surface of the base material 12.
  • the temperature during deposition (for example, the temperature of a boat in which a deposition material is placed when a vacuum deposition apparatus is used) is preferably from 100 to 3,000°C, particularly preferably from 500 to 3,000°C.
  • the pressure during deposition (for example, when using a vacuum deposition apparatus, the absolute pressure in a tank in which the deposition material is placed is preferably 1 Pa or less, particularly preferably 0.1 Pa or less.
  • the underlayer 14 is formed using a deposition material
  • one deposition material may be used, or two or more deposition materials containing different elements may be used.
  • the evaporation method of the deposition material include the resistance heating method in which the deposition material is melted and evaporated on a resistance heating boat made of a high melting point metal, and the electron gun method in which the deposition material is irradiated with an electron beam to directly heat the deposition material to melt and evaporate the surface.
  • the electron gun method is preferred as the evaporation method of the deposition material because it can evaporate high melting point substances because it can be heated locally, and because the area not irradiated by the electron beam is at a low temperature, there is no risk of reaction with the container or contamination with impurities.
  • the deposition material used in the electron gun method is preferably a molten granular body or a sintered body because it is less likely to scatter even when an air current is generated.
  • the surface layer 22 on the underlayer 14 contains a condensate of compound 1.
  • the condensates of compound 1 include those in which a hydrolyzable silyl group or the like in compound 1 undergoes a hydrolysis reaction to form a silanol group (Si—OH), which undergoes a condensation reaction between molecules to form a Si—O—Si bond, and those in which a silanol group in compound 1 undergoes a condensation reaction with a silanol group or a Si—OM group (wherein M is an alkali metal element) on the surface of the underlayer 14 to form a Si—O—Si bond.
  • the surface layer 22 may also contain a condensate of a compound other than the compound contained in the present composition. That is, the surface layer 22 contains a compound having a reactive silyl group in a state in which a part or all of the reactive silyl groups of the compound have undergone a condensation reaction.
  • the thickness of the surface layer 22 is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the surface layer 22 is equal to or greater than the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. When the thickness of the surface layer 22 is equal to or less than the upper limit of the above range, the utilization efficiency is high.
  • the thickness of the surface layer 22 is a thickness obtained by an X-ray diffractometer for thin film analysis. The thickness of the surface layer 22 can be calculated from the vibration period of an interference pattern obtained by an X-ray reflectance method using an X-ray diffractometer for thin film analysis.
  • the second article is an article 20 having a substrate 10 with an underlayer and a surface layer 22 in this order, in which the substrate 10 with an underlayer contains an oxide containing silicon, and the surface layer 22 contains a condensate of Compound 1.
  • the substrate 10 with an undercoat layer has the composition of the undercoat layer 14 in the first article, and therefore the surface layer 22 has excellent abrasion resistance even when the surface layer 22 is directly formed on the substrate 10 with an undercoat layer.
  • the material of the substrate 10 with an undercoat layer in the second article may be any material having the composition of the undercoat layer 14, and may be, for example, a glass substrate.
  • the details of the material of the substrate 10 with an undercoat layer are similar to those of the substrate 12 and the undercoat layer 14, and therefore will not be described here.
  • the configuration of the surface layer 22 is also the same as that of the first article described above, and therefore a description thereof will be omitted here.
  • the article of the present invention include optical members, touch panels, anti-reflective films, anti-reflective glass, SiO 2 -treated glass, tempered glass, sapphire glass, quartz substrates, and mold metals that are used as part of the components of the following products.
  • Products car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic electroluminescence displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.
  • the method for producing an article of the present invention is a method for forming a surface layer by a dry coating method or a wet coating method using Compound 1, the present composition, or the present surface treatment agent.
  • Compound 1 the composition, and the surface treatment agent can be used as is in a dry coating method, and are suitable for forming a surface layer with excellent adhesion by the dry coating method.
  • the dry coating method include vacuum deposition, CVD, sputtering, and the like.
  • the vacuum deposition method is suitable for use in terms of suppressing the decomposition of the composition and the simplicity of the device.
  • a pellet-like material may be used in which a metal porous body made of a metal material such as iron or steel supports compound 1, etc.
  • the pellet-like material supporting compound 1, etc. can be produced by impregnating a metal porous body with a solution containing compound 1, and drying the material to remove the liquid medium.
  • the present surface treatment agent (coating liquid) containing a liquid medium can be suitably used in wet coating methods.
  • Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.
  • an operation for promoting the reaction between the compound 1 and the substrate may be carried out as necessary.
  • Examples of such an operation include heating, humidification, and light irradiation.
  • the substrate on which the surface layer is formed can be heated in a humid atmosphere to promote reactions such as hydrolysis of hydrolyzable groups, reaction between hydroxyl groups and silanol groups on the surface of the substrate, and formation of siloxane bonds by condensation reaction of silanol groups.
  • compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, pouring a solvent onto the surface layer, wiping it off with a cloth soaked in the solvent, etc.
  • Compound M1 is represented by the following formula (M1) and can be used, for example, to produce compound 1.
  • R f is a fluoroalkylene group having 1 to 6 carbon atoms
  • R m1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group
  • L m2 is a single bond or a divalent organic group
  • R m2 is a single bond, an alkylene group, or an alkylene group having an etheric oxygen atom
  • y is an integer of 2 or more
  • a plurality of R f s or R m2s may be the same or different.
  • the fluoroalkylene group for Rf has 3 to 6 carbon atoms
  • the fluoroalkylene group having 3 to 6 carbon atoms may be linear or may have a branched or cyclic structure.
  • Specific examples and preferred embodiments of (OR f ) y are the same as those of (OR f3 ) y1 in formula (1).
  • the alkyl group for R m1 has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.
  • the alkyl group having 3 or more carbon atoms may be linear or may have a branched or cyclic structure.
  • Examples of the divalent organic group in L m2 include a divalent aliphatic hydrocarbon group (such as an alkylene group or a cycloalkylene group) and a divalent aromatic hydrocarbon group (such as a phenylene group), of which a divalent aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
  • the number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
  • the divalent organic group for L m2 is an alkylene group having 3 or more carbon atoms
  • the alkylene group having 3 or more carbon atoms may be linear or branched.
  • Preferred embodiments of the alkylene group and the alkylene group having an etheric oxygen atom in R m2 are the same as those of R 2 in formula (1).
  • compound M1 include compounds represented by the following formula, where n is an integer of 1 or more.
  • Compound M1 can be produced, for example, by the method described in the Examples section below using the following compound M1-1 as a raw material.
  • R fm is a fluoroalkylene group having 1 to 6 carbon atoms
  • R m is a hydrogen atom or an alkyl group
  • ym is an integer of 1 or more
  • the fluoroalkylene group for R fm has 3 to 6 carbon atoms
  • the fluoroalkylene group having 3 to 6 carbon atoms may be linear or may have a branched or cyclic structure.
  • ym is 2 or more, specific examples and preferred embodiments of (OR fm ) ym are the same as those of (OR f3 ) y1 in formula (1).
  • the alkyl group for R m preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the alkyl group having 3 or more carbon atoms may be linear or may have a branched or cyclic structure.
  • ym is an integer of 1 or more, preferably 1 to 200, more preferably 1 to 150, and even more preferably 1 to 100.
  • compound M1-1 include the compound represented by the following formula:
  • Example 1 to 8 are working examples
  • Example 9 is a comparative example.
  • the present invention is not limited to these examples.
  • Example 8 ⁇ Synthesis of Compound 8-1> 0.50 g of compound 4-8, 0.035 g of potassium hydroxide aqueous solution, 0.039 g of benzyl alcohol, and 1.0 g of 1,3-bis(trifluoromethyl)benzene (AGC Seimi Chemical Co., Ltd.) were added to a 50 mL recovery flask equipped with a stirrer and stirred at 80° C. for 17 hours, after which 20 g of AC-2000 and 1.0 M hydrochloric acid aqueous solution were added and the liquids were separated. The resulting organic phase was concentrated with an evaporator and purified by column chromatography to obtain 0.30 g of compound 8-1. m in compound 8-1 was 7.
  • Example 9 The perfluoropolyether group-containing silane compound (F) described in WO 2019-151445 was used as compound 9.
  • ⁇ Method for measuring contact angle> The contact angle of about 2 ⁇ L of distilled water or n-hexadecane placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were taken at five different points on the surface of the surface layer, and the average value was calculated. The 2 ⁇ method was used to calculate the contact angle.
  • DM-500 manufactured by Kyowa Interface Science Co., Ltd.
  • ⁇ Abrasion resistance (steel wool)> For the surface layer, a reciprocating traverse tester (manufactured by KNT Co., Ltd.) was used in accordance with JIS L0849:2013 (ISO 105-X12:2001) to reciprocate steel wool Bonstar (#0000) 15,000 times at a pressure of 98.07 kPa and a speed of 320 cm/min, and then the water contact angle was measured by the above method. The smaller the decrease in water repellency (water contact angle) after friction, the smaller the decrease in performance due to friction and the more excellent the friction resistance.
  • the evaluation criteria are as follows. A (Excellent): The change in water contact angle after 15,000 reciprocating strokes is less than 2 degrees.
  • ⁇ Slip resistance> The dynamic friction coefficient of the surface layer against artificial skin (PBZ13001, manufactured by Idemitsu Technofine Co., Ltd.) was measured using a load-varying friction and wear test system (HHS2000, manufactured by Shinto Scientific Co., Ltd.) under the conditions of contact area: 3 cm x 3 cm, load: 0.98 N. The larger the dynamic friction coefficient, the more excellent the slip resistance.
  • the evaluation criteria are as follows. A (Excellent): Dynamic friction coefficient is 0.6 or more. B (Good): Dynamic friction coefficient is 0.5 or more and less than 0.6. C (Acceptable): Dynamic friction coefficient is 0.4 or more and less than 0.5. D (unacceptable): Dynamic friction coefficient is less than 0.4.
  • An artificial fingerprint liquid (a liquid consisting of oleic acid and squalene) was applied to the flat surface of a silicone rubber stopper, and then excess oil was wiped off with a nonwoven fabric (Bencotto (registered trademark) M-3, manufactured by Asahi Kasei Corporation) to prepare a fingerprint stamp.
  • the fingerprint stamp was placed on the surface layer and pressed with a load of 9.8 N for 10 seconds.
  • the haze of the area where the fingerprint was attached was measured with a haze meter and set as the initial value.
  • the area where the fingerprint was attached was wiped off with a load of 4.9 N using a reciprocating traverse tester (manufactured by KNT Corporation) equipped with tissue paper.
  • the haze value was measured for each reciprocating wipe, and the number of wipes at which the haze became 10% or less from the initial value was measured. The fewer the number of wipes, the easier it was to remove fingerprint stains, and the better the fingerprint stain wiping ability.
  • the evaluation criteria are as follows. A (Excellent): Wipe less than three times. B (Good): Wipe off 4 to 5 times. C (Acceptable): Wipe 6 to 8 times. D (Fail): Wiping was done more than 9 times.
  • An article having a surface layer containing Compound 1 is useful as, for example, an optical article, a touch panel, an anti-reflective film, an anti-reflective glass, a SiO 2 -treated glass, a reinforced glass, a sapphire glass, a quartz substrate, a mold metal, etc., which are used as parts of the following products.
  • Products car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.), copiers, personal computers (PCs), liquid crystal displays, organic electroluminescence displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.
  • PDAs personal digital assistants
  • portable audio players car audio, game devices
  • eyeglass lenses camera lenses, lens filters, sunglasses, medical equipment (gastroscopes, etc.)
  • copiers personal computers (PCs), liquid crystal displays, organic electroluminescence displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.

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Abstract

L'invention concerne : un composé, une composition et un agent de traitement de surface pouvant former une couche de surface ayant une excellente résistance à l'abrasion, une excellente aptitude à l'enlèvement des empreintes digitales et une excellente résistance au glissement ; un article ayant une couche de surface formée à partir du composé, etc ; et un procédé de production de l'article. L'invention concerne également un nouveau composé qui peut être utilisé dans la production du composé susmentionné.　Le composé selon la présente invention est représenté par la formule (1).　Formule (1) : Rf1-Rf2-(ORf3)y1-R1-L1-(R2-T1)x1. Rf1 est un groupe organique exempt d'atome de fluor contenant une structure cyclique ou un groupe hydrocarboné à chaîne en C3 ou supérieure, Rf2 est un groupe fluoroalkylène en C1-6, etc, Rf3 est un groupe fluoroalkylène en C1-6, R1 est un groupe alkylène en C1-20, etc, L1 est un groupe de valence 1 + x1, etc, R2 est un groupe alkylène, etc, T1 est un groupe réactif, y1 est un nombre entier supérieur ou égal à 2, et x1 est un nombre entier de 1 à 10.
PCT/JP2024/011434 2023-03-27 2024-03-22 Composé, composition, agent de traitement de surface, article et procédé de production d'article WO2024203923A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019039341A1 (fr) * 2017-08-22 2019-02-28 Ａｇｃ株式会社 Composé éther contenant du fluor, composition éther contenant du fluor, liquide de revêtement, article et procédé de fabrication de celui-ci
WO2019049753A1 (fr) * 2017-09-05 2019-03-14 Ａｇｃ株式会社 Composé éther contenant du fluor, composition et article
WO2020162371A1 (fr) * 2019-02-08 2020-08-13 Ａｇｃ株式会社 Composé éther fluoré, composition d'éther fluoré, liquide de revêtement, article ainsi que procédé de fabrication de celui-ci, et procédé de fabrication de composé fluoré

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019039341A1 (fr) * 2017-08-22 2019-02-28 Ａｇｃ株式会社 Composé éther contenant du fluor, composition éther contenant du fluor, liquide de revêtement, article et procédé de fabrication de celui-ci
WO2019049753A1 (fr) * 2017-09-05 2019-03-14 Ａｇｃ株式会社 Composé éther contenant du fluor, composition et article
WO2020162371A1 (fr) * 2019-02-08 2020-08-13 Ａｇｃ株式会社 Composé éther fluoré, composition d'éther fluoré, liquide de revêtement, article ainsi que procédé de fabrication de celui-ci, et procédé de fabrication de composé fluoré

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