WO2024038870A1 - Composé, composition, agent de traitement de surface, liquide de revêtement, article et procédé de fabrication d'un article - Google Patents

Composé, composition, agent de traitement de surface, liquide de revêtement, article et procédé de fabrication d'un article Download PDF

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WO2024038870A1
WO2024038870A1 PCT/JP2023/029585 JP2023029585W WO2024038870A1 WO 2024038870 A1 WO2024038870 A1 WO 2024038870A1 JP 2023029585 W JP2023029585 W JP 2023029585W WO 2024038870 A1 WO2024038870 A1 WO 2024038870A1
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group
compound
carbon atoms
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fluorine
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Japanese (ja)
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一麦 國府田
汐織 落合
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
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/18—Polycyclic halogenated hydrocarbons
    • C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic

Definitions

  • the present disclosure relates to compounds, compositions, surface treatment agents, coating liquids, articles, and methods for producing articles.
  • Fluorine-containing ether compounds containing fluorine atoms have excellent properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency, and are useful for electrical and electronic materials, It is used in a wide variety of fields such as 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, and is therefore suitable as a surface treatment agent.
  • a surface treatment agent containing a fluorine-containing ether compound has the ability to maintain its water and oil repellency even when the surface layer is repeatedly rubbed with fingers (friction resistance), and the ability to easily remove fingerprints attached to the surface layer by wiping. It is used in applications that require long-term maintenance of fingerprint stain removability, for example, as a surface treatment agent for members constituting the surface of touch panels that are touched by fingers, glasses lenses, and displays of wearable terminals.
  • Patent Document 1 proposes a surface treatment agent containing a specific fluorine-containing silane compound as a surface treatment agent for imparting water repellency, oil repellency, etc. and forming a durable surface treatment layer.
  • glass-coated casings are sometimes used for mobile devices such as smartphones and tablet terminals, and the above-mentioned surface treatment agent is sometimes used on the casing side.
  • wireless chargers are increasingly being used as chargers for mobile phones.
  • the surface layer formed by current surface treatment agents can be slippery, and there is a risk of the mobile device slipping off when being operated, placed on a desk, or on the wireless charger.
  • the present invention includes a compound, a composition, a surface treatment agent, a coating liquid, a surface layer formed from the compound, etc., which can form a surface layer that can suppress slipping while maintaining abrasion resistance and fingerprint stain removability.
  • the object of the present invention is to provide an article having excellent abrasion resistance, fingerprint stain removability, and slip-off prevention effect, and a method for manufacturing the article.
  • R f1 is a fluorine-containing alicyclic condensed ring which may have a hetero atom and may have a substituent
  • R 10 is a hydrogen atom, an alkyl group or fluoroalkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent
  • Ar is an aryl group that may have a substituent
  • X 2 is an alkali metal ion or ammonium ion
  • X 3 is a halide ion
  • X 4 is a halogen atom
  • R a1 is a hydrolyzable group or a hydroxyl group
  • R a11 is a hydrocarbon group
  • z1 is an integer from 1 to 3
  • the plurality of R 10 , R a1 or R a11 may be the same or different from each other.
  • a surface treatment agent comprising the compound of any one of [1] to [3] above or the composition of [4] above.
  • a coating liquid comprising the compound of any one of [1] to [3] above, or the composition of [4] above, and a liquid medium.
  • a method for manufacturing an article comprising forming a surface layer by a dry coating method using the surface treatment agent of [5] above.
  • a method for manufacturing an article comprising forming a surface layer by a wet coating method using the coating liquid of [6] above.
  • the present disclosure provides a compound, a composition, a surface treatment agent, a coating liquid, a surface layer formed from the compound, etc. that can form a surface layer that can suppress slipping while maintaining abrasion resistance and fingerprint stain removability.
  • the present invention provides an article with excellent abrasion resistance, fingerprint stain removability, and slip-off prevention effect, and a method for manufacturing the article.
  • FIG. 1 is a schematic cross-sectional view showing an example of an article of the present disclosure.
  • a (fluoro)alkyl group is a general term for an alkyl group and a fluoroalkyl group. This also applies to (fluoro)alkylene groups, etc.
  • the fluoroalkyl group is a general term for perfluoroalkyl groups and partial fluoroalkyl groups.
  • a perfluoroalkyl group means a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms.
  • a partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are substituted with a fluorine atom and has one or more hydrogen atoms. That is, a fluoroalkyl group is an alkyl group having one or more fluorine atoms.
  • “Reactive silyl group” is a general term for hydrolyzable silyl group and silanol group (Si-OH), and "hydrolyzable silyl group” refers to a group that can undergo a hydrolysis reaction to form a silanol group. means.
  • Organic group means a hydrocarbon group which may have a substituent and may have a heteroatom or other bond in the carbon chain.
  • Hydrocarbon group refers to an aliphatic hydrocarbon group (straight-chain alkylene group, branched alkylene group, cycloalkylene group, etc.), an aromatic hydrocarbon group (phenylene group, etc.), and a group consisting of a combination thereof.
  • Surface layer means a layer formed on the surface of a base material.
  • the “molecular weight” of the polyfluoroether chain is the number average molecular weight calculated by determining the number (average value) of oxyfluoroalkylene units based on the terminal group by 1 H-NMR and 19 F-NMR. " ⁇ " indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.
  • R f1 is a fluorine-containing alicyclic condensed ring which may have a hetero atom and may have a substituent
  • R 11 is 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
  • Compound 1 has a structure of a fluoropolyether chain, a linking group, and a reactive group in contact with the substrate surface, and a fluorine-containing alicyclic condensed ring is placed at the end of the fluoropolyether chain.
  • the reactive group side is likely to be arranged on the base material side. Since the reactive group has a strong chemical bond with the base material, the resulting surface layer has excellent wear resistance.
  • a fluoropolyether chain having a fluorine-containing alicyclic condensed ring at the end is arranged on the surface opposite to the base material. Therefore, the obtained surface layer has excellent water and oil repellency and fingerprint stain removability.
  • Compound 1 has a bulky fluorine-containing alicyclic condensed ring at the end of the fluoropolyether chain, compared to a surface treatment agent whose terminal end is a fluoroalkyl group, the fluoropolyether chain on the surface is It is presumed that the movement of the chain is restricted. As a result, the surface layer formed by Compound 1 has a high coefficient of friction. For these reasons, articles equipped with a surface layer obtained using Compound 1 can be prevented from sliding down while maintaining water and oil repellency and abrasion resistance (hereinafter also referred to as anti-slip properties or anti-slip properties). ).
  • R f1 is a fluorine-containing alicyclic condensed ring which may have a hetero atom or a substituent. Note that the alicyclic condensed ring is a residue having a bond bonding to R f2 or O. Compound 1 has excellent anti-slip properties because R f1 is an alicyclic condensed ring.
  • the condensed ring may be a two-ring condensed ring, a polycyclic condensed ring having three or more rings, or a bridged condensed ring.
  • Examples of the two-ring condensed ring include bicyclo[4.4.0]decane (formula (A1) below), bicyclo[2.2.1]heptane (formula (A2) below, norbornane), bicyclo[2. 2.2] octane (formula (A3) below), bicyclo[3.2.0]heptane (formula (A4) below), bicyclo[5.3.0]decane (formula (A5) below), bicyclo[3 .1.1] heptane (formula (A6) below), bicyclo[3.2.2]nonane, and the like.
  • polycyclic fused rings examples include tricyclo[7.4.0.0 2,7 ]tridecane (formula (A7) below), tricyclo[8.4.0.0 3,8 ]tetradecane (formula (A7) below), tricyclo[8.4.0.0 3,8 ]tetradecane (formula (A7) below), A8)), perhydrophenalene (formula (A9) below), tricyclo[3.3.1.1 3,7 ]decane (formula (A10) below, adamantane), perhydropyrene (formula (A11) below) etc.
  • the bridged condensed ring refers to a condensed ring including condensation other than ortho condensation, and includes, for example, the following formula (A2), formula (A3), formula (A10), and the like.
  • a bridged condensed ring is particularly preferred from the viewpoint of anti-slip properties.
  • the alicyclic condensed ring may be a heterocycle having a heteroatom in the skeleton.
  • heteroatoms include O, N, S, Si, and the like.
  • the alicyclic fused ring in R f1 has at least one fluorine atom. Containing fluorine atoms, it has excellent water and oil repellency and fingerprint stain removal properties.
  • the substituent is preferably a fluoroalkyl group, an oxyfluoroalkyl group, or an oxo group, and more preferably a perfluoroalkyl group.
  • the alicyclic condensed ring in R f1 has a bond that is bonded to R f2 or O.
  • the position of the bond is not particularly limited, but even in the case of a heterocycle, a carbon atom may have a bond. preferable.
  • Examples of the alicyclic condensed ring in R f1 include rings of the following formulas (A1) to (A11). Note that the carbon atom in the formula may be replaced with the above-mentioned heteroatom, and at least one of the hydrogen atoms in the formula may be substituted with fluorine and may be replaced with the above-mentioned substituent.
  • 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 may be linear or branched.
  • the number of carbon atoms in R f2 is preferably 1 to 6, more preferably 1 to 3, from the viewpoint of ease of synthesis.
  • fluoroalkyl group in R f2 include -CF 2 -, -CHF-, -CF 2 CF 2 -, -CF 2 CHF-, -CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 -, -CF 2 CHFCHF-, -CF 2 CF (CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, -CF 2 CHFCF 2 CF 2 -, -CF 2 CF (CF 3 )-CF 2 -, - Examples include CF 2 C(CF 3 ) 2 -CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 -, -CF 2 CF 2 CF 2 CF 2 CF 2 - , and the like.
  • R 11 may be a linear or branched fluoroalkylene group having 1 to 6 carbon atoms.
  • R f2 is preferably a single bond or a fluoroalkylene group having 1 to 6 carbon atoms and not having the above bond.
  • y1 is a fluoropolyether chain, and y1 is an integer of 1 or more.
  • the fluoropolyether chain in y1 preferably has a structure represented by the following formula (G1).
  • G f1 is a fluoroalkylene group having 1 carbon number
  • 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 an integer of 0 or 1 or more
  • m1+m2+m3+m4+m5+m6 y1 in formula (1)
  • the bonding order of (OG f1 ) to (OG f6 ) in formula (G1) is arbitrary.
  • m1 to m6 in formula (G1) represent the numbers of (OG f1 ) to (OG f6 ), respectively, 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 the respective units.
  • the above-mentioned fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group, or may be a fluoroalkylene group having a branched or ring structure.
  • G f1 examples include -CF 2 - and -CHF-.
  • G f2 examples include -CF 2 CF 2 -, -CHFCF 2 -, -CHFCHF-, -CH 2 CF 2 -, -CH 2 CHF-, and the like.
  • G f3 include -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 -, -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)-CF 2 -, -CF(CH 3
  • 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 -, -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 CHFCF 2 -, -CF 2 CHFCHF 2 -, -CHFCHFCF 2 -, -CH 2 CHFCHF 2 -, -CF 2 CH 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 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 -, -CF 2 CH 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 CF 2 CHFCF 2 CF 2 -, -CH 2 CF 2 CHFCF 2 CF 2 CH 2 -, -cycloC 5 F 8 - etc.
  • G F6 is -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- , -CHFCHFCHFCHFCHFCHFF- , -CHFCF 2 CF 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 perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group.
  • -cycloC 5 F 8 - means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group.
  • -cycloC 6 F 10 - means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.
  • (OR f2 ) y1 preferably has a structure represented by the following formulas (G2) to (G4) from the viewpoint of superior water and oil repellency, abrasion resistance, and fingerprint stain removability.
  • the symbols in formulas (G2) to (G4) are the same as in formula (G1) above.
  • m1 is preferably 1 to 50, more preferably 1 to 30.
  • m2 is preferably 1 to 50, more preferably 1 to 30.
  • m4 is preferably 1 to 50, more preferably 1 to 30.
  • m3 is preferably 1 to 50, more preferably 1 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, substantially 100%, That is, a perfluoropolyether chain is more preferred. If the fluorine atom content is 60% or more, the amount of fluorine in the fluoropolyether chain increases, and the slipperiness and fingerprint removability are further improved.
  • the ratio of fluorine atoms here is a value calculated using the following formula (I).
  • Formula (I): Percentage of fluorine atoms (%) (number of fluorine atoms) / ⁇ (number of fluorine atoms) + (number of hydrogen atoms) ⁇ x 100
  • R 1 is a single bond, a fluoroalkylene group having 1 to 20 carbon atoms, an alkylene group, or an alkylene group having an etheric oxygen atom.
  • R 1 is a single bond
  • R f3 located at the end of y1 has a structure in which it directly bonds with L 1 .
  • R 1 is an alkylene group
  • the alkylene group may be linear, branched, or have a ring structure, and may have an etheric oxygen atom between carbon atoms. May have.
  • R 1 is preferably a linear alkylene group from the viewpoint of wear resistance. Further, from the viewpoint of ease of synthesis, etc., the number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 1 to 3.
  • R 2 is a fluoroalkylene group
  • the alkylene group may be linear, branched, or have a ring structure.
  • L 1 is a 1+x1-valent group that may have a single bond or a heteroatom such as N, O, S, Si, etc., and may have a branch point.
  • the atoms bonded to R 1 and R 2 in L 1 are each independently an N, O, S, Si atom, or a carbon atom constituting a branch point.
  • R 1 and R 2 in formula (1) are directly bonded.
  • the present compound has a structure in which (OR f3 ) y1 and R 2 are directly bonded.
  • L 1 is a group with a valence of 3 or more
  • L 1 is at least one branch point (hereinafter referred to as “branch point P 1 ”).
  • N is a branch point P 1
  • the branch point P 1 is expressed, for example, by *-N(-**) 2 .
  • * is a bond on the R 1 side
  • ** is a bond on the R 2 side.
  • the branch point P 1 is represented by, for example, *-C(-**) 3 or *-CR 29 (-**) 2 .
  • * and ** are the same as when N is the branch point P1
  • R29 is a monovalent group, such as a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, and the like.
  • the branch point P 1 is represented by, for example, *-Si(-**) 3 or *-SiR 29 (-**) 2 .
  • * and ** are the same as when N becomes the branch point P 1
  • R 29 is the same as when C becomes the branch point P 1 .
  • the ring structure constituting the branch point P1 is a 3- to 8-membered aliphatic ring, a 3- to 8-membered aliphatic ring, and Preferably, one type selected from the group consisting of ⁇ 8-membered aromatic rings, 3- to 8-membered heterocycles, and fused rings consisting of two or more of these rings, and the ring structure listed in the following formula: is particularly preferred.
  • organopolysiloxane residue constituting the branch point P1 examples include the following groups.
  • R 25 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 25 is preferably 1 to 10, more preferably 1.
  • L 1 having a valence of two or more is -C(O)N(R 26 )-, -N(R 26 )C(O)-, -C(O)O-, -OC(O)-, -C( O)-, -O-, -N(R 26 )-, -S-, -OC(O)O-, -NHC(O)O-, -OC(O)NH-, -NHC(O)N (R 26 )-, -SO 2 N(R 26 )-, -N(R 26 )SO 2 -, -Si(R 26 ) 2 -, -OSi(R 26 ) 2 -, -Si(CH 3 ) It may have at least one bond (hereinafter referred to as "bond B 1 ") selected from the group consisting of 2 -Ph-Si(CH 3 ) 2 - and divalent organopolysiloxane residues.
  • bond B 1 bonds
  • R 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group.
  • the number of carbon atoms in the alkyl group of R 26 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing Compound 1.
  • Examples of the divalent organopolysiloxane residue include groups of the following formula.
  • R 27 in the following formula is a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group.
  • the number of carbon atoms in the alkyl group and alkoxy group of R 27 is preferably 1 to 10, more preferably 1.
  • the bond B 1 is a group consisting of -C(O)NR 26 -, -N(R 26 )C(O)-, -C(O)-, and -NR 26 -. At least one type of bond selected from -C(O)NR 26 -, -N(R 26 )C(O)- or -C( O)- is more preferred.
  • Specific examples of trivalent or higher L 1 include one or more branch points P 1 (for example, ⁇ *-P 1 (-**) x1 ⁇ ), one or more branch points P 1 and one or more bonds.
  • R 28 is a single bond or a divalent organic group
  • * is a bond on the R 1 side
  • ** is a bond on the R 2 side.
  • the atoms bonded to R 1 and R 2 are each independently an N, O, S, Si atom, or a carbon atom having an oxo group ( ⁇ O). That is, the atoms adjacent to R 1 and R 2 are each constituent elements of bond B 1 .
  • L 1 having a valence of two or more include a single bond, one or more bonds B 1 (for example, *-B 1 -**, *-B 1 -R 28 -B 1 -**), etc. It will be done.
  • 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.
  • Examples of the divalent organic group in R 28 include divalent aliphatic hydrocarbon groups (alkylene group, cycloalkylene group, etc.), divalent aromatic hydrocarbon groups (phenylene group, etc.), and carbon It may have a bond B 1 between two or more carbon atoms of a hydrocarbon group.
  • the number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
  • the above L 1 is preferably a group represented by any one of the following formulas (E1) to (E7) from the viewpoint of ease of manufacturing the present compound.
  • E 1 is a single bond, -B 5 -, -B 6 -R 40 -, or -B 6 -R 40 -B 5 -, and R 40 is an alkylene group or a group having 2 or more carbon atoms.
  • B 5 is -C(O)NR E6 -, -C(O)-, -NR E6 - or -O-
  • B 6 is -C(O)NR E6 -, -C(O)-, or -NR E6 -
  • E 2 is a single bond or -B 6 -R 40 -
  • E 3 is E 1 when the atom in Z 1 to which E 3 is bonded is a carbon atom, and is E 2 when the atom in Z 1 to which E 3 is bonded is a nitrogen atom
  • E 11 is a single bond, -O-, an alkylene group, or a bond between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR E6 -, -C(O)-, -NR
  • E 23 is a single bond or -R 40 -B 6 -, and two E 23s may be the same or different
  • E 24 is E 22 when the atom in Z 1 to which E 24 is bonded is a carbon atom
  • two or more E24s may be the same or different
  • E 25 is a single bond or -R 40 -B 6 -, and when it has two or more E 25s , two or more E 25s may be the same or different
  • E 26 is a single bond or -R 40 -B 6 -
  • Z 1 is a group having an (e4+1) valence ring structure having a carbon atom or nitrogen atom to which E 3 is directly bonded and a carbon atom or nitrogen atom to which E 24 is directly bonded
  • R E1 is a hydrogen atom or an alkyl group, and when it has two or more R E
  • the number of carbon atoms in the alkylene group of R 40 is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer. , 1 to 4 are more preferred. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
  • Examples of the ring structure in Z 1 include the ring structures described above, and preferred forms are also the same. Note that since E 24 is directly bonded to the ring structure in Z 1 , for example, an alkylene group is not 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 to 2, from the viewpoint of ease of manufacturing the present compound.
  • the number of carbon atoms in the alkyl group moiety of the acyloxy group in R E2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing Compound 1.
  • g4 is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3, from the viewpoint of ease of manufacturing the present compound and superior abrasion resistance and fingerprint stain removability of the surface layer.
  • L 1 include groups represented by any of the following formulas (E11) to (E17).
  • E G is represented by the following formula (E G ), and two or more E Gs included in L 1 may be the same or different.
  • the symbols other than G are the same as those in equations (E1) to (E7).
  • E 3 is a single bond or -R 45 -B 6 -, R 45 is an alkylene group, or -C(O)NR 46 - between the carbon atoms of the alkylene group having 2 or more carbon atoms, A group having -C(O)-, -NR 46 - or -O-, or -(OSi(R 24 ) 2 ) p -O-, and two or more E 3s may be the same or different. Good too. k is 2 or 3.
  • R 46 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • R 24 is an alkyl group, a phenyl group, or an alkoxy group, and two R 24s may be the same or different.
  • p is an integer from 0 to 5, and when p is 2 or more, two or more (OSi(R 24 ) 2 ) may be the same or different.
  • the number of carbon atoms in the alkylene group of E 3 is preferably 1 to 10, more preferably 1 to 6, from the viewpoint of easy production of the present compound and superior abrasion resistance, light resistance, and chemical resistance of the surface layer. , 1 to 4 are more preferred. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
  • the number of carbon atoms in the alkyl group of R 23 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
  • the number of carbon atoms in the alkyl group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of manufacturing the present compound.
  • the number of carbon atoms in the alkoxy group of R 24 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of excellent storage stability of the present compound.
  • p is preferably
  • R 2 is an alkylene group in which the atom bonded to L 1 may be an etheric oxygen atom and may have an etheric oxygen atom between carbon atoms, and when there is a plurality of R 2 s, there may be a plurality of R 2 s.
  • R 2 may be the same or different.
  • the R 2 is preferably a group represented by the following formula (H1).
  • R g11 is an alkylene group having 1 to 12 carbon atoms, and multiple R g11s may be the same or different from each other
  • R g12 is an alkylene group having 1 to 30 carbon atoms
  • a4 is 0 or 1
  • a5 is an integer greater than or equal to 0
  • * is a bond that connects L1
  • ** is a bond bonded 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 selected as appropriate from the viewpoint of ease of synthesis.
  • a5 is the repeating number of R g11 O, and from the viewpoint of durability as a surface layer, it is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1.
  • the alkylene group for R g11 may be any linear or branched alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.
  • the alkylene group is preferably a linear alkylene group.
  • the alkylene group for R g12 may be any linear or branched alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 2 to 20 carbon atoms.
  • the alkylene group of R g12 may have 1 to 12 carbon atoms, 1 to 10 carbon atoms, 2 to 6 carbon atoms, or 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 30 carbon atoms, R 44 is an alkylene group having 1 to 12 carbon atoms, and when there is a plurality of R 44s , the plurality of R 44s may be the same or different from each other, y3 is an integer greater than or equal to 0, * is a bond that binds to R f4 at the terminal of (OR f4 ) y3 .
  • R 43 when R 43 is a single bond, Compound 1 has a structure in which O at the terminal of (OR 44 ) y3 is directly bonded to R f4 at the terminal of (OR f4 ) y3 . Moreover, when y3 is 0, compound 1 has a structure in which R 43 is directly bonded to T 1 .
  • R 43 is a single bond or an alkylene group having 1 to 30 carbon atoms, preferably a single bond or an alkylene group having 1 to 12 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 6 carbon atoms.
  • R 44 is an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms.
  • the alkylene group in R 43 and R 44 is preferably a linear or branched alkylene group, more preferably a linear alkylene group.
  • T 1 is a reactive group, and the present compound exhibits various functions due to the reactivity of T 1 .
  • Such functions include, for example, the function of improving adhesion to the surface of the substrate, the function of imparting photocurability or thermosetting property to the present compound, the function of imparting acidity/alkalinity to the present compound, and the function of imparting specific properties of the present compound. Examples include a function to adjust solubility in a solvent, and a function as a precursor when synthesizing other compounds.
  • R 10 is a hydrogen atom, an alkyl group or fluoroalkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group which may have a substituent
  • Ar is an aryl group that may have a substituent
  • X 2 is an alkali metal ion or ammonium ion
  • X 3 is a halide ion
  • X 4 is a halogen atom
  • R a1 is a hydrolyzable group or a hydroxyl group
  • R a11 is a hydrocarbon group
  • z1 is an integer from 1 to 3
  • the plurality of R 10 , R a1 or R a11 may be the same or different from each other.
  • the fluoroalkyl group for R 10 preferably has 1 to 6 carbon atoms.
  • the fluoroalkyl group may have other substituents.
  • This compound, which has a fluoroalkyl group as T has a high fluorine content, and has various properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency. Excellent characteristics.
  • substituents that the fluoroalkyl group may have include halogen atoms such as fluorine atoms and chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and the same substituents as those exemplified as the functional group T. Things can be mentioned.
  • Examples of the aryl group for Ar and R10 include a phenyl group and a naphthyl group, and may further have a substituent.
  • substituents that the aryl group may have include halogen atoms such as fluorine atoms and chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and those similar to those exemplified as the functional group T. can be mentioned.
  • the alkyl group in R 10 preferably has 1 to 6 carbon atoms.
  • the alkyl group may have other substituents. Examples of substituents that the alkyl group may have include halogen atoms such as chlorine atoms, alkyl groups having 1 to 6 carbon atoms, and those similar to those exemplified as the functional group T. .
  • Reactive group T1 includes hydroxy group, N-hydroxy group, aldehyde group, ketone group, amino group, quaternary ammonium group, nitrile group, imino group, diazo group, carboxy group, carboxylate, acid anhydride group, sulfonate group, etc.
  • This compound having a group, a sulfonate, a phosphoric acid group, or a phosphate is endowed with various properties such as acidity, alkalinity, and hydrophilicity by the functional group T. It provides functions such as improved properties and adhesion to specific substrates.
  • Examples of the counter ion of the quaternary ammonium salt include halide ions.
  • Counter ions for carboxylates, sulfonates, and phosphates include alkali metal ions, ammonium ions, and the like.
  • Examples of the group having a carbon-carbon double bond include a vinyl group, an acryloyloxy group, a methacryloyloxy group, an olefin, and the like. This compound having a carbon-carbon double bond can be combined with a photoinitiator to prepare a photocurable composition, and the cured coating film obtained from the composition has water and oil repellency and hard coat properties. It has both.
  • this compound having an isocyanate group, an epoxy group, a glycidyl group, an oxetanyl group, or a mercapto group can be used in combination with an epoxy curing agent to prepare a thermosetting or photocurable composition, and the cured coating obtained from the composition can be used in combination with an epoxy curing agent.
  • the film has both water and oil repellency and hard coat properties.
  • the amide bond, ester bond, ether bond, thioether bond, siloxane bond, urea bond in the reactive group T1 is a bond that connects the alkyl group, fluoroalkyl group, aryl group, heteroaryl group, etc. contained in T. . It may also have other functionality-imparting groups via these bonds.
  • the reactive group T 1 of the present compound is preferably a hydroxyl group, an amino group, or a group having a carbon-carbon double bond from the viewpoint of synthesis, chemical stability, adhesion to a substrate, and the like. Furthermore, among the groups having a carbon-carbon double bond, an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an olefin is preferable.
  • T is preferably a group having one reactive silyl group.
  • a group represented by the following formula (2) is preferable.
  • R a1 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group
  • R a11 is a hydrocarbon group
  • z1 is an integer from 1 to 3
  • each of the multiple R a1 , R a11 , and z1 may be the same or different.
  • R a1 When R a1 is a hydroxyl group, it constitutes a silanol (Si-OH) group together with the Si atom.
  • a hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction.
  • the silanol groups further react intermolecularly to form Si--O--Si bonds. Further, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group (base material -OH) on the surface of the base material to form a chemical bond (base material -O-Si). Since Compound 1 has T 1 of 1 or more, it has excellent wear resistance after the surface layer is formed.
  • Examples of the hydrolyzable group for R a1 include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an isocyanate group (-NCO), and the like.
  • the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
  • the acyl group is preferably an acyl group having 1 to 6 carbon atoms.
  • the acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
  • the group having a hydrolyzable group for R a1 may be, for example, a group having a hydrolyzable group exemplified above.
  • the group having a hydrolyzable group is preferably -O-L A -L B.
  • L A is an alkylene group which may have an etheric oxygen atom
  • L B is a hydrolyzable group.
  • the alkylene group preferably has 1 to 10 carbon atoms.
  • the alkylene group represented by L A may have an ether oxygen atom between carbon atoms. The number of the etheric oxygen atoms may be 1 or 2 or more.
  • L A is an alkylene group having an etheric oxygen atom
  • the atom bonded to the -O- side in -OLA -L B is a carbon atom constituting the alkylene group having an etheric oxygen atom. It is preferable.
  • the hydrolyzable group represented by L B has the same meaning as the hydrolyzable group represented by R a1 , and the preferred embodiments are also the same.
  • R a1 is particularly 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, since the storage stability of compound 1 is excellent and outgas is suppressed during the reaction, and from the viewpoint of long-term storage stability, an ethoxy group is preferable. Particularly preferred is a methoxy group from the viewpoint of shortening the hydrolysis reaction time.
  • the 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, an allyl group, and the like, and 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 within one T 1 may be 1 to 3, preferably 2 or 3, and more preferably 3 from the viewpoint of adhesion to the base material.
  • Specific examples of T 1 include -Si(OCH 3 ) 3 , -SiCH 3 (OCH 3 ) 2 , -Si(OCH 2 CH 3 ) 3 , -SiCl 3 , -Si(OCOCH 3 ) 3 , -Si( NCO) 3 etc. From the viewpoint of ease of handling during production, -Si(OCH 3 ) 3 is particularly preferred.
  • the number x1 of T 1 in one molecule of compound 1 may be from 1 to 20, and from the viewpoint of ease of synthesis and ease of handling of compound 1, x1 is preferably from 1 to 12, and from 1 to 20. 6 is more preferred. When there are two or more T 1 's in one molecule of compound 1, the T 1 's may have the same structure or different structures.
  • T 1 having no reactive silyl group include the following structures.
  • R a represents an alkyl group, a fluoroalkyl group, or an aryl group that may have a substituent
  • R b represents a fluoroalkyl group, or an aryl group that may have a substituent.
  • * indicates a bond.
  • L 1 -(R 2 -T 1 ) x1 include groups represented by the following formulas. * indicates a bond.
  • ⁇ in the above (CH 2 ) ⁇ is an integer representing the number of methylene groups, preferably from 1 to 30, more preferably from 1 to 20, even more preferably from 2 to 20, may be from 2 to 10, and from 2 to 30. It may be 6. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
  • a plurality of ⁇ 's contained in the same compound may be the same or different, but are preferably the same. For example, all of the plurality of ⁇ s contained in the same compound are 2, 3, 8, 9, and 11.
  • Compound 1 examples include compounds represented by the following formula.
  • F in the condensed ring indicates that the condensed ring has a fluorine atom.
  • n and m are integers from 1 to 200.
  • Method for producing compound 1 Although the method for producing Compound 1 is not particularly limited, it will be explained by giving a specific example.
  • a method for adding the fluorine-containing alicyclic condensed ring R f1 to the fluoropolyether chain (OR f3 ) y1 for example, a compound represented by the following formula (3) and a compound represented by the following formula (4) are used. Examples include a method of reacting with a compound.
  • R f31 -D 1 ...Formula (3) D 2 -(OR f3 ) y1 -D 3 ...Formula (4) however, R f31 is a group containing an alicyclic condensed ring, D 1 is a group containing a group capable of reacting with D 2 , D2 is a group containing a group capable of reacting with D1 , 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, D 1 and D 2 are groups that become R f2 in formula (1) after the reaction, Other symbols are the same as those in formula (1) above.
  • the combination of D 1 and D 2 is not particularly limited, and includes, for example, a combination of a hydroxyl group and a carboxy group, a combination of hydroxyl groups, a combination of a hydroxyl group and an olefin, a combination of a hydroxyl group and a fluorine-containing olefin, and the like.
  • R f31 may be a fluorine-containing condensed ring, and may be fluorinated after the above reaction.
  • the compound-containing composition of the present disclosure (hereinafter also referred to as “the present composition”) contains Compound 1 and a fluorine-containing ether compound other than Compound 1. Further, it may contain both Compound 1 synthesized from Compound 3A and Compound 1 synthesized from Compound 3B. Note that this composition does not contain a liquid medium, which will be described later.
  • fluorine-containing ether compounds include both compounds that are unavoidably included and compounds that are used in combination depending on the application.
  • Compounds used in combination with 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 that are commercially available as surface treatment agents. When the present composition contains a known fluorine-containing ether compound, new effects such as supplementing the properties of Compound 1 may be exhibited.
  • Examples of known fluorine-containing ether compounds include those described in the following literature. perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No. 11-029585, Silicon-containing organic fluorine-containing polymer described in Japanese Patent No. 2874715, Organosilicon compounds described in Japanese Patent Application Publication No. 2000-144097, perfluoropolyether-modified aminosilane described in Japanese Patent Application Publication No.
  • 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, Examples include Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, and Optool (registered trademark) UD120 manufactured by Daikin Industries.
  • SURECO registered trademark 2101S manufactured by AGC
  • Examples include Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509, and Optool (registered trademark) UD120 manufactured by Daikin Industries.
  • the content ratio when Compound 1 is combined with a known fluorine-containing ether compound, the content ratio may be adjusted as appropriate depending on the application and the like.
  • the content of Compound 1 in the present composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 75% by mass. By setting it as the said range, while fully demonstrating the characteristic of the compound 1, the characteristic of the fluorine-containing ether compound used in combination can also be fully obtained.
  • Examples of compounds that are inevitably included include fluorine-containing ether compounds that are by-produced in the manufacturing process of Compound 1 (hereinafter also referred to as "by-product fluorine-containing ether compounds").
  • by-product fluorine-containing ether compounds include unreacted compounds (for example, compound 3 or compound 4), and fluorine-containing ethers in which a part of the allyl group isomerized to an inner olefin during hydrosilylation in the production of compound 1. Examples include compounds.
  • the by-product fluorine-containing ether compound can also be removed by purification. Further, it may be contained in the present composition within a range where the properties of Compound 1 can be fully exhibited. Thereby, the purification process of the by-product fluorine-containing ether compound can be simplified.
  • the content of Compound 1 in the present composition is preferably 60% by mass or more and less than 100% by mass, and 70% by mass or more and less than 100% by mass. More preferably, 80% by mass or more and less than 100% by mass are particularly preferred.
  • the content of the by-product fluorine-containing ether compound is preferably more than 0% by mass and not more than 40% by mass, more preferably more than 0% by mass and not more than 30% by mass, particularly more than 0% by mass and not more than 20% by mass. preferable.
  • the initial water and oil repellency, abrasion resistance, fingerprint stain removability, light resistance and chemical resistance of the surface layer will further improve. Excellent.
  • examples of compounds that are inevitably included include additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reactions of hydrolyzable silyl groups.
  • the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid.
  • the basic catalyst include sodium hydroxide, potassium hydroxide, and ammonia. The content of these in the present composition is preferably 0 to 9.999% by mass, particularly preferably 0 to 0.99% by mass.
  • the surface treatment agent containing Compound 1 (hereinafter also referred to as the present surface treatment agent) has the ability to prevent the water and oil repellency from decreasing even when the surface layer is repeatedly rubbed with fingers (friction resistance), and to improve the surface layer by wiping.
  • the coating liquid of the present disclosure (hereinafter also referred to as the present coating liquid) contains Compound 1 and a liquid medium.
  • the present coating liquid may be in a liquid form, and may be a solution or a dispersion.
  • the present coating liquid only needs to contain Compound 1, and may contain impurities such as by-products generated in the manufacturing process of Compound 1.
  • the concentration of Compound 1 in the present coating liquid is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass.
  • an organic solvent is preferred.
  • the organic solvent may be a fluorine-containing organic solvent, a non-fluorine organic solvent, or may contain both solvents.
  • the fluorine-containing organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and the like.
  • the fluorinated alkane compounds having 4 to 8 carbon atoms are preferred.
  • C 6 F 13 H manufactured by AGC Corporation, Asahiklin (registered trademark) AC-2000
  • C 6 F 13 C 2 H 5 manufactured by AGC Corporation, Asahiklin (registered trademark) AC-6000
  • C 2 F 5 CHFCHFCF 3 manufactured by Chemours, Bartrel (registered trademark) XF
  • fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene.
  • fluoroalkyl ether compounds having 4 to 12 carbon atoms are preferred.
  • CF 3 CH 2 OCF 2 CF 2 H manufactured by AGC, Asahiklin (registered trademark) AE-3000
  • C 4 F 9 OCH 3 manufactured by 3M, Novec (registered trademark) 7100
  • C 4 F 9 OC 2 H 5 manufactured by 3M Company, Novec (registered trademark) 7200
  • C 2 F 5 CF OH 3 )C 3 F 7
  • fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
  • fluoroalcohol examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.
  • non-fluorine organic solvents compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferable, such as hydrocarbon-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, Examples include ether organic solvents and ester organic solvents.
  • the present coating liquid preferably contains 75 to 99.999% by mass of the liquid medium, more preferably 85 to 99.99% by mass, and even more preferably 90 to 99.9% by mass.
  • the present coating liquid may contain other components as long as the effects of the present disclosure are not impaired.
  • other components include known additives such as acid catalysts and basic catalysts that promote hydrolysis and condensation reactions of hydrolyzable silyl groups.
  • the content of other components in this coating liquid is preferably 10% by mass or less, more preferably 1% by mass or less.
  • the total concentration of Compound 1 and other components (hereinafter also referred to as solid content concentration) of this coating liquid is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and 0.01% by mass. It is more preferably from 10% by weight, and particularly preferably from 0.01 to 1% by weight.
  • the solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating in a convection dryer at 120° C. for 4 hours.
  • FIG. 1 is a schematic cross-sectional view showing an example of the article of the present disclosure.
  • a first article of the present disclosure is an article 20 having a base material 12, a base layer 14, and a surface layer 22 in this order, wherein the base layer 14 contains an oxide containing silicon, and the surface layer 22 contains a condensate of the present composition.
  • the material and shape of the base material 12 in the first article may be appropriately selected depending on the use of the article 20, etc.
  • Examples of the material of the base material 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof.
  • the glass may be chemically strengthened.
  • examples of the base material 12 required to have water and oil repellency include base materials for touch panels, base materials for displays, and base materials constituting the housings of electronic devices.
  • the base material for a touch panel and the base material for a display have translucency. "Having light transmittance" means that the perpendicular incidence type visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more.
  • As the material for the touch panel base material glass or transparent resin is preferable.
  • the surface of the base material 12 on which the base layer 14 is provided may be subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc.
  • surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc.
  • the surface that has been subjected to surface treatment has even better adhesion between the base material 12 and the base layer 14, and as a result, the abrasion resistance of the surface layer 22 is further improved.
  • corona discharge treatment or plasma treatment is preferable since the wear resistance of the surface layer 22 is further excellent.
  • the base layer 14 is a layer containing at least an oxide containing silicon, and may further contain other elements. Since the base layer 14 contains silicon oxide, T1 of the present composition is dehydrated and condensed, and Si-O-Si bonds are formed with the base layer 14, resulting in a surface layer 22 having excellent wear resistance. It is formed.
  • the content of silicon oxide in the base layer 14 may be 65% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.
  • the content of silicon oxide is the remainder obtained by subtracting the total content of other elements (in the case of oxides, the amount converted into oxides) from the mass of the base layer 14.
  • the oxides in the base layer 14 further include alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, and chromium. , molybdenum, and tungsten. By containing these elements, the bond between the base layer 14 and the present composition is strengthened, and wear resistance is improved.
  • the base layer 14 contains one or more selected from iron, nickel, and chromium
  • the total content thereof is preferably 10 to 1,100 ppm by mass relative to silicon oxide, and 50 to 1,100 mass ppm. ppm is more preferable, even more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass.
  • the base layer 14 contains one or more selected from aluminum and zirconium
  • the total content thereof is preferably 10 to 2,500 ppm by mass, more preferably 15 to 2,000 ppm by mass, and 20 to 2,000 ppm by mass. More preferably 1,000 ppm by mass.
  • the base layer 14 contains an alkali metal element
  • the total content thereof is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and further preferably 1.0 to 10% by mass. preferable.
  • examples of the alkali metal elements include lithium, sodium, potassium, rubidium, and cesium.
  • platinum group elements the total content thereof is preferably 0.02 to 800 mass ppm, more preferably 0.04 to 600 mass ppm, and still more preferably 0.7 to 200 mass ppm. preferable.
  • platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium.
  • the base layer 14 contains one or more selected from boron and phosphorus
  • the total content of these is the sum of boron and phosphorus relative to the molar concentration of silicon, from the viewpoint of wear resistance of the surface layer 22.
  • the molar concentration ratio is preferably 0.003 to 9, preferably 0.003 to 2, and more preferably 0.003 to 0.5.
  • the base layer 14 contains alkaline earth metal elements
  • the total content of these elements is determined by the total molar concentration of the alkaline earth metal elements relative to the molar concentration of silicon, from the viewpoint of wear resistance of the surface layer 22.
  • the ratio is preferably 0.005 to 5, preferably 0.005 to 2, and more preferably 0.007 to 2.
  • examples of the alkaline earth metal elements include lithium, sodium, potassium, rubidium, and cesium.
  • the base layer 14 is preferably a silicon oxide layer containing alkali metal atoms.
  • the average concentration of alkali metal atoms in a region with a depth of 0.1 to 0.3 nm from the surface in contact with the surface layer 22 is 2.0 ⁇ 10 19 atoms/cm 3 or more. It is preferable that there be.
  • the average concentration of the alkali metal atoms is preferably 4.0 ⁇ 10 22 atoms/cm 3 or less.
  • the thickness of the base layer 14 is preferably 1 to 200 nm, particularly preferably 2 to 20 nm. If the thickness of the base layer 14 is at least the lower limit of the above range, the effect of improving the adhesion by the base layer 14 is likely to be sufficiently achieved. If the thickness of the base layer 14 is less than or equal to the upper limit of the above range, the wear resistance of the base layer 14 itself will be high. Examples of methods for measuring the thickness of the base layer 14 include a method of observing a cross section of the base layer 14 using an electron microscope (SEM, TEM, etc.), a method using an optical interference film thickness meter, a spectroscopic ellipsometer, a step meter, etc. .
  • Examples of the method for forming the base layer 14 include a method of depositing a vapor deposition material having a desired composition of the base layer 14 onto the surface of the base material 12.
  • An example of the vapor deposition method is a vacuum vapor deposition method.
  • the vacuum evaporation method is a method in which a evaporation material is evaporated in a vacuum chamber and adhered to the surface of the base material 12.
  • the temperature during vapor deposition eg, the temperature of the boat on which the vapor deposition material is placed when using a vacuum vapor deposition apparatus
  • the temperature during vapor deposition is preferably 100 to 3,000°C, particularly preferably 500 to 3,000°C.
  • the pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the absolute pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, particularly preferably 0.1 Pa or less.
  • one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.
  • Methods for evaporating the evaporation material include the resistance heating method, in which the evaporation material is melted and evaporated on a resistance heating boat made of high-melting point metal, and the evaporation material is irradiated with an electron beam to directly heat the evaporation material, melting the surface.
  • the electron gun method which evaporates the gas.
  • the method of evaporating the evaporation material is that it is possible to evaporate high-melting point substances because it can be locally heated, and because the area not hit by the electron beam is at a low temperature, there is no risk of reaction with the container or contamination with impurities. Gun law is preferred.
  • the evaporation material used in the electron gun method is preferably a molten granule or a sintered material because it is less likely to scatter even if an air current is generated.
  • the surface layer 22 on the base layer 14 contains a condensate of the compounds contained in the present composition.
  • a silanol group (Si-OH) is formed by a hydrolysis reaction of the hydrolyzable silyl group in the compound contained in the present composition, and a silanol group (Si-OH) is formed by a condensation reaction between molecules.
  • -O-Si bonds are formed, and the silanol groups in compound 1 undergo a condensation reaction with the silanol groups or Si-OM groups (where M is an alkali metal element) on the surface of the underlayer 14. Including those in which Si--O--Si bonds are formed.
  • the surface layer 22 may 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 where some 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, particularly preferably 1 to 50 nm. If the thickness of the surface layer 22 is at least the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. If the thickness of the surface layer 22 is less than or equal to the upper limit of the above range, the utilization efficiency is high.
  • the thickness of the surface layer 22 is the thickness obtained with an X-ray diffractometer for thin film analysis.
  • the thickness of the surface layer 22 can be calculated from the vibration period of the interference pattern obtained by obtaining an interference pattern of reflected X-rays by the X-ray reflectance method using an X-ray diffractometer for thin film analysis.
  • a second article of the present disclosure is an article 20 having a base layer-coated base material 10 and a surface layer 22 in this order, wherein the base layer-coated base material 10 contains an oxide containing silicon, and the surface layer No. 22 contains the condensate of the present composition.
  • the wear resistance of the surface layer 22 is improved even if the surface layer 22 is directly formed on the base material 10 with a base layer. Excellent in sex.
  • the material of the base layer-attached base material 10 in the second article may be any material as long as it has the composition of the base layer 14, and may be, for example, a glass base material.
  • the details of the material of the base layer-attached base material 10 are the same as those of the base material 12 and the base layer 14, so a detailed description thereof will be omitted here. Further, since the structure of the surface layer 22 is also the same as that of the first article, a description thereof will be omitted here.
  • a method for manufacturing an article according to the present disclosure is a method of forming a surface layer by a dry coating method or a wet coating method using the compound 1, the surface treatment agent, or the coating liquid.
  • Compound 1 and the present surface treatment agent can be used as they are in the dry coating method. Further, the present composition and the present surface treatment agent are suitable for forming a surface layer with excellent adhesion by a dry coating method. Examples of the dry coating method include vacuum deposition, CVD, and sputtering. A vacuum evaporation method is preferably used from the viewpoint of suppressing decomposition of the present composition and the simplicity of the apparatus. For vacuum deposition, a pellet-like substance in which the present composition is supported on a metal porous body made of a metal material such as iron or steel may be used. A pellet-like substance supporting the present composition can be produced by impregnating a porous metal body with a solution of the present composition and drying to remove the liquid medium. The present coating liquid can be used as the solution of the present composition.
  • This coating liquid can be suitably used in a wet coating method.
  • Wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, casting, Langmuir-Blodgett, and gravure. Examples include the coating method.
  • an operation may be performed to promote the reaction between the present composition and the base material, if necessary.
  • Such operations include heating, humidification, light irradiation, and the like.
  • a hydrolysis reaction of hydrolyzable groups, a reaction between hydroxyl groups, etc. on the surface of the base material and silanol groups, and a condensation reaction of silanol groups are performed. It can promote reactions such as the formation of siloxane bonds.
  • compounds in the surface layer that are not chemically bonded to other compounds or the base material may be removed as necessary. Specific methods include, for example, a method in which a solvent is poured onto the surface layer, a method in which the surface layer is wiped off with a cloth impregnated with a solvent, and the like.
  • Example 2 ⁇ Synthesis of compound (2-1)> Instead of compound (1-2) in Example 1, 1,3,3,4,5,5,6,6,7,7-Decafluorobicyclo[2.2.1]heptan-2-ol was used, The following compound (2-1) was obtained by synthesis in the same manner as in Example 1.
  • Example 8 According to Synthesis Examples 1 to 3 of JP-A-2017-82194, a perfluoropolyether group-containing silane compound (8-1) shown below was obtained. CF 3 O (CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 C (CH 2 OCH 2 CH 2 CH 2 Si(OMe) 3 ) 3 . ⁇ (8-1)
  • the substrates were surface-treated using each of the compounds obtained in Examples 1 to 8 to obtain articles 1 to 8.
  • the surface treatment method the following dry coating method and wet coating method were used for each example. Chemically strengthened glass was used as the base material.
  • the obtained articles 1 to 8 were evaluated by the following method. The results are shown in Table 1.
  • the dry coating was performed using a vacuum evaporation device (VTR350M, manufactured by ULVAC) (vacuum evaporation method).
  • VTR350M vacuum evaporation device
  • 0.5 g of each compound obtained in Examples 1 to 8 was filled into a molybdenum boat in a vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 1 ⁇ 10 ⁇ 3 Pa or less.
  • the boat containing the compound is heated at a temperature increase rate of 10°C/min or less, and when the deposition rate exceeds 1 nm/sec using a crystal oscillation film thickness meter, the shutter is opened to form a film on the surface of the substrate. started.
  • the shutter was closed to complete the film formation on the surface of the substrate.
  • the base material on which the compound was deposited was heat-treated at 200°C for 30 minutes, and washed with C 6 F 13 H (manufactured by AGC Corporation, Asahi Clean (registered trademark) AC-2000) to coat the surface of the base material. An article having layers was obtained.
  • Articles with a surface layer containing Compound 1 include, for example, optical articles used as parts of the following products, touch panels, antireflection films, antireflection glass, SiO 2 treated glass, tempered glass, and sapphire glass. It is useful as a quartz substrate, mold metal, etc.
  • Products Car navigation, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastrocameras, etc.) ), copying machines, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, anti-reflection glass, nanoimprint templates, molds, etc.
  • Base material with base layer 12 Base material 14: Base layer 20: Article 22: Surface layer

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Abstract

L'invention concerne : un composé ayant une excellente résistance à l'abrasion et une excellente résistance au glissement ; une composition ; un agent de traitement de surface ; un liquide de revêtement ; un article ; et un procédé de production dudit article.　Le composé selon la présente divulgation est représenté par la formule (1).　Formule (1) : Rf1-Rf2-(ORf3)y1-R1-L1(-R2-T1)x1. Rf1 étant un cycle aliphatique qui peut avoir un hétéroatome et peut avoir un groupe substituant, Rf2 étant un groupe fluoroalkylène ayant de 1 à 6 atomes de carbone ou un groupe fluoroalkylène ayant de 1 à 6 atomes de carbone et qui peut avoir -NR11-, -C(=O)-, -C(=O)NR11- ou C(=O)-O- dans une liaison carbone-carbone, Rf3 étant un groupe fluoroalkylène ayant de 1 à 6 atomes de carbone, et T1 étant un groupe réactif. De plus, les symboles dans la formule autres que ceux mentionnés ci-dessus sont tels que définis dans la description.
PCT/JP2023/029585 2022-08-18 2023-08-16 Composé, composition, agent de traitement de surface, liquide de revêtement, article et procédé de fabrication d'un article WO2024038870A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008239701A (ja) * 2007-03-26 2008-10-09 Asahi Glass Co Ltd 表面処理された基材の製造方法
JP2017082194A (ja) * 2015-07-31 2017-05-18 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008239701A (ja) * 2007-03-26 2008-10-09 Asahi Glass Co Ltd 表面処理された基材の製造方法
JP2017082194A (ja) * 2015-07-31 2017-05-18 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物

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