WO2023167197A1 - Article et son procédé de fabrication, et agent de traitement de surface - Google Patents

Article et son procédé de fabrication, et agent de traitement de surface Download PDF

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Publication number
WO2023167197A1
WO2023167197A1 PCT/JP2023/007367 JP2023007367W WO2023167197A1 WO 2023167197 A1 WO2023167197 A1 WO 2023167197A1 JP 2023007367 W JP2023007367 W JP 2023007367W WO 2023167197 A1 WO2023167197 A1 WO 2023167197A1
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group
independently
formula
integer
groups
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PCT/JP2023/007367
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English (en)
Japanese (ja)
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礼奈 森安
悟 波北
孝史 野村
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ダイキン工業株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present disclosure relates to an antifouling article, a method for producing the same, and a surface treatment agent.
  • Patent Documents 1 and 2 a primer layer and an antifouling layer are provided on the base material in order to impart antifouling properties to the organic base material.
  • An object of the present disclosure is to provide an article having a surface treatment layer with excellent weather resistance and abrasion resistance, a method for producing the same, and a surface treatment agent.
  • the present disclosure includes the following aspects.
  • an organic substrate a primer layer formed from a primer containing a coupling agent having an organic reactive group and a hydrolyzable silyl group in one molecule, located on the organic substrate; a surface treatment layer formed from a surface treatment agent containing a fluoropolyether group-containing silane compound ⁇ located immediately above the primer layer,
  • the fluoropolyether group-containing silane compound ⁇ is The following formula ( ⁇ 1) or formula ( ⁇ 2): [In the formula, R 1 is a monovalent organic group containing a polyether chain, R 1' is a divalent organic group containing a polyether chain, X 1 is each independently a silane-containing reactive cross-linking group, Each X 2 is independently a monovalent group.
  • R21 is OCF2 or OC2F4 ;
  • R 22 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or 2 independently selected from these groups or a combination of three groups, g is an integer from 2 to 100; ]; —(R 21 —R 22 ) g —R r —(R 22′ —R 21′ ) g′ — (f4)
  • R 21 is OCF 2 or OC 2 F 4 ;
  • R 22 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or 2 independently selected from these groups or a combination of three groups
  • R 21′ is OCF 2 or OC 2 F 4 ;
  • R 22′ is a group selected from OC 2 F 4 , OC 3 F 6
  • f is an integer of 1 or more and 200 or less
  • a, b, c, d and e are each independently an integer of 0 or more and 200 or less
  • the order of existence of each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula.
  • X 1 is the following formula: -L 1 - ⁇ Si(R a ) s (R b ) t (R c ) u (R d ) v ⁇ n
  • L 1 is a single bond or a divalent linking group
  • R a , R b and R c each independently represents a halogen, an alkoxy group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an acetoxy group having 1 to 10 carbon atoms, or an acetoxy group having 1 to 10 carbon atoms.
  • the organic reactive group of the coupling agent is at least one selected from the group consisting of amino group, glycidyl group, epoxy group, vinyl group, methacrylic group, acrylic group, styryl group, phenyl group, isocyanate group and mercapto group.
  • the surface treatment agent further contains a crosslinkable compound,
  • the crosslinkable compound has the following formula (Q1): A[Z q1 -M q (OR q1 ) wn1 (R q2 ) wn2-wn1 ] wa1 [Z q2 -R q3 ] wa2 (Q1)
  • A is a monovalent to decavalent organic group
  • Z q1 is each independently a single bond or a divalent organic group
  • M q is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr, or Zn
  • each R q1 is independently a hydrogen atom or a C 1-6 alkyl group
  • each R q2 is independently a hydrogen atom or a hydrocarbon group
  • M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr, or Zn; each R q is independently a hydrogen atom, a C 1-6 alkyl group, or R q1 —CO—; R q1 is a monovalent hydrocarbon group; each R q′ is independently a C 1-3 alkyl group or a C 1-3 alkoxy group; mq is the valence of said M; nq is 0 or more and the valence of M or less.
  • the fluoropolyether group-containing silane compound ⁇ is The following formula ( ⁇ 1) or formula ( ⁇ 2): [In the formula, R 1 is a monovalent organic group containing a polyether chain, R 1' is a divalent organic group containing a polyether chain, X 1 is each independently a silane-containing reactive cross-linking group, Each X 2 is independently a monovalent group.
  • an article having a surface treatment layer with excellent weather resistance and wear resistance, a method for producing the same, and a surface treatment agent are provided.
  • An article of one embodiment of the present disclosure comprises an organic substrate, a primer layer located on the organic substrate, and a surface treatment layer located directly on the primer layer.
  • the primer layer is formed from a primer containing a coupling agent having an organic reactive group and a hydrolyzable silyl group in one molecule.
  • the surface treatment layer is formed from a surface treatment agent containing a fluoropolyether group-containing silane compound ⁇ (hereinafter sometimes referred to as a PFPE silane compound ⁇ ) represented by the above formula (formula ( ⁇ 1) or formula ( ⁇ 2)). It is formed.
  • Organic substrate is not particularly limited as long as at least part of the region where the primer layer is formed is made of an organic material.
  • Organic materials include, for example, natural resins, synthetic resins, elastomers, rubbers, and fibers (eg, natural fibers, synthetic fibers, regenerated fibers).
  • organic substrates include hard-coated inorganic/organic substrates, painted inorganic/organic substrates, and fiber fabrics (eg, woven fabrics and non-woven fabrics).
  • Examples of synthetic resins include polycarbonate resins, poly(meth)acrylate resins, polyethylene terephthalate resins, triacetyl cellulose resins, polyimide resins, modified (transparent) polyimide resins, polycycloolefin resins, and polyethylene naphthalate resins.
  • the organic material may be polycarbonate resin.
  • Examples of rubber include nitrile rubber, hydrogenated nitrile rubber, ethylene propylene rubber, chloroprene rubber, acrylic rubber, urethane rubber, butyl rubber, natural rubber, fluororubber, and silicone rubber.
  • the shape of the organic substrate is not particularly limited, and may be, for example, plate-like, film, or other forms.
  • the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article.
  • the surface of the organic base material may have hydroxyl groups. Hydroxyl groups may be introduced onto the surface of the organic base material by plasma treatment (for example, corona discharge) or ion beam irradiation.
  • the surface of the organic substrate may have silanol groups. A silanol group is generated when the hydrolyzable silyl group of the coupling agent contained in the primer is hydrolyzed. When the hydroxyl groups or silanol groups on the surface of the organic base material react with the silanol groups of the coupling agent, dehydration condensation can occur to form strong chemical bonds.
  • a primer layer is located on the organic substrate.
  • the primer layer enhances adhesion between the organic substrate and the surface treatment layer.
  • the thickness of the primer layer is not particularly limited. From the viewpoint of adhesion, the thickness of the primer layer may be, for example, 1 nm or more, or 5 nm or more. The thickness of the primer layer may be, for example, 50 nm or less, or 30 nm or less. In one aspect, the thickness of the primer layer is 1 nm or more and 50 nm or less.
  • a primer layer is formed from a primer.
  • a primer contains a coupling agent having an organic reactive group and a hydrolyzable silyl group in one molecule.
  • the concentration of the coupling agent may be, for example, 0.05% by mass or more, 0.1% by mass or more, or 0.5% by mass or more with respect to 100% by mass of the primer. .
  • the concentration of the coupling agent may be, for example, 20% by mass or less, 10% by mass or less, or 5% by mass or less. In one aspect, the concentration of the coupling agent is, for example, 0.05% by mass or more and 20% by mass or less with respect to 100% by mass of the primer.
  • a coupling agent has an organic reactive group and a hydrolyzable silyl group in one molecule. These functional groups respectively react with the PFPE silane compound ⁇ and/or the functional groups on the surface of the organic substrate to enhance the adhesion between the surface treatment layer and the organic substrate.
  • organic reactive group there may be one organic reactive group (for example, at least one of the groups "A" in the general formula of the coupling agent described below) in one molecule of the coupling agent, or there may be two or more.
  • the organic reactive group is not particularly limited. Examples of organic reactive groups include at least one selected from the group consisting of amino groups, glycidyl groups, epoxy groups, vinyl groups, methacryl groups, acryl groups, styryl groups, phenyl groups, isocyanate groups and mercapto groups. .
  • the multiple organic reactive groups may be the same or different.
  • the organic reactive group may be an amino group.
  • the hydrolyzable group (for example, (for example, at least one of the groups “B” in the general formula of the coupling agent described below and forming a hydrolyzable silyl group together with the adjacent Si atom) is the coupling agent There may be one in one molecule, there may be two or more, and there may be three.
  • the hydrolyzable group is not particularly limited as long as it is hydrolyzed to form a silanol group together with the adjacent Si atom
  • the hydrolyzable group includes, for example, an alkoxy group, an acetoxy group and a chlorine atom.
  • the hydrolyzable group may be an alkoxy group.
  • the alkoxy group may have 1 to 5 carbon atoms. to 3, and may be 1 or 2.
  • the coupling agent may have two or more alkoxy groups having 1 to 5 carbon atoms bonded to Si. and may be heterogeneous
  • the carbon chain of the alkoxy group may be linear or branched.
  • hydrolyzable silyl group examples include a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a tris(2-methoxyethoxy)silyl group, a dimethoxyalkylsilyl group, a diethoxyalkylsilyl group, a di Examples include propoxyalkylsilyl groups and bis(2-methoxyethoxy)alkylsilyl groups.
  • a hydrolyzable silyl group may be at least one of a trimethoxysilyl group and a triethoxysilyl group.
  • the coupling agent is, for example, the following general formula: (AR CP ) 4-ns -Si-B ns (Wherein, at least one of A is the above organic reactive group, at least one of B is the above hydrolyzable group, and each R CP is independently a single bond or a divalent organic group and ns is an integer from 1 to 3.) is represented by
  • —Si—B ns constitutes a hydrolyzable silyl group.
  • a other than the organic reactive group may be, for example, a hydrogen atom.
  • B other than the hydrolyzable group may be, for example, a hydrocarbon group.
  • ns may be 2 or more and may be 3.
  • R CP is a single bond or a divalent organic group, and may be a divalent organic group.
  • R CP is, for example, a C 1-6 alkylene group, —(CH 2 ) cp1 —O—(CH 2 ) cp2 — (cp1 is an integer of 1 to 6, cp2 is an integer of 1 to 6, ), or -phenylene-(CH 2 ) cp3 - (cp3 is an integer of 0 to 6).
  • R CP may be a C 1-3 alkylene group, may be a C 2-3 alkylene group, or may be -CH 2 CH 2 CH 2 -. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
  • Examples of coupling agents include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxysilane.
  • propyltriethoxysilane 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, sidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysi
  • the primer may further contain other additives.
  • Other additives include, for example, thickeners, leveling agents, defoamers, antistatic agents, antifog agents, UV absorbers, radical scavengers, pigments, dyes and fillers.
  • the primer may contain at least one of an ultraviolet absorber and a radical scavenger.
  • ultraviolet absorbers examples include benzophenone-based compounds, benzotriazole-based compounds, triazine-based compounds, radically polymerizable compounds, and inorganic compounds.
  • the UV absorber may be a triazine-based compound.
  • Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octo xybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4 -methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-benzoyl-2,4- dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, 4,6-dibenzo
  • Benzotriazole-based UV absorbers include, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-( 2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di -tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis( ⁇ , ⁇ '-dimethylbenzyl)phenyl]benzotriazole), 2-(2'-hydroxy-3'- tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy
  • triazine-based UV absorbers examples include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazines.
  • radically polymerizable ultraviolet absorbers examples include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-diethoxy)benzophenone, 2-hydroxy-4-(acryloxy-triethoxy) Benzophenone, 2-(2′-hydroxy-5′-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, 2-(2′-hydroxy-5′-methacrylyloxypropyl-3-tert- butylphenyl)-5-chloro-2H-benzotriazole.
  • inorganic UV absorbers examples include cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, and titanium oxide.
  • radical scavengers examples include hindered amine compounds.
  • hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethylpiperidyl)sebacate, bis(1,2 , 2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, 1-[2-[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6 -tetramethylpiperidine, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • the (total) concentration of the ultraviolet absorber and/or radical scavenger is, for example, 1% by mass or more, may be 2% by mass or more, or is 3% by mass or more with respect to 100% by mass of the primer. good.
  • the (total) concentration of the ultraviolet absorber and/or radical scavenger is, for example, 10% by mass or less, may be 8% by mass or less, or 6% by mass or less with respect to 100% by mass of the primer. good.
  • the (total) concentration of the ultraviolet absorber and/or radical scavenger is 1% by mass or more and 10% by mass or less with respect to 100% by mass of the primer.
  • Organic solvent The primer may be diluted with an organic solvent.
  • the organic solvent is not particularly limited. Examples of organic solvents include lower alcohols such as ethanol, butanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; aromatic hydrocarbons such as xylene and toluene. n-hexane, n-hebutane, and other aliphatic hydrocarbons; ethyl acetate, butyl acetate, and other esters.
  • the surface treatment layer is positioned directly above the primer layer.
  • the surface treatment layer imparts antifouling performance to the organic substrate. Since the surface treatment layer used in the present disclosure is excellent in wear resistance and weather resistance, antifouling performance is maintained even when used for a long period of time under severe environmental conditions outdoors.
  • the thickness of the surface treatment layer is not particularly limited. From the viewpoint of wear resistance and weather resistance, the thickness of the surface treatment layer may be 1 nm or more, and may be 100 nm or more. The thickness of the surface treatment layer may be 2000 nm or less, 500 nm or less, or 200 nm or less. In one aspect, the thickness of the surface treatment layer is 1 nm or more and 2000 nm or less.
  • a surface treatment layer is formed from a surface treatment agent.
  • the surface treatment agent contains PFPE silane compound ⁇ .
  • the concentration of the PFPE silane compound ⁇ is, for example, 0.001% by mass or more, may be 0.005% by mass or more, or may be 0.01% by mass or more with respect to 100% by mass of the surface treatment agent. .
  • the concentration of the PFPE silane compound ⁇ is, for example, 1% by mass or less, may be 0.5% by mass or less, or may be 0.2% by mass or less. In one aspect, the concentration of the PFPE silane compound ⁇ is 0.001% by mass or more and 1% by mass or less.
  • the fluoropolyether group-containing silane compound ⁇ (PFPE silane compound ⁇ ) has a polyether chain and a silane-containing reactive cross-linking group.
  • the PFPE silane compound ⁇ further has an isocyanuric skeleton (hereinafter also referred to as an isocyanuric ring).
  • the isocyanuric skeleton improves the abrasion resistance and weather resistance of the resulting surface treatment layer.
  • hydrocarbon group means a group containing carbon and hydrogen and having one hydrogen atom removed from a hydrocarbon.
  • hydrocarbon groups include, but are not limited to, hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups, An aromatic hydrocarbon group etc. are mentioned.
  • the above "aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
  • Hydrocarbon groups may also contain one or more ring structures.
  • Such hydrocarbon groups may have one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the terminal or in the molecular chain.
  • the substituents of the "hydrocarbon group” are not particularly limited, but include, for example, halogen atoms; C 1-6 alkyl optionally substituted by one or more halogen atoms group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl groups, C 6-10 aryl groups and 5-10 membered heteroaryl groups.
  • organic group means a group containing carbon.
  • the organic group is not particularly limited, but may be a hydrocarbon group.
  • the “divalent to decavalent organic group” means a divalent to decavalent group containing carbon.
  • Such divalent to decavalent organic groups are not particularly limited, but include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group.
  • Examples of divalent organic groups include, but are not particularly limited to, divalent groups in which one hydrogen atom is further eliminated from a hydrocarbon group.
  • hydrolyzable group means a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction.
  • R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl.
  • the hydroxyl group is not particularly limited, but may be one produced by hydrolysis of a hydrolyzable group.
  • the PFPE silane compound ⁇ is represented by the following formula ( ⁇ 1) or formula ( ⁇ 2).
  • R 1 is a monovalent organic group containing a polyether chain
  • R 1' is a divalent organic group containing a polyether chain
  • X 1 is each independently a silane-containing reactive cross-linking group
  • Each X 2 is independently a monovalent group.
  • R 1 may be a monovalent organic group containing a polyether chain (excluding those containing a urethane bond).
  • R 1′ may be a divalent organic group containing a polyether chain (excluding those containing a urethane bond).
  • X 10 may be F.
  • a, b, c, d, e and f may each independently be an integer from 0 to 100.
  • the sum of a, b, c, d, e and f may be 5 or more, 10 or more, 15 or more, or 20 or more.
  • the sum of a, b, c, d, e and f may be 200 or less, 100 or less, 60 or less, 50 or less, or 30 or less.
  • the repeating units in the polyether chain may be linear or branched and may contain ring structures.
  • the repeating units in the polyether chain may in particular be linear.
  • -( OC6F12 ) - is, for example, -(OCF2CF2CF2CF2CF2CF2 ) - , -( OCF ( CF3 ) CF2CF2CF2 )-, - ( OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 )-, - (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 )-, - (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 )- or -(OCF 2 CF 2 CF 2 CF 2 CF(CF 3 ))- and -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-.
  • -(OC 5 F 10 )- is, for example, -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 ) CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, or -(OCF 2 CF 2 CF 2 CF(CF 3 ))-.
  • it may be -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-.
  • -(OC 4 F 8 )- is, for example, -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-,-( OCF2CF2CF (CF3))-,-(OC(CF3)2CF2)-,-(OCF2C(CF3)2 ) - , - ( OCF ( CF3 ) CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )-, or -(OCF 2 CF(C 2 F 5 ))-.
  • -(OCF 2 CF 2 CF 2 CF 2 )- it may be -(OCF 2 CF 2 CF 2 CF 2 )-.
  • -(OC 3 F 6 )- is, for example, -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )-, or -(OCF 2 CF(CF 3 ))- .
  • it may be -(OCF 2 CF 2 CF 2 )-.
  • -(OC 2 F 4 )- is -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-.
  • the repeating unit is linear. By making the repeating unit linear, the surface lubricity of the surface treatment layer can be improved.
  • the repeating unit is branched. By branching the repeating unit, the coefficient of dynamic friction of the surface treatment layer can be increased.
  • the ring structure may be the following three-, four-, five-, or six-membered ring. [In the formula, * indicates a binding position. ]
  • the ring structure is preferably a four-, five- or six-membered ring, more preferably a four- or six-membered ring.
  • the repeating unit having a ring structure can preferably be the following units. [In the formula, * indicates a binding position. ]
  • the polyether chain is each independently represented by any of the following formulas (f1) to (f6) at each occurrence.
  • d is an integer from 1 to 200, e is 0 or 1; ];
  • c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 or more and 200 or less, the sum of c, d, e and f is greater than or equal to 2;
  • the order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ];
  • R21 is OCF2 or OC2F4 ;
  • R 22 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or 2 independently selected from these groups or a combination of three groups, g is an integer from 2 to 100; ];
  • R 21 is OCF 2 or OC 2 F 4 ;
  • R 22 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or 2 independently selected from these groups or a combination of three groups,
  • R 21′ is OCF 2 or OC 2 F 4 ;
  • R 22′ is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or independently selected from these groups a combination of two or three groups,
  • g is an integer from 2 to 100,
  • g' is an integer from 2 to 100,
  • Rr is (In the formula, * indicates the binding position.) is. ]
  • f is an integer of 1 or more and 200 or less
  • a, b, c, d and e are each independently an integer of 0 or more and 200 or less
  • the order of existence of each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula.
  • d is an integer of 5-200, 10-100, 15-50 or 25-35.
  • OC3F6 may be ( OCF2CF2CF2 ) , (OCF( CF3 ) CF2 ) or ( OCF2CF ( CF3 )), ( OCF2CF2CF2 ) good.
  • ( OC2F4 ) may be ( OCF2CF2 ) or ( OCF ( CF3 )), and may be ( OCF2CF2 ) .
  • e is zero. In another aspect, e is 1.
  • e and f may each independently be an integer of 5-200, or an integer of 10-200.
  • the sum of c, d, e and f may be 5 or more, 10 or more, 15 or more, or 20 or more.
  • the above formula (f2) is -(OCF 2 CF 2 CF 2 CF 2 ) c -(OCF 2 CF 2 CF 2 ) d -(OCF 2 CF 2 ) e -(OCF 2 ) f - expressed.
  • formula (f2) is represented by -(OC 2 F 4 ) e -(OCF 2 ) f -.
  • R 21 may be OC 2 F 4 .
  • R 22 may be a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or a combination of two or three groups independently selected from these groups. , OC 3 F 6 and OC 4 F 8 .
  • the combination of two or three groups mentioned above is not particularly limited, but for example, -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 -, -OC 3 F 6 OC 2 F 4 - , -OC 3 F 6 OC 3 F 6 -, -OC 3 F 6 OC 4 F 8 -, -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -, -OC 4 F 8 OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC4F8- , -OC2F4OC3F6OC2F4- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ,
  • _ _ _ _ _ _ _ _ _ _ _ g may be 3 or more and may be an integer of 5 or more. g may be an integer of 50 or less.
  • OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 can be either linear or branched and can be linear.
  • the above formula (f3) is -(OC 2 F 4 -OC 3 F 6 ) g - or (OC 2 F 4 -OC 4 F 8 ) g -.
  • R 21 , R 22 and g have the same meanings as described in formula (f3) above, and have the same aspects.
  • R 21′ , R 22′ and g′ have the same meanings as R 21 , R 22 and g in formula (f3) above, respectively, and have the same aspects.
  • R r is preferably [In the formula, * indicates a binding position. ] and more preferably [In the formula, * indicates a binding position. ] is.
  • e may be 1 or more and 100 or less, or an integer of 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f may be 5 or more, 10 or more, or 10 or more and 100 or less.
  • f may be 1 or more and 100 or less, or may be an integer of 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f may be 5 or more, 10 or more, or 10 or more and 100 or less.
  • polyether chain is represented by formula (f1).
  • polyether chain is represented by formula (f2).
  • the polyether chain is represented by formula (f3).
  • the polyether chain is represented by formula (f4).
  • the polyether chain is represented by formula (f5).
  • the polyether chain is represented by formula (f6).
  • the greater the ratio of e to f (hereinafter referred to as the "e/f ratio"), the greater the stability of the PFPE silane compound ⁇ .
  • the smaller the e/f ratio the better the surface lubricity of the surface-treated layer.
  • the e/f ratio is, for example, 0.1 or more.
  • the e/f ratio is, for example, 10 or less.
  • the e/f ratio may be 0.2 or greater.
  • the e/f ratio may be 5 or less, 2 or less, 1.5 or less, or 0.85 or less. In one aspect, the e/f ratio is, for example, 0.1 or more and 10 or less.
  • the average molecular weight of the polyether chain is not particularly limited.
  • the average molecular weight of the polyether chain is, for example, 500 or more, may be 1,500 or more, or may be 2,000 or more.
  • the average molecular weight of the polyether chains is, for example, 30,000 or less, and may be 10,000 or less. In one aspect, the average molecular weight of the polyether chain is from 500 to 30,000.
  • average molecular weight means number average molecular weight and is measured by 19 F-NMR.
  • the average molecular weight of the polyether chain is, for example, 500 or more, may be 1,000 or more, may be 2,000 or more, or may be 3,000 or more.
  • the average molecular weight of the polyether chain may be, for example, 30,000 or less, may be 20,000 or less, may be 15,000 or less, may be 10,000 or less, may be 6,000 or less. .
  • the average molecular weight of the polyether chain is from 500 to 30,000.
  • the average molecular weight of the polyether chain is, for example, 4,000 or more, may be 5,000 or more, or may be 6,000 or more.
  • the average molecular weight of the polyether chains is, for example, 30,000 or less, and can be 10,000 or less. In one aspect, the average molecular weight of the polyether chain is from 4,000 to 30,000.
  • R 1 is, for example, the following formula: R 3 -(PAO) -L ⁇ 2- (Wherein, PAO is the above polyether chain, R3 is an alkyl group or a fluorinated alkyl group, L ⁇ 2 is a single bond or a divalent linking group. ) is a monovalent organic group represented by
  • R 1′ is, for example, the following formula: -L ⁇ 3- (PAO) -L ⁇ 2- (Wherein, PAO is the above polyether chain, L ⁇ 2 is a single bond or a divalent linking group, L ⁇ 3 is a single bond or a divalent linking group, L ⁇ 2 is bonded to the right isocyanuric ring of formula ( ⁇ 2), and L ⁇ 3 is bonded to the left isocyanuric ring. ) is a monovalent organic group represented by
  • the carbon number of R 3 is, for example, 1 to 16, may be 1 to 8, may be 1 to 6, or may be 1 to 3.
  • R 3 may be linear or branched.
  • R 3 is, for example, a linear or branched C 1-16 alkyl group or a fluorinated alkyl group.
  • the number of carbon atoms in the alkyl group may be 1-8, 1-6, or 1-3.
  • R 3 may be a straight chain C 1-3 alkyl group or a fluorinated alkyl group.
  • R 3 may be a C 1-16 fluorinated alkyl group, a CF 2 H—C 1-15 fluoroalkylene group, or a C 1-16 perfluoroalkyl group.
  • R 3 may be a linear or branched C 1-16 perfluoroalkyl group.
  • the number of carbon atoms in the perfluoroalkyl group may be 1-6, or 1-3.
  • R 3 may be a linear C 1-3 perfluoroalkyl group.
  • R 3 is, for example, —CF 3 , —CF 2 CF 3 , or CF 2 CF 2 CF 3 .
  • L ⁇ 2 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2).
  • L ⁇ 2 may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond.
  • L ⁇ 2 may be a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one of an ether bond and an ester bond.
  • L ⁇ 2 has the formula: -(CX 121 X 122 ) o -(L') p -(CX 123 X 124 ) q -
  • X 121 to X 124 are each independently H, F, OH, or —OSi(OR 125 ) 3 (three R 125 are each independently is an alkyl group)
  • L ⁇ 2 is represented by the following formula: -(CF 2 ) m11 -(CH 2 ) m12 -O-(CH 2 ) m13 - [Wherein, m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, m13 is an integer of 1 to 3]
  • L ⁇ 2 examples include -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -O-CH 2 -, -CO-O-CH 2 -CH(OH)-CH 2 -, -(CF 2 ) n1 - (n1 is an integer of 0 to 4), -CH 2 -, -C 4 H 8 -, -(CF 2 ) n2 -(CH 2 ) n3 - (n2 and n3 are independently are integers of 0 to 4), -CF 2 CF 2 CH 2 OCH 2 CH(OH)CH 2 -, and -CF 2 CF 2 CH 2 OCH 2 CH(OSi(OCH 3 ) 3 )CH 2 - mentioned.
  • L ⁇ 3 is -(CX 126 X 127 ) r -(CX 121 X 122 ) o -(L') p -(CX 123 X 124 ) q -
  • X 121 to X 124 , L′, o, p and q have the same meanings as defined in L ⁇ 2 above, X 126 and X 127 are independently H, F or Cl and may be F; r is an integer from 1 to 6, —(CX 126 X 127 ) r — is attached to (PAO) and (CX 123 X 124 ) q is attached to the isocyanuric ring.
  • X 1 is a monovalent silane-containing reactive cross-linking group. X1 contributes to adhesion to the substrate. X 1 may chemically react with the material of the substrate.
  • X 1 has the formula: -L ⁇ 1 - ⁇ Si(R a ) s (R b ) t (R c ) u (R d ) v ⁇ n
  • L ⁇ 1 is a single bond or a divalent linking group
  • R a , R b and R c each independently represents a halogen, an alkoxy group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an acetoxy group having 1 to 10 carbon atoms, or an acetoxy group having 1 to 10 carbon atoms.
  • L ⁇ 1 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2).
  • L ⁇ 1 may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond.
  • L ⁇ 1 may be a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one of an ether bond and an ester bond.
  • L ⁇ 1 examples include -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -O-CH 2 -, -CO-O-CH 2 -CH(OH)-CH 2 -, -CH 2 - and -C 4 H 8 - are included.
  • R a , R b and R c are monovalent groups bonded to Si. At least one of R a , R b and R c may be a halogen, a C 1-10 alkoxy group, or a C 1-10 amino group. Other R a , R b and R c may be an acetoxy group having 1 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, or a glycidyl group having 3 to 10 carbon atoms. Each of R a , R b and R c may be an alkoxy group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
  • halogen may be Cl, Br or I and may be Cl.
  • the alkoxy group may have 1 to 5 carbon atoms.
  • Alkoxy groups may be linear, cyclic, or branched.
  • a hydrogen atom of the alkoxy group may be substituted with a fluorine atom or the like.
  • the alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and may be a methoxy group or an ethoxy group.
  • R d is a divalent group bonded to two Si. Each R d is independently —O—, —NH—, —C ⁇ C—, or a silane bond. R d can be —O—, —NH—, or —C ⁇ C—. R d allows two or more silicon atoms to be linked via R d in a linear, ladder-like, cyclic, or bicyclic manner. When n is an integer of 2 or more, silicon atoms may be bonded to each other.
  • X 1 has the formula: -L ⁇ 1 - ⁇ Si(R a ) s (R b ) t (R c ) u (R d′ ) v ⁇ n
  • L ⁇ 1 is a single bond or a divalent linking group
  • R a , R b and R c each independently represents a halogen, an alkoxy group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, an acetoxy group having 1 to 10 carbon atoms, or an acetoxy group having 1 to 10 carbon atoms.
  • R d' are each independently -Z-SiR d1 p' R d2 q' R d3 r' (wherein each Z is independently a single bond or a divalent linking group, each R d1 is independently R d′′ ; R d′′ is synonymous with R d′ ; In R d ' , up to 5 Si are linearly linked via the Z group, each R d2 is independently a hydroxyl group or a hydrolyzable group; each R d3 is independently a hydrogen atom or a lower alkyl group, each p' is independently an integer of 0 to 3; each q' is independently an integer of 0 to 3; each r' is independently an integer of 0 to 3, However, the sum of p', q' and r' is 3. ) is a group represented by s, t and u are each independently 0 or 1; v is an integer
  • Z is, for example, -C 2 H 4 -, -C 3 H 6 -, -CO-O-CH 2 -CH(OH)-CH 2 -, -CH 2 -, and -C 4 H 8 - is mentioned.
  • R d′ When at least one R d1 is present in R d′ above, two or more Si atoms linked in a straight chain via a Z group are present in R d ′ , and The maximum number of Si atoms linked in a chain is five.
  • the “number of Si atoms linearly linked via Z groups in R d′ ” is equal to the repeating number of —Z—Si— linearly linked in R d′. Become.
  • the following shows an example in which a Si atom is linked via a Z group in Rd ' .
  • * means the site of bonding to Si of the main chain, ... is that a predetermined group other than ZSi is bonded, that is, all three bonds of the Si atom are ... , it means the end point of the ZSi iteration.
  • the number on the right side of Si means the number of occurrences of Si linked in a straight chain via Z groups counted from *. That is, the chain in which the ZSi repeat terminates at Si 2 has "the number of Si atoms connected in a straight chain via the Z group in R d'" of 2.
  • the number of Si atoms linearly linked via a Z group in R d' is 1 (left formula) or 2 in all chains (right formula).
  • the number of Si atoms linearly linked via a Z group in R d′ is 1 or 2, and may be 1.
  • Each R d2 independently represents a hydroxyl group or a hydrolyzable group.
  • the hydroxyl group is not particularly limited, but may be one produced by hydrolysis of a hydrolyzable group.
  • R d2 can be —OR 4 (R 4 is a substituted or unsubstituted C 1-3 alkyl group, which can be a methyl group).
  • Each R d3 independently represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is an alkyl group having 1 to 20 carbon atoms, may be an alkyl group having 1 to 6 carbon atoms, or may be a methyl group.
  • q' may be 2 or more, 2 or 3, or 3 at the terminal R d1 in R d ' (R d' when R d1 is absent). you can
  • R d has at least one -Si(-Z-SiR d2 q' R d3 r' ) 2 or Si(-Z-SiR d2 q' R d3 r' ) 3 at the terminal end. may have —Si(—Z—SiR d2 q′ R d3 r′ ) 3 . (-Z-SiR d2 q' R d3 r' ) may be (-Z-SiR d2 3 ).
  • all of the terminal portions of R d are —Si(—Z—SiR d2 q′ R d3 r′ ) 3 and may be —Si(—Z—SiR d2 3 ) 3 .
  • X 1 has the formula: -L ⁇ 1 - ⁇ C(R a6 ) s6 (R b6 ) t6 (R c6 ) u6 (R d6 ) v6 ⁇ n6
  • L ⁇ 1 is a single bond or a divalent linking group
  • R a6 , R b6 and R c6 are each independently hydrogen, halogen, alkoxy group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms, acetoxy group having 1 to 10 carbon atoms, 3 to 10 allyl group, glycidyl group having 3 to 10 carbon atoms, OCOR 67 (wherein R 67 is an alkyl group having 1 to 6 carbon atoms), OH or Y 6 —SiR 65 j6 R 66 3-j6 , each R d6 is independently —O—, —NH—, —C ⁇ C—, or —Z 6 —CR
  • halogen may be Cl, Br or I and may be Cl.
  • the alkoxy group may have 1 to 5 carbon atoms.
  • Alkoxy groups may be linear, cyclic, or branched.
  • a hydrogen atom of the alkoxy group may be substituted with a fluorine atom or the like.
  • the alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and may be a methoxy group or an ethoxy group.
  • Z 6 is, for example, a C 1-6 alkylene group, —(CH 2 ) g —O—(CH 2 ) h — (g may be an integer of 0 to 6, and may be an integer of 1 to 6; h may be an integer of 0 to 6 and may be an integer of 1 to 6), or -phenylene-(CH 2 ) i - (i is an integer of 0 to 6 and good.)
  • Z 6 may be a C 1-3 alkylene group. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
  • R 61 independently represents R d6′ at each occurrence.
  • R d6' has the same meaning as R d6 .
  • R d6 up to 5 Cs are linearly linked via Z 6 groups. That is, when at least one R 61 is present in R d6 , two or more Si atoms linked in a straight chain via a Z 6 group are present in R d6, and through such a Z 6 group The maximum number of C atoms linked in a straight chain is 5.
  • the “number of C atoms linearly linked via Z 6 groups in R d6 ” is equal to the repeating number of —Z 6 —C— linearly linked in R d6 .
  • the number of C atoms linearly linked via Z 6 groups in R d6 is 1 (left formula) or 2 in all chains (right formula).
  • the number of C atoms linearly linked via the Z 6 group in R d6 is 1 or 2, and may be 1.
  • R 62 represents -Y 6 -SiR 65 j6 R 66 3-j6 .
  • Each occurrence of Y6 independently represents a divalent organic group.
  • Y 6 is a C 1-6 alkylene group, —(CH 2 ) g′ —O—(CH 2 ) h′ — (g′ may be an integer of 0 to 6, 1 to may be an integer of 6. h' may be an integer of 0 to 6 and may be an integer of 1 to 6) or -phenylene-(CH 2 ) i' - (i' is may be an integer from 0 to 6).
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
  • Y 6 can be a C 1-6 alkylene group or phenylene-(CH 2 ) i′ —.
  • light resistance particularly ultraviolet resistance, can be improved.
  • R 65 independently represents a hydroxyl group or a hydrolyzable group.
  • hydrolyzable group examples include those similar to those described above.
  • R 65 is —OR (R is a substituted or unsubstituted C 1-3 alkyl group, which may be a methyl group or an ethyl group, and may be a methyl group).
  • Each occurrence of R 66 independently represents a hydrogen atom or a lower alkyl group.
  • the number of carbon atoms in the lower alkyl group may be 1-20, or 1-6.
  • R 66 may be a methyl group.
  • j6 is an integer of 1 to 3, may be 2 or 3, or may be 3 independently for each (-Y-SiR 65 j6 R 66 3-j6 ) unit.
  • Each occurrence of R 63 independently represents a hydrogen atom or a lower alkyl group.
  • the number of carbon atoms in the lower alkyl group may be 1-20, or 1-6.
  • R 63 may be a methyl group.
  • p6 is an integer from 0 to 3 independently at each occurrence.
  • q6 is independently an integer from 0 to 3 at each occurrence.
  • r6 is independently an integer from 0 to 3 at each occurrence. However, the sum of p6, q6 and r6 is 3.
  • q6 is 2 or more, may be 2 or 3, and is 3 good.
  • the number of Si atoms having a hydroxyl group or a hydrolyzable group in formula ( ⁇ 1) may be 1 to 6, may be 2 to 4, or may be 3. .
  • the number of Si atoms having a hydroxyl group or a hydrolyzable group in formula ( ⁇ 2) may be 2 to 12, 4 to 8, or 6.
  • v in X 1 is 3 and each R d' is independently -Z-SiR d2 q' R d3 r' .
  • X 1 is, for example, -L ⁇ 1 -SiR 5 3 , -L ⁇ 1 -Si(OR 6 ) 3 , -L ⁇ 1 -Si(NR 6 2 ) 3 , or -L ⁇ 1 -Si(OCOR 6 ) 3 (
  • L ⁇ 1 may be a halogen atom for R 5 and an alkyl group having 1 to 4 carbon atoms independently for R 6 .
  • X 1 has the formula: -L ⁇ 1 - ⁇ Si(R a ) s (R b ) t (R c ) u (R d ) v ⁇ n , or -L ⁇ 1 - ⁇ C(R a6 ) s6 (R b6 ) t6 (R c6 ) u6 ( Rd6 ) v6 ⁇ n6 [In the formula, each symbol has the same meaning as described above. ] is represented by
  • each X 2 may independently be a monovalent organic group comprising a polyether chain as described above. Suitable groups for the above organic groups are the same as for R 1 .
  • X 2 may each independently be the above silane-containing reactive cross-linking group.
  • X 2 can be the same as X 1 .
  • each X2 may be independently at least one group selected from the group consisting of silicone residues, silsesquioxane residues and silazane groups.
  • silicone residue examples include the following groups.
  • L 2 is a single bond or a divalent linking group
  • n30 is an integer of 1 to 20
  • m30 is an integer of 0 to 10
  • each R 31 is independently a monovalent and at least one of R 31 in each group is a reactive group.
  • Examples of reactive groups include H, a halogen atom, OR 310 (R 310 is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms), -L 3 -SiR 311 3 (L 3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R 311 is a halogen atom.), -L 3 -Si(OR 312 ) 3 (L 3 is as described above, R 312 is independent is an alkyl group having 1 to 4 carbon atoms.), -L 3 -Si(NR 312 2 ) 3 (L 3 and R 312 are as described above), -L 3 -Si(OCOR 312 ) 3 (L 3 and R 312 are as described above), and at least one selected from the group consisting of any of these groups.
  • groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, uryl group, halogenated uryl group, urea group, halogenated urea group, —CONR 313 COR 314 (R 313 and R 314 are independently H, alkyl group or halogenated alkyl group), sugar chain-containing group, alkylene polyether is at least one selected from the group consisting of a group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
  • L2 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2).
  • L2 may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond.
  • L 2 may be a single bond, a C 1-10 alkylene group, or a C 1-10 divalent hydrocarbon group containing at least one of an ether bond and an ester bond.
  • L 2 examples include -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -O-CH 2 -, -CO-O-CH 2 -CH(OH)-CH 2 -, -CH 2 - and -C 4 H 8 - are included.
  • the above silicone residue may be the following groups.
  • L 2 is a single bond or a divalent linking group
  • R 34 is each independently a monovalent group
  • at least one of the R 34 possessed by each group is a reactive is the base.
  • Examples of reactive groups include —H, —OR 340 (R 340 is an alkyl group having 1 to 4 carbon atoms), halogen atom, —OH, —O—CR 340 ⁇ CH 2 (R 340 is as described above). , —OCOR 340 (R 340 is as described above), —OCOOR 341 (R 341 is an alkyl or halogenated alkyl group), —NR 340 2 (R 340 is as described above), and any of these groups is at least one selected from the group consisting of groups including
  • groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, uryl group, halogenated uryl group, urea group, halogenated urea group, —CONR 342 COR 343 (R 342 and R 343 are independently H, alkyl group or halogenated alkyl group), sugar chain-containing group, alkylene polyether is at least one selected from the group consisting of a group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
  • L2 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2). Suitable values for L2 are as described above.
  • the silsesquioxane residue includes the following groups.
  • L2 is a single bond or a divalent linking group
  • R37 is each independently a monovalent group
  • at least one of the R37 in each group is a reactive group
  • p30 is independently an integer from 0 to 5000.
  • groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, uryl group, halogenated uryl group, urea group, halogenated urea group, —CONR 372 COR 373 (R 372 and R 373 are independently H, alkyl group or halogenated alkyl group), sugar chain-containing group, alkylene polyether is at least one selected from the group consisting of a group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
  • L2 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2). Suitable values for L2 are as described above.
  • X2 may be a group different from the above-described monovalent organic group containing a polyether chain, silane-containing reactive cross-linking group, silicone residue, silsesquioxane residue and silazane group.
  • X2 is independently H, alkyl group, halogenated alkyl group, alkyl ester group, halogenated alkyl ester group, alkyl ether group, halogenated alkyl ether group, alkylamide group, halogenated alkylamide group, uryl group, halogenated uryl group, urea group, halogenated urea group, —OCOOR j (R j is an alkyl group or a halogenated alkyl group), —CONR k COR l (R k and R l are independently H, an alkyl group or halogenated alkyl groups), sugar chain-containing groups, alkylene polyether groups, arene groups, halogenated arene groups, groups containing heterocycles, aryl groups, halogenated aryl groups, silicone residues (with reactive groups ) and silsesquioxane residues (excluding those having a reactive group).
  • silicone residue examples include the following groups.
  • the above reactive groups are those exemplified as reactive groups that can constitute R 37 .
  • L4 is a single bond or a divalent linking group, and each R41 is independently a group other than a monovalent reactive group.
  • groups other than reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, uryl groups, Halogenated uryl group, urea group, halogenated urea group, —CONR k COR l (R k and R l are independently H, alkyl group or halogenated alkyl group), group containing sugar chain, alkylene polyether group, arene It may be at least one selected from the group consisting of a group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group.
  • L4 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2).
  • L 4 may be a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, a single bond, a C 1-10 It may be an alkylene group or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond and an ester bond.
  • L 4 examples include -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -O-CH 2 -, -CO-O-CH 2 -CH(OH)-CH 2 - and the like.
  • Examples of the silsesquioxane residue include the following groups.
  • the above reactive groups are those exemplified as reactive groups that can constitute R 37 .
  • L 4 is a single bond or a divalent linking group
  • R 41 is each independently a group other than a monovalent reactive group
  • p30 is independently an integer of 0 to 5,000.
  • groups other than reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, uril group, halogenated uryl group, urea group, halogenated urea group, —CONR k COR l (R k and R l are independently H, an alkyl group or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group , an arene group, a halogenated arene group, a heterocycle-containing group, an aryl group, and a halogenated aryl group.
  • L4 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2). Suitable for L4 are as described above.
  • the silazane group includes the following groups.
  • L 5 is a single bond or a divalent linking group
  • m31 is an integer of 2 to 100
  • n31 is an integer of 100 or less
  • R 42 is each independently H, carbon 1 to 10 alkyl groups, alkenyl groups, cycloalkyl groups having 5 to 12 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkylsilyl groups, alkylcyano groups and alkoxy groups having 1 to 4 carbon atoms.
  • L5 is a single bond or a divalent linking group that directly bonds to the isocyanuric ring of formula ( ⁇ 1) or formula ( ⁇ 2).
  • L5 may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond.
  • L 5 may be a single bond, a C 1-10 alkylene group, or a C 1-10 divalent hydrocarbon group containing at least one of an ether bond and an ester bond.
  • L 5 examples include -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -O-CH 2 -, and -CO-O-CH 2 -CH(OH)-CH 2 -. mentioned.
  • silazane group examples include the following groups.
  • the average molecular weight of R 1 is not particularly limited.
  • the average molecular weight of R 1 is, for example, 500 or more, may be 1,500 or more, or may be 2,000 or more.
  • the average molecular weight of R 1 is, for example, 30,000 or less, and may be 10,000 or less. In one aspect, R 1 has an average molecular weight of 500 to 30,000.
  • the average molecular weight of the PFPE silane compound ⁇ is not particularly limited. From the viewpoint of UV resistance and abrasion resistance, the average molecular weight of the PFPE silane compound ⁇ is, for example, 500 or more, may be 1,000 or more, or may be 2,000 or more. The average molecular weight of the PFPE silane compound may be 10,000 or less, and may be 6,000 or less. In one aspect, the average molecular weight of the PFPE silane compound ⁇ is, for example, 500 or more and 10,000 or less.
  • the PFPE silane compound ⁇ is represented by the above formula ( ⁇ 1).
  • the PFPE silane compound ⁇ is a mixture of the compound represented by the formula ( ⁇ 1) and the compound represented by the formula ( ⁇ 2).
  • the content of the compound represented by formula ( ⁇ 1) in the mixture may be 1 mol% or more, 10 mol% or more, 50 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more.
  • the content of the compound represented by formula ( ⁇ 1) may be less than 100 mol%, and may be 99 mol% or less, 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.
  • the content of the PFPE silane compound ⁇ in the surface treatment agent is, for example, 0.01% by mass or more, may be 0.1% by mass or more, may be 1% by mass or more, or may be 5% by mass or more. you can
  • the content of the PFPE silane compound ⁇ in the surface treatment agent is, for example, 99.9% by mass or less, may be 50% by mass or less, may be 30% by mass or less, or may be 20% by mass or less. .
  • the content of the PFPE silane compound ⁇ in the surface treatment agent is 0.01% by mass or more and 99.9% by mass or less.
  • the content of the PFPE silane compound ⁇ may be 100 mol% (that is, the surface treatment agent contains only the compound ⁇ as a non-volatile component), and may be 99.9 mol. % or less, 99 mol % or less, 98 mol % or less, or 95 mol % or less.
  • the content of the PFPE silane compound ⁇ may be 1 mol% or more, 10 mol% or more, 30 mol% or more, or 50 mol%. or more, may be 60 mol % or more, may be 70 mol % or more, or may be 80 mol % or more.
  • PFPE silane compound ⁇ can be produced, for example, by the method described in International Publication No. 2018/056410.
  • the surface treatment agent may further contain a fluoropolyether group-containing silane compound ⁇ (hereinafter also referred to as PFPE silane compound ⁇ ) other than the PFPE silane compound ⁇ .
  • PFPE silane compound ⁇ has perfluoropolyether groups and Si with hydroxyl groups or hydrolyzable groups.
  • PFPE silane compound ⁇ does not have an isocyanuric skeleton.
  • the perfluoropolyether group of the PFPE silane compound ⁇ has the following formula: - (OC 6 F 12 ) a1 - (OC 5 F 10 ) b1 - (OC 4 F 8 ) c1 - (OC 3 F 6 ) d1 - (OC 2 F 4 ) e1 - (OCF 2 ) f1 - contains a polyether chain represented by [Wherein, a1, b1, c1, d1, e1 and f1 are each independently an integer of 0 or more and 200 or less, and are bracketed with a1, b1, c1, d1, e1 or f1 The order of existence of each repeating unit is arbitrary in the formula. ]
  • a1, b1, c1, d1 and e1 are each independently an integer of 0 or more and 100 or less, and f1 is an integer of 1 or more and 200 or less.
  • the sum of a1, b1, c1, d1, e1 and f1 may be 5 or more, 10 or more, or 10 or more and 100 or less.
  • the repeating unit in the polyether chain of the PFPE silane compound ⁇ may be linear or branched, particularly linear. Specific examples of repeating units in the polyether chain of the PFPE silane compound ⁇ include those similar to those of the PFPE silane compound ⁇ .
  • the polyether chains of the PFPE silane compound ⁇ are each independently a group represented by any one of the formulas (f1) to (f6) listed as the polyether chains in the PFPE silane compound ⁇ . may be a group represented by formula (f2) or (f3).
  • the polyether chain of the PFPE silane compound ⁇ has at least 1, alternatively 5 or more, or even 10 or more OCF 2 units.
  • the PFPE silane compound ⁇ has the following formula (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2), or (E1) can be a compound represented by
  • each Rf is independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, PFPE stands for perfluoropolyether group.
  • the alkyl group having 1 to 16 carbon atoms may be linear or branched.
  • the number of carbon atoms may be 1-6, or 1-3.
  • Rf may be a linear C 1-3 alkyl group.
  • Rf may be a CF 2 H—C 1-15 fluoroalkylene group or a perfluoroalkyl group having 1 to 16 carbon atoms, and may be a perfluoroalkyl group having 1 to 16 carbon atoms.
  • Rf may be a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. The number of carbon atoms in the perfluoroalkyl group may be 1-6, or 1-3. Rf may be a linear perfluoroalkyl group having 1 to 3 carbon atoms. Rf is, for example, -CF 3 , -CF 2 CF 3 , or CF 2 CF 2 CF 3 .
  • the perfluoropolyether group is as described above.
  • each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group.
  • the number of carbon atoms in the lower alkyl group may be 1-20, and may be 1-6.
  • R 12 may be a methyl, ethyl or propyl group.
  • R 13 at each occurrence independently represents a hydrogen atom or a halogen atom.
  • a halogen atom may be an iodine atom, a chlorine atom or a fluorine atom, and may be a fluorine atom.
  • each occurrence of R 14 is independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may be an alkyl group having 1 to 4 carbon atoms.
  • each occurrence of R 15 independently represents a hydroxyl group or a hydrolyzable group.
  • n is independently for each (—SiR 14 n R 15 3-n ) unit an integer of 0 to 3, may be an integer of 0 to 2, and 0 can be However, in the formula, all n cannot be 3 at the same time. In other words, at least one R 15 is present in the formula.
  • t is each independently an integer of 1 to 10, may be an integer of 1 to 6, may be 2 to 10, and is an integer of 2 to 6 It's okay.
  • X 101 each independently represents a single bond or a divalent to decavalent organic group.
  • X 101 mainly consists of a perfluoropolyether portion (ie, Rf-PFPE portion or PFPE- portion) that provides water repellency and surface slipperiness, and a silane portion (ie, ⁇ is understood as a linker that connects the groups bracketed with Therefore, X 101 may be a single bond or any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.
  • X 102 at each occurrence independently represents a single bond or a divalent organic group.
  • X 102 is, for example, an alkylene group having 1 to 20 carbon atoms and may be —(CH 2 ) u — (where u is an integer of 0 to 2).
  • ⁇ is an integer of 1-9 and ⁇ ' is an integer of 1-9. These ⁇ and ⁇ ' can vary depending on the valence of X101 .
  • the sum of ⁇ and ⁇ ' is the same as the valence of X101 .
  • the sum of ⁇ and ⁇ ′ is 10 when X 101 is a 10-valent organic group.
  • ⁇ is 9 and ⁇ ′ is 1, for example.
  • ⁇ is 5 and ⁇ ′ is 5.
  • ⁇ can be 1 and ⁇ ′ can be 9.
  • ⁇ and ⁇ ′ are 1 when X 101 is a single bond or a divalent organic group.
  • ⁇ is the value obtained by subtracting 1 from the valence of X101 .
  • X 101 is a divalent to heptavalent, divalent to tetravalent, or divalent organic group.
  • X 101 is a divalent to tetravalent organic group, ⁇ is 1-3, and ⁇ ′ is 1.
  • X 101 is a divalent organic group, ⁇ is 1 and ⁇ ' is 1.
  • the formulas (A1) and (A2) are represented by the following formulas (A1') and (A2').
  • X 105 each independently represents a single bond or a divalent to decavalent organic group.
  • X 105 mainly consists of a perfluoropolyether portion (that is, Rf-PFPE portion or PFPE- portion) that provides water repellency and surface slipperiness, etc., and a silane portion (that is, ⁇ is understood as a linker that connects the groups bracketed with Therefore, X 105 may be a single bond or any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.
  • ⁇ is an integer of 1-9
  • ⁇ ' is an integer of 1-9
  • ⁇ and ⁇ ' are determined according to the valence of X105 .
  • the sum of ⁇ and ⁇ ' is the same as the valence of X105 .
  • the sum of ⁇ and ⁇ ' is ten when X 105 is a decavalent organic group.
  • ⁇ is 9 and ⁇ ' is 1.
  • ⁇ is 5 and ⁇ ' is 5.
  • ⁇ can be 1 and ⁇ ' can be 9.
  • ⁇ and ⁇ ' are 1 when X 105 is a single bond or a divalent organic group.
  • ⁇ is the value of the valence of X 105 minus one.
  • X 105 is a divalent to heptavalent, divalent to tetravalent, or divalent organic group.
  • X 105 is a divalent to tetravalent organic group, ⁇ is 1-3, and ⁇ ' is 1.
  • X 105 is a divalent organic group, ⁇ is 1 and ⁇ ' is 1.
  • the formulas (B1) and (B2) are represented by the following formulas (B1') and (B2').
  • X 107 each independently represents a single bond or a divalent to decavalent organic group.
  • X 107 mainly consists of a perfluoropolyether portion (that is, Rf-PFPE portion or PFPE- portion) that mainly provides water repellency and surface slipperiness, and a silane portion (that is, ⁇ is understood as a linker that connects the groups bracketed with Therefore, X 107 may be a single bond or any organic group as long as the compounds represented by formulas (C1) and (C2) can exist stably.
  • ⁇ is an integer of 1-9 and ⁇ ' is an integer of 1-9.
  • ⁇ and ⁇ ' are determined according to the valence of X107 .
  • the sum of ⁇ and ⁇ ' is the same as the valence of X107 .
  • the sum of ⁇ and ⁇ ' is 10 when X 107 is a decavalent organic group.
  • ⁇ is 9 and ⁇ ' is 1, for example.
  • ⁇ is 5 and ⁇ ′ is 5.
  • ⁇ can be 1 and ⁇ ′ can be 9.
  • ⁇ and ⁇ ′ are 1 when X 107 is a single bond or a divalent organic group.
  • ⁇ is the value obtained by subtracting 1 from the valence of X107 .
  • k is independently at each occurrence an integer from 0 to 3
  • l at each occurrence is independently an integer from 0 to 3
  • m is independently an integer from 0 to 3 at each occurrence.
  • the sum of k, l and m is three.
  • X 107 is a divalent to heptavalent, divalent to tetravalent, or divalent organic group.
  • X 107 is a divalent to tetravalent organic group, ⁇ is 1-3, and ⁇ ′ is 1.
  • X 107 is a divalent organic group, ⁇ is 1 and ⁇ ' is 1.
  • the formulas (C1) and (C2) are represented by the following formulas (C1') and (C2').
  • R a3 at each occurrence independently represents —Z 3 —SiR 71 p1 R 72 q1 R 73 r1 .
  • Z3 is, for example, a divalent organic group. It is desirable that Z3 does not form a siloxane bond with the terminal Si atom (Si atom to which R a3 is bonded) of the molecular main chain in formula (C1) or formula (C2).
  • Z 3 is, for example, a C 1-6 alkylene group, —(CH 2 ) g3 —O—(CH 2 ) h3 — (g3 is an integer of 1 to 6, h3 is an integer of 1 to 6 ), or -phenylene-(CH 2 ) i3 - (i3 is an integer of 0 to 6).
  • Z 3 may be a C 1-3 alkylene group, may be a C 2-3 alkylene group, or may be -CH 2 CH 2 -. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
  • R 71 independently represents R a′ at each occurrence.
  • R a' has the same meaning as R a3 .
  • the maximum number of Sis that are linearly linked via Z 3 groups is five. That is, in the above Ra3 , when at least one R71 is present, two or more Si atoms linked in a straight chain via a Z group are present in Ra3 , and a linear chain is present via a Z3 group. The maximum number of Si atoms linked like each other is five. “The number of Si atoms linearly linked via Z 3 groups in R a3 ” is equal to the repeating number of —Z 3 —Si— linearly linked in R a3 .
  • the number of Si atoms linked in a straight chain via Z 3 groups in R a3 is 1 (left formula) or 2 (right formula) in all chains. .
  • the —Si—R a3 moiety containing Si bonded to X 107 in formulas (C1) and (C2) two Si are linked in the left formula and three Si are linked in the right formula.
  • “the number of Si atoms linearly linked via Z 3 groups in R a3 ” is 1 or 2, and may be 1 in all chains.
  • k is 3 and "the number of Si atoms linearly linked via Z 3 groups in R a3 " is 1 in all chains.
  • R 72 independently represents a hydroxyl group or a hydrolyzable group.
  • R 72 may be -OR (R is a substituted or unsubstituted C 1-3 alkyl group, which may be a methyl group).
  • R 73 may be independently a hydrogen atom or a lower alkyl group. The number of carbon atoms in the lower alkyl group may be 1-20, or 1-6.
  • R 73 may be a methyl group.
  • p1 is independently on each occurrence an integer from 0 to 3
  • q1 is independently on each occurrence an integer from 0 to 3
  • r1 is independently on each occurrence 0 Integer from ⁇ 3.
  • the sum of p1, q1 and r1 is 3.
  • q1 at the terminal R a3 ' (R a3 itself if no R a3 ' is present) is 2 or more, may be 2 or 3, and is 3 good.
  • R a3 has at least one —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 2 or Si(—Z 3 —SiR 72 q1 R 73 r1 ) 3 at the terminal end. and may have —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 3 .
  • a unit of (-Z 3 -SiR 72 q1 R 73 r1 ) may be (-Z 3 -SiR 72 3 ).
  • the terminal portions of R a may all be —Si(—Z 3 —SiR 72 q1 R 73 r1 ) 3 , and may be —Si(—Z 3 —SiR 72 3 ) 3 .
  • At least one R 72 is present in formulas (C1) and (C2) above.
  • each occurrence of R b3 independently represents a hydroxyl group or a hydrolyzable group.
  • R b3 may be —OR (R is a substituted or unsubstituted C 1-3 alkyl group, which may be a methyl group).
  • each occurrence of R c3 independently represents a hydrogen atom or a lower alkyl group.
  • the number of carbon atoms in the lower alkyl group may be 1-20, or 1-6.
  • R c3 may be a methyl group.
  • X 109 each independently represents a single bond or a divalent to decavalent organic group.
  • X 109 mainly consists of a perfluoropolyether portion (that is, Rf-PFPE portion or PFPE- portion) that provides water repellency and surface slipperiness, and a silane portion (that is, ⁇ is understood as a linker that connects the groups bracketed with Therefore, X 109 may be a single bond or any organic group as long as the compounds represented by formulas (D1) and (D2) can exist stably.
  • ⁇ is an integer of 1-9 and ⁇ ' is an integer of 1-9.
  • ⁇ and ⁇ ' can vary depending on the valence of X109 .
  • the sum of ⁇ and ⁇ ' is the same as the valence of X109 .
  • the sum of ⁇ and ⁇ ' is ten when X 109 is a decavalent organic group.
  • .delta. is 9 and .delta.' is 1, for example.
  • ⁇ is 5 and ⁇ ′ is 5.
  • ⁇ can be 1 and ⁇ ′ can be 9.
  • ⁇ and ⁇ ' are 1 when X 109 is a divalent organic group.
  • ⁇ is the value obtained by subtracting 1 from the valence of X109 .
  • X 109 is a divalent to heptavalent, divalent to tetravalent, or divalent organic group.
  • X 109 is a divalent to tetravalent organic group, ⁇ is 1-3, and ⁇ ' is 1.
  • X 109 is a divalent organic group, ⁇ is 1 and ⁇ ' is 1.
  • the formulas (D1) and (D2) are represented by the following formulas (D1') and (D2').
  • R d3 at each occurrence independently represents -Z 3 '-CR 81 p4 R 82 q4 R 83 r4 .
  • Z 3 ' at each occurrence independently represents an oxygen atom or a divalent organic group.
  • Z 3 ' is, for example, a C 1-6 alkylene group, -(CH 2 ) g4 -O-(CH 2 ) h4 - (g4 is an integer of 0 to 6, and may be an integer of 1 to 6 h4 is an integer of 0 to 6 and may be an integer of 1 to 6), or -phenylene-(CH 2 ) i4 - (i4 is an integer of 0 to 6).
  • Z 3 ′ may be a C 1-3 alkylene group, may be a C 2-3 alkylene group, or may be CH 2 CH 2 . These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
  • R 81 independently represents R d3′′ .
  • R d3′′ has the same meaning as R d3 .
  • R d3 up to 5 Cs are linearly linked via the Z 3 ′ group. That is, in the above R d3 , when at least one R 81 is present, there are two or more Si atoms linked in a straight chain via the Z 3 'group in R d3 , The maximum number of C atoms linked in a straight chain is five.
  • the “number of C atoms linearly linked via a Z 3 ′ group in R d3 ” is the number of repetitions of —Z 3′ -C— linearly linked in R d3 . equal.
  • the number of C atoms linearly linked via the Z 3 ' group in R d3 is 1 (left formula) or 2 pcs (right formula).
  • the number of C atoms linearly linked via the Z 3 ' group in R d3 is 1 or 2 in all chains, and may be 1 .
  • R 82 represents -Y 3 -SiR 85 j R 86 3-j .
  • Y 3 each independently represents a divalent organic group at each occurrence.
  • Y 3 is a C 1-6 alkylene group, —(CH 2 ) g5 —O—(CH 2 ) h5 — (g5 is an integer of 0 to 6 and an integer of 1 to 6 h5 is an integer of 0 to 6 and may be an integer of 1 to 6), or -phenylene-(CH 2 ) i5 - (i5 is an integer of 0 to 6) be.
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. .
  • Y 3 can be a C 1-6 alkylene group or phenylene-(CH 2 ) i5 —.
  • the light resistance, especially UV resistance, can be higher.
  • R 85 independently represents a hydroxyl group or a hydrolyzable group.
  • R 85 may be —OR (R is a substituted or unsubstituted C 1-3 alkyl group, which may be an ethyl group or a methyl group, and may be a methyl group).
  • R 86 independently represents a hydrogen atom or a lower alkyl group.
  • the number of carbon atoms in the lower alkyl group may be 1-20, or 1-6.
  • R 86 may be a methyl group.
  • j is an integer of 1 to 3, may be 2 or 3, or may be 3 independently for each (-Y 3 -SiR 85 j R 86 3-j ) unit.
  • Each occurrence of R 83 independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group. Each occurrence of R 83 may be independently a hydrogen atom or a lower alkyl group. The number of carbon atoms in the lower alkyl group may be 1-20, or 1-6. R 83 may be a methyl group.
  • p4 is independently at each occurrence an integer from 0 to 3
  • q4 is independently at each occurrence an integer from 0 to 3
  • r4 is independently at each occurrence 0 Integer from ⁇ 3.
  • the sum of p4, q4 and r4 is 3.
  • q4 at the terminal R d3 ′′ (R d3 itself if R d3′′ is absent) in R d3 is 2 or more, may be 2 or 3, and may be 3 .
  • R e3 at each occurrence independently represents —Y 3 —SiR 85 j R 86 3-j .
  • Y 3 , R 85 , R 86 and j have the same meanings as described for R 82 above.
  • each occurrence of R f3 independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group.
  • Each occurrence of R f3 may be independently a hydrogen atom or a lower alkyl group.
  • the number of carbon atoms in the lower alkyl group may be 1-20, or 1-6.
  • R f3 may be a methyl group.
  • k′ is independently at each occurrence an integer from 0 to 3
  • l′ at each occurrence is independently an integer from 0 to 3
  • m' is independently an integer from 0 to 3 at each occurrence.
  • the sum of k', l' and m' is 3.
  • At least one k' is 2 or 3, and may be 3.
  • k' is 2 or 3, and may be 3.
  • l' is 2 or 3, and may be 3.
  • At least one q4 is 2 or 3, or at least one l' is 2 or 3. That is, there are at least two -Y 3 -SiR 85 j R 86 3-j groups in the formula.
  • G 5 is -R 17 -O-, -R 17 -CONH-, -CONH- or a single bond. From a phototolerance point of view, G 5 can be -R 17 -CONH- or CONH-. From a chemical resistance point of view, G 5 may be -R 17 -O-.
  • R 17 is an alkylene group.
  • R 17 may be an alkylene group having 1 to 4 carbon atoms, or may be —CH 2 — from the viewpoint of ease of production.
  • Z 5 is a (a5+b5)-valent hydrocarbon group, or a hydrocarbon group having 2 or more carbon atoms and having one or more etheric oxygen atoms between the carbon atoms of the hydrocarbon group, and (a5+b5)-valent is the basis of Z 5 is a residue obtained by removing hydroxyl groups from a polyhydric alcohol having (a5+b5) hydroxyl groups when G 5 is —R 17 —O— and c5 is 1.
  • Z 5 can be the following group.
  • Z5 may be a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group in terms of excellent reactivity of the hydroxyl group.
  • Z 5 is a group represented by the following formula (Z-1), a group represented by the following formula (Z-2), or a group represented by the following formula (Z-3) in terms of availability of raw materials.
  • R E is an alkyl group and may be a methyl group or an ethyl group.
  • a5 is an integer of 1 or more.
  • b5 is an integer of 1 or more.
  • (a5+b5) is 3 or more.
  • a5 is 1, b5 is 4 or more.
  • b5 is 1 or more.
  • a5 [Rf-PFPE-G 5 ] may be the same or different.
  • b5 [(OR 16 ) c5 -SiR 14 n R 15 3-n ] may be the same or different.
  • c5 is 0 or 1;
  • a5 may be from 1 to 10, or from 1 to 4. When a5 is 1 or more, the water and oil repellency, abrasion resistance, fingerprint stain removability, and lubricity of the surface treatment layer are more easily improved. When a5 is 10 or less, the surface treatment layer has a good appearance. (a5+b5) may be 3-15, and may be 3-12.
  • b5 When a5 is 1, b5 is 4 or more, may be 4-10, or may be 4-5. When a5 is 1 and b5 is 4 or more, the abrasion resistance of the surface treatment layer is likely to be improved. When b5 is 10 or less, the appearance of the surface treatment layer and the stability of the compound are likely to be improved.
  • b5 is an integer of 1 or more, may be an integer of 1 to 10, or may be an integer of 1 to 4.
  • a5 is an integer of 2 or more, the lubricity of the surface treatment layer is enhanced, and frictional force is less likely to be applied to the surface treatment layer. Therefore, even if b5 is 1, the wear resistance of the surface treatment layer is likely to be improved.
  • b5 is 10 or less, the appearance of the surface treatment layer and the stability of the compound are likely to be improved.
  • c5 is 0 or 1.
  • c5 may be 0 because the compound has excellent light resistance.
  • c5 may be 1 for the ease of manufacturing the compound.
  • X 101 , X 105 , X 107 , and X 109 are each independently represented by, for example, the formula: -(R 20 ) p2 -(X 20 ) q2 -
  • R 20 is a single bond, —(CH 2 ) s′ —, or an o-, m- or p-phenylene group, which may be —(CH 2 ) s′ —; s′ is an integer from 1 to 20, 1 to 6, 1 to 3, or 1 or 2;
  • X 20 represents -(X 21 ) l' -, X 21 is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R 330 ) 2 -, -( Si(R 330 ) 2 O) m′′ -Si(R 330 ) 2 -, -CONR 331 -,
  • R 20 and X 20 are one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group may be substituted by
  • X 101 , X 105 , X 107 , and X 109 are each independently -(R 20 ) p2 -(X 20 ) q2 -
  • R 20 represents —(CH 2 ) s′ —; s' is an integer from 1 to 20,
  • X 20 represents -(X 21 ) l' -,
  • X 21 at each occurrence independently represents a group selected from the group consisting of —O—, —CONR 331 —, —O—CONR 331 —, and (CH 2 ) n′ —;
  • R 331 at each occurrence independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group;
  • n', at each occurrence, is independently an integer from 1 to 20;
  • l' is an integer from 1 to 10,
  • p2 is 0 or 1;
  • q2 is 0 or 1;
  • at least one of p2 and q2
  • R 20 and X 20 are one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group may be substituted by
  • X 101 , X 105 , X 107 and X 109 are each independently -(R 20 ) p2 -(X 20 ) q2 -R 32 -.
  • R 32 represents a single bond, -(CH 2 ) t' - or an o-, m- or p-phenylene group and may be -(CH 2 ) t' -.
  • t' is an integer from 1-20, 2-6, or 2-3.
  • R 32 (typically the hydrogen atom of R 32 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group good.
  • X 101 , X 105 , X 107 , and X 109 are each independently single bond, —X f —C 1-20 alkylene group, -X f -R 20 -X c -R 32 -, or -X f -X d -R 32 - [In the formula: R 20 and R 32 are as defined above; X f is a single bond or a perfluoroalkylene group having 1 to 6, 1 to 4, or 1 to 2 carbon atoms, and may be a difluoromethylene group. ] can be
  • X 101 , X 105 , X 107 , and X 109 are each independently single bond, —X f —C 1-20 alkylene group, -Xf- ( CH2 ) s'- Xc- , —X f —(CH 2 ) s′ —X c —(CH 2 ) t′ — —X f —X d —, or —X f —X d —(CH 2 ) t′ — [In the formula, X f , s′ and t′ have the same meanings as above. ] is.
  • X c is -O-, -S-, -C(O)O-, -CONR 331- , -O-CONR 331- , —Si(R 330 ) 2 —, —(Si(R 330 ) 2 O) m′′ —Si(R 330 ) 2 —, —O—(CH 2 ) u′ —(Si(R 330 ) 2 O) m′′ —Si(R 330 ) 2 —, —O—(CH 2 ) u′ —Si(R 330 ) 2 —O—Si(R 330 ) 2 —CH 2 CH 2 —Si(R 330 ) 2 —O—Si(R 330 ) 2 —, —O—(CH 2 ) u′ —Si(OCH 3 ) 2 OSi(OCH 3 ) 2 —, —CONR 331 —(CH 2 )
  • X d is -S-, -C(O)O-, -CONR 331- , -O-CONR 331- , —CONR 331 —(CH 2 ) u′ —(Si(R 330 ) 2 O) m′′ —Si(R 330 ) 2 —, —CONR 331 —(CH 2 ) u′ —N(R 331 )—, or —CONR 331 —(o-, m- or p-phenylene)—Si(R 330 ) 2 — [In the formula, each symbol has the same meaning as described above. ] represents
  • X 101 , X 105 , X 107 , and X 109 are each independently single bond, —X f —C 1-20 alkylene group, —X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —, or —X f —X d —(CH 2 ) t′ — [In the formula, each symbol has the same meaning as described above. ] can be
  • X 101 , X 105 , X 107 , and X 109 are each independently a single bond —X f —C 1-20 alkylene group, —X f —(CH 2 ) s′ —X c —, or —X f —(CH 2 ) s′ —X c —(CH 2 ) t′ —
  • X c is —O—, —CONR 331 —, or O—CONR 331 —;
  • R 331 at each occurrence independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group; s' is an integer from 1 to 20, t' is an integer from 1 to 20;
  • s' is an integer from 1 to 20
  • t' is an integer from 1 to 20;
  • X 101 , X 105 , X 107 , and X 109 are each independently single bond, —X f —C 1-20 alkylene group, —X f —(CH 2 ) s′ —O—(CH 2 ) t′ —, —X f —(CH 2 ) s′ —(Si(R 330 ) 2 O) m′′ —Si(R 330 ) 2 —(CH 2 ) t′ —, —X f —(CH 2 ) s′ —O—(CH 2 ) u′ —(Si(R 330 ) 2 O) m′′ —Si(R 330 ) 2 —(CH 2 ) t′ —, or —X f- ( CH2 ) s'- O- ( CH2 ) t' -Si( R330 ) 2- ( CH2 ) u'- Si( R330 ) 2- ( C
  • --(C v H 2v )-- may be linear or branched.
  • -(C v H 2v )- can be, for example, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )-, -CH(CH 3 )CH 2 -.
  • X 101 , X 105 , X 107 and X 109 groups are each independently a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (typically a C 1-3 perfluoroalkyl group).
  • X 101 , X 105 , X 107 and X 109 are attached to the PFPE group on the left side of each formula.
  • X f may be a single bond in formulas (A1), (B1), (C1) and (D1).
  • X f in formulas (A2), (B2), (C2) and (D2) may be a perfluoroalkylene group having 1 to 6, 1 to 4, or 1 to 2 carbon atoms, or a difluoromethylene group; It's okay.
  • the X 101 , X 105 , X 107 , and X 109 groups can each independently be other than —O—C 1-6 alkylene groups.
  • the X 101 , X 105 , X 107 , and X 109 groups are, for example, of the formula:
  • each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, which may be a methyl group;
  • D is —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CF 2 O(CH 2 ) 3 —, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, —CONH—(CH 2 ) 3 —, -CON(CH 3 )-(CH 2 ) 3 -, -CON(Ph)-(CH 2 ) 3 -, where Ph means phenyl, and
  • each R 42 is independently a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, may be a methyl group or a methoxy group, or may be a methyl group .
  • E is a group selected from E is -(CH 2 ) n - (n is an integer of 2 to 6)
  • D is attached to PFPE in the backbone of the molecule and E is attached to the group opposite PFPE.
  • X 101 , X 105 , X 107 and X 109 are: single bond, —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 6 —, -CF2 - CH2 -O- CH2- , —CF 2 —CH 2 —O—(CH 2 ) 2 —, —CF 2 —CH 2 —O—(CH 2 ) 3 —, —CF 2 —CH 2 —O—(CH 2 ) 6 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi
  • X 101 , X 105 , X 107 , and X 109 are each independently of the formula: —(R 35 ) x1 —(CFR 36 ) y1 —(CH 2 ) z1 — [In the formula: x1, y1 and z1 are each independently an integer from 0 to 10; the sum of x1, y1 and z1 is greater than or equal to 1; The order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula. ] is represented by
  • each occurrence of R 35 is independently an oxygen atom, phenylene, carbazolylene, —NR 350 — (wherein R 350 represents a hydrogen atom or an organic group) or a divalent organic group; Alternatively, it may be a divalent polar group.
  • the lower alkyl group is, for example, an alkyl group having 1 to 6 carbon atoms (eg methyl, ethyl, n-propyl). Lower-alkyl groups may be optionally substituted with one or more fluorine atoms.
  • Each occurrence of R 36 is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, and may be a fluorine atom.
  • the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 6 or 1 to 3 carbon atoms, may be a perfluoroalkyl group having 1 to 3 carbon atoms, a trifluoromethyl group or a pentafluoroalkyl group. It may be an ethyl group or a trifluoromethyl group.
  • the X 101 , X 105 , X 107 , and X 109 groups have the formula:
  • each R 51 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, which may be a methyl group;
  • each X 101 group any of the following groups attached to PFPE of the molecular backbone: —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CF 2 O(CH 2 ) 3 —, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, —CONH—(CH 2 ) 3 —, -CON(CH 3 )-(CH 2 ) 3 -, -CON(Ph)-(CH 2 ) 3 -, where Ph means phenyl, or
  • each R 52 is independently a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, may be a methyl group or a methoxy group, or may be a methyl group.
  • Some of the other Ts are groups opposite PFPE in the molecular backbone (i.e., carbon atoms in formulas (A1), (A2), (D1) and (D2); also formula (B1) below, Si atoms in (B2), (C1) and (C2), and the remaining T, if present, are each independently a methyl group, a phenyl group, a C 1-6 alkoxy group, a radical scavenging group, or an ultraviolet absorbing group is.] is represented by
  • the radical-scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation.
  • Radical scavenger groups include, for example, residues of benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates, hindered amines, hindered phenols, or triazines. mentioned.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays.
  • UV-absorbing groups include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and residues of benzoxazoles. groups.
  • the radical-scavenging group or UV-absorbing group has the following formula:
  • X 101 , X 105 , X 107 and X 109 can each independently be a 3- to 10-valent organic group.
  • the PFPE silane compound ⁇ is a compound represented by formula (A1), (B1), (C1), (D1), or (E1) above.
  • the PFPE silane compound ⁇ is a compound represented by formula (A2), (B2), (C2), or (D2) above.
  • the PFPE silane compound ⁇ is a compound represented by the above formula (A1), (A2), (C1), (C2), (D1), (D2), or (E1). These compounds can have a plurality of Si atoms having hydroxyl groups or hydrolyzable groups at their ends, so that the wear resistance can be further improved.
  • the PFPE silane compound ⁇ is a compound represented by (C1), (C2), (D1), (D2), or (E1) above.
  • the PFPE silane compound ⁇ is a compound represented by (C1), (C2), (D1), or (D2) above.
  • the PFPE silane compound ⁇ is a compound represented by formulas (A1) and (A2) above.
  • the PFPE silane compound ⁇ is a compound represented by formulas (B1) and (B2) above.
  • the PFPE silane compound ⁇ is a compound represented by the above formulas (C1) and (C2). This can further improve wear resistance and surface slipperiness.
  • the compounds represented by the above formulas (C1) and (C2) are also highly miscible with compounds containing an isocyanuric skeleton such as the PFPE silane compound ⁇ .
  • the PFPE silane compound ⁇ is a compound represented by formulas (D1) and (D2) above.
  • the PFPE silane compound ⁇ is a compound represented by formula (E1) above.
  • the average molecular weight of the PFPE silane compound ⁇ may be 1,000 or more, 1,500 or more, or 2,000 or more.
  • the average molecular weight of the PFPE silane compound ⁇ may be 30,000 or less, and may be 10,000 or less. In one aspect, the average molecular weight of the PFPE silane compound ⁇ is 1,000 or more and 10,000 or less.
  • the weight ratio of PFPE silane compound ⁇ to PFPE silane compound ⁇ is 1:99 to 99:1, 5:95 to 90:10, 30:70 to 90:10, or 30: It may be 70-70:30.
  • the compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2), and (E1) are produced by known methods. can do.
  • the surface treatment agents of the present disclosure may further include other compounds other than PFPE silane compounds ⁇ and ⁇ .
  • Other compounds typically include compounds in which the isocyanuric ring of the PFPE silane compound ⁇ is opened (another silane compound), and compounds derived from the synthesis of the PFPE silane compound ⁇ .
  • silane compounds include the following formula ( ⁇ 1') and formula ( ⁇ 2'):
  • each symbol has the same meaning as the formula ( ⁇ 1) and formula ( ⁇ 2). ] and compounds of the formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1 ), (D2) and (E1).
  • the perfluoropolyether group having no OCF 2 units is represented by, for example, the following formula: - (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 X 10 6 ) d - (OC 2 F 4 ) e - [In the formula, each symbol has the same meaning as the above polyether chain. ] is represented by
  • the perfluoropolyether group having no OCF 2 units has the following formula: -(OC 3 X 10 6 ) d - [wherein d and X 10 have the same meanings as above, and X 10 may be F; ] and a group represented by the following formula: -( OC2F4 - R2'' ) g'' - wherein R 2′′ is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 and g′′ is an integer of 2-100. ] may be represented by
  • —(OC 3 X 10 6 ) d — may be —(OC 3 F 6 ) d —, —(OCF(CF 3 )CF 2 ) d — or (OCF 2 CF 2 CF 2 ) d — may be -(OCF 2 CF 2 CF 2 ) d -.
  • the content of the other silane compound is, for example, 0.01 to 20 mol parts, may be 0.1 to 15 mol parts, or may be 1 to 10 mol parts with respect to 100 mol parts of the PFPE silane compound ⁇ . , 3 to 5 mol parts.
  • Compounds derived from the synthesis of PFPE silane compound ⁇ include, for example, R 1 —OSO 2 CF 3 or CF 3 SO 2 OR 1′ —OSO 2 CF 3 .
  • the surface treatment agent may further contain a crosslinkable compound.
  • the crosslinkable compound causes a sol-gel reaction of the PFPE silane compound ⁇ .
  • surface segregation of the PFPE silane compound ⁇ is promoted, and the antifouling property can be further improved.
  • the crosslinkable compound has the following formula (Q1): A[Z q1 -M q (OR q1 ) wn1 (R q2 ) wn2-wn1 ] wa1 [Z q2 -R q3 ] wa2 (Q1) [In the formula: A is a monovalent to decavalent organic group, Z q1 is each independently a single bond or a divalent organic group, M q is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr, or Zn; each R q1 is independently a hydrogen atom or a C 1-6 alkyl group, each R q2 is independently a hydrogen atom or a hydrocarbon group, wn1 is each independently 1 or more (the valence of M q ⁇ 1) or less; wn2 are each independently (valence of M q ⁇ 1), Z q2 is each independently a single bond or a divalent organic group, each R q3 is independently a
  • A is a monovalent to decavalent organic group, preferably monovalent to octavalent, more preferably monovalent to hexavalent, still more preferably monovalent to tetravalent, still more preferably monovalent to trivalent, particularly preferably 2 or It is a trivalent organic group.
  • A is a divalent organic group.
  • the divalent organic group preferably has the following formula: -[(R A1 ) a11 -(R A2 ) a12 -(R A3 ) a13 ]- [In the formula: Each R A1 is independently an alkylene group, preferably a C 1-20 alkylene group, more preferably a C 1-10 alkylene group, still more preferably a C 1-6 alkylene group, still more preferably a C 1-4 alkylene group is the basis, Each R A2 is independently a cycloalkylene group, preferably a C 3-20 cycloalkylene group, more preferably a C 3-10 cycloalkylene group, still more preferably a C 5-8 cycloalkylene group, still more preferably C a 5-7 cycloalkylene group, each R A3 is independently an arylene group, preferably a C 6-20 arylene group, more preferably a C 6-10 arylene group, still more preferably a C 6-8 arylene group,
  • A is R A1 (an alkylene group as described above).
  • the alkylene group in R A1 may be linear or branched, but is preferably linear.
  • A is a trivalent organic group.
  • the trivalent organic group preferably has the following formula: [In the formula: Each X a is independently a single bond or a divalent organic group. ] is represented by
  • X a is a single bond.
  • X a is a divalent organic group.
  • the divalent organic group for X a is preferably an alkylene group or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, more preferably a single bond. , a C 1-10 alkylene group, or a C 1-10 divalent hydrocarbon group containing at least one bond selected from the group consisting of an ether bond and an ester bond.
  • the divalent organic group in X a preferably has the following formula: -(CF 2 ) m111 -(CH 2 ) m112 -O-(CH 2 ) m113 - (Wherein, m111 is an integer of 1 to 3, m112 is an integer of 1 to 3, and m113 is an integer of 1 to 3.)
  • the divalent organic group for X a is not particularly limited, but specifically, —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, —C 4 H 8 —, —C 4 H 8 —O—CH 2 —, —CO—O—CH 2 —CH(OH) —CH 2 —, —(CF 2 ) n15 — (n15 is an integer of 0 to 4), —(CF 2 ) n25 —(CH 2 ) m25 — (n25 and m25 are each independently 0 4), —CF 2 CF 2 CH 2 OCH 2 CH(OH)CH 2 —, —CF 2 CF 2 CH 2 OCH 2 CH(OSi(OCH 3 ) 3 )CH 2 — etc.
  • Each Z q1 is independently a single bond or a divalent organic group.
  • Z q1 is a single bond.
  • each Z q1 is independently a divalent organic group.
  • the divalent organic groups in Z q1 are each independently an alkylene group, preferably a C 1-20 alkylene group, more preferably a C 1-10 alkylene group, still more preferably a C 1-6 alkylene group, and still more A C 1-4 alkylene group is preferred.
  • Mq is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr, or Zn.
  • Mq is preferably Si, Ti or Zr, more preferably Si.
  • Each R q1 is independently a hydrogen atom or a C 1-6 alkyl group.
  • each R q1 is independently a C 1-6 alkyl group, preferably a C 1-3 alkyl group, more preferably a C 1-2 alkyl group.
  • Each R q2 is independently a hydrogen atom or a hydrocarbon group.
  • Each R q2 is independently a hydrocarbon group.
  • the hydrocarbon group in R q2 is preferably a C 1-6 alkyl group, preferably a C 1-3 alkyl group, more preferably a C 1-2 alkyl group.
  • Each wn1 is independently from 1 to (valence of M q ⁇ 1), and wn2 is (valence of M q ⁇ 1).
  • wn1 is preferably 2 or more (valence of M q ⁇ 1) or less, more preferably 3 or more (valence of M q ⁇ 1) or less, and still more preferably (valence of M q ⁇ 1).
  • Each Z q2 is independently a single bond or a divalent organic group.
  • Z q2 is a single bond.
  • each Z q2 is independently a divalent organic group.
  • the divalent organic group in Z q2 above is preferably a C 1-6 alkylene group, —(CH 2 ) z21 —O—(CH 2 ) z22 — (wherein z21 is an integer of 0 to 6, for example is an integer of 1 to 6, and z22 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z23 -phenylene-(CH 2 ) z24 - (wherein z23 is is an integer from 0 to 6, such as an integer from 1 to 6, and z24 is an integer from 0 to 6, such as an integer from 1 to 6).
  • Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups. is preferably unsubstituted.
  • Z 1 is a C 1-6 alkylene group, or —(CH 2 ) z21 —O—(CH 2 ) z22 —, wherein z21 is an integer of 0-6, such as an integer of 1-6 and z22 is an integer from 0 to 6, such as an integer from 1 to 6).
  • Each R q3 is independently a reactive group.
  • Each R q3 group above is independently an isocyanate group, an epoxy group, or a vinyl group.
  • the reactive group is an isocyanate group.
  • the reactive group is an epoxy group.
  • the reactive group is a vinyl group.
  • wa1 is an integer from 1 to 10
  • wa2 is an integer from 0 to 10
  • the sum of wa1 and wa2 is the valence of A.
  • wa1 is an integer from 1 to 10 and wa2 is 0.
  • wa1 is an integer of 1-10 and wa2 is an integer of 1-10.
  • wa1 is 1 or 2 and wa2 is 0 or 1, preferably wa1 is 1 and wa2 is 1.
  • M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr, or Zn.
  • M is preferably Si, Ti or Zr, more preferably Si.
  • Each R q is independently a hydrogen atom, a C 1-6 alkyl group, or R q1 —CO—.
  • Each R q is independently preferably a C 1-6 alkyl group, more preferably a C 1-3 alkyl group, still more preferably a C 1-2 alkyl group.
  • Each R q' is independently a C 1-3 alkyl group or a C 1-3 alkoxy group.
  • the alkyl group in R q′ above is preferably a methyl group or an ethyl group, more preferably a methyl group.
  • the alkoxy group in R q′ above is preferably a methoxy group or an ethoxy group, more preferably an ethoxy group.
  • nq is the valence of M
  • nq is 0 or more and the valence of M or less.
  • nq is the valence of M.
  • (mq-nq) is 1.
  • the concentration of the crosslinkable compound is, for example, 3 parts by mass or more, and may be 10 parts by mass or more with respect to 100 parts by mass of the surface treatment agent.
  • the concentration of the crosslinkable compound is, for example, 30 parts by mass or less, and may be 20 parts by mass or less. In one aspect, the concentration of the crosslinkable compound is 3 parts by mass or more and 30 parts by mass or less.
  • a surface treatment agent containing a crosslinkable compound may further contain an acid catalyst.
  • the content of the acid catalyst may be 0.1 parts by mass or more, or may be 0.5 parts by mass or more with respect to 100 parts by mass of the surface treatment agent.
  • the content of the acid catalyst may be 5 parts by mass or less, and may be 3 parts by mass or less. In one aspect, the content of the acid catalyst is 0.1 parts by mass or more and 5 parts by mass or less.
  • acid catalysts include inorganic acids such as nitric acid, hydrochloric acid and sulfuric acid; dicarboxylic acids such as oxalic acid and hexafluoroglutaric acid; and organic acids such as p-toluenesulfonic acid and trifluoroacetic acid.
  • Acid catalysts can be hydrochloric acid, oxalic acid and nitric acid.
  • Organic solvent The surface treatment agent may be diluted with an organic solvent.
  • the organic solvent is not particularly limited as long as it can uniformly disperse and dissolve the PFPE silane compound ⁇ and the like.
  • the organic solvent includes, for example, perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro- 1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg, bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons; hydrofluoroethers (HFE).
  • perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms
  • polyfluoroaromatic hydrocarbons eg, bis(trifluoromethyl)benzene
  • polyfluoroaliphatic hydrocarbons hydrofluoroethers (HFE).
  • examples of the organic solvent include lower alcohols such as ethanol, butanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve. aromatic hydrocarbons such as xylene and toluene; aliphatic hydrocarbons such as n-hexane and n-heptane; and esters such as ethyl acetate and butyl acetate. These organic solvents can be used alone or as a mixture of two or more containing fluorine-containing solvents.
  • Polyfluoroaliphatic hydrocarbons include, for example, C 6 F 13 CH 2 CH 3 (eg, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1, 1, 2, 2, 3, 3, 4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.).
  • Hydrofluoroethers (HFE) include, for example, perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (eg, Novec (trademark) 7000 manufactured by Sumitomo 3M), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (e.g.
  • NovecTM 7100 manufactured by Sumitomo 3M Limited perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) (e.g. NovecTM 7200 manufactured by Sumitomo 3M Limited), Alkyl perfluoroalkyl ethers ( perfluoroalkyl groups and alkyl may be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (eg, Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.).
  • the organic solvent may be a hydrofluoroether and may be perfluorobutyl methyl ether ( C4F9OCH3 ) and/or perfluorobutylethyl ether ( C4F9OC2H5 ) .
  • the surface treatment agent includes a (non-reactive) fluoropolyether compound (typically a perfluoro(poly)ether compound) that can be understood as a fluorine-containing oil (hereinafter referred to as "fluorine-containing oil").
  • fluorine-containing oil can be The fluorine-containing oil can improve the surface lubricity of the surface treatment layer.
  • the fluorine-containing oil is not particularly limited.
  • examples thereof include perfluoropolyether compounds represented by the following general formula (3).
  • Rf 11 represents a C 1-16 alkyl group optionally substituted with one or more fluorine atoms (typically a C 1-16 perfluoroalkyl group).
  • Rf 21 represents a C 1-16 alkyl group optionally substituted by one or more fluorine atoms (typically a C 1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom .
  • Rf 11 and Rf 21 may each independently be a C 1-3 perfluoroalkyl group.
  • a1, b1, c1 and d1 each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are independently integers of 0 or more and 300 or less. The sum of a1, b1, c1 and d1 is at least 1, may be 1-300, and may be 20-300.
  • each repeating unit bracketed with subscript a1, b1, c1 or d1 is arbitrary in the formula.
  • -( OC4F8 )- is -( OCF2CF2CF2CF2 ) - , -(OCF( CF3 ) CF2CF2 )- , -( OCF2CF ( CF3 ) CF2 ) - , -( OCF2CF2CF ( CF3 ))-, - ( OC( CF3 ) 2CF2 )-, -( OCF2C ( CF3 ) 2 ) - , -(OCF( CF3 )CF( CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )-, or -(OCF 2 CF(C 2 F 5 ))-, and -(OCF 2 CF 2 CF 2 CF 2 )-.
  • -(OC 3 F 6 )- may be -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )-, or -(OCF 2 CF(CF 3 ))- , —(OCF 2 CF 2 CF 2 )—.
  • -(OC 2 F 4 )- may be -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-, and may be -(OCF 2 CF 2 )-.
  • the perfluoropolyether compound is represented by either of the following general formulas (3a) and (3b). These are used singly or as a mixture of two or more.
  • b1′′ is an integer of 1 or more and 100 or less.
  • a1′′ and b1′′ are each independently 0 or more and 30 or less, and may be an integer of 1 or more and 30 or less.
  • c1′′ and d1′′ are each independently an integer of 1 or more and 300 or less. The order of existence of each repeating unit enclosed in parentheses with subscripts a1′′, b1′′, c1′′, and d1′′ is arbitrary in the formula.
  • the average molecular weight of the fluorine-containing oil may be from 1,000 to 30,000. Thereby, the surface slipperiness can be further improved.
  • the content of the fluorine-containing oil may be, for example, 0.1 to 500 parts by mass, or may be 1 to 400 parts by mass, with respect to a total of 100 parts by mass of the PFPE silane compound ⁇ and PFPE silane compound ⁇ . It may be up to 300 parts by mass.
  • Fluorine-containing oil has the general formula: Rf31 -F [wherein Rf 31 is a C 5-16 perfluoroalkyl group; ] or a chlorotrifluoroethylene oligomer.
  • the surface treatment agent may contain a (non-reactive) silicone compound, which may be understood as silicone oil (hereinafter referred to as “silicone oil”). Thereby, the surface lubricity of the surface treatment layer can be improved.
  • silicone oil hereinafter referred to as “silicone oil”.
  • silicone oils include linear or cyclic ones with 2,000 or less siloxane bonds.
  • Linear silicone oils may be so-called straight silicone oils and modified silicone oils.
  • straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
  • Modified silicone oils include those obtained by modifying straight silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • Cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil.
  • the content of the silicone oil may be, for example, 0 to 300 parts by mass, or 0 to 200 parts by mass with respect to a total of 100 parts by mass of the PFPE silane compound ⁇ and PFPE silane compound ⁇ .
  • the surface treatment agent may further contain other additives.
  • Other additives include, for example, thickeners, leveling agents, antifoaming agents, antistatic agents, antifogging agents, ultraviolet absorbers, radical scavengers, pigments, dyes, fillers, catalysts, alcohols, transition metals, halogens compound ions, and compounds containing atoms with lone pairs of electrons in their molecular structures.
  • the surface treatment agent may contain at least one of an ultraviolet absorber and a radical scavenger.
  • Ultraviolet absorbers and radical scavengers include those exemplified as those that can be included in the primer.
  • the (total) concentration of the ultraviolet absorber and/or radical scavenger is, for example, 0.5% by mass or more, and may be 1.0% by mass or more, relative to 100% by mass of the surface treatment agent. 0% by mass or more.
  • the concentration of the ultraviolet absorber and/or radical scavenger is, for example, 3.0% by mass or less, and may be 2.5% by mass or less. In one aspect, the concentration of the ultraviolet absorber and/or radical scavenger is 0.5% by mass or more and 3.0% by mass or less.
  • catalysts include acids (eg, acetic acid, formic acid, trifluoroacetic acid), bases (eg, ammonia, triethylamine, diethylamine), and transition metals (eg, Ti, Ni, Sn).
  • acids eg, acetic acid, formic acid, trifluoroacetic acid
  • bases eg, ammonia, triethylamine, diethylamine
  • transition metals eg, Ti, Ni, Sn
  • Alcohols include, for example, alcohol compounds having 1 to 6 carbon atoms.
  • transition metals examples include platinum, ruthenium, and rhodium.
  • halide ions examples include chloride ions.
  • a compound containing an atom having a lone pair in its molecular structure contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom, a sulfur atom, or a nitrogen atom. You can stay.
  • the compound containing an atom having a lone pair in its molecular structure is, for example, at least one selected from the group consisting of aliphatic amine compounds, aromatic amine compounds, phosphoramide compounds, amide compounds, urea compounds and sulfoxide compounds. is.
  • the compound may be at least one selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphate amides, urea compounds and sulfoxide compounds, and from sulfoxide compounds, aliphatic amine compounds and aromatic amine compounds It may be at least one selected from the group consisting of and may be a sulfoxide compound.
  • Examples of aliphatic amine compounds include diethylamine and triethylamine.
  • Examples of aromatic amine compounds include aniline and pyridine.
  • Phosphoramide compounds include, for example, hexamethylphosphoramide.
  • Examples of amide compounds include N,N-diethylacetamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylformamide, N,N-dimethylformamide and N-methylpyrrolidone.
  • Urea compounds include tetramethylurea.
  • Sulfoxide compounds include dimethylsulfoxide (DMSO), tetramethylenesulfoxide, methylphenylsulfoxide, diphenylsulfoxide.
  • a compound containing an atom with a lone pair of electrons in its molecular structure may be dimethylsulfoxide or tetramethylenesulfoxide.
  • a method for manufacturing an article according to the present disclosure comprises forming a primer layer on an organic substrate using a primer containing a coupling agent having an organic reactive group and a hydrolyzable silyl group in one molecule; and forming a surface treatment layer directly on the primer layer using a surface treatment agent containing a PFPE silane compound ⁇ .
  • the primer and surface treatment agent are respectively as described above.
  • the method of applying the primer is not particularly limited.
  • the application method includes, for example, a wet coating method.
  • Wet coating methods include, for example, dip coating, spin coating, flow coating, spray coating, roll coating, and gravure coating.
  • the primer may be applied by spin coating.
  • the amount of primer applied is not particularly limited.
  • the primer is applied, for example, so that the thickness of the primer layer is 1 nm or more and 50 nm or less.
  • heat treatment may be performed to remove the organic solvent contained in the primer.
  • the heat treatment conditions are appropriately set according to the type and amount of the organic solvent, the thickness of the primer layer, and the like.
  • the method of applying the surface treatment agent is not particularly limited. Examples of the coating method include the wet coating method described above.
  • the surface treatment agent may be applied by a spray coating method.
  • the amount of surface treatment agent to be applied is not particularly limited.
  • the surface treatment agent is applied, for example, so that the thickness of the surface treatment layer is 1 nm or more and 50 nm or less.
  • Post-treatment may be performed after the surface treatment agent is applied.
  • the post-treatment can improve the durability of the surface treatment layer.
  • the post-treatment may be heating.
  • the heating conditions are not particularly limited.
  • the heating temperature may be, for example, 60-250°C, or 100-180°C.
  • the heating time may be, for example, 30 minutes to 5 hours, or 1 to 3 hours.
  • the post-treatment may be to sequentially supply moisture and heat.
  • the water acts on the hydrolyzable groups bonded to Si of the PFPE silane compound ⁇ in the surface treatment agent, and the compound can be rapidly hydrolyzed.
  • Heating facilitates the progress of the dehydration condensation reaction between the groups bonded to Si after hydrolysis between the PFPE silane compounds ⁇ .
  • the heating causes the groups bonded to Si after hydrolysis of the PFPE silane compound ⁇ to react with the reactive groups existing on the surface of the organic substrate.
  • the reactive groups present on the surface of the organic substrate are hydroxyl groups, a dehydration condensation reaction can proceed. As a result, bonds are formed between the PFPE silane compound ⁇ and also between the PFPE silane compound ⁇ and the organic substrate.
  • the method of supplying water is not particularly limited.
  • Moisture supply is caused, for example, by condensation due to a temperature difference between a film formed by a surface treatment agent (precursor of the surface treatment layer; hereinafter also referred to as a "precursor layer”) and the surrounding atmosphere, and water vapor to the precursor layer. (Steam) is performed by spraying.
  • the temperature of the surroundings or moisture when supplying moisture is not particularly limited.
  • the temperature is, for example, 0 to 250° C., may be 60° C. or higher, or may be 100° C. or higher.
  • the temperature may be 180° C. or lower, and may be 150° C. or lower.
  • the heating is performed in a dry atmosphere exceeding 60°C, for example.
  • a heating method is not particularly limited.
  • an organic substrate with a precursor layer may be placed in an atmosphere above 60° C. and at an unsaturated water vapor pressure.
  • the heating temperature may be above 100°C, may be 250°C or lower, and may be 180°C or lower. Heating may be performed under normal pressure.
  • the post-treatment may be one in which water supply and dry heating are continuously performed.
  • a continuous work-up is carried out, for example, by using superheated steam.
  • Superheated steam is obtained by heating saturated steam to a temperature higher than the boiling point.
  • Superheated steam is high-temperature steam obtained by heating water to a temperature above its boiling point (over 100° C. under normal pressure, generally 250° C. or lower, for example, 180° C. or lower).
  • the temperature difference between the superheated steam and the precursor layer first causes dew condensation on the surface of the precursor layer, thereby supplying moisture to the precursor layer.
  • the temperature difference between the superheated steam and the precursor layer becomes smaller, the moisture on the surface of the precursor layer evaporates in the dry atmosphere of the superheated steam, and the moisture content on the surface of the precursor layer gradually decreases.
  • the precursor layer While the moisture content on the surface of the precursor layer is decreasing, i.e., while the precursor layer is in a dry atmosphere, the precursor layer is brought into contact with the superheated steam to increase the temperature of the superheated steam (100° C. under normal pressure). above). That is, only by exposing the precursor layer to superheated steam, moisture supply and drying heating are performed continuously.
  • the above post-treatment does not have to be performed.
  • the organic substrate may be allowed to stand still for 8 hours or longer, preferably 12 hours or longer, and more preferably 15 hours or longer.
  • the temperature during standing may be room temperature, for example 20 to 35°C.
  • the present disclosure includes surface treatment agents used in the manufacture of the articles described above.
  • the surface treatment agent includes the PFPE silane compound ⁇ described above. Details such as the concentration of the PFPE silane compound ⁇ and other components that may be contained in the surface treatment agent are as described above.
  • the article of the present disclosure maintains antifouling performance even after long-term use under severe environmental conditions such as wind and rain and adhesion of contaminants outdoors.
  • the surface treatment agent of the present disclosure can form an antifouling layer with excellent wear resistance and weather resistance.
  • Target base material resin [Example 1] (1) Preparation of Organic Substrate A polycarbonate substrate (thickness: 2 mm, planar dimensions: 100 mm x 100 mm) was washed with water and alcohol to obtain an organic substrate.
  • Primer 3-Aminopropyltrimethoxysilane was added to ethanol to obtain a primer with an APTMS concentration of 1.0% by mass.
  • Primer Layer A primer was applied to the surface of the organic substrate by spin coating. Then, it was dried at 130° C. for 5 minutes to form a primer layer with a thickness of 5 nm.
  • Example 2 An article was obtained in the same manner as in Example 1, except that the PFPE-containing silane compound (B) was used instead of the PFPE-containing silane compound (A).
  • Example 3 PFPE-containing silane compound (C) was used instead of PFPE-containing silane compound (A), and tetraethoxysilane (crosslinking compound, TEOS) was added to the surface treatment agent so that the concentration was 4.5%.
  • TEOS crosslinking compound
  • Example 4 An article was obtained in the same manner as in Example 1, except that 3-glycidoxypropyltrimethoxysilane (GPTMS) was added instead of APTMS.
  • GTMS 3-glycidoxypropyltrimethoxysilane
  • Adhesion Adhesion of the surface treatment layer was evaluated by a cross-cut test. Specifically, 11 cuts were made on the test surface using a utility knife to reach the base material, 100 cuts were made in a grid with a cut interval of 2 mm, Cellotape (registered trademark) was strongly crimped to the part, and the edge of the tape was was pulled off at once at an angle of 45°. After peeling off the tape, the grid pattern was painted with a black oil-based pen (manufactured by Zebra Co., Ltd., trade name: McKee), and the portion where the ink was not repelled was defined as the defective portion of the surface treatment layer. Evaluation criteria are as follows.
  • Antifouling property B (ability to wipe off oil-based ink)
  • a straight line of about 3 cm was drawn in one direction with a constant load using a black oil-based pen (manufactured by Zebra Co., Ltd., trade name: McKee). After leaving it for 10 minutes, it was wiped off three times with a cellulose nonwoven fabric to evaluate the wiping performance. Evaluation criteria are as follows. G: The oil-based ink was completely wiped off within 3 times NG: The oil-based ink could not be completely wiped off
  • Abrasion resistance Durability was evaluated by cotton friction. Specifically, the obtained article was placed horizontally, and cotton (manufactured by Asahi Kasei Corp., trade name: BEMCOT (registered trademark) M3-II) was brought into contact with the surface treatment layer. The cotton was slid at a speed of 60 reciprocations/minute while applying a load of 1 kg/cm 2 . The static contact angle of water (contact angle with water) was measured every 1000 reciprocations.
  • the static contact angle of water was measured by the following method using a fully automatic contact angle meter DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.). 2 ⁇ L of water was dropped from a microsyringe onto an article placed horizontally, and a still image was taken with a video microscope 1 second after dropping. The water contact angle was measured at five different points, and the average value was taken as the water contact angle of the article.
  • FIG. 1 shows the relationship between the cumulative irradiation dose (total exposure dose) and the contact angle of water.
  • Target base material rubber
  • Example 5 (1) Preparation of organic substrate A substrate made of nitrile rubber (thickness: 5 mm, planar dimensions: 50 mm x 100 mm) was washed with water and alcohol to obtain an organic substrate.
  • Primer Layer A primer was applied to the surface of the organic substrate by spin coating. After that, it was dried at 120° C. for 5 minutes to form a primer layer with a thickness of 5 nm.
  • Formation of surface treatment layer A surface treatment agent was applied by spin coating. After that, it was dried by heating in the air at 120° C. for 30 minutes to form a surface treatment layer. Thus, an article having a rubber organic substrate, a primer layer and a surface treatment layer was obtained.
  • Comparative Example 4 was an untreated product in which the primer layer and the surface treatment layer were not formed.
  • the resin articles produced in Examples 1 to 4 are excellent in wear resistance and weather resistance in addition to initial antifouling performance.
  • the rubber articles produced in Examples 5 and 6 are also excellent in wear resistance and weather resistance in addition to the initial antifouling performance. .
  • the article of the present disclosure has excellent wear resistance and weather resistance, and is particularly suitable for outdoor use.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un article ayant une couche traitée en surface qui présente une excellente résistance aux intempéries et une excellente résistance à l'abrasion, et son procédé de fabrication, ainsi qu'un agent de traitement de surface. Cet article est pourvu : d'un matériau de base organique ; d'une couche d'apprêt qui est située sur le matériau de base organique et qui est formée d'une amorce contenant un agent de couplage qui possède un groupe réactif organique et un groupe silyle hydrolysable dans la molécule ; et d'une couche traitée en surface qui est située immédiatement au-dessus de la couche d'apprêt et qui est formée d'un agent de traitement de surface contenant un composé silane contenant un groupe fluoropolyéther. Le composé silane contenant un groupe fluoropolyéther est représenté par la formule (α1) ou la formule (α2) [dans les formules, chaque symbole est tel que défini dans la description].
PCT/JP2023/007367 2022-03-01 2023-02-28 Article et son procédé de fabrication, et agent de traitement de surface WO2023167197A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152392A1 (fr) * 2015-03-24 2016-09-29 セメダイン株式会社 Composition durcissable
WO2018207811A1 (fr) * 2017-05-12 2018-11-15 Ａｇｃ株式会社 Article antisalissure et procédé de production d'un article antisalissure
WO2021024964A1 (fr) * 2019-08-02 2021-02-11 ダイキン工業株式会社 Composé isocyanul contenant du fluor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152392A1 (fr) * 2015-03-24 2016-09-29 セメダイン株式会社 Composition durcissable
WO2018207811A1 (fr) * 2017-05-12 2018-11-15 Ａｇｃ株式会社 Article antisalissure et procédé de production d'un article antisalissure
WO2021024964A1 (fr) * 2019-08-02 2021-02-11 ダイキン工業株式会社 Composé isocyanul contenant du fluor

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