WO2022059620A1 - 撥水撥油層付き基材、および撥水撥油層付き基材の製造方法 - Google Patents

撥水撥油層付き基材、および撥水撥油層付き基材の製造方法 Download PDF

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WO2022059620A1
WO2022059620A1 PCT/JP2021/033352 JP2021033352W WO2022059620A1 WO 2022059620 A1 WO2022059620 A1 WO 2022059620A1 JP 2021033352 W JP2021033352 W JP 2021033352W WO 2022059620 A1 WO2022059620 A1 WO 2022059620A1
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group
repellent
water
oil
compound
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French (fr)
Japanese (ja)
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隆太 高下
豊和 遠田
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2022550530A priority Critical patent/JP7768139B2/ja
Priority to KR1020237003301A priority patent/KR20230069905A/ko
Priority to CN202180063695.6A priority patent/CN116194226A/zh
Publication of WO2022059620A1 publication Critical patent/WO2022059620A1/ja
Priority to US18/104,853 priority patent/US20230256469A1/en
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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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • B05D5/086—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers having an anchoring layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • 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
    • 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
    • B05D1/60—Deposition of organic layers from vapour phase
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • 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
    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/548—No curing step for the last layer
    • B05D7/5483—No curing step for any layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • 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
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • 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
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/30—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant
    • B05D2401/33—Form of the coating product, e.g. solution, water dispersion, powders or the like the coating being applied in other forms than involving eliminable solvent, diluent or dispersant applied as vapours polymerising in situ
    • 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
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

Definitions

  • the present invention relates to a base material with a water-repellent oil-repellent layer and a method for manufacturing a base material with a water-repellent oil-repellent layer.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a base material with a water-repellent oil-repellent layer and a base material with a water-repellent oil-repellent layer having excellent wear resistance.
  • the present invention is the following [1] to [12]. [1] It has a base material, a base layer formed on the surface of the base material, and a water-repellent and oil-repellent layer formed on the surface of the base layer.
  • the underlayer is at least one selected from the group consisting of silicon and the group 1 element, the 2nd group element, the 4th group element, the 5th group element, the 13th group element, and the 15th group element in the periodic table. Contains oxides containing one specific element and
  • the water-repellent oil-repellent layer is composed of a hydrolyzed condensate of a fluorine-containing ether compound selected from the group consisting of a compound represented by the formula (A1) and a compound represented by the formula (A2).
  • R f is a fluoroalkyl group having 1 to 20 carbon atoms.
  • R f1 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • R f2 is a hydrocarbon group having a (1 + b) -valent fluorine atom, and when at least the carbon atom bonded to R 1 has a fluorine atom and there are a plurality of R f2s , even if the R f2s are the same. May be different, R 1 is an alkylene group having 1 to 20 carbon atoms. R 2 is an alkylene group which may have a fluorine atom having 2 to 20 carbon atoms, and a plurality of R 2 may be the same or different.
  • R 3 is an alkyl group which may have a hydrogen atom or a fluorine atom having 1 to 10 carbon atoms, and when there are a plurality of R 3 , the plurality of R 3 may be the same but different.
  • T is ⁇ Si (R) 3-c (L) c , and a plurality of Ts may be the same or different.
  • R is an alkyl group L is a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different.
  • m is an integer from 1 to 20 and a is an integer of 1 to 3, and when there are a plurality of a, the plurality of a may be the same or different.
  • b is an integer of 1 or more, and when there are a plurality of b, the plurality of b may be the same or different.
  • c is 2 or 3, and a plurality of cs may be the same or different.
  • b is 1, a is 2 or 3.
  • the R f2 has b partial structures "-CQC- * (where Q is a hydrogen atom, a fluorine atom or CF 3 , and-* is a bond that bonds to R 1 )".
  • the specific element is any one of [1] to [3], which is at least one selected from the group consisting of Group 1 elements, Group 2 elements, and Group 13 elements in the periodic table.
  • [5] The base material with a water-repellent oil-repellent layer according to any one of [1] to [4], wherein the specific element is a Group 1 element in the periodic table.
  • [6] The base material with a water-repellent oil-repellent layer according to any one of [1] to [5], wherein b is 1.
  • Base material With the water- and oil-repell
  • R f is a fluoroalkyl group having 1 to 20 carbon atoms.
  • R f1 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • R f2 is a hydrocarbon group having a (1 + b) -valent fluorine atom, and when at least the carbon atom bonded to R 1 has a fluorine atom and there are a plurality of R f2s , even if the R f2s are the same. May be different, R 1 is an alkylene group having 1 to 20 carbon atoms.
  • R 2 is an alkylene group which may have a fluorine atom having 2 to 20 carbon atoms, and a plurality of R 2 may be the same or different.
  • R 3 is an alkyl group which may have a hydrogen atom or a fluorine atom having 1 to 10 carbon atoms, and when there are a plurality of R 3 , the plurality of R 3 may be the same but different.
  • T is ⁇ Si (R) 3-c (L) c , and a plurality of Ts may be the same or different.
  • R is an alkyl group L is a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different.
  • m is an integer from 1 to 20 and a is an integer of 1 to 3, and when there are a plurality of a, the plurality of a may be the same or different.
  • b is an integer of 1 or more, and when there are a plurality of b, the plurality of b may be the same or different.
  • c is 2 or 3, and a plurality of cs may be the same or different.
  • b is 1, a is 2 or 3.
  • the R f2 has b partial structures "-CQF- * (where Q is a hydrogen atom, a fluorine atom or CF 3 , and-* is a bond that binds to R 1 )".
  • the present invention it is possible to provide a base material with a water-repellent oil-repellent layer and a base material with a water-repellent oil-repellent layer having excellent wear resistance.
  • the compound represented by the formula (A1) is referred to as a compound (A1).
  • Compounds and the like represented by other formulas are also similar to these.
  • the meanings of the following terms in the present specification are as follows.
  • the "reactive silyl group” is a general term for a hydrolyzable silyl group and a silanol group (Si—OH).
  • the reactive silyl group is, for example, T in formula (A1) or formula (A2), i.e. —Si (R) 3-c (L) c .
  • the "hydrolyzable silyl group” means a group capable of forming a silanol group by a hydrolyzing reaction.
  • the "molecular weight" of the polyfluoropolyether chain is determined by 1 H-NMR and 19 F-NMR. It is a number average molecular weight calculated by obtaining the number (average value) of oxyfluoroalkylene units based on the terminal group.
  • the terminal group is, for example, R f in the formula (A1) or T in the formula (A1) or the formula (A2).
  • the "molecular weight" of the polyfluoropolyether chain is R f by 1 H-NMR and 19 F-NMR. It is a molecular weight calculated by determining the structure.
  • the base material with a water-repellent oil-repellent layer of the present invention has a base material, a base layer, and a water-repellent oil-repellent layer in this order.
  • FIG. 1 is a cross-sectional view schematically showing an example of a base material with a water-repellent and oil-repellent layer of the present invention.
  • the base material 10 with a water- and oil-repellent layer has a base material 12, a base layer 14 formed on one surface of the base material 12, and a water- and oil-repellent layer 16 formed on the surface of the base layer 14.
  • FIG. 1 is a cross-sectional view schematically showing an example of a base material with a water-repellent and oil-repellent layer of the present invention.
  • the base material 10 with a water- and oil-repellent layer has a base material 12, a base layer 14 formed on one surface of the base material 12, and a water- and oil-repellent layer 16 formed on the surface of the base
  • the base material 12 and the base layer 14 are in contact with each other, but the base material with a water-repellent and oil-repellent layer is not shown between the base material 12 and the base layer 14. It may have a layer of. Further, in the example of FIG. 1, the base layer 14 and the water-repellent oil-repellent layer 16 are in contact with each other, but the base material with the water-repellent oil-repellent layer has another material (not shown) between the base layer 14 and the water-repellent oil-repellent layer 16. It may have a layer. In the example of FIG.
  • the base layer 14 is formed on the entire surface of one surface of the base material 12, but the base layer 14 is not limited to this, and the base layer 14 is formed only on a part of the region of the base material 12. May be good.
  • the water- and oil-repellent layer 16 is formed on the entire surface of the base layer 14, but the water- and oil-repellent layer 16 is not limited to this, and the water- and oil-repellent layer 16 is formed only in a part of the base layer 14. It may be formed.
  • the base layer 14 and the water-repellent oil-repellent layer 16 are formed only on one surface of the base material 12, but the base layer 14 and the water-repellent layer 16 are not limited to this.
  • the oil repellent layer 16 may be formed.
  • the base material is not particularly limited as long as it is a base material that is required to be imparted with water and oil repellency.
  • Specific examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof.
  • the glass may be chemically strengthened.
  • As the base material a touch panel base material and a display base material are preferable, and a touch panel base material is particularly preferable.
  • the base material for the touch panel preferably has translucency. "Having translucency" means that the vertically incident visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more.
  • the material of the base material for the touch panel is preferably glass or a transparent resin. Further, examples of the base material include the following.
  • the glass or resin is used for the exterior portion (excluding the display unit) of a device such as a glass or resin, a mobile phone (for example, a smartphone), a mobile information terminal, a game machine, or a remote control.
  • the shape of the base material may be a plate shape or a film shape.
  • the base material may be a base material having one surface or both sides subjected to surface treatment such as corona discharge treatment, plasma treatment, and plasma graft polymerization treatment.
  • surface treatment such as corona discharge treatment, plasma treatment, and plasma graft polymerization treatment.
  • the surface-treated surface has better adhesion between the base material and the base layer, and as a result, the water- and oil-repellent layer has better wear resistance. Therefore, it is preferable to apply a surface treatment to the surface of the base material on the side in contact with the base layer.
  • the underlayer is at least one selected from the group consisting of silicon and group 1 elements, group 2 elements, group 4 elements, group 5 elements, group 13 elements, and group 15 elements of the periodic table. It is a layer containing an oxide containing a specific element.
  • Group 1 elements of the periodic table mean lithium, sodium, potassium, rubidium and cesium.
  • Group 1 elements include lithium, sodium, and potassium because a water- and oil-repellent layer can be formed more uniformly on the underlayer without defects, or the composition of the underlayer can be more suppressed from variation between samples. Is preferable, and sodium and potassium are particularly preferable.
  • the underlayer may contain two or more Group 1 elements.
  • Group 2 element in the periodic table means beryllium, magnesium, calcium, strontium and barium.
  • Group 2 elements include magnesium, calcium, and barium because a water- and oil-repellent layer can be formed more uniformly on the base layer without defects, or the variation in the composition of the base layer between samples is further suppressed. Is preferable, and magnesium and calcium are particularly preferable.
  • the underlayer may contain two or more Group 2 elements.
  • Group 4 elements of the periodic table mean titanium, zirconium, and hafnium.
  • Group 4 element titanium and zirconium are preferable because the water- and oil-repellent layer can be formed more uniformly on the base layer without defects, or the variation in the composition of the base layer between the samples is further suppressed.
  • Titanium is particularly preferred.
  • the base layer may contain two or more Group 4 elements.
  • Group 5 elements in the periodic table mean vanadium, niobium and tantalum.
  • vanadium is particularly preferable because the water- and oil-repellent layer has more excellent wear resistance.
  • the base layer may contain two or more Group 5 elements.
  • the 13th group element (hereinafter, also referred to as "13th group element") in the periodic table means boron, aluminum, gallium and indium.
  • Group 13 elements boron, aluminum, and gallium are used because a water- and oil-repellent layer can be formed more uniformly on the base layer without defects, or the variation in the composition of the base layer between samples is further suppressed. Is preferable, and boron and aluminum are particularly preferable.
  • the underlayer may contain two or more Group 13 elements.
  • the 15th group element (hereinafter, also referred to as "15th group element") in the periodic table means nitrogen, phosphorus, arsenic, antimony and bismuth.
  • Group 15 elements include phosphorus, antimony, and bismuth because a water- and oil-repellent layer can be formed more uniformly on the base layer without defects, or the variation in the composition of the base layer between samples is further suppressed. Is preferable, and phosphorus and bismuth are particularly preferable.
  • the underlayer may contain two or more Group 15 elements.
  • Group 1 elements, Group 2 elements, and Group 13 elements are preferable because the water- and oil-repellent layer has better wear resistance, and Group 1 and Group 2 elements are more. Group 1 elements are preferred, and Group 1 elements are particularly preferred. As the specific element, only one kind of element may be contained or two or more kinds of elements may be contained.
  • the oxide contained in the base layer may be a mixture of oxides of the above elements (silicon and a specific element) alone (for example, a mixture of silicon oxide and an oxide of a specific element), or the above elements may be used. It may be a composite oxide containing two or more kinds, or it may be a mixture of an oxide of the above element alone and a composite oxide.
  • the ratio of the total molar concentration of the specific element in the base layer to the molar concentration of silicon in the base layer (specific element / silicon) is 0.02 to 2. It is preferably 90, more preferably 0.10 to 2.00, and particularly preferably 0.20 to 1.80.
  • the molar concentration (mol%) of each element in the underlayer can be measured, for example, by depth direction analysis by X-ray photoelectron spectroscopy (XPS) using ion sputtering.
  • the base layer may be a single layer or a plurality of layers.
  • the base layer may have irregularities on the surface.
  • the thickness of the base layer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and particularly preferably 2 to 20 nm.
  • the thickness of the base layer is at least the above lower limit value, the adhesiveness of the water-repellent oil-repellent layer by the base layer is further improved, and the wear resistance of the water-repellent oil-repellent layer is more excellent.
  • the thickness of the base layer is not more than the above upper limit value, the wear resistance of the base layer itself is excellent.
  • the thickness of the base layer is measured by observing the cross section of the base layer with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the water- and oil-repellent layer is composed of a hydrolyzed condensate of a fluorine-containing ether compound selected from the group consisting of the compound (A1) and the compound (A2).
  • the fluorine-containing ether compound is a fluorine-containing compound having a reactive silyl group. That is, the water- and oil-repellent layer contains a condensate in which some or all of the reactive silyl groups of the fluorine-containing compound have undergone a hydrolysis reaction and a dehydration condensation reaction.
  • the water-repellent and oil-repellent layer may be composed of a hydrolyzed condensate of the compound (A1), may be composed of a hydrolyzed condensate of the compound (A2), or may be composed of a compound ( It may be composed of both the hydrolyzed condensate of A1) and the hydrolyzed condensate of compound (A2).
  • R f is a fluoroalkyl group having 1 to 20 carbon atoms.
  • R f1 is a fluoroalkylene group having 1 to 6 carbon atoms.
  • R f2 is a hydrocarbon group having a (1 + b) -valent fluorine atom, and when at least the carbon atom bonded to R 1 has a fluorine atom and there are a plurality of R f2s , even if the R f2s are the same. May be different, R 1 is an alkylene group having 1 to 20 carbon atoms.
  • R 2 is an alkylene group which may have a fluorine atom having 2 to 20 carbon atoms, and a plurality of R 2 may be the same or different.
  • R 3 is an alkyl group which may have a hydrogen atom or a fluorine atom having 1 to 10 carbon atoms, and when there are a plurality of R 3 , the plurality of R 3 may be the same but different.
  • T is ⁇ Si (R) 3-c (L) c , and a plurality of Ts may be the same or different.
  • R is an alkyl group L is a hydrolyzable group or a hydroxyl group, and two or more Ls in T may be the same or different.
  • m is an integer from 1 to 20 and a is an integer of 1 to 3, and when there are a plurality of a, the plurality of a may be the same or different.
  • b is an integer of 1 or more, and when there are a plurality of b, the plurality of b may be the same or different.
  • c is 2 or 3, and a plurality of cs may be the same or different.
  • b is 1, a is 2 or 3.
  • Both the compound (A1) and the compound (A2) react with the polyfluoropolyether chain [R f -O- (R f1 O) m- ] or [-O- (R f1 O) m- ]. It has a sex silyl group and a specific linking group -R f2 [-R 1 -C (-R 2- ) a ] b that links the polyfluoropolyether chain to the reactive silyl group.
  • the compound (A1) is a compound having a structure of "monovalent polyfluoropolyether chain-linking group-reactive silyl group”
  • the compound (A2) is a "reactive silyl group-linking group-2 valent”. It is a compound having a structure of "polyfluoropolyether chain-linking group-reactive silyl group”.
  • the linking group is composed of a hydrocarbon group. Therefore, the chemical stability is improved with respect to the linking group containing an ether bond and the like contained in the compounds widely used conventionally.
  • R f is a fluoroalkyl group having 1 to 20 carbon atoms.
  • the number of carbon atoms of the fluoroalkyl group of Rf is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3 from the viewpoint of having more excellent water and oil repellency or abrasion resistance of the water and oil repellent layer. ..
  • a perfluoroalkyl group is preferable because the water- and oil-repellent layer has more excellent water- and oil-repellent properties or abrasion resistance.
  • the compound (A1) in which R f is a perfluoroalkyl group has a terminal CF 3- .
  • a water- and oil-repellent layer having low surface energy can be formed, so that the water- and oil-repellent layer has more excellent water- and oil-repellent resistance and abrasion resistance.
  • the fluoroalkyl group of R f include CF 3- , CF 3 CF 2- , CF 3 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2- , CF 3 CF (CF 3 )-.
  • the structure represented by the following formula (D1) is preferable from the viewpoint that the water-repellent oil-repellent layer has more excellent water-repellent and oil-repellent properties or friction resistance.
  • R f11 O m1 (R f12 O) m2 (R f13 O) m3 (R f14 O) m4 (R f15 O) m5 (R f16 O) m6 ...
  • R f11 is a fluoroalkylene group having 1 carbon atom.
  • R f12 is a fluoroalkylene group having 2 carbon atoms.
  • R f13 is a fluoroalkylene group having 3 carbon atoms.
  • R f14 is a fluoroalkylene group having 4 carbon atoms.
  • R f15 is a fluoroalkylene group having 5 carbon atoms.
  • R f16 is a fluoroalkylene group having 6 carbon atoms.
  • m1, m2, m3, m4, m5, and m6 independently represent integers of 0 or 1 or more, m1 + m2 + m3 + m4 + m5 + m6 are integers of 1 to 200, and when there are a plurality of R f11 to R f16 , the plurality of R f11 ⁇ R f16 may be the same or different.
  • the binding order of (R f11 O) to (R f16 O) in the formula (D1) is arbitrary.
  • M1 to m6 in the formula (D1) represent the number of (R f11 O) to (R f16 O ), respectively, and do not represent the arrangement.
  • (R f15 O) m5 indicates that the number of (R f15 O) is m5, and does not represent the block arrangement structure of (R f5 O) m5 .
  • the description order of (R f11 O) to (R f16 O) does not represent the binding order of each unit.
  • the fluoroalkylene group having 3 to 6 carbon atoms may be a linear fluoroalkylene group, or may be a fluoroalkylene group having a branched or ring structure.
  • R f1 it is preferable that 50 to 100% of the total number of m is a perfluoroalkylene group, more preferably 80 to 100% is a perfluoroalkylene group, and all of them are perfluoroalkylene groups. It is particularly preferable to have.
  • R f11 include CHF and CF 2 .
  • Specific examples of R f12 include CF 2 CF 2 , CF 2 CHF, and CF 2 CH 2 .
  • R f13 examples include CF 2 CF 2 CF 2 , CF 2 CF 2 CHF, CF 2 CHF CF 2 , CF 2 CF 2 CH 2 , CF 2 CH 2 CF 2 , and CF (CF 3 ) CF 2 . ..
  • R f14 include CF 2 CF 2 CF 2 CF 2 , CF 2 CF 2 CF 2 CH 2 , CHF CF 2 CF 2 CF 2 , CF 2 CH 2 CF 2 CF 2 , CF (CF 3 ) CF 2 CF.
  • Perfluorocyclobutane-1,2-diyl group can be mentioned.
  • R f15 examples include CF 2 CF 2 CF 2 CF 2 CF 2 , CF 2 CF 2 CF 2 CH 2 , CHF CF 2 CF 2 CF 2 , CF 2 CF 2 CH 2 CF 2 CF 2 .
  • R f16 include CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 , CF 2 CF 2 CF 2 CF 2 CH 2 , CF 2 CF 2 CF 2 CF 2 CHF.
  • R f2 is a hydrocarbon group having a (1 + b) -valent fluorine atom, and at least the carbon atom bonded to R 1 has a fluorine atom.
  • R f2 a hydrocarbon having b partial structures "-CQF- * (where Q is a hydrogen atom, a fluorine atom or CF 3 and-* is a bond that bonds to R 1 )". It is preferably a group.
  • the hydrocarbon group include linear or branched chain hydrocarbon groups, aliphatic hydrocarbon rings, aromatic hydrocarbon rings, and combinations thereof. Hydrocarbon groups may have double or triple bonds in the carbon chain.
  • Examples of the combination include those in which a chain hydrocarbon group and an aliphatic hydrocarbon ring are bonded, and those in which a chain hydrocarbon group and an aromatic hydrocarbon ring are bonded.
  • the carbon number of R f2 is preferably 1 to 18, and more preferably 1 to 16.
  • R f2 is a divalent group.
  • R f2 in this case include a fluoroalkylene group.
  • R f2 in the case of b is preferably a fluoroalkylene group having 1 to 6 carbon atoms, and perfluoro having 1 to 6 carbon atoms.
  • An alkylene group is particularly preferred.
  • Specific examples of R f2 in this case are -CHF- *, -CF 2- *, CF 2 CF 2- *, CF 2 CHF- * , CH 2 CF 2- *, CF 2 CF 2 CF 2- *.
  • R f2 is a (1 + b) valence group having one or more branch points P selected from a tertiary carbon atom, a quaternary carbon atom, and a ring structure.
  • branch point As the carbon atoms constituting the branch point, tertiary carbon atoms and quaternary carbon atoms are preferable because the compound can be easily produced and the water- and oil-repellent layer has more excellent water- and oil-repellent properties or friction resistance. ..
  • the ring structure constituting the branch point is a 3- to 8-membered aliphatic ring, 6 to 8 because it is easy to produce a compound and the water- and oil-repellent layer has better water- and oil-repellent properties or abrasion resistance. Examples thereof include an aromatic ring of a member ring and a fused ring composed of two or more of these rings. Examples of the ring structure constituting the branch point include the ring structure shown in the following equation. The following ring structure may be substituted with a fluorine atom. Further, the ring structure may have an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or the like which may have a halogen atom as a substituent.
  • R f2 a combination of two or more divalent fluoroalkylene groups and one or more branching points P is preferable.
  • R f2 has a hydrocarbon ring
  • a combination of a hydrocarbon ring having three or more branch points P and two or more divalent fluoroalkylene groups is preferable.
  • R f2 is trivalent or higher is shown below.
  • RF represents ( R f1 O) m
  • ⁇ * represents a bond that binds to R 1
  • RF does not constitute R f 2 .
  • R 1 is an alkylene group having 1 to 20 carbon atoms. R 1 does not have a fluorine atom.
  • the carbon number of R 1 is preferably 5 to 20, and particularly preferably 7 to 10 from the viewpoint that the water and oil repellent layer has more excellent water and oil repellency or abrasion resistance. Further, from the viewpoint that the water- and oil-repellent layer has more excellent water- and oil-repellent properties or abrasion resistance, the carbon number of R 1 is preferably an odd number, and particularly preferably 3, 5, 7 or 9.
  • R 2 is an alkylene group which may have a fluorine atom having 2 to 20 carbon atoms.
  • the carbon number of R2 is preferably 3 to 20 and more preferably 3 to 10 from the viewpoint that the water and oil repellent layer is more excellent in water and oil repellency or abrasion resistance. It is preferable that at least one of the plurality of R 2 has 3 to 10 carbon atoms because the water-repellent oil-repellent layer has more excellent water-repellent and friction-resistant properties.
  • R 3 is an alkyl group which may have a hydrogen atom or a fluorine atom having 1 to 10 carbon atoms.
  • R3 an alkyl group which may have a hydrogen atom and a fluorine atom having 1 to 8 carbon atoms is preferable, and a hydrogen atom is preferable because the water- and oil-repellent layer has more excellent water-repellent and oil-repellent properties or abrasion resistance. Is more preferable.
  • T is —Si (R) 3-c (L) c and is a reactive silyl group.
  • a reactive silyl group is a group in which either one or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom.
  • a hydrolyzable group is a group that becomes a hydroxyl group by a hydrolytic reaction. That is, the hydrolyzable silyl group becomes a silanol group (Si—OH) by the hydrolysis reaction. The silanol group further undergoes an intramolecular dehydration condensation reaction to form a Si—O—Si bond.
  • the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material to form a chemical bond (base material-O-Si).
  • the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanate group.
  • the alkoxy group an alkoxy group having 1 to 6 carbon atoms is preferable.
  • the halogen atom a chlorine atom is preferable.
  • the acyl group an acyl group having 1 to 6 carbon atoms is preferable.
  • an acyloxy group having 1 to 6 carbon atoms is preferable.
  • an alkoxy group and a halogen atom are preferable from the viewpoint of easy production of a compound.
  • an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgas during coating and the compound is excellent in storage stability, and an ethoxy group is used when long-term storage stability of the compound is required. Is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.
  • the number of carbon atoms of the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2 from the viewpoint of easy production of a compound.
  • c, 2 and 3 are preferable, and 3 is more preferable, from the viewpoint that the adhesion of the water-repellent and oil-repellent layer becomes stronger.
  • the plurality of Ts may be the same or different. From the viewpoint of easy production of the compound, it is preferable that a plurality of T's are the same group.
  • two or more Ts are arranged at each end from the viewpoint that the water- and oil-repellent layer has more excellent water- and oil-repellent properties or friction resistance.
  • a is 2 or 3.
  • b is preferably 1 from the viewpoint that the water- and oil-repellent layer has more excellent water- and oil-repellent properties or abrasion resistance.
  • all b are 1.
  • a is preferably 3 from the viewpoint that the water- and oil-repellent layer has more excellent water- and oil-repellent properties or abrasion resistance.
  • all a are 3.
  • Examples of the compound (A1) and the compound (A2) include the compounds of the following formulas. Further, from the viewpoint of durability, the present compound preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) of 1.2 or less.
  • n3 and n4 in the formula represent the number of repeating units, and each is an integer of 1 to 100 independently.
  • the compound (A1) can be produced, for example, by a method in which the following compound (A11) and the compound (1a) are hydrosilylated.
  • the compound (A2) can be produced, for example, by a method in which the following compound (A21) and the compound (1a) are hydrosilylated.
  • These hydrosilylation reactions can be carried out by known methods.
  • R f -O- (R f1 O) m -R f2 [-R 1 -C (-R 20 -CH CH 2 ) a (-R 3 ) 3-a ] b ...
  • the compound (A11) can be produced, for example, by a method of reacting the following compound (A12) with the following compound (B2).
  • the compound (A21) can be produced, for example, by a method of reacting the following compound (A22) with the following compound (B2).
  • A12) L 2 -CH 2 -R f2- O- (R f1 O) m -R f2- CH 2 -L 2 ...
  • L 2 is a sulfonate group (-O-SO 2 -R 22 )
  • R 22 is an organic group.
  • the reaction of the above scheme (1) can be carried out under relatively mild conditions and in high yield.
  • Specific examples of the sulfonate group include a tosylate group (OTs), a mesylate group (OMs), a triflate group (OTf), and a nonaflate group (ONf). Of these, a triflate group is preferable from the viewpoint of the reaction yield of the scheme (1).
  • the compound (A12) or the compound (A22) is a compound represented by the following compound (A13) or the compound (A23) in the presence of an organic amine compound such as triethylamine or pyridine, and trifluoromethanesulfonic anhydride, tosil lolide, and the like. It can be produced by a method of reacting mesylate or the like to form a sulfonate.
  • a 1 , A 2 and n in the formula are as described above.
  • Compound (A13) and compound (A23) can be produced with reference to, for example, International Publication No. 2017/038830.
  • the compound (B2) can be produced, for example, by a method of reacting the following compound (B1) with metallic magnesium.
  • (CH 2 CH-R 20- ) a (R 3- ) 3-a C-R 21 -X ... (B1)
  • R 20 , R 21 , R 3 , X and a in the formula are the same as those of compound (B2).
  • the amount of the compound (B2) used is 1 to 1 to the total number of the sulfonate groups L2 contained in the compound (A12) or the compound (A12) from the viewpoint of improving the yield of the target product. It is preferably 30 equivalents, more preferably 3 to 20 equivalents, and particularly preferably 5 to 15 equivalents.
  • a transition metal compound as a catalyst from the viewpoint of improving reactivity and increasing yield.
  • the transition metal compound can be appropriately selected and used from known catalysts used in the Grignard reaction.
  • the transition metal compound the compound containing the elements of Group 3 to 12 of the periodic table is preferable as the transition metal, and the compound containing the elements of Group 8 to Group 11 is particularly preferable.
  • the Group 8 to Group 11 elements preferably contain one or more elements selected from the group consisting of copper, nickel, palladium, cobalt, and iron, and particularly preferably contain copper. preferable.
  • the transition metal compound contains copper
  • the copper may be any of 0-valent, monovalent, divalent, and trivalent compounds, but from the viewpoint of catalytic ability, a salt of monovalent or divalent copper or a salt of divalent copper or It is preferably a complex salt. Further, copper chloride is more preferable from the viewpoint of easy availability.
  • the amount of the transition metal compound used is preferably 0.1 to 50 mol%, more preferably 1 to 30 mol%, and 2 to 20 mol% with respect to the total number of sulfonate groups L2. Is particularly preferred.
  • a ligand may be used in combination with the transition metal compound.
  • the yield of the target product is improved by using the ligand.
  • the ligand may not be used.
  • Specific examples of the ligand include 1,3-butadiene, phenylpropine, and tetramethylethylenediamine (TMEDA).
  • TEDA tetramethylethylenediamine
  • the reaction of scheme (1) is usually carried out in a solvent.
  • the solvent can be appropriately selected from the solvents capable of dissolving the compound (A12), the compound (A13) and the compound (B2).
  • the solvent may be a mixed solvent of one kind alone or a combination of two or more kinds.
  • the solvent may be a solvent inert to the reaction. There is no particular limitation.
  • ether solvents such as diethyl ether, tetrahydrofuran and dioxane are preferable, and tetrahydrofuran is more preferable.
  • a mixed solvent in which an ether solvent and a fluorine solvent are combined is preferable.
  • fluorocarbon solvents include hydrofluorocarbons (1H, 4H-perfluorobutane, 1H-perfluorohexane, 1,1,1,3,3-pentafluorobutane, 1,1,2,2,3,3).
  • reaction of the scheme (1) for example, a solution containing the compound (A12) or the compound (A13) is prepared, a transition metal compound and a ligand are added if necessary, and then the separately prepared compound (B2) is added. It can be carried out by adding a solution.
  • the reaction temperature of the scheme (1) may be, for example, ⁇ 20 ° C. to 66 ° C. (boiling point of tetrahydrofuran), preferably ⁇ 20 ° C. to 40 ° C.
  • the thickness of the water-repellent and oil-repellent layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm.
  • the thickness of the water-repellent oil-repellent layer is at least the lower limit, the effect of the water-repellent oil-repellent layer can be sufficiently obtained.
  • the thickness of the water-repellent and oil-repellent layer is not more than the above upper limit, the utilization efficiency is high.
  • the thickness of the water- and oil-repellent layer can be calculated from the vibration cycle of the reflected X-ray interference pattern obtained by the X-ray reflectivity method (XRR) using an X-ray diffractometer for thin film analysis.
  • a base layer containing an oxide containing silicon and the above-mentioned specific element is formed on the base material, and then the compound (A1) and the compound (A1) and the compound (A1) are formed on the base layer.
  • a water- and oil-repellent layer made of a hydrolysis condensate of a fluorine-containing ether compound selected from the group consisting of the compound (A2) is formed.
  • the base layer is formed by a vapor deposition method using a vapor deposition material or a wet coating method.
  • the vapor deposition material used in the vapor deposition method includes silicon and oxides containing specific elements.
  • Specific examples of the form of the vapor-deposited material include powder, melt, sintered body, granulated body, and crushed body, and from the viewpoint of handleability, melted body, sintered body, and granulated body are preferable.
  • the molten material means a solid material obtained by melting the powder of the vapor-filmed material at a high temperature and then cooling and solidifying it.
  • the sintered body means a solid substance obtained by firing the powder of the vapor-filmed material, and if necessary, the powder is press-formed and the molded body is used instead of the powder of the vapor-filmed material. May be good.
  • the granulated material means a solid substance obtained by kneading a powder of a vapor-deposited material and a liquid medium (for example, water, an organic solvent) to obtain particles, and then drying the particles.
  • the thin-film deposition material can be produced, for example, by the following method. -A method of obtaining a powder of a vapor-deposited material by mixing a powder of silicon oxide and a powder of an oxide of a specific element. -A method of obtaining granules of a vapor-deposited material by kneading the powder and water of the vapor-deposited material to obtain particles and then drying the particles.
  • -Silicon-containing powder for example, silicon oxide powder, silica sand, silica gel
  • specific element-containing powder for example, specific element oxide powder, carbonate, sulfate, nitrate, oxalic acid
  • a method of obtaining a sintered body by drying a mixture of (salt, hydroxide) and water, and then firing the dried mixture or a compact obtained by press-molding the dried mixture.
  • -Powder containing silicon for example, powder made of silicon oxide, silica sand, silica gel
  • powder containing a specific element for example, powder of oxide of a specific element, carbonate, sulfate, nitrate, oxalic acid.
  • a method of obtaining a melt by melting a salt (salt, hydroxide) at a high temperature and then cooling and solidifying the melt.
  • the vapor deposition method using a vapor deposition material include a vacuum vapor deposition method.
  • the vacuum vapor deposition method is a method in which a vapor deposition material is evaporated in a vacuum chamber and adhered to the surface of a base material.
  • the temperature at the time of vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the temperature of the boat on which the vapor deposition material is placed) is preferably 100 to 3000 ° C, particularly preferably 500 to 3000 ° C.
  • the pressure at the time of vapor deposition (for example, when a vacuum vapor deposition apparatus is used, the pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, and particularly preferably 0.1 Pa or less.
  • one thin-film deposition material may be used, or two or more thin-film deposition materials containing different elements may be used.
  • the vapor deposition material evaporation method include a resistance heating method in which the vapor deposition material is melted and evaporated on a refractory metal resistance heating boat, an electron beam is applied to the vapor deposition material, and the vapor deposition material is directly heated to surface.
  • the refractory substance can also be evaporated, and since the temperature is low where the electron beam does not hit, there is no risk of reaction with the container or contamination of impurities.
  • the gun method is preferred.
  • a plurality of boats may be used, or all the vaporized materials may be put in a single boat and used.
  • the vapor deposition method may be co-deposited or alternate vapor deposition or the like.
  • silica and a specific source are mixed and used in the same boat
  • silica and a specific element source are co-deposited in separate boats
  • silica and a specific element source are co-deposited in separate boats and alternately vapor-deposited.
  • the conditions and order of vapor deposition are appropriately selected depending on the composition of the underlying layer.
  • a base layer is formed on a substrate by a wet coating method using a coating liquid containing a compound containing silicon, a compound containing a specific element, and a liquid medium.
  • silicon compound examples include silicon oxide, silicic acid, a partial condensate of silicic acid, alkoxysilane, and a partial hydrolysis condensate of alkoxysilane.
  • Specific examples of compounds containing specific elements include oxides of specific elements, alkoxides of specific elements, carbonates of specific elements, sulfates of specific elements, nitrates of specific elements, oxalates of specific elements, and water of specific elements. Examples include oxides.
  • liquid medium examples include water and an organic solvent.
  • organic solvent examples include a fluorinated organic solvent and a non-fluorinated organic solvent.
  • the organic solvent may be used alone or in combination of two or more.
  • fluorinated organic solvent examples include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
  • the fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, for example, C 6 F 13 H (AC-2000: product name, manufactured by AGC), C 6 F 13 C 2 H 5 (AC-6000: product name). , AGC), C 2 F 5 CHFCHFCF 3 (Bertrel: product name, manufactured by DuPont).
  • fluorinated aromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
  • fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable, and for example, CF 3 CH 2 OCF 2 CF 2 H (AE-3000: product name, manufactured by AGC), C 4 F 9 OCH 3 (Novec-7100).
  • fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
  • fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol and hexafluoroisopropanol.
  • non-fluorine-based organic solvent a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used.
  • a hydrocarbon-based organic solvent and a ketone-based organic solvent are used.
  • Ether-based organic solvent, ester-based organic solvent, alcohol-based organic solvent and examples.
  • Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.
  • Specific examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • ether-based organic solvent examples include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
  • ester-based organic solvent examples include ethyl acetate and butyl acetate.
  • alcohol-based organic solvent examples include isopropyl alcohol, ethanol, and n-butanol.
  • the content of the liquid medium is preferably 0.01 to 20% by mass, particularly preferably 0.1 to 10% by mass, based on the total mass of the coating liquid used for forming the base layer.
  • the wet coating method for forming the base layer include a spin coating method, a wipe coating method, a spray coating method, a squishy coating method, a dip coating method, a die coating method, an inkjet method, a flow coating method, and a roll coating method.
  • the cast method, the Langmuir Brodget method, and the gravure coat method can be mentioned.
  • the drying temperature of the coating film is preferably 20 to 200 ° C, particularly preferably 80 to 160 ° C.
  • the water- and oil-repellent layer is dried using a composition containing compound (A1) or compound (A2), or compound (A1) or compound (A2) and a liquid medium (hereinafter, also referred to as "composition"). It can be formed by either a coating method or a wet coating method. Specific examples of the liquid medium contained in the composition are the same as those of the liquid medium mentioned in the coating liquid for forming the base layer, and thus the description thereof will be omitted.
  • the water-repellent and oil-repellent layer can be produced, for example, by the following method.
  • the dry coating method include a vacuum vapor deposition method, a CVD method, and a sputtering method.
  • the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of the fluorine-containing compound and the simplicity of the apparatus.
  • a pellet-like substance obtained by impregnating a metal porous body such as iron or steel with a compound (A1) or a compound (A2) or a composition may be used.
  • the drying temperature after the composition is wet-coated is preferably 20 to 200 ° C, particularly preferably 80 to 160 ° C.
  • the content of the compound (A1) or the compound (A2) in the composition is preferably 0.01 to 50% by mass, particularly preferably 1 to 30% by mass, based on the total mass of the composition.
  • the content of the liquid medium in the composition is preferably 50 to 99.99% by mass, particularly preferably 70 to 99% by mass, based on the total mass of the composition.
  • an operation for promoting the reaction between the compound (A1) or the compound (A2) and the base layer may be performed, if necessary.
  • the operation include heating, humidification, and light irradiation.
  • a substrate with a base layer on which a water- and oil-repellent layer is formed is heated in a water-containing atmosphere to hydrolyze the reactive silyl group contained in the compound (A1) or the compound (A2) into a silanol group.
  • the formation of a siloxane bond by the condensation reaction of the silanol group, the condensation reaction between the silanol group on the surface of the base layer and the silanol group of the fluorine-containing compound, and the like can be promoted.
  • the compounds in the water-repellent and oil-repellent layer that are not chemically bonded to other compounds or the silicon oxide layer may be removed, if necessary.
  • Specific methods include, for example, a method of pouring a solvent over the water-repellent oil-repellent layer, a method of wiping with a cloth soaked with the solvent, and a method of acid-cleaning the surface of the water-repellent oil-repellent layer.
  • the base material with a water- and oil-repellent layer of the present invention is an optical member, a touch panel, an antireflection film, an antireflection glass, a SiO 2 treated glass, a tempered glass, a sapphire glass, and a quartz substrate used as a part of the following product parts. , Useful as mold metal, etc.
  • Products Car navigation, mobile phones, digital cameras, digital video cameras, mobile information terminals (PDAs), portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (gastric cameras, etc.) ), Copies, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, antireflection films, antireflection glass, nanoimprint templates, molds, etc.
  • Examples 1 and 8 to 11 are comparative examples, and examples 2 to 7 and 12 are examples. However, the present invention is not limited to these examples.
  • the blending amount of each component in the table described later indicates a mass standard.
  • the obtained solution was washed with methanol and then subjected to flash column chromatography using silica gel to obtain 0.202 g of the following compound (A-3') which is a precursor of the compound (A-3).
  • the average value of the number of repeating units p is 22, and the average value of q is 25.
  • Example 1 30 g of silicon oxide (manufactured by Canon Optron) and 0.11 g of compound (A-1) were placed as a vapor deposition material (vapor deposition source) on a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M manufactured by ULVAC Kiko). .. A glass substrate was placed in the vacuum vapor deposition apparatus, and the inside of the vacuum vapor deposition apparatus was exhausted until the pressure became 5 ⁇ 10 -3 Pa or less. The boat on which silicon oxide was placed was heated to 2,000 ° C. and vacuum-deposited on a glass substrate to form a base layer having a thickness of 10 nm.
  • the boat on which the compound (A-1) is placed is heated to 700 ° C.
  • the compound (A-1) is vacuum-deposited on the surface of the base layer to form a water- and oil-repellent layer having a thickness of 10 nm, and then 140. Heat-treated at ° C for 30 minutes. In this way, the base material with the water-repellent and oil-repellent layer of Example 1 was obtained.
  • Example 2 The same procedure as in Example 1 was carried out except that the sintered body 1 obtained in the following procedure was used as the vapor deposition material for the base layer to obtain a base material with a water-repellent and oil-repellent layer of Example 2.
  • Erich Intensive Mixer EL-1 manufactured by Japan Eirich, hereinafter referred to as "EL-1"
  • EL-1 Erich Intensive Mixer
  • 2.5 g of soda ash manufactured by Soda Ash Japan
  • silica particles SC5500-SQ trade name, Admatex
  • the stirring speed was changed to 4800 rpm, 40.2 g of distilled water was added while stirring, and the mixture was further stirred at 4800 rpm for 60 seconds. Finally, the mixture was stirred at 1200 rpm for 60 seconds.
  • the obtained particles were taken out from EL-1 and dried at 150 ° C. for 30 minutes, and then fired at 1,150 ° C. for 1 hour to obtain a sintered body 1.
  • Example 3 The amount of soda ash (manufactured by Soda Ash Japan) added is 7.5 g, the amount of silica particles SC5500-SQ (trade name, manufactured by Admatex) is 250 g, and the same procedure as in Example 2 is carried out for firing. I got unity 2. The same procedure as in Example 1 was carried out except that the sintered body 2 was used to obtain a substrate with a water-repellent and oil-repellent layer of Example 3.
  • Example 4 The amount of soda ash (manufactured by Soda Ash Japan) added is 25 g, the amount of silica particles SC5500-SQ (trade name, manufactured by Admatex) is 250 g, and the same procedure as in Example 2 is carried out to carry out the sintered body. I got 3. The same procedure as in Example 1 was carried out except that the sintered body 3 was used to obtain a substrate with a water-repellent and oil-repellent layer of Example 4.
  • Example 5 The amount of soda ash (manufactured by Soda Ash Japan) added is 50 g, the amount of silica particles SC5500-SQ (trade name, manufactured by Admatex) is 250 g, and the same procedure as in Example 2 is carried out to carry out the sintered body. I got 4. The same procedure as in Example 1 was carried out except that the sintered body 3 was used to obtain a substrate with a water-repellent and oil-repellent layer of Example 5.
  • Example 6 The same procedure as in Example 1 was carried out except that the sintered body 5 obtained in the following procedure was used as the vapor deposition material for the base layer to obtain the base material with the water-repellent and oil-repellent layer of Example 6.
  • EL-1 7.5 g of magnesium oxide (MgO manufactured by Wako Pure Chemical Industries, Ltd.) and 250 g of silica particles SC5500-SQ (trade name, manufactured by Admatex Co., Ltd.) were added, and the mixture was stirred and mixed at 2400 rpm for 30 seconds. The stirring speed was changed to 4800 rpm, 40.2 g of distilled water was added while stirring, and the mixture was further stirred at 4800 rpm for 60 seconds. Finally, the mixture was stirred at 1200 rpm for 60 seconds. The obtained particles were taken out from EL-1 and dried at 150 ° C. for 30 minutes, and then fired at 1,150 ° C. for 1 hour to obtain a sintered body 5.
  • MgO magnesium oxide
  • SC5500-SQ trade
  • Example 7 The same procedure as in Example 1 was carried out except that the sintered body 6 obtained in the following procedure was used as the vapor deposition material of the base layer to obtain a base material with a water-repellent and oil-repellent layer of Example 7.
  • EL-1 7.5 g of boric acid particles (Optibor: product name, manufactured by Hayakawa Shoji Co., Ltd.) and 250 g of silica particles SC5500-SQ (trade name, manufactured by Admatex Co., Ltd.) are added, and the mixture is stirred and mixed at 2400 rpm for 30 seconds. did.
  • the stirring speed was changed to 4800 rpm, 40.2 g of distilled water was added while stirring, and the mixture was further stirred at 4800 rpm for 60 seconds. Finally, the mixture was stirred at 1200 rpm for 60 seconds.
  • the obtained particles were taken out from EL-1 and dried at 150 ° C. for 30 minutes, and then fired at 1,150 ° C. for 1 hour to obtain a sintered body 6.
  • Example 8 The base material with the water-repellent and oil-repellent layer of Example 8 was formed in the same manner as in Example 1 except that 0.12 g of the compound (A-2) was arranged as the vapor deposition material (deposited source).
  • Example 9 The sintered body 2 was used in the same manner as in Example 3 except that 0.15 g of the compound (A-2) was arranged as the vapor deposition material (deposit source) to form the base material with the water-repellent and oil-repellent layer of Example 9. ..
  • Example 10 The sintered body 7 was formed in the same manner as in Example 7 except that 0.15 g of the compound (A-2) was arranged as the vapor deposition material (deposited source) to form the base material with the water-repellent and oil-repellent layer of Example 10.
  • Example 11 The base material with the water-repellent and oil-repellent layer of Example 11 was formed in the same manner as in Example 1 except that 0.16 g of the compound (A-3) was arranged as the vapor deposition material (deposited source).
  • Example 12 The base material with the water-repellent and oil-repellent layer of Example 12 was formed in the same manner as in Example 3 except that 0.14 g of the compound (A-3) was arranged as the vapor deposition material (deposited source).
  • the end point B is the point where the molar concentration (mol%) of any element present only in the substrate with respect to all the elements detected by XPS analysis exceeds 30% of the molar concentration (mol%) in the substrate for the first time. And said.
  • the starting point A to the ending point B was defined as the base layer, and the ratio of the average value of the molar concentration (mol%) of the target element to the average value of the molar concentration (mol%) of silicon in the base layer was calculated.
  • X-ray photoelectron spectroscopy analyzer ESCA-5500 manufactured by ULVAC-PHI ⁇ Measurement conditions> X-ray source; Monochromatic AlK ⁇ ray Photoelectron detection angle; 75 degree pass energy with respect to sample surface; 117.4 eV Step energy; 0.5 eV / step Spatter ion; C 60 ion spatter gun raster size with acceleration voltage of 10 kV; 3 x 3 mm 2 Spatter interval; 0.4 minutes Spatter rate of thermal oxide film (SiO 2 film) on silicon wafer of spatter gun; 2.20 nm / min Measurement pitch; 0.88 nm (converted to thermal oxide film on silicon wafer)
  • ⁇ Measurement method of contact angle> The contact angle of about 2 ⁇ L of distilled water placed on the surface of the water- and oil-repellent layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Surface Science Co., Ltd.). Measurements were made at five different points on the surface of the water- and oil-repellent layer, and the average value was calculated. The 2 ⁇ method was used to calculate the contact angle.
  • ⁇ Initial contact angle> For the water- and oil-repellent layer, the initial water contact angle was measured by the above measuring method. The evaluation criteria are as follows. Initial water contact angle: ⁇ (excellent): 115 degrees or more. ⁇ (possible): 105 degrees or more and less than 115 degrees. ⁇ (impossible): Less than 105 degrees.
  • ⁇ Abrasion resistance (steel wool)> For the water- and oil-repellent layer, a reciprocating traverse tester (manufactured by KENT) was used in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), and the steel wool bonster (# 0000) was pressured at 98.07 kPa and speed. : After reciprocating 10,000 times at 320 cm / min, the water contact angle was measured. The smaller the decrease in water repellency (water contact angle) after rubbing, the smaller the decrease in performance due to friction, and the better the friction resistance. The evaluation criteria are as follows. ⁇ (Hide): The change in water contact angle after 10,000 round trips is less than 1 degree.
  • ⁇ (Good) The change in water contact angle after 10,000 round trips is 2 degrees or more and less than 3 degrees.
  • ⁇ (impossible) Change in water contact angle after 10,000 round trips is 4 degrees or more.
  • the base layer contains a specific element
  • the water-repellent and oil-repellent layer is the addition of compound (A1) (that is, compound (A-1)) or compound (A2) (that is, compound (A-3)).
  • the initial water contact angle was more than acceptable, and the wear resistance was more than good.
  • wear resistance was not possible.
  • Examples 9 and 10 in which the base layer contains a specific element but the water- and oil-repellent layer is formed by using a compound other than the compound (A1) and the compound (A2) (that is, the compound (A-2)) are wear-resistant. Was acceptable and inadequate.
  • Examples 2 to 6 and 12 in which the base layer contains a group 1 element (Na) and a group 2 element (Mg) as specific elements have excellent wear resistance or higher.
  • Examples 3, 4, 12 in which the base layer contains a Group 1 element (Na) as a specific element and the ratio of the total molar concentration of the specific element to the molar concentration of silicon in the base layer is 0.02 to 2.90. was excellent in wear resistance.
  • Base material with water-repellent and oil-repellent layer 12 Base material 14 Base layer 16 Water- and oil-repellent layer

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PCT/JP2021/033352 2020-09-16 2021-09-10 撥水撥油層付き基材、および撥水撥油層付き基材の製造方法 Ceased WO2022059620A1 (ja)

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