Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
• • 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
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/001—General methods for coating; Devices therefor
  • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/0075—Cleaning of glass
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D171/02—Polyalkylene oxides
  • C09D171/03—Polyepihalohydrins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/76—Hydrophobic and oleophobic coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/11—Deposition methods from solutions or suspensions
  • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/11—Deposition methods from solutions or suspensions
  • C03C2218/112—Deposition methods from solutions or suspensions by spraying
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/151—Deposition methods from the vapour phase by vacuum evaporation
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/154—Deposition methods from the vapour phase by sputtering

Definitions

• the present invention relates to a method for producing a water- and oil-repellent article comprising a base material, a surface layer having excellent water- and oil-repellency and abrasion resistance, and a base layer provided between the base material and the surface layer, and a water- and oil-repellent article.
• This invention relates to a method for improving water and oil removability in articles.
• touch panel display devices In recent years, with the advancement of IoT, automobiles, industrial equipment, etc. are becoming more electronic, and the incorporation of touch panel display devices, camera devices, and various other types of sensor devices is progressing rapidly. Touch panel displays often come into direct contact with fingers and are prone to dirt such as sebum. When cameras, sensors, and the like are used outdoors, adhesion of water droplets, dust, oil, and the like from rain to the device surface may become a problem. In order to make it difficult for water, oil, etc. to adhere, or to make it easier to remove adhering water, oil, etc., it is desired that the surface of such a device be made water- and oil-repellent.
• Dynamic contact angles include the advancing contact angle ( ⁇ A ) and receding contact angle ( ⁇ R ) described in JIS R3257, and the smaller the difference between them ( ⁇ A ⁇ R ), the more the droplet moves. It is known that it is easy to use (Non-Patent Document 1). In other words, when ⁇ A ⁇ R is small, droplets can be easily removed and water and oil repellency can be said to be high.
• Fluoropolyether group-containing compounds have very low surface free energy, so they have water and oil repellency, chemical resistance, lubricity, mold releasability, stain resistance, etc. Utilizing its properties, it is widely used industrially as water-, oil-, and stain-proofing agents for paper and textiles, lubricants for magnetic recording media, oil-proofing agents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, its properties also mean that it is non-adhesive and non-adhesive to other substrates, and although it can be applied to the surface of the substrate, it is difficult to make the film adhere to it. .
• silane coupling agents are well known as agents that bond organic compounds to the surface of substrates such as glass or cloth, and are widely used as coating agents for the surfaces of various substrates.
• a silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. Hydrolyzable silyl groups cause a self-condensation reaction with moisture in the air to form a film. The coating becomes a durable and strong coating due to the hydrolyzable silyl group chemically and physically bonding to the surface of glass, metal, or the like.
• Patent Documents 1 to 6 Japanese Patent No. 6260579, Japanese Patent No. 6828744, Japanese Patent No. 5761305). , Japanese Patent No. 6451279, Japanese Patent No. 6741074, Japanese Patent No. 6617853).
• a cured coating (water- and oil-repellent layer (antifouling coating thin film) on the surface of a glass substrate surface treated with a composition containing a fluoropolyether group-containing polymer in which a hydrolyzable silyl group is introduced into the fluoropolyether group-containing compound. (also referred to as a layer)) has excellent abrasion resistance against steel wool and has high slip properties.
• Patent Documents 7 to 13 International Publication No. 2014/097388, JP 2020-132498, JP 2020-090652, Patent No. 5655215) (Japanese Patent No. 6601492, Japanese Patent No. 5494656, International Publication No. 2019/035271).
• the water- and oil-repellent layer which is the surface layer, can be produced by a dry method or a wet method, such as vacuum deposition, spray coating, or dip coating.
• the silicon oxide serving as the base layer can be produced by a dry method such as electron beam evaporation, sputtering film formation, or chemical vapor deposition, or a wet method such as dip coating or spin coating.
• the base layer is produced by a dry method, it is better to also produce the surface layer by a dry method.
• the base layer is produced by a wet method, it is better to also produce the surface layer by a wet method. Although it was good, there were cases where the water and oil repellency was not sufficiently exhibited.
• the following documents can be cited as prior art related to the present invention.
• the present invention was made in view of the above circumstances, and includes a method for producing a water- and oil-repellent article having a water- and oil-repellent surface layer having excellent water- and oil-repellency and abrasion resistance on a base material, and a water- and oil-repellent article.
• the object of the present invention is to provide a method for improving the removability of water and oil from articles.
• the present inventors discovered a base material, a silicon oxide base layer formed on the outer surface of the base material, and a silicon oxide base layer formed on the outer surface of the silicon oxide base layer.
• a base material a silicon oxide base layer formed on the outer surface of the base material
• a silicon oxide base layer formed on the outer surface of the silicon oxide base layer a silicon oxide base layer formed on the outer surface of the silicon oxide base layer.
• a fluoropolyether group with a specific structure which will be described later, is added as a water- and oil-repellent surface layer on a silicon oxide base layer formed by a dry method.
• a layer containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a cured product of a partially hydrolyzed condensate thereof is formed by a wet method, water and oil repellency and abrasion It has been discovered that a water- and oil-repellent surface layer with excellent durability can be formed, and the present invention has been completed.
• the present invention provides a method for manufacturing a water- and oil-repellent article having a water- and oil-repellent surface layer as described below, and a method for improving the removability of water and oil in a water- and oil-repellent article.
• a water- and oil-repellent article comprising a base material, a silicon oxide base layer formed on the outer surface of the base material, and a water- and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer.
• the water- and oil-repellent surface layer is mainly composed of a cured product of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a partially hydrolyzed condensate thereof;
• the fluoropolyether group-containing polymer having a degradable silyl group contains one or more fluoropolyether group-containing polymers represented by the following formula (1), (4), or (7), and contains silicon oxide.
• a method for producing a water- and oil-repellent article wherein a base layer is formed by a dry method, and a water- and oil-repellent surface layer is formed by a wet method.
• Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O ) t (C 6 F 12 O) u - C d F 2d -
• d is an integer from 0 to 5 independently for each unit, and p, q, r, s, t and u are each independently 0 is an integer of ⁇ 150, the sum of p, q, r, s, t, and u is an integer of 1 ⁇ 250, and each of these units may be linear or branched.Also, Each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.) is a divalent polyfluorooxyalkylene structure-containing group, and A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is
• R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond, a fluorine atom, a silicon atom and a divalent hydrocarbon group which may have one or more types selected from siloxane bonds.
• Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom, or G, are independently monovalent groups represented by the following formula (5).
• W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or 1 represented by the following formula (6) It is the basis of valence.
• T is a single bond or a divalent group
• L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms
• E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W
• l is an integer from 0 to 20.
• Rf is the same as above
• a 3 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom
• J is independently a monovalent group represented by the following formula (8), and has two or more Ws in J.
• T has 2 to 2 carbon atoms and may contain a single bond or one or more bonds selected from the group consisting of a siloxane bond, a sylalkylene bond, a silyarylene bond, and a diorganosilylene group.
• the water- and oil-repellent surface layer comprises one or more fluoropolyether group-containing polymers represented by the above formula (1), (4) or (7) and/or a partially hydrolyzed condensate thereof, and the following formula: (10) [In the formula, Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O ) t (C 6 F 12 O) u - C d F 2d - (However, d is an integer from 0 to 5 independently for each unit, and p, q, r, s, t and u are each independently 0 is an integer of ⁇ 150, the sum of p, q, r, s, t, and u is an integer of 1 ⁇ 250, and each of these units may be linear or branched.Also, Each repeating unit shown in parentheses with
• a method for manufacturing the water- and oil-repellent article. [16] A water- and oil-repellent article comprising a base material, a silicon oxide base layer formed on the outer surface of the base material, and a water- and oil-repellent surface layer formed on the outer surface of the silicon oxide base layer.
• the water- and oil-repellent surface layer is mainly composed of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a cured product of a partially hydrolyzed condensate thereof, and the surface layer has the hydrolyzable silyl group.
• the fluoropolyether group-containing polymer contains one or more fluoropolyether group-containing polymers represented by the following formula (1), (4), or (7), and a silicon oxide base layer is formed by a dry method.
• a method for improving the removability of water and oil in a water- and oil-repellent article characterized by forming a water- and oil-repellent surface layer by a wet method.
• Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O ) t (C 6 F 12 O) u - C d F 2d -
• d is an integer from 0 to 5 independently for each unit, and p, q, r, s, t and u are each independently 0 is an integer of ⁇ 150, the sum of p, q, r, s, t, and u is an integer of 1 ⁇ 250, and each of these units may be linear or branched.Also, Each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.) is a divalent polyfluorooxyalkylene structure-containing group, and A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is
• R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond, a fluorine atom, a silicon atom and a divalent hydrocarbon group which may have one or more types selected from siloxane bonds.
• Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom, or G, are independently monovalent groups represented by the following formula (5).
• W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or 1 represented by the following formula (6) It is the basis of valence.
• T is a single bond or a divalent group
• L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms
• E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W
• l is an integer from 0 to 20.
• Rf is the same as above
• a 3 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom
• J is independently a monovalent group represented by the following formula (8), and has two or more Ws in J.
• V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond
• M is independently represented by the following formula (9). is a monovalent group shown, (In the formula, Y, S and W are the same as above, and f is an integer from 1 to 3.) e is 1 or 2.
• a base material obtained by the production method of the present invention a silicon oxide base layer formed on the outer surface of the base material by a dry method, and a silicon oxide base layer formed on the outer surface of the silicon oxide base layer by a wet method.
• a water- and oil-repellent article comprising a water- and oil-repellent surface layer mainly composed of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a cured product of a partially hydrolyzed condensate thereof, Excellent water and oil repellency and abrasion durability.
• the method for producing a water- and oil-repellent article of the present invention includes a base material, a silicon oxide underlayer formed on the outer surface of the base material, and a water-repellent repellent formed on the outer surface of the silicon oxide underlayer.
• a method for producing a water- and oil-repellent article comprising an oil surface layer, the water- and oil-repellent surface layer comprising a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a partially hydrolyzed condensate thereof.
• the main component is a cured product
• the fluoropolyether group-containing polymer having a hydrolyzable silyl group contains a fluoropolyether group-containing polymer with a specific structure
• a silicon oxide base layer is formed by a dry method.
• the water- and oil-repellent surface layer is formed by a wet method.
• "mainly composed of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a cured product of a partially hydrolyzed condensate thereof" means the sum of the components constituting the water- and oil-repellent surface layer.
• the content of the cured product of the fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or its partially hydrolyzed condensate is 50% by mass or more (50 to 100% by mass), preferably It means 70% by mass or more (70 to 100% by mass), more preferably 90% by mass or more (90 to 100% by mass).
• the water- and oil-repellent article obtained by the manufacturing method of the present invention is composed of a base material, a silicon oxide base layer formed by a dry method, and a water- and oil-repellent surface layer formed by a wet method.
• the water- and oil-repellent surface layer includes a fluoropolyether group-containing polymer having a specific structure of hydrolyzable silyl groups and/or a partially hydrolyzed polymer on the outer surface of a silicon oxide underlayer formed on a base material. It is formed by a surface treatment agent containing a condensate.
• Glass, metal, or resin can be used as the base material.
• glass include soda glass (also known as soda lime glass), crown glass, lead glass, borosilicate glass, crystallized glass, quartz glass, aluminosilicate glass (also known as aluminosilicate glass), Tempax, and Pyrex ( (registered trademark), Neoceram, etc., but are not limited to these.
• soda glass also known as soda lime glass
• crown glass also known as soda lime glass
• lead glass borosilicate glass, crystallized glass
• quartz glass also known as aluminosilicate glass
• Tempax also known as aluminosilicate glass
• Pyrex (registered trademark), Neoceram, etc.
• the shape of the glass substrate may be plate-like, film-like, or other forms.
• the metal examples include pure metals such as aluminum, titanium, chromium, iron, cobalt, zinc, nickel, and copper, stainless steel (for example, SUS304 mirror finish), alloys such as brass, Kovar, and Inconel, and zinc and nickel. Examples include, but are not limited to, those plated with chromium or the like.
• the shape of the metal base material may be plate-like, rod-like, spherical, or other shapes.
• the resin examples include polycarbonate resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide (PA) resins, polyimide (PI) resins, and cellulose resins such as triacetyl cellulose.
• Resins, styrene resins such as polystyrene (PS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, etc.
• thermoplastic organic resins such as polyolefin resins such as polymers, norbornene resins, and (meth)acrylic resins.
• the shape of the resin base material may be plate-like, film-like, or other forms.
• the surface of the base material may be pretreated before forming the silicon oxide underlayer. By performing the pretreatment, good adhesion between the base material and the silicon oxide underlayer can be obtained, and high abrasion durability can be obtained.
• the method for pre-treating the base material is not particularly limited as long as it is a method that can remove contaminants on the surface of the base material and make the surface of the base material hydrophilic.
• Examples include alcohol cleaning treatment using alcohol such as ethanol and 2-propanol, alkaline cleaning treatment using alkaline cleaning agents, plasma cleaning treatment using oxygen or argon plasma, and radical cleaning treatment using OH radicals. These methods may be used in combination.
• Alkaline cleaning treatment using an alkaline cleaning agent is preferred, and plasma cleaning treatment using plasma and radical cleaning treatment using OH radicals are more preferred. It is more preferable to perform a plasma cleaning treatment using plasma or a radical cleaning treatment using OH radicals following the alkaline cleaning treatment using an alkaline cleaning agent.
• Hydrophilicity can be evaluated by the contact angle of water on the substrate, and is preferably 40° or less, more preferably 20° or less, and even more preferably 10° or less. Note that the water contact angle is measured in accordance with JIS R 3257:1999.
• a functional layer may be formed between the base material and the silicon oxide underlayer.
• the functional layer include an antireflection film layer and a hard coat layer. Note that when an antireflection film layer whose outermost layer is a silicon oxide film is formed as a functional layer, the outermost silicon oxide film can be used as a silicon oxide base layer.
• the silicon oxide base layer is made of a silicon oxide film, and a dry method is adopted as a method for forming the silicon oxide film.
• the dry method include physical vapor deposition (PVD) and chemical vapor deposition (CVD), of which physical vapor deposition (PVD) is preferred.
• Wet coating methods include a method using silica nanoparticles, a sol-gel method using silicon alkoxide, and a method using silica glass conversion by reaction of polysilazane with moisture.
• the base layer cannot exhibit sufficient water and oil repellency.
• a resistance heating evaporation method, an electron beam evaporation method, a sputtering film formation method, etc. can be used.
• electron beam evaporation method and sputtering film formation method can be suitably used.
• Electron beam evaporation methods include a method in which granular or plate-shaped SiO 2 is irradiated with an electron beam to evaporate the SiO 2 and deposited on a substrate, and a method in which SiO 2 is deposited while irradiating the substrate with an ion beam. (ion beam assist method).
• the pressure during film formation is preferably 1 x 10 -4 to 5 x 10 -1 Pa, and the film formation rate is preferably 0.01 to 2 nm/sec.
• the temperature of the film-forming substrate is preferably 25 to 300°C.
• Examples of sputtering film forming methods include reactive sputtering in which a Si target is sputtered, deposited on a base material, and oxidized on the base material to obtain silicon oxide.
• Sputter sources include DC plasma, RF plasma, electron cyclotron resonance (ECR) plasma, and ion beam. Oxidation of Si can be performed by introducing oxygen gas or by irradiating oxygen plasma (radical assist method).
• the pressure during film formation is preferably 1 ⁇ 10 -4 to 1 Pa.
• the film formation rate is preferably 0.1 to 1 nm/sec.
• the temperature of the film-forming substrate is preferably 25 to 300°C.
• a thermal CVD method a CVD method assisted by a reactive species, a photoCVD method, etc. can be used.
• the CVD method assisted by reactive species is a method in which a precursor is converted into silicon oxide by a chemical reaction of reactive species and deposited on a glass substrate. , radicals, etc. can be used.
• methods for forming a silicon oxide film by a CVD method using plasma containing oxygen include methods described in Patent Documents 9 and 10 (Japanese Patent Application Laid-open No. 2020-090652, Japanese Patent No. 5655215).
• a silicon compound is used as the silicon oxide precursor.
• Examples include SiH 4 , Si 2 H 6 , tetraethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, and the like. Tetraethoxysilane, hexamethyldisiloxane, and hexamethyldisilazane are preferably used.
• the CVD conditions for forming the silicon oxide film are appropriately set depending on the type of substrate and precursor used.
• the substrate temperature is preferably 30°C or higher and lower than 150°C, more preferably 30 to 140°C.
• the substrate temperature is preferably 30°C or more and less than 250°C, more preferably 30 to 150°C.
• the thickness of the silicon oxide underlayer is preferably 3 to 150 nm, more preferably 3 to 50 nm. If the film thickness of the silicon oxide base layer is less than 3 nm, good adhesion with the water- and oil-repellent surface layer may not be obtained due to the presence of voids in the silicon oxide base layer, and if it exceeds 150 nm, oxidation may occur. Poor adhesion with the water- and oil-repellent surface layer may occur due to insufficient strength of the silicon base layer itself.
• the film thickness of the silicon oxide underlayer can be measured by X-ray reflectometry (XRR) or cross-sectional observation using an electron microscope.
• the surface of the silicon oxide base layer may be pretreated before forming the water- and oil-repellent surface layer.
• the pretreatment provides good adhesion between the silicon oxide base layer and the water- and oil-repellent surface layer, resulting in high abrasion durability.
• the method for pre-treating the silicon oxide base layer is not particularly limited as long as it is capable of removing contaminants on the surface of the silicon oxide base layer.
• plasma cleaning treatment using oxygen plasma or argon plasma, radical cleaning treatment using OH radicals, etc. can be suitably used.
• the water- and oil-repellent surface layer is mainly composed of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a cured product of a partially hydrolyzed condensate thereof. It is formed using a surface treatment agent containing a fluoropolyether group-containing polymer having a degradable silyl group and/or a partially hydrolyzed condensate thereof.
• Examples of the fluoropolyether group-containing polymer having a hydrolyzable silyl group include Japanese Patent No. 6260579, Japanese Patent No. 6828744, Japanese Patent No. 5761305, Japanese Patent No. 6451279, Japanese Patent No.
• Patent Documents 1 to 6, 14 to 27 Compounds described in Japanese Patent Publication No. 2014-218639 and International Publication No. 2013/121984 (Patent Documents 1 to 6, 14 to 27) can be used.
• the fluoropolyether group-containing polymer having a hydrolyzable silyl group will be explained in more detail.
• the fluoropolyether group-containing polymer having a hydrolyzable silyl group has the following formula (11) at at least one, preferably 1 to 3 terminals in the molecule.
• R is an alkyl group having 1 to 4 carbon atoms or a phenyl group
• X is independently a hydrolyzable group
• a is 2 or 3.
• It has at least 2, preferably 2 to 3 (that is, at least 2, preferably 2 to 9, more preferably 2 to 6 in the molecule) groups represented by (hydrolyzable silyl groups).
• polyfluorocarbon compound represented by -(C b F 2b O) m - (wherein b is an integer of 1 to 6 independently for each unit, and m is an integer of 1 to 250) in the molecule.
• b is an integer of 1 to 6 independently for each unit, and m is an integer of 1 to 250
• it has an oxyalkylene structure.
• X is a hydrolyzable group that may be different from each other.
• examples of such X include alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, methoxymethoxy group, Alkoxy substituted alkoxy groups with 2 to 10 carbon atoms such as methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, acyloxy groups with 2 to 10 carbon atoms such as acetoxy group, propionoxy group, vinyloxy group, allyloxy group, propenoxy group, isopropenoxy group
• R is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, of which a methyl group and an ethyl group are preferred.
• a is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to the base material.
• b is an integer of 1 to 6 independently for each unit, preferably an integer of 1 to 4
• m is an integer of 1 to 4. It is an integer of 250, preferably an integer of 1 to 140.
• repeating unit represented by -C b F 2b O- examples include units represented by the following formula. -CF 2 O-, -CF 2 CF 2 O-, -CF 2 CF 2 CF 2 O-, -CF( CF3 ) CF2O- , -CF 2 CF 2 CF 2 O-, -CF 2 CF 2 CF 2 CF 2 CF 2 O-, -C( CF3 ) 2O- Among these, repeating units represented by the following formula are particularly preferred. -CF 2 O-, -CF 2 CF 2 O-
• polyfluorooxyalkylene structure may be composed of one type of the above repeating unit, or may be composed of a combination of two or more types.
• one or more fluoropolyether group-containing polymers represented by the following formula (1), (4), or (7) are used as the fluoropolyether group-containing polymer having a hydrolyzable silyl group. It includes. In particular, all of the fluoropolyether group-containing polymers having hydrolyzable silyl groups are one or more fluoropolyether group-containing polymers represented by formulas (1), (4), and (7). preferable.
• Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O ) t (C 6 F 12 O) u - C d F 2d -
• d is an integer from 0 to 5 independently for each unit, and p, q, r, s, t and u are each independently 0 is an integer of ⁇ 150, the sum of p, q, r, s, t, and u is an integer of 1 ⁇ 250, and each of these units may be linear or branched.Also, Each repeating unit shown in parentheses with p, q, r, s, t, and u may be randomly bonded.) is a divalent polyfluorooxyalkylene structure-containing group, and A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is
• Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom, or G, are independently monovalent groups represented by the following formula (5).
• W is the same as above, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or 1 represented by the following formula (6) It is the basis of valence.
• T is a single bond or a divalent group
• L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms
• E is a monovalent hydrocarbon group having 1 to 6 carbon atoms, or W
• l is an integer from 0 to 20.
• Rf is the same as above
• a 3 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom
• J is independently a monovalent group represented by the following formula (8), and has two or more Ws in J.
• V is a divalent hydrocarbon group having 2 to 15 carbon atoms which may have a single bond or an ether bond
• M is independently represented by the following formula (9). is a monovalent group shown, (In the formula, Y, S and W are the same as above, and f is an integer from 1 to 3.) e is 1 or 2.
• Rf is -C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O)
• u -C d F 2d - is a group containing a divalent polyfluorooxyalkylene structure (perfluoropolyether structure), and d is independently 0 for each unit. It is an integer of ⁇ 5, preferably an integer of 0 ⁇ 2, and more preferably 0 or 1.
• p, q, r, s, t and u are each independently an integer of 0 to 150, preferably an integer of 0 to 100, more preferably an integer of 0 to 60, p, q, r, The sum of s, t and u is an integer of 1 to 250, preferably an integer of 3 to 140, more preferably an integer of 7 to 70.
• Each of these units may be linear or branched. Note that the repeating units shown in parentheses with p, q, r, s, t, and u may be randomly combined.
• the divalent polyfluorooxyalkylene structure-containing group represented by Rf can be represented by the following structure.
• p', q', r', s', t' and u' are each independently an integer of 1 to 150, and p', q', r', s', t' and u'
• the total of these units is 12 to 250, and each of these units may be linear or branched.Also, p', q', r', s', t' and u' are attached. Each repeating unit shown in parentheses may be randomly bonded.
• d' is an integer of 0 to 5 independently for each unit. Each of these units may be linear or branched. Also good.
• a 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom, or D (i.e. , -QZ (W) shown by the formula (2) described later (a monovalent group represented by ⁇ ), whose terminal is CF 3 - or CF 2 H- and which may contain an oxygen atom
• D i.e. , -QZ (W) shown by the formula (2) described later (a monovalent group represented by ⁇ ), whose terminal is CF 3 - or CF 2 H- and which may contain an oxygen atom
• the valent fluorine-containing hydrocarbon group is preferably a fluoroalkyl group having 1 to 6 carbon atoms.
• Examples of such a monovalent fluorine-containing hydrocarbon group in which the terminal of A 1 is CF 3 - or CF 2 H- and may contain an oxygen atom include the following groups.
• a 1 -Rf-D, D is independently a monovalent group represented by the following formula (2).
• Q is a single bond or a divalent organic group
• Q other than a single bond is preferably an amide bond (for example, an unsubstituted amide bond, an N-methyl substituted amide bond, an N-phenyl (substituted amide bond), ether bond, ester bond, sulfide bond, urethane bond, siloxane bond, triazine bond, diorganosilylene group (e.g., dialkylsilylene group such as dimethylsilylene group), sylarylene bond (e.g., silphenylene bond) and an unsubstituted or substituted divalent carbon having 1 to 15 carbon atoms, preferably 2 to 15 carbon atoms, which may contain one or more bonds selected from the group consisting of silalkylene bonds (for example, silethylene bonds) It is a hydrogen group, more preferably an unsubstituted or fluorine-substituted divalent hydrocarbon group having 1 to
• examples of divalent hydrocarbon groups include alkylene groups such as methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, etc. group, an arylene group such as a phenylene group, or a combination of two or more of these groups (alkylene/arylene group, etc.).
• R 1 is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group.
• R 1 may be the same or different.
• R 2 is an alkylene group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), or 6 carbon atoms such as phenylene group. ⁇ 10 arylene groups.
• Examples of Q other than such a single bond include the following groups.
• the bond on the left side is bonded to Rf, and the bond on the right side is bonded to Z. (In the formula, t is an integer from 2 to 4.)
• Z is a trivalent to octavalent group, preferably a trivalent to octavalent organopolysiloxane residue having a silicon atom, a nitrogen atom, and a siloxane bond. group, preferably 3 to 8 valent, preferably 3 or 4 selected from linear, branched or cyclic organopolysiloxane residues having 3 to 13 silicon atoms, more preferably 3 to 5 silicon atoms It is the basis of valence.
• n is An integer of 2 to 6, preferably an integer of 2 to 4).
• examples of trivalent to octavalent linear, branched or cyclic organopolysiloxane residues having siloxane bonds include those shown below.
• R 1 is the same as above.
• g is an integer of 3 to 12, preferably 3 or 4
• h is an integer of 3 to 8, preferably 3 or 4
• j is an integer of 0 to 8.
• R 4 is independently R 1 or the following formula (a) (In the formula, R 1 is the same as above, j1 is an integer of 1 to 6, preferably 1, and the bond on the left side is bonded to Si.) is a group represented by, R 5 is independently a single bond or the following formula (b) (In the formula, R 2 and R 4 are the same as above, j2 is an integer of 0 to 6, preferably an integer of 0 to 3, and j3 is an integer of 0 to 6, preferably an integer of 0 to 2. (j2+j3 is an integer from 1 to 6, and each repeating unit shown in parentheses may be randomly bonded. The bond on the left bonds to Si.) It is a group represented by, and at least one of R 4 is represented by formula (a). ]
• W is independently a monovalent hydrolyzable silyl group-containing group represented by the following formula (3). (In the formula, R, It is the basis.)
• R, X, and a are the same as R, X, and a in the above formula (11), and the same ones as R, X, and a in the above formula (11) can be exemplified.
• Y is a single bond or a divalent hydrocarbon group which may have one or more types selected from a fluorine atom, a silicon atom, and a siloxane bond;
• the divalent hydrocarbon group which may have one or more types selected from atoms and siloxane bonds include an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms containing a fluorine atom, Alkylene groups containing arylene groups having 6 to 8 carbon atoms (alkylene/arylene groups), divalent groups in which alkylene groups are bonded to each other via a sylalkylene structure or sylarylene structure, and 2 to 10 silicon atoms.
• Y other than a single bond include those shown below.
• fluoropolyether group-containing polymer represented by the above formula (1) examples include those shown below. (In the formula, A 1 and Rf are the same as above.)
• a 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and may contain an oxygen atom, or G (i.e. , a monovalent group represented by formula (5); -C(B)(W) 2 ), which has a CF 3 - or CF 2 H- terminal and may contain an oxygen atom.
• the fluorine-containing hydrocarbon group is preferably a fluoroalkyl group having 1 to 6 carbon atoms.
• Examples of such a monovalent fluorine-containing hydrocarbon group in which the terminal of A 2 is CF 3 - or CF 2 H- and may contain an oxygen atom include the following groups.
• a 2 -Rf-G, G is independently a monovalent group represented by the following formula (5).
• W is the same as above, and the same W as exemplified in the above formula (2) can be exemplified.
• examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for S include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and octyl group, vinyl group, allyl group, etc. alkenyl groups, phenyl groups, aryl groups such as tolyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, and alkyl groups having 1 to 3 carbon atoms and phenyl groups are preferred.
• T is a single bond or a divalent group, preferably a single bond, a siloxane bond, a silalkylene bond (for example, a silethylene bond, a silpropylene bond, bond), sylarylene bond (e.g., silphenylene bond), and diorganosilylene group (e.g., dialkylsilylene group such as dimethylsilylene group, dialkoxysilylene group such as dimethoxysilylene group).
• a siloxane bond for example, a silalkylene bond (for example, a silethylene bond, a silpropylene bond, bond), sylarylene bond (e.g., silphenylene bond), and diorganosilylene group (e.g., dialkylsilylene group such as dimethylsilylene group, dialkoxysilylene group such as dimethoxysilylene group).
• divalent hydrocarbon groups include alkylene groups such as methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, etc. group, an arylene group such as a phenylene group, or a combination of two or more of these groups (alkylene/arylene group, etc.), with a propylene group being preferred.
• T other than a single bond include those shown below.
• the bond on the right side is bonded to L or E.
• L is independently an alkylene group such as a methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group), etc. is a divalent hydrocarbon group having 1 to 4 carbon atoms, and each (LO) unit may have a single carbon number or a mixture of carbon atoms.
• l is an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 6.
• E is an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or a carbon number 1 to 4 such as a phenyl group.
• 6, or W W is the same as above, and examples thereof include those exemplified for W in formula (2) above.
• Examples of the monovalent group represented by the above formula (6); -T-(LO) l -E include those shown below.
• Examples of the monovalent group represented by the above formula (5); -C(B)(W) 2 (ie, G in formula (4)) include those shown below.
• fluoropolyether group-containing polymer represented by the above formula (4) examples include those shown below. (In the formula, A 2 and Rf are the same as above.)
• the monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms.
• Examples of such a monovalent fluorine-containing hydrocarbon group in which the terminal of A 3 is CF 3 - or CF 2 H- and may contain an oxygen atom include the following groups.
• a 3 -Rf-J J is independently a monovalent group represented by the following formula (8), and in J, the above W (monovalent hydrolyzable silyl group-containing group) It has two or more.
• Y, S, and W are the same as above, and can be exemplified by the same things as those exemplified for Y in the above formula (3), S in the above, and W in the above formula (2), respectively.
• f is an integer from 1 to 3.
• Examples of the monovalent group represented by the above formula (9); -Y-C(S) 3-f (W) f (ie, M in formula (8)) include those shown below.
• fluoropolyether group-containing polymer represented by the above formula (7) examples include those shown below. (In the formula, A 3 and Rf are the same as above.)
• a surface containing a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a partially hydrolyzed condensate thereof for forming a water- and oil-repellent surface layer In addition to the above-mentioned fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a partially hydrolyzed condensate of the polymer, the treatment agent further contains a hydrolyzable silyl group represented by the following formula (10).
• a mixture i.e., a fluoropolyether group-containing polymer composition
• a fluoropolyether group-containing polymer containing a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof (hereinafter referred to as a polymer not containing a hydrolyzable silyl group).
• the "partial (hydrolyzed) condensate” refers to a partial condensate or a partially hydrolyzed condensate.
• a 4 is independently a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and which may contain an oxygen atom, -OR 3 , -COOR 3 or -PO(OR 3 ) 2 ( R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. ]
• a 4 is independently a monovalent fluorine-containing hydrocarbon group whose terminal is CF 3 - or CF 2 H- and which may contain an oxygen atom, -OR 3 , -COOR 3 or -
• the monovalent fluorine-containing hydrocarbon group which is PO(OR 3 ) 2 and which has a CF 3 - or CF 2 H- terminal and may contain an oxygen atom is an example of a monovalent fluorine-containing hydrocarbon group which is CF 3 - or CF 2 H- at the terminal and which may contain an oxygen atom.
• Examples of the monovalent fluorine-containing hydrocarbon group which is 2 H- and may contain an oxygen atom are the same as those exemplified above.
• R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and octyl group.
• examples include alkyl groups such as vinyl groups, alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups and tolyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, and R 3 is a hydrogen atom, a carbon An alkyl group of 1 to 3 and a phenyl group are preferred.
• -OR 3 , -COOR 3 , -PO(OR 3 ) 2 of A 4 include -OH, -OCH 3 , -COOH, -COOCH 3 , -PO(OH) 2 , -OC 2 H 5 , -COOC 2H5 is an example.
• Examples of the fluoropolyether group-containing polymer represented by the above formula (10) include those shown below. (In the formula, p", q", r", s", t" and u” are each independently an integer of 0 to 150, and p", q", r", s", t" and u" The total of (The repeating units shown in parentheses may be combined randomly.)
• the surface treatment agent used to form the water- and oil-repellent surface layer is attached to the terminal of a molecular chain represented by the above formula (1), (4), or (7).
• a fluoropolyether group-containing polymer mixture fluoropolyether group-containing polymer composition contained in a surface treatment agent
• a mixture of a single-end type polymer and/or a both-end type polymer and a polymer that does not contain a hydrolyzable silyl group is particularly within the range where the water- and oil-repellent surface layer to be formed is mainly composed of the above-mentioned fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a cured product of a partially hydrolyzed condensate thereof.
• a hydrolyzable silyl group is added to the entire fluoropolyether group-containing polymer composition consisting of a single-terminated polymer and/or a double-terminated polymer and a polymer that does not contain a hydrolyzable silyl group. It is desirable that the proportion of the polymer not contained is 0 to 30 mol%, particularly 0 to 10 mol%.
• the number average molecular weight of the fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or its partially hydrolyzed condensate, or the fluoropolyether group-containing polymer composition is 1,000 to 20,000.
• the range is within the range. More preferably, the number average molecular weight is 2,000 to 10,000, particularly preferably 3,000 to 8,000.
• the number average molecular weight can be calculated from the characteristic peak intensity ratio of 19 F-NMR analysis.
• a fluoropolyether group-containing polymer and/or a partially hydrolyzed condensate thereof, or a fluoropolyether group-containing polymer composition can be obtained by rectification or molecular distillation.
• a fluoropolyether group-containing polymer and/or a partially hydrolyzed condensate thereof, or a fluoropolyether group-containing polymer composition having a hydrolyzable silyl group having a number average molecular weight within the above range is a fluoropolyether group-containing polymer.
• the fluorine compound used when synthesizing can also be prepared by using in advance a compound having the above number average molecular weight.
• the surface treatment agent may optionally contain a hydrolysis condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), or an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added.
• acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferred.
• the amount added is a catalytic amount, and is usually 0.01 to 5 parts by weight, particularly 0.1 parts by weight, per 100 parts by weight of a fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or a partially hydrolyzed condensate thereof. ⁇ 1 part by mass.
• the surface treatment agent may contain a solvent.
• the solvent is preferably a fluorine-modified aliphatic hydrocarbon solvent (perfluoroheptane, perfluorooctane, etc.), a fluorine-modified olefin solvent (methoxyperfluoroheptene, etc.), a fluorine-modified aromatic hydrocarbon solvent (m-xylene, etc.).
• fluorine-modified ether solvents methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.
• fluorine-modified alkyl amines include solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzene, mineral spirits, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
• fluorine-modified solvents are preferable in terms of solubility and wettability, and in particular, 1,3-trifluoromethylbenzene, m-xylene hexafluoride, perfluoro(2- butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are preferred.
• Two or more of the above solvents may be mixed to uniformly dissolve the fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or its partially hydrolyzed condensate, or the fluoropolyether group-containing polymer composition. It is preferable that the The optimum concentration of the fluoropolyether group-containing polymer having a hydrolyzable silyl group and/or its partially hydrolyzed condensate to be dissolved in the solvent may be appropriately selected depending on the method of using the surface treatment agent, and is not limited. It's not something you can do. It is usually dissolved in an amount of 0.01 to 30% by weight, preferably 0.02 to 25% by weight, and more preferably 0.05 to 20% by weight.
• a wet method such as a brush coating method, a dip coating method, or a spray coating method is adopted.
• a spray coating method or a dip coating method it is preferable to use a spray coating method or a dip coating method.
• a water- and oil-repellent surface layer formed by a dry method such as a vapor deposition process (physical vapor deposition (PVD) method or chemical vapor deposition (CVD) method) cannot exhibit sufficient water- and oil-repellency.
• PVD physical vapor deposition
• CVD chemical vapor deposition
• a curing treatment it is preferable to apply at 60 to 150°C, preferably 60 to 120°C, and a relative humidity of 95% or less for 30 minutes to 24 hours, preferably 30 minutes to 2 hours. .
• the thickness of the water- and oil-repellent surface layer is usually 2 to 100 nm, preferably 3 to 20 nm. If the film thickness of the water- and oil-repellent surface layer is less than 2 nm, the coverage of the water- and oil-repellent surface layer may be low, resulting in poor water- and oil-repellency and durability. Oiliness and durability may decrease.
• the thickness of the water- and oil-repellent surface layer can be measured by the above-mentioned XRR or spectroscopic ellipsometry.
• the water- and oil-repellent surface layer has a receding contact angle ( ⁇ WR ) with respect to water of 101° or more, and that the water- and oil-repellent surface layer It is preferable that the receding contact angle ( ⁇ OR ) with respect to oleic acid is 64° or more.
• the difference ( ⁇ W ) between the advancing contact angle ( ⁇ WA ) and the receding contact angle ( ⁇ WR ) of the water- and oil-repellent surface layer with respect to water is 20° or less, and the water- and oil-repellent surface layer
• the difference ( ⁇ O ) between the advancing contact angle ( ⁇ OA ) and the receding contact angle ( ⁇ OR ) with respect to oleic acid is preferably 20° or less.
• the removability of water and oil in the obtained water- and oil-repellent article can be improved.
• the number average molecular weight is a value calculated from the characteristic peak intensity ratio of 19 F-NMR analysis.
• the film thickness of the silicon oxide underlayer described above was obtained by X-ray reflectance measurement. That is, simulation fitting was performed on the measured profile to determine the film thickness.
• the measurement conditions are shown below.
• Measuring device SmartLab (manufactured by Rigaku)
• X-ray source Rotating anticathode (Cu), output 45kV, 200mA
• Input optical system Ge (111)
• Solar slit 5.0°
• Light receiving side RS1 0.1mm
• RS2 0.1mm
• Scanning conditions Scanning axis 2 ⁇ / ⁇ Scanning speed 0.2°/min Step width 0.002°
• the oil-repellent surface layer was cured and fixed to obtain a base material having a 10 nm thick water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer.
• the film thickness of the above water- and oil-repellent surface layer was determined by quantifying the intensity of fluorescent X-rays derived from elemental fluorine using a fluorescent X-ray measuring device (manufactured by Rigaku Co., Ltd., product name: Fluorescent X-ray measuring device Primini), and using a calibration curve. Calculated using a fluorescent X-ray measuring device (manufactured by Rigaku Co., Ltd., product name: Fluorescent X-ray measuring device Primini), and using a calibration curve. Calculated using
• a base material having a 10 nm thick water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained.
• the film thickness of the above water- and oil-repellent surface layer was determined by quantifying the intensity of fluorescent X-rays derived from elemental fluorine using a fluorescent X-ray measuring device (manufactured by Rigaku Co., Ltd., product name: Fluorescent X-ray measuring device Primini), and using a calibration curve. Calculated using
• the film thickness of the above water- and oil-repellent surface layer was determined by quantifying the intensity of fluorescent X-rays derived from elemental fluorine using a fluorescent X-ray measuring device (manufactured by Rigaku Co., Ltd., product name: Fluorescent X-ray measuring device Primini), and using a calibration curve. Calculated using
• a base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 1, except that a silicon oxide base layer was formed by the following method.
• a silicon oxide base layer was formed by the following method.
• a substrate that had been subjected to alkaline cleaning and plasma cleaning in the same manner as in Comparative Example 1 was set in an electron beam evaporation apparatus (ACE-1350, manufactured by Synchron), and a silicon oxide film with a thickness of 10 nm was deposited using SiO 2 granules as the evaporation source. Formed geological strata. The formation conditions are shown below.
• Vapor deposition source SiO 2 granules (2mm) Ultimate pressure (pressure during film formation): 1 ⁇ 10 -3 Pa Deposition rate (film forming rate): 1 nm/sec Film forming substrate temperature: 25°C The thickness of the silicon oxide base layer was obtained by X-ray reflectance measurement in the same manner as the thickness measurement of the silicon oxide base layer by dip coating of silica nanoparticles.
• Example 1 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 4, except that a surface treatment agent was prepared using the compound (B) shown in the above formula.
• Example 2 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 5, except that a surface treatment agent was prepared using the compound (B) shown in the above formula.
• Example 3 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 4, except that a surface treatment agent was prepared using the compound (C) shown in the above formula.
• Example 4 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 5, except that a surface treatment agent was prepared using the compound (C) shown in the above formula.
• Example 5 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 4, except that a surface treatment agent was prepared using the compound (D) shown in the above formula.
• Example 6 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 5, except that a surface treatment agent was prepared using the compound (D) shown in the above formula.
• Example 7 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 4, except that a surface treatment agent was prepared using the compound (E) shown in the above formula.
• Example 8 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 5, except that a surface treatment agent was prepared using the compound (E) shown in the above formula.
• Example 9 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 4, except that a surface treatment agent was prepared using the compound (F) shown in the above formula.
• Example 10 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Comparative Example 5, except that a surface treatment agent was prepared using the compound (F) shown in the above formula.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 7, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 8, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 9, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• Example 11 The base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Example 1, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1. A base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• Example 12 The base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Example 2, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1. A base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 10, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 11, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 12, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 13, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• Example 13 The base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Example 3, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1. A base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• Example 14 The base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Example 4, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1. A base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 14, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 19, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 20, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 21, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• Example 15 The base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Example 7, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1. A base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• Example 16 The base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Example 8, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1. A base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• the base material was mirror-polished SUS304 (size: 100 mm x 50 mm x 1.0 mm (thickness)), and fluorocarbon was washed in the same manner as in Comparative Example 22, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a polyether group-containing polymer was obtained.
• Example 17 Soda lime glass (size: 100 mm x 50 mm x 0.7 mm (thickness)) was used as the base material, the following antireflection film was formed on the base material, and the outermost layer was used as a silicon oxide base layer.
• a base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 3.
• Example 18 A base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 17, except that the water- and oil-repellent surface layer was formed in the same manner as in Example 4.
• Example 19 A silicone hard coat polycarbonate (HC/PC) plate (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD manufactured by Sabic) was used as the base material, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 3.
• Example 20 A silicone hard coat polycarbonate (HC/PC) plate (100 mm x 50 mm x 3 mm (thickness)) (LEXAN MARGARD manufactured by Sabic) was used as the base material, except that alkaline cleaning and plasma cleaning were performed in the same manner as in Comparative Example 1.
• a base material having a water- and oil-repellent surface layer made of a fluoropolyether group-containing polymer was obtained in the same manner as in Example 4.
• the number of abrasion cycles that maintain a water contact angle of 100° or more is defined as the number of cloth abrasion durability. If the cloth abrasion durability is 30,000 times or more, it is ⁇ (excellent), and if it is 20,000 times or more but less than 30,000 times, it is ⁇ (good). 10,000 times or more but less than 20,000 times is rated ⁇ (acceptable), and less than 10,000 times is rated ⁇ (impossible), as shown in Table 5.
• the test environmental conditions are 25° C. and 40% relative humidity. Examples 11 to 18 and Comparative Examples 30 to 42 showed good cloth abrasion durability.

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