WO2017022638A1 - Substrat de verre approprié en tant que verre de protection, etc., d'un dispositif d'affichage mobile - Google Patents

Substrat de verre approprié en tant que verre de protection, etc., d'un dispositif d'affichage mobile Download PDF

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Publication number
WO2017022638A1
WO2017022638A1 PCT/JP2016/072214 JP2016072214W WO2017022638A1 WO 2017022638 A1 WO2017022638 A1 WO 2017022638A1 JP 2016072214 W JP2016072214 W JP 2016072214W WO 2017022638 A1 WO2017022638 A1 WO 2017022638A1
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group
glass substrate
formula
alkoxysilane
layer
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PCT/JP2016/072214
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English (en)
Japanese (ja)
Inventor
政太郎 大田
洋介 飯沼
和輝 江口
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日産化学工業株式会社
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Priority to JP2017532556A priority Critical patent/JP6773036B2/ja
Priority to CN201680057980.6A priority patent/CN108139506B/zh
Priority to KR1020187006069A priority patent/KR102633247B1/ko
Publication of WO2017022638A1 publication Critical patent/WO2017022638A1/fr

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    • 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
    • C03C17/34—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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • 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
    • 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
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to a glass substrate having high scratch resistance, slipperiness, good visibility, and low reflectance, in particular, a glass substrate suitably used as a cover glass of a mobile display device.
  • cover glass for protecting the surface of a display element is often used in liquid crystal display elements such as mobile devices and touch panels. Further, glass plates having excellent scratch resistance and good visibility are used in protective glasses such as watches and camera viewfinders (see Patent Documents 1 and 2).
  • the cover glass in such a display element is required to have a high hardness and a high scratch resistance so that it is more difficult to break and scratch.
  • a diamond-like carbon (DLC) layer or the like is formed on a glass substrate in order to increase hardness and scratch resistance, it is usually formed on the glass substrate in order to impart the slip property of the cover glass.
  • DLC diamond-like carbon
  • An object of the present invention is to provide a glass substrate having excellent scratch resistance, corrosion resistance, and good visibility, in particular, a glass substrate suitably used as a cover glass of a display device such as a mobile device or a touch panel. It is in.
  • an alkoxysilane represented by the following formula (1) In a glass substrate having a fluorine coating layer on the surface side and a diamond-like carbon (DLC) layer on the substrate side, an alkoxysilane represented by the following formula (1), an alkoxysilane represented by the following formula (2), A glass substrate comprising an intermediate layer made of a polysiloxane-containing film obtained by polycondensation of an alkoxysilane containing benzene between the fluorine coating layer and the DLC layer.
  • DLC diamond-like carbon
  • R 1 ⁇ Si (OR 2 ) 3 ⁇ P (1)
  • R 1 is a hydrocarbon group having 1 to 12 carbon atoms substituted with a ureido group
  • R 2 is an alkyl group having 1 to 5 carbon atoms
  • p represents an integer of 1 or 2.
  • R 3 is a hydrogen atom, or a hetero atom, a halogen atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and having 1 to 8 carbon atoms.
  • a hydrocarbon group, R 4 is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.) 2.
  • the alkoxysilane represented by the formula (1) is at least one selected from the group consisting of ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane and ⁇ -ureidopropyltripropoxysilane.
  • the glass substrate of said 1 or 2 whose alkoxysilane represented by Formula (2) is tetraalkoxysilane whose n is 0 in Formula (2). 4). 4.
  • the alkoxysilane represented by the formula (1) is contained in an amount of 0.5 to 60 mol% in the total alkoxysilane, and the alkoxysilane represented by the formula (2) in the total alkoxysilane is 40 to 99.5 mol. 5.
  • the present invention has high scratch resistance and slippage, and it is unexpected by having a specific polysiloxane intermediate layer in addition to the fluorine coating layer on the surface and the DLC layer on the substrate side. Further, since the transmittance can be improved and the reflectance is also lowered, a glass substrate having excellent visibility is provided.
  • the intermediate layer of the above specific polysiloxane can be cured at a low temperature of 300 ° C.
  • FIG. 1 is a schematic cross-sectional view showing an example of a glass substrate according to an embodiment of the present invention.
  • Glass substrate As the glass substrate of the present invention, a glass plate made of alkali glass, quartz glass, sapphire glass, alumina silicon glass or the like can be widely used.
  • the thickness is not particularly limited, but is usually preferably 0.1 to 2.0 mm, more preferably 0.2 to 1.3 mm.
  • the glass plate may be chemically strengthened or air-cooled strengthened in order to increase the strength.
  • the glass substrate of the present invention has a DLC layer on the substrate side and a fluorine coating layer on the surface side.
  • the DLC layer on the substrate side of the glass substrate is formed in order to impart high scratch resistance and corrosion resistance.
  • the DLC layer in the present invention is easily obtained by a sputtering method using a hydrocarbon gas such as acetylene or methane as a raw material, preferably a plasma CVD method, a sputtering method, an ionization vapor deposition method, among others.
  • the raw material can also contain hydrogen.
  • the DLC layer in the present invention has a thickness of preferably 50 to 150 nm, more preferably 70 to 130 nm. Further, the refractive index is preferably 1.7 or less, more preferably 1.5 or less, in order to achieve low reflection.
  • the DLC layer may be porous, and the volume ratio of pores is preferably 40 to 70%, more preferably 45 to 65%.
  • the fluorine coating layer on the surface side of the glass substrate is formed in order to improve the slipperiness and improve the ease of operation and the prevention of fingerprint adhesion.
  • a glass substrate having a fluorine coating layer on its surface is known, for example, from International Publication WO2013 / 115191, Japanese Patent Application Laid-Open No. 2014-218639, etc., and these known coating materials can also be used in the present invention.
  • the fluorine coating layer in the present invention is, for example, R f —Q 1 —SiX 1 3 (R f is a perfluoroalkyl having 1 to 6 carbon atoms, and Q 1 contains a fluorine atom having 1 to 10 carbon atoms.
  • a divalent organic group, and X 1 is a hydrolyzable group such as a halogen atom or an alkoxy group.
  • a silane compound having a perfluoroalkyl group such as CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 SiCl 3, CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 It is formed from a fluorine-containing polymer such as a polycondensation product of a perfluoro (poly) ether group-containing silane compound such as Si (CH 2 CH ⁇ CH 2 ) 3 .
  • a liquid in which these fluoropolymers are dispersed in a medium is applied on the DLC layer of the glass substrate, dried and heated to form a fluorine coating layer.
  • the thickness of the fluorine coating layer is preferably 1 to 30 nm, more preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, friction durability and antifouling property.
  • the intermediate layer in the present invention is used between the fluorine coating layer and the DLC layer, and contains polysiloxane having a ureido group as described below. Thereby, a film having sufficient hardness and adhesion can be formed even at a low temperature of 100 to 300 ° C. That is, the intermediate layer in the present invention is obtained by polycondensation of an alkoxysilane represented by the following formula (1) and, if necessary, an alkoxysilane containing an alkoxysilane represented by the following formula (2). Contains siloxane.
  • R 1 is a hydrocarbon group having 1 to 12 carbon atoms having a ureido group.
  • R 1 is preferably a hydrocarbon group of 1 to 7, more preferably 1 to 5, and any hydrogen atom thereof, preferably 3 to 15 hydrogen atoms, particularly preferably 3 to 11 hydrogen atoms.
  • the hydrocarbon group is preferably an alkyl group.
  • R 2 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
  • p represents an integer of 1 or 2.
  • the alkoxysilane represented by the formula (1) is an alkoxysilane represented by the formula (1-1) when p is 1.
  • the alkoxysilane represented by the formula (1) is an alkoxysilane represented by the formula (1-2) when p is 2.
  • alkoxysilane represented by the formula (1-1) are listed below, but are not limited thereto.
  • ⁇ -ureidopropyltriethoxysilane or ⁇ -ureidopropyltrimethoxysilane is particularly preferable because it is easily available as a commercial product.
  • alkoxysilane represented by the formula (1-2) will be given, but the invention is not limited to these.
  • bis [3- (triethoxysilyl) propyl] urea is particularly preferable because it is easily available as a commercial product.
  • the alkoxysilane represented by the formula (1) is preferably 0.5 mol% or more, more preferably 1.0 mol% or more, further preferably 2 in all alkoxysilanes used for obtaining the intermediate layer. 0.0 mol% or more. Moreover, 100 mol% may be sufficient as the alkoxysilane represented by Formula (1) in all the alkoxysilanes used in order to obtain an intermediate
  • R 3 is a hydrogen atom or a carbon atom which may be substituted with a hetero atom, a halogen atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group. It is a hydrocarbon group of the number 1-6.
  • R 4 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.
  • n represents an integer of 0 to 3, preferably 0 to 2.
  • R 3 in the formula (2) examples include aliphatic hydrocarbons; ring structures such as aliphatic rings, aromatic rings or heterocycles; unsaturated bonds; heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms Or an organic group having 1 to 6 carbon atoms, which may have a branched structure.
  • R 3 may be substituted with a halogen atom, a vinyl group, an amino group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group, an acryloxy group, or the like.
  • R 4 has the same meaning as R 2 described above, and the preferred range is also the same.
  • alkoxysilane represented by Formula (2) is not limited to this. That is, in the alkoxysilane represented by the formula (2), specific examples of the alkoxysilane when R 3 is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, and the like. .
  • alkoxysilanes represented by formula (2) and formula (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, Propyltriethoxysilane, methyltripropoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3- Aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-amino) Eth
  • the alkoxysilane in which n is 0 is tetraalkoxysilane.
  • Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formula (1).
  • tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
  • the amount used is preferably 40 to 99.5 mol%, more preferably 50 to 50%, based on the total alkoxysilane used for obtaining the intermediate layer. It is 99.5 mol%, more preferably 60 to 99.5 mol%.
  • the alkoxysilane represented by the formula (1) is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less in all alkoxysilanes used for obtaining the intermediate layer. is there.
  • the polysiloxane forming the intermediate layer in the present invention is preferably a polycondensation of an alkoxysilane represented by the formula (1) and, if necessary, an alkoxysilane containing the alkoxysilane represented by the formula (2). Obtained. As long as the properties of the intermediate layer are not impaired, a plurality of types of alkoxysilanes represented by formula (1) and alkoxysilanes represented by formula (2) may be used in combination.
  • Examples of the polycondensation method in the present invention include a method of hydrolyzing and condensing the alkoxysilane in an organic solvent such as alcohol or glycol.
  • the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis.
  • complete hydrolysis theoretically, it is sufficient to add 0.5 moles of water of all alkoxide groups in the alkoxysilane, but it is usually preferable to add an excess amount of water over 0.5 moles.
  • the amount of water can be appropriately selected as desired, but it is preferably 0.5 to 2.5 moles of all alkoxy groups in the alkoxysilane.
  • acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid and fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine
  • a catalyst such as a metal salt such as hydrochloric acid, sulfuric acid or nitric acid is preferably used. It is also preferable to further promote hydrolysis / condensation reaction by heating a solution in which alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. Examples thereof include a method of heating and stirring at 50 ° C. to reflux for 1 to 24 hours.
  • a method of heating and polycondensing a mixture of an alkoxysilane, an organic solvent, and an organic acid such as formic acid, oxalic acid, maleic acid, and fumaric acid can be used.
  • a method of polycondensation by heating a mixture of alkoxysilane, solvent and oxalic acid can be mentioned.
  • succinic acid to alcohol in advance to make an alcohol solution of succinic acid
  • alkoxysilane is mixed while the solution is heated.
  • the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane.
  • Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that the liquid does not evaporate or volatilize.
  • a mixture of alkoxysilanes may be mixed in advance, or a plurality of types of alkoxysilanes may be mixed sequentially.
  • the solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even when alkoxysilane does not melt
  • organic solvent in the condensation reaction examples include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol and 1,3-propanediol.
  • alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol and 1,3-propanediol.
  • the polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO 2 (hereinafter referred to as SiO 2 conversion concentration). ) Is preferably 20% by mass or less. By selecting an arbitrary concentration within this concentration range, it is possible to obtain a homogeneous solution while suppressing gel formation.
  • the polysiloxane polymerization solution obtained above may be used as it is to form an intermediate layer, and if necessary, the polymerization solution may be concentrated or a solvent may be added. It may be diluted or replaced with another solvent.
  • the solvent to be used (hereinafter also referred to as additive solvent) may be the same as the polymerization solvent, or may be another solvent.
  • the additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
  • Such an additive solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate in addition to the solvents mentioned as examples of the polymerization solvent. It is done. A liquid whose viscosity is adjusted with these solvents can be applied on a substrate by spin coating, flexographic printing, ink jetting, slit coating, or the like, thereby improving the coating property when an intermediate layer is formed.
  • the coating liquid for forming the intermediate layer contains other components other than the above polysiloxane, for example, inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and further components such as surfactants. May be included.
  • inorganic fine particles fine particles such as silica fine particles, alumina fine particles, titania fine particles, or magnesium fluoride fine particles are preferable, and those in a colloidal solution state are particularly preferable.
  • the inorganic fine particles preferably have an average particle diameter (D50) of 0.001 to 0.2 ⁇ m, and more preferably 0.001 to 0.1 ⁇ m. When the average particle diameter exceeds 0.2 ⁇ m, the transparency of the formed intermediate layer may be lowered.
  • D50 average particle diameter
  • the dispersion medium for inorganic fine particles examples include water and organic solvents.
  • the colloidal solution preferably has a pH or pKa of 1 to 10 from the viewpoint of the stability of the polysiloxane liquid. 2 to 7 are more preferable.
  • organic solvent used for the dispersion medium of the colloidal solution examples include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred.
  • the organic solvent can be used alone or in combination of two or more.
  • metalloxane oligomer and metalloxane polymer single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used.
  • the metalloxane oligomer and metalloxane polymer may be obtained by hydrolysis or the like from monomers such as metal alkoxides, nitrates, hydrochlorides, and carboxylates.
  • the metalloxane oligomer and metalloxane polymer may be commercially available products. Examples thereof include methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, SS-101, etc. manufactured by Colcoat, and titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Ltd. Can be mentioned. These may be used alone or in combination of two or more.
  • leveling agent and surfactant known ones, in particular, commercially available products can be used.
  • method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.
  • the intermediate layer can be obtained by applying the polysiloxane solution of the present invention on the DLC layer of the glass substrate and thermosetting.
  • a known or well-known method can be employed for applying the polysiloxane solution.
  • a dip method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, an air knife coating method, a flexographic printing method, an ink jet method, a slit coating method and the like can be employed.
  • a good coating film can be formed by the flexographic printing method, the slit coating method, the ink jet method, the spray coating method, and the gravure coating method.
  • the polysiloxane solution is preferably filtered using a filter or the like before application.
  • the formed coating film is preferably dried at room temperature to 120 ° C., more preferably 50 to 100 ° C., followed by heat curing at 100 to 600 ° C., more preferably 150 ° C. or more.
  • the time required for drying is preferably 1 minute to 30 minutes, more preferably 1 minute to 10 minutes.
  • the heat curing time is preferably 10 minutes to 24 hours, more preferably 30 minutes to 24 hours.
  • the intermediate layer used in the glass substrate of the present invention can provide a cured film having sufficient hardness even at a curing temperature exceeding 180 ° C.
  • the thickness of the intermediate layer in the present invention is preferably 10 to 500 nm, more preferably 30 to 300 nm.
  • thermosetting It is also effective to irradiate energy rays (ultraviolet rays or the like) using a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp or the like prior to thermosetting.
  • energy rays ultraviolet rays or the like
  • the curing temperature can be further lowered, or the hardness of the coating can be increased.
  • the irradiation amount of the energy beam can be appropriately selected as necessary, but it is usually preferably from several hundred to several thousand mJ / cm 2 .
  • a fluorine coating layer is provided on the surface of the intermediate layer obtained as described above.
  • a fluorine coating layer is known as described above, and is formed by a known method.
  • FIG. 1 is a schematic cross-sectional view showing an example of a glass substrate according to an embodiment of the present invention.
  • the glass 1 includes a fluorine coating layer 2, an intermediate layer 3, a DLC layer 4, and a glass substrate 5.
  • the intermediate layer 3 is an intermediate layer formed on the DLC layer.
  • the fluorine coating layer is formed by applying and baking the liquid containing the fluorine-containing polymer described above.
  • the glass base plate of the present invention is obtained by using a glass substrate having a DLC layer, forming an intermediate layer on the DLC layer, and then forming a fluorine coating layer on the intermediate layer.
  • TEOS Tetraethoxysilane UPS: 3-Ureidopropyltriethoxysilane MeOH: Methanol EtOH: Ethanol IPA: Isopropyl alcohol PGME: Propylene glycol monomethyl ether HG: Hexylene glycol BCS: Ethylene glycol monobutyl ether AF: manufactured by FT-Net Fluoromat P-5425 "
  • GC gas chromatography
  • GC measurement was performed under the following conditions using Shimadzu GC-14B (manufactured by Shimadzu Corporation).
  • Sample injection volume 1 ⁇ L
  • injection temperature 240 ° C.
  • detector temperature 290 ° C.
  • carrier gas nitrogen (flow rate 30 mL / min)
  • detection method FID method.
  • Example 1 The polysiloxane solution (A) (50 g) obtained in Production Example 1 is diluted with PGME (30 g), HG (10 g), BCS (5 g), and PB (5 g), and a coating solution for film formation (A1) It was. On the DLC layer of the glass substrate (thickness: 0.7 mm) on which the DLC layer having a thickness of 100 nm was formed by the sputtering method, the coating solution for coating film formation (A1) was applied with a spin coater to form a coating film. Next, after the glass plate on which the coating film has been formed is dried on a hot plate at 80 ° C. for 3 minutes, the glass plate is cured in a clean oven at 300 ° C.
  • the glass substrate of Sample 1 (Example 1) was obtained by curing at 170 ° C. for 20 minutes in a clean oven.
  • Example 1 the AF coating film was directly applied on the DLC layer of the glass substrate without using the polysiloxane solution (A) obtained in Production Example 1 and without forming an intermediate layer.
  • a glass substrate of Sample 2 (Comparative Example 1) was obtained by carrying out in the same manner as in Example 1 except that the coating film of the fluorine coating layer was formed.
  • Example 2 In Example 1, it carries out similarly to Example 1 except having used the polysiloxane solution (B) obtained by the comparative manufacture example 1 instead of the polysiloxane solution (A) obtained by manufacture example 1. Thus, a glass substrate of Sample 3 (Comparative Example 2) was obtained.
  • the glass substrate of the present invention is widely used as a cover glass for display elements such as mobile devices and touch panels.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Surface Treatment Of Glass (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un substrat de verre qui convient en particulier en tant que verre de protection ou analogue pour un dispositif d'affichage mobile, le substrat de verre présentant une résistance élevée aux rayures et un caractère lisse supérieur, une bonne visibilité et un facteur de réflexion faible. Le substrat de verre comporte, entre une couche de revêtement fluoré sur un côté de surface avant et une couche de carbone sous forme de diamant amorphe (DLC) sur un côté du substrat, une couche intermédiaire contenant un polysiloxane obtenu par la polycondensation d'un alcoxysilane, y compris un alcoxysilane représenté par la formule (1) et, selon les besoins, un alcoxysilane représenté par la formule (2). (1) : R1[Si(OR2)3]P. (Dans la formule (1), R1 représente un groupe hydrocarbure en C1-12 substitué par un groupe uréido, R2 représente un groupe alkyle en C1-5 et p représente un nombre entier choisi entre 1 et 2). (2): (R3)nSi(OR4)4-n. (Dans la formule (2), R3 représente un atome d'hydrogène ou un groupe hydrocarbure en C1-8 pouvant être substitué par un hétéroatome, un atome d'halogène, un groupe vinyle, un groupe amino, un groupe glycidoxy, un groupe mercapto, un groupe méthacryloxy, un groupe isocyanate ou un groupe acryloxy, R4 représente un groupe alkyle en C1-5 et n représente un nombre entier compris entre 0 et 3).
PCT/JP2016/072214 2015-07-31 2016-07-28 Substrat de verre approprié en tant que verre de protection, etc., d'un dispositif d'affichage mobile WO2017022638A1 (fr)

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JP2017532556A JP6773036B2 (ja) 2015-07-31 2016-07-28 モバイルディスプレイ機器のカバーガラス等に好適なガラス基板
CN201680057980.6A CN108139506B (zh) 2015-07-31 2016-07-28 适合于移动显示设备的玻璃盖片等的玻璃基板
KR1020187006069A KR102633247B1 (ko) 2015-07-31 2016-07-28 모바일 디스플레이 기기의 커버 유리 등에 바람직한 유리 기판

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WO2019069642A1 (fr) * 2017-10-03 2019-04-11 信越化学工業株式会社 Élément hydrophobe et oléophobe et procédé pour fabriquer un élément hydrophobe et oléophobe
WO2019124269A1 (fr) * 2017-12-21 2019-06-27 Ａｇｃ株式会社 Article équipé d'une couche fonctionnelle et procédé de fabrication d'un article équipé d'une couche fonctionnelle
CN110914720A (zh) * 2017-06-01 2020-03-24 因特瓦克公司 具有用于改善耐久性的纳米叠层的光学涂层

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KR102277769B1 (ko) * 2018-11-23 2021-07-15 주식회사 엘지화학 실리카 유리막
CN113072866A (zh) * 2021-03-10 2021-07-06 宁波威霖住宅设施有限公司 一种玻璃电子屏用表面自清洁涂料及其使用方法
WO2023027305A1 (fr) * 2021-08-27 2023-03-02 삼성전자주식회사 Matériau extérieur pour dispositif de cuisson et son procédé de préparation
CN114302604B (zh) * 2022-01-18 2024-03-15 Oppo广东移动通信有限公司 盖板、其制备方法及电子设备

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WO2019124269A1 (fr) * 2017-12-21 2019-06-27 Ａｇｃ株式会社 Article équipé d'une couche fonctionnelle et procédé de fabrication d'un article équipé d'une couche fonctionnelle

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JPWO2017022638A1 (ja) 2018-07-12
CN108139506A (zh) 2018-06-08
TWI704050B (zh) 2020-09-11
KR20180036762A (ko) 2018-04-09
CN108139506B (zh) 2019-11-15
JP6773036B2 (ja) 2020-10-21
KR102633247B1 (ko) 2024-02-02

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