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WO2019139008A1 - Substrat avec film mince, et procédé de fabrication de celui-ci - Google Patents

Substrat avec film mince, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2019139008A1
WO2019139008A1 PCT/JP2019/000247 JP2019000247W WO2019139008A1 WO 2019139008 A1 WO2019139008 A1 WO 2019139008A1 JP 2019000247 W JP2019000247 W JP 2019000247W WO 2019139008 A1 WO2019139008 A1 WO 2019139008A1
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WO
WIPO (PCT)
Prior art keywords
thin film
film
less
coated substrate
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/000247
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English (en)
Japanese (ja)
Inventor
瑶子 宮本
山本　透
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2019564699A priority Critical patent/JP7186184B2/ja
Publication of WO2019139008A1 publication Critical patent/WO2019139008A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • 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

Definitions

  • the present invention relates to a method of manufacturing a thin film-coated substrate and a thin film-coated substrate.
  • a thin film is formed for the purpose of improving the function of the substrate application.
  • a thin film containing silica as a main component is formed on the surface of the substrate.
  • a thin film containing silica as a main component is obtained, for example, by using a hydrolyzable silicon compound represented by silicon alkoxide as a silica source, and hydrolyzing and polycondensation of this hydrolyzable silicon compound by a so-called sol-gel method. It manufactures (for example, nonpatent literature 1).
  • a thin film containing silica as a main component and further not containing an alkali component is, for example, a mixture of water glass (aqueous solution of sodium silicate and / or potassium silicate) and an aqueous solution of lithium silicate.
  • An object of the present invention is to provide a method for producing a thin film-coated substrate, which can contain a durable thin film containing silica (SiO 2 ) as a main component and having durability more easily than the conventional method.
  • the present invention is a method for producing a thin film-coated substrate, wherein the thin film contains SiO 2 as a main component
  • the manufacturing method is Applying a coating liquid for forming the thin film on a substrate; Drying the liquid film of the coating liquid applied to the substrate to obtain a dry film, and obtaining a substrate with a dry film; A alkali removal treatment step of reducing or removing an alkaline component from the dry film in the dry film-attached substrate; In this order, The coating liquid contains water-soluble lithium silicate as a main component of solid content, and water as a main component of solvent.
  • a method for producing a thin film-coated substrate is provided.
  • a thin film containing SiO 2 as a main component and having durability can be manufactured more easily than the conventional method. Furthermore, according to the present invention, it is possible to provide a thin film-coated substrate provided with a thin film containing SiO 2 as a main component.
  • the thin film of the thin film-coated substrate obtained by the manufacturing method of the present embodiment contains silica (SiO 2 ) as a main component.
  • SiO 2 silica
  • the thin film A as main components SiO 2 refers to the content of SiO 2 in the thin film is not less than 50 wt%.
  • the manufacturing method of the present embodiment is Applying a coating liquid for forming the thin film on a substrate; Drying the liquid film of the coating liquid applied to the substrate to obtain a dry film, and obtaining a substrate with a dry film; A alkali removal treatment step of reducing or removing an alkaline component from the dry film in the dry film-attached substrate; In this order.
  • the coating liquid used in the manufacturing method of this embodiment contains water-soluble lithium silicate as a main component of solid content, and contains water as a main component of a solvent.
  • the manufacturing method of the present embodiment applies a coating liquid containing a water-soluble lithium silicate and water to a substrate, and after drying the coated liquid film, the obtained dried film is de-alkalied. It's a simple way of applying processing. According to the manufacturing method of the present embodiment, it is possible to obtain a substrate provided with a thin film containing SiO 2 as a main component by a method simpler than the conventional method.
  • Coating process A coating solution for forming a thin film containing SiO 2 as a main component is prepared.
  • the coating liquid contains water-soluble lithium silicate as a main component of solid content.
  • that the coating liquid contains the water-soluble lithium silicate as the main component of the solid content means that the content of the water-soluble lithium silicate in the solid content of the coating liquid is 50% by mass or more.
  • the solid content of the coating liquid preferably contains 70% by mass or more of water-soluble lithium silicate, more preferably 80% by mass or more, and may be composed of water-soluble lithium silicate .
  • the molar ratio of SiO 2 to Li 2 O (SiO 2 / Li 2 O) It is to be 1 or more and 20 or less and preferably, 2 to 10 Is more preferable, and 3 or more and 8 or less is particularly preferable.
  • the concentration of the water-soluble lithium silicate and the concentration of the solid content of the coating solution may be appropriately selected depending on the film thickness of the thin film and the coating method of the coating solution.
  • the concentration of the water-soluble lithium silicate in the coating liquid may be 0.01% by mass or more and 25% by mass or less.
  • the coating liquid contains water as a main component of the solvent.
  • a coating liquid contains water as a main component of a solvent means that the content rate of water in the solvent of a coating liquid is 50 mass% or more.
  • the solvent of the coating liquid preferably contains 70% by mass or more of water, more preferably 90% by mass or more, and may be water.
  • the coating liquid may contain, for example, glycerin or the like as a solvent other than water.
  • the coating liquid may further contain a surfactant.
  • a coating liquid contains surfactant, 0.1 mass% or less is preferable, and, as for the content rate of surfactant in a coating liquid, 0.01 mass% or less is more preferable.
  • the surfactant for example, a siloxane-polyalkylene oxide copolymer can be used.
  • the coating liquid preferably contains substantially no alkali metal component other than lithium, and preferably contains substantially no alkali metal silicate other than lithium silicate. This improves the durability of the thin film.
  • a coating liquid does not contain alkali metal components other than lithium substantially means that the content rate of alkali metal components other than lithium in a coating liquid is 0.1 mass% or less.
  • the content of the alkali metal silicate other than lithium silicate in the coating liquid is 0.1% by mass that the coating liquid does not substantially contain an alkali metal silicate other than lithium silicate. It says that it is the following.
  • Any known method such as spin coating, roll coating, bar coating, dip coating, spray coating, slot die coating and the like can be used as a method of applying the coating liquid to the substrate.
  • Spray coating is excellent in mass productivity.
  • Roll coating and bar coating are excellent in mass uniformity and uniformity of coating appearance.
  • the thickness of the liquid film formed by applying the coating liquid to the substrate is not particularly limited, but can be, for example, several micrometers to several tens of micrometers.
  • the substrate is, for example, a transparent substrate.
  • a glass substrate can be used as the transparent substrate.
  • a glass substrate for example, a glass plate, a glass plate with a film including a transparent conductive layer (for example, a glass substrate with a transparent conductive film, a glass plate with a low emission film (Low-E (Low Emissivity) film)), etc. Is used.
  • a glass plate for example, a glass plate with a film including a transparent conductive layer
  • the glass plate is not particularly limited, but in order to smooth the surface of the thin film provided on the main surface thereof, those having excellent microscopic surface smoothness are preferred.
  • the glass plate may be float plate glass having a smoothness such that the arithmetic average roughness Ra of its main surface is, for example, 1 nm or less, preferably 0.5 nm or less.
  • the arithmetic mean roughness Ra in the present specification is a value defined in JIS B0601-1994.
  • the glass plate may be template glass having macroscopic irregularities of a size that can be confirmed with the naked eye on its surface.
  • corrugation here is the unevenness
  • the average spacing Sm of irregularities on the surface of the template glass is preferably 0.3 mm or more, more preferably 0.4 mm or more, particularly preferably 0.45 mm or more, 2.5 mm or less, furthermore 2.1 mm or less, particularly 2.0 mm or less And, in particular, 1.5 mm or less.
  • the average interval Sm means an average value of intervals of one cycle of peak and valley obtained from a point where the roughness curve intersects the average line.
  • the surface asperities of the template glass plate preferably have a maximum height Ry of 0.5 ⁇ m to 10 ⁇ m, particularly 1 ⁇ m to 8 ⁇ m, as well as the average spacing Sm in the above range.
  • the average interval Sm and the maximum height Ry are values defined in JIS (Japanese Industrial Standard) B0601-1994.
  • Arithmetic mean roughness Ra can be several nm or less, for example, 1 nm or less. Therefore, even if it is template glass, it can be used suitably for a base material of a substrate with a thin film of this embodiment as a glass plate which is excellent in microscopic surface smoothness.
  • the glass plate may have the same composition as a normal template glass, a flat glass for construction, and a flat glass for automobiles.
  • the content of iron oxide which is a typical coloring component is 0.06 mass% or less, particularly 0.02 or less, in terms of Fe 2 O 3. % Or less is preferred.
  • the case of colored glass it may be a glass plate containing, for example, 0.3% by mass or more and 1.5% by mass or less of iron oxide.
  • the glass plate may be a coated glass plate including a transparent conductive layer.
  • a coated glass plate including a transparent conductive layer is formed of a glass plate and a coating including a transparent conductive layer provided on at least one of the main surfaces of the glass plate.
  • arithmetic mean roughness Ra of the surface of a film is, for example, preferably 10 nm or more and 20 nm or less, and more preferably 13 nm or more and 17 nm or less.
  • the surface roughness of the thin film containing SiO 2 formed in the manufacturing method of the present embodiment provided on the film containing the transparent conductive layer is preferably, for example, 2 nm or more and 10 nm or less 6 nm or more and 10 nm or less, or 2 nm or more and 6 nm or less.
  • the film may have a laminated structure including one or more base layers and a transparent conductive oxide layer disposed in order from the main plane of the glass plate.
  • an underlayer containing silicon oxycarbide (SiOC) as a main component and having a thickness of 20 nm or more and 120 nm or less can be mentioned.
  • the underlayer of the first example may consist essentially of silicon oxycarbide.
  • that the underlayer contains silicon oxycarbide as the main component means that the content of silicon oxycarbide in the underlayer is 50% by mass or more.
  • that the underlayer is substantially made of silicon oxycarbide means that the content of silicon oxycarbide in the underlayer is 90% by mass or more.
  • the underlayer in the first example preferably has a thickness of 30 nm or more and 100 nm or less, and more preferably 30 nm or more and 60 nm or less.
  • a first underlayer consisting essentially of tin oxide and having a thickness of 10 nm to 90 nm, and SiO 2 substantially, having a thickness of 10 nm to 90 nm
  • a second underlayer having the following formula:
  • the fact that the first underlayer substantially consists of tin oxide means that the content of tin oxide in the first underlayer is 90% by mass or more.
  • the second underlayer substantially consisting of SiO 2 means that the content of SiO 2 in the second underlayer is 90% by mass or more.
  • the first underlayer preferably has a thickness of 10 nm to 70 nm, and more preferably 12 nm to 40 nm.
  • the second underlayer preferably has a thickness of 10 nm to 70 nm, and more preferably 12 nm to 40 nm.
  • a first underlayer substantially consisting of SiO 2 and having a thickness of 10 nm to 30 nm, and substantially consisting of tin oxide, and having a thickness of 10 nm to 90 nm
  • a third underlayer which is substantially composed of SiO 2 and has a thickness of 10 nm or more and 90 nm or less.
  • the first base layer consists essentially of SiO 2 is, SiO 2 content rate in the first underlying layer means that 90 mass% or more.
  • the fact that the second underlayer substantially consists of tin oxide means that the content of tin oxide in the second underlayer is 90% by mass or more.
  • the third underlayer substantially consisting of SiO 2 means that the content of SiO 2 in the third underlayer is 90% by mass or more.
  • the first underlayer preferably has a thickness of 10 nm or more and 20 nm or less.
  • the second underlayer preferably has a thickness of 10 nm to 70 nm, and more preferably 12 nm to 40 nm.
  • the third underlayer preferably has a thickness of 10 nm to 70 nm, and more preferably 12 nm to 40 nm.
  • the transparent conductive oxide layer As a first example of the transparent conductive oxide layer, a transparent conductive oxide layer substantially comprising fluorine-containing tin oxide and having a thickness of 200 nm or more and 400 nm or less can be mentioned.
  • the transparent conductive oxide layer substantially consists of fluorine-containing tin oxide means that the content of fluorine-containing tin oxide in the transparent conductive oxide layer is 90% by mass or more.
  • the coating functions as a low emission film.
  • the transparent conductive oxide layer of the first example the transparent conductive oxide layer preferably has a thickness of 300 nm or more and 400 nm or less.
  • the underlayer preferably has a two-layer structure like the underlayer of the second example.
  • the thin film provided in the surface of the base material with a film containing the transparent conductive oxide layer of a 1st example has a physical film thickness of 10 nm or more and 100 nm or less.
  • a transparent conductive oxide layer substantially comprising fluorine-containing tin oxide and having a thickness of 400 nm or more and 800 nm or less can be mentioned.
  • the transparent conductive oxide layer substantially consists of fluorine-containing tin oxide means that the content of fluorine-containing tin oxide in the transparent conductive oxide layer is 90% by mass or more.
  • the coating functions as a transparent conductive film.
  • the transparent conductive oxide layer of the second example the transparent conductive oxide layer preferably has a thickness of 500 nm to 700 nm.
  • the underlayer preferably has a two-layer structure like the underlayer of the second example.
  • the thin film provided in the surface of the base material with a film containing the transparent conductive oxide layer of a 2nd example has a physical film thickness of 40 nm or more and 250 nm or less.
  • a first transparent conductive oxide layer substantially comprising antimony-containing tin oxide and having a thickness of 100 nm to 300 nm, and substantially fluorine-containing oxidized layer
  • the transparent conductive oxide layer which has a laminated structure containing the 2nd transparent conductive oxide layer which consists of tin and has thickness of 150 nm or more and 400 nm or less is mentioned.
  • the fact that the first transparent conductive oxide layer is substantially made of antimony-containing tin oxide means that the content of the antimony-containing tin oxide in the first transparent conductive oxide layer is 90% by mass or more.
  • the second transparent conductive oxide layer substantially consists of fluorine-containing tin oxide means that the content of the fluorine-containing tin oxide in the second transparent conductive oxide layer is 90% by mass or more.
  • the coating functions as a low emission film.
  • the first transparent conductive oxide layer preferably has a thickness of 150 nm to 200 nm
  • the second transparent conductive oxide layer has a thickness of 200 nm to 300 nm It is preferable to have a length.
  • the base layer preferably has a two-layer structure like the base layer of the second example.
  • the thin film provided in the surface of the base material with a film containing the transparent conductive oxide layer of a 3rd example has a physical film thickness of 10 nm or more and 100 nm or less.
  • the thin film-coated substrate obtained by forming a thin film by the manufacturing method of the present embodiment on the surface on which the low radiation film is formed using the low radiation film-coated glass plate as a substrate is a low radiation film-coated glass plate
  • the low radiation film-coated glass plate may have another low radiation film on the surface opposite to the surface on which the thin film of the present embodiment is formed.
  • This other low emission film may be the same as the above-mentioned low emission film, but it is a film including a laminate in which a dielectric layer, a layer containing silver as a main component, and another dielectric layer are stacked in this order. It may be
  • the liquid film of the coating film applied to the substrate is dried to obtain a substrate with a dried film.
  • the method of drying the liquid film is not particularly limited. Below, the 1st example and the 2nd example of a preferable drying method are demonstrated.
  • the maximum temperature reached by the surface of the liquid film is 60 ° C. or more and less than 300 ° C., preferably 80 ° C. or more and 250 ° C. or less, and 90 ° C. or more and 220 ° C. or less C. is more preferable, and 100.degree. C. or more and 200.degree. C. or less are more preferable.
  • the time during which the surface temperature of the liquid film is 60 ° C. or more (preferably 80 ° C. or more, more preferably 100 ° C. or more) is 2 seconds or more (preferably 10 seconds or more, more preferably 18 seconds or more) Is preferred.
  • this first example may be referred to as "low temperature drying".
  • the maximum temperature reached by the surface of the liquid film is 300 ° C. or higher, preferably 400 ° C. or higher, and more preferably 500 ° C. or higher.
  • the upper limit of the maximum temperature reached by the surface of the liquid film is not particularly limited, for example, it is less than the temperature at which the substrate is deformed.
  • the heating for drying the liquid film can be used also as the heating in the step of heating and forming the base material.
  • the time during which the surface temperature of the liquid film reaches the maximum temperature is not limited, and if the maximum temperature reaches the above temperature, the time during which the temperature is maintained may be short.
  • this second example may be referred to as "high temperature drying".
  • the drying step may be performed by, for example, hot air drying.
  • the drying step may be carried out by holding the substrate coated with the liquid film for a predetermined time in a heating furnace set to a predetermined temperature.
  • the composition of the resulting dried film substantially corresponds to the composition of the solid content of the coating liquid.
  • the alkali removal treatment is performed to reduce or remove the alkali component from the dried film of the dry film-coated substrate.
  • the de-alkali treatment step includes, for example, a water washing step in which the dried film is brought into contact with a washing solution containing water as a main component.
  • the cleaning liquid containing water as a main component means that the content of water in the cleaning liquid is 80% by mass or more.
  • the cleaning solution may not contain a special cleaning agent, and may consist essentially of water.
  • that the cleaning solution substantially consists of water means that the content of water in the cleaning solution is 95% by mass or more.
  • the water contained in the cleaning agent does not have to be pure water, and may be city water (industrial tap water).
  • the temperature of the cleaning agent can be, for example, 5 ° C. or more and 95 ° C. or less, preferably 10 ° C. or more and 80 ° C. or less, and more preferably 15 ° C. or more and 45 ° C. or less.
  • the time for which the dry film is in contact with the washing solution is, for example, 2 seconds or more.
  • the time for which the dry film is in contact with the cleaning solution may be 30 seconds or less or 15 seconds or less.
  • the dry film of the present invention may be subjected to a sufficient dealkalization treatment in the above time.
  • the time for which the dry film is in contact with the cleaning solution is preferably longer, and may be 4 seconds or more and 2 minutes or less, or 30 seconds or less.
  • mechanical force may be applied to the dried film.
  • a mechanical force may be applied to the dry film using a brush, a sponge, ultrasonic waves, or the like.
  • the Li 2 O content in the thin film is preferably less than 3% by mass, more preferably less than 1% by mass, in the water-washing step, and more preferably 0.5% by mass It is more preferable to set it as the following, and especially preferable to set it as 0.3 mass% or less.
  • the thin film may be substantially free of Li 2 O.
  • the thin film is Substantially free of Li 2 O, the content of Li 2 O in the thin film means less than 0.05% by weight.
  • the content of Li 2 O in the thin film may be 0.05% by mass or more and 0.5% by mass or less, or 0.1% by mass or more and 0.5% by mass or less.
  • the Li 2 O content in the thin film is preferably 3% by mass or more and 12% by mass or less in the water-washing step.
  • a post heat treatment step of heating the thin film may be further performed after the de-alkali treatment step.
  • the maximum temperature reached by the surface of the thin film of the thin film-coated substrate is 300 ° C. or higher, preferably 400 ° C. or higher, and more preferably 550 ° C. or higher.
  • the upper limit of the maximum temperature reached by the surface of the thin film is not particularly limited, but is, for example, less than the temperature at which the substrate is deformed.
  • the heating for drying the liquid film can be used also as the heating in the step of heating and forming the base material.
  • the post heat treatment step of heating the thin film may not be performed after the de-alkali treatment step.
  • a thin film-coated substrate comprising a transparent substrate and a thin film provided on at least a part of the surface of the transparent substrate, wherein the thin film is SiO 2 Contained as a main component, the content of Li 2 O in the thin film is 12% by mass or less (eg, less than 3% by mass, or 3% by mass to 12% by mass), and the physical thickness of the thin film is 5 nm or more and 500 nm It is possible to obtain a substrate with a thin film, which is the following.
  • the physical film thickness of the thin film is adjusted by appropriately adjusting the coating conditions of the coating liquid (the concentration of the coating liquid, the thickness of the liquid film formed on the substrate, etc.) It is possible.
  • a preferable first example of the physical thickness of the thin film is, for example, 10 nm or more and 100 nm or less, preferably 15 nm or more and 80 nm or less, more preferably 20 nm or more and 39 nm or less.
  • the second preferred example of the physical thickness of the thin film is, for example, 40 to 250 nm, preferably 50 to 200 nm, more preferably 50 to 150 nm, and still more preferably 80 to 120 nm.
  • the thin film having the physical film thickness of this second example is particularly combined with a substrate having a green color tone (for example, a low emission film-coated glass plate having a transparent conductive oxide layer formed of fluorine-containing tin oxide) In this case, there is an effect that the color tone does not change depending on the presence or absence of the thin film.
  • the content of Li 2 O in the thin film is preferably less than 3% by mass by adjusting the conditions of the de-alkali treatment step, and 1 mass It is more preferable that the amount be less than 5% by mass, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.
  • the thin film may be substantially free of Li 2 O.
  • the thin film is washed so as to be substantially free of Li 2 O in the de-alkali treatment step, it is possible to obtain a thin film-coated substrate provided with a thin film substantially free of Li 2 O.
  • the content of Li 2 O is 0.05% by mass or more and 0.5% by mass or less by adjusting the conditions of the de-alkali treatment step.
  • the Li 2 O content in the thin film is adjusted to 3% by mass or more and 12% by mass or less by adjusting the conditions of the de-alkali treatment step. Is preferred.
  • the coating liquid used in the coating step contains substantially no alkali metal component other than lithium or substantially contains no alkali metal silicate other than lithium silicate.
  • a thin film-coated substrate provided with a thin film substantially free of an alkali metal component other than lithium can be obtained.
  • Example 1 Preparation of Coating Liquid> Water soluble lithium silicic acid aqueous solution ("lithium silicate 35", Nissan Chemical Industries, Ltd., SiO 2 / Li 2 O molar ratio: 3.5, SiO 2 content: 20% by mass, solvent: water only) and further solid It diluted with water so that the amount might be 1.7 mass%.
  • lithium silicate 35 Nissan Chemical Industries, Ltd., SiO 2 / Li 2 O molar ratio: 3.5, SiO 2 content: 20% by mass, solvent: water only
  • a glass plate was used as a substrate.
  • This glass plate was a glass plate with a low radiation film.
  • This low radiation film is a 25 nm thick tin oxide layer (first base layer), a 25 nm thick SiO 2 layer (second base layer), and a 340 nm thick fluorine-containing tin oxide from the main surface side of the glass plate
  • a layer transparent conductive oxide layer
  • the coating liquid of Example 1 was applied by spin coating on the low emission film of this glass plate.
  • the glass plate is held horizontally on a spin coating apparatus, the coating liquid is dropped on the central portion of the glass plate, the glass plate is rotated at a rotation speed of 1500 rpm, and the rotation speed is maintained for 30 seconds. , Stopped the rotation of the glass plate. Thereby, the liquid film of the coating liquid for thin film formation was formed on the low radiation film of the glass plate.
  • the glass plate on which the liquid film was formed was held in an electric furnace set at 350 ° C. for 25 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 102 ° C., the time of 60 ° C. or more was 18 seconds, and the time of 80 ° C. or more was 10 seconds.
  • the dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • the de-alkali treatment was performed by hand-washing the dried membrane with city water for 5 times with a sponge at 25 ° C. city water. During the handwashing, the dried film was in contact with city water for about 10 seconds. Thereafter, the thin film was allowed to dry naturally.
  • Example 2 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying process of Example 2 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 350 ° C. for 55 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 142 ° C., the time of 60 ° C. or more was 48 seconds, and the time of 80 ° C. or more was 40 seconds. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 3 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying process of Example 3 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 350 ° C. for 100 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 180 ° C., the time of 60 ° C. or more was 93 seconds, and the time of 80 ° C. or more was 85 seconds. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 4 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying process of Example 4 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 350 ° C. for 130 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 200 ° C., the time of 60 ° C. or more was 123 seconds, and the time of 80 ° C. or more was 115 seconds. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 5 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying process of Example 5 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 350 ° C. for 250 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 250 ° C., the time of 60 ° C. or more was 243 seconds, and the time of 80 ° C. or more was 235 seconds. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 6 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying step of Example 6 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 350 ° C. for 550 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 280 ° C., the time of 60 ° C. or more was 543 seconds, and the time of 80 ° C. or more was 535 seconds. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 7 A thin film-coated substrate is produced by the same method as in Example 1 except that the solid content concentration of the coating liquid, the coating method of the coating liquid, and the drying step during thin film formation are different, and each property is evaluated did.
  • the solid content concentration of the coating liquid of Example 7 was 0.1% by mass.
  • the coating liquid was applied onto the low emission film of the glass plate by a spray coating method. Specifically, using a commercially available spray gun, the coating liquid was sprayed from above the main surface of the horizontally held glass plate.
  • the drying process is as follows. The liquid film was dried with hot air using a hot air generator.
  • the set temperature of the hot air was set to 200 ° C., and the distance between the hot air discharge nozzle and the glass plate was set to 50 mm, and the hot air was applied to the liquid film for 219 seconds.
  • the maximum temperature reached in the liquid film of the glass plate was 177 ° C., the time of 60 ° C. or more was 177 seconds, and the time of 80 ° C. or more was 170 seconds.
  • the dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 8 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step during thin film formation was different from the de-alkali treatment step, and each property was evaluated.
  • the drying step of Example 8 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 350 ° C. for 55 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 142 ° C., the time of 60 ° C. or more was 48 seconds, and the time of 80 ° C. or more was 40 seconds. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • the dealkalization treatment of Example 8 was carried out using city water at a temperature of 25 ° C., specifically, by applying running water from a tap of tap water to the drying film for 5 seconds. Thereafter, the thin film was allowed to dry naturally.
  • Example 9 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step during thin film formation was different from the de-alkali treatment step, and each property was evaluated.
  • the drying step of Example 9 was the same as the drying step of Example 7.
  • the substrate with a dry film was conveyed at 1 m / min so that the dry film was in contact with the brush of 100 mm in diameter rotating at 60 rpm.
  • the brush was supplied with city water at 25 ° C. During this time, the dried film was in contact with city water for about 6 seconds.
  • Example 10 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying process of Example 10 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 760 ° C. for 30 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 320 ° C. Immediately after the glass plate on which the liquid film was formed was put into the electric furnace, the temperature of the liquid film became 80 ° C. or higher. That is, the time when the liquid film was 80 ° C. or more was 30 seconds or more which was held in the electric furnace. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 11 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying step of Example 11 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 760 ° C. for 65 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 420 ° C. Immediately after the glass plate on which the liquid film was formed was put into the electric furnace, the temperature of the liquid film became 80 ° C. or higher. That is, the time when the liquid film was 80 ° C. or more was 65 seconds or more which was held in the electric furnace. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 12 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying step of Example 12 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 760 ° C. for 100 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 480 ° C. Immediately after the glass plate on which the liquid film was formed was put into the electric furnace, the temperature of the liquid film became 80 ° C. or higher. That is, the time when the liquid film was 80 ° C. or more was 100 seconds or more which was held in the electric furnace. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 13 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying step of Example 13 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 760 ° C. for 150 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 570 ° C. Immediately after the glass plate on which the liquid film was formed was put into the electric furnace, the temperature of the liquid film became 80 ° C. or higher. That is, the time when the liquid film was 80 ° C. or more was 150 seconds or more which was held in the electric furnace. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 14 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying step of Example 14 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 760 ° C. for 215 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 620 ° C. Immediately after the glass plate on which the liquid film was formed was put into the electric furnace, the temperature of the liquid film became 80 ° C. or higher. That is, the time when the liquid film was 80 ° C. or more was 215 seconds or more which was held in the electric furnace. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 15 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and each characteristic was evaluated.
  • the drying step of Example 15 is as follows. The glass plate on which the liquid film was formed was held in an electric furnace set at 760 ° C. for 275 seconds, then taken out of the electric furnace and dried. At this time, the maximum temperature reached in the liquid film of the glass plate was 670 ° C. Immediately after the glass plate on which the liquid film was formed was put into the electric furnace, the temperature of the liquid film became 80 ° C. or higher. That is, the time when the liquid film was 80 ° C. or more was 275 seconds or more which was held in the electric furnace. The dried glass plate was allowed to cool to room temperature, and a dried film was formed on the glass plate.
  • Example 16 After the thin film-coated substrate was produced in the same manner as in Example 2, that is, after the de-alkali treatment step of Example 2, a post heat treatment step was carried out to produce a thin film-coated substrate of Example 16. The properties of the obtained thin film-coated substrate were evaluated in the same manner as in Example 1. In the post-heat treatment step carried out in Example 16, the glass plate on which the thin film was formed was held in an electric furnace set at 760 ° C. for 225 seconds, and then taken out of the electric furnace. At this time, the maximum temperature reached in the thin film of the glass plate was 650 ° C.
  • Example 17 After a thin film-coated substrate was produced in the same manner as in Example 2, that is, after the de-alkali treatment step of Example 2, a post heat treatment step was carried out to produce a thin film-attached substrate of Example 17. The properties of the obtained thin film-coated substrate were evaluated in the same manner as in Example 1.
  • the glass plate on which the thin film was formed was held in an electric furnace set at 760 ° C. for 250 seconds, and then taken out of the electric furnace. At this time, the maximum temperature reached in the thin film of the glass plate was 670 ° C.
  • Example 1 A thin film-coated substrate was produced in the same manner as in Example 1 except that the drying step at the time of thin film formation was different, and the de-alkali treatment step was not performed, and the respective characteristics were evaluated.
  • the liquid film was dried by natural drying at room temperature.
  • Comparative example 2 A thin film was not formed on the glass plate with the low radiation film used in Example 1, and naturally the drying step and the de-alkali treatment step were not performed. That is, the glass plate with the low radiation film used in Example 1 was taken as Comparative Example 2.
  • the surface roughness Ra was calculated by scanning a 10 ⁇ m ⁇ 10 ⁇ m range with an atomic force microscope (SP-400, manufactured by SII-NT).
  • the haze ratio was measured with a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH-2000).
  • fingerprint stain removability After wiping the surface of the thin film with a cotton cloth moistened with water, fingerprint stain removability was evaluated as follows according to whether or not fingerprint marks were observed even if exhaled breath. :: After wiping 10 times with a cotton cloth moistened with water, no trace of fingerprints is observed even if exhaled breath. ⁇ : no fingerprint marks are observed even after exhaling after wiping with cotton cloth dampened with water 30 times. ⁇ : After wiping 30 times with a cotton cloth moistened with water, a slight fingerprint trace is observed when exhaled. ⁇ : After wiping 30 times with a cotton cloth moistened with water, fingerprints are easily observed by exhaling breath.
  • the alkali resistance test was performed on the thin film-coated substrate according to the following method. With respect to the thin film-coated substrate after this alkali resistance test, fingerprint removability and optical properties (haze ratio) were evaluated. The fingerprint removability was evaluated based on the same criteria as the above-mentioned "Fingerprint dirt removability evaluation”. ⁇ Alkali resistance test 1 The alkali resistance test 1 was conducted by immersing the thin film-coated substrate in 1N NaOH at 23 ° C. in accordance with the alkali resistance test defined for the heat ray reflective glass of JIS R3221.
  • the immersion time in this alkali resistance test 1 is 6 hours, and the haze ratio of the substrate with a thin film after immersion is compared with the haze ratio of the substrate (a substrate without a thin film) in the state where the thin film is not formed. And evaluated as follows.
  • ⁇ The haze ratio of the thin film-coated substrate after immersion is at least 0.1% lower than the haze ratio of the thin film-free substrate
  • ⁇ The haze ratio of the thin film-coated substrate after immersion is higher than the haze ratio of the thin film-free substrate Less than 0.1% lower ⁇ alkali resistance test 2
  • the alkali resistance test 2 was performed only for some examples.
  • the alkali resistance test 2 was the same as the alkali resistance test 1 except that the immersion time was 24 hours.
  • a thin film-coated substrate provided with a thin film containing SiO 2 as a main component and having durability can be manufactured and provided by a simple method.

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Abstract

Le procédé de fabrication de substrat avec film mince de l'invention est destiné à fabriquer un substrat sur lequel est formé un film mince contenant un ＳｉＯ2 en tant que composant principal. Le procédé de fabrication de l'invention inclut dans l'ordre : une étape d'application au cours de laquelle un liquide d'application destiné à la formation du film mince est appliqué sur le substrat ; une étape de séchage au cours de laquelle un film liquide dudit liquide d'application ainsi appliqué sur ledit substrat, est séché, formant ainsi un film sec, et un substrat avec film sec est obtenu ; et une étape de traitement de désalcalinisation au cours de laquelle un composant alcalin est réduit ou éliminé dudit film sec dans ledit substrat avec film sec. Ledit liquide d'application contient un silicate de lithium hydrosoluble en tant que composant principal de matière solide, et contient une eau en tant que composant principal de solvant.
PCT/JP2019/000247 2018-01-11 2019-01-08 Substrat avec film mince, et procédé de fabrication de celui-ci Ceased WO2019139008A1 (fr)

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JPWO2021054289A1 (fr) * 2019-09-18 2021-03-25
JP2021173096A (ja) * 2020-04-28 2021-11-01 馬居化成工業株式会社 コンクリートの補修方法およびコンクリートの補修剤
WO2022114038A1 (fr) * 2020-11-27 2022-06-02 Ａｇｃ株式会社 Verre d'isolation thermique
JP2024501681A (ja) * 2020-12-23 2024-01-15 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 薄膜の作製方法、特にゾル－ゲル法による方法

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JP2024501681A (ja) * 2020-12-23 2024-01-15 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 薄膜の作製方法、特にゾル－ゲル法による方法

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