WO2022039268A1 - イージークリーンコーティング付きガラス物品 - Google Patents

イージークリーンコーティング付きガラス物品 Download PDF

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Publication number
WO2022039268A1
WO2022039268A1 PCT/JP2021/030656 JP2021030656W WO2022039268A1 WO 2022039268 A1 WO2022039268 A1 WO 2022039268A1 JP 2021030656 W JP2021030656 W JP 2021030656W WO 2022039268 A1 WO2022039268 A1 WO 2022039268A1
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WIPO (PCT)
Prior art keywords
glass
coating
water
cerium
glass plate
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/JP2021/030656
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English (en)
French (fr)
Japanese (ja)
Inventor
瑶子 渡邊
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
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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 JP2022544025A priority Critical patent/JP7600246B2/ja
Priority to CN202510305130.4A priority patent/CN119977356A/zh
Priority to EP21858411.8A priority patent/EP4201904A4/en
Priority to BR112023002135A priority patent/BR112023002135A2/pt
Priority to CN202180058180.7A priority patent/CN116075489B/zh
Priority to US18/042,156 priority patent/US20230322616A1/en
Publication of WO2022039268A1 publication Critical patent/WO2022039268A1/ja
Anticipated expiration legal-status Critical
Priority to JP2024211751A priority patent/JP2025032203A/ja
Ceased legal-status Critical Current

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    • 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
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/228—Other specific oxides
    • 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
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/445—Organic continuous phases
    • 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
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • 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
    • C03C2217/75—Hydrophilic and oleophilic 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
    • 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
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium

Definitions

  • the present invention relates to a glass article with an easy clean coating.
  • a film called Easy to clean coating may be formed on the surface of various substrates.
  • the easy clean coating makes it easier to remove dirt adhering to the surface of the substrate.
  • Easy clean coatings typically contain fluorine-containing organic compounds.
  • a typical base material on which an easy clean coating is formed is a glass base material.
  • a commercially available coating liquid containing a fluoroalkyl group-containing silicon alkoxide is applied to the surface of the glass substrate to form an easy clean coating.
  • Patent Document 1 discloses a technique for providing an adhesion promoter layer between a glass substrate and an easy clean coating.
  • the adhesion promoter layer is specifically a silicon mixed oxide layer, which improves the sustainability of easy-clean properties.
  • An object of the present invention is to provide a coated glass article having improved easy cleanliness.
  • the present invention A glass substrate and an easy clean coating on the glass substrate are provided.
  • the coating contains cerium oxide and
  • the contact angle of water on the surface of the coating is 60 ° or more and 130 ° or less.
  • Provided is a coated glass article.
  • a coated glass article having improved easy cleanliness is provided.
  • FIG. 6 is a schematic cross-sectional view illustrating the progress of evaporation of water droplets on a hydrophilic surface. It is a schematic cross-sectional view explaining the progress of evaporation of a water drop on a surface imparted with water repellency by a fluorine-containing organic compound. It is a figure which shows the result of having observed the coated glass article produced in Example 1 with a scanning electron microscope (SEM). It is a figure which shows the result of having observed the coated glass article produced in Example 2 by SEM. It is a figure which shows the result of having observed the coated glass article produced in Example 4 by SEM. It is a figure which shows the result of having observed the coated glass article produced in Example 5 by SEM.
  • SEM scanning electron microscope
  • Example 10 It is a figure which shows the observation result of the dirt adhesion test / tap water carried out in Example 10. It is a figure which shows the observation result of the dirt adhesion test / tap water carried out in Example 11. It is a figure which shows the observation result of the dirt adhesion test / tap water carried out in the comparative example 4.
  • FIG. It is a figure which shows the observation result of the dirt adhesion test / tap water carried out in the comparative example 5. It is a figure which shows the observation result before the dirt adhesion test / hand soap under running water washing carried out in Example 12. It is a figure which shows the observation result after the dirt adhesion test / washing with running water of the hand soap carried out in Example 12.
  • the "main component” means a component having a content of 50% or more, particularly 60% or more on a mass basis.
  • substantially free means that the content is less than 1% and even less than 0.1% on a mass basis.
  • substantially flat means that no unevenness having a height or a depth of 500 nm or more is confirmed except for fine particles and fine particle-like convex portions on the surface when observed by SEM.
  • Room temperature is used as a term to mean a temperature in the range of 5 to 35 ° C, especially 10 to 30 ° C.
  • the coated glass article provided by this embodiment is A glass substrate and an easy clean coating on the glass substrate are provided.
  • the coating contains cerium oxide and
  • the contact angle of water on the surface of the coating is 60 ° or more and 130 ° or less.
  • the coated glass articles provided by this embodiment are, for example, A step of applying a coating liquid containing cerium oxide as a solid content or a coating liquid containing chelated cerium ions on a glass base material to form a coating film on the glass base material. A step of drying the coating film to form an easy clean coating is provided.
  • the cerium oxide can be provided by a production method containing CeO 2 .
  • the coating material used is an organic material that can realize a high contact angle represented by a fluorine-containing organic compound.
  • a fluorine-containing organic compound that can realize a high contact angle represented by a fluorine-containing organic compound.
  • scattered spot-like stains tend to remain as the water droplets adhering to the surface evaporate. This stain is formed by spot-like fine particles or solutes contained in the attached water droplets in a trace area. Uneven distribution of stains is often observed even on the surface of uncoated glass.
  • the ring-shaped stains that remain on the hydrophilic glass surface are sometimes referred to as "coffee rings.” Dirt that remains concentrated in a spot or ring shape is easily noticeable and may not be easily removed depending on the degree of concentration.
  • the mechanism by which dirt remains in a ring shape can be understood from Fig. 1.
  • the water droplet 10 adhering to the hydrophilic surface 21 of the glass substrate 20 shrinks as the evaporation of water progresses, and eventually disappears.
  • the water droplet 10 tends to shrink while maintaining the contact area with the hydrophilic surface 21. Therefore, the central portion of the water droplet 10 contracts more than the peripheral portion.
  • a flow 31 from the central portion to the peripheral portion 11p is generated in the vicinity of the surface 21 of the base material 20 inside the shrinking water droplet 11. Due to this minute flow 31, foreign matter contained in the water droplet 11 and fine particles which are precipitated solutes gather at the peripheral edge portion 11p and are deposited in a ring shape.
  • the mechanism by which dirt remains in spots can be understood from Fig. 2.
  • the water droplet 10 adhering to the water-repellent surface 22 of the glass substrate 20 shrinks as the evaporation of water progresses, and eventually disappears.
  • the water droplet 10 tends to shrink while maintaining a high contact angle with the surface 22. Therefore, inside the water droplet 10 shrinking to the smaller water droplet 11, a flow 32 from the peripheral portion to the central portion 11c is generated in the vicinity of the surface 22 of the base material. Due to this minute flow 32, the fine particles contained in the water droplets gather in the central portion 11c and precipitate in the form of spots.
  • the stains that appear as the water droplets evaporate tend not to concentrate. It was found to be in. In other words, on this coating, after the water droplets evaporate, the tendency of the water droplet-derived stains to adhere to a specific site is alleviated. It was also confirmed that the stains that were relatively spread and adhered on this coating were easier to remove than the stains that were concentrated and adhered.
  • the coated glass article according to the present embodiment can have an improved easy clean property by alleviating the uneven distribution of the attached stains.
  • cerium oxide can function as a water-repellent material.
  • the water repellency due to the cerium oxide can reach 75 ° or more, 80 ° or more, and even 85 ° or more in terms of the contact angle of water. So far, this degree of contact angle has been realized by surface treatment using an organic water repellent.
  • the organic water repellent is usually decomposed in the process of heating to about 300 ° C., but the cerium oxide is stably present even when heated to a higher temperature.
  • the contact angle of water on the surface of the coating after the glass article is exposed to heat treatment at 760 ° C. and 4 minutes can be 60 ° or more and 130 ° or less, particularly 70 ° or more and 110 ° or less.
  • the contact angle of water after exposure to heat treatment can reach 75 ° or more, 80 ° or more, and even 85 ° or more.
  • the contact angle of water on the surface of the coating may temporarily decrease immediately after the heat treatment, and therefore may be measured after a period of time from the heat treatment. It may take tens of days to recover the contact angle. Therefore, the contact angle may be measured, for example, after the glass article is exposed to heat treatment at 760 ° C. for 4 minutes and further stored in the air at room temperature for 40 days.
  • the glass base material and the coating constituting the coated glass article of the present embodiment will be described, the characteristics that can be achieved by the present embodiment and the use of the article will be described, and finally, the manufacturing method of the present embodiment will be described. explain.
  • the glass substrate may be made of various types of glass called soda-lime glass, borosilicate glass, aluminosilicate glass, non-alkali glass, quartz glass and the like.
  • the glass substrate may contain SiO 2 as a main component.
  • the glass substrate may be a glass plate, a glass container, a glass lid, a glass tube, a glass valve, a glass lens or other molded body.
  • the glass container is, for example, a glass vial, a glass ampoule, or a glass bottle, but may have other shapes called a tray, a petri dish, or the like.
  • the shape of the glass lid is not limited as long as it functions as a lid, and may have a shape that can be used as a lid of a cooking utensil, for example.
  • the glass plate may have a flat plate shape, but may have a bending shape given by a bending process.
  • the thickness of the glass plate is not particularly limited, but is, for example, in the range of 0.5 to 12 mm.
  • the glass plate may be treated so as to be suitable for use as a window glass of a building, a vehicle, or the like.
  • the glass plate may be subjected to a strengthening treatment.
  • the glass plate may be tempered glass.
  • the strengthening treatment wind-cooled strengthening that rapidly cools after heating to form a compressive stress layer on the surface and chemical strengthening that forms a compressive stress layer on the surface by ion exchange of alkali metal ions are known.
  • the glass plate may be integrated with another glass plate by laminating and / or multi-layering.
  • a coating may be formed on the surface of the glass plate in order to impart or control properties other than water repellency.
  • the film include a Low-E film, a conductive film, a reflection-suppressing film, a colored film, and the like.
  • the colored film is, for example, a ceramic coating.
  • the ceramic coating is formed for the purpose of imparting decorativeness, making a part of the area opaque, and the like.
  • the above-mentioned treatment of the glass plate often involves heating the glass plate.
  • the bending process of a glass plate includes a step of heating and softening the glass plate.
  • the laminating process and the multi-layer process are also performed depending on the type of resin film sandwiched between the glass plates or the type of sealing material used to seal the space between the glasses. May be heated to high temperatures. After undergoing these heatings, the water repellency of the easy clean coating made of an organic substance is greatly reduced, and the easy clean property is also impaired. For this reason, the formation of the coating had to be carried out after the treatment involving heating of the glass plate. Such process restrictions may hinder the efficiency of mass production.
  • evenly applying the coating liquid to a curved surface is much more difficult than applying it on the surface of a flat plate.
  • the step of applying the coating liquid to the flat strip-shaped glass that has not been cut and processed so as to have a curved surface individually can be carried out remarkably efficiently.
  • the glass substrate on which the coating is formed can be heated to carry out various treatments on the glass substrate.
  • the various treatments for the glass plate are selected from the group consisting of bending treatment involving heating (heat bending treatment), air cooling strengthening treatment, chemical strengthening treatment, laminating processing, multi-layer processing, and film forming treatment. At least one, especially a heat bending treatment and / or an air cooling strengthening treatment.
  • the glass substrate may be a glass plate that has undergone at least one treatment selected from the group consisting of heat bending treatment and air cooling strengthening treatment.
  • the temperature applied to the above heat treatment is usually at most 760 ° C. or lower.
  • a heat bending treatment and / or an air cooling strengthening treatment is performed, and then a coating liquid for forming an easy clean coating is applied to the main surface of the glass plate.
  • the coating liquid is applied to the main surface of the flat glass plate to form an easy clean coating, and then the glass plate is subjected to heat bending treatment and air cooling strengthening treatment. At least one process selected from the group can be performed.
  • the glass plate provided in this form may have a coating on at least one of its main surfaces and no coating on the end faces of the glass plate.
  • a thick coating may be locally formed on the end face where the coating liquid tends to collect. Therefore, avoiding this is advantageous in terms of ensuring the aesthetic appearance of the product.
  • the coating may contain cerium oxide in an amount of 10% by mass or more, 30% by mass or more, and may further contain as a main component.
  • the coating may be a film that is substantially free of components other than cerium oxide.
  • the coating may have a surface exposed to cerium oxide.
  • the cerium oxide preferably contains CeO 2 , an oxide of tetravalent cerium. CeO 2 is a desirable component from the viewpoint of enhancing easy cleanliness over Ce 2 O 3 , that is, an oxide of trivalent cerium.
  • the coating may contain Ce 2 O 3 as a cerium oxide.
  • the easy clean coating on a base material such as glass usually has a multi-layer structure of a metal oxide layer that provides a base and an overcoat layer of an organic compound.
  • the overcoat layer is often composed of a hydrolyzed polycondensate of a hydrolyzable organosilicon compound in order to bond strongly with the metal oxide layer.
  • the hydrolyzable organosilicon compound is an organic compound suitable for improving water repellency, typically a fluoroalkyl group-containing compound.
  • the coating may be substantially free of the hydrolyzed polycondensate of the hydrolyzable organosilicon compound. Further, the coating may be substantially free of fluorine-containing organic compounds, particularly fluoroalkyl group-containing compounds.
  • the coating may be a single-layer film or a multi-layer film composed of a plurality of layers, but the single-layer film is advantageous in reducing mass production costs.
  • the easy clean coating of the present embodiment can provide easy clean properties even if it is a single-layer film.
  • the coating includes a layer containing a cerium oxide as the uppermost layer of the multi-layer film.
  • the base layer may be interposed between the glass base material and the coating.
  • the underlayer is, for example, a metal oxide layer, and specifically, even if the mass-based content of cerium oxide is lower than that of the surface coating, and even if the layer is substantially free of cerium oxide. good.
  • the underlayer may contain at least one selected from the group consisting of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide.
  • An example of a desirable base layer is a layer containing silicon oxide as a main component.
  • the base layer itself may be a plurality of layers.
  • the underlying layer, which is a multi-layer film, may be, for example, a Low-E film.
  • the easy clean coating of the present embodiment can provide a water contact angle of 60 ° or more, 65 ° or more, 70 ° or more, 75 ° or more, and even 80 ° or more, 85 ° or more, and in some cases 90 ° or more. can.
  • the upper limit of the contact angle of water is not particularly limited, but is, for example, 130 ° or less, 120 ° or less, 110 ° or less, 105 ° or less, 100 ° or less, 95 ° or less.
  • the contact angle of water can be measured by dropping 4 mg (about 4 ⁇ L) of purified water onto the surface of the coating.
  • the easy clean coating of the present embodiment does not completely lose its water repellency even when heated to a high temperature, for example, 500 ° C. or even 760 ° C.
  • the coating of the present embodiment is, for example, 60 ° or higher, 65 ° or higher, 70 ° or higher, 75 ° or higher, 80 ° or higher, 85 ° or higher, even after the glass article is exposed to heat treatment at 760 ° C. and 4 minutes.
  • it is possible to provide a contact angle of water which is 90 ° or more and 130 ° or less, 120 ° or less, 110 ° or less, 105 ° or less, and further 100 ° or less and 95 ° or less.
  • the water repellency of the easy clean coating of this embodiment may temporarily decrease after being heated at a high temperature.
  • the measured value may not be stable immediately after the film formation and may show a low value.
  • the contact angle of water gradually increases and becomes more stable and shows the above-mentioned degree of contact angle only by exposing it to the atmosphere and storing it at room temperature.
  • the period required for recovery and stability is about 30 to 40 days. Therefore, it is desirable to measure the contact angle after heat treatment at high temperature after storing in the air at room temperature for a predetermined period.
  • Easy clean coating may contain organic components.
  • the organic component may be an organic compound or an organic group bonded to an oxide or the like constituting a film.
  • the content of the organic component in the coating is not particularly limited, but may be 0.01% or more, further 0.1% or more, 10% or less, and further 1% or less on a mass basis.
  • Coatings that have not been exposed to high temperature heat treatment may contain relatively high content of organic components. However, the coating may be substantially free of organic components.
  • the organic group contained in the easy clean coating may contain an epoxy group.
  • the epoxy group is a preferred functional group suitable for use in the production examples described below. As will be described later, the epoxy group is consumed by reacting with other components, specifically an acid, but the excessively added epoxy group may remain in the coating.
  • the epoxy groups remaining in the coating can act as cross-linking agents, especially during heat treatment, and affect the structure of the membrane.
  • the easy clean coating may contain an inorganic compound other than cerium oxide.
  • oxides other than cerium oxide include silicon oxides, aluminum oxides, zirconium oxides, titanium oxides, ruthenium oxides, and rare earth oxides other than cerium.
  • Cerium oxide is easy to obtain and inexpensive among rare earth oxides.
  • the coating may be free of rare earth oxides other than cerium oxide.
  • the inorganic compound may be, for example, a nitride, a carbide, or the like other than the oxide.
  • the film thickness of the Easy Clean coating is, for example, 2 to 1000 nm, and particularly 5 to 500 nm.
  • the film thickness of the coating may be 7 nm or more, further 10 nm or more, 300 nm or less, and further 200 nm or less.
  • the easy clean coating may have a dense structure, but may also have holes inside.
  • the porosity of the coating may be, for example, 20% or more, 25% or more, 30% or more, and in some cases 40% or more, 85% or less, 70% or less, 60% or less, and in some cases 50% or less. May be.
  • a coating with an appropriate porosity may have excellent optical properties. Specifically, by controlling the porosity, it is possible to eliminate the interference color that may occur due to the coating, improve the visible light transmittance and the reflectance, and the like.
  • the easy clean coating may have a plurality of fine particles on its surface.
  • the fine particles may be cerium oxide fine particles.
  • the cerium oxide contained in the coating may be contained as fine particles partially exposed on the surface of the film as fine particles.
  • the surface of the coating may be substantially flat. As described above, whether or not the surface is substantially flat is determined based on the flatness of the surface excluding the fine particles, that is, excluding the unevenness imparted by the fine particles.
  • the particle size of the cerium oxide fine particles may be in the range of 100 nm to 1.5 ⁇ m and further may be in the range of 250 nm to 1 ⁇ m. The particle size of the fine particles can be measured by SEM observation.
  • the fine particles having the above particle size may be present at a density in the range of 1 to 100 and further 2 to 20 on a 5 ⁇ m square of the film surface.
  • the presence of fine particles can contribute to the improvement of water repellency through the development of fine irregularities.
  • the crystallite size of the cerium oxide fine particles contained in the easy clean coating is not particularly limited, but may be in the range of, for example, 1 to 100 nm, and further may be in the range of 2 to 20 nm.
  • the easy clean coating may be formed on only one main surface of the glass plate or on both main surfaces of the glass plate.
  • the water repellency that the glass article of this embodiment can provide is as described above.
  • the glass article of the present embodiment may have, for example, the following optical properties.
  • the visible light transmittance may be 65% or more, 70% or more, 80% or more, and further 85% or more.
  • the upper limit of the visible light transmittance is not particularly limited, but is, for example, 95%.
  • the visible light reflectance may be 20% or less, 15% or less, 10% or less, and further 8% or less.
  • the lower limit of the visible light reflectance is not particularly limited, but is, for example, 2%.
  • the visible light reflectance is the visible light reflectance for the surface on which the coating is formed, in other words, the reflectance of visible light that reaches the glass substrate through the coating from the outside of the glass article.
  • the haze rate is, for example, 20% or less, preferably 10% or less, further 5% or less, and particularly 4% or less. According to this embodiment, a haze rate of 1% or less and even 0.5% or less can be achieved.
  • the preferable ranges of the visible light transmittance, the visible light reflectance, and the haze rate are as follows. The range in parentheses is more preferable. Visible light transmittance: 80-95% (85-95%), Haze rate: 5% or less (4% or less), Visible light reflectance on the surface of the coated glass substrate: 2-20% (2-8%)
  • the coated glass article according to the present embodiment can be used for various purposes, but is particularly suitable for use as a glass article used in an environment to which water droplets adhere. Water droplets are usually supplied from natural water such as rain or fog, or tap water.
  • the coated glass articles according to the present embodiment include glass for buildings, glass for transport machines, glass for stores, glass for furniture, glass for home appliances, glass for signage, glass for mobile devices and glass for solar cells. It may be an article corresponding to at least one selected from the group consisting of.
  • the coated glass article according to the present embodiment is an article corresponding to at least one selected from the group consisting of window glass, roof glass, bathroom glass, mirror, store glass, mobile device glass and solar cell glass. You may.
  • the window glass is, for example, a window glass of a building or a transport aircraft, and so is a roof glass. Buildings are not limited to houses and buildings, but include greenhouses, arcades, and other structures fixed to land. Transport aircraft include vehicles, ships and aircraft. Vehicles are, for example, automobiles or railroad vehicles.
  • Bathroom glass is, for example, a bathroom glass partition and a glass door.
  • the mirror is, for example, a mirror in a bathroom and a bathroom.
  • Store glass is, for example, a show window, a counter, a table, a glass door of a refrigerating or freezing case, a showcase of food, or the like.
  • the glass for a mobile device is, for example, a glass that covers a display portion of a mobile device such as a smartphone or a tablet PC, and in some cases, a glass that constitutes a housing of the mobile device.
  • the glass for a solar cell is, for example, a cover glass arranged on the light incident side of the solar cell.
  • tempered glass is often used in each of the above-mentioned applications.
  • the glass article of the present embodiment may be manufactured by a method other than the following manufacturing methods.
  • the manufacturing method of the present embodiment comprises a step of applying a coating liquid containing cerium oxide as a solid content on a glass substrate to form a coating film on the glass substrate, and a step of drying the coating film. It is equipped and the cerium oxide contains CeO 2 .
  • the "cerium oxide" as a solid content does not have to exist as a complete oxide as long as it is a component that can supply cerium oxide to the coating, and cerium that can supply cerium oxide after dehydration condensation. Also includes acid hydroxides and cerium hydroxides.
  • This manufacturing method may further include a step of preparing a coating liquid.
  • the coating liquid may contain a polar solvent, particularly a lower alcohol having 5 or less carbon atoms as a solvent.
  • the lower alcohol may be methanol and / or ethanol.
  • the step of preparing the coating liquid may include hydrolyzing the cerium compound containing trivalent cerium.
  • the hydrolyzable cerium compound is preferably a compound that dissolves in a polar solvent, and specifically, it may be selected from water-soluble cerium compounds.
  • the cerium compound may be, for example, at least one selected from the group consisting of cerium halide and cerium nitrate.
  • the cerium halide is, for example, cerium chloride (III) or cerium bromide (III).
  • preferred cerium compounds, including cerium nitrate (III) are trivalent cerium compounds.
  • the present invention is not limited to this, and the cerium compound may contain tetravalent cerium.
  • an acid or alkali is added to the coating liquid in order to promote the hydrolysis of the metal compound.
  • an acid or an alkali may be added.
  • more preferred additives are organic compounds that function as acid scavengers, specifically epoxy group-containing organic compounds, especially water-soluble epoxides.
  • the water-soluble epoxide is an epoxy group-containing compound having a solubility in water at 20 ° C. of 1 g / 100 mL or more.
  • the water-soluble epoxide may be a monofunctional epoxide or a polyfunctional epoxide.
  • the monofunctional water-soluble epoxide is, for example, an epoxy group-containing alkane such as propylene oxide (1,2-epoxypropane) or 1,2-epoxybutane, as well as a lauryl alcohol EO adduct glycidyl ether and a phenol EO adduct glycidyl ether. And so on.
  • the polyfunctional water-soluble epoxide is, for example, a glycerol polyglycidyl ether, a polyglycerol diglycidyl ether, or a sorbitol polyglycidyl ether.
  • the cerium compound is preferably hydrolyzed in the presence of a water-soluble epoxide.
  • the acid produced by the hydrolysis of the cerium compound is consumed and the hydrolysis reaction is promoted.
  • tetravalent cerium is likely to be generated from tetravalent cerium. This phenomenon is considered to be due to the improvement in the stability of tetravalent cerium in the high pH region.
  • the prepared coating liquid is applied on the glass substrate.
  • the coating liquid can be applied by a known method such as spin coating, bar coating, spray coating, nozzle flow coating, roll coating and the like.
  • the production method of the present embodiment may further include a step of applying at least one treatment selected from washing and drying to the coating film.
  • the wet coating as it is applied contains organic compounds contained in the coating liquid, such as water-soluble epoxides and ring-opening reaction products thereof, together with cerium oxide. At least some of the organic compounds in the wet coating are removed from the coating by a treatment that is washing and / or drying, especially washing.
  • a treatment that is washing and / or drying, especially washing.
  • an organic solvent particularly a polar organic solvent having 5 or less carbon atoms is suitable.
  • An example of a preferred wash is performed with lower alcohols and ketones in sequence.
  • the lower alcohol is an alcohol having 5 or less carbon atoms, as described above.
  • ketones are ketones having 7 or less carbon atoms, 5 or less, and further 3 or less. Due to the removal of the organic compound, pores may be formed in the coating after drying, and fine irregularities may be formed on the surface thereof. The porosity and the size of the fine irregularities can be controlled by the amount of the organic compound added and the like.
  • the manufacturing method exemplified above is particularly suitable for forming an easy clean coating having a desired porosity and fine irregularities.
  • the production method of the present embodiment may further include a step of holding at least one selected from the coating liquid and the coating film in a wet state for a predetermined time.
  • This step can be carried out, for example, by holding at least one selected from the prepared coating liquid and the wet coating film at a temperature of 5 to 80 ° C. and 0.5 to 48 hours.
  • the coating liquid or the coating film undergoes so-called "aging", and the ratio of tetravalent cerium increases.
  • a coating liquid is preferable as the target for aging.
  • the coating liquid For example, as the conversion of the coating liquid to tetravalent cerium progresses, color development due to tetravalent cerium is observed. A coating liquid containing only trivalent cerium is colorless unless it contains other materials that cause coloring. As the tetravalent cerium is produced, the coating liquid can typically be colored first brownish and then further yellowish. In order to produce a sufficient amount of tetravalent cerium during retention, it is desirable to keep the pH of the coating solution not too low. For pH control, for example, the amount of water-soluble epoxide that acts as an acid scavenger may be adjusted appropriately.
  • the process of tetravalent cerium formation can be monitored by the absorption spectrum from the ultraviolet region to the visible region. For example, the absorption edge of the ultraviolet region of the coating liquid moves to the long wavelength region as tetravalent cerium is produced. Continued aging until the absorption edge is present, for example, in the region of 350 nm or higher, particularly 360 nm or higher, produces a sufficient amount of tetravalent cerium to form an easy clean coating.
  • the preferable amount of the water-soluble epoxide added differs depending on the type and the like.
  • the mixing ratio of cerium (III) contained in the cerium compound and propylene oxide is expressed as a molar ratio of 1:10 to 1:90, 1:15 to 1:80, Further, it may be in the range of 1:20 to 1:70, particularly 1:25 to 1:50.
  • an epoxy group-containing organic compound such as a water-soluble epoxide may be further supplied.
  • the epoxy group-containing organic compound may be supplied to the membrane for cleaning the membrane.
  • the supply of the epoxy group-containing organic compound after hydrolysis can contribute to the early stabilization of the contact angle of water after film formation. It can also contribute to improving the contact angle of water after heat treatment.
  • the manufacturing method of the present embodiment may further include a step of forming an easy clean coating on the glass substrate and then performing a treatment accompanied by heating on the glass substrate.
  • the treatment involving heating is at least one selected from the group consisting of the above-mentioned examples, and is particularly a heat bending treatment and / or an air cooling strengthening treatment.
  • the glass substrate of the present embodiment can be used without undergoing such treatment.
  • the manufacturing method in the present embodiment includes a step of applying a coating liquid containing chelated cerium ions on a glass substrate to form a coating film on the glass substrate, and a step of drying the coating film. It can also be implemented as a method of providing.
  • general chelating agents such as EDTA and acetylacetone can be used without particular limitation.
  • the cerium ion in the coating liquid may be trivalent cerium. At least a part of the chelated trivalent cerium ion is easily oxidized to tetravalent in the drying step after the coating liquid is applied and further in the heat treatment step.
  • the production method utilizing chelation does not require the action of an acid scavenger such as a water-soluble epoxide, but can be carried out in the same manner as the above-mentioned method except for this point.
  • the glass article with an easy clean coating of the present embodiment is not limited to that produced by the liquid phase film forming method exemplified above.
  • the glass article with an easy clean coating of the present embodiment can also be manufactured by using, for example, a vacuum film forming method typified by a sputtering method.
  • Visible light transmittance and visible light reflectance are obtained from the visible ultraviolet absorption spectrum measured with a spectrophotometer (Hitachi, 330 type), and the haze rate is obtained using a haze meter (Suga Tester, HZ-V3 type). It was measured.
  • the contact angle of water was measured by dropping 4 mg of purified water onto the coating surface using a contact angle measuring device (DMs-401 type manufactured by Kyowa Surface Science Co., Ltd.). However, the contact angle of water was determined after the coating was formed and left in the air at room temperature for 20 days. The contact angle of water after the heat treatment was measured when the coated glass plate was left in the air at room temperature for 40 days after the heat treatment.
  • DMs-401 type manufactured by Kyowa Surface Science Co., Ltd.
  • the coated glass plate was heated in an electric furnace set at 760 ° C. for 4 minutes, taken out of the furnace, wrapped in ceramic wool, and cooled to room temperature at a cooling rate that did not cause thermal cracking. Even after the heat treatment, the contact angle of water and the like were measured.
  • Example 1 0.168 g of cerium (III) chloride heptahydrate (99.9%, manufactured by Sigma-Aldrich) was dissolved in 2 mL of anhydrous methanol (manufactured by Sigma-Aldrich) to obtain a colorless and transparent cerium (III) chloride solution. .. This solution contains 9.6% by mass of cerium (III) chloride. Next, 1.75 g of a cerium (III) chloride solution and 0.859 g of propylene oxide (manufactured by TIC, ⁇ 99.0%) were mixed to obtain a stock solution. In this stock solution, the molar ratio of Ce to propylene oxide is 1: 33.0.
  • the concentration of CeCl 3 is 0.075 mmol / L.
  • the coating was then aged at room temperature with continued stirring overnight. During aging, the coating liquid became colorless and transparent, cloudy, brown, and then pale yellow. From the evaluation of the visible ultraviolet absorption spectrum of the coating liquid during aging, it was confirmed that at least a part of the trivalent cerium ion was oxidized to tetravalent.
  • Highly transparent glass manufactured by Nippon Sheet Glass Co., Ltd., Opti White (registered trademark) 3 mm thick
  • the aged coating liquid was applied to the glass substrate.
  • the coating was performed using a spin coater (manufactured by Mikasa Co., Ltd., 1H-360S type) at a substrate rotation speed of 1000 rpm and a rotation holding time of 10 seconds after coating.
  • the wet film obtained by applying the coating liquid was washed with isopropyl alcohol and then with acetone. The wet film after washing was held in an electric dryer set at 60 ° C. to obtain a coated glass plate.
  • Example 2 A coated glass plate was obtained in the same manner as in Example 1 except that the cleaning with a 38% ethanol solution of cyclohexene oxide (manufactured by Fujifilm, 95%) was carried out instead of the washing with acetone.
  • Example 3 A coated glass plate was obtained in the same manner as in Example 1 except that the molar ratio of Ce and propylene oxide in the stock solution of Example 1 was 1: 65.7.
  • Example 4 A CeO 2 film was formed on the surface of the glass substrate used in Example 1 by magnetron sputtering using a CeO 2 target to obtain a coated glass plate.
  • Example 5 To 268.8 g of a mixed solvent mainly composed of ethanol (Futaba Chemical Co., Ltd., Fine Eta A-10), 4.04 g of cerium nitrate (III) hexahydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added, and then acetylacetone (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added. 67.2 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 g of propylene glycol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added and stirred in a constant temperature bath at 40 ° C. for 24 hours to obtain a coating liquid.
  • a mixed solvent mainly composed of ethanol Flutaba Chemical Co., Ltd., Fine Eta A-10
  • cerium nitrate (III) hexahydrate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • acetylacetone manufactured by Fuji Film Wa
  • Cleaned high-transparency glass manufactured by Nippon Sheet Glass Co., Ltd., Opti White (registered trademark) 3 mm thick
  • 20 cm x 30 cm was prepared and used as a glass substrate.
  • the coating liquid was applied to the glass substrate by the spray coating method. After air-drying, the mixture was dried in an oven set at 250 ° C. for 10 minutes and then fired in a muffle furnace set at 760 ° C. for 4 minutes to obtain a coated glass plate.
  • Example 5 unlike Examples 1 to 3, the coating liquid was not aged. However, in Example 5, since cerium was chelated with acetylacetone, cerium was oxidized during 10 minutes of drying and 4 minutes of calcination to produce tetravalent cerium. The formation of tetravalent cerium can be confirmed, for example, by analyzing the coating film by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • Example 6 A coated glass plate was obtained in the same manner as in Example 5, except that the spin coating method was carried out so as to have a thinner coating than in Example 5.
  • Example 7 A coated glass plate was obtained in the same manner as in Example 5, except that the spin coating method was carried out so as to have a thinner coating than in Example 6.
  • Example 8 The same as in Example 5 except that a glass plate having a SiO 2 layer formed therein (OptiShower manufactured by Pilkington Co., Ltd .; SiO 2 layer thickness 15 nm) was used as the glass substrate and a coating was formed on the SiO 2 layer. And obtained a coated glass plate.
  • a glass plate having a SiO 2 layer formed therein OptiShower manufactured by Pilkington Co., Ltd .; SiO 2 layer thickness 15 nm
  • Example 9 A coated glass plate was obtained in the same manner as in Example 5 except that a glass plate on which a Low-E film was formed was used as a glass substrate and a coating was formed on the Low-E film.
  • the Low-E film was a multilayer film in which two SnO layers having a thickness of 25 nm, two layers of SiO having a thickness of 25 nm, and two layers of SnO having a thickness of 340 nm doped with fluorine were laminated in this order from the glass plate side.
  • This Low-E film is formed by a known method using a CVD method.
  • Example 1 A coated glass plate was obtained in the same manner as in Example 1 except that the molar ratio of Ce and propylene oxide in the stock solution of Example 1 was 1: 6.7.
  • Example 2 A coated glass plate was prepared in the same manner as in Example 1 except that the molar ratio of Ce and propylene oxide in the stock solution of Example 1 was 1: 0, that is, except that propylene oxide was not added. Obtained.
  • Comparative Example 3 is a glass plate itself without a coating.
  • the contact angle of water in this comparative example was measured after the glass plate was washed and left in the air at room temperature for 20 days, and after the heat treatment described above, it was left in the air at room temperature for 40 days.
  • Example 4 A pink interference color was observed from Example 4, but no interference color due to the coating was observed from the other examples.
  • Example 1 the contact angle of water immediately after film formation was less than 70 °, but gradually increased.
  • Example 2 the contact angle of 70 ° or more was measured immediately after the film formation. Further, in each example, when the contact angle of water was measured 100 days after the film formation and the heat treatment, the measured value was 70 ° or more and stable in each case. Storage up to the 100th day was also carried out in the air at room temperature.
  • Example 2 As in Example 1, the absorption edge of the absorption spectrum of the coating liquid moved to the long wavelength side during aging. On the other hand, in Comparative Examples 1 and 2, no change of the absorption edge to the long wavelength side was observed during aging.
  • Example 1 For Examples 1, 2, 4 and 5, the surface of the coating was observed using SEM after the heat treatment. The results are shown in FIG. 3 (Example 1), FIG. 4 (Example 2), FIG. 5 (Example 4) and FIG. 6 (Example 5).
  • the surfaces of the coatings of Examples 1 and 2 were substantially flat, but fine irregularities were imparted by the cerium oxide fine particles present on the surface. It can be confirmed that more cerium oxide fine particles are present on the film surface of Example 2 (FIG. 4) than in Example 1 (FIG. 3).
  • Example 8 and 9 using a glass plate having a SiO 2 layer or the like formed as a base layer, the contact angle of water was lowered as compared with Example 5 in which a coating was directly formed on the surface of the glass plate. It is considered that this is because the diffusion movement of the glass component from the glass plate to the coating was suppressed.
  • Example 2 When the crystallite size of cerium oxide after heat treatment was measured by using an X-ray diffraction method, it was 4.85 nm for Example 1 and 2.10 nm for Example 2. In Example 2, it is considered that the growth of the crystallite was inhibited by the added epoxy group-containing organic compound (cyclohexene oxide).
  • Example 10 A stain adhesion test / tap water was carried out on the coated glass plate prepared in Example 1 (before heat treatment). The results are shown in FIG.
  • Example 11 A stain adhesion test / tap water was carried out on the coated glass plate prepared in Example 4 (before heat treatment). The results are shown in FIG.
  • Comparative Example 4 A stain adhesion test / tap water was carried out on the glass plate of Comparative Example 3 (before heat treatment), that is, the glass plate on which no coating was formed. The results are shown in FIG.
  • Example 5 A coating was formed on the surface of the glass substrate used in Example 1 using an antifouling coating agent. Specifically, a coating agent prepared by diluting "Optur DSX-E” manufactured by Daikin Industries, Ltd. to 0.1% by mass with a solvent ("Novec7200" manufactured by 3M Co., Ltd.) was prepared, and this was sprayed on the surface of a glass substrate. It was dried to obtain a coated glass plate.
  • "Optur DSX-E” contains a fluoroalkyl group-containing compound as a water-repellent component at a concentration of 20% by mass. The contact angle of water on the surface of the obtained coating was 93 °. A stain adhesion test / tap water was carried out on this coated glass plate. The results are shown in FIG.
  • Example 12 A stain adhesion test / hand soap was carried out on the coated glass plate prepared in Example 4 (before heat treatment). The observation results before washing with tap water are shown in FIG. 11A, and the observation results after washing are shown in FIG. 11B.
  • Comparative Example 6 A stain adhesion test / hand soap was carried out on the glass plate of Comparative Example 3 (before heat treatment), that is, the glass plate on which the coating was not formed.
  • the observation results before washing with tap water are shown in FIG. 12A, and the observation results after washing are shown in FIG. 12B.
  • Comparative Example 7 A stain adhesion test / hand soap was carried out on the coated glass plate produced in Comparative Example 5. The observation results before washing with tap water are shown in FIG. 13A, and the observation results after washing are shown in FIG. 13B.

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See also references of EP4201904A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023135421A1 (en) * 2022-01-13 2023-07-20 Pilkington Group Limited Corrosion-resistant and/or cleanable coated glass substrate
EP4464675A4 (en) * 2022-01-13 2025-12-24 Nippon Sheet Glass Co Ltd GLASS ITEM

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CN116075489A (zh) 2023-05-05
CN116075489B (zh) 2025-04-01
CN119977356A (zh) 2025-05-13
JP7600246B2 (ja) 2024-12-16
BR112023002135A2 (pt) 2023-03-07
US20230322616A1 (en) 2023-10-12
EP4201904A4 (en) 2024-12-18
JP2025032203A (ja) 2025-03-11
EP4201904A1 (en) 2023-06-28
JPWO2022039268A1 (https=) 2022-02-24
CL2023000466A1 (es) 2023-08-04

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