WO2022054961A1 - Élément de revêtement - Google Patents

Élément de revêtement Download PDF

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Publication number
WO2022054961A1
WO2022054961A1 PCT/JP2021/033815 JP2021033815W WO2022054961A1 WO 2022054961 A1 WO2022054961 A1 WO 2022054961A1 JP 2021033815 W JP2021033815 W JP 2021033815W WO 2022054961 A1 WO2022054961 A1 WO 2022054961A1
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WO
WIPO (PCT)
Prior art keywords
cover member
antibacterial
glass plate
member according
fine particles
Prior art date
Application number
PCT/JP2021/033815
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English (en)
Japanese (ja)
Inventor
瑞穂 小用
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日本板硝子株式会社
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Filing date
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Application filed by 日本板硝子株式会社 filed Critical 日本板硝子株式会社
Publication of WO2022054961A1 publication Critical patent/WO2022054961A1/fr

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23Oxides
    • C03C17/25Oxides by deposition from the liquid phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present invention relates to a cover member provided on a protected member such as a display.
  • Patent Document 1 discloses a glass substrate provided with a functional layer having fingerprint resistance. This glass substrate is used as a cover member for touching a finger such as a touch sensor. Further, it is disclosed that the functional layer of the glass substrate has functions such as anti-glare function and antibacterial function in addition to fingerprint resistance.
  • Patent Document 1 discloses that when a functional layer having a plurality of functions as described above is provided, the plurality of functions are exerted by one functional layer.
  • an antiglare function and an antibacterial function are provided. It is conceivable to provide a functional layer to have.
  • a specific functional layer having an antiglare function and an antibacterial function has not yet been proposed, and a cover member having such a functional layer has been desired.
  • the present invention has been made to solve this problem, and an object of the present invention is to provide a cover member having antiglare performance and antibacterial performance.
  • a plate-shaped base material having a first surface and a second surface, the first surface having a predetermined surface roughness,
  • the antibacterial film formed on the first surface and Equipped with The antibacterial membrane is The holding layer formed on the first surface and
  • a cover member comprising: antibacterial fine particles held by the holding layer and having an average particle size equal to or larger than the film thickness of the holding layer.
  • Item 2. The cover member according to Item 1, wherein the surface roughness of the holding layer is smaller than the surface roughness of the first surface of the base material and smaller than 120 nm.
  • Item 3. The cover member according to Item 1 or 2, wherein the maximum film thickness of the holding layer is smaller than the surface roughness of the base material.
  • Item 4 The cover member according to any one of Items 1 to 3, wherein the holding layer of the antibacterial film contains silicon oxide as a main component.
  • the base material is formed of a glass plate having the first surface and the second surface.
  • Item 4. The cover member according to any one of Items 1 to 4.
  • Item 6 The cover member according to Item 5, wherein the glass plate is formed of float glass, and the bottom surface of the float glass constitutes the first surface.
  • Item 7 The cover member according to any one of Items 1 to 4, wherein the base material comprises a glass plate and a base layer formed on one surface of the glass plate and having the predetermined surface roughness.
  • Item 8. The cover member according to Item 7, wherein the base layer includes a base layer containing silicon oxide as a main component and fine particles held in the base layer.
  • Item 9. The cover member according to Item 7 or 8, wherein the glass plate is formed of float glass, and the base layer is formed on the top surface of the float glass.
  • Item 10 The cover member according to any one of Items 5 to 9, wherein the thickness of the glass plate is 3 mm or less.
  • Item 11 Item 2. The cover member according to Item 10, wherein the average particle size of the fine particles is smaller than the average particle size of the antibacterial fine particles.
  • Item 12. The cover member according to any one of Items 1 to 11, wherein the distance between the antibacterial fine particles on the holding layer is 1 to 200 ⁇ m.
  • Item 13 The cover member according to any one of Items 1 to 12, wherein the average particle size of the antibacterial fine particles is 0.1 to 10 ⁇ m.
  • Item 14 The cover member according to any one of Items 1 to 13, wherein a fingerprint-resistant layer formed on at least a part of the antibacterial film is formed.
  • Item 15. Item 12. The cover member according to Item 14, wherein the fingerprint-resistant layer has a thinner film thickness than the antibacterial film.
  • Item 16 The cover member according to Item 14 or 15, wherein the fingerprint-resistant layer is formed on a part of the antibacterial film.
  • Item 17. The cover member according to any one of Items 1 to 16, wherein the antibacterial fine particles are made of copper.
  • Item 18 The cover member according to any one of Items 1 to 17, further comprising an antireflection film arranged between the base material and the antibacterial film.
  • Item 19 The cover member according to any one of Items 1 to 18, which is arranged so as to cover the surface of a display, a keyboard, or an electronic blackboard.
  • FIG. 1 It is sectional drawing which shows one Embodiment of the cover member which concerns on this invention. It is an enlarged sectional view of FIG. It is a photograph which shows the surface property of the antibacterial film which concerns on Example. It is an enlarged photograph of the antibacterial fine particles of the antibacterial film which concerns on Example.
  • the cover member according to the present embodiment is configured to protect protected members such as a display, a keyboard, and an electronic blackboard, and to make these members visible from the outside.
  • the display includes not only a general desktop display but also a display used for various devices such as mobile PCs, tablet PCs, and in-vehicle devices such as car navigation systems.
  • FIG. 1 is a cross-sectional view of a cover member.
  • the cover member 10 includes a glass plate 1 having a first surface and a second surface, and an antibacterial film 2 laminated on the first surface of the glass plate 1. ing. Then, the cover member 10 is arranged so as to cover the above-mentioned protected member 100. At this time, the second surface of the glass plate 1 is arranged so as to face the protected member 100, and the antibacterial film 2 is arranged so as to face the outside.
  • the cover member 10 includes a glass plate 1 having a first surface and a second surface, and an antibacterial film 2 laminated on the first surface of the glass plate 1.
  • the glass plate 1 can be formed of, for example, other glass such as general-purpose soda lime glass, borosilicate glass, aluminosilicate glass, and non-alkali glass. Further, the glass plate 1 can be molded by the float method. According to this manufacturing method, a glass plate 1 having a smooth surface can be obtained. However, the glass plate 10 may have irregularities on the main surface, and may be, for example, template glass. The template glass can be molded by a manufacturing method called a rollout method. The template glass produced by this method usually has periodic irregularities in one direction along the main surface of the glass plate.
  • molten glass is continuously supplied on a molten metal such as molten tin, and the supplied molten glass is made to flow on the molten metal to form a strip.
  • the glass thus formed is called a glass ribbon.
  • the glass ribbon is cooled toward the downstream side, cooled and solidified, and then pulled up from the molten metal by a roller. Then, it is transported to a slow cooling furnace by a roller, slowly cooled, and then cut. In this way, a float glass plate is obtained.
  • the surface in contact with the molten metal is referred to as a bottom surface
  • the surface opposite to the bottom surface is referred to as a top surface.
  • the bottom surface and the top surface may be unpolished. Since the bottom surface is in contact with the molten metal, when the molten metal is tin, the concentration of tin oxide contained in the bottom surface is higher than the concentration of tin oxide contained in the top surface.
  • the first surface of the glass plate 1 is the bottom surface
  • the second surface is the top surface.
  • the bottom surface that is, the second surface
  • the rollers cause scratches called so-called microcracks. Therefore, in general, the bottom surface of the float glass plate has more scratches than the top surface.
  • the bottom surface of the glass plate 1 is etched to remove a layer having a high concentration of tin oxide. Since tin oxide has a large refractive index, it is possible to improve the transmittance by removing it. Further, by etching, a fine unevenness having a predetermined surface roughness is formed on the bottom surface.
  • the surface roughness Ra of the bottom surface is, for example, preferably 10 to 500 nm, more preferably 40 to 200 nm, and particularly preferably 50 to 150 nm. Ra is the arithmetic mean roughness of the roughness curve defined by JIS B0601: 2001. This point is the same in the holding layer 21 of the antibacterial film 2 described later.
  • the frost treatment is a treatment for forming irregularities on the surface of the glass plate by, for example, immersing the glass plate in a mixed solution of hydrogen fluoride and ammonium fluoride and chemically surface-treating the immersed surface.
  • the sandblasting treatment is a treatment for forming irregularities on the surface of the glass plate by, for example, blowing crystalline silicon dioxide powder, silicon carbide powder, or the like onto the surface of the glass plate with pressurized air. Further, after the unevenness is created in this way, it is generally performed to chemically etch the surface of the glass plate in order to adjust the surface shape. By doing so, cracks generated by sandblasting or the like can be removed.
  • etching a method of immersing a glass plate as an object to be treated in a solution containing hydrogen fluoride as a main component is preferably used.
  • Wet blasting is a high-speed process in which abrasive grains composed of solid particles such as alumina and a liquid such as water are uniformly agitated into a slurry from an injection nozzle to the surface of a glass plate using compressed air. It is a process of forming unevenness on the surface of the glass plate by injecting with.
  • the thickness of the glass plate 1 is not particularly limited, but it is better to be thin for weight reduction.
  • it is preferably 0.3 to 3 mm, and more preferably 0.6 to 2.5 mm. This is because if the glass plate 10 is too thin, the strength is lowered, and if it is too thick, the protected member 100 visually recognized via the cover member 10 may be distorted.
  • the glass plate 1 is usually a flat plate, but may be a curved plate.
  • the surface shape of the protected member to be protected is a non-planar surface such as a curved surface
  • the glass plate 1 may be bent so as to have a constant curvature as a whole, or may be locally bent.
  • the main surface of the glass plate 1 may be configured by, for example, a plurality of planes connected to each other by a curved surface.
  • the radius of curvature of the glass plate 1 can be, for example, 5000 mm or less.
  • the lower limit of the radius of curvature can be, for example, 10 mm or more, but may be even smaller, for example, 1 mm or more, especially in a locally bent portion.
  • a glass plate having the following composition can also be used.
  • the% indications indicating the components of the glass plate 1 mean mol% unless otherwise specified.
  • substantially composed means that the total content of the listed components is 99.5% by mass or more, preferably 99.9% by mass or more, and more preferably 99.95. It means that it occupies more than mass%.
  • substantially free means that the content of the component is 0.1% by mass or less, preferably 0.05% by mass or less.
  • the present invention is based on the composition of float glass (hereinafter, may be referred to as "SL in a narrow sense” or simply “SL”) widely used as a glass composition suitable for producing a glass plate by the float method.
  • Composition range considered by those skilled in the art as soda lime silicate glass suitable for the float method hereinafter, may be referred to as "SL in a broad sense”
  • SL in a broad sense Composition range considered by those skilled in the art as soda lime silicate glass suitable for the float method
  • SiO 2 is a main component constituting the glass plate 1, and if the content thereof is too low, the chemical durability and heat resistance such as water resistance of the glass are lowered. On the other hand, if the content of SiO 2 is too high, the viscosity of the glass plate 1 at a high temperature becomes high, which makes melting and molding difficult. Therefore, the content of SiO 2 is appropriately in the range of 66 to 72 mol%, preferably 67 to 70 mol%.
  • Al 2 O 3 improves the chemical durability of the glass plate 1 such as water resistance, and further facilitates the movement of alkali metal ions in the glass to increase the surface compressive stress after chemical strengthening, and the stress layer. It is an ingredient for deepening the depth.
  • the content of Al 2 O 3 is too high, the viscosity of the glass melt is increased, T 2 and T 4 are increased, and the clarity of the glass melt is deteriorated to produce a high-quality glass plate. Becomes difficult.
  • the content of Al 2 O 3 is in the range of 1 to 12 mol%.
  • the content of Al 2 O 3 is preferably 10 mol% or less, preferably 2 mol% or more.
  • MgO MgO is an essential component that improves the solubility of glass. From the viewpoint of obtaining this effect, it is preferable that MgO is added to the glass plate 1. Further, when the content of MgO is less than 8 mol%, the surface compressive stress after chemical strengthening tends to decrease, and the depth of the stress layer tends to become shallow. On the other hand, if the content is increased beyond an appropriate amount, the strengthening performance obtained by chemical strengthening deteriorates, and in particular, the depth of the surface compressive stress layer sharply becomes shallow. This adverse effect has the least MgO among alkaline earth metal oxides, but the content of MgO in this glass plate 1 is 15 mol% or less. Further, when the content of MgO is high, T 2 and T 4 are increased, and the clarity of the glass melt is deteriorated, which makes it difficult to manufacture a high-quality glass plate.
  • the content of MgO is in the range of 1 to 15 mol%, preferably 8 mol% or more and 12 mol% or less.
  • CaO CaO has the effect of reducing the viscosity at high temperatures, but if the content is too high beyond an appropriate range, the glass plate 1 tends to be devitrified and the movement of sodium ions in the glass plate 1 is inhibited. I will.
  • the surface compressive stress after chemical strengthening tends to decrease.
  • the surface compressive stress after chemical strengthening is remarkably reduced, the depth of the compressive stress layer is remarkably shallow, and the glass plate 1 is easily devitrified.
  • the CaO content is in the range of 1 to 8 mol%.
  • the CaO content is preferably 7 mol% or less, preferably 3 mol% or more.
  • SrO, BaO greatly reduce the viscosity of the glass plate 1, and when contained in a small amount, the effect of lowering the liquidus temperature TL is more remarkable than that of CaO.
  • SrO and BaO remarkably hinder the movement of sodium ions in the glass plate 1 even when added in a very small amount, greatly reduce the surface compressive stress, and the depth of the compressive stress layer becomes considerably shallow.
  • the glass plate 1 does not substantially contain SrO and BaO.
  • (Na 2 O) Na 2 O is a component for increasing the surface compressive stress and deepening the depth of the surface compressive stress layer by substituting sodium ions with potassium ions.
  • the stress relaxation during the chemical strengthening treatment exceeds the generation of surface compressive stress due to ion exchange in the chemical strengthening treatment, and as a result, the surface compressive stress tends to decrease. be.
  • Na 2 O is a component for improving the solubility and lowering T 4 and T 2 , while if the content of Na 2 O is too high, the water resistance of the glass is significantly lowered.
  • the glass plate 1 if the Na 2 O content is 10 mol% or more, the effect of reducing T 4 and T 2 is sufficiently obtained, and if it exceeds 16 mol%, the surface compressive stress is significantly reduced due to stress relaxation. Become.
  • the Na 2 O content in the glass plate 1 of the present embodiment is appropriately in the range of 10 to 16 mol%.
  • the Na 2 O content is preferably 12 mol% or more, more preferably 15 mol% or less.
  • K 2 O is a component that improves the solubility of glass. Further, in the range where the K 2 O content is low, the ion exchange rate in chemical strengthening increases and the depth of the surface compressive stress layer becomes deep, while the liquidus temperature TL of the glass plate 1 decreases. Therefore, it is preferable to contain K 2 O at a low content.
  • K 2 O has a smaller effect of lowering T 4 and T 2 than Na 2 O, but a large amount of K 2 O inhibits the clarification of the glass melt. Further, the higher the K 2 O content, the lower the surface compressive stress after chemical strengthening. Therefore, it is appropriate that the content of K 2 O is in the range of 0 to 1 mol%.
  • the glass plate 1 of the present embodiment may contain 1 mol% or less of Li 2 O, but it is preferable that the glass plate 1 does not contain Li 2 O substantially.
  • B 2 O 3 is a component that lowers the viscosity of the glass plate 1 and improves the solubility.
  • the content of B 2 O 3 is too high, the glass plate 1 tends to be phase-separated, and the water resistance of the glass plate 1 is lowered.
  • the compound formed by B 2 O 3 and the alkali metal oxide may volatilize and damage the refractory in the glass melting chamber.
  • the inclusion of B 2 O 3 shallows the depth of the compressive stress layer during chemical strengthening. Therefore, it is appropriate that the content of B 2 O 3 is 0.5 mol% or less. In the present invention, it is more preferable that the glass plate 1 contains substantially no B 2 O 3 .
  • Fe 2 O 3 Normally, Fe exists in glass in the state of Fe 2+ or Fe 3+ and acts as a colorant. Fe 3+ is a component that enhances the ultraviolet absorption performance of glass, and Fe 2+ is a component that enhances the heat ray absorption performance.
  • the glass plate 1 is used as a cover glass for a display, it is required that the coloring is inconspicuous, so that the Fe content is preferably low.
  • Fe is often unavoidably mixed with industrial raw materials. Therefore, the iron oxide content converted to Fe 2 O 3 is often 0.15% by mass or less, and more preferably 0.1% by mass or less, with the entire glass plate 1 as 100% by mass. It is preferable, more preferably 0.02% by mass or less.
  • TiO 2 is a component that lowers the viscosity of the glass plate 1 and at the same time increases the surface compressive stress due to chemical strengthening, but may give the glass plate 1 a yellow color. Therefore, it is appropriate that the content of TiO 2 is 0 to 0.2% by mass. In addition, it is inevitably mixed with an industrial raw material that is usually used, and may be contained in the glass plate 1 in an amount of about 0.05% by mass. Since the glass is not colored if the content is at this level, it may be contained in the glass plate 1 of the present embodiment.
  • ZrO 2 ZrO 2 may be mixed into the glass plate 1 from the refractory bricks constituting the glass melting kiln, especially when the glass plate is manufactured by the float method, and the content thereof may be about 0.01% by mass.
  • ZrO 2 is a component that improves the water resistance of glass and also enhances the surface compressive stress due to chemical strengthening.
  • a high content of ZrO 2 may cause an increase in the working temperature T 4 and a sharp increase in the liquid phase temperature TL , and in the production of a glass plate by the float method, crystals containing precipitated Zr are present. It tends to remain as a foreign substance in the manufactured glass. Therefore, it is appropriate that the content of ZrO 2 is 0 to 0.1% by mass.
  • SO 3 In the float method, sulfates such as Glauber's salt (Na 2 SO 4 ) are widely used as clarifying agents. The sulfate decomposes in the molten glass to generate a gas component, which promotes defoaming of the glass melt, but a part of the gas component dissolves and remains in the glass plate 1 as SO 3 .
  • SO 3 is preferably 0 to 0.3% by mass.
  • CeO 2 is used as a clarifying agent. CeO 2 contributes to defoaming because O 2 gas is generated in the molten glass by CeO 2 . On the other hand, if there is too much CeO 2 , the glass will be colored yellow. Therefore, the content of CeO 2 is preferably 0 to 0.5% by mass, more preferably 0 to 0.3% by mass, and even more preferably 0 to 0.1% by mass.
  • SnO 2 (SnO 2 ) It is known that in a glass plate formed by the float method, tin diffuses from the tin bath on the surface in contact with the tin bath during molding, and the tin exists as SnO 2 . In addition, SnO 2 mixed with the glass raw material contributes to defoaming. In the glass plate 1 of the present invention, SnO 2 is preferably 0 to 0.3% by mass.
  • the glass plate 1 according to the present embodiment is substantially composed of the components listed above.
  • the glass plate 1 according to the present embodiment may contain components other than the components listed above, preferably in a range in which the content of each component is less than 0.1% by mass.
  • Examples of the components permitted to be contained include As 2 O 5 , Sb 2 O 5 , Cl, and F added for the purpose of defoaming the molten glass in addition to the above-mentioned SO 3 and Sn O 2 .
  • As 2 O 5 , Sb 2 O 5 , Cl, and F it is preferable not to add As 2 O 5 , Sb 2 O 5 , Cl, and F because they have a large adverse effect on the environment.
  • another example in which the content is allowed is ZnO, P 2 O 5 , GeO 2 , Ga 2 O 3 , Y 2 O 3 , and La 2 O 3 .
  • Even components other than the above derived from industrially used raw materials are permitted as long as they do not exceed 0.1% by mass. Since these components are appropriately added or inevitably mixed as needed, the glass plate 1 of the present embodiment may be substantially free of these components. do not have.
  • the density of the glass plate 1 is reduced to 2.53 g ⁇ cm -3 or less, further to 2.51 g ⁇ cm -3 or less, and in some cases 2.50 g ⁇ cm -3 or less. be able to.
  • the density of soda lime glass mass-produced by the float method is about 2.50 g ⁇ cm -3 . Therefore, considering mass production by the float method, the density of the glass plate 1 is close to the above value, specifically, 2.45 to 2.55 g ⁇ cm -3 , especially 2.47 to 2.53 g ⁇ . cm -3 is preferable, and 2.47 to 2.50 g ⁇ cm -3 is more preferable.
  • the elastic modulus of the glass plate 1 can be increased to 70 GPa or more, and further to 72 GPa or more.
  • the glass plate 1 containing sodium is brought into contact with a molten salt containing a monovalent cation having an ionic radius larger than that of the sodium ion, preferably a potassium ion, and the sodium ion in the glass plate 1 is brought into contact with the above monovalent cation.
  • the chemical strengthening of the glass plate 1 according to the present invention can be carried out by performing the ion exchange treatment of replacement by. As a result, a compressive stress layer to which compressive stress is applied to the surface is formed.
  • molten salt examples include potassium nitrate.
  • a mixed molten salt of potassium nitrate and sodium nitrate can also be used, but since it is difficult to control the concentration of the mixed molten salt, a molten salt of potassium nitrate alone is preferable.
  • the surface compressive stress and the compressive stress layer depth in the tempered glass article can be controlled not only by the glass composition of the article but also by the temperature and treatment time of the molten salt in the ion exchange treatment.
  • a tempered glass article having a very high surface compressive stress and a very deep compressive stress layer By contacting the above glass plate 1 with the molten salt of potassium nitrate, it is possible to obtain a tempered glass article having a very high surface compressive stress and a very deep compressive stress layer. Specifically, a tempered glass article having a surface compressive stress of 700 MPa or more and a compressive stress layer depth of 20 ⁇ m or more can be obtained, and further, a compressive stress layer depth of 20 ⁇ m or more and a surface compressive stress of 750 MPa or more. You can also get certain tempered glass articles.
  • FIG. 2 is an enlarged cross-sectional view showing an outline of the antibacterial membrane.
  • the antibacterial film 2 includes a holding layer 21 laminated on the first surface of the glass plate 1 and antibacterial fine particles 22 held by the holding layer 21. These will be described below.
  • the holding layer 21 is laminated on the first surface of the glass plate 1, unevenness is also formed on the surface of the holding layer 21 along the unevenness of the first surface. Since the surface roughness Ra of the holding layer 21 is smaller than the surface roughness of the first surface of the glass plate 1, it is preferably 120 nm or less, more preferably 100 nm or less, for example. On the other hand, the surface roughness Ra of the holding layer 21 is preferably, for example, 20 nm or more, and more preferably 40 nm or more. As described above, when the surface roughness Ra of the holding layer 21 is 20 nm or more and smaller than 120 nm, the antiglare function is exhibited.
  • the Rsm on the surface of the holding layer is preferably more than 0 ⁇ m and 35 ⁇ m or less, more preferably 1 ⁇ m to 30 ⁇ m, and particularly preferably 2 ⁇ m to 20 ⁇ m.
  • Rsm is the average length of the roughness curve elements defined by JIS B0601: 2001. Rsm that is not too large is suitable for suppressing so-called sparkles.
  • the maximum thickness D of the holding layer 21 is, for example, preferably 10 to 500 nm, more preferably 20 to 200 nm, and particularly preferably 30 to 80 nm. If the maximum thickness D is too thick, the antibacterial fine particles 22 described later may be buried in the holding layer 21, and the antibacterial function may be suppressed. In addition, there is a risk that the holding layer 21 may be peeled off from the glass plate 1 or the film may be cracked. On the other hand, if the maximum thickness D is too thin, the antibacterial fine particles 22 cannot be retained, and the antibacterial fine particles may be detached from the holding layer 21, which is not preferable.
  • the maximum thickness D means the thickness from the deepest concave portion of the first surface of the glass plate 1 to the highest convex portion of the holding layer 21 as shown in FIG.
  • the holding layer 21 serves as a binder for holding antibacterial fine particles.
  • the holding layer 2 contains silicon oxide, which is an oxide of Si, and preferably contains silicon oxide as a main component.
  • the holding layer 21 containing silicon oxide as a main component is suitable for lowering the refractive index of the film and suppressing the reflectance of the film.
  • the holding layer 21 may contain a component other than silicon oxide, or may contain a component partially containing silicon oxide.
  • the component partially containing silicon oxide includes, for example, a portion composed of a silicon atom and an oxygen atom, and is a component in which an atom other than both atoms, a functional group or the like is bonded to the silicon atom or the oxygen atom in this portion. ..
  • the atom other than the silicon atom and the oxygen atom include a nitrogen atom, a carbon atom, a hydrogen atom, and a metal element described in the next paragraph.
  • the functional group for example, an organic group described as R in the next paragraph can be exemplified. Strictly speaking, such a component is not silicon oxide in that it is not composed only of silicon atoms and oxygen atoms.
  • the silicon oxide portion composed of silicon atoms and oxygen atoms as "silicon oxide", which is consistent with the practice in the art.
  • the silicon oxide portion is also treated as silicon oxide.
  • the atomic ratio of a silicon atom to an oxygen atom in silicon oxide does not have to be stoichiometric (1: 2).
  • the holding layer 21 may contain a metal oxide other than silicon oxide, specifically, a metal oxide component or a metal oxide portion containing other than silicon.
  • the metal oxide that can be contained in the holding layer 21 is not particularly limited, but is, for example, an oxide of at least one metal element selected from the group consisting of Al, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn. Is.
  • the holding layer 21 may contain an inorganic compound component other than an oxide, for example, a nitride, a carbide, a halide, or the like, or may contain an organic compound component.
  • Metal oxides such as silicon oxide can be formed from hydrolyzable organometallic compounds.
  • the hydrolyzable silicon compound include the compound represented by the formula (1).
  • R n SiY 4-n (1)
  • R is an organic group containing at least one selected from an alkyl group, a vinyl group, an epoxy group, a styryl group, a methacryloyl group and an acryloyl group.
  • Y is a hydrolyzable organic group or a halogen atom which is at least one selected from an alkoxy group, an acetoxy group, an alkenyloxy group and an amino group.
  • the halogen atom is preferably Cl.
  • n is an integer from 0 to 3, preferably 0 or 1.
  • an alkyl group for example, an alkyl group having 1 to 3 carbon atoms, particularly a methyl group is suitable.
  • an alkoxy group for example, an alkoxy group having 1 to 4 carbon atoms, particularly a methoxy group and an ethoxy group are suitable.
  • Two or more compounds represented by the above formula may be used in combination. Examples of such a combination include a combination of a tetraalkoxysilane in which n is 0 and a monoalkyltrialkoxysilane in which n is 1.
  • the compound represented by the formula (1) forms a network structure in which silicon atoms are bonded to each other via oxygen atoms after hydrolysis and polycondensation.
  • the organic group represented by R is contained in a state of being directly bonded to a silicon atom.
  • the antibacterial fine particles 22 may contain fine particles having an antibacterial function, for example, made of copper, silver, zinc oxide, or the like.
  • the antibacterial fine particles 22 can be aggregates of these fine particles, but can also be aggregates containing dispersants and binders in addition to these fine particles. Alternatively, it can be the fine particles that are not aggregates. However, in the following, for convenience of explanation, the term "antibacterial fine particles” means an aggregate of fine particles unless otherwise specified.
  • the average particle size of the fine particles constituting the aggregate is, for example, preferably 10 to 150 nm, more preferably 15 to 100 nm, and particularly preferably 20 to 80 nm.
  • the average particle size of the antibacterial fine particles 22 which are aggregates is larger than the maximum thickness of the holding layer 21, for example, preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 5 ⁇ m. It is particularly preferably 1 to 4 ⁇ m.
  • the antibacterial fine particles 22 protrude from the holding layer 21 and exert an antibacterial function.
  • the antibacterial fine particles 22 may be covered with the holding layer 21, but even if the holding layer 21 is covered, the antibacterial function is not significantly suppressed because the holding layer 21 is thin.
  • the interval L of the antibacterial fine particles 22 held in the holding layer 21 is preferably 1 to 200 ⁇ m, more preferably 2 to 100 ⁇ m, and particularly preferably 3 to 70 ⁇ m. If the distance L between the antibacterial fine particles 22 is too narrow, the area of the holding layer 21 exposed between them becomes narrow, and the antiglare function may be impaired. On the other hand, if the distance L between the antibacterial fine particles 22 is too wide, the antibacterial function may be reduced.
  • the method for measuring the average particle size of the antibacterial fine particles 22 and the interval between the antibacterial fine particles 22 is described in Section (6) of Examples described later.
  • the content of the antibacterial fine particles contained in the antibacterial membrane 2 is preferably 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 18% by weight or less, and 15% by weight or less in this order.
  • the lower limit is preferably 0.1% by weight or more, 5% by weight or more, and 10% by weight or more in this order.
  • the method for forming the antibacterial film 2 is not particularly limited, but can be formed as follows, for example. First, a material constituting the above-mentioned matrix, for example, tetraethoxysilane is used as a solution under acidic conditions to generate a precursor solution. Further, the dispersion liquid containing the antibacterial fine particles 22 described above, for example, the copper fine particle dispersion liquid is diluted with propylene glycol or the like to generate a fine particle dispersion liquid. Then, the precursor liquid and the fine particle dispersion liquid are mixed to generate a coating liquid for an antibacterial film.
  • a material constituting the above-mentioned matrix for example, tetraethoxysilane is used as a solution under acidic conditions to generate a precursor solution.
  • the dispersion liquid containing the antibacterial fine particles 22 described above for example, the copper fine particle dispersion liquid is diluted with propylene glycol or the like to generate a fine particle dispersion liquid. Then, the precursor liquid and
  • the concentration of the antibacterial fine particles 22 in this coating liquid is preferably, for example, 100 to 8000 ppm, more preferably 500 to 5000 ppm. If the concentration of the antibacterial fine particles 22 is too high, the visible light transmittance of the cover member 10 may decrease and the haze may increase. On the other hand, if the concentration of the antibacterial fine particles 22 is too low, the antibacterial function may not be exhibited.
  • the coating method is not particularly limited, and for example, a flow coating method, a spray coating method, a spin coating method, or the like can be adopted.
  • the applied coating liquid is dried in an oven or the like at a predetermined temperature (for example, 80 to 120 ° C.) in order to volatilize the alcohol content in the solution, and then, for example, for hydrolysis and decomposition of organic chains.
  • the antibacterial film 2 can be obtained by sintering at a predetermined temperature (for example, 200 to 500 ° C.).
  • the visible light transmittance is preferably 85% or more, and more preferably 90% or more.
  • the haze rate of the cover member 10 is, for example, 20% or less, further 15% or less, particularly 10% or less, and in some cases, 1 to 8%, further 1 to 6%.
  • the gloss can be evaluated by the mirror glossiness.
  • the 60 ° mirror gloss of the cover member 10 is, for example, 60 to 130%, further 70 to 120%, and particularly 80 to 110%. These mirror glossiness are values measured for the surface on which the antibacterial film 2 is formed.
  • a cover member for a display of an in-vehicle device such as a car navigation system
  • a member having a gloss of 120 to 140% is generally used.
  • the relational expression (a) is established between the 60 ° mirror glossiness G and the haze rate H (%), and it is more preferable that the relational expression (b) is established.
  • H ⁇ -0.2G + 25 (a) H ⁇ -0.2G + 24.5 (b)
  • Gloss can be measured according to "Method 3 (60 degree mirror gloss)" of “Mirror gloss measuring method” of JIS Z8741-1997, and haze can be measured according to JIS K7136: 2000.
  • the cover member 10 according to the present embodiment can exert the following effects. That is, unevenness is formed on the first surface of the glass plate 1, and an antibacterial film 2 having a holding layer 21 and antibacterial fine particles 22 is formed on the first surface. Therefore, the surface of the holding layer 21 is also formed with irregularities along the irregularities of the glass plate 1, whereby the antiglare function is exhibited. Further, since the antibacterial film 2 contains antibacterial fine particles 22 having an average particle size larger than the maximum thickness of the holding layer 21, the antibacterial fine particles 22 are arranged so as to protrude from the holding layer 21. As a result, the antibacterial function is exhibited. As described above, the antibacterial film 2 of the cover member 1 according to the present embodiment can have both an antiglare function and an antibacterial function at the same time.
  • the bottom surface of the glass plate 1 is etched to form irregularities, but the top surface can be etched to form irregularities in the same manner.
  • a base layer having irregularities can be formed on any one surface of the glass plate 1.
  • the base layer can be formed, for example, by a base layer formed of the same material as the holding layer 21 described above and fine particles held by the base layer.
  • the shape of the fine particles is not particularly limited, but is preferably spherical.
  • the fine particles may be substantially composed of spherical particles. However, some of the fine particles may have a shape other than a spherical shape, for example, a flat plate shape.
  • the fine particles may be composed of only spherical particles.
  • the spherical particles refer to particles having a ratio of the longest diameter to the shortest diameter passing through the center of gravity of 1 or more and 1.8 or less, particularly 1 or more and 1.5 or less, and the surface of which is formed of a curved surface.
  • the average particle size of the spherical particles may be 5 nm to 200 nm, more 10 nm to 100 nm, and particularly 20 nm to 60 nm.
  • the average particle size of the spherical particles is determined by the average of the individual particle sizes, specifically, the average value of the shortest diameter and the longest diameter described above, and the measurement is preferably 30 particles based on the SEM image. It is desirable to carry out for 50 particles. As described above, by using fine particles having an average particle size smaller than that of the antibacterial fine particles 22, it is possible to form irregularities as a base for forming an appropriate surface roughness Ra on the holding layer 21 of the antibacterial film 2. ..
  • the material constituting the fine particles is not particularly limited, but preferably contains a metal oxide, particularly silicon oxide.
  • the metal oxide may contain, for example, an oxide of at least one metal element selected from the group consisting of Al, Ti, Zr, Ta, Nb, Nd, La, Ce and Sn.
  • the fine particles may be phyllosilicate mineral particles.
  • the phyllosilicate mineral contained in the phyllosilicate mineral particles is also called a layered silicate mineral.
  • Examples of the phyllosilicate mineral include kaolin minerals such as kaolinite, dikite, nacrite, and haloysite, serpentine such as chrysotile, lizardite, and amesite, and octahedral smectites such as montmorillonite and biderite, saponite, hectrite, and soconite.
  • 2 octahedral mica such as 3 octahedral smectite, vermiculite, paragonite, illite, seradonite
  • 3 octahedral mica such as gold mica, anite, lepidrite
  • 2 octahedral brittle mica such as margarite, clintite, 3 octahedral fragile mica such as anandite
  • 2 octahedral chlorite such as donbasite, 2.3 octahedral chlorite such as cucumberite and sudowite
  • 3 octahedral chlorite such as clinochlorite and chamosite, pyrophylli Examples include light, talc, 2 octahedral vermiculite, and 3 octahedral vermiculite.
  • the phyllosilicate mineral particles preferably contain minerals belonging to smectite, kaolin, or talc.
  • minerals belonging to smectite montmorillonite is suitable.
  • montmorillonite belongs to the monoclinic system
  • kaolin belongs to the triclinic system
  • talc belongs to the monoclinic system or the triclinic system.
  • Such an underlayer can be formed in the same manner as the above-mentioned antibacterial film. That is, the precursor liquid and the fine particle dispersion liquid as described above are mixed to generate a coating liquid for a base layer, which is applied to the surface of a glass plate and then sintered to form a base layer having irregularities on the surface. Can be formed.
  • the surface roughness Ra of the base layer can be the same as the surface roughness Ra of the first surface of the glass plate 1 described above.
  • the refractive index of the base layer and the antibacterial film 2 can be brought close to each other. Therefore, the antiglare function can be exhibited more effectively.
  • a glass plate (float glass) formed by the float method can be chemically strengthened to form a base layer with respect to the top surface.
  • the top surface having a high concentration of sodium ions is exchanged with alkaline ions such as potassium ions more than the bottom surface, so that the top surface is easily warped so as to be convex. Therefore, when the above-mentioned base layer is formed on the top surface, the laminated base layer shrinks and the warp is alleviated. Therefore, from the viewpoint of suppressing warpage, it is preferable to form a base layer on the top surface of the chemically strengthened glass plate.
  • a known antireflection film can be arranged between the base layer and the antibacterial film 2.
  • the base layer of the base layer described above is an example, and can be appropriately changed.
  • the base layer can be formed of a material containing silicon oxide as a main component, but is not limited thereto. If silicon oxide is used as the main component, the refractive index (reflectance) of the base layer tends to be low. In addition, the chemical stability of the base layer is also good. In addition, the adhesion with the glass plate 1 is good.
  • silicon oxide is the main component means that SiO 2 is contained in an amount of 50% by mass or more, but it is preferably contained in an amount of 90% by mass or more.
  • the base layer may be composed of only silicon oxide, or may contain a small amount of components other than silicon oxide.
  • the components include Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr. , Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi and compounds such as one or more ions and / or oxides selected from lanthanoid elements. ..
  • the base layer containing silicon oxide as a main component includes those formed from a coating composition containing a silicon oxide precursor, those formed from a coating composition containing silicon oxide particles as particles, and other components not containing silicon oxide as a main component. Examples thereof include those formed by a resin film or the like.
  • the composition of the holding layer 21 is not particularly limited, and as described above, any material may be used as long as it has a predetermined surface roughness on the surface and can hold the antibacterial fine particles 22.
  • a fingerprint resistant layer can also be formed on the surface of the antibacterial film 2.
  • the swipe operation on the cover member 10 becomes easy, and the stains such as fingerprints become easy to wipe off.
  • the fingerprint resistant film can be formed, for example, as follows.
  • the fingerprint-resistant film can have hydrophobic properties and sparse oil properties, that is, both sparse medium properties, so as to minimize the wetting of the cover member 10 by water and oil. Therefore, the wetting properties of a surface with a fingerprint resistant film are not only hydrophobic, i.e., the contact angle between the surface and water is preferably greater than 90 °, but also oleophobic, i.e., surface and oil.
  • the fingerprint-resistant film can be, for example, a film containing a silane containing an alkyl group and / or a fluoroalkyl group, for example, 3,3,3-trifluoropropyltrimethoxysilane or pentylriethoxysilane.
  • the fingerprint resistant film is based on a compound having a hydrocarbon group, even if the CH bond is a fluoro-based surface layer in which the CH bond is partially or preferably substantially entirely replaced by the CF bond. good.
  • such compounds are represented, for example, in formula (RF) n SiX 4-n , where RF is C 1 to C 22 -alkyl perfluorohydrocarbons or -alkyl perfluoropolyethers, preferably. C 1 to C 10 -alkyl perfluorohydrocarbons or -alkyl perfluoropolyethers, where n is an integer of 1 to 3 and X is a hydrolyzable group such as a halogen or alkoxy group-OR (where R).
  • the hydrolyzable group X can react, for example, with the terminal OH group of the coating on the glass substrate and thus be attached to this group by the formation of a covalent bond.
  • Perfluorohydrocarbons are preferably used to reduce the surface energy of the surface due to the low polarity of the fluorine surface bonds at the ends.
  • the fingerprint resistant film can be derived, for example, from a single layer of molecular chains with a fluorine end group, a fluoropolymer coating, or silicon oxide-suit particles pre-equipped with or treated with a fluorine end group. ..
  • the fingerprint-resistant film is preferably immersed, vapor-deposited, sprayed, applied with a roll or roller or blade, vacuum-deposited by heat or sputtered, preferably by liquid phase methods such as spraying, immersion coating, printing, roller coating, spin coating. Alternatively, it can be applied to the surface by other suitable methods. Immersion or spraying is particularly preferred. After applying the coating, it is advantageously cured over a suitable period of time and in a suitable time.
  • the thickness of the fingerprint-resistant film can be, for example, 50 to 1000 nm. If the thickness of the fingerprint-resistant film is too large, the antibacterial performance may be suppressed. On the other hand, if the thickness of the fingerprint-resistant film is too small, the fingerprint-resistant performance may be reduced.
  • the fingerprint-resistant film can be formed on the entire surface of the antibacterial film 2, but it can also be formed on a part of the antibacterial film 2.
  • a part of the cover member 10 is arranged on a protected member 100 such as a keyboard that performs a key touch operation, a fingerprint resistant film is not formed on the key, and another swipe operation is performed, for example.
  • the fingerprint-resistant layer can be formed only in the area to be covered.
  • a mask layer can be formed on a part of the glass plate 1 so that the protected member 100 cannot be seen from the outside in the portion where the mask layer is formed.
  • a mask layer can be formed on the peripheral edge of the glass plate 1 so that the protected member 100 cannot be seen from the outside on the peripheral edge of the cover member 10.
  • parts such as wiring and brackets of the protected member 100 can be hidden from the outside.
  • the material of the mask layer may be appropriately selected according to the embodiment as long as it can shield the field of view from the outside, and for example, dark ceramics such as black, brown, gray, and navy blue may be used.
  • a sheet material can be attached.
  • black ceramic is selected as the material of the mask layer
  • black ceramic is laminated on the surface of the cover member 10 opposite to the surface on which the antibacterial film 2 is formed by screen printing or the like, and glass is used. Heat the ceramic laminated together with the plate. Then, when the ceramic is cured, the mask layer is completed.
  • the ceramic used for the mask layer various materials can be used. For example, the ceramic having the composition shown in Table 1 below can be used for the mask layer.
  • Main component Copper oxide, Chromium oxide, Iron oxide and Manganese oxide * 2
  • Main component Bismuth borosilicate, Zinc borosilicate
  • the cover member according to the present invention can be colored transparent or translucent by coloring at least one of a glass plate 1, an antibacterial film 2, and an underlayer.
  • Example A cover member according to Example 1 was formed by laminating a base layer on a float glass plate of 50 mm x 50 mm and further laminating an antibacterial film.
  • Cleansolve P-7 Nitric acid and kaolin TS90 are dissolved in Cleansolve P-7 manufactured by Japan Alcohol Trading Co., Ltd.
  • Cleansolve P-7 is a mixed solvent containing ethanol as a main component, isopropyl alcohol, and normal propyl alcohol.
  • the precursor liquid was applied to the glass plate by flow coating, and then dried in an oven set at 200 ° C. to form an underlayer.
  • Retention layer A precursor solution for a retention layer having the following composition was prepared (unit is g). Then, these mixed solutions were stirred at 60 ° C. for 7 hours, and a precursor solution was obtained by a hydrolysis reaction of TEOS.
  • a coating solution for an antibacterial film having the following composition was prepared for this precursor solution (unit: g). Copper was used as the antibacterial fine particles, and a dispersion diluted with propylene glycol to a concentration of 1% was prepared. Then, the materials in Table 4 were mixed while stirring in the order from top to bottom. Then, this mixed solution was stirred at room temperature to obtain a coating liquid.
  • this coating liquid was applied onto the base layer by roll coating, air-dried for 10 minutes, and then heated in an oven set at 300 ° C. for 30 minutes to form an antibacterial film.
  • the cover member according to this embodiment was completed. The following tests were performed on this cover member.
  • the gloss was 119.2. Therefore, sufficient anti-glare performance can be exhibited.
  • the haze rate was 3.2%, which was sufficiently low.
  • the haze rate was measured by a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. At this time, the antibacterial film was used as the incident surface, the haze rate was measured at three points of the sample, and the average value was taken as the haze rate.
  • the surface roughness Ra of the antibacterial film was 52 nm.
  • the average length Rsm of the roughness curve element of the antibacterial film was 16.2 ⁇ m.
  • the antibacterial activity was 6.1. Since it is evaluated to have antibacterial activity at 2.0 or higher, sufficient antibacterial performance was confirmed in this example.
  • the antiviral activity was 1.6.
  • FIG. 3 is a photograph of the surface texture of the antibacterial film of the example observed by SEM
  • FIG. 4 is an enlarged view of the antibacterial fine particles shown in the photograph of FIG.
  • a plurality of white dots shown in FIG. 3 indicate antibacterial fine particles.
  • the antibacterial fine particles according to this example are aggregates of copper particles.
  • the particle size of the antibacterial fine particles shown in FIG. 3 was 1 to 4 ⁇ m.
  • the maximum distance between the antibacterial fine particles was 50 ⁇ m, the minimum was 5 ⁇ m, and the average was 25 ⁇ m.
  • the average particle size was calculated by the following method. First, three SEM images with a magnification of 1000 times were acquired in different fields of view. Next, the following measurement was performed in the range of 90 ⁇ mx 120 ⁇ m (the range surrounded by the broken line in FIG. 3). First, the length in the major axis direction and the length in the minor axis direction of the antibacterial fine particles are measured, and the average of them is taken as the particle size of one antibacterial fine particle. Then, the same measurement was performed for any antibacterial fine particles at 10 points per image, for a total of 30 points, and the average of them was taken as the average particle size.
  • the distance between the antibacterial fine particles was calculated as follows. First, three SEM images with a magnification of 1000 times were acquired in different fields of view. Next, the spacing between arbitrary adjacent antibacterial fine particles was measured. The same measurement was performed for any 10 sets of antibacterial fine particles at 10 points per image, for a total of 30 points, and the average of them was taken as the distance between the antibacterial fine particles.

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Abstract

L'invention concerne un élément de revêtement qui permet d'obtenir à la fois un effet antireflet et un effet antibactérien. Cet élément de revêtement comprend : un substrat en forme de plaque qui comporte une première surface et une seconde surface, la première surface présentant une rugosité de surface déterminée ; et un film antibactérien qui est formé sur la première surface. Le film antibactérien comprend : une couche de retenue qui est formée sur la première surface ; et de fines particules antibactériennes qui sont retenues par la couche de retenue et qui présentent un diamètre de particule moyen qui est au moins égal à l'épaisseur de couche de la couche de retenue.
PCT/JP2021/033815 2020-09-14 2021-09-14 Élément de revêtement WO2022054961A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11171592A (ja) * 1997-12-15 1999-06-29 Nippon Sheet Glass Co Ltd 撥水性物品及びその製造方法
JP2000154106A (ja) * 1998-11-17 2000-06-06 Casio Comput Co Ltd 抗菌性物品及びその製造方法
JP2008221201A (ja) * 2007-02-16 2008-09-25 Fujifilm Corp 親水性部材及びその製造方法
JP2013136496A (ja) * 2011-11-28 2013-07-11 Nippon Sheet Glass Co Ltd 防眩性ガラス基板およびその製造方法
WO2016185960A1 (fr) * 2015-05-15 2016-11-24 三菱電機株式会社 Revêtement antibactérien ainsi qu'article équipé de celui-ci, procédé de formation de ce revêtement antibactérien, et liquide d'application pour formation de revêtement antibactérien
JP2017530079A (ja) * 2014-09-12 2017-10-12 ショット アクチエンゲゼルシャフトSchott AG 耐性を持つ多機能表面特性を有するコーティングされたガラス基板又はガラスセラミック基板、該基板を製造する方法及び該基板の使用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11171592A (ja) * 1997-12-15 1999-06-29 Nippon Sheet Glass Co Ltd 撥水性物品及びその製造方法
JP2000154106A (ja) * 1998-11-17 2000-06-06 Casio Comput Co Ltd 抗菌性物品及びその製造方法
JP2008221201A (ja) * 2007-02-16 2008-09-25 Fujifilm Corp 親水性部材及びその製造方法
JP2013136496A (ja) * 2011-11-28 2013-07-11 Nippon Sheet Glass Co Ltd 防眩性ガラス基板およびその製造方法
JP2017530079A (ja) * 2014-09-12 2017-10-12 ショット アクチエンゲゼルシャフトSchott AG 耐性を持つ多機能表面特性を有するコーティングされたガラス基板又はガラスセラミック基板、該基板を製造する方法及び該基板の使用
WO2016185960A1 (fr) * 2015-05-15 2016-11-24 三菱電機株式会社 Revêtement antibactérien ainsi qu'article équipé de celui-ci, procédé de formation de ce revêtement antibactérien, et liquide d'application pour formation de revêtement antibactérien

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