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WO2003062165A1 - Vitrage a revetement anti-reflets - Google Patents

Vitrage a revetement anti-reflets Download PDF

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Publication number
WO2003062165A1
WO2003062165A1 PCT/JP2003/000512 JP0300512W WO03062165A1 WO 2003062165 A1 WO2003062165 A1 WO 2003062165A1 JP 0300512 W JP0300512 W JP 0300512W WO 03062165 A1 WO03062165 A1 WO 03062165A1
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WO
WIPO (PCT)
Prior art keywords
glass plate
reflection film
low
glass
visible light
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/JP2003/000512
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English (en)
Japanese (ja)
Inventor
Takashi Muromachi
Hideki Okamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Publication of WO2003062165A1 publication Critical patent/WO2003062165A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass

Definitions

  • the present invention relates to a glass plate with a low reflection film, and more particularly to a glass plate with a low reflection film for automobiles, which is suitable for windshield laminated glass for automobiles.
  • Glass sheets for automobiles are required to have the ability to shield infrared rays in order to reduce the cooling load.
  • a glass plate ing from the source one da-lime-silica glass containing from 0.3 to 1% total iron as calculated F e 2 0 3, which were combined in the intermediate layer containing an infrared shielding fine particles Glass has been proposed.
  • the ability to block infrared rays with iron oxide and fine particles is substantially limited by laws and regulations that require that the visible light transmittance of a given glass window of a vehicle exceed a specified value (70%, or 75% in some regions). Is restricted. In glass sheets for automobiles, iron is added only in a range that satisfies the visible light transmittance that complies with laws and regulations, or infrared shielding fine particles are added to the intermediate film to reduce the solar transmittance.
  • a low-reflection film on the windshield glass of automobiles has also been proposed to use a low-reflection film on the windshield glass of automobiles to prevent reflection of dashports.
  • the present applicant discloses in Japanese Patent Application Laid-Open No. 2000-256042 that at least one surface of a transparent glass substrate has a refractive index ( ⁇ ⁇ ) of 1.65 to 2 as a first layer counted from the glass surface side.
  • a thin film having a thickness of 110 to 150 nm is formed.
  • the refractive index (n 2 ) is 1.37 to 1.49.
  • a thin film layer composed mainly of silica with a film thickness of 81 to 100 nm is laminated, and visible light is incident from the film surface side at incident angles of 12 degrees and 60 degrees, respectively.
  • a low-reflection glass article for automobiles that has a stimulus purity of 22% or less and 10% or less, respectively, when reflected.
  • a low-reflection film has been used to prevent glare on dashboards of automotive glass plates.
  • a low-reflection film by using a low-reflection film, it is possible to not only prevent glare but also prevent infrared rays from being reflected. And to maintain and improve visible light transmittance.
  • the present invention is a glass plate provided with a low-reflection film on which a low-reflection film composed of two layers is formed, having a visible light transmittance of 70% or more and a solar transmittance of 55% or less, the value obtained by subtracting the the visible light transmittance from the visible light transmittance in a state other than the low-reflection film is not less than 2%, the glass plate, 0 iron oxide F e 2 0 3 basis. 3 -1% by mass, preferably 0.5-1% by mass.
  • FIG. 1 is a sectional view showing an example of a glass plate provided with a low reflection film according to the present invention.
  • FIG. 2 is a cross-sectional view showing another example of the glass plate with a low reflection film according to the present invention.
  • the present invention utilizes the effect that the low reflection film provided on the transparent body suppresses the reflection of light, thereby increasing the amount of transmitted light of the transparent body. For example, using a glass plate having a visible light transmittance of at least 68%, while maintaining a visible light transmittance of at least 70%, the solar transmittance of a glass plate without a low reflection film is substantially reduced. maintain.
  • the value obtained by subtracting the solar transmittance of the glass plate provided with the low reflection film from the solar transmittance excluding the low reflection film can be set to 1% or less.
  • the visible light transmittance of the glass plate provided with a low reflection film is 70% or more, and the visible light transmittance excluding the low reflection film is less than 70%.
  • the visible light transmittance of the glass plate provided with a low reflection film is 75% or more, and the visible light transmittance excluding the low reflection film is less than 75%.
  • the solar radiation transmittance can be reduced to 50% or less, and further to 45% or less, while maintaining the visible light transmittance at 70% or more.
  • the visible light transmittance of 75% or more corresponds to the legal regulations on glass windows for automobiles in Europe.
  • the low-reflection film for example, has a refractive index ( ⁇ ⁇ ⁇ ⁇ .68 to 2.3 and a film thickness (dt) of 100 to 140 nm, counted from the glass side,
  • the glass plate a single glass plate of a green, bronze, drip, UV cut bronze, or UV cut bronze system, preferably a daline or UV cut green glass can be used.
  • the glass plate may be a laminated glass formed by bonding at least two single glass plates via a thermoplastic interlayer. It is preferable that the interlayer film of the laminated glass contains ITO fine particles having a particle diameter of 0.2 xm or less, for example, in a ratio of 0.01 to 0.8% by mass with respect to the interlayer film.
  • the same or different types of glass plates selected from the single glass plate and the clear glass plate exemplified above may be appropriately used in combination. However, the combination of clear glass plates should be excluded.
  • laminated glass at least two single glass plates But both, F e 2 ⁇ 3 iron oxide conversion from 0.3 to 1 wt%, preferably 0.5 to 1 wt%, preferably has a composition containing.
  • the low-reflection film has a visible light reflectance of 4.8% or less and 11.0% or less when visible light is incident from the film surface side at incident angles of 12 degrees and 60 degrees, respectively. You may have.
  • the low-reflection film has a visible light reflectance when visible light is incident from the film surface side at incident angles of 12 degrees and 60 degrees, respectively. It may have a visible light reflectance that is at least 2.4% and at least 3.5% smaller than the visible light reflectance at the plane of incidence at angles of 12 degrees and 60 degrees, respectively.
  • the low-reflection film has a stimulating purity of 22% or less and 10% or less, respectively, when visible light is incident from the film surface side at incident angles of 12 degrees and 60 degrees, respectively. Is also good.
  • the first layer of the low reflective film containing S i 0 2 and T i 0 2, or may be substantive to the thin film consisting of only T I_ ⁇ 2.
  • the second layer may be composed mainly of S i 0 2, but may also be a thin film made of substantially only S i 0 2.
  • the refractive index of the first layer (If 11 is less than 1.68, a sufficient effect of reducing the reflected light intensity with respect to incident light from a high incident angle to a low incident angle cannot be obtained. (If n is greater than 2.3, the reflectance at a specific wavelength Although it can be lowered, when viewed over the entire visible range, coloring and reflection become strong, the visible light transmittance becomes 70% or less, and the desired reflection reduction effect cannot be obtained.
  • the preferred range of the refractive index ( ⁇ ,) of the first layer is from 1.70 to 1.95.
  • the thickness of the first layer film (d) is smaller than 100 nm, the reflectivity at a high incident angle is large.
  • the thickness (d) of the first layer film is larger than 140 nm, the low incident angle is small. , The reflectance increases.
  • the first layer preferably contains Si 2 and Ti 0 2 as main components or substantially only Ti 0 2 .
  • the first layer is composed mainly of S i 0 2 and T i 0 2 , or substantially only T i 0 2 , a film having excellent durability can be obtained.
  • the second layer (low-refractive-index film) of the low-reflection film has a refractive index (n 2 ) of 1.4 to 1.5 and a thickness (d 2 ) of 80 to: L 10 nm.
  • the density of the film becomes smaller and the unevenness of the surface becomes larger. For this reason, the abrasion resistance, chemical resistance, antifouling property, weather resistance, etc. are deteriorated, and it is difficult to realize an optical thin film having both durability and durability. If the refractive index (n 2 ) of the second layer exceeds 1.5, a desired reflection reduction effect cannot be obtained.
  • the preferable refractive index (n 2 ) of the second layer is from 1.40 to 1.47.
  • the thickness (d 2 ) of the second film is less than 80 nm, the intensity of the reflected light cannot be sufficiently reduced.
  • the thickness (d 2 ) of the second film exceeds 100 nm, the reflectance at low incident angles increases.
  • the second layer preferably consists essentially S i 0 2.
  • a film whose second layer is substantially made of SiO 2 is preferable because it has excellent chemical stability, thermal stability, and mechanical strength.
  • the refractive index of the SiO 2 film is about 1.45, although it depends on the manufacturing method. If therefore lower refractive index of the film is required, or to form a minute irregular shape on the surface of the S io 2 film, as S i 0 2 film inside the independent foam or through pores like porous, the apparent May be lowered. Further, inorganic fine particles having a low refractive index may be put in the film to lower the refractive index.
  • a sol-gel method a sputtering method, or a CVD method.
  • the sol-gel method is desirable from the viewpoint of cost.
  • the first layer and the second layer constituting the low reflection film of the present invention are formed by a sol-gel method, a uniform film can be easily obtained and high durability can be obtained in addition to good film forming properties. is there.
  • the coating method of the coating solution by the sol-gel method includes spin coating, dip coating, meniscus coating, flow coating, Roll coating, gravure coating, flexographic printing, screen printing, and the like.
  • the coating liquid composition comprises a titanium compound, a silicon compound and a solvent, and can be obtained by mixing the titanium compound and the silicon compound in an organic solvent.
  • the coating liquid composition contains a silicon compound and a solvent. And can be obtained by mixing a silicon compound with an organic solvent.
  • titanium alkoxide As a titanium compound which is a starting material of titanium oxide contained in the first layer, titanium alkoxide, titanium alkoxide chloride, titanium chelate and the like are used.
  • the titanium alkoxide include titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, titanium methoxypropoxide, titanium stearyl oxide, titanium 2-ethylhexoxide, and the like. Can be exemplified.
  • titanium alkoxide chloride examples include titanium chloride triisopropoxide, titanium dichloride diethoxide and the like. Titanium chelate is titanium triisopropoxaside (2,4-pentanedio) Net), titanium diisopropoxide (bis-2,4-pentanedionate), titanium aryl acetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium di-n- Butoxide (bis-2,4-pentanedione) is used.
  • the silicon compound which is the starting material of silicon oxide contained in the first and second layers, is obtained by mixing silicon alkoxide with a solvent such as alcohol and promoting hydrolysis and polymerization with an acidic or basic catalyst. Is used.
  • silicon alkoxide silicon methoxide, silicon ethoxide, or an oligomer thereof is used.
  • the boron compound to be contained is, for example, polon methoxide, polonethoxide, polon n-propoxide, boron i-propoxide, boron n-butoxide, or polone. S-butoxide, boron t-butoxide and chelating compounds thereof are used.
  • Aluminum compounds added as a coating liquid composition for forming the second layer include aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum i-propoxide, aluminum n-butoxide, and aluminum. s-butoxide, aluminum t-butoxide and their chelating compounds are used.
  • chelate compound aluminum (di-s-butoxide) ethyl acetate, aluminum (S-butoxide) bisethyl acetate, aluminum (di-propoxide) ethyl acetate, and the like are conveniently used.
  • the acid catalyst contained in the coating liquid composition for forming the first and second layers includes hydrochloric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, oxalic acid, trichloroacetic acid, trifluoroacetic acid, phosphoric acid, and hydrofluoric acid , Formic acid and the like are used. salt Ammonia and amines are used as the basic catalyst.
  • the organic solvent used in the coating liquid composition for forming the first layer and the second layer depends on the coating method.
  • the above-mentioned solvents may be used alone or in combination of a plurality of solvents in order to adjust the viscosity and surface tension of the coating liquid. Small amounts of stabilizers, leveling agents, thickeners, etc. may be added as necessary. The amount of the solvent used also depends on the thickness of the ⁇ -refractive index film and low-refractive index film finally obtained and the coating method to be employed. In general, the solvent should be used so that the total solids is in the range of 1 to 20%.
  • the low-reflection film thus obtained has excellent properties such as transparency, environmental resistance, and scratch resistance.
  • properties such as transparency, environmental resistance, and scratch resistance.
  • even if the layers are stacked it is possible to suppress film peeling and generation of cracks in the process of densification of the first layer and the second layer. It is considered that this film peeling and cracks occur due to the difference in thermal shrinkage.
  • a light irradiation method described below can be used. That is, after coating the coating liquid composition by the coating method, This is a method of repeating the coat drying step, in which a step of irradiating the coating film with an electromagnetic wave having a shorter wavelength than that of the coating film is performed, followed by a step of coating the next coating liquid.
  • Examples of electromagnetic waves having a wavelength shorter than that of visible light include ⁇ -rays, X-rays, and ultraviolet rays.
  • ultraviolet irradiation is preferable from the viewpoint of practicality of the apparatus in consideration of irradiation of a substrate having a large area.
  • Excimer lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, etc. are used as ultraviolet light sources.
  • a high-pressure mercury lamp that efficiently emits light at wavelengths of 254 nm and 303 nm with a main wavelength of 365 nm, 1 O mW / cm 2 or more, preferably 50 mW / cm 2 It is desirable to irradiate the coating film with an irradiation intensity of 100 mWZ cm 2 or more, more preferably.
  • - using such ultraviolet light source 1 0 O m J / cm 2 or more, preferably 5 0 0 m JZ cm 2 or more, more preferably 1 0 0 O m J / cm 2 or more radiation energy, above It is good to irradiate the surface coated with the above coating liquid composition. This makes it possible to obtain a low-reflection film having a laminated structure that is excellent in properties such as transparency, environmental resistance, and scratch resistance at low temperatures and is less likely to crack.
  • Drying and / or baking by heat may be performed simultaneously while irradiating ultraviolet rays.
  • a drying method by ultraviolet irradiation and a drying step by thermal drying, preferably at a temperature of 250 ° C. or lower, may be used simultaneously. By using the ultraviolet irradiation in this way, the drying process can be sped up and productivity can be dramatically improved.
  • the visible light transmittance of the glass plate alone is, for example, a glass plate having a value less than the minimum value (70%, or 75% in some regions) according to laws and regulations for glass plates for automobiles. Less than the above minimum value and 6 Use a glass plate that is at least 8%. That is, for example, as a colored glass plate, a green, bronze, gray, high performance UV cut green glass, high performance UV cut bronze glass, or the like is preferable. In particular, it is more preferable that the window material for automobiles be of a green color, especially if it is easy to obtain heat ray / ultraviolet ray absorption performance.
  • coloring components used in such a colored glass plate include iron, cobalt, nickel, and the like.
  • the soda lime silica glass containing iron as a coloring component as represented by mass percentage to the mother glass soda lime silica, total iron from 0.3 to 1% in terms F e 2 O s, preferably 0. It is preferably soda lime silica glass containing 5-1%.
  • the absorption of light in the near-infrared region is dominated by divalent iron among the total iron.
  • 6 and 2 0 3-converted 60 (divalent iron) it is more preferred ratio of total iron as calculated F e 2 0 3 is 0.2 0 to 0.40.
  • soda lime silica glass substantially expressed by mass percentage and having the following composition. Expressed in mass%,
  • a mother glass composition consisting of
  • UV and infrared absorbing glass UV and infrared absorbing glass.
  • the mother glass composition in the ultraviolet and infrared absorbing glass includes so 3 :
  • it contains 0.07 to 0.30%.
  • iron oxide present in glass in the form of F e 2 0 3 and F e 0.
  • F e 2 0 3 together with the C E_ ⁇ 2, T i 0 2
  • F e O is a component for increasing the heat ray absorptivity.
  • the amount of total iron oxide (T-F e 2 ⁇ 3), when in the range of from 0.3 to 1.0%, in order to obtain a desired total solar energy absorption, F e OZT- F e 2 0 3 ratio, as the amount of F E_ ⁇ of from 0.20 to 0.40 range is it is preferably Re of ⁇ this case, numerical values in terms of normal F e 2 0 3 Used.
  • the glass of the above composition range, C O_ ⁇ , N I_ ⁇ , M nO, V 2 0 5 , Mo 0 3 , etc., also the S N_ ⁇ 2 as a reducing agent, one or more kinds as colorants May be added in an amount of 0 to 1% in a range that does not impair the greenish color tone intended by the present invention.
  • C O_ ⁇ may grant a blue hue, is effective in the color tone of the glass can be inhibited from yellowing by F e 2 0 3, C E_ ⁇ 2, T i 0 2 quantity increase,
  • the preferred range is from 3 to 20 ppm.
  • so 3 contains iodine such as borate nitrate (sodium sulfate) added to the raw materials
  • iodine such as borate nitrate (sodium sulfate) added to the raw materials
  • borate nitrate sodium sulfate
  • the amount of S_ ⁇ 3 plays a very important role.
  • This ultraviolet infrared ⁇ absorbing glass while containing F e 2 0 3, C e 0 2 as an oxidizing agent relatively large amounts, it is necessary to set the degree of reduction higher than normal.
  • lump undissolved in the sand (so-called scum) and a ream with a large amount of silica (so-called silica-rich ream) are likely to occur.
  • silica-rich ream a ream with a large amount of silica
  • sulfide ion-containing materials for example, sulfides such as iron sulfide, blast furnace slag, for example, calmite manufactured by Calmite, and rivermite manufactured by Kawatetsu Mining
  • sulfide ion-containing materials for example, sulfides such as iron sulfide, blast furnace slag, for example, calmite manufactured by Calmite, and rivermite manufactured by Kawatetsu Mining
  • the upper limit of the visible light transmittance of only the glass plate is not particularly limited in the present invention.
  • a glass plate having a visible light transmittance of less than 75% is preferable because the increase in the visible light transmittance by the low reflection film is effective.
  • the glass plate is not limited to a colored glass plate, and may be, for example, a glass plate with a heat ray reflective film.
  • it may be a tempered glass plate or an untempered glass plate. In terms of shape, it may be a flat plate or a bent glass.
  • a single glass plate but also a laminated glass plate or a multi-layer glass plate may be used.
  • the above description of the colored glass plate is for a case where the glass plate is a single plate.
  • the glass plate when composed of laminated glass, at least one single glass plate may be the transparent and colored glass plate described above, and the other single glass plate may be a clear plate.
  • the glass plate in the present invention preferably has a thickness of 1.5 to 6.5 m (in the case of laminated glass or double-glazed glass, the thickness is defined as the distance between the outer surfaces of each glass plate).
  • the glass plate with a low reflection film according to the present invention will be described in detail using examples.
  • the glass plate with a low reflection film according to the first embodiment has the following configuration.
  • UVG 2.1 mm is a UV cut green glass plate with a thickness of 2.1 mm.
  • FIG. 1 schematically shows a cross-sectional structure of the glass plate with a low-reflection film for an automobile of Example 1.
  • the glass sheet 1 with a low-reflection film for automobiles connects the outside single glass sheet 1 1 and the inside single glass sheet 1 2 via the interlayer 13 (PVB film).
  • the low-reflection film 2 (21, 22) is formed on the interior surface of the laminated glass.
  • a low-reflection film was formed on the surface of the glass plate 12 on the inside of the vehicle as follows.
  • High refractive index film which is the first layer consists of T I_ ⁇ 2 and S I_ ⁇ 2. It was formed by a sol-gel method. The film thickness was 130 nm, and the refractive index was 1.75.
  • the low refractive index film as the second layer was composed of Si 2 and was formed by a sol-gel method.
  • the film thickness was 90 nm, and the refractive index was 1.45.
  • a laminated glass was produced using the above-mentioned glass substrates 11 and 12 using a normal intermediate film (PVB film) 13 through a known laminating process.
  • PV film normal intermediate film
  • Example 1 is an example in which a low reflection film was formed on the glass substrate of Sample 6.
  • Example 2 a glass plate with a low reflection film was produced in the same manner as in Example 1, except that the thickness of one UVG glass plate was changed to 1.8 mm.
  • Example 2 corresponds to an example in which a low reflection film was formed on the glass substrate of Sample 11.
  • the visible light transmittance was improved from 74% to 76% by forming the low reflection film.
  • UVG2.3 //-UVG2.3 69. .0 6.5 .5 / 12.8 38, .8 0. 9 UVG 6.0 (single board) 69, .5 6. .6 / 13.2 39, .1 0. • 1 sunf. 10 UVG2 • 1 / IT0 / UVG2.1 69. 0 6. 1 / 12.4 35. 5 0.2 Samp. 11 UVG2 • 1 / Normal / UVG1.8 74.
  • Table 3 shows the optical characteristics of the glass plate with a low-reflection film for automobiles obtained in Example 1. In addition, the optical characteristics of other examples are also shown.
  • Example 2 UVG2.1 / Normal / UVG1.8 76.0 3.9 / 9.2 44.0 0.1
  • Example 3 UVG2. 1 / IT0 / UVG2.1 71.2 3.6 / 8.8 36.2 0.2
  • Example 4 UVG2.3 / Normal / UVG2.3 71.2 3.5 / 8.7 39.5 0.1
  • Example 5 GRN2.1 //-7J1 / GRN2.1 81.3 4.2 / 10.1 52.7 0.1
  • Example 1 the visible light transmittance was 74%, indicating an increase in visible light transmittance of about 2% as compared with Sample 6 due to the low reflection film.
  • the visible light reflectance showed a reduction effect of 3% at 12 degrees and about 4% at 60 degrees.
  • the solar transmittance was reduced by about 35% compared to the laminated glass of the uncolored glass plate of Reference Example 1. From this, it was found that Example 1 had both excellent low reflection performance and excellent solar shading performance. (Example 3)
  • the glass plate with a low reflection film for an automobile according to the third embodiment has the following configuration.
  • Example 3 Composition: UVG 2. mmZ ITO dispersion interlayer ZUVG 2.1 mmZ low reflection film
  • the ITO fine particles were dispersed in the interlayer at a ratio of 0.1% by mass.
  • ITO fine particles with a particle size of 0.2 m or less are dispersed in a plasticizer (3GH, manufactured by Sekisui Chemical Co., Ltd.) so that the solid content is about 10%.
  • the liquid was prepared.
  • PVB polyvinyl butyral
  • 3GH plasticizer
  • a laminated glass was produced in the same process as in Example 1, except that an intermediate film in which ITO fine particles were dispersed was used instead of the ordinary intermediate film.
  • Table 3 shows the optical characteristics.
  • Example 3 the visible light transmittance is 71.2%, which satisfies the automotive glass standard of 70% or more. Further, the solar radiation transmittance was further reduced by about 5% as compared with Example 1. From this, it was found that Example 3 has both excellent low reflection performance and solar shading performance.
  • the glass plate with a low-reflection film for a vehicle according to the fourth embodiment has the following configuration.
  • Example 4 is the same as Example 1, except that the thickness of the glass substrate is different. It is a glass plate with a low reflection film. Table 3 shows the optical characteristics.
  • Example 4 is an example in which a low-reflection film was formed on the glass substrate of Sample 8.
  • Example 4 the visible light transmittance of the basic sample 8 was 69%, whereas the visible light transmittance was increased by forming the low-reflection film. It came to satisfy the glass standard. In addition, the visible light reflectance and the solar radiation transmittance were further reduced as compared with Example 1. From this, it was found that Example 4 had both excellent low reflection performance and solar shading performance.
  • the glass plate with a low-reflection film for a vehicle according to the fifth embodiment has the following configuration.
  • Example 5 is an example in which a low reflection film was formed on the glass substrate of Sample 4. According to Example 5, the visible light reflectance and the solar radiation transmittance were reduced as compared with Reference Example 1. Although Example 5 was inferior to Examples 1 to 3, it was found that both excellent low reflection performance and solar shading performance were compatible.
  • the glass plate with a low reflection film for a vehicle according to the sixth embodiment has the following configuration.
  • Example 6 a single UV-cut green glass plate (6 mm thick, This is an example in which a low reflection film applied to the present invention is formed on the sample 9).
  • the visible light transmittance of the basic sample 9 was 69.5%, whereas the visible light transmittance was 69.5% due to the effect of forming the low reflection film. Increased to 71.5%.
  • the visible light reflectance and solar radiation transmittance were also reduced, indicating that both low reflection performance and solar shading performance were achieved.
  • a low reflective film is applied to a glass plate that absorbs in the visible light region. For this reason, excellent low reflection performance and high visible light transmittance can both be achieved. Furthermore, when the glass sheet constituting the glass sheet with a low reflection film according to the present invention is a heat ray absorbing glass, both low reflection performance and solar shading performance can be achieved.
  • the glass plate with a low reflection film according to the present invention since the low reflection film is formed on the surface, reflection loss on the surface of the glass plate can be suppressed. As a result, the transmittance as a glass plate can be improved, so that the ability of the glass substrate to absorb solar radiation can be further increased.
  • the visible light transmittance is 70% or more and 75% or more, respectively.
  • the visible light transmittance is 70% or more and 75% or more, respectively.
  • the transmittance as a glass plate can be improved, as described above, so that a high absorption glass plate is used. can do.
  • excellent solar shading performance can be obtained even when the amount of dispersion of expensive ITO fine particles is small. This greatly contributes to cost reduction.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention concerne un vitrage à revêtement anti-reflets constitué de deux couches, caractérisé en ce qu'il présente une transmissivité de la lumière d'au moins 70% et une transmissivité d'insolation égale ou inférieure à 55%, la valeur obtenue par la déduction de la transmissivité de la lumière visible du vitrage exempt du revêtement anti-reflets à partir de ladite transmissivité de la lumière visible est d'au moins 2%, et en ce qu'il contient des oxydes de fer en une quantité de 0,3 à 1 en pourcentage massique en termes de Fe2O3. Le vitrage permet un accroissement de l'absorption d'insolation correspondant à la transmissivité accrue due au revêtement anti-reflets.
PCT/JP2003/000512 2002-01-22 2003-01-22 Vitrage a revetement anti-reflets Ceased WO2003062165A1 (fr)

Applications Claiming Priority (2)

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JP2002-12560 2002-01-22
JP2002012560A JP2005298219A (ja) 2002-01-22 2002-01-22 自動車用低反射膜付きガラス板

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WO2003062165A1 true WO2003062165A1 (fr) 2003-07-31

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CN107099776A (zh) * 2017-04-21 2017-08-29 咸宁南玻节能玻璃有限公司 一种高清中性色低辐射镀膜玻璃及制备方法
CN114349359A (zh) * 2021-12-27 2022-04-15 盐城牧东光电科技有限公司 一种低反射高透光性盖板及其制作工艺

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Publication number Priority date Publication date Assignee Title
FR2907112B1 (fr) * 2006-10-16 2009-10-02 Eurokera S N C Sa Plaque vitroceramique et son procede de fabrication
CN111971258A (zh) * 2018-04-05 2020-11-20 Ａｇｃ株式会社 夹层玻璃
EP3825742A4 (fr) * 2018-07-17 2022-05-04 Agc Inc. Élément optique
JP2025520787A (ja) * 2022-06-30 2025-07-03 フーイャォ グラス インダストリー グループ カンパニー リミテッド 合わせ窓ガラス

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Publication number Priority date Publication date Assignee Title
US6068914A (en) * 1996-05-14 2000-05-30 Saint-Gobain Vitrage Glazing pane having an anti-reflection coating
JP2000256042A (ja) * 1999-03-10 2000-09-19 Nippon Sheet Glass Co Ltd 自動車用低反射ガラス物品
EP1136457A1 (fr) * 1999-09-14 2001-09-26 Asahi Glass Company Ltd. Verre stratifie
US6387515B1 (en) * 1998-12-21 2002-05-14 Saint-Gobain Vitrage Transparent substrate comprising an antireflection coating

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US6068914A (en) * 1996-05-14 2000-05-30 Saint-Gobain Vitrage Glazing pane having an anti-reflection coating
US6387515B1 (en) * 1998-12-21 2002-05-14 Saint-Gobain Vitrage Transparent substrate comprising an antireflection coating
JP2000256042A (ja) * 1999-03-10 2000-09-19 Nippon Sheet Glass Co Ltd 自動車用低反射ガラス物品
EP1136457A1 (fr) * 1999-09-14 2001-09-26 Asahi Glass Company Ltd. Verre stratifie

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107099776A (zh) * 2017-04-21 2017-08-29 咸宁南玻节能玻璃有限公司 一种高清中性色低辐射镀膜玻璃及制备方法
CN107099776B (zh) * 2017-04-21 2019-11-08 咸宁南玻节能玻璃有限公司 一种高清中性色低辐射镀膜玻璃及制备方法
CN114349359A (zh) * 2021-12-27 2022-04-15 盐城牧东光电科技有限公司 一种低反射高透光性盖板及其制作工艺
CN114349359B (zh) * 2021-12-27 2023-06-09 盐城牧东光电科技有限公司 一种低反射高透光性盖板及其制作工艺

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