WO1999025660A1 - Verre absorbant les ultraviolets/l'infrarouge, feuille de verre absorbant les ultraviolets/l'infrarouge, feuille de verre absorbant les ultraviolets/l'infrarouge recouverte d'un film colore, et verre a vitres pour vehicules - Google Patents
Verre absorbant les ultraviolets/l'infrarouge, feuille de verre absorbant les ultraviolets/l'infrarouge, feuille de verre absorbant les ultraviolets/l'infrarouge recouverte d'un film colore, et verre a vitres pour vehicules Download PDFInfo
- Publication number
- WO1999025660A1 WO1999025660A1 PCT/JP1998/005039 JP9805039W WO9925660A1 WO 1999025660 A1 WO1999025660 A1 WO 1999025660A1 JP 9805039 W JP9805039 W JP 9805039W WO 9925660 A1 WO9925660 A1 WO 9925660A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ultraviolet
- absorbing glass
- glass
- less
- infrared
- Prior art date
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- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- SCCMALBMEASKCM-UHFFFAOYSA-N diethyl bis(triethoxysilyl) silicate Chemical compound CCO[Si](OCC)(OCC)O[Si](OCC)(OCC)O[Si](OCC)(OCC)OCC SCCMALBMEASKCM-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- GYTROFMCUJZKNA-UHFFFAOYSA-N triethyl triethoxysilyl silicate Chemical compound CCO[Si](OCC)(OCC)O[Si](OCC)(OCC)OCC GYTROFMCUJZKNA-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
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
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/479—Metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
Definitions
- UV / IR absorbing glass UV / IR absorbing glass, UV / IR absorbing glass plate, UV / IR absorbing glass plate coated with colored film and window glass for vehicles
- the present invention relates to an ultraviolet-ray and infrared-absorbing glass having a green color tone, particularly a thin ultraviolet-ray-absorbing glass having a light green color tone and a high visible light transmittance suitable for automotive glass or architectural glass.
- the present invention relates to a plate, an ultraviolet-ray absorbing glass plate coated with a colored film in which a red-based colored film is formed on the ultraviolet-ray absorbing glass, and a window glass for a vehicle using the ultraviolet-ray absorbing glass plate coated with the colored film.
- the ultraviolet and infrared ray absorbing glass having a greenish color disclosed in Japanese Patent Publication No. Hei 6-88812 is expressed as a coloring component in soda-lime glass in a weight percentage of 0.65 to 1.25% Fe. 2 ⁇ 3-converted total iron oxide, 0.2 to 1.4% of Flip 6_Rei 2 or from 0.1 to 1.36% of Ce_ ⁇ 2 and 0.02 to 0.85 percent of T I_ ⁇ 2, Is contained.
- infrared ray ultraviolet absorbing glasses having a relatively light green color tone there is an infrared ray ultraviolet absorbing glass disclosed in JP-A-5-78147, and this glass is represented by weight% as a mother composition. 68 to 72% of the S I_ ⁇ 2 and, from 1.6 to 3 0% a l 2 ⁇ 3, 8. 5 ⁇ :.. L 1. 0% of C A_ ⁇ , 2.0 to 4 2% of Mg ⁇ , 12.0 to 16.0% of Na 2 ⁇ , and from 0.5 to 3.
- Infrared ultraviolet absorbing glass disclosed in JP-A-8 208 266 is 0. in% by weight as a coloring component in Soviet one da-lime-silica glass 52 to 0.63% of F e 2 ⁇ 3 all converted iron oxide, 0.9 to 2% of the total Ce_ ⁇ 2, from 0.2 to 0. 6% T I_ ⁇ 2 is contained, the F e 2 ⁇ 3 in the total iron as calculated as F e 2 0 3
- the converted amount of divalent iron is 28-38%.
- Infrared ultraviolet absorbing glass disclosed in 208254 JP is in% by weight as a base pair formation 67-75% of S I_ ⁇ 2, from 0.05 to 3 0% A i 2 ⁇ 3, from 7.0 to 1 1.0% of C aO, 2. 0 ⁇ 4.
- the coloring of ultrafine metal particles by surface plasmon has excellent heat resistance and light resistance, and has been used for coloring glass and ceramics for a long time.
- gold fine particles are formed by applying an alkoxide solution of chloroauric acid and silane on a glass substrate and then processing the solution. Wearing.
- the conventional ultraviolet and infrared absorbing and absorbing glass described in each of the aforementioned publications has the following problems.
- the infrared-ultraviolet absorption capacity is set to a range where visible light transmittance is allowed (for example, In the case of a windshield for an automobile, it is increased as much as possible by 70% or more.
- the green color tone of the glass is relatively deep, ie, 2.4 to 3.3% in terms of stimulus purity.
- pale green tones may be preferred for automotive glass, and pale green tones may be preferred for architectural glass.
- the surface of the glass plate may be coated with various coatings.
- the visible light transmittance of the glass plate is reduced. It is reduced by the coating.
- the lower limit for example, a value slightly higher than 70%
- the glass after coating will not be obtained. Since the visible light transmittance of the plate tends to be less than 70%, it may be difficult to apply a desired coating.
- the infrared-ultraviolet absorbing glass disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 5-78147 is an infrared-ultraviolet absorbing glass having a relatively light green color tone, and the visible light transmittance of this glass is also 5 mm. The maximum thickness is about 71%, which is not high.
- the infrared and ultraviolet absorbing glass disclosed in the publication has a relatively pale green color tone having an excitation purity of 5% or less, the specific excitation purity value is 3.2% or more. The green tones are not very pale.
- the JP-8 2 0 8 2 6 6 No. infrared ultraviolet absorbing glass disclosed in Japanese is relatively visible light transmittance is high infrared ultraviolet absorbing glass, 0 total iron as calculated as F e 2 ⁇ 3 . 5 2-0. containing 6 3 percent, the amount of bivalent iron as calculated as F e 2 ⁇ 3 contains 2 8-3 8% Zentetsuchu.
- This glass has a high solar absorption capacity, Although the sunlight transmittance is obtained, the visible light transmittance is 72.0 to 74.4% for 3.5 mm thickness and 71.4 to 72.9% for 5 mm thickness, which is not very high.
- the infrared and ultraviolet absorbing glass disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 9-208254 has relatively high transparency and high solar absorption, but has a visible light transmittance of 65.5 to 67 at a thickness of 5 mm. 6%, which is not high. Also, the stimulus purity is 2.9% or more, and the green color tone is not so pale. Disclosure of the invention
- the present invention solves the above-mentioned conventional problems, and has a thin greenish color tone, which is suitable as an ultraviolet and infrared absorbing light green glass having a greenish color tone, particularly a glass for automobiles or architectural glass, and has a visible light.
- An object of the present invention is to provide a window glass for a vehicle using the same.
- the ultraviolet-infrared absorbing glass according to the first embodiment of the present invention has an i ⁇ 2 of 65 to 80%, expressed in terms of% by weight,
- the ultraviolet-infrared absorbing glass plate according to the second embodiment of the present invention is an ultraviolet-infrared absorbing glass plate composed of the ultraviolet-infrared absorbing glass of the present invention, and transmits visible light measured using an A light source.
- the transmittance is 75% or more
- the sunlight transmittance is 60% or less
- the ultraviolet ray rate specified in the ISO standard is 15% or less
- the dominant wavelength measured using C is 495 to 535 nm.
- the stimulus purity measured using a C light source shall be 2.5% or less.
- the ultraviolet ray absorbing glass plate coated with the colored film according to the third embodiment of the present invention has a thickness of 30 to 300 nm, containing silicon oxide and fine gold particles on the surface of such an ultraviolet ray absorbing glass plate. It is characterized by being coated with a red coloring film.
- a vehicle window glass is a vehicle window glass including at least two glass plates joined via an intermediate layer or a space layer made of a transparent resin, At least one of the above is a colored skin-coated ultraviolet and infrared absorbing glass plate with a transmittance of 70% or less measured using A, a sun evasion rate of 70% or less, specified in IS ⁇ standards.
- the UV transmittance measured is 15% or less, and the color tone measured using the C light source is represented by a and b using the Lab3 ⁇ 4fe system, but is 1 2 ⁇ a ⁇ 4 and 1 3 ⁇ b ⁇ 3, respectively. Something is fine.
- S i ⁇ 2 is a main component forming the skeleton of glass.
- S I_ ⁇ 2 decreases the durability of the glass is less than 6 5%, dissolution of the glass becomes difficult if it exceeds 80%. Therefore, the content of Si 2 is 65-80%.
- a 1 2 0 3 is not an essential component, Ru component der to improve the durability of the glass. However dissolution of the glass becomes difficult when the content of A 1 2 Rei_3 exceeds 5%.
- the content of A 1 2 ⁇ 3 is in the range from 0 to 5%, preferably 0.1 to 2.5% range.
- Ca ⁇ is used to improve the durability of glass and to adjust the devitrification temperature and viscosity during molding. If C a ⁇ is less than 5% or exceeds 15%, the devitrification temperature increases. Therefore, the content of Ca ⁇ is 5 to 15%.
- MgO is not an essential component, it can be used to improve the durability of glass as well as CaO and to adjust the devitrification temperature and viscosity during molding. If MgO exceeds 10%, the devitrification temperature rises. If the total of 1 ⁇ 8 ⁇ and 3 ⁇ is less than 5%, the durability of the glass decreases, and if it exceeds 15%, the devitrification temperature increases. Therefore, the content of Mg ⁇ is 0 to 10%, and the total content of Mg ⁇ and CaO is 5 to 15%.
- N a 2 0 are used as glass melting accelerator.
- N a 2 C ⁇ l poor solubility promoting effect is less than 0%, N a 2 0 durability of the glass is lowered when exceeding 8% l.
- the content of N a 2 ⁇ is 1 0-1 8%.
- K 20 is not an essential component, but can be used as a glass melting accelerator like Na 2 2 . Since K 2 ⁇ raw material is more expensive than N a 2 0, it is undesirable to blend beyond 5%, is used in the range of 0 5%. The sum of the N a 2 ⁇ and K 2 ⁇ or the poor solubility promoting effect is less than 1 0%, N a 2 ⁇ and sum of K 2 0 is the durability of the glass exceeds 2 0% reduced. Therefore the total content of N a 2 ⁇ and K 2 ⁇ is 1 0-2 0%.
- S_ ⁇ 3 is a component which promotes refining of the glass.
- S_ ⁇ 3 In conventional melt method becomes insufficient refining effect is less than 0.5 0 5% or remain in the glass SO 2 generated by the decomposition exceeds 3% 0.1 as a foam, the foam by reboiled Is more likely to occur.
- the content of S_ ⁇ 3 is 0.0 5 to 0.3 percent, the desirable range is 0.0 5 to 0.1 5%.
- B 2 0 3 is not an essential component, improving the durability of the glass, the glass soluble It can be used as a component that promotes resolvability and enhances ultraviolet absorption.
- B 2 0 3 exceeds 5%, the transmittance in the visible range also decreases, the transmission color is easily strip beautiful yellowish inconvenience during molding due to volatilization of B 2 Rei_3 occurs.
- the content of B 2 ⁇ 3 is 5% 0.
- Iron oxide is present in glass in the form of F e 2 ⁇ 3 and F e 0.
- F e 2 ⁇ 3 is a component for improving the ultraviolet absorptivity with C E_ ⁇ 2 below
- F e O is a component for increasing the heat ray absorptivity.
- total iron oxide.. (T - F e 2 Os) is 0. 3 5 ⁇ 0 5 5%, F e O is from 0.08 to 0 1 5%, in terms of F e 0 / T- F e 2 ⁇ normal F e 2 ⁇ 3 3 ratio (as the amount of F E_ ⁇ when calculating the ratio of the F e OZT- F e 2 ⁇ 3 Must be in the range of 0.20 or more and less than 0.27.
- the ratio of Fe OZT—Fe 2 ⁇ 3 increases (or decreases).
- the ratio of F e 0 / T- F e 2 0 3 can be more adjusted to adjust the amount of the reducing agent.
- the content of 6 ⁇ is 0.08 to 0.12%.
- the amount of C E_ ⁇ 2 to obtain a desired ultraviolet absorbing effect 0. 8 to 1. 5% Must be in range.
- Flip 6_Rei 2 is not sufficient ultraviolet absorbing effect is less than 0.8%, 1. exceeds 5% absorption in the short wavelength side of the visible light too large, with the visible light transmittance decreases, permeation
- the color tone becomes strongly yellowish, which is not preferable.
- the content of C e 0 2 is desirably particularly 1. 0% or more and less than 1. 4%.
- T 0 2 is not an essential component, an ultraviolet absorption as with F e 2 ⁇ 3 and C e 0 2 Since it is a component that enhances the yield, the optical properties (visible light transmittance)
- T i 0 2 When the amount of T i 0 2 is large, the glass tends to take on a yellow tint.Therefore, the content of T i ⁇ 2 is set to 0 to 0.5%, but it is particularly preferable that the content is 0.15% or less. It is most preferable that the content be 0.05% or less.
- Mn_ ⁇ is not an essential component, because F e 2 ⁇ 3, F e O and C E_ ⁇ 2 are included at the same time, or adjusting the transmission color tone, the F E_ ⁇ / T-F e 2 ⁇ 3 It is an effective component for adjusting the ratio. If the amount of Mn ⁇ increases, the effect of coloring itself appears, so the upper limit of the Mn O content is 350 ppm.
- the glass of the above composition range the S n0 2 may be added in a range of 0 to 1% as a reducing agent.
- the coloring agents to which the present invention is usually used within a range not to impair the color tone of pale greenish of interest C O_ ⁇ , C r 2 O 3, N I_ ⁇ , V 2 ⁇ 5, Mo 0 3, etc. May be added at the same time, but the addition of a colorant is not preferred because it increases the color tone and reduces the visible light transmittance.
- the ultraviolet / infrared absorbing glass of the present invention preferably has the following characteristics at any thickness of 3.25 to 6.25 mm.
- Visible light transmittance (Ya) measured in the wavelength range of 380 to 770 nm using A light source is 75% or more, especially 77.5% or more
- the dominant wavelength (D w) measured in the wavelength range of 380 to 770 nm using a C light source is 495 to 535 nm
- the chromaticity represented by a and b is 1 ⁇ a ⁇ — 3 and 1 l ⁇ b ⁇ 4, respectively, using the transmission color tone Lab color system measured using a C light source. Especially-7 ⁇ a-5, 1 ⁇ b ⁇ 3
- ⁇ UV transmittance (Tuv) specified in ISO 90500 is 15% or less
- the ultraviolet / infrared absorbing glass plate of the present invention is composed of the ultraviolet / infrared absorbing glass having the above composition, and preferably has a thickness of 3.25 to 6.25 mm, and has the following optical characteristics.
- Visible light transmittance (Ya) measured in the wavelength range of 380 to 770 nm using A light source is 75% or more, preferably 77.5% or more.
- the dominant wavelength (D w) measured in the wavelength range of 380 to 770 nm using a C light source is 495 to 535 nm
- the chromaticity represented by a and b is preferably _8 ⁇ a ⁇ _3, —l ⁇ b, using the transmission color tone Lab color system measured using a C light source. ⁇ 4, more preferably 1 7 ⁇ a—5, 1 ⁇ b ⁇ 3
- ⁇ UV transmittance (Tuv) specified in ISO 90500 is 15% or less
- ⁇ Stimulation purity (Pe) measured using a C light source is 2.5% or less, preferably 2.0% or less
- the ultraviolet-ray absorbing glass plate coated with the colored film of the present invention comprises a surface of such an ultraviolet-ray absorbing glass plate of the present invention coated with a red colored film having a thickness of 30 to 300 nm containing silicon oxide and fine gold particles. It was done.
- This reddish colored film is colored by the surface plasmon absorption of the fine gold particles inside, but the absorption area in the spectral absorption characteristics shifts and the dish tone changes according to the value of the refractive index of the matrix surrounding the fine gold particles. I do.
- the colored film exhibiting a red color according to the present invention has a thickness of 30 to 30 Onm in which ultrafine gold particles are dispersed in a matrix containing silicon oxide as a main component in consideration of durability and the like. Is used.
- This coating is expressed in terms of% by weight, and more than 50% and less than 95% of silicon oxide, at least one selected from the group consisting of zirconium oxide, tantalum oxide, titanium oxide, aluminum oxide and cerium oxide, 0 to 30%, As a colored child It is preferable to contain 5 to 20% of all gold as a main component.
- the colored film may be formed on both surfaces of the glass substrate, but is usually formed on one surface of the glass substrate. Each component of the composition of the colored film will be described below.
- Silicon oxide is necessary as a low-refractive-index matrix material to fix fine gold particles and make the color of ultrafine gold particles red. Further, it is necessary to lower the reflectance of the film. If the content is too small, the reflectance of the film becomes too high, or the surface plasmon absorption of the fine gold particles shifts to a longer wavelength, and the colored film becomes more bluish. In addition, even if it is too much, coloring becomes less effective. Therefore, the content of San ⁇ containing not more than 95% exceeded 50% by weight percent Teng to S i 0 2, preferably 6 0-9 3%.
- the red-colored film according to the present invention may include at least one selected from the group consisting of zirconium oxide, tantalum oxide, titanium oxide, aluminum oxide and cerium oxide for adjusting the color tone. preferable. If the amount of these color tone adjusting components is too large, the reflectance of the film becomes too high. Therefore, the total content of these color tone adjusting components is preferably 0 to 30%, more preferably 0 to 15%.
- the fine gold particles are necessary for coloring the red-based colored film to a bright color. If the amount is too large, the fine gold particles float on the surface of the film, and the durability of the film decreases. Conversely, if the amount of the fine gold particles is too small, sufficient coloring cannot be obtained. Therefore, the content of the gold fine particles is preferably 5 to 20% by weight, more preferably 7 to 17%.
- the thickness of the red-colored film is too small, sufficient coloring cannot be obtained.On the other hand, when the thickness is too large, the film strength is reduced and cracks are easily formed. Is preferably 50 to 250 nm, more preferably 50 to 200 nm.
- the refractive index of the red membranous is too high, the visible light reflectance of the coated UV-infrared absorbing glass plate becomes high, which is not desirable in appearance.
- the composition is adjusted to have a refractive index, more preferably 1.40 to: L.60, and still more preferably 1.45 to 1.55.
- Such a red-based coating is made of a compound forming fine gold particles, a silicon oxide raw material, and, if necessary, a raw material of zirconium oxide, tantalum oxide, titanium oxide, aluminum oxide and cerium oxide, and other additives. After applying a solution consisting of a solvent on a glass substrate It is obtained by drying and drying.
- the silicon oxide raw material is not particularly limited as long as it can form a transparent and high-strength film by a sol-gel method and has excellent stability. Specific examples include the following.
- metal alkoxides are preferable as the raw material for the elemental iS acid, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Further, a condensate of these dimers or more (n ⁇ 2) or a mixture of a fiber composite is also used in the present invention.
- Condensate with monomer ( ⁇ 1)
- Alkyl trialkoxysilanes in which the " ⁇ " portion of the alkoxy group of the silicon alkoxide is substituted with an alkyl group can also be used.
- an alkoxy group may be a methyl group, an ethyl group, a propyl group, a butyl group, a 2-butyl group.
- Linear or branched alkyl groups such as ethylbutyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group, aryl group, r-methacryloxypropyl group, and acryloxy group.
- Alkenyl groups such as propyl group; aryl groups such as phenyl, tolyl, and xylyl groups; aralkyl groups such as benzyl group and phenethyl group; or mercaptopropyl group, archloropropyl group, and Those substituted by a minopropyl group and the like can be exemplified.
- Raw materials for the fine gold particles include, in addition to chlorides such as chloroauric acid, gold sulfides, cyano complex salts, halogeno complex salts, thiolate salts, thiosulfato complex salts, sulfite complex salts, and gold acid, organic metal compounds, etc. Can be used. Of these, chlorides are preferred due to their stability and availability. Auric acid is preferred.
- titanium alkoxide As a raw material of titanium oxide, an organic compound of titanium such as titanium alkoxide, titanium acetylacetonate, and titanium carboxylate is preferably used.
- titanium alkoxide may be converted into acetyl acetonate with acetyl acetone, or commercially available titanium acetyl acetonate may be used. Furthermore, it is conceivable to use carboxylate.
- Raw materials for zirconium oxide include tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-propoxy zirconium, tetraisopropoxy zirconium isopropanol complex, tetraisobutoxy zirconium, tetrazirconium N-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-t-butoxyzirconium, etc. can be conveniently used.
- An alkoxide of a zirconium halide such as zirconium monochloride trialkoxide or zirconium dichloride dialkoxide, in which the alkoxy group of the compound represented by the general formula (4) is replaced by a halogen group, can also be used.
- a zirconium alkoxide obtained by chelating the above zirconium alkoxide with a ⁇ -ketoester compound is also preferably used.
- ketoester conjugates of chelating agents for this chelate ⁇ include CH 3 COC Hs C OOR (where R is such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate) Acetoacetate represented by CH 3 , C 2 H 5 , C 3 H 7 , or C 4 H 9 ).
- R is such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate
- Acetoacetate represented by CH 3 , C 2 H 5 , C 3 H 7 , or C 4 H 9 acetoacetate alkyl esters, particularly methyl acetoacetate and ethyl acetoacetate, are preferred because they can be obtained relatively inexpensively.
- Other chelating agents, for example, zirconium alkoxide chelated with acetylaceton are insoluble in solvents such as alcohols, and thus precipitate, making it impossible to prepare a coating solution.
- alkoxy zirconium oxide in which at least one of the above-mentioned alkoxy groups of the zirconium alkoxide is replaced by an organic acid such as acetic acid, propionic acid, butanoic acid, acrylic acid, methacrylic acid, and stearic acid. It is also possible to use organic acids.
- a tantalum alkoxide—an organic tantalum compound or the like is preferable.
- cerium oxide As a raw material of cerium oxide, cerium alkoxide, cerium acetyl acetate, cerium carboxylate, and other cerium arsenic compounds can be suitably used.
- cerium-free compounds such as nitrates, chlorides and sulfates can also be used, but cerium nitrates and cerium acetyl acetate are preferred in view of stability and availability.
- aluminum alkoxide ⁇ organic aluminum compound, inorganic aluminum compound and the like are preferable.
- the alkoxides may be inorganic acids such as hydrochloric acid, sulfuric acid and sulfuric acid. Acids and organic acids such as acetic acid, oxalic acid, formic acid, propionic acid, and ⁇ -toluenesulfonic acid are used.
- the amount used is from 0.01 to 2, preferably from 0.05 to 1.5, in a molar ratio to the metal alkoxide.
- water is required for the hydrolysis of the metal alkoxide, and the amount of water used is preferably in the range of 0.01 to 10 mol of water per 1 mol of the metal alkoxide.
- the reddish feM ⁇ in the present invention is, as described above, a color tone of at least one of oxygen, italium, and, if necessary, zirconium oxide, tantalum oxide, titanium oxide, aluminum oxide, and cerium oxide.
- a small amount of, for example, 15% by weight or less of boron oxide having the same function as silicon oxide may be contained, and bismuth oxide, it ⁇ lead acid,
- they may be contained in a total of 15% by weight or less.
- the composition for red-colored TO formation as a coating liquid is obtained by dissolving the above-mentioned red-colored composition raw materials in an organic solvent, respectively, and mixing them at a ratio of.
- the appearance and the mixing ratio of the above-mentioned red-colored i-forming materials are determined according to the miscibility of the solvent used with each of the raw material compounds, the stability of the red-colored-forming composition, and the color tone of the red-colored film. It is preferable to determine in consideration of abrasion resistance, chemical durability and the like.
- the organic solvent used here depends on the method of coating the key material for forming a reddish color when forming the reddish color. For example, when forming a red-colored film by a gravure coating method, a flexographic printing method, or a roll coating method, a solvent having a low evaporation rate is preferable. This is because a solvent that evaporates quickly evaporates before sufficient leveling is performed.
- Evaporation of the solvent is targeted by the relative evaporation index, which is 100 for that of butyl acetate.
- Solvents having this value of 40 or less are classified as solvents having extremely slow evaporation, and such solvents are preferred as organic solvents for the gravure coating method, flexographic printing method, and roll coating method.
- ethyl cellosolve, butyl cellosolve, cellosolve acetate, diethylene glycol monoethyl ether, hexylene glycol, diethylene glycol, ethylene glycol, tripropylene glycol, diacetone alcohol, tetrahydrofurfuryl alcohol and the like can be mentioned.
- the solvent of the coating liquid used in the present invention desirably contains at least one such solvent, but a plurality of the above solvents may be used to adjust the viscosity, surface tension, etc. of the coating liquid. Absent.
- solvents having a high evaporation rate and a relative evaporation rate exceeding 100 for example, methanol (relative evaporation index: 310), ethanol (relative evaporation index: 340), and n-propanol (relative evaporation index: 300)
- a solvent such as 0) may be added to a solvent having a relative evaporation rate index of 40 or less.
- the coating method used in the present invention is not particularly limited, but examples thereof include a spin coating method, a dip coating method, a spray coating method, and a printing method.
- Printing methods such as the gravure coating method, flexographic printing method, roll coating method, and screen printing method have a high wettability and the use efficiency of the red coating composition for coating is high.
- the red dress according to the present invention is obtained by applying a red dressing material on a glass substrate by the above coating method, and then oxidizing at 100 to 400 ° C. for 5 to 200 minutes. After that, the film is formed into a thin film having a thickness of 30 to 300 nm by heating at 500 to 700 ° C. or higher for 10 seconds to 5 minutes.
- the fine gold particles contributing to coloring are formed by the above-mentioned drying, and are stabilized by the above-mentioned baking.
- an ultraviolet- and infrared-absorbing glass plate with a colored film coated on only one surface of a glass substrate is used for a vehicle window such as an automobile or a building window
- a thin surface is required to reduce damage to the colored film. It is preferable to install it so that it is on the inside of the car (indoor side) (in other words, the glass surface on which the light is not covered is on the outside of the car).
- the emissivity of the coated UV-infrared absorbing glass plate is too high, especially the approximate reflectance of the glass surface where the jacket is not coated, the glass is glaring when viewed from outside or from Therefore, it is preferable to select a coating composition such that the visible light reflectance, particularly the reflectance on the glass surface side, is 10.0% or less.
- the coated feJM-coated ultraviolet / infrared absorbing glass plate of the present invention is used for the transmission color tone measured using a C light source.
- the chromaticity represented by is 2 ⁇ a ⁇ 4, and 3 ⁇ b ⁇ 3, and the lightness represented by L is 40 ⁇ L ⁇ 90.
- the ⁇ 2 ⁇ a ⁇ 2,-2 ⁇ b ⁇ 2 and the brightness is 50 ⁇ L ⁇ 90.
- the ⁇ ⁇ of the transmitted color tone is-1.
- the brightness is preferably 50 ⁇ L ⁇ 90, and most preferably, the chromaticity of the transmission color tone is-0.5 ⁇ a ⁇ 0.5, — 0.5 ⁇ b ⁇ 0.5, and the brightness is 50 ⁇ L ⁇ 90.
- the ultraviolet ray infrared absorbing glass plate coated with the colored film has an ultraviolet transmittance (Tuv) of 15% or less, particularly 12% or less, especially 10% or less, as specified in ISO 950, and a sunlight transmittance of (Tg) is preferably 60% or less.
- Tuv ultraviolet transmittance
- Tg sunlight transmittance
- the colored infrared absorbing glass plate of the present invention is used as an automobile window glass plate, in particular, the color tone reflected from the outside of the vehicle, that is, as viewed from the glass surface side on which the marrow is not covered.
- the reflection color tone should be close to medium color.
- the reflection be in the range of 4.0 ⁇ a ⁇ 4.0, -5.0 ⁇ b ⁇ 3.0, and the particularly preferred chromaticity of the reflected color is 3.03.0 ⁇ a ⁇
- the range is 3.0, -3.0 ⁇ b ⁇ 3.0.
- the visible light reflectance (Rg) from the glass surface side and the visible reflectance (Rg) from the reddish colored film surface side are each preferably 10% or less.
- the coated ultraviolet-infrared absorbing glass plate of the present invention has a thickness of 3.25 to 6.25 mm, a transmittance of 70% or less, a solar transmittance of 70% or less, and a UV thigh ratio of 1%. It is preferable that the chromaticity of the transmitted color tone is 1 ⁇ 2 ⁇ a ⁇ 4, ⁇ 3 ⁇ b ⁇ 3.
- the outside infrared absorbing glass plate of the present invention may be a different glass plate (a colored or non-colored glass plate not covered with a dressing, and a colored or uncoated ultraviolet infrared absorbing glass plate).
- the same kind of glass plate may be used) through a film of an intermediate layer having a thickness of about 2 to 2.0 mm made of a transparent resin material such as polyvinyl butyral or polyester, and preferably the red They can be used as a laminated glass plate by bonding them together so that the system coloring film is on the inside (ie, facing the film of the intermediate layer).
- the outer line absorbing glass plate and the other glass plate are arranged at an interval (for example, 0.1 to 3 mm), preferably such that the reddish clothing is on the inside.
- the surrounding area is sealed with an airtight material, and the inner space is filled with dry air or gas or a high degree of vacuum is used, so that it can be used as a laminated glass plate (double glazing unit).
- the laminated glass sheet or laminated glass sheet has a visible radiation rate (Ya) of 70% or more, a solar rate (Tg) of 70% or less, and an ISO 9
- the UV transmittance (Tuv) specified in 0500 is 15% or less, and the transmission color tone measured using a C light source is represented by &, b using the & 13 color system.
- the chromaticity is preferably 2 ⁇ a ⁇ 4 and 1 ⁇ 3 ⁇ b ⁇ 3, respectively, and such a joined body is particularly suitable as a window glass for vehicles.
- the joined glass plates preferably have a thickness of 1.0 to 3.5 mm, particularly 1.0 to 2.5 mm.
- a curved fiber-shaped colored fiber of the present invention having a thickness of about 2.5 sculptures and a sculpture size, and a red-colored garment of the same size and shape as this are formed.
- the ultraviolet-infrared absorbing glass plate of the present invention is not overlapped with a polyvinyl butyral film with a thickness of about 0.7 mm therebetween so that the upper surface faces the polyvinyl butyral film.
- This laminated glass plate can be formed by a known bending and laminated glass process, using the above-mentioned uncoated bent cover-like ultraviolet and infrared absorbing glass plate and ultraviolet and infrared absorbing glass plate as starting materials. .
- the laminated glass sheet is particularly suitable as a vehicle front door window (side window next to the driver's seat) or front window.
- Visible light transmittance Ya: JISR3106 (measured using A light source)
- Principal wavelength JISZ8701 (measured using C light source)
- JIS Z8730 (measured using C light source) Reflected chromaticity (a, b): JISZ8722, JISZ8730 UV transmittance (Tuv): ISO 950
- the glass was polished to a thickness of about 5.0 mm and its optical properties were measured.
- the transmission color tone measured using the C light source is represented by chromaticity a and b according to the La b color system, and in all the examples, the value of a is 18 to 13 and the value of b is __________________________ For Examples 2 to 5, the value of a was 17 to -5 and the value of b was 1-3.
- Example 2 In the same manner as in Example 1, five kinds of glass raw materials were prepared, heated and melted to obtain a glass having a thickness of about 10 mm.
- composition of this glass is as shown in Table 3.
- the composition in the table is expressed in ppm.
- the values are expressed in% by weight, except for those shown in FIG.
- Table 4 shows the Fe ⁇ content, the Fe ⁇ content (Fe O / T-Fe Os) relative to the total iron oxide content, and the optical property values of each comparative example.
- the thickness of the sample for which the optical properties were measured was about 5 mm for Comparative Examples 1 and 3 to 5 and about 4 mm for Comparative Example 2.
- Comparative Example 1 is Fe O / T -F e 20 3 ratio is greater than the present invention range
- Comparative example 2 is the case the total iron oxide, is C E_ ⁇ 2 and F E_ ⁇ content is outside the scope of the present invention
- Comparative example 3 is total iron oxide a case F E_ ⁇ content and Fe_ ⁇ _ZT_F e 2 ⁇ 3 ratio is outside the range of the present invention
- Comparative example 4 is total iron oxide, Ce_ ⁇ 2, F E_ ⁇ content and FeO / TF e 2 ⁇ 3 ratio is out of the range of the present invention
- Comparative Example 5 is C e ⁇
- the composition (% by weight) of the glass substrate used in the following Examples and Comparative Examples and The optical characteristics are as shown in Table 5 below.
- the thickness of the glass substrate was 4.8 mm for glass substrate 1, 4.9 mm for glass substrate 2, and 4.80 mm for glass substrate 3.
- titanium oxide stock solution B To 1 mol of titanium isopropoxide being stirred, 2 mol of acetylacetone was added dropwise via a dropper. This solution was used as titanium oxide stock solution B. This stock solution B corresponds to 1 6.5% by weight at T I_ ⁇ 2 solids concentration.
- cerium nitrate stock solution A titanium oxide stock solution B, silicon oxide stock solution C, aluminum oxide stock solution D, boron oxide stock solution E and gold stock solution F were mixed in the amounts shown in Table 6, and finally mixed with ethyl acetate solution. If necessary, trimethylolpropane acrylate ethylene oxide 6 was added in an amount shown in Table 6 to prepare a coating solution 1 G to 1 K.
- Table 6 Example Coating solution stock solution A stock solution B stock solution C stock solution D stock solution E stock solution F EC E06
- the resulting reddish garments showed good results in terms of chemical resistance and abrasion resistance.
- the obtained reddish colored infrared ray absorbing glass plate has a visible light rate (Ya) of 70% or more, an ultraviolet rate (Tuv) of 12% or less, a solar radiation rate (Tg) of 60% or less, 9 % or less of the glass surface Friendly 3 ⁇ 41 ⁇ Iritsu (R g), 9% or less of the film surface friendly view) had a 1 Iritsu (Rg).
- Table 8 Example film mm. (% By weight) Refractive index
- the coating liquids L and M prepared above were spin-coated at 1000 rpm or 3000 rpm for 15 seconds on one surface of green colored glass substrate ⁇ with a thickness of 4.9 mm and dimensions of 10 Omm x 100 mm as shown in Table 11. Was. After begging, processing was performed at 250 for 2 hours to deposit Tetsuko Kin. Further, the coating was performed at 720 ° C. for 120 seconds to obtain a glass plate coated with a colored film.
- the coating liquid, coating spin rate, film composition, wisteria, and refractive index of these glass plates are shown in Table 11, and the ratio (Ya), thigh ratio (T g), and ultraviolet transmittance are shown in Table 11. (Tuv), and & 1) ⁇ , Ii ⁇ 1 ⁇ degrees (a 2 + b 2 ) i 2 are shown in Table 12, and the visible reflectance and the reflectance when the light is projected from the glass surface side respectively are shown in Table 12.
- A, b glass surface reflection ⁇ ) due to light La b3 ⁇ 4 ⁇ , and the approximate reflectance (film surface visible light reflectance) and color of the reflected light Lab display when light is projected from the surface side, respectively.
- Table 13 shows the degrees a and b (JM reflection color ⁇ ).
- the coated glass plate obtained showed a visible light efficiency of 70% or more, and the thigh color tone was gray, but the ultraviolet i ⁇ ii rate (Tuv) was 21.
- Example 7 L 1 1.5 g of the gold stock solution F prepared in the above was added and mixed and stirred to prepare a coating solution.
- This coating solution was spin-coated on a green colored glass substrate (3) having a size of 4.80 mnn to 100 mm X 100 mm at a rotation speed of 2000 rpm for 15 seconds. After J, the mixture was treated at 250 ° C for 2 hours to precipitate gold fine particles. This was further placed in a heating furnace, heated to 610 ° C in 2 hours, allowed to stand for 10 minutes, and then cooled naturally to obtain a glass sheet with a coating.
- the silicon oxide stock solution C, the oxidized zirconium stock solution M, the cobalt oxide stock solution N, and the gold M solution F were each taken and mixed as shown in Castle 15, and finally, the ethyl acetate solution (EC) was shown in Table 15. The indicated amount was added to prepare a coating solution.
- This coating solution was spin-coated at 2500 rpm on one surface of a green colored glass substrate having a thickness of 4.8 mm and dimensions of 10 Omm ⁇ 100 mm. After sculpture, it was treated at 250 ° C for 2 hours to deposit gold thighs. Further, baking was performed at 720 ° C for 120 seconds to obtain a glass plate having a colored film. Table 15 Stock solution c Stock solution F Stock solution M Stock solution N EC
- the obtained clothes showed good results in terms of chemical resistance and abrasion resistance.
- the obtained coated glass plate has a visible ray rate (Ya) of 70% or more, an ultraviolet ray rate (Tuv) of 12% or less, a thick
- the film had an emissivity of 9% or less and an emissivity of 5%.
- Table 16 Example film (% by weight) mm Refractive index
- the ultraviolet and infrared absorbing glass and the ultraviolet and infrared absorbing glass plate of the present invention a relatively high visible light transmittance is maintained without giving an excessively dark green color tone, and excellent ultraviolet absorption is achieved. It is possible to provide an ultraviolet and infrared ray absorbing glass and an ultraviolet and infrared ray absorbing glass plate having an appropriate infrared absorbing ability. Further, since the ultraviolet and infrared absorbing glass and the ultraviolet and infrared absorbing glass plate of the present invention maintain a relatively pale green color tone and a high visible light transmittance, a case where a light color tone is preferred or a coating is applied. It is particularly useful as window glass for automobiles and as glass for construction.
- a coated ultraviolet-absorbing glass plate having a high luminosity, a neutral gray color tone and excellent ultraviolet absorption performance is obtained.
- a good vehicle window glass can be obtained using a glass plate.
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98951746A EP1029827A4 (en) | 1997-11-13 | 1998-11-10 | ULTRAVIOLET / INFRARED ABSORBENT GLASS, ULTRAVIOLET / INFRARED ABSORBENT GLASS PANEL, ULTRAVIOLET / INFRARED ABSORBENT GLASS PANEL COATED WITH A COLORED FILM, AND VEHICLE GLAZING |
US09/437,229 US6340646B1 (en) | 1997-11-13 | 1999-11-10 | Colored film-coated ultraviolet/infrared absorbent glass plate and window glass of vehicle |
US09/785,406 US6468934B2 (en) | 1997-11-13 | 2001-02-20 | Ultraviolet/infrared absorbent glass |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9/312520 | 1997-11-13 | ||
JP31252097 | 1997-11-13 | ||
JP9/316852 | 1997-11-18 | ||
JP31685297 | 1997-11-18 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/437,229 Continuation US6340646B1 (en) | 1997-11-13 | 1999-11-10 | Colored film-coated ultraviolet/infrared absorbent glass plate and window glass of vehicle |
Publications (1)
Publication Number | Publication Date |
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WO1999025660A1 true WO1999025660A1 (fr) | 1999-05-27 |
Family
ID=26567203
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/005039 WO1999025660A1 (fr) | 1997-11-13 | 1998-11-10 | Verre absorbant les ultraviolets/l'infrarouge, feuille de verre absorbant les ultraviolets/l'infrarouge, feuille de verre absorbant les ultraviolets/l'infrarouge recouverte d'un film colore, et verre a vitres pour vehicules |
Country Status (3)
Country | Link |
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US (2) | US6340646B1 (ja) |
EP (1) | EP1029827A4 (ja) |
WO (1) | WO1999025660A1 (ja) |
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US6391400B1 (en) | 1998-04-08 | 2002-05-21 | Thomas A. Russell | Thermal control films suitable for use in glazing |
US7632767B2 (en) | 2005-03-22 | 2009-12-15 | Nippon Sheet Glass Company, Limited | Infrared absorbent green glass composition and laminated glass including the same |
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US6391400B1 (en) | 1998-04-08 | 2002-05-21 | Thomas A. Russell | Thermal control films suitable for use in glazing |
US7632767B2 (en) | 2005-03-22 | 2009-12-15 | Nippon Sheet Glass Company, Limited | Infrared absorbent green glass composition and laminated glass including the same |
JPWO2020170711A1 (ja) * | 2019-02-19 | 2021-12-23 | セントラル硝子株式会社 | ヘッドアップディスプレイ装置 |
JP7328575B2 (ja) | 2019-02-19 | 2023-08-17 | セントラル硝子株式会社 | ヘッドアップディスプレイ装置 |
Also Published As
Publication number | Publication date |
---|---|
US20010018393A1 (en) | 2001-08-30 |
EP1029827A4 (en) | 2003-07-09 |
US6468934B2 (en) | 2002-10-22 |
EP1029827A1 (en) | 2000-08-23 |
US6340646B1 (en) | 2002-01-22 |
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