CN113692396A - 涂覆有薄层堆叠体和搪瓷层的玻璃片材 - Google Patents
涂覆有薄层堆叠体和搪瓷层的玻璃片材 Download PDFInfo
- Publication number
- CN113692396A CN113692396A CN202180002005.6A CN202180002005A CN113692396A CN 113692396 A CN113692396 A CN 113692396A CN 202180002005 A CN202180002005 A CN 202180002005A CN 113692396 A CN113692396 A CN 113692396A
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- China
- Prior art keywords
- layer
- enamel
- stack
- glass sheet
- material according
- 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.)
- Granted
Links
- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 109
- 239000011521 glass Substances 0.000 title claims abstract description 107
- 239000010409 thin film Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims description 219
- 239000000049 pigment Substances 0.000 claims description 28
- 239000011229 interlayer Substances 0.000 claims description 21
- 238000005452 bending Methods 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 150000004767 nitrides Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 238000007650 screen-printing Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 239000002346 layers by function Substances 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000181 anti-adherent effect Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 230000009970 fire resistant effect Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000006133 sodium aluminosilicate glass Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 20
- 238000010304 firing Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007547 defect 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
- 239000003085 diluting agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- 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
- B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
- B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
- B32B17/10284—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on intermediate layer
-
- 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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3655—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing at least one conducting layer
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/001—Double glazing for vehicles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/002—Windows; Windscreens; Accessories therefor with means for clear vision, e.g. anti-frost or defog panes, rain shields
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/003—Rear seat windscreens
-
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Abstract
本发明的主题是一种包含玻璃片材的材料，该玻璃片材在其面之一的至少一部分上涂覆有薄层堆叠体，所述堆叠体在其表面的至少一部分上涂覆有不包含铋的搪瓷层，所述搪瓷层涂覆有不粘层。
Description
本发明涉及包括涂覆有薄层堆叠体和搪瓷层的玻璃片材的材料的领域。此类材料特别旨在加入用于机动车辆的弯曲层压窗玻璃中，例如用于车顶或挡风玻璃。
层压窗玻璃是其中两个玻璃片材通过层压中间层粘合性结合的窗玻璃。后者特别地允许在发生破裂时保留玻璃碎片，而且还提供其他功能，特别是在防止破裂和进入或改善声学性质方面。
这些窗玻璃通常包含各种类型的旨在赋予不同性质的涂层。
搪瓷层，通常黑色和不透明的，通常被沉积在窗玻璃的一部分上，通常呈外围条带的形式，旨在隐藏用于将窗玻璃附接和定位在车身窗口聚合物密封件和保护其免受紫外线辐射。搪瓷区域还隐藏了用于连接内部后视镜和各种连接器和传感器的区域。
在层压窗玻璃中，这些搪瓷层通常被布置在面2上，所述面通常从旨在被定位在车辆外侧的面开始编号。因此，面2是与层压中间层接触的面。从车辆外部看，搪瓷层的美学外观对汽车制备商特别重要。搪瓷通常通过在高于500℃下焙烧包含玻璃料和颜料的组合物而获得。玻璃料由低熔点玻璃微粒组成，其在焙烧热处理的作用下软化并粘附在玻璃片材上。由此，形成了一个通常不透明的矿物层，具有高耐化学性和机械性，它完美地粘附在玻璃上，同时保持颜料颗粒。焙烧步骤通常与玻璃片材的弯曲同时进行。
在制备层压窗玻璃的背景下，窗玻璃的两个玻璃片材一起进行弯曲，其中旨在被定位在车辆内部的玻璃片材通常布置在承载搪瓷的另一玻璃片材上方。这时，搪瓷必须具有不粘性质，以防止在弯曲期间两个玻璃片材之间的任何粘合。为此，通常使用含铋的搪瓷，即由含氧化铋的玻璃料获得的搪瓷。
通常呈薄层堆叠体形式的涂层也可以存在于层压窗玻璃的玻璃片材上。它可以特别是导电层，其可以提供两种类型的功能。一方面，当提供电流源时，导电层可以消散通过焦耳效应产生的热。它这时是加热层，例如用于除霜或除雾。另一方面，由于它们反射红外辐射，这些层具有阳光控制或低辐射性质。这时，这些层因为通过减少用于加热或空调的消耗，改善热舒适性或节省能源而受到重视。这些层的堆叠体通常被布置在层压窗玻璃的面3上，因此也与层压中间层接触。
然而，可以有益的是，在下文将详细描述的一些情况中，在同一玻璃片材上并因此在所讨论的玻璃片材的同一面上具有搪瓷层和薄层堆叠体，以便在层压窗玻璃内部保护这些涂层。
然而，已经观察到，当涂覆有薄层堆叠体的玻璃片材必须提供含有铋的搪瓷层(因此是不粘的)时，在弯曲期间在堆叠体和搪瓷之间发生不希望的相互作用，尤其导致搪瓷的美学外观变差。已经特别地观察到，当堆叠体包含至少一个氮化物层时，在搪瓷和堆叠体之间的界面附近在搪瓷内形成气泡，导致搪瓷附着力的显著降低，改变了光学外观其(特别是玻璃一侧，即与搪瓷相反的一侧的颜色)并降低其耐化学性，尤其是对耐酸性。
已经提出了针对该问题的多种解决方案。
可以例如通过研磨剂预先去除在要沉积搪瓷层的位置处的薄层堆叠体，以便将搪瓷沉积为与玻璃片材直接接触并且防止搪瓷层和薄层堆叠体之间的任何粘附问题。然而，机械研磨产生可见的划痕，包括在搪瓷层上。
申请WO2014/133929提出了使用特殊玻璃料用于搪瓷的思想，该玻璃料在焙烧期间能够溶解薄层堆叠体以直接附接到玻璃上。然而，这样的方法是昂贵的。
申请WO2019/106264则提出通过在堆叠体和包含铋的搪瓷之间添加氧化物层来改进薄层堆叠体。
本发明的目的是针对上述问题提出一种更简单且成本更低的解决方案。
为此，本发明的主题是一种包含玻璃片材的材料，该玻璃片材在其面之一的至少一部分上涂覆有薄层堆叠体，所述堆叠体在其表面的至少一部分上涂覆有不包含铋的搪瓷层，所述搪瓷层涂覆有不粘层。
本发明的另一个主题是一种获得根据本发明的材料的方法，包括以下步骤：
-提供一种玻璃片材，在其面之一的至少一部分上涂覆有薄层堆叠体，然后
-在薄层堆叠体的表面的至少一部分上沉积不含铋的搪瓷层的步骤，然后
-在所述搪瓷层上沉积不粘层的步骤。
本发明的另一个主题是一种弯曲层压窗玻璃，特别地用于机动车辆的挡风玻璃或车顶，其包括根据本发明的材料，该材料通过层压中间层粘合地连接到附加玻璃片材上，使得搪瓷层和薄层堆叠体面向所述中间层，特别地在窗玻璃的面2上。
最后，本发明的一个主题是一种获得如前文所定义的弯曲层压窗玻璃的方法，包括以下步骤：
- 提供根据本发明的材料或根据前述方法获得的材料和附加玻璃片材，然后
- 使该材料和附加玻璃片材同时弯曲的步骤，然后
- 通过层压中间层将所述材料与附加玻璃片材层压的步骤，使得搪瓷层和薄层堆叠体朝向所述中间层。
与上述申请WO2014/133929中提出的相反，薄层堆叠体不会因搪瓷的沉积而退化。因此，根据本发明的材料以叠置方式具有薄层堆叠体和搪瓷层，后者不与玻璃片材接触。
使用不含铋的搪瓷层允许防止在弯曲期间发生任何不希望的相互作用，特别是与包括至少一个基于氮化物的层的薄层堆叠体的相互作用。然而由于这些搪瓷不能防止在弯曲期间在两个玻璃片材之间的粘合，所以在搪瓷层上设置了不粘层。
“不粘”层旨在表示在弯曲期间能够阻止两个玻璃片材粘合的层。
玻璃片材可以是平坦的或弯曲的。在沉积薄层堆叠体和随后的搪瓷层时，玻璃片材通常是平坦的，然后被弯曲。因此，玻璃片材在根据本发明的材料(中间产品)中通常是平坦的并且在根据本发明的弯曲层压窗玻璃(成品)中是弯曲的。
玻璃典型地是硅钠钙玻璃，但也可以是其他玻璃，例如硼硅酸盐或铝硅酸盐玻璃。玻璃片材优选通过浮法，即通过将熔融玻璃浇铸到熔融锡浴上的方法获得。
玻璃片材可由透明玻璃或有色玻璃制成，优选由有色玻璃，例如绿色、灰色或蓝色玻璃制成。为此，玻璃片材的化学组成有利地包含0.5至2％重量含量的氧化铁。它还可以包含其他着色剂，例如氧化钴、氧化铬、氧化镍、氧化铒、或硒。
玻璃片材优选具有在0.7-19mm，特别地1-10mm，特别地2-6mm，甚至2-4mm范围内的厚度。
玻璃片材的横向尺寸应根据打算将它包括在其中的层压窗玻璃的横向尺寸进行调整。玻璃片材优选具有至少1平方米的表面积。
玻璃片材优选在该玻璃片材的面的至少70%，特别地至少90%，甚至整个表面上涂覆有薄层堆叠体。实际上，某些区域可以没有被涂覆以特别设置允许波通过的连通窗。
堆叠体优选在其表面的2至25％，特别地3至20％，甚至5至15％上涂覆有搪瓷层。搪瓷层优选包括周边条带，即在其自身上方再封闭的条带，其在玻璃片材周边的任何点处向玻璃片材内部延伸一定宽度，通常在1至20cm之间。
不粘层优选覆盖整个搪瓷层。有利地，不粘层仅涂覆搪瓷层；这时，它不存在于未涂覆有搪瓷层的区域中。
薄层堆叠体优选地与玻璃片材接触。搪瓷层优选地与薄层堆叠体接触。不粘层优选与搪瓷层接触。在本文中，薄层堆叠体、搪瓷层和不粘层统称为“涂层”。根据本发明的材料优选由这些涂层组成。
在本文中，“接触”旨在表示物理接触。表述“基于”优选旨在表示所讨论的层包含按重量计至少50％，特别地60％，甚至70％，甚至80％或90％的所考虑的材料的事实。该层甚至可以基本上由这种材料组成或由这种材料组成。“基本上由……组成”应当理解为意味着该层可以包含对其性质没有影响的杂质。术语“氧化物”或“氮化物”不必然意味着氧化物或氮化物是化学计量的。事实上，它们可以是亚化学计量的、超化学计量的或化学计量的。
堆叠体优选包括至少一个基于氮化物的层。氮化物特别地选自铝、硅、锆、钛中的至少一种元素的氮化物。它可以包括这些元素中至少两种或三种的氮化物，例如氮化硅锆或氮化硅铝。优选地基于氮化物的层是基于氮化硅的层，更特别地是基本上由氮化硅构成的层。当氮化硅层通过阴极溅射进行沉积时，它通常包含铝，因为习惯做法是用铝掺杂硅靶以加快沉积速度。
基于氮化物的层优选具有在2至100nm，特别地5至80nm范围内的物理厚度。
基于氮化物的层通常用于许多薄层堆叠体中，因为它们具有有利的阻挡性质，在它们防止在堆叠体中存在的其他层的氧化，特别地下面将描述的功能层的氧化的意义上而言。
堆叠体优选包括至少一个功能层，特别地导电功能层。功能层优选包括在两个薄介电层之间，其至少一个是基于氮化物的层。其它可能的介电层是例如氧化物或氮氧化物层。
至少一个导电功能层有利地选自：
-金属层，特别地由银或铌制成，甚至由金制成，和
-透明导电氧化物层，特别地选自氧化铟锡、掺杂的氧化锡(例如掺杂氟或锑)、掺杂的氧化锌(例如掺杂铝或镓)。
这些层因其低辐射率而特别得到重视，这赋予窗玻璃优异的绝热性质。在装备陆地交通工具(特别地机动车辆、轨道车辆)或其它空中或海上交通工具的窗玻璃中，低辐射窗玻璃允许在炎热的天气中向外反射一部分太阳辐射，从而限制所述车辆的乘客舱的热量，并必要时降低空调花费。相反，在寒冷的天气中，这些窗玻璃允许将热量保持在乘客舱内，从而减少所需的加热能量。这同样适用于配备建筑物的窗玻璃的情况。
根据一种优选实施方案，薄层堆叠体包括至少一个银层，特别地一个、两个、三个甚至四个银层。银层的物理厚度或必要时银层的厚度总和优选在2-20nm之间，特别地在3-15nm之间。
根据另一种优选实施方案，薄层堆叠体包括至少一个氧化铟锡层。其物理厚度优选在30-200nm之间，特别地在40-150nm之间。
为了在弯曲步骤期间保护该或每个导电薄层(无论是金属的还是基于透明导电氧化物)，这些层中的每一个优选被至少两个介电层包围。介电层优选基于选自硅、铝、钛、锌、锆、锡中的至少一种元素的氧化物、氮化物和/或氧氮化物。
薄层堆叠体的至少一部分可以通过各种已知技术，例如化学气相沉积(CVD)，或通过阴极溅射，特别地磁场辅助阴极溅射(磁控管方法)进行沉积。
薄层堆叠体优选地通过阴极溅射，特别地磁场辅助阴极溅射进行沉积。在这种方法中，等离子体在包含要沉积的化学元素的靶的附近的高真空下产生。通过轰击该靶，等离子体的活性物质轰击出所述元素，该元素沉积在玻璃片材上形成所需的薄层。当该层由从靶上轰击出的元素与包含在等离子体中的气体之间的化学反应产生的材料制成时，该方法被称为“反应性”方法。这种方法的主要优点在于，通过使玻璃片材在不同靶下连续运行(通常在同一设备中)，可以在同一条生产线上沉积非常复杂的层堆叠体。
上述堆叠体具有导电和红外反射性质，用于提供加热功能(除霜、除雾)和/或隔热功能。
当薄层堆叠体旨在提供加热功能时，必须提供电流供应。这尤其可以是通过丝网印刷在玻璃片材的两个相对边缘位置的薄层堆叠体上沉积的银膏条。
搪瓷层优选由包含至少一种颜料和至少一种玻璃料的组合物形成。搪瓷层优选不包含氧化铅。
搪瓷组合物通常还包含有机介质，其旨在促进组合物在基材上的施用以及组合物与基材的临时粘附，并且在搪瓷的焙烧过程中被消除。介质通常包括溶剂、稀释剂、油和/或树脂。在本文中，“搪瓷组合物”用于描述在玻璃片材上沉积湿搪瓷层的液体组合物。术语“搪瓷层”用于描述在焙烧后的最终层，而术语“湿搪瓷层”用于描述焙烧前的搪瓷层。
搪瓷层优选通过丝网印刷进行沉积。为此，将丝网印刷丝网放置在玻璃片材上，该丝网包括网孔，其中一些被堵塞，然后将搪瓷组合物沉积在丝网上，然后施加刮板以迫使搪瓷组合物在其中丝网没有被堵塞的区域中穿过丝网，以形成湿润的搪瓷层。
搪瓷层的沉积包括焙烧步骤，优选在至少600℃，甚至650℃，且至多700℃的温度下，优选在用于使玻璃片材弯曲的后续处理期间进行。
颜料优选包含一种或多种选自铬、铜、铁、锰、钴、镍的氧化物的氧化物。例如，它可以是铬酸铜和/或铁。
在本发明的优选实施方案中，搪瓷层基于硼硅酸锌。
更特别地，搪瓷层有利地具有包含以下氧化物的化学组成，其重量含量在以下提及的限度内变化：
所述组合物有利地包含至少一种碱金属氧化物，特别地氧化钾，其含量最多为5%，和/或氧化钠，其含量范围为2-15%，特别地5-13%。该组合物优选包含含量为1至10％，特别地2至7％的氧化钛(TiO2)。该组合物还包含颜料，例如铬酸铜。在这种情况下，Cr2O3和CuO的典型含量分别为8%至20%和3%至12%。
搪瓷的化学组成可以通过常规的化学分析方法确定，特别地由焙烧的搪瓷进行确定。因此，这确切地是焙烧的搪瓷层的化学组成，而不是用于形成搪瓷的玻璃料的化学组成。
搪瓷层优选地是不透明的，具有黑色色调。其亮度L*，在玻璃一侧的反射中测量，优选小于5。如上所述，它有利地在玻璃片材的周边形成条带。搪瓷层由此能够隐藏和保护密封件、连接元件或传感器免受紫外线辐射。
不粘层优选是基于耐火颗粒(特别地颜料)的层或溶胶-凝胶层。不粘层优选不含铋，因为已经观察到铋的存在会产生缺陷，即使不粘层不与薄层堆叠体接触。
耐火颗粒表示在弯曲期间不经历任何转变的颗粒。
耐火颗粒可以是例如氧化铝颗粒。耐火颗粒可以有利地是颜料。
颜料优选包含一种或多种过渡金属氧化物，特别地选自铬、铜、铁、锰、钴、镍和钛的氧化物。
颜料优选为氧化钛颜料，其具有优异的不粘性质。尽管这些颜料是白色的(而搪瓷通常是黑色的)，但这些颜料不会改变从车辆外部看到的搪瓷的外观。当在最终的层压窗玻璃中，附加的玻璃片材或层压中间层是着色的时，由这些颜料赋予的颜色也不会对从乘客舱内部观察的外观造成损害。
基于颜料的层优选包含至少40重量％，特别地至少60重量％，甚至至少80重量％的颜料。
根据一个优选的实施方案，不粘层由颜料组成。这些颜料通过下伏的搪瓷层固定到玻璃片材上：其在弯曲期间软化允许使布置在其上的颜料固定。
根据另一个实施方案，不粘层包含颜料和玻璃质粘合剂。玻璃质粘合剂不包含铋并且可以基于与下伏的搪瓷相同的玻璃料。为了获得不粘性质，不粘层中颜料的重量比例必须为至少40重量％。获得这种类型的层的一种非常简单的方法在于将一定比例的颜料添加到与用于沉积下面的搪瓷层的搪瓷组合物相同的搪瓷组合物中。
根据另一个实施方案，不粘层是溶胶-凝胶层。溶胶-凝胶层旨在表示通过溶胶-凝胶方法获得的层。溶胶-凝胶层优选基于二氧化硅。
溶胶-凝胶法是这样一种方法，其中通过各种方式，例如喷涂、幕涂、层流涂布、辊涂、丝网印刷等，将含有待产生的层的前体的溶胶沉积在玻璃片材上。在此，通过丝网印刷的方法是优选的，因为它容易地允许仅在玻璃片材的一部分上沉积溶胶-凝胶层，在这种情况下仅在覆盖有搪瓷的区域上(并且有利地在整个区域上)。
溶胶优选包含要生产的层的有机金属前体，例如原硅酸四乙酯(TEOS)。然后通常将该层干燥然后退火以使其致密。退火优选在与搪瓷的焙烧相同的步骤期间进行，因此通常在玻璃片材的弯曲期间进行。
不粘层优选地具有在5-100μm之间的厚度(特别地在湿润状态下)。当该层基于耐火颗粒时，其厚度优选在10-100μm之间，特别地在12-30μm之间。当该层是溶胶-凝胶层时，其厚度优选在5-20μm之间。
优选地，沉积搪瓷层的步骤和沉积不粘层的步骤通过丝网印刷进行。
在不粘层由颜料组成的情况下，颜料与有机介质混合，然后在弯曲期间或在任选的预焙烧期间除去有机介质。
在沉积不粘层之前，沉积搪瓷层的步骤之后优选地是干燥步骤，典型地在100-200℃之间的温度下进行。
在通过丝网印刷沉积基于耐火颗粒的不粘层的情况下，后者必须具有与所使用的印刷丝网兼容的尺寸。颗粒优选地具有在5-40μm之间的D90。在这里，粒度分布是体积分布，例如通过激光粒度分析进行确定。
沉积不粘层的步骤之后优选地是预焙烧步骤，优选地在150-600℃之间的温度下的预焙烧步骤。这种预焙烧允许消除有机介质，或通常任选存在于层中的任何有机组分。
预焙烧步骤通常在使用基于铋的搪瓷的情况下进行实施，以通过引起其部分结晶来发展这种搪瓷的不粘性质。然而，该步骤必须在高温下，通常在至少500℃进行，而在本方法的范畴中进行的预焙烧可以有利地在较低温度下进行。
在弯曲层压窗玻璃中，根据本发明的材料通过层压中间层粘合地结合到附加玻璃片材，使得涂层面向所述中间层。涂层优选位于窗玻璃的面2上，即，在旨在位于车辆外部的玻璃片材的面向层压中间层的面上。
弯曲可以特别地通过重力(玻璃在其自重作用下变形)或通过压制在通常为550至650℃的温度下进行。玻璃片材优选通过在它们之间布置中间层粉末(提供几十微米的空间，通常为20至50μm)而保持分开。中间层粉末例如基于碳酸钙和/或碳酸镁。
在弯曲期间，内部玻璃片材(旨在定位在乘客舱内)通常放置在外部玻璃片材上方。因此，在弯曲步骤期间，附加玻璃片材被设置在根据本发明的材料上方。
层压步骤可以通过在高压釜中处理来进行，例如在110至160℃的温度下和在10至15巴范围内的压力下进行。在高压釜中处理之前，可以通过压延或施加负压消除被禁锢在玻璃片材和层压中间层之间的空气。
如上所述，附加片材优选是层压窗玻璃的内片材，即位于窗玻璃凹侧上的片材，旨在被定位在车辆乘客舱内。因此，涂层布置在层压窗玻璃的表面2上。
附加玻璃片材可由钠钙硅玻璃或硼硅酸盐或铝硅酸盐玻璃制成。它可以由透明或有色玻璃制成。其厚度优选在0.5-4mm之间，特别地在1-3mm之间。
根据优选实施方案，附加玻璃片材的厚度在0.5-1.2mm之间。附加玻璃片材特别地由硅铝酸钠制成，优选是化学增强的。附加玻璃片材优选为层压窗玻璃的内片材。本发明特别适用于其中难以在面3上布置薄层堆叠体的这种类型的结构。化学增强(也称为“离子交换”)在于使玻璃表面与熔融钾盐(例如硝酸钾)接触以通过将玻璃的离子(在这里为钠离子)与具有更大离子半径的离子(在这里为钾离子)交换来增强玻璃的表面。这种离子交换允许在玻璃表面和一定厚度上形成压缩应力。优选地，表面应力为至少300MPa，特别地400甚至500MPa，并且至多700MPa，并且受压缩区域的厚度为至少20μm，通常在20-50μm之间。应力分布可以使用装有Babinet补偿器的偏光显微镜以已知方式进行确定。化学钢化步骤优选在380-550℃的温度下进行，持续时间为30分钟至3小时。化学增强优选在弯曲步骤之后但在层压步骤之前进行。所获得的窗玻璃优选为机动车辆挡风玻璃，特别地加热挡风玻璃。
根据另一个优选实施方案，附加玻璃片材在与面向层压中间层的面(优选面4，附加片材为内片材)相对的面上承载附加的薄层堆叠体，特别地低辐射性堆叠体，其包含透明导电氧化物，特别地氧化铟锡(ITO)。本发明还特别适用于这种类型结构，对于这种结构在同一玻璃片材的两个面(面3和4)上布置薄层堆叠体是棘手的。在该实施方案中，层压中间层和/或附加玻璃片材优选是着色的，带有涂层的玻璃片材能够由透明玻璃制成。所获得的窗玻璃优选是机动车辆车顶。
作为后一种优选实施方案的示例，可以提及层压弯曲车顶，其包含，从车辆外侧，透明玻璃片材，该透明玻璃片材在面2上涂覆有包含至少一个银层的薄层堆叠体，然后是搪瓷层，然后是不粘层，由有色PVB制成的层压中间层，和由有色玻璃制成的附加玻璃片材，该附加玻璃片材在面4上带有低发射率的薄层堆叠体，特别地基于ITO的薄层堆叠体。
层压中间层优选包括至少一个聚乙烯醇缩醛片材，特别地聚乙烯醇缩丁醛(PVB)片材。
层压中间层可以是有色或无色的，以便在必要时调节窗玻璃的光学或热性质。
层压中间层可以有利地具有吸声性质以吸收空气来源或固体来源的声音。为此，它可以特别地由三个聚合物片材组成，包括围绕内聚合物片材的两个“外”PVB片材，内聚合物片材任选地由PVB制成，其硬度低于外片材的硬度。
层压中间层还可具有绝热性质，特别地红外辐射反射性质。为此，它可以包括具有低发射率的薄层涂层，例如包括银薄层的涂层或具有不同折射率的交替介电层涂层，其被沉积在由两个外PVB片材包围的内PET片材上。
层压中间层的厚度通常在0.3-1.5mm，特别地0.5-1mm的范围内。在使用抬头显示系统(HUD)的情况下，层压中间层可以在窗玻璃边缘具有比在窗玻璃中心更小的厚度，以防止形成重影。
以下示例性实施例以非限制性方式说明本发明。
2.1mm厚的玻璃片材，其预先通过阴极溅射用薄层堆叠体涂覆(该薄层堆叠体包括用氧化锌层、氮化硅层和NiCr阻挡层保护的两个银层)，通过丝网印刷涂覆有湿厚度为25微米的搪瓷层。
在根据本发明的实施例中，搪瓷层“E1”(由Ferro公司以参考号144011出售的搪瓷)基于硼硅酸锌玻璃料(不含铋)和基于铬和铜的氧化物的黑色颜料。
在比较例中，搪瓷层“E2”(由Prince公司以参考号DV173770/N出售的搪瓷)基于硼硅酸铋锌玻璃料和基于铬和铜的氧化物的黑色颜料。
在搪瓷层上，在150℃的温度下干燥后，根据实施例，通过丝网印刷沉积具有以下组成的不粘层：
-A1：TiO2颜料，湿厚度约10μm，具有3至5μm数量级的D50和10μm数量级的D90。
-A2：溶胶-凝胶二氧化硅，湿厚度约为7µm，由Ferro公司以参考号TLU0059B01出售的溶液进行沉积
-A3：搪瓷层E2，湿厚度为25µm
-A4：80重量%的搪瓷E1与20重量%的TiO2颜料的混合物，湿厚度为10微米。
然后将如此涂覆的玻璃片材在570℃下进行120秒的预焙烧处理。
然后在玻璃片材上在涂层一侧放置由2.1mm厚的着色玻璃制成并在面4上用基于ITO的低发射率堆叠体覆盖的附加玻璃片材。将基于碳酸钙的提供几十微米空间的中间层粉末插入两个玻璃片材之间。然后使该组件经受480秒的在600℃的弯曲热处理。
下面的表1总结了获得的结果，对于每个实施例(比较例C1至C3和根据本发明的实施例1至3)给出了搪瓷层和不粘层(当它存在时)的种类以及在外观和粘合方面的结果。
通过测量反射亮度L*(光源D65，参考观察者10°)来评估外观，更特别地从面1看到的黑色。通过目视观察定性评价粘合性。
[表1]
| 实施例 | C1 | C2 | 1 | 2 | C3 | 3 |
| 搪瓷 | E2 | E1 | E1 | E1 | E1 | E1 |
| 不粘层 | - | - | A1 | A2 | A3 | A4 |
| L* | 20 | <5 | <5 | <5 | 15 | <5 |
| 粘合性 | 否 | 是 | 否 | 否 | 否 | 否 |
比较例C1和C2不使用不粘层。实施例C1表明，由于在弯曲期间在搪瓷和薄层堆叠体之间的相互作用，如果含铋搪瓷不导致粘合，则不允许获得所需的黑色色调。比较例C2的不含铋的搪瓷允许实现所需的色调，但观察到在两个玻璃片材之间的结合。
比较例C3使用与堆叠体接触的不含铋的搪瓷，在不含铋的搪瓷上有与附加玻璃片材接触的含铋搪瓷。这样就防止了粘合，但含铋搪瓷的存在，即使它不与薄层堆叠体接触，也会损害外观。
根据本发明的实施例1至3表明，与不含铋的搪瓷结合使用不粘层允许同时获得不存在粘合和令人满意的外观。
Claims (14)
1.一种包含玻璃片材的材料，该玻璃片材在其面之一的至少一部分上涂覆有薄层堆叠体，所述堆叠体在其表面的至少一部分上涂覆有不包含铋的搪瓷层，所述搪瓷层涂覆有不粘层。
2.根据权利要求1的材料，其中薄层堆叠体包含至少一个基于氮化物的层，尤其基于至少一种选自铝、硅、锆、钛的元素的氮化物的层。
3.根据前述权利要求中任一项所述的材料，使得所述堆叠体包含至少一个功能层，尤其导电功能层。
4.根据前一项权利要求所述的材料，其中至少一个导电功能层选自金属层，尤其银层或铌层，和透明导电氧化物层，尤其选自氧化铟锡、掺杂的氧化锡、掺杂的氧化锌的透明导电氧化物的层。
5.根据前述权利要求中任一项所述的材料，使得搪瓷层基于硼硅酸锌。
6.根据前述权利要求中任一项所述的材料，使得搪瓷层是不透明的，具有黑色色调，并在玻璃片材的周边形成条带。
7.根据前述权利要求中任一项所述的材料，其中所述不粘层是基于耐火颗粒的层，尤其基于颜料的层。
8.根据权利要求1至6中任一项所述的材料，其中所述不粘层是溶胶-凝胶层，尤其基于二氧化硅的溶胶-凝胶层。
9.一种弯曲层压窗玻璃，尤其用于机动车辆的挡风玻璃或车顶，其包括根据前述权利要求中任一项所述的材料，该材料通过层压中间层与附加玻璃片材粘合性结合，使得搪瓷层和薄层堆叠体面向所述中间层，尤其是在窗玻璃的面2上。
10.根据前一项权利要求所述的弯曲层压窗玻璃，其中所述附加玻璃片材具有0.5至1.2mm的厚度，特别地由化学增强的铝硅酸钠玻璃制成。
11.根据权利要求9所述的弯曲层压窗玻璃，其中所述附加玻璃片材在与面向所述层压中间层的面相对的面上承载附加薄层堆叠体，特别地包含透明导电氧化物的低发射率堆叠体。
12.一种获得根据权利要求1至8中任一项所述的材料的方法，包括以下步骤：
-提供在其面之一的至少一部分上涂覆有薄层堆叠体的玻璃片材，然后
-在薄层堆叠体的表面的至少一部分上沉积不含铋的搪瓷层的步骤，然后
-在所述搪瓷层上沉积不粘层的步骤。
13.根据前一项权利要求所述的方法，其中搪瓷层的沉积步骤和不粘层的沉积步骤通过丝网印刷进行。
14.一种获得根据权利要求9至11中任一项所述的弯曲层压窗玻璃的方法，其包括以下步骤：
-提供根据权利要求1至8中任一项所述的或根据权利要求12或13中任一项的方法获得的材料和附加玻璃片材，然后
-使材料和附加玻璃片材同时弯曲的步骤，然后
-通过层压中间层将所述材料与附加玻璃片材层压的步骤，使得搪瓷层和薄层堆叠体面向所述中间层。
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| MX2022011337A (es) | 2022-10-07 |
| KR20220155569A (ko) | 2022-11-23 |
| EP4118043A1 (fr) | 2023-01-18 |
| BR112022010007A2 (pt) | 2022-08-16 |
| WO2021180749A1 (fr) | 2021-09-16 |
| US20230134399A1 (en) | 2023-05-04 |
| CN113692396B (zh) | 2024-01-30 |
| FR3108114A1 (fr) | 2021-09-17 |
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