MXPA00005915A - Patterned coated articles and methods for producing the same - Google Patents
Patterned coated articles and methods for producing the sameInfo
- Publication number
- MXPA00005915A MXPA00005915A MXPA/A/2000/005915A MXPA00005915A MXPA00005915A MX PA00005915 A MXPA00005915 A MX PA00005915A MX PA00005915 A MXPA00005915 A MX PA00005915A MX PA00005915 A MXPA00005915 A MX PA00005915A
- Authority
- MX
- Mexico
- Prior art keywords
- coating
- substrate
- article
- metal
- coatings
- Prior art date
Links
- 239000000758 substrate Substances 0.000 claims abstract description 237
- 239000011248 coating agent Substances 0.000 claims abstract description 186
- 238000000576 coating method Methods 0.000 claims abstract description 186
- 229910052751 metal Inorganic materials 0.000 claims abstract description 90
- 239000002184 metal Substances 0.000 claims abstract description 90
- 239000010409 thin film Substances 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 239000003086 colorant Substances 0.000 claims abstract description 15
- TWXTWZIUMCFMSG-UHFFFAOYSA-N nitride(3-) Chemical compound [N-3] TWXTWZIUMCFMSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 239000004065 semiconductor Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 39
- 230000000694 effects Effects 0.000 claims description 32
- 239000011521 glass Substances 0.000 claims description 24
- 239000011247 coating layer Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 238000009501 film coating Methods 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 239000010408 film Substances 0.000 claims description 14
- -1 silicon nitrides Chemical class 0.000 claims description 13
- 230000000007 visual effect Effects 0.000 claims description 12
- 239000002250 absorbent Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- 230000001747 exhibiting Effects 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 238000005118 spray pyrolysis Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 230000001590 oxidative Effects 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N Germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- CXKCTMHTOKXKQT-UHFFFAOYSA-N Cadmium oxide Chemical compound [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910000447 germanium oxide Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 229910001929 titanium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N Indium(III) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N Silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N Zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000005329 float glass Substances 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 235000014692 zinc oxide Nutrition 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N Hafnium(IV) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N Niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N Tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 2
- 235000015450 Tilia cordata Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N Tin(II) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 2
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical compound [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 claims description 2
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 2
- 238000000608 laser ablation Methods 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical class [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 238000005488 sandblasting Methods 0.000 claims description 2
- 238000000992 sputter etching Methods 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000005121 nitriding Methods 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229910000676 Si alloy Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims 1
- 238000003486 chemical etching Methods 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 239000005368 silicate glass Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000011135 tin Substances 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims 1
- 229910001935 vanadium oxide Inorganic materials 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 230000000873 masking Effects 0.000 abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 8
- 238000001771 vacuum deposition Methods 0.000 abstract description 3
- 238000001755 magnetron sputter deposition Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 64
- 239000004408 titanium dioxide Substances 0.000 description 30
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000001264 neutralization Effects 0.000 description 7
- 241000720913 Fuchsia Species 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 230000001066 destructive Effects 0.000 description 5
- 229910020203 CeO Inorganic materials 0.000 description 4
- 230000035507 absorption Effects 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229910052904 quartz Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N Silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N Bismuth(III) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical compound [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 description 1
- 241001342895 Chorus Species 0.000 description 1
- BIXHRBFZLLFBFL-UHFFFAOYSA-N Germanium nitride Chemical compound N#[Ge]N([Ge]#N)[Ge]#N BIXHRBFZLLFBFL-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L Magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 206010051854 Secondary transmission Diseases 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910007676 ZnO—SiO2 Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive Effects 0.000 description 1
- 230000001678 irradiating Effects 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 230000001546 nitrifying Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
The present invention is directed to an article with a patterned appearance provided by a visually observable contrast between one or more generally transparent thin film coatings deposited over a substrate. At least one of the deposited coatings exhibits a reflected color and/or contrast and visible differing transmitted color and/or contrast or a plurality of coatings together exhibit different reflected colors and/or contrasts. The coatings are selected from the group of:metals depositable by magnetron sputtering vacuum deposition, chemical vapor deposition, pyrolytic coating, or sol-gel techniques, metal oxide coatings, metal nitride coatings, semi-conductor containing coatings, metal oxynitrides and mixtures thereof. The present invention is also directed to a method of making the articles having a visually observable patterned appearance involving masking and applying the coating or applying the coating and removing a portion of the coating to form the pattern.
Description
ARTICLES COATED WITH DRAWING AND METHODS TO PRODUCE THEM
C7AMPO OF THE INVENTION z: =
The invention relates in general to a transparent article having a visually observable contrast between coatings deposited on a substrate or between coatings deposited on a substrate and uncoated surfaces of the substrate, to obtain a surface with pattern. One of the coatings exhibits a different reflected color and transmitted color, at least one of which differs from the reflected color or color transmitted from the other coating (s) or the uncoated surface of the substrate. The invention also relates to methods of making the articles.
BACKGROUND OF THE INVENTION Coated articles, in particular glass substrates in which one or more coatings have been deposited, are currently available. The coatings can be deposited by several processes, including magnetron vacuum cathode deposition (MSVD), chemical vapor deposition (CVD), a spray pyrolysis process and the sol -gel method, among others.
It is known that some coatings or combinations of coatings alter the interaction between electromagnetic energy, more particularly the energy of visible light and the substrate, for example, alter reflected, transmitted or absorbed visible light, part of which is produced by fatigue. of interference effects, as seen in U.S. Patent 4,902,581 (Criss). "Interference effect" means the constructively or visually observable destructive combination of visible light rays or waves when transmitted or reflected by the coatings and / or the substrate. Absorption occurs in some materials in the visible region of the light spectrum where "electromagnetic energy does not pass through the material." The interference effect is usually observed visually as a decrease in reflected light (eg, antireflective coatings). , as a color transmitted and / or as a reflected color that differs from what would have been observed in the absence of the interference effect - The formation of highly saturated, low-reflectance color coatings in monolithic glazing using colorless coatings for interference effects, it is described in United States Patent No. 5,112,693 issued to Gillery In light of the technology currently used, it would be advantageous to provide articles, for example, for decorative or aesthetic applications, among others, by using coatings on a substrate to exhibit differential interference effects.
COMPENDIUM OF THE INVENTION _ Z, The present invention relates to an article having a visually observable pattern. The pattern is obtained by contrast between at least a first portion and at least another portion of a substrate, for example, a glass, metal or ceramic substrate. The at least first portion has a thin film coating, for example, generally transparent, that exhibits a first color or contrast visually observable when viewed "under reflected light (hereinafter referred to as" reflected color ") and a second color or visually obtrusive contrast that can be seen under transmitted light (hereinafter color transmitted) The at least one other portion for obtaining the contrast may be uncoated, coated with one or more thin film coatings without color (ie neutral) ) or coating layers, and / or coated with one or more thin film coatings having a reflected color and / or transmitted color, wherein at least one of the reflected color and / or color transmitted from the at least one other portion differs from the color. reflected color and / or the color transmitted from the at least one first portion The transmitted color may be that of light transmitted through a substrate The at least one coating for the thin film layer or otherwise referred to as the thin film coating, it can be chosen from metals, metal oxides, metal nitrides, semiconductor materials and mixtures and combinations thereof. All these materials must have the capacity to be deposited by magnetron vacuum catholic deposition ("MSVD"), chemical vapor deposition
("CVD"), pyrolytic coating techniques or sol-gel techniques or the like known to those skilled in the art.
The present invention also relates to a method for obtaining an article that has a visual drawing appearance by the following steps. First, at least one surface portion of a substrate is masked, for example, a glass, metal and / or ceramic substrate. At least one coating is deposited, for example, by MSVD, CVD, spray pyrolysis or sol gel techniques, in the form of a thin film on the masked and unmasked portions of one or more surfaces of the substrate. The mask together with the coating deposited on the mask is removed to expose the surface portion to obtain a pattern appearance as a contrast between the deposited thin film coating and the at least one surface portion of the substrate. The present invention also relates to a method for obtaining an article having a visual drawing aspect involving the following steps. At least one coating is obtained which can exhibit a first reflected color and / or a first color transmitted to a first thin film coating thickness and a second reflected color, a second transmitted color or both, at one or more different thicknesses on a or several surface portions of a substrate. The thickness of one or more layers of thin film of one or more types of coatings is varied one or more times in the thickness dimensions of the thin film of the coating on one or more surface portions of the substrate in the form of a drawing to obtain an appearance of drawing when the article is observed under reflected light, transmitted light, or both. As through the use of different types of thin film coatings, the drawing aspect is formed by contrasting the colors or contrasts reflected and / or transmitted. The original surface portion of the substrate in any embodiment of the article and method of the present invention may have a coated, uncoated, rough or textured surface. The thickness can be varied during the deposition step of the coating by differentially depositing the coating on selected portions of the substrate surface. Alternatively, the thickness may be varied after the deposition has been deposited by removing a coating portion in the form of a pattern. The coating can be applied as a thin film to the substrate and then heated or simultaneously in an oxidizing atmosphere or nitrurahte to obtain the drawing appearance with one or more oxide or nitride materials. A portion of the coating can be removed by depositing the coating on a mask during the deposition step, and then removing the mask and the coating deposited thereon. Alternatively, a portion of the coating can be removed or the original substrate can be roughened or textured by etching or milling. Combinations of the foregoing are also contemplated within the scope of the present invention. In addition, the drawing-like article can be produced by forming a laminate with one or more substrates without drawing, or with one or more patterned articles.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a top plan view of an article having a drawing aspect according to the present invention. Fig. 2 is a cross-sectional view taken at 10 along the line II-II of Fig. 1; Fig. 3 is a top plan view of an alternative embodiment of the article of the present invention; is a cross-sectional view along line IV-IV of Figure 3. Figure 5 is a view similar to Figure 2 of an alternative embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to an article having a drawing aspect provided by the contrast and / or color visually observable between one or more portions of a surface of the article. For example, the contrast may be between portions of a thin film coating deposited on a surface of the substrate, between thin film coatings deposited on the substrate, between coated and uncoated surface portions of thin film of the substrate and combinations of the foregoing. For example, one of the coatings may exhibit a reflected color and a different transmitted color visually observable. In general, for this difference to be visually observable, the difference for the average human eye is preferably from about two MacAdam units, more preferably about 3 MacAdam units and more preferably about 10 MacAdam units. The color and reflectance can be measured in a Spectrogard Color System spectrophotometer that can be obtained from Pacific Instruments as described in U.S. Patent 5,417,827 (Finley et al.). Another non-exclusive example of such contrast difference is when the reflectance of the first portion is less than or equal to the reflectance of the at least another portion of the substrate. A specific example of this would be a thin film coating of silver on a glass substrate. The present invention also relates to methods of making the articles. The invention is described in more detail in the following explanation, where like elements are indicated by analogous reference numbers. With reference now to the. Figures 1 and 2, an article 20 is shown having a visually observable drawing aspect. The article 20 includes a substrate 22 having a coating 24 deposited on first selected portions of the surface of the substrate, as shown in Figure 2. Although the coating layer 24 of Figure 2 is illustrated as the top coating layer on the substrate, additional thin film or non-thin film coating layers can be placed on top of the coating layer 24. Some of these are the solar control coating layers, color or tinting coat layers, and coating layers. pyrolytic self-cleaning, as is known to those skilled in the art. More particularly, and as shown in Figure 2, another portion 26 of the substrate 22 is not coated to obtain the shape of pattern 28. The shape of pattern 28 more clearly illustrated in Figure 1 is butterfly-shaped; however, the present invention is not limited thereto, and the shape of the pattern 28 can be any form of drawing that includes, but is not limited to, graphic representations, text, decorative images, or a plurality of images or combinations thereof. In general, in the sense in which it is used herein, the term "drawing" refers to a design for a coating layer on the surface of a substrate or the surface of a coating on a substrate. "Draw" is the process of creating the design form or selected aspect on a surface resulting in the formation of a "patterned" surface. The visually observable pattern results from the visible contrast between the uncoated surface portion 26 of the substrate 22 and the coated surface portion of the substrate 24. With reference to FIG. 2, when directed from diffuse white light rays from a white light source (not shown) to the substrate 24 as illustrated by the arrow
29, the spokes collide with the surface of the article at a plurality of incident angles. The surface reflects a portion of the rays. A portion of the rays is transmitted through the surface. In addition, another portion is absorbed or trapped within the article and can give rise to transmission, reflection and / or internal or secondary absorption. Although it is appreciated that such reflections, transmissions and / or secondary absorptions can have an effect on primary reflectances and transmissions, the following explanation refers to primary visible light, as opposed to reflected and secondarily transmitted, which forms the main component of light visible and transmitted visible observed from and to. through the substrate. Furthermore, although it is recognized that a plurality of rays will be reflected or transmitted simultaneously, for reasons of simplicity of the following explanation, the reflectance or transmission of one or at most two representative rays will be explained to explain the present invention. Referring next to Figure 2, the rays reflected by the uncovered portion 26 of article 20 are illustrated by arrow 30. The reflected light rays will appear in neutral color when viewed along the direction illustrated by arrow 29 In contrast, when the same white light is reflected by the surfaces 31a and 31b of the coating 24 as a thin film layer along the direction illustrated by the arrows 32a and 32b, respectively, the constructive and destructive interference exerted by the coating 24 on the reflected light waves will make the reflected light appear to have a dye or color (eg, a reflected color) when viewed along the direction indicated by the arrow 29. When the white light source (not shown) is placed on the opposite side of the substrate 22 and its rays of light are directed towards the article 20, the rays will also collide with the article 20 from a plurality of angles and incidence. Also, as explained above, a portion of the visible light rays will be reflected, transmitted or absorbed, as explained above, and further, as explained above, although reflectance, absorption or secondary transmission may occur. , the explanation of the present application will refer to the primary reflected or transmitted light rays. As also explained above, although it is recognized that a plurality of rays will be reflected or transmitted simultaneously, for reasons of simplicity of the following explanation, the reflectance or transmission of one or at most two representative rays will be discussed to explain the present invention . Referring next to Figure 2, when the white light source (not shown) is placed on the opposite side of the substrate 22 and directed towards the article 20 along the direction illustrated by the arrow 34, a portion of the light rays is reflected by the surface (not shown). A portion of the light rays is transmitted through the substrate 22, through the uncoated portion 26 of the substrate 22, along the direction illustrated by the arrow 36, and will appear colorless or neutral when viewed at along the direction illustrated by the arrow 29. In contrast, when the same white light is transmitted through the substrate 22 and through the coating 24 along the direction indicated by the arrow 38, it will appear to have a dye or color ( for example, a transmitted color) when viewed along the direction indicated by arrow 29 due to interference effects exerted by coating 24 on visible light waves as they pass through coating 24.
When diffused white light strikes both main surfaces 33 and 35 of article 20 along the directions illustrated by arrows 29 and 34, respectively, the color observed upon viewing article 20 along the direction illustrated by date 29 will vary depending on whether the reflected color is observed along the direction illustrated by arrows 32a and 32b or the color transmitted through article 20 is observed., article 20 appears to have a first color when viewed under reflected light, and a second color when Toajo light is seen transmitted when white light diffuses on both major surfaces 33 and 35 and article 20 is seen along the direction illustrated by the date 29. In an alternative embodiment of the present invention, not shown, the uncoated surface portion 26 of the substrate 22 and the surface portion with the coating 24 deposited thereon can be inverted. In this embodiment, the coating 24 would be present on the substrate 22 as the body of the pattern, for example, the butterfly illustrated in FIG. 1, as the first portion of the substrate. In this case, the body of the drawing has a first color or tint when viewed under reflected light and a second color- or tint when viewed under transmitted light. The uncoated surface portion of the substrate 22 has a neutral appearance under reflected light and is transmitted as the other portion of the substrate. In the alternative embodiment of the present invention illustrated in Figures 3 and 4, an article 40 is shown, and as in the previous embodiment, the thickness of one or more coating layers is of the order of the thin film thickness. The article 40 includes a substrate 22 having at least one major surface 29 with a coating 24. A second coating 42 has been deposited on first selected portions of the coating 24 as illustrated in Figures 3 and 4. The coating portion 44 not coated with the coating 42 is the body of a pattern defined by the number 46 as the other portion of the surface of the substrate 22. The article 40 has a visually observable pattern appearance, for example, the butterfly pattern shape , provided by the observed visible color contrast between the thin film coating layers 24 and 42. Although, for the purposes of the present invention it is only necessary that one of the coatings 24 and 42 exhibit a different reflected color and a different transmitted color. or second reflected color, in a preferred embodiment of the present invention both coatings J24 and 42 exhibit such interfering effect. In this embodiment, when diffused white light is directed towards the surface of the article 40 along the direction illustrated by the arrow 48, and is reflected by the coating surfaces 49a and 49b along the direction illustrated by the arrows 50a and 50b, the constructive and destructive interference provided by the coating 24 on the reflected light waves will cause the reflected light to have a reflected color when viewed along the direction illustrated by the arrow 48. When light is directed white towards the surface of article 40 along the direction illustrated by arrow 64 and is reflected by surfaces 51a, 51b and 51c through both coatings 42 and 24 along the direction illustrated by arrows 58a, 58b and 58c, it will also appear to have a reflected color. However, the destructive and constructive interference exerted by the combined coatings 24 and 42 will result in the reflected color differing from that of the single coat 24, resulting in different reflected colors. Similarly, when white light is directed towards article 40 along the direction illustrated by arrow 63 and transmitted through article 40 along the direction illustrated by date 54, it will appear to have a color transmitted due to the interference effects exerted by the coating 24 when seen along the direction illustrated by Ha arrow 48. When the white light directed towards the article 40 along the direction illustrated by the date 63 is transmitted through article 40 along the direction illustrated by arrow 62, it will appear to have a color transmitted when viewed along the direction illustrated by arrow 48. However, the destructive and constructive interference exerted by the combined coatings 24 and 42 will cause the transmitted color to differ from that of the single thin film coating layer 24, resulting in different transmitted colors. Thus, the drawing of article 40 will be observed as the contrast between the two colors reflected under reflected light and as the contrast between the two colors transmitted when seen low, transmitted light. When irradiating white light on both surfaces of article 40 along the directions illustrated by arrows 48 and 63, the transmitted or reflected color observed when the article is viewed along the direction illustrated by arrow 48 will vary according to whether or not note the reflected colox or the transmitted color of the single coating 24 or of the combined coating layers 24 and 42. Thus, article 40 appears to have four colors when viewed along a direction illustrated by the date 48, including a pair of different reflected colors when seen under reflected light, and a couple of different transmitted colors when seen under transmitted light in these conditions. As you can see, it is not necessary that the four colors are different. For example, it may be desirable that the pattern can only be observed visually under reflected light. To obtain this effect, the transmitted color of the pattern is matched to the transmitted color of the combined coatings 24 and 42, while its reflected color remains in contrast to the reflected color of the combined coatings 24 and 42. As can also be seen, this effect is not limited to reflected light, and can be reversed, for example, to obtain a pattern that is not visually observable under reflected light, but is visually observable under transmitted light. As can be appreciated, the single thickness coating layer 24 on the portion 44 of the substrate 22 and the combined thickness coating layers 24 and 42 on the other portion, or in this case the remainder, of the surface of the substrate 42 is they can be inverted by depositing the combined thickness of the coatings 24 and 42 as thin film layers on the portion 44 of the substrate 22 along the pattern 46, while the remainder of the surface of the substrate 22 has only the single thickness coating 24. The color difference to produce the pattern can be made with identical or different coatings 24 and 42. When the coatings 24 are of the same material, it is only necessary to provide a differential thickness between the coatings 24 and 42 in the shape of the pattern out of the shape of the pattern, difference in thickness which is sufficient to produce a different interference effect visually. observable, to obtain a drawing aspect of the surface of the article of the present invention. This is illustrated in Figure 5 where an article 80 is shown having only a single coating 82 deposited thereon. The covering 82 is provided in the form of a pattern similar to that illustrated in Figures 3 and 4; however, instead of applying two separate coatings, the coating 82 is obtained as a single coating with a portion 84 of a different thickness from the portion 86. The difference in thickness is sufficient to provide the visually observable interference effects described above and, in turn, the drawing aspect of article 80. Although not shown, as can be appreciated, the present invention is not limited to articles such as articles 40 and 80 having a single thickness difference between portions of the different coatings or between portions of the same coating. The invention contemplates articles having one or more coatings, each of which may include several portions of different thickness to obtain articles having an unlimited number of colors or dyes in the form of drawing to obtain multicolored drawing shapes of great complexity . For example, a coated article can be formed by coating a surface of a substrate, eg, a neutral glass substrate, with a first metal oxide coating, more in particular a titanium dioxide coating, at a coating layer thickness. of, for example, approximately 515 Angstroms, to obtain a surface that looks like silver under diffuse white light reflected. A portion of the silver receiving surface can be masked in the form of a pattern, for example, as a silhouette of a butterfly, and both the other masked portion and the first unmasked portion of the silver reflecting surface can then be coated with a additional coating of titanium dioxide to a total coating layer thickness of, for example, about 770 Angstroms to obtain a gold-like surface under reflected white diffused light. When removing the masked portion to reveal the other silver receiving portion, low reflected light is observed that the article has a silver butterfly on what is seen as a contrasting gold background. The silver butterfly can be masked again, and a portion of the gold receiving surface can also be masked in the pattern of a butterfly silhouette, and both the masked portions and the unmasked portions of the surface can be coated with a additional coating of titanium dioxide to a total coating layer thickness of, for example, about 1028 Angstroms, to obtain another first portion of surface that looks fuchsia under reflected diffuse white light. When removing both masks, it will appear that the article has a silver butterfly and a golden butterfly in other portions of the surface on what is seen as a fuchsia contrast background under diffuse white reflected light. Likewise, the silver butterfly can be masked again, or it can be the golden butterfly. A portion of the fuchsia reflecting surface may also be masked in the form of a butterfly silhouette as a third first portion. The surface can be coated with an additional coating of titanium dioxide to a total thickness of the coating layer of, for example, about 1258 Angstroms to obtain a third first surface that looks blue under reflected white diffused light. When removing the masks, you will see in the article a drawing aspect that includes a silver butterfly silhouette, a golden butterfly silhouette and a fuchsia butterfly silhouette as the third other portion of the surface on which it is observed that there is a blue background under reflected light. This process can be repeated on portions of the substrate to obtain articles in which forms of drawing of great complexity and variation of colors and multiple designs have been formed. Substrates compatible with the present invention include ceramic substrates and transparent substrates including rigid materials, such as glass, including coated glass and rigid or flexible plastic or polymeric materials, such as polycarbonates and acrylates, and non-transparent substrates, such as opaque coated glass, and metal substrates such as polished metals and the like. Other examples of glass substrates include: sodium silicate glass and lime, especially floating glass prepared or manufactured. These substrate materials, as is known to those skilled in the art, may be transparent, although they may also be highly absorbent, but of low visible light transmission. The substrates can also be material on transparent substrates, such as glass, so that they have mirror coating glass. Metallic substrates can range from the like to stainless steel to any metal such as copper, aluminum, silver and the like, or to any of said substrates with a plurality of said metals as coating (s) on the substrate. In addition, substrates can have a polished, rough, textured surface to obtain a contrast effect. In general, any sandblasting process or attack known in the art can produce the rough or textured surface on the substrate.
The stiffer substrates may have a second main surface generally opposite the first major surface in spaced relationship to give thickness to the substrate. When said types of substrates are transparent, the first portion of the substrate may be on the first main surface and the other portion on the opposite major surface. This would be done in an article such as that shown in Figures 3 and 4, where the second covering 42 or the covering 24 is on the surface 66. In addition, the substrates, alternatively or in addition to having an opaque coating on the main surface opposite the surface with the visual appearance of drawing, can have any coating known to those skilled in the art. A non-exclusive example includes low emissivity coatings known in the art. For example, in Figure 2, such a coating would be in all, preferably, or in part of the surface 35 of the substrate 26. Typical thicknesses known in the art can be used for these types of coatings, as well as for substrates . With these types of coatings that reduce the transmittance of visible light through the substrate, the single or multiple coatings in the thin film layers on the substrate that give the drawing appearance will be used, resulting in a second color or reflector contrast. . This is opposed to the coatings used as thin film layers where the coating (s) give rise to a second color or contrast from transmitted visible light. The interference effect is generally observed where the coating to produce the interference effect is non-absorbent or intermediate absorber of visible light or any combination of these. When the material is full or highly absorbent, little or no light is reflected or transmitted to produce an "observable interference effect." Accordingly, coatings compatible with the present invention that provide the interference effect include thin film coatings. ranging from nonabsorbent to those that are less than highly absorbent, but include those which are intermediate absorbers of visible light.The generally transparent films of metals, metal oxides and / or nitrides of metals and mixtures and combinations thereof are suitable examples of such film coatings Such coatings include, but are not limited to, titanium oxides, in particular titanium dioxide, tantalum oxides, tin oxides, niobium oxides, zinc stannate, zinc oxides, zirconium oxides, germanium oxide, aluminum oxide, indium oxide, cadmium oxide, hafnium oxide, tungsten oxide, nadium oxide, chromium oxide, molybdenum oxide, iridium oxide, nickel oxide, silicon oxide; silicon nitrides, silicon-known alloys in the material, germanium nitride, nickel-chromium nitride, titanium nitrides, tantalum nitride, niobium nitride, and zirconium nitride, and mixtures thereof, and also including oxynitrides of metal and its alloys. The non-conductive materials in the above list of materials are silicon oxides and nitrides and germanium oxides and nitrides. Other useful materials include: cerium oxide, Si02, Ca02, Al203, Tn ^ Oj, Ce03 or the like, and a mixture thereof, for example, Zr02-SiO2 or the like, and those which can form a transparent film. The coating composition may include another component, such as two component materials of the series: ZnO-SiO2, ZnO-Al203,
ZnO-Ge02, ZnO-Zr02, Ti02-Si02, Ti02 - Al20, -TiO, -CeQ2, Ti02 - ZrQ2, CeO, - SiO CeO, CeO. GeC2, CeO, - ZrO, materials of a series of three or more components. Non-exclusive examples of metal-containing coating are chrome, nickel chrome, stainless steel, aluminum, gold, silver and their alloys. By the term "thin film" it is understood that the coating as a single layer has a thickness of the order of fractions of wavelength and visible light or that has a profiled surface of periodic structures with profile dimensions of the order of the wavelengths of light in the order in which colors are generated. interference by the coating or coatings on the substrate when light is reflected and / or transmitted by the surfaces of the substrate and the coating or coatings. The coatings may be deposited on a substantially flat curved or parallel main surface of the substrate or on any flat parallel surface which is then bent by any method known to those skilled in the art. Preferably, the single thin film coating layer has a thickness less than one thickness on the substrate or on a previously coated substrate. MSVD, CVD, spray pyrolysis and / or sol-gel techniques are useful for applying the coating or coatings to the substrates to exhibit the desired interference effect, but the MSVD process is a preferred process. The MSVD process allows to control the thickness of the coating, the formation of the drawing and the composition of the coating. Where the coating exhibiting interference effects includes a metal oxide coating, metal nitride coating or combinations thereof, the coating can be obtained using the MSVD process by cathode deposition of a metal cathode in a non-reactive atmosphere, eg, argon , to obtain a metallic coating on the substrate, and then heating the substrate in an oxidizing and / or nitrifying atmosphere to obtain the metal oxide coating, the metal nitride coating or combinations thereof on the substrate. When this method of forming a coating is employed, and when the surface is to be masked as described below with a masking agent, the heating step can be performed before or after the masking step or steps. Alternatively, the coating exhibiting interference effects can be deposited on an oxide, nitride or its mixture by cathodic deposition by reaction of a metal cathode or combination of metal cathodes in an atmosphere selected from the group consisting of oxidizing atmospheres, nitride atmospheres and their combinations Also targets of metal, metal oxide, metallic nitride and / or metal oxynitride can be subject to deposition in inert atmospheres, for example, oxygen, or atmospheres including an inert gas, for example, argon combined with a reactive gas, for example, nitrogen and / or oxygen. It is also possible in an alternative direction to deposit a metal coating with subsequent oxidation or nitruration. Such metals are titanium, cobalt, nickel, zirconium, tantalum, niobium and chromium and any of the aforementioned metals and their mixtures. The interference effect itself, and, in turn, its visually observable result (e.g., reflected or transmitted color) can be modified with respect to any individual coating, among other ways, by varying the thickness of the coating described above.; and / or varying the components of the coating composition (for example, modification of one or more components of the coating so that it is "highly absorbent in a portion of the visible spectrum, can alter the reflected color transmitted.) Drawing of the article of the present invention can be modified, among other ways, by modifying the observed interference effects of an individual coating as described above, and / or by varying the combination of the coatings deposited on the substrate, and / or by varying the substrate (e.g., a transparent glass substrate will provide a reflected interference effect different from that of an opaque metal substrate.) The provision of coatings of varying thicknesses can be realized with several methods In one embodiment, the deposition technique itself ( for example, including, but not limited to, MSVD, CVD, spray pyrolysis or sol-gel) it can direct or control so as to provide coatings having differential thickness on the surface of the substrate (or coatings previously deposited thereon) in the form of a pattern. This can be done, for example, by directing the spray pattern toward the surface of the substrate in a spray pattern that provides coatings of variable thickness in the desired pattern shape. In an alternative embodiment, the coating can be uniformly deposited on the surface of the substrate (or the coatings previously deposited thereon), and then milled or etched in the form of a pattern with variable thickness. Milling may include abrading a portion of the coating or ion milling. The attack can be chemical, for example, by attacking the coating surface with an attack solution.
In another embodiment of the present invention, a masking agent can be used to obtain coatings of varying thickness. The mask can have any shape, including, but not limited to, a masking solution, gel, paste, powder, tape, metal or film. The coating can then be uniformly or non-uniformly deposited on the masked and unmasked portions of the substrate surface. You can use silkscreen or printing methods such as inkjet printing, offset printing, or the application of removable adhesives. Then, the masked portions, together with the coating deposited thereon, are removed to obtain coating or variable coating combinations. When the method of forming the coating includes oxidation and / or nitruration operations as described above, such operations may be performed before or after the operation or masking operations to obtain the desired article with the appearance of a pattern. In addition, the present invention may include a sequence of coating steps, such as vacuum deposition techniques in conjunction with laser drawing formation of the deposited layer (s). The masking that is normally required to achieve the controlled deposition of the colored film layers during vacuum deposition is replaced by laser drawing formation to remove the film from the areas where it is not desired after having deposited the film. This combination of thin film coating and laser ablation involves a sequence of passs, i.e., film deposition followed by laser drawing formation. This sequence can be repeated as many times as you want the final drawing aspect. Any suitable laser known to those skilled in the art can be used as useful with thin film coatings of metal, metal oxide and / or metal nitride. In an alternative embodiment of the present invention for multiple thin film coating layers of the metal and / or semiconductor containing coatings, coatings or intermediate layers may be used between one or more of the multiple layers of thin film. Suitable intermediate coatings are those of dielectric materials, non-absorbent inorganic or organic materials. Non-exclusive examples are: metal oxide, such as titanium dioxide, niobium pentaoxide (Nb2Os), tin oxide, zinc oxide, indium oxide (optionally doped with tin oxide), bismuth oxide, zirconium oxide and analogous materials known to those skilled in the art. Another suitable material is silicon nitride. Another suitable dielectric material includes a thin composite film containing zirconium nitride and silicon nitride (collectively referred to as "SiZrN") manufactured by co-deposition from two targets or from an alloy target of a DC cylindrical magnetrom. Others include dielectric materials formed of a suitable dielectric with low refractive index, for example, magnesium fluoride. Other intermediate layer materials can be non-absorbent inorganic and organic coatings. Non-absorbent organic coatings such as polyester film, polyvinyl pyrrolidone film, and polyvinyl butyrate film are also useful intermediate layer materials. In addition to the use of intermediate coatings or intermediate layers, the article of the present invention can be a component in a laminated structure. One or more articles with the drawing aspect are sealed with or without other substrates without drawing and / or intermediate layers in the laminate. Any process known to those skilled in the art of making laminates of glass or other substrates mentioned above can be used. The invention is further illustrated with the following non-limiting examples. EXAMPLE 1 A substrate including a piece of clear floating glass that measured approximately 30, 48 cm wide by approximately 30.48 cm long (12 by 12 inches) by approximately 6 millimeters thick, was coated with a titanium metal coating in the following manner. The substrate was placed in an MSVD chamber and placed under a titanium cathode on a conveyor device in preparation for deposition of a titanium metal coating thereon. The cathode was energized at a power of approximately 3.4 kw. The substrate was passed under the three-pass cathode to obtain a coating of titanium metal on a surface of the substrate. The substrate was removed after the MSVD apparatus and a portion of the surface of the article thus coated received a mask in a configuration in the form of a printed text. The substrate was then placed in the MSVD coating chamber and both masked and unmasked portions of the substrate were coated with additional titanium metal by energizing the cathode at approximately 3.4 kw and passing the substrate under the cathode another two passes, with a total of five passes. The substrate was removed from the MSVD chamber and the mask was removed together with the titanium metal deposited on the mask.
The substrate was then introduced into a furnace that was maintained at a temperature of about 648.8 ° C (1200 ° F) at room atmosphere for about seven minutes to oxidize the titanium metal coatings to a titanium metal dioxide coating. . The portion of the coating that had previously been masked had an oxidation thickness of approximately 770 / Angstroms and appeared to have a gold color under reflected diffuse white light supplied by a GE Trimline T8 500K fluorescent lamp. The portion of the coating that had not previously been masked had an oxidation thickness of approximately 1,259 Angstroms and appeared to have a blue color under reflected diffuse white light supplied by a GE Trimline T8 500K fluorescent lamp. It was observed that the article thus prepared had gold colored text letters on what was observed to be a blue background when the coated surface of the substrate was observed under reflected diffused white light supplied by a GE Trimline T8 5OOK fluorescent lamp. "EXAMPLE 2 A substrate was coated including a piece of clear float glass measuring about 30.48 cm wide by about 30.48 cm long (12 by 12 inches) by about 6 millimeters thick with titanium metal and masked as described in example 1, except that the process was repeated to obtain several coatings and masks on the surface.As the extraction of the masks and the oxidation of the substrate, it was observed that the substrate had several drawings of variable reflected colors More particularly, a first titanium metal coating was obtained on the substrate by passing the substrate below the cathode described in Example 1. The substrate was passed twice below the cathode The substrate was removed from the MSVD camera, and a portion of the first titanium metal coating received a first mask in a configuration in the form of a printed text, said mask was applied, as well as all following masks, as an adhesive. The substrate was then placed in the MSVD coating chamber and both the masked and unmasked portions of the substrate were coated with a second coating of titanium metal energizing the cathode at approximately 3.4 kw and passing the substrate under the cathode another pass. additional, with a total of three passes. The substrate was removed again from the MSVD chamber, and a portion of the second titanium metal coating received a second mask also in the form of printed text, second mask which was placed on a substrate area other than that occupied by the first mask . The substrates were then placed in an MSVD coating chamber and both masked and unmasked portions of the substrate were coated with a third titanium metal coating energizing the cathode at approximately 3.4 kw and passing the substrate below the cathode one pass additional, with a total of four passes. The substrate was removed again from the MSVD chamber, and a portion of the third titanium metal coating received a third mask in the form of a printed text, third mask which was placed on a substrate area different from that occupied by the first or second masks . The substrate was placed back in the MSVD coating chamber, and both masked and unmasked portions of the substrate were coated with a fourth titanium metal coating energizing the cathode at approximately 3.4 kw and passing the substrate below the cathode one pass additional, with a total of five passes. The substrates were removed from the MSVD chamber and the first, second and third masks were removed together with the titanium metal deposited on each respective mask, stripping the respective adhesives from the substrate. The substrate was reintroduced in an oven that was maintained at a temperature of approximately 648, 8 ° C
(1,200 ° F) with ambient atmosphere for approximately seven minutes to oxidize the titanium metal coatings to titanium oxide coatings. The portion of the coating that had previously been masked with the first mask, the oxidation was about 515 Angstroms thick and appeared to have a silver color under reflected diffused white light supplied by a GE fluorescent lamp (Trimline T8 500K.) The portion of the coating that had previously been masked with the second mask, the The oxidation was approximately 770 Angstroms thick and appeared to have a gold color under reflected diffuse white light supplied by a GE Trimline T8 500K fluorescent lamp.The portion of the coating that had previously been masked with the third mask, had an oxidation. thickness of approximately 1028 Angstroms and appeared to have a fuchsia color under reflected diffuse white light supplied by a GE Trimline T8 5OOK fluorescent lamp.The coating portion that had not been masked, corresponding to the fourth titanium metal coating, had a thickness of about 1,258 Angstroms and seemed to have a c blue odor under diffuse reflected white light supplied by a fluorescent lamp GE Trimline T8 500K1- It was observed that the article thus prepared had a text area printed in silver, a separate area of text printed in chorus color and another separate area of printed text in fuchsia on what was observed to be a blue background when the coated surface of the substrate was observed under diffuse reflected white light supplied by a GE Trimline T8 500K fluorescent lamp. EXAMPLE 3 A substrate including a piece of clear float glass measuring about 30.48 cm wide by about 30.48 cm long (12 by 12 inches) by about 6 millimeters thick can receive a mask in the form of a pattern. The masks can be formed on the glass substrate by applying a masking solution on the surface of the substrate by immersing a desired pattern shape in the masking solution and pressing the pattern shape to the surface of the substrate and removing the drawing form from the substrate. surface of the substrate. The drawing form can be made from any absorbent material, including a single or compress. The masking solution remaining on the surface of the substrate is allowed to dry to form a mask in the form of a pattern on the surface of the glass substrate. The substrate can then be placed in an MSVD chamber and placed under a titanium cathode on a conveyor device in preparation for the deposition of a titanium metal coating thereon. The white cathode MSVD can measure approximately 12.7 cm (5 inches) by approximately 43.18 cm (17 inches). The blank may be subjected to deposition to obtain a titanium metal coating over the entire surface of the substrate, including both masked and unmasked portions thereof. The MSVD deposition chamber can be rarefied at a pressure of about 10"5 torr and filled with argon gas at a pressure of about 4 microns, after which the cathode can be energized at a power of about 3 kw to about 370 The substrate can be passed below the cathode four passes at a rate of approximately 304.8 cm (120 inches) per minute to obtain a titanium metal coating approximately 529 Angstroms thick on a surface of the substrate. The mask can then be removed from the substrate by washing the surface of the substrate with a solvent that dissolves the mask, to obtain a first portion of the substrate corresponding to the shape of the uncoated pattern surrounded by the second portion. of the surface on which the titanium metal coating has been deposited, the substrate can then be placed in a oven with ambient atmosphere maintained at a temperature of about 704.4 ° C (1300 ° F) for about 3.5 minutes to oxidize the titanium metal to a coating of titanium oxide with a thickness of about 950 Angstroms. The oxidation of titanium in titanium dioxide will form an article that will have a visually observable design aspect. When viewed under reflected "white" visible light supplied by a fluorescent lamp GE Trimline T8 5OOK, the uncoated portion of the substrate will appear as a floating glass surface of neutral color with a visible reflective of approximately 8%. Under the same reflected light, the portion of the substrate coated with titanium dioxide will appear as a reddish bronze coating with a visible reflectance of approximately 21%, exhibiting coordinates of observation chromaticity 1931 2 ° CIÉ of approximately x = 0.385 ey = 0.344, due to the interference effect produced by the titanium dioxide coating present on the surface of the substrate. When viewed under transmitted "white" visible light supplied by a "GE Trimline T8 5OOK" fluorescent lamp, the uncoated portions will appear again as neutral floating glass, while the portion coated with titanium dioxide will appear to be blue, due to the effect of interference produced by the coating of titanium dioxide present on the surface of the substrate EXAMPLE 4 An article with a visual drawing aspect according to example 3 can be prepared, except that the entire substrate can be coated with the metal coating titanium with a thickness of approximately 529 Angstroms before masking The unmasked, titanium-coated substrate can be heated to oxidize the titanium metal to titanium dioxide to form a first coating of titanium dioxide having a thickness of approximately 950 Angstroms on the surface of the substrate, as described in example 3. Next The first coating of titanium dioxide can be masked in the same manner as described in Example 3 to obtain a pattern on a surface of the glass substrate, as set forth in Example 3. Then it can be coated the substrate with a second coating of titanium metal introducing the masked / coated substrate with titanium dioxide into the MSVD chamber and subjecting it to two passes further below the cathode of titanium metal to obtain a coating of titanium metal on the substrate of approximately 774 Angstroms thick. "~ The mask can be removed as described in Example 3 to expose the first titanium dioxide coating, then the substrate in the furnace can be heated to oxidize the second coating of titanium metal to titanium dioxide, to form a titanium dioxide coating that is approximately 1,390 Angstroms thick on the portion of the surface of the substrate that had not been masked The portions of the surface of the substrate that had been masked will have the titanium dioxide coating of approximately 950 Angstroms As can be seen, before the oxidation of the second titanium metal coating, a visually observable pattern-like article will be formed consisting of the unmasked portion of the substrate surface that will expose the first coating of titanium dioxide, which contrasts with the second coating of titanium metal, the oxidation of the second coating of titanium metal to titanium dioxide, the portion of the titanium dioxide coating on the surface of the substrate that is approximately 950 Angstroms in thickness, will appear under reflected light supplied by a GE Trimline T8 500K fluorescent lamp as a reddish bronze coating with a visible reflectance of about 31% which exhibits chromaticity coordinates 1931 of observation _L ° CIÉ of about x = 0.385 ey = 0.344, prevented from the interference effect produced by the coating of titanium dioxide present on the surface of the substrate. When viewed under transmitted "white" visible light supplied by the GE Trimline T8 500K fluorescent lamp, the 930 Angstroms titanium dioxide-coated portion of the substrate surface will appear to be blue, due to the interference effect produced by the coating of titanium dioxide of 950 Angstroms thick on the surface of the substrate. Also upon oxidation of the second coating of titanium metal to titanium dioxide, the portion of the titanium dioxide coating on the surface of the substrate having approximately 1390 Angstroms in thickness will appear under reflected light supplied by a GE Trimline T8 500K fluorescent lamp. blue color with a visible reflectance of about 24% which exhibits chromaticity coordinates 1931 of observation 2 ° CIÉ of about x = 0.227 ey = 0.290, due to the interference effect produced by the titanium dioxide coating of approximately 1390 Angstroms in thickness, present on the surface of the substrate. When viewed under transmitted "white" visible light supplied by the GE Trimline T8 5OOK fluorescent lamp, the titanium dioxide-coated portion of 1,390 Angstroms in thickness from the surface of the substrate will appear to be orange, due to the interference effect produced by the titanium dioxide coating of approximately 1390 Angstroms in thickness present on the surface of the substrate. The above examples are offered to illustrate the present invention and are not intended to limit the invention. Various modifications are included within the scope of the invention, which is defined by the following claims.
Claims (47)
1. An article having a visually observable pattern, including: "a substrate that reflects, transmits or reflects and transmits visible light and that has at least one major surface, at least one generally transparent coating selected from the group of coatings containing metal, and coatings containing semiconductor and its combinations, deposited as a thin film on a first portion on at least one surface of the substrate, said coating exhibiting a reflected color and a transmitted color, and at least another portion of at least one surface of the substrate that can visually contrast with the first coated portion of the substrate surface and wherein the first portion and the at least one other portion are positioned relative to one another in the substrate in the form of a pattern to obtain an article having a visual drawing appearance.
2. The article of claim 1, wherein the at least one other portion includes an uncoated portion of the substrate.
3. The article of claim 1, wherein the substrate is selected from the group of metal, glass and ceramic.
4. The article of claim 1, wherein the thin film coating is the top coating layer of the main surface of the substrate.
The article of claim 1, wherein the substrate is selected from the group of curved substrates and flat substrates.
6. The article of claim 1, wherein the at least one other portion of the surface of the substrate has a rough surface.
7. The article of claim 6, wherein the rough surface is due to sandblasting or acid attack.
8. The article of claim 1, wherein the substrate is transparent.
9. The article of claim 1, wherein the substrate has a second major surface opposed to the first major surface spaced apart to give thickness to the substrate.
10. The article of claim 9, wherein the substrate has a coating of low emissivity on the surface other than that having the transparent coating containing metal on a first portion of the surface. -
11. The article of claim 9, wherein the substrate has an opaque coating on the surface other than that which has the transparent coating containing metal in the first portion of the surface.
12. The article of claim 9, wherein the substrate is transparent and the second portion of the substrate is on the surface other than the surface on which the first portion is placed on the substrate.
13. The article of claim 1, wherein another first portion and the at least one other portion includes at least one other generally transparent coating, different from the first coating, deposited as a thin film on the at least one other portion of the substrate, said other coating exhibiting a reflected color and a transmitted color, wherein at least one of the reflected color and the transmitted color of the at least one other portion differs from at least the reflected color and the transmitted color of the coating of the first original portion.
14. The article of claim 13, wherein the substrate has the same thin film coating on the first portion and the at least one other portion of the surface of the substrate where the thin film coating on one of the first and at least another portion of the surface has a different thickness of the first coating.
15. The article of claim 13, wherein the first thin film coating makes at least a portion of the substrate all but transparent.
16. The article of claim 1, wherein the transparent thin film coating is a metal containing coating selected from the group of metals, metal oxides, metal nitrides and their combinations and mixtures.
17. The article of claim 1, wherein the transparent thin film coating is a semiconductor containing coating selected from the group of silicon oxides, silicon nitrides, silicon alloys, germanium oxides, and germanium nitrides and their combinations and mixtures.
18. The article of claim 1, including transparent thin film coatings deposited on, different portions of the surface of the substrate relative to each other, but in mutual relation, to obtain a plurality of visually testable portions of the substrate surface to give rise to a ~ a plurality of images such as the visual drawing aspect.
19. The article of claim 1, wherein the visually contrastable portion provides at least one decorative image.
20. The article of claim 1, wherein the coating has variable thicknesses to produce different colors by interference effects.
21. The article of claim 1, wherein the thin film coating is selected from metals that give a coating transparent to the application by MSVD, CVD, spray pyrolysis and sol-gel.
22. The article of claim 1, wherein the coating is a metal-containing coating selected from the group of chromium, chromium nickel, stainless steel, aluminum, gold, silver and its alloys.
23. The article of claim 22 has a second coating containing metal that is different from an elemental metal.
24. The article of claim 1, wherein the metal-containing coating is selected from the group of: metal oxides selected from the group of: "Titanium oxides, tantalum oxides, tin oxides, zinc oxides, niobium oxide, zirconium oxides, germanium oxide, aluminum oxide, indium oxide, cadmium oxide, hafnium oxide, tungsten oxide, vanadium oxide, chromium oxide, molybdenum oxide, iridium oxide, nickel oxide, and nitrides are selected from group of silicon nitrides, aluminum nitride, chromium nitride, zirconium nitride, titanium nitride, niobium nitride, tantalum nitride and nickel chromium nickel nitrides and oxynitrides thereof and mixtures and combinations of any and all of them.
25. The article of claim 1, wherein the coating is deposited as a thin film layer to exhibit the desired interference effect by the methods of MSVD, CVD, spray pyrolysis or spl-gel.
26. The article of claim 18, wherein between any two thin film coatings in the first portion of the surface and in the at least one other portion of the surface there are one or more coating layers selected from dielectric and inorganic and organic coatings not absorbents
27. The article of claim 26, wherein the non-absorbent organic coating is selected from the group of: polyester film, polyvinyl pyrrolidone film, polyvinyl butyrate film.
28. The article of claim 1, wherein the thin film coating is non-absorbing visible light.
29. The article of claim 1, which has a plurality of substrates as laminate.
30. The article of claim 29, wherein more than one substrate has the thin film coating and the visually observable pattern.
31. The article of claim 29 that is transparent.
32. The article of claim 1, wherein the substrate is selected from the group of: glass, coated glass, opaque coated glass, soda lime silicate glass, prepared or manufactured float glass, rigid or flexible polymeric materials, polycarbonates, polyacrylates , metallic substrates selected from polished metals, stainless steel, copper, aluminum and silver.
33. An article having a visually observable pattern, including: a transparent substrate having a major surface; a generally transparent coating containing metal deposited on a first portion of the surface of the substrate selected from the group of metal oxides, metal nitrides, metals that produce transparent coatings upon application (of MSVD, CVD, spray pyrolysis or sol-gel, and mixtures thereof, said coating exhibiting a reflected color and a transmitted color, and at least one other portion of the surface of the substrate that is visually contrastible with the first portion of the substrate and wherein the first portion and the other portion are placed on the surface of the substrate. substrate in the form of a drawing to obtain an article having a visual drawing aspect.
34. A method of providing an article that has the appearance of a visual drawing, including the steps of: a. providing a substrate that reflects and / or transmits visible light with at least one major surface; b. providing at least one mask on a portion of at least one main surface of the substrate in the form of a pattern to obtain a first masked portion of the surface of the substrate and at least one other unmasked portion of the surface of the substrate; c. providing at least one coating selected from the group of coatings containing metal and semiconductor containing coatings on the first masked portion of the substrate and the other unmasked portion of the surface of the substrate in at least one layer of thin film, and said coating exhibits a reflected color and a color transmitted; and d. removing the mask to expose an uncoated portion of the substrate beneath the mask; whereby a pattern aspect is formed on the surface of the substrate, where the pattern aspect is formed as a contrast between the coated portion of the substrate and the uncoated portion of the substrate.
35. The method of claim 34, wherein the coating for the thin film layer is obtained by depositing the metal-containing coating selected from the group of metal oxide coatings, metal nitride coatings, and metals that produce transparent coatings in MSVD, CVD applications , spray pyrolysis or sol-gel, and their mixtures.
36. The method of claim 34, including repeating steps b, c and d to obtain multiple drawings.
37. The product of the process of claim 34.
38. E product of the process of claim 36.
39. The method of claim 34, wherein the coating for the thin film layer is obtained by: i) depositing the metal-containing coating; and ii) heating the substrate in an oxidizing or nitriding atmosphere to obtain the metal oxide coating or coating of metal nitrides or combinations thereof on the substrate to form the drawing aspect.
40. The method of claim 39, wherein the coating is selected from: a) a metal-containing coating selected from the group of: titanium, tin, zinc stannate, zinc, zirconium, nickel-chromium and mixtures thereof; and b) silicon and mixtures of a) and b).
41. The method of claim 34, which includes repeating steps b, c and d, wherein for the repetition of step a) the coating that is obtained is the deposition of at least one metal-containing coating, and includes: heating the substrate in an oxidizing atmosphere or nitrurant to obtain the metal oxide coating or metal nitride coating or combinations thereof on the substrate to form the drawing aspect, steps i) and ii) are also repeated to obtain multiple patterns.
42. The method of claim 41, wherein, with the repetition of step c) more than twice, step ii) is repeated less times than step i) so that more than one layer of thin film of the coating is heated together.
43. A method of providing an article that has a visual drawing aspect, including the steps of: a. providing a substrate having at least one major surface; b. depositing a first thin film transparent coating on the surface of the substrate; c. placing at least one mask on a portion of the surface of the substrate in the form of a pattern to obtain a first masked portion of the surface of the substrate and at least another unmasked portion of the surface of the substrate; d. depositing an additional thin film transparent coating on one or more of the first masked portion of the substrate and the at least one other unmasked portion of the substrate surface; and e. remove the mask to expose the first coating; wherein at least one of the first coating and the second coating is selected from the group consisting of metal oxide coatings, metal nitride coatings and their mixtures exhibiting a reflected color and a transmitted color and wherein the first coating and second coating they are visually testable from one another to give a visual drawing aspect to said article.
44. The method of claim 43 includes heating the substrate in an oxidizing or nitriding atmosphere to obtain the metal oxide coating or the metal nitride coating or combinations thereof in the substrate from the coating of the substrate.
45. The method of claim 43, which includes repeating steps c, d and e to obtain multiple images.
46. A method of providing an article that has a visual drawing aspect, including the steps of: a. providing a substrate having at least one major surface; b. depositing at least one thin film transparent coating exhibiting a color of the group of: reflected color and color uniformly transmitted on the surface of the substrate to obtain a first portion of the surface of the substrate; and c. removing by attack a portion of the coating to form a pattern at a different thickness from another portion of the surface of the substrate, whereby the other portion and the first portion are visually testable from each other to give a visual drawing appearance to said article .
47. The method of claim 46, wherein the attack is performed by a process selected from the group of: laser ablation, ion milling and chemical etching.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/068,828 | 1997-12-24 | ||
| US09199976 | 1998-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA00005915A true MXPA00005915A (en) | 2001-07-03 |
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