CN110437647A - 陶瓷色料 - Google Patents
陶瓷色料 Download PDFInfo
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- CN110437647A CN110437647A CN201910359372.6A CN201910359372A CN110437647A CN 110437647 A CN110437647 A CN 110437647A CN 201910359372 A CN201910359372 A CN 201910359372A CN 110437647 A CN110437647 A CN 110437647A
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- 239000000049 pigment Substances 0.000 title claims abstract description 134
- 239000000919 ceramic Substances 0.000 title claims abstract description 110
- 230000000694 effects Effects 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 42
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 436
- 239000000758 substrate Substances 0.000 claims description 219
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 140
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 138
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 130
- 239000000377 silicon dioxide Substances 0.000 claims description 70
- 229910052681 coesite Inorganic materials 0.000 claims description 68
- 229910052906 cristobalite Inorganic materials 0.000 claims description 68
- 229910052682 stishovite Inorganic materials 0.000 claims description 68
- 229910052905 tridymite Inorganic materials 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 229910052593 corundum Inorganic materials 0.000 claims description 29
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims description 23
- 150000004706 metal oxides Chemical class 0.000 claims description 23
- 238000007639 printing Methods 0.000 claims description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 20
- 238000010304 firing Methods 0.000 claims description 18
- -1 polysiloxanes Polymers 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 12
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052573 porcelain Inorganic materials 0.000 claims description 11
- 210000003298 dental enamel Anatomy 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910005451 FeTiO3 Inorganic materials 0.000 claims description 5
- 229910003087 TiOx Inorganic materials 0.000 claims description 5
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052863 mullite Inorganic materials 0.000 claims description 5
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910020776 SixNy Inorganic materials 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 4
- 235000013312 flour Nutrition 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910003079 TiO5 Inorganic materials 0.000 claims 11
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims 2
- 229910002588 FeOOH Inorganic materials 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 229920001709 polysilazane Polymers 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000007650 screen-printing Methods 0.000 description 8
- 229910001512 metal fluoride Inorganic materials 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000548 poly(silane) polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052914 metal silicate Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 3
- 239000011452 unfired brick Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 229940035427 chromium oxide Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- 229910009815 Ti3O5 Inorganic materials 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XHTYLQIVWOTDHP-UHFFFAOYSA-N [Cr].[Si](O)(O)(O)O Chemical compound [Cr].[Si](O)(O)(O)O XHTYLQIVWOTDHP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 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
- 238000013459 approach Methods 0.000 description 1
- 229910000062 azane Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
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- 238000007641 inkjet printing Methods 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- TWWDDFFHABKNMQ-UHFFFAOYSA-N oxosilicon;hydrate Chemical compound O.[Si]=O TWWDDFFHABKNMQ-UHFFFAOYSA-N 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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Abstract
本发明涉及用于金属、陶瓷和玻璃态制品装饰的陶瓷色料，其包含效果颜料和含硅聚合物以及制备陶瓷釉的方法。
Description
技术领域
本发明涉及用于金属、陶瓷和玻璃态(glassy)制品装饰的陶瓷色料，其包含效果颜料和含硅聚合物以及制备陶瓷釉的方法。
背景技术
通常，陶瓷釉中的装饰性应用使用颜料(例如效果颜料)的混合物，和一种或多种陶瓷熔块混合物。烧成温度和熔块的组成由待涂覆的制品确定。不同应用的典型烧成温度范围例如是：
搪瓷，500-850℃，
玻璃，550-650℃，
三次烧成(triple-fired)陶器，740-900℃，
三次烧成瓷砖，900-1150℃，
一次烧成陶器，1000-1300℃，
一次烧成瓷砖，1100-1250℃。
对于相应的应用，烧制过程的温度必须足够高，以确保由陶瓷色料制成耐磨和封闭的涂层。烧成温度朝向相应玻璃熔块的软化或熔化温度。开始时存在的玻璃颗粒随后软化并形成连续的基质和光滑的表面。这里出现的问题是，颜料，特别是来自珠光颜料的类别的代表，通常不能承受住(survive)由氧化熔体(熔块组分)和在烧制过程中的高温组成的侵蚀性条件而没有损坏。
从现有技术中已知，在陶瓷或玻璃态涂层中使用珠光颜料时必须预期着色强度和珠光效果的显著损失。
为了防止这种情况，这些颜料必须封装在额外的保护层中，或者在这种高温应用领域中使用珠光颜料限于珠光颜料和改性釉底料或助熔剂(flux)的特殊组合。
因此，过去已经努力通过应用技术改进，例如改变熔块颗粒的颗粒形式和尺寸，改变熔块颗粒的化学组成或增强颜料浓度来优化陶瓷制品在装饰应用中的珠光效果。
此外，已经努力通过用绝缘保护层(用于这种热和化学极其苛刻的这类应用)覆盖(sheathing)来稳定效果颜料，特别是珠光颜料。
这描述于EP 3 159 380 A1、EP 220 509 A1、EP 307 771 A1、EP 307 771 A1、DE39 32 424 C1、GB 2 096 592 A、US专利5,783,506、US 4,353,991、EP 0 419 843 A1、CN101462895 A和DE 198 59 420 A1中。
现有技术中已知的这些解决方案，例如颜料的包封，在生产中是复杂的，因为必须在生产中进行施加保护层的进一步处理步骤。另外，取决于保护层的组成，可能发生不利影响，例如，釉的浑浊和颜料中的颜色变化或施加介质中的颜色效果的较差控制。
通过应用技术改进(例如颜料浓度，熔块颗粒的组成和形式)的第二种方法总是需要足够高的温度以确保陶瓷色料的成膜性。通过熔块的高碱浓度或足够高的温度可以保证光滑且机械稳定的层。两种变体都可能对效果颜料产生负面影响，在这种苛刻的条件下趋于分解。
在以下专利申请中描述了在低温下用包含用于制备耐刮擦层的含硅聚合物的混合物涂覆金属、玻璃和其它表面：
WO 2010099520、WO 20081368610A1、WO 2014086619、WO 2013170124、CN103725074、WO 2011085995、US 9701576B2、WO 2013156617、KR 2017044000、CN105820599、CN 104403382、KR 1405322、CN 103788733、JP 2010009958、US 20170212548、CN 1560157、US 6436543、KR 2016100783、CN 102863856、KR 2010124920、JP 04080275和DE 1230154。
虽然现有技术中已知几种方法和混合物，但它们都不能满足在陶瓷，金属或玻璃样体如瓷砖或瓷器上形成陶瓷釉的所有需要，尤其是不能在700℃和1300℃之间的烧成温度下，或者不能满足在金属体例如搪瓷上在450-850℃的温度下形成陶瓷釉的所有需要。
因此，本发明的目的是提供一种制备陶瓷釉的方法，并开发一种含有珠光颜料的陶瓷色料，其不显示出现有技术方法和组合物的缺点。
令人惊讶的是，现在已经发现，通过在根据本发明的方法中使用包含效果颜料和含硅聚合物的陶瓷色料，可以避免微粒熔块和珠光颜料的组合的缺点。
发明内容
因此，本发明涉及制备陶瓷釉和釉面制品的方法，包括以下步骤：
(a)通过混合至少一种基于薄片状基材和/或折射率R.I.>1.5的未涂覆的薄片状基材的效果颜料、至少一种含硅聚合物、任选的溶剂、任选的粘合剂、任选的吸收性陶瓷颜料，以及任选的至少一种添加剂制备陶瓷色料，
(b)在陶瓷或金属体上印刷或涂覆步骤(a)中获得的陶瓷色料，
(c)干燥步骤(b)中获得的陶瓷或金属体，
(d)在450-1300℃范围的温度下烧制步骤(c)中获得的陶瓷或金属体。
本发明优选涉及制备陶瓷釉和釉面制品的方法，其中将包含至少一种基于薄片状基材和/或折射率>1.5的未涂覆的薄片状基材的效果颜料和至少一种含硅聚合物和任选的溶剂，任选的粘合剂，任选的吸收性陶瓷颜料和任选的至少一种添加剂的陶瓷色料施加到陶瓷制品上，并在≥700℃的温度下烧制，或者在温度≥450℃，优选≥500℃的金属体上烧制。
在根据本发明的陶瓷色料中，基于薄片状基材以及折射率>1.5的未涂覆的薄片状基材的效果颜料可以单独使用或彼此组合使用。优选地，使用基于薄片状基材的效果颜料。
本发明还涉及包含至少一种含硅聚合物和至少一种基于薄片状基材的效果颜料的陶瓷色料。所述基材可以选自薄片状基材如例如合成云母薄片、天然云母薄片、玻璃薄片和二氧化硅薄片。优选地，效果颜料基于耐高温的薄片，例如Al2O3薄片、SiC薄片、SixNyCz薄片(x＝0.5-1.0；y＝0.25-0.5；z＝0.25-0.5)、B4C薄片、BN薄片、石墨薄片、TiO2薄片和Fe2O3薄片，尤其是Al2O3薄片、SiC薄片、B4C薄片、BN薄片、石墨薄片、TiO2薄片和Fe2O3薄片。优选地，陶瓷色料中效果颜料的比例为至少0.1wt％，基于含硅聚合物。
折射率R.I.大于施加的陶瓷釉的薄片状基材(大约>1.5)还可以纯的形式使用或添加(不含任何涂层)。在这种情况下，可以获得有吸引力的闪光效果。优选地，使用R.I.>1.5的未涂覆的薄片状基材，其选自Al2O3薄片、SiC薄片、SixNyCz薄片(x＝0.5-1.0；y＝0.25-0.5；z＝0.25-0.5)、B4C薄片、BN薄片、石墨薄片、TiO2薄片和Fe2O3薄片，尤其是Al2O3薄片、SiC薄片、B4C薄片、BN薄片、石墨薄片、TiO2薄片和Fe2O3薄片。陶瓷色料中未涂覆的薄片状基材的比例为至少0.1wt％，基于含硅聚合物。
令人惊讶的是，根据本发明的陶瓷色料和方法适用于陶瓷制品如瓷砖或瓷器的装饰，温度范围为700℃-1300℃，优选720℃-1150℃，特别是740℃-900℃。根据本发明的陶瓷色料和方法也适用于诸如搪瓷之类的金属制品的装饰，温度范围为450℃-950℃，优选500℃-900℃，特别是550℃-850℃。
本发明的一个优点是可以降低珠光效果和着色强度的损失。优选地，与现有技术的方法相比，可以实现相当强的珠光效果和更高的着色强度。而且，可以获得具有光滑表面的釉。
包含根据本发明制造的釉的陶瓷制品可以优选地提供这样的优点，即在高达1100℃的高温应用中，所需的光学效果是稳定的并且可以以可再现的方式获得。
含硅聚合物优选选自聚硅氧烷、聚硅氮烷(全氢聚硅氮烷以及有机聚硅氮烷)、聚倍半硅氧烷、聚碳硅烷、聚碳硅氧烷、聚硅烷、聚甲硅烷基碳二亚胺、聚倍半硅氧烷碳二亚胺(polysilsesquicarbodiimide)、聚倍半硅氮烷、聚硼硅烷、聚硼硅氮烷、聚硼硅氧烷、聚硼倍半硅氧烷、聚硅氮烷/聚硅氧烷嵌段共聚物和聚硅氧氮烷(polysiloxazane)。也可以使用含硅聚合物的混合物。
聚合物(一种或多种)的选择取决于陶瓷薄膜的要求规格和待涂覆制品所需的烧成温度。本领域技术人员可以选择合适的聚合物，因为含硅聚合物形成玻璃态结构的温度取决于聚合物的化学组成和分子量。
优选的聚合物例如为聚硅氧烷、聚倍半硅氧烷、聚硼硅氧烷和聚硅氮烷，特别是聚硅氮烷、聚硅氧烷和/或聚倍半硅氧烷，其中聚硅氮烷、聚硅氧烷和聚倍半硅氧烷的每一种单独代表本发明优选的实施方案。
特别地，可以使用下式的聚倍半硅氧烷聚合物：
然而
R1和R2为彼此相同或不同的基团并且选自氢、烷基、烯(alkene)、环烷基、芳基、亚芳基和烷氧基，和
m和n彼此独立地为选自1-100范围的数字的整数，
条件是各个材料的沸点超过150℃。
尤其地，甲基-苯基聚倍半硅氧烷对于本发明是有利的。
特别地可以使用式(1)的聚硅氮烷：
-(SiR'R"-NR"')n- 式(1)
其中R'、R"和R'"相同或不同并且彼此独立为氢或未取代的或取代的烷基、芳基、乙烯基或(三烷氧基甲硅烷基)烷基，n为整数和n的大小使得聚硅烷氮的数均分子量为150至150000g/mol。
在一个优选的实施方案中，所使用的聚硅氮烷为式(1)的聚硅氮烷，其中R'、R"、和R"'彼此独立地为来自氢、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、苯基、甲苯基、乙烯基或3-(三乙氧基甲硅烷基)丙基、3-(三甲氧基甲硅烷基丙基)的基团。
在另一个优选的实施方案中，可以使用根据式(2)的优选的聚硅氮烷：
-(SiR'R"-NR"')n-(SiR*R**-NR***)p- 式(2)
其中R'、R"、R"'、R*、R**和R***彼此独立地为氢或未取代或取代的烷基、芳基、乙烯基或(三烷氧基甲硅烷基)-烷基基团，n和p具有使得聚硅烷氮的数均分子量为150至150000g/mol的大小。
更特别优选的是化合物，其中R'、R'"和R***为氢和R"、R*和R**为甲基；或
R'、R'"和R***为氢和R"和R*为甲基和R**为乙烯基；或R1、R'"、R*和R***为氢和R"和R**为甲基。
同样优选使用的是式(3)的聚硅氮烷：
-(SiR'R"-NR"')n-(SiR*R**-NR***)p-(SiR1R2-NR3)q- 式(3)
其中R'、R"、R"'、R*、R**、R'***、R1、R2和R3彼此独立地为氢或未取代或取代的烷基、芳基、乙烯基或(三烷氧基甲硅烷基)烷基，n、p和q具有使得聚硅烷氮的数均分子量为150至150000g/mol的大小。
更特别优选的是聚硅氮烷，其中R'、R'"和R***为氢和R"、R*、R**和R2为甲基，R3为(三乙氧基甲硅烷基)丙基和R1为烷基或氢。
除了含硅聚合物之外，可以使用式M(OR)x的金属醇盐，以改变最终形成的玻璃组成。优选第二和第三主族金属以及过渡金属，尤其是Zr、Zn、Ca、Mg和Al的金属醇盐。
另外，陶瓷色料可包含粘合剂，例如含硅树脂。商业树脂例如由Wacker以商品名Silres或由Arkema以商品名Synolac获得。然而，粘合剂的选择通常不限于含硅树脂。只要赋予相容性，可以使用所有种类的有机粘合剂，例如聚酯、聚氨酯、环氧树脂、醇酸树脂、丙烯酸酯等。
除了这些组分外，陶瓷色料还可包含其它填料、添加剂(例如分散添加剂、流变添加剂、增稠剂、消泡剂)、溶剂例如丝网印刷油或陶瓷吸收性颜料例如绿色铬-氧化物颜料、黑色尖晶石颜料、浅黄色-金红石-颜料(buff-rutile-pigments)、镉红色和黄色、钴-蓝颜料，可由Shepperd或Ferro商购获得。添加剂可由BYK或其他制造商获得。可能的添加剂的实例是：Aerosil、Byk 405、Byk 410、Mowital B 30H(Kuraray)、Crayvallac PA3BA 20(Arkema)、Byk 065、KoralisionFG 100、TEGO Dispers 652。
为了通过陶瓷色料在陶瓷基材上制备精细色彩网格(colour grid)和浮雕状印刷品，使用丝网印刷油，其防止印刷后色浆的跑掉(running)并产生具有清晰轮廓的印刷品。此外，丝网印刷油确保陶瓷色料适用于施加到转印纸上。丝网印刷油的实例是Ferro的市售221-ME和Screenprint Bulk 803035MR。
陶瓷色料中效果颜料的比例优选为至少0.1wt％，尤其是0.1-99.9wt％，基于含硅聚合物。其它优选的范围可以是0.1-98wt％，0.5-95wt％和1-91wt％，基于含硅聚合物。
尤其地，在本发明的这些实施方案中，含硅聚合物优选为聚硅氮烷、聚硅氧烷和/或聚倍半硅氧烷，其中聚硅氮烷、聚硅氧烷和聚倍半硅氧烷的每一种单独表示本发明优选的实施方案，特别是聚倍半硅氧烷。
陶瓷色料中未涂覆薄片状基材的比例可与效果颜料相同。
优选地，根据本发明的陶瓷色料包含0.1-99.9重量％的至少一种效果颜料和/或至少一种未涂覆的薄片状基材、0.1-99.9重量％的至少一种含硅聚合物(陶瓷前驱体聚合物(preceramic polymer))、0-50％重量的至少一种溶剂、0-90％重量的至少一种粘合剂、0-20％重量的至少一种添加剂，其中百分比基于陶瓷色料的重量并且和为100％。
形成工件上的封闭且机械稳定的玻璃态膜的温度优选处于低于玻璃熔块的常规方法所需的温度。由于在根据本发明的方法中，在烧制过程中形成玻璃层并且可以避免玻璃熔点附近的温度，所以不存在颜料在高温下在氧化熔体中分解并且珠光效果消失的危险。
此外，这种途径有助于避免侵蚀性和适得其反的碱性玻璃组分。对于现有技术方法，需要一定量的碱以采用玻璃熔点至待涂覆工件的烧制过程的相应温度窗口。
对于根据本发明的陶瓷色料，不存在这种限制。有利地，温度窗口可以通过选择含硅聚合物来限定，并且可以在每个烧成温度下实现高色度珠光效果。
所有已知的效果颜料适用于本发明，特别是珠光颜料。效果颜料可以优选基于选自合成云母薄片、天然云母薄片的基材和非常特别优选基于耐高温的薄片，例如Al2O3薄片、SiC薄片、B4C薄片、BN薄片、石墨薄片、TiO2薄片和Fe2O3薄片，尤其是Al2O3薄片。
最后，如果使用基于在高温下稳定的薄片状基材的珠光颜料，通常可以实现特别高的温度稳定性。这里可以提及的实例为：刚玉-Al2O3、金刚砂-SiC、氮化硼-BN、石墨和赤铁矿-Fe2O3。
还可以使用不同基材的混合物或具有不同颗粒尺寸的相同基材的混合物。基材可以任何重量比彼此混合。优选使用10：1至1:10的混合物，特别是1：1的混合物。特别优选由具有不同颗粒尺寸的基材薄片组成的基材混合物，特别是S级分(10-200μm)、N级分(10-60μm)和F级分(5-25μm)的混合物，以及F级分(5-25μm)和M级分(1-15μm)的混合物。
基础基材的尺寸本身并不重要，并且可以与特定应用和期望的目标效果/目标纹理匹配：例如，缎光(satin)或高度闪光。
通常，薄片状基材的厚度为0.05-5μm，优选0.1-2μm，特别是0.1-1μm。另外两个维度的尺寸通常为1-500μm，优选1-250μm和特别是1-60μm。
未涂覆的薄片状基材可以在与用于效果颜料的基材相同或类似的实施方案中用于根据本发明的陶瓷色料中。
珠光颜料的基础基材上的至少一个单独层的厚度对于颜料的光学性质是必要的，如已经在许多专利和专利申请中描述的，例如在DE 14 67 468、DE 19 59 988、DE 20 09566、DE 22 14 545、DE 22 15 191、DE 22 44 298、DE 23 13 331、DE 25 22 572、DE 31 37808、DE 31 37 809、DE 31 51 343、DE 31 51 354、DE 31 51 355、DE 32 11 602、DE 32 35017或还在本领域技术人员已知的其他专利文献和其它出版物中描述的。
颜料必须具有至少一个光学活性层，优选高折射率层(例如TiO2、Fe2O3、SnO2等)。这里的高折射率层是指所有具有n≥1.8，优选n≥2.0的折射率的层。
用于珠光颜料的合适的基材薄片可以是掺杂的或未掺杂的。如果它们是掺杂的，则掺杂优选为Al、N、B、Ti、Zr、Si、In、Sn或Zn或其混合物。此外，来自过渡金属(V、Cr、Mn、Fe、Co、Ni、Cu、Y、Nb、Mo、Hf、Ta、W)的其他离子和来自镧系元素的离子可用作掺杂剂。
在Al2O3的情况下，基材优选是未掺杂的或掺杂有TiO2、ZrO2或ZnO。Al2O3薄片优选为刚玉。合适的Al2O3薄片优选是掺杂或未掺杂的α-Al2O3薄片，特别是TiO2掺杂的α-Al2O3薄片。如果基材是掺杂的，则基于基材，掺杂的比例优选为0.01-5.00重量％，特别是0.10-3.00重量％。
合适的Al2O3薄片具有等效直径分布(equivalence diameter distribution)，根据该等效直径分布，90％的颗粒在5-45μm，优选5-40μm的范围内。
Al2O3薄片的D50值优选在15-30μm的范围内，非常特别优选在15-25μm的范围内。
D10值优选在5-15μm的范围内，非常特别优选在6-10μm的范围内。
在整个申请中，使用Malvern MS 2000测定D10、D50和D90值。
Al2O3薄片的厚度优选为50-1200nm，优选150-800nm，特别是200-450nm。
在非常特别优选的实施方案中，Al2O3薄片的厚度<500nm，优选150-450nm，特别是150-400nm。
Al2O3薄片的长径比(aspect ratio)(直径/厚度比)优选为10-1000，特别是50-500。
在进一步优选的实施方案中，Al2O3薄片的长径比为30-200，特别是50-150。
在优选的实施方案中，薄片状基材涂覆有一个或多个透明、半透明和/或不透明层，所述层包含金属氧化物、金属氧化物水合物、金属硅酸盐、金属低氧化物、金属、金属氟化物、金属氮化物、金属氮氧化物或这些材料的混合物。金属氧化物、金属氧化物水合物、金属硅酸盐、金属低氧化物、金属、金属氟化物、金属氮化物或金属氧氮化物层或其混合物可具有低折射率(折射率<1.8)或高折射率(折射率≥1.8)。合适的金属氧化物和金属氧化物水合物是本领域技术人员已知的所有金属氧化物或金属氧化物水合物，例如氧化铝、氧化铝水合物、氧化硅、氧化硅水合物、氧化铁、氧化锡、氧化铈、氧化锌、氧化锆、氧化铬、硅酸锆ZrSiO4、莫来石、氧化钛，特别是二氧化钛、氧化钛水合物及其混合物，例如钛铁矿或铁板钛矿。可以使用的金属低氧化物是例如低价钛氧化物(例如Ti2O3或γ-Ti3O5)。合适的金属硅酸盐是硅酸铝、Mg硅酸盐、C硅酸盐或Ba硅酸盐；混合的碱土金属硅酸盐，例如Ca/Mg硅酸盐、Zr硅酸盐或所述硅酸盐的混合物。合适的金属是例如铬、铝、镍、银、金、钛、铜或合金，和合适的金属氟化物是例如氟化镁。可以使用的金属氮化物或金属氮氧化物是例如金属钛、锆和/或钽的氮化物或氮氧化物。金属氧化物、金属、金属氟化物和/或金属氧化物水合物层，和非常特别优选金属氧化物和/或金属氧化物水合物层优选施加到载体上。此外，还可以存在包含高-和低-折射率金属氧化物、金属氧化物水合物、金属或金属氟化物层的多层结构，其中高折射率层和低折射率层优选交替。特别优选包含高折射率层和低折射率层的层包(layer package)，其中这些层包中的一个或多个可以施加到载体上。此处高折射率层和低折射率层的顺序可以与载体匹配，以便将载体结合到多层结构中。在另一个实施方案中，金属氧化物、金属硅酸盐、金属氧化物水合物、金属低氧化物、金属、金属氟化物、金属氮化物或金属氧氮化物层可以与着色剂或其他元素混合或掺杂。合适的着色剂或其他元素是，例如，无机有色颜料，例如有色金属氧化物、例如磁铁矿，氧化铬(III)或有色颜料，例如，Thenard's Blue(Co/Al尖晶石)或者元素，例如钇或锑，以及通常来自钙钛矿、烧绿石、金红石和尖晶石的结构类的颜料。包含这些层的珠光颜料在其质色调(mass tone)方面表现出很大的颜色变化，并且在许多情况下可能由于干涉而呈现出角度依赖的颜色变化(随角异色(colour flop))。
在一个优选的实施方案中，载体上的外层是高折射率金属氧化物。该外层可以另外在上述层包上，或者在高折射率载体的情况下，可以是层包的一部分，并且例如由TiO2、低价钛氧化物、Fe2O3、SnO2、ZnO、ZrO2、Ce2O3、CoO、Co3O4、V2O5、Cr2O3和/或其混合物，例如钛铁矿或铁板钛矿组成。
金属氧化物、金属氧化物水合物、金属硅酸盐、金属低氧化物、金属、金属氟化物、金属氮化物或金属氧氮化物层或其混合物的厚度通常为3至300nm，并且在金属氧化物、金属氧化物水合物、金属低氧化物、金属氟化物、金属氮化物或金属氧氮化物层或其混合物的情况下，优选20至200nm。金属层的厚度优选为4至50nm。
光学层优选由TiO2、ZrO2、Fe2O3、Fe3O4、SnO2、ZnO或混合物或其组合组成。该层可以是未掺杂的或掺杂的。合适的掺杂剂是例如碱土金属或其化合物，特别是钙和镁。基于各层，掺杂比例通常最大为5重量％。
光学层特别优选为多层体系中的TiO2层、Fe2O3层、TiO2/Fe2O3混合层、铁板钛矿层(Fe2TiO5)或这些层的组合，例如TiO2-SiO2-TiO2或Fe2O3-SiO2-Fe2O3。
二氧化钛可以以金红石或锐钛矿变型的形式存在于高折射率涂层中，优选以金红石的形式存在。制备金红石的方法描述于例如现有技术的U.S.5,433,779、U.S.4,038,099、U.S.6,626,989、DE 25 22 572 C2和EP 0 271 767 B1中。用作添加剂以将TiO2转化为金红石的薄氧化锡层(<10nm)优选在TiO2沉淀之前施加到基材薄片上。
光学活性层的厚度在每种情况下优选为30至350nm，特别是50至250nm。
特别优选用于根据本发明的陶瓷色料的基于薄片状基材的珠光颜料如下所示：
基材薄片+TiO2
基材薄片+Fe2O3
基材薄片+Fe3O4
基材薄片+TiO2/Fe2O3
基材薄片+FeTiO3
基材薄片+Fe2TiO5
基材薄片+ZrO2
基材薄片+ZnO
基材薄片+SnO2
基材薄片+Cr2O3
基材薄片+Ce2O3
基材薄片+TiOx(还原)，其中x＝1.50–1.95
基材薄片+TiO2+Fe2O3
基材薄片+TiO2+Fe3O4
基材薄片+Fe2O3+TiO2
基材薄片+TiO2+SiO2+TiO2
基材薄片+TiO2+SnO2+TiO2
基材薄片+TiO2+Al2O3+TiO2
基材薄片+Fe2O3+SiO2+TiO2
基材薄片+TiO2/Fe2O3+SiO2+TiO2
基材薄片+TiO2/Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3
基材薄片+TiO2+SiO2+TiO2/Fe2O3
基材薄片+TiO2+SiO2
基材薄片+TiO2+Al2O3
基材薄片+TiO2+MgO x SiO2+TiO2
基材薄片+Fe2O3+MgO x SiO2+TiO2
基材薄片+TiO2/Fe2O3+MgO x SiO2+TiO2
基材薄片+TiO2/Fe2O3+MgO x SiO2+TiO2/Fe2O3
基材薄片+TiO2/Fe2O3+MgO x SiO2+TiO2+TiO2/Fe2O3
基材薄片+TiO2+MgO x SiO2+TiO2/Fe2O3
基材薄片+SnO2+TiO2+SiO2+SnO2+TiO2
基材薄片+SnO2+TiO2+SnO2+TiO2
基材薄片+SnO2+TiO2+Fe2O3+SiO2+SnO2+TiO2+Fe2O3
基材薄片+Fe2O3+SnO2+TiO2
基材薄片+Fe2O3+SnO2+Fe2O3
基材薄片+TiO2+SnO2+TiO2
基材薄片+TiO2/Fe2O3+SnO2+TiO2
基材薄片+TiO2/Fe2O3+SnO2+TiO2/Fe2O3
基材薄片+SnO2+TiO2+Fe2O3+SnO2+TiO2+Fe2O3.
基材薄片+Fe2TiO5+SnO2+Fe2TiO5
基材薄片+Fe2TiO5+SiO2+Fe2TiO5
在另一个优选的实施方案中，首先将第一低折射率层施加到基材薄片上。本申请中的低折射率层是指折射率<1.8的层。
基材上低折射率层优选选自Al2O3、SiO2、硅酸铬ZrSiO4、莫来石3Al2O3x 2SiO2或2Al2O3xSiO2(烧结或电熔(fused)莫来石)或碱土金属硅酸盐(MSiO3，其中M＝Mg2+、Ca2+、Sr2+或Ba2+，或M2Si3O8，其中M＝Mg2+、Ca2+、Sr2+或Ba2+)。
在基材表面上具有低折射率层(LRL)的优选的颜料特征在于以下结构：
基材薄片+LRL+TiO2
基材薄片+LRL+Fe2O3
基材薄片+LRL+Fe3O4
基材薄片+LRL+TiO2/Fe2O3
基材薄片+LRL+FeTiO3
基材薄片+LRL+Fe2TiO5
基材薄片+LRL+ZrO2
基材薄片+LRL+ZnO
基材薄片+LRL+SnO2
基材薄片+LRL+Cr2O3
基材薄片+LRL+Ce2O3
基材薄片+LRL+TiOx(还原)，其中x＝1.50–1.95
基材薄片+LRL+TiO2+Fe2O3
基材薄片+LRL+TiO2+Fe3O4
基材薄片+LRL+Fe2O3+TiO2
基材薄片+LRL+TiO2+SiO2+TiO2
基材薄片+LRL+TiO2+SnO2+TiO2
基材薄片+LRL+TiO2+Al2O3+TiO2
基材薄片+LRL+Fe2O3+SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2+SiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2+SiO2
基材薄片+LRL+TiO2+Al2O3
基材薄片+LRL+TiO2+MgO x SiO2+TiO2
基材薄片+LRL+Fe2O3+MgO x SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+MgO x SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+MgO x SiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2/Fe2O3+MgO x SiO2+TiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2+MgO x SiO2+TiO2/Fe2O3
基材薄片+LRL+SnO2+TiO2+SiO2+SnO2+TiO2
基材薄片+LRL+SnO2+TiO2+SnO2+TiO2
基材薄片+LRL+SnO2+TiO2+Fe2O3+SiO2+SnO2+TiO2+Fe2O3
基材薄片+LRL+Fe2O3+SnO2+TiO2
基材薄片+LRL+Fe2O3+SnO2+Fe2O3
基材薄片+LRL+TiO2+SnO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SnO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SnO2+TiO2/Fe2O3
基材薄片+LRL+SnO2+TiO2+Fe2O3+SnO2+TiO2+Fe2O3
基材薄片+LRL+Fe2TiO5+SnO2+Fe2TiO5
基材薄片+LRL+Fe2TiO5+SiO2+Fe2TiO5
在根据本发明的陶瓷色料中也可以使用不同的珠光颜料作为混合物。优选地，仅使用一种珠光颜料。
本发明的优选实施方案包含优选的效果颜料和/或未涂覆的薄片状基材和优选的含硅聚合物。尤其优选的是其中所有组分以其特别优选的变体使用的组合。特别优选的是优选的效果颜料和优选的含硅聚合物以其优选的比例的组合。包含这种组合和丝网印刷油的配制剂也是优选的。
本申请中的层或涂层是指薄片状基材的完全覆盖。
珠光颜料可以相对容易地制备。基材薄片的覆盖物优选通过湿化学方法进行，其中可以使用为制备珠光颜料而开发的湿化学涂覆方法。这种类型的方法例如描述于DE 1467 468、DE 19 59 988、DE 20 09 566、DE 22 14 545、DE 22 15 191、DE 22 44 298、DE 2313 331、DE 25 22 572、DE 31 37 808、DE 31 37 809、DE 31 51 343、DE 31 51 354、DE 3151 355、DE 32 11 602、DE 32 35 017或还描述于本领域技术人员已知的其它专利文献和其它出版物中。
此外，基材的涂覆也可以通过在流化床反应器中的气相涂覆来进行，其中，例如，EP 0 045 851 A1和EP 0 106 235A1中对于制备珠光颜料提出的方法可以相应地使用。
在湿涂覆的情况下，将基材颗粒悬浮在水中，并在适合水解的pH下加入一种或多种可溶性金属盐，选择该pH以使金属氧化物或金属氧化物水合物直接沉淀在薄片中，而无二次沉淀发生。通过同时计量加入碱或酸，pH通常保持恒定。随后将颜料分离，洗涤并干燥并任选煅烧，其中煅烧温度可相对于每种情况下存在的涂层进行优化。通常，煅烧温度在250至1000℃之间，优选在350至900℃之间。如果需要，可以在施加单独的涂层后分离颜料，干燥并任选煅烧，然后重新悬浮以沉淀其它层。
例如，如果要还原TiO2或TiO2/Fe2O3层，则优选在干燥后通过随后在500至1200℃，优选在500至1000℃，特别在500至800℃在还原条件下(优选在合成气体(N2/H2)下)煅烧0.5-5h，优选0.5-2h进行最终珠光颜料的还原。然而，在使用已在釉中还原条件下煅烧的颜料时，已证明同样有助于在待上釉工件的烧制条件下选择还原条件。
为了改善与印刷介质的润湿性和/或相容性，根据应用领域，经常建议对成品珠光颜料进行无机或有机后涂覆或后处理。合适的后涂覆或后处理例如为在DE专利22 15 191、DE-A 31 51 354、DE-A 32 35 017或DE-A 33 34 598中描述的方法。该后涂覆简化了颜料的处理，特别是掺入各种介质中。为了改善与施加介质的润湿性、分散性和/或相容性，包含有机或合并的有机/无机后涂层的功能涂层可以是可行的，例如使用硅烷，如例如在DE10348174、EP 0090259、EP 0 342 533、EP 0 632 109、EP 0 888 410、EP 0 634 459、EP 1203795、WO 94/01498、WO 96/32446、WO 99/57204、WO 2004/092284、US 5,759,255、US 5,571,851、WO 01/92425或在J.J.Ponjeé,Philips Technical Review,Vol.44,No.3,81ff.和P.H.Harding J.C.Berg,J.Adhesion Sci.Technol.Vol.11No.4,pp.471-493中所描述。后涂层仅占0.1-5wt％，优选0.5-3wt％的比例，基于珠光颜料。
在本发明的一个具体实施方案中，珠光颜料是疏水或两亲性后涂覆的，其在通过印刷浆料施用时，产生在印刷介质中更均匀分布，并因此在工件上更均匀的颜色分布的优点。
本发明扩大了着色的陶瓷釉在烧制或未烧制的砖、室内或室外用途的地板和墙砖，卫生陶瓷，如浴缸、洗脸盆和坐便器(toilet pan)、瓷器陶器、陶器和陶瓷制品的颜色范围，其通过吸引人的干涉色(银色、金色、青铜色、铜色、红色、紫色、蓝色、蓝绿色(turquoise)、绿色)，以及使用所谓的质色调珠光颜料，其特征在于干涉和吸收颜色的组合，特别是金、黄铜、青铜、铜、红和绿色颜色(shade)的区域。此外，其还促进了完全新颖的色彩效果，例如视角依赖的所谓的随角异色效果。此外，珠光颜料的选择促进了新颖的光学效果，例如闪耀/闪光效果和粗糙或精细结构。
本发明还涉及根据本发明的陶瓷色料用于在烧制或未烧制的砖、室内或室外用途的地板和墙砖、卫生陶瓷、瓷器、搪瓷、金属工件、陶器和陶瓷制品上的陶瓷釉的用途。陶瓷色料可以施加于无釉、釉面或上釉且烧制体上。
本发明还涉及根据本发明的陶瓷色料在制品上制造装饰性要素的用途，所述制品展示出瓷器(porcelain)、瓷(china)、骨灰瓷、陶瓷、玻璃或搪瓷的外表面。
因此，本发明还涉及包含根据本发明的陶瓷色料的配制剂。尤其提及的是用于在所述工件上转印的转印介质(transfer media)。
本发明还涉及釉面制品，例如烧制或未烧制的砖、室内或室外使用的地板和墙砖、卫生陶瓷、瓷器、搪瓷、金属工件、陶器和陶瓷制品(ceramicware)，其包含基于根据本发明陶瓷色料的陶瓷釉。
根据本发明，陶瓷色料可以优选通过将珠光颜料与相应量的聚合物组分和印刷介质组合来制备。在混合物均匀化之后，可以通过常规方法将其施加到工件上。陶瓷色料可以成像方式施加以产生光学图案或施加在大面积上。
所获得的陶瓷色料可通过标准印刷工艺如调制泥浆过程(slip process)，喷涂或转移印刷施加到工件上。
陶瓷色料优选通过丝网印刷施加在陶瓷制品上。对于光滑的表面，可以使用直接印刷，并且对于不平坦的表面，可以使用具有转印介质的转印。原则上，陶瓷色料可以通过可用于工件的所有印刷方法(即喷墨印刷、柔版印刷、凹版印刷、移印(tampon printing))施加。此外，陶瓷还可以通过用于涂覆的方法如喷涂，刮刀，涂漆，浸涂，淋釉涂覆(waterfall application)来施加。尤其是在搪瓷技术中，浸渍或浴涂也是常见的。优选的例子是直接或转印的丝网印刷。然而，也可以使用刷子、冲压(stamping)或用铅笔书写的手工装饰。
在施加陶瓷色料之后，优选通过在干燥箱或通风橱中在60-110℃的温度下加热来干燥涂覆的工件，以蒸发存在的溶剂。
然后将印刷或涂覆和干燥的陶瓷制品在700℃-1300℃，优选800℃-1200℃，特别是850-1150℃的温度下烧制。
印刷或涂覆和干燥的金属制品随后在450℃-950℃，优选500℃-900℃，特别是550℃-850℃的温度下烧制。
然后将印刷或涂覆和干燥的陶瓷或金属制品在烧制周期(加热+保持+冷却)下烧制0.5-72小时，优选0.5-30小时，特别是0.5-3小时。
保持时间本身在1分钟至68小时变化，优选1分钟至25小时，特别是1分钟至2小时。
加热时间本身在0.2-36小时变化，优选0.25-15小时，特别是0.25-4小时。
冷却时间本身在0.2-36小时变化，优选0.25-15小时，特别是0.25-4小时。
优选地，随后将印刷和干燥的陶瓷制品在>700℃，优选>800℃，特别是>1000℃的温度下烧制。
优选地，印刷和干燥的制品通过例如以下温度曲线在烧成炉中烧制
180min：加热至1100℃，
3min：在1100℃下保持
120min：快速冷却至600℃，
300min：缓慢冷却至室温。
本发明的优选的实施方案包括组分，尤其是效果颜料和含硅聚合物，和/或工艺条件(以它们优选的，尤其是它们特别优选的变体)。尤其优选的是其中所有组分和特征都是特别优选的变体的组合。
具体实施方式
以下实施例旨在解释本发明，而不限制。
实施例
为了制备陶瓷色料，称出根据表1的实施例1-298的效果颜料并且用相应量的聚倍半硅氧烷和Ferro的印刷油221ME均匀化。
聚倍半硅氧烷在烧制后具有26％SiO2的所得固体含量。
在实施例中使用的珠光颜料均是可商购的并且具有表2中列出的组成(在“粒径”栏中，d10–d90值使用Malvern测量，并在每种情况下指出)：
获得的印刷浆料通过刮刀和丝网印刷施加到瓷砖上。在所有情况下，印刷的瓷砖在干燥箱或通风橱中在60-110℃的温度下干燥，以蒸发印刷油中存在的溶剂。
然后通过根据图1的温度曲线在烧成炉中烧制印刷和干燥的瓷砖。
180min：加热至1100℃，
3min：在1100℃下保持，
120min：快速冷却至600℃，
300min：缓慢冷却至室温。
作为时间函数的温度程序如图1所示。
根据本发明的实施例的釉面砖的特征在于，在500-1300℃的相应高温应用中，所需的光学效果是稳定的并且可以以可再现的方式获得。
表1
表2
Claims (17)
1.一种制备釉面制品的方法，包括以下步骤：
(a)通过混合至少一种基于薄片状基材和/或折射率R.I.>1.5的未涂覆的薄片状基材的效果颜料、至少一种含硅聚合物、任选的溶剂、任选的粘合剂、任选的吸收性陶瓷颜料，以及任选的至少一种添加剂制备陶瓷色料，
(b)在陶瓷或金属体上印刷或涂覆步骤(a)中获得的陶瓷色料，
(c)干燥步骤(b)中获得的陶瓷或金属体，
(d)在450-1300℃范围的温度下烧制步骤(c)中获得的陶瓷或金属体。
2.根据权利要求1的方法，其特征在于在步骤(d)中陶瓷体在700-1300℃的温度下烧制或金属体在450-950℃的温度下烧制。
3.根据权利要求1-2的一项或多项的方法，其特征在于陶瓷色料中效果颜料的比例为至少0.1wt％，基于含硅聚合物。
4.根据权利要求1-3的一项或多项的方法，其特征在于效果颜料基于薄片状的基材，其选自合成云母薄片、天然云母薄片、玻璃薄片、Al2O3薄片、SiO2薄片、Fe2O3薄片、B4C薄片、TiO2薄片、SiC薄片、SixNyCz薄片，其中x＝0.5-1.0；y＝0.25-0.5；z＝0.25-0.5、BN薄片和石墨薄片。
5.根据权利要求1-4的一项或多项的方法，其特征在于用一种或多种金属氧化物、金属硫化物、稀土金属氧化物和/或一种或多种金属或其混合物的一个或多个层覆盖效果颜料的薄片状基材。
6.根据权利要求1-5的一项或多项的方法，其特征在于效果颜料的薄片状基材用一个或多个层在表面上覆盖，所述一个或多个层选自TiO2、Fe2O3、ZrO2、SnO2、TiO2/Fe2O3、Fe2TiO5、FeTiO3、FeOOH、Fe3O4、Cr2O3和TiOx，其中x＝1.50-1.95。
7.根据权利要求1-6的一项或多项的方法，其特征在于薄片状基材具有0.05-5.0μm的颗粒厚度。
8.根据权利要求1-7的一项或多项的方法，其特征在于陶瓷色料包含至少一种聚硅氮烷、至少一种聚硅氧烷和/或至少一种聚倍半硅氧烷作为含硅聚合物。
9.根据权利要求1-8的一项或多项的方法，其特征在于陶瓷色料包含印刷油。
10.根据权利要求1-9的一项或多项的方法，其特征在于效果颜料选自以下颜料的组：
基材薄片+TiO2
基材薄片+Fe2O3
基材薄片+Fe3O4
基材薄片+TiO2/Fe2O3
基材薄片+FeTiO3
基材薄片+Fe2TiO5
基材薄片+ZrO2
基材薄片+ZnO
基材薄片+SnO2
基材薄片+Cr2O3
基材薄片+Ce2O3
基材薄片+TiOx(还原的)，其中x＝1.50–1.95
基材薄片+TiO2+Fe2O3
基材薄片+TiO2+Fe3O4
基材薄片+Fe2O3+TiO2
基材薄片+TiO2+SiO2+TiO2
基材薄片+TiO2+SnO2+TiO2
基材薄片+TiO2+Al2O3+TiO2
基材薄片+Fe2O3+SiO2+TiO2
基材薄片+TiO2/Fe2O3+SiO2+TiO2
基材薄片+TiO2/Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3
基材薄片+TiO2+SiO2+TiO2/Fe2O3
基材薄片+TiO2+SiO2
基材薄片+TiO2+Al2O3
基材薄片+TiO2+MgO x SiO2+TiO2
基材薄片+Fe2O3+MgO x SiO2+TiO2
基材薄片+TiO2/Fe2O3+MgO x SiO2+TiO2
基材薄片+TiO2/Fe2O3+MgO x SiO2+TiO2/Fe2O3
基材薄片+TiO2/Fe2O3+MgO x SiO2+TiO2+TiO2/Fe2O3基材薄片+TiO2+MgO x SiO2+TiO2/Fe2O3
基材薄片+SnO2+TiO2+SiO2+SnO2+TiO2
基材薄片+SnO2+TiO2+SnO2+TiO2
基材薄片+SnO2+TiO2+Fe2O3+SiO2+SnO2+TiO2+Fe2O3基材薄片+Fe2O3+SnO2+TiO2
基材薄片+Fe2O3+SnO2+Fe2O3
基材薄片+TiO2+SnO2+TiO2
基材薄片+TiO2/Fe2O3+SnO2+TiO2
基材薄片+TiO2/Fe2O3+SnO2+TiO2/Fe2O3
基材薄片+SnO2+TiO2+Fe2O3+SnO2+TiO2+Fe2O3.
基材薄片+Fe2TiO5+SnO2+Fe2TiO5
基材薄片+Fe2TiO5+SiO2+Fe2TiO5。
11.根据权利要求1-10的一项或多项的方法，其特征在于基材薄片上的效果颜料具有第一低折射率层(＝LRL)，其包含Al2O3、SiO2、硅酸锆ZrSiO4、莫来石3Al2O3 x 2SiO2或2Al2O3x SiO2(烧结或电熔莫来石)或碱土金属硅酸盐(MSiO3，其中M＝Mg2+、Ca2+、Sr2+或Ba2+，或M2Si3O8，其中M＝Mg2+、Ca2+、Sr2+或Ba2+)和选自以下颜料的组：
基材薄片+LRL+TiO2
基材薄片+LRL+Fe2O3
基材薄片+LRL+Fe3O4
基材薄片+LRL+TiO2/Fe2O3
基材薄片+LRL+FeTiO3
基材薄片+LRL+Fe2TiO5
基材薄片+LRL+ZrO2
基材薄片+LRL+ZnO
基材薄片+LRL+SnO2
基材薄片+LRL+Cr2O3
基材薄片+LRL+Ce2O3
基材薄片+LRL+TiOx(还原的)，其中x＝1.50–1.95
基材薄片+LRL+TiO2+Fe2O3
基材薄片+LRL+TiO2+Fe3O4
基材薄片+LRL+Fe2O3+TiO2
基材薄片+LRL+TiO2+SiO2+TiO2
基材薄片+LRL+TiO2+SnO2+TiO2
基材薄片+LRL+TiO2+Al2O3+TiO2
基材薄片+LRL+Fe2O3+SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2+SiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2+SiO2
基材薄片+LRL+TiO2+Al2O3
基材薄片+LRL+TiO2+MgO x SiO2+TiO2
基材薄片+LRL+Fe2O3+MgO x SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+MgO x SiO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+MgO x SiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2/Fe2O3+MgO x SiO2+TiO2+TiO2/Fe2O3
基材薄片+LRL+TiO2+MgO x SiO2+TiO2/Fe2O3
基材薄片+LRL+SnO2+TiO2+SiO2+SnO2+TiO2
基材薄片+LRL+SnO2+TiO2+SnO2+TiO2
基材薄片+LRL+SnO2+TiO2+Fe2O3+SiO2+SnO2+TiO2+Fe2O3
基材薄片+LRL+Fe2O3+SnO2+TiO2
基材薄片+LRL+Fe2O3+SnO2+Fe2O3
基材薄片+LRL+TiO2+SnO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SnO2+TiO2
基材薄片+LRL+TiO2/Fe2O3+SnO2+TiO2/Fe2O3
基材薄片+LRL+SnO2+TiO2+Fe2O3+SnO2+TiO2+Fe2O3
基材薄片+LRL+Fe2TiO5+SnO2+Fe2TiO5
基材薄片+LRL+Fe2TiO5+SiO2+Fe2TiO5。
12.包含至少一种含硅聚合物和至少一种效果颜料的陶瓷色料，所述效果颜料基于薄片状基材和/或至少一种折射率R.I.>1.5的未涂覆的薄片状基材，所述薄片状基材选自Al2O3薄片、SiC薄片、B4C薄片、BN薄片、石墨薄片、TiO2薄片和Fe2O3薄片，所述未涂覆的薄片状基材选自Al2O3薄片、SiC薄片、SixNyCz薄片，其中x＝0.5-1.0；y＝0.25-0.5；z＝0.25-0.5、B4C薄片、BN薄片、石墨薄片、TiO2薄片和Fe2O3薄片。
13.根据权利要求12的陶瓷色料，其特征在于效果颜料在陶瓷色料中的比例为至少0.1wt％，基于含硅聚合物。
14.根据权利要求12-13的一项或多项的陶瓷色料，其特征在于其包含至少一种聚硅氮烷、至少一种聚硅氧烷和/或至少一种聚倍半硅氧烷作为含硅聚合物。
15.根据权利要求12-14的一项或多项的陶瓷色料用于未烧制或烧制的砖、未烧制或烧制的陶器、陶瓷制品、陶瓷釉、装饰瓷砖、瓷釉或如搪瓷的金属装饰的用途。
16.包含根据权利要求12-14的一项或多项的陶瓷色料的配制剂。
17.根据权利要求12-14的一项或多项的陶瓷色料用于在展示出瓷器、瓷、骨灰瓷、陶瓷、玻璃或搪瓷的外表面的制品上制造装饰性要素的用途。
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-
2019
- 2019-04-29 EP EP19171590.3A patent/EP3564200A1/en not_active Withdrawn
- 2019-04-30 CN CN201910359372.6A patent/CN110437647A/zh active Pending
- 2019-05-03 US US16/402,321 patent/US20190337862A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636850A (zh) * | 2021-08-31 | 2021-11-12 | 浙江锦诚新材料股份有限公司 | 一种刚玉-尖晶石窑口耐火浇注料及预制件的制备方法 |
| CN113636850B (zh) * | 2021-08-31 | 2022-08-12 | 浙江锦诚新材料股份有限公司 | 一种刚玉-尖晶石窑口耐火浇注料及预制件的制备方法 |
| CN114276700A (zh) * | 2022-01-06 | 2022-04-05 | 广西七色珠光材料股份有限公司 | 一种无钛金色珠光颜料及其制备方法和用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20190337862A1 (en) | 2019-11-07 |
| EP3564200A1 (en) | 2019-11-06 |
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