CN118344140A - 氧化锆组合物、氧化锆预烧体和氧化锆烧结体、以及齿科用制品 - Google Patents
氧化锆组合物、氧化锆预烧体和氧化锆烧结体、以及齿科用制品 Download PDFInfo
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- CN118344140A CN118344140A CN202410461826.1A CN202410461826A CN118344140A CN 118344140 A CN118344140 A CN 118344140A CN 202410461826 A CN202410461826 A CN 202410461826A CN 118344140 A CN118344140 A CN 118344140A
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- zirconia
- oxide
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 306
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 229940023487 dental product Drugs 0.000 title abstract description 11
- 239000003086 colorant Substances 0.000 claims abstract description 276
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 36
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 34
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 31
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 26
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 238000004383 yellowing Methods 0.000 claims description 8
- 150000001463 antimony compounds Chemical class 0.000 claims description 7
- 150000001785 cerium compounds Chemical class 0.000 claims description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 2
- 238000002845 discoloration Methods 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002506 iron compounds Chemical class 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052845 zircon Inorganic materials 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910006501 ZrSiO Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000009694 cold isostatic pressing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001513 hot isostatic pressing Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000003114 praseodymium compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000006103 coloring component Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- -1 cr) 2O4) Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000000504 luminescence detection Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001062 red colorant Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
Classifications
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Abstract
本发明涉及氧化锆组合物、氧化锆预烧体和氧化锆烧结体、以及齿科用制品。提供由烤瓷导致的褪色受到抑制的氧化锆烧结体。氧化锆烧结体含有:着色剂A和着色剂B之中的至少一者;以及,着色剂C:锆与钒的复合氧化物,其中,所述着色剂A为氧化铒,所述着色剂B为氧化镍。
Description
本发明申请是PCT专利申请PCT/JP2015/080728,申请日为2015年10月30日、发明名称为“氧化锆组合物、氧化锆预烧体和氧化锆烧结体、以及齿科用制品”的发明专利申请的分案申请,母案进入中国的申请号为201580059232.7。
技术领域
[针对相关申请的记载]
本发明基于日本专利申请:日本特愿2014-223636号(2014年10月31日申请)要求优先权,将该申请的全部记载内容通过引用而援引记载于本说明书中。
本发明涉及含有颜料的氧化锆烧结体。此外,本发明涉及用于制造该氧化锆烧结体的氧化锆组合物和氧化锆预烧体。进而,本发明涉及使用了该氧化锆烧结体的齿科用制品。
背景技术
近年来,作为齿科用的修补物(覆盖冠、齿冠、牙冠、装接假牙等),从审美性和安全性的观点出发,使用氧化锆等陶瓷来代替金属。并且,通过在陶瓷的外框上烧结玻璃等烤瓷来重现天然牙齿的外观(例如,参照专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2007-126360号公报。
发明内容
发明要解决的问题
从本发明的观点出发,提供下述分析。
为了使修补物看起来像天然牙齿,有时也向成为基材的陶瓷本体中添加着色成分。通常,天然牙齿显现黄色和红色,因此向陶瓷中添加显黄色和红色的着色剂。作为该黄色系着色剂和红色系着色剂,大多添加对于人体而言安全的镨化合物和铁化合物。然而,若在添加有镨化合物和/或铁化合物的陶瓷上承载烤瓷并烧结,则有时得不到期望的颜色。考虑这是因为:在烤瓷中作为抗黄变材料而添加的锑化合物、铈化合物等会抑制镨化合物、铁化合物等所带来的显色。因而,期望显色不会被锑化合物、铈化合物等抑制且能够重现出与天然牙齿相同颜色的陶瓷。
用于解决问题的方法
根据本发明的第1视点,提供氧化锆烧结体,其含有:着色剂A和着色剂B之中的至少一者;以及,着色剂C:锆和钒的复合氧化物,其中,所述着色剂A为氧化铒,所述着色剂B为氧化镍。
根据本发明的第2视点,提供氧化锆烧结体,其含有选自下述组中的至少1个着色剂,所述组包含:着色剂A:氧化铒;着色剂B:氧化镍;着色剂C:锆和钒的复合氧化物;着色剂D:铁、钴和铬的复合氧化物、锆和硅的复合氧化物、二氧化硅、以及氧化镍的混合物;以及,着色剂E:锆、硅、钴和镍的复合氧化物。
根据本发明的第3视点,提供含有氧化锆、氧化钇和着色剂的组合物。着色剂包含:着色剂A和着色剂B之中的至少一者;以及,着色剂C:锆和钒的复合氧化物,其中,所述着色剂A为氧化铒,所述着色剂B为氧化镍。
根据本发明的第4视点,提供含有氧化锆、氧化钇和着色剂的组合物。着色剂包含选自下述组中的至少1个着色剂,所述组包含:着色剂A:氧化铒;着色剂B:氧化镍;着色剂C:锆和钒的复合氧化物;着色剂D:铁、钴和铬的复合氧化物、锆和硅的复合氧化物、二氧化硅、以及氧化镍的混合物;以及,着色剂E:锆、硅、钴和镍的复合氧化物。
根据本发明的第5视点,提供含有氧化锆、氧化钇和着色剂的预烧体。着色剂包含:着色剂A和着色剂B之中的至少一者;以及,着色剂C:锆和钒的复合氧化物,其中,所述着色剂A为氧化铒,所述着色剂B为氧化镍。
根据本发明的第6视点,提供含有氧化锆、氧化钇和着色剂的预烧体。着色剂包含选自下述组中的至少1个着色剂,所述组包含:着色剂A:氧化铒;着色剂B:氧化镍;着色剂C:锆和钒的复合氧化物;着色剂D:铁、钴和铬的复合氧化物、锆和硅的复合氧化物、二氧化硅、以及氧化镍的混合物;以及,着色剂E:锆、硅、钴和镍的复合氧化物。
根据本发明的第7视点,提供具备各视点中的任一氧化锆烧结体的齿科用制品。
发明的效果
即使烧结了含有锑化合物和/或铈化合物的烤瓷,也能够抑制氧化锆烧结体的褪色。
上述各视点的优选方式如下所述。
根据上述第1视点的优选方式,氧化锆烧结体含有0.002质量%~0.4质量%的着色剂A、0.0002质量%~0.03质量%的着色剂B、以及0.005质量%~0.1质量%的着色剂C。
根据上述第1视点的优选方式,氧化锆烧结体含有0.01质量%~0.02质量%的着色剂B、以及0.06质量%~0.08质量%的着色剂C。
根据上述第2视点的优选方式,氧化锆烧结体含有着色剂A、着色剂B和着色剂C中的至少一者;以及,着色剂D和着色剂E中的至少一者。
根据上述第2视点的优选方式,氧化锆烧结体含有0.005质量%~0.02质量%的着色剂C、以及0.06质量%~0.08质量%的着色剂E。
根据上述第2视点的优选方式,氧化锆烧结体含有0.07质量%~0.09质量%的着色剂C、以及0.05质量%~0.2质量%的着色剂D。
根据上述第2视点的优选方式,氧化锆烧结体含有0.007质量%~0.06质量%的着色剂B、以及0.01质量%~0.06质量%的着色剂D。
根据上述第2视点的优选方式,氧化锆烧结体含有0.01质量%~0.04质量%的着色剂A、0.05质量%~0.07质量%的着色剂C、以及0.05质量%~0.08质量%的着色剂D。
根据上述第2视点的优选方式,氧化锆烧结体含有0.002质量%~0.3质量%的着色剂A、0.0005质量%~0.03质量%的着色剂B、0.005质量%~0.07质量%的着色剂C、以及0.004质量%~0.04质量%的着色剂D。
根据上述第3视点的优选方式,组合物含有0.002质量%~0.4质量%的着色剂A、0.0002质量%~0.03质量%的着色剂B、以及0.005质量%~0.1质量%的着色剂C。
根据上述第3视点的优选方式,组合物含有0.01质量%~0.02质量%的着色剂B、以及0.06质量%~0.08质量%的着色剂C。
根据上述第4视点的优选方式,组合物含有着色剂A、着色剂B和着色剂C中的至少一者;以及,着色剂D和着色剂E中的至少一者。
根据上述第4视点的优选方式,组合物含有0.02质量%~0.03质量%的着色剂C、以及0.06质量%~0.08质量%的着色剂E。
根据上述第4视点的优选方式,组合物含有0.07质量%~0.09质量%的着色剂C、以及0.08质量%~0.12质量%的着色剂D。
根据上述第4视点的优选方式,组合物含有0.007质量%~0.06质量%的着色剂B、以及0.01质量%~0.06质量%的着色剂D。
根据上述第4视点的优选方式,组合物含有0.01质量%~0.04质量%的着色剂A、0.05质量%~0.07质量%的着色剂C、以及0.05质量%~0.08质量%的着色剂D。
根据上述第4视点的优选方式,组合物含有0.002质量%~0.3质量%的着色剂A、0.0005质量%~0.03质量%的着色剂B、0.005质量%~0.07质量%的着色剂C、以及0.004质量%~0.04质量%的着色剂D。
根据上述第4视点的优选方式,提供将组合物在800℃~1200℃下进行烧成而制作的预烧体。
根据上述第4视点的优选方式,提供将组合物在1300℃~1600℃下进行烧成而制作的氧化锆烧结体。
根据上述第5视点的优选方式,预烧体含有0.002质量%~0.4质量%的着色剂A、0.0002质量%~0.03质量%的着色剂B、以及0.005质量%~0.1质量%的着色剂C。
根据上述第5视点的优选方式,预烧体含有0.01质量%~0.02质量%的着色剂B、以及0.06质量%~0.08质量%的着色剂C。
根据上述第6视点的优选方式,预烧体含有着色剂A、着色剂B和着色剂C中的至少一者;以及,着色剂D和着色剂E中的至少一者。
根据上述第6视点的优选方式,预烧体含有0.02质量%~0.03质量%的着色剂C、以及0.06质量%~0.08质量%的着色剂E。
根据上述第6视点的优选方式,预烧体含有0.07质量%~0.09质量%的着色剂C、以及0.08质量%~0.12质量%的着色剂D。
根据上述第6视点的优选方式,预烧体含有0.007质量%~0.06质量%的着色剂B、以及0.01质量%~0.06质量%的着色剂D。
根据上述第6视点的优选方式,预烧体含有0.01质量%~0.04质量%的着色剂A、0.05质量%~0.07质量%的着色剂C、以及0.05质量%~0.08质量%的着色剂D。
根据上述第6视点的优选方式,预烧体含有0.002质量%~0.3质量%的着色剂A、0.0005质量%~0.03质量%的着色剂B、0.005质量%~0.07质量%的着色剂C、以及0.004质量%~0.04质量%的着色剂D。
根据上述第6视点的优选方式,提供将预烧体在1300℃~1600℃下进行烧成而制作的氧化锆烧结体。
根据上述第7视点的优选方式,齿科用制品还具备层叠于氧化锆烧结体的烤瓷层。烤瓷层含有抗黄变材料。
根据上述第7视点的优选方式,抗黄变材料含有锑化合物和铈化合物之中的至少一者。
针对本发明的第1实施方式所述的氧化锆烧结体进行说明。本发明的氧化锆烧结体是以部分稳定化氧化锆晶粒为主进行烧结而得到的烧结体,作为基体相而具有部分稳定化氧化锆。本发明的氧化锆烧结体中,氧化锆的主要结晶相是正方晶系和立方晶系中的至少一者。氧化锆也可以含有正方晶系和立方晶系这两者。在未进行水热处理试验的阶段中,氧化锆烧结体优选实质上不含单斜晶系。
本发明的氧化锆烧结体中,不仅包括使已成形的氧化锆颗粒在常压下~不加压的条件下烧结而得到的烧结体,还包括利用HIP(Hot Isostatic Pressing;热等静压制)处理等高温加压处理使其致密化而得到的烧结体。
本发明的氧化锆烧结体含有氧化锆(zirconia)、其稳定剂和着色剂。氧化锆烧结体也可以含有其它的添加物。作为添加物,可列举出例如氧化钛、氧化铝、二氧化硅等。
作为部分稳定化氧化锆中的稳定剂,可列举出例如氧化钙(CaO)、氧化镁(MgO)、氧化钇(Y2O3)(以下成为“三氧化二钇”)、氧化铈(CeO2)等氧化物的氧化物。使用后述着色剂时,更优选使用三氧化二钇。稳定剂优选添加能够使氧化锆实现部分稳定化的量。例如,作为稳定剂而使用氧化钇时,氧化钇的含有率在氧化锆烧结体整体中相对于部分稳定化氧化锆优选可以添加2mol%~7mol%。氧化锆烧结体中的稳定剂的含有率例如可通过电感耦合等离子体(ICP;Inductively CoupledPlasma)发光分光分析、荧光X射线分析等来测定。应予说明,添加稳定剂而部分地实现稳定化的氧化锆被称为部分稳定化氧化锆(PSZ;Partially Stabilized Zirconia)。
接着,针对用于制造本发明的氧化锆烧结体的组合物和预烧体进行说明。组合物和预烧体成为上述本发明的氧化锆烧结体的前体(中间制品)。预烧体是将组合物以不会发生烧结的温度进行烧成(即预烧)而得到的。此外,预烧体还包括经成形加工而得到的产物。例如,通过CAD/CAM(Computer-Aided Design/Computer-AidedManufacturing)系统对经预烧的氧化锆盘进行加工而得到的齿科用制品(例如,齿冠形状的修补物)也属于预烧体。
组合物和预烧体含有氧化锆晶粒、稳定剂和着色剂(颜料)。组合物和预烧体可以含有其它的添加物。作为添加物,可列举出例如氧化钛、氧化铝、二氧化硅等。
作为组合物和预烧体中的稳定剂,可列举出例如氧化钙(CaO)、氧化镁(MgO)、三氧化二钇、氧化铈(CeO2)等氧化物。稳定剂优选添加能够使正方晶系氧化锆颗粒实现部分稳定化的量。例如,作为稳定剂而使用三氧化二钇时,三氧化二钇的含有率相对于氧化锆与三氧化二钇的总mol数优选为2mol%~7mol%。
本发明的组合物还包括:粉体、将粉体添加至溶剂而得到的流体、以及将粉体成形为特定形状而得到的成形体。即,组合物可以为粉末状,也可以为糊剂状~湿式组合物(即,可以在溶剂中,也可以包含溶剂)。此外,组合物可以含有粘结剂、颜料等添加物。应予说明,在上述含有率的计算中,未考虑溶剂、粘结剂等添加物的质量。
本发明的组合物为成形体时,可以通过任意的成形方法进行成形,例如,可以利用压制成形、注射成形、光造形法来进行成形,也可以实施多阶段的成形。例如,可以在将本发明的组合物进行压制成形后,进一步实施CIP(Cold Isostatic Pressing;冷等静压制)处理。
本发明的预烧体可通过将本发明的组合物在常压下以800℃~1200℃进行烧成来获得。
本发明的预烧体通过在常压下以1350℃~1600℃进行烧成,从而形成本发明的氧化锆烧结体。
本发明的氧化锆烧结体、组合物和预烧体中,作为着色成分,可以含有金属氧化物和市售的着色剂之中的至少一者。具有上述那种色度的氧化锆烧结体、组合物和预烧体例如可以包含选自下述组中的至少1个氧化物或化合物,所述组包含:氧化铒(Er2O3);氧化镍(NiO);锆和钒的复合氧化物((Zr,V)O2);铁、钴和铬的复合氧化物((Co,Fe)(Fe,Cr)2O4);锆和硅的复合氧化物(锆石(ZrSiO4));二氧化硅(SiO2);以及锆、硅、钴和镍的复合氧化物((Co,Ni)O·ZrSiO4)。
以下,着色剂的含有率是相对于氧化锆烧结体、组合物和预烧体中的氧化锆、稳定剂和着色剂的总质量的含有比例。此外,氧化锆烧结体和预烧体中,着色剂不限定于以烧成前的化合物的形态存在。着色剂有时也与氧化锆烧结体和预烧体中的成分发生反应。本申请中,氧化锆烧结体、组合物和预烧体中的着色剂的含有率以烧成前(添加时)的化合物作为基准来计算。关于说明书和权利要求书中记载的化学式,为了容易理解地表现出组成的内容而示出代表性组成,不一定严密地表示化学计量比的组成关系。上述组成的允许范围根据在实施本发明且实现其效果的基础上能够实际获取的材料来确定。
氧化锆烧结体、组合物和预烧体例如可以含有氧化铒(Er2O3)(以下称为“着色剂A”)。氧化锆烧结体、组合物和预烧体可以含有氧化镍(NiO)(以下称为“着色剂B”)。氧化锆烧结体、组合物和预烧体可以含有锆和钒的复合氧化物((Zr,V)O2)(以下称为“着色剂C”)。氧化锆烧结体、组合物和预烧体可以包含:含有铁、钴和铬的复合氧化物((Co,Fe)(Fe,Cr)2O4)、锆和硅的复合氧化物(锆石(ZrSiO4))、二氧化硅(SiO2)、以及氧化镍(NiO)的混合物((Co,Fe)(Fe,Cr)2O4)/ZrSiO4/SiO2/NiO)(以下称为“着色剂D”)。氧化锆烧结体、组合物和预烧体可以一并含有锆、硅、钴和镍的复合氧化物((Co,Ni)O·ZrSiO4)(以下称为“着色剂E”)。氧化锆烧结体、组合物和预烧体可以含有选自下述组中的至少1个着色剂,所述组包含着色剂A、着色剂B、着色剂C、着色剂D和着色剂E。
添加着色剂A时,存在氧化锆烧结体显红色的倾向。添加着色剂B时,存在氧化锆烧结体显红色的倾向。添加着色剂C时,存在氧化锆烧结体显黄色的倾向。添加着色剂D时,存在氧化锆烧结体显灰色的倾向。添加着色剂E时,存在氧化锆烧结体显灰色的倾向。尤其是,作为氧化镨(Pr6O11)的替代物,可以使用例如锆和钒的复合氧化物((Zr,V)O2)(例如,着色剂C)。作为氧化铁(Fe2O3)的替代物,可以使用氧化铒(Er2O3)(例如,着色剂A)和/或氧化镍(NiO)(例如,着色剂B)。
各着色剂还可以含有上述列举出的成分之外的成分。例如,着色剂C中除了含有上述成分之外,还可以含有铁化合物、镍化合物、铌化合物、钛化合物等。例如,着色剂D除了含有上述成分之外,还可以含有锰化合物、钒化合物等。例如,着色剂E中除了含有上述成分之外,还可以含有铁化合物。各着色剂除了含有与氧化锆烧结体的显色相关的成分之外,还可以含有与显色无关的成分。
以下,关于着色剂B的含有率,针对除了着色剂B之外的着色剂中含有的NiO成分未做考虑。上述着色剂的任意组合中,各着色剂的含有率均可以按照例如NiO成分的总量不超过某一上限或者不低于下限的方式进行调整。
氧化锆烧结体、组合物和预烧体可以含有着色剂A、着色剂B、着色剂C、着色剂D和着色剂E之中的至少2个着色剂。氧化锆烧结体、组合物和预烧体可以含有0质量%~0.5质量%的着色剂A。氧化锆烧结体、组合物和预烧体可以含有0质量%~0.06质量%的着色剂B。氧化锆烧结体、组合物和预烧体可以含有0质量%~0.2质量%的着色剂C。氧化锆烧结体、组合物和预烧体可以含有0质量%~0.2质量%的着色剂D。氧化锆烧结体、组合物和预烧体可以含有0质量%~0.1质量%的着色剂E。
作为着色剂C,可以使用例如日陶颜料工业株式会社制造的“Z-300黄”。作为着色剂D,可以使用例如川村化学株式会社制造的“4555グレー”。作为着色剂E,可以使用例如日陶颜料工业株式会社制造的“H-150グレー”。
第1实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为64~76、a*为-6~3、b*为3~27。具有这种色度的氧化锆烧结体可以具有天然牙齿那样的颜色。
本申请中,基于L*a*b*表色系的色度(L*,a*,b*)是如后述实施例那样地制作试样并将背景设为黑色而测定的数值。
接着,针对本发明的组合物、预烧体和氧化锆烧结体的制造方法的一例进行说明。
首先,将氧化锆和稳定剂在水中进行湿式混合来形成浆料。接着,使浆料干燥并造粒。接着,对造粒物进行预烧来制作1次粉末。
接着,向各粉末中添加着色剂。适当调整着色剂的添加量,用以表现出各层的颜色。并且,针对各层,将氧化锆粉碎混合直至在水中达到期望的粒径,形成氧化锆浆料。接着,使浆料干燥并造粒。添加氧化铝、氧化钛、粘结剂等添加剂时,可以在制作1次粉末时进行添加,也可以在制作2次粉末时进行添加。
接着,进行压制成形,从而制作本发明组合物形式的成形物。
不制作预烧体的情况下,通过将组合物以1400℃~1600℃、优选以1450℃~1550℃进行烧成,使氧化锆粉末进行烧结,从而制造本发明的氧化锆烧结体。也可以在成形物的阶段成形至期望的形状。
制作预烧体的情况下,将组合物以800℃~1200℃进行烧成,从而制作预烧体。接着,通过将预烧体以1400℃~1600℃、优选以1450℃~1550℃进行烧成,使氧化锆粉末进行烧结,从而制造本发明的氧化锆烧结体。成形可以在预烧体的阶段通过切削加工等来实施,也可以在烧结后实施。成形可以利用CAD/CAM系统来实施。
齿科用制品的制造方法中,除了将预烧体或烧结体成形为齿冠形状之外,与烧结体的上述制造方法相同。
根据第1实施方式,即使将含有锑化合物和/或铈化合物的烤瓷烧结于氧化锆烧结体,也能够抑制氧化锆烧结体的褪色。由此,可容易地制作与患者的牙齿颜色具有相同颜色的齿科用制品。
以下的实施方式中,针对本发明的烧结体、预烧体和组合物,着眼于色度和组成来进行说明。针对除此之外的事项,与上述的第1实施方式相同。
针对本发明的第2实施方式所述的氧化锆烧结体进行说明。
第2实施方式所述的氧化锆烧结体、预烧体和组合物可以含有着色剂A和着色剂B之中的至少一者;以及着色剂C。氧化锆烧结体、预烧体和组合物可以含有0质量%~0.4质量%的着色剂A、0.0002质量%~0.03质量%的着色剂B、以及0.005质量%~0.1质量%的着色剂C。由此能够重现出天然牙齿的特定颜色。
第2实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为66~76、a*为-6~3、b*为3~27。
根据第2实施方式,能够得到与第1实施方式相同的效果。
针对本发明的第3实施方式所述的氧化锆烧结体进行说明。
第3实施方式所述的氧化锆烧结体、预烧体和组合物可以含有0.002质量%~0.4质量%的着色剂A、0.0002质量%~0.03质量%的着色剂B、以及0.005质量%~0.1质量%的着色剂C。由此,能够重现出天然牙齿的特定颜色。
第3实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为66~76、a*为-4~3、b*为3~27。
根据第3实施方式,能够得到与第1实施方式相同的效果。
针对本发明的第4实施方式所述的氧化锆烧结体进行说明。
第4实施方式所述的氧化锆烧结体、预烧体和组合物可以含有0.01质量%~0.02质量%的着色剂B、以及0.06质量%~0.08质量%的着色剂C。由此,能够重现出天然牙齿的特定颜色。
第4实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为70~74、a*为-6~-3、b*为22~26。
根据第4实施方式,能够得到与第1实施方式相同的效果。
针对本发明的第5实施方式所述的氧化锆烧结体进行说明。
第5实施方式所述的氧化锆烧结体、预烧体和组合物可以含有选自下述组中的至少1个着色剂,所述组包含着色剂A、着色剂B、着色剂C、着色剂D和着色剂E。氧化锆烧结体、预烧体和组合物优选含有着色剂A、着色剂B和着色剂C中的至少一者;以及,着色剂D和着色剂E中的至少一者。
第5实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为64~75、a*为-3~3、b*为7~19。
根据第5实施方式,可以得到与第1实施方式相同的效果。
针对本发明的第6实施方式所述的氧化锆烧结体进行说明。
第6实施方式所述的氧化锆烧结体、预烧体和组合物可以含有0.005质量%~0.02质量%的着色剂C、以及0.06质量%~0.08质量%的着色剂E。
第6实施方式所述的氧化锆烧结体优选的是,L*a*b*表色系中的L*为74~75、a*为-2~-1、b*为10~11。
根据第6实施方式,可以得到与第1实施方式相同的效果。
针对本发明的第7实施方式所述的氧化锆烧结体进行说明。
第7实施方式所述的氧化锆烧结体、预烧体和组合物可以含有0.07质量%~0.09质量%的着色剂C、以及0.05质量%~0.2质量%的着色剂D。
第7实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为68~69、a*为-3~-2、b*为18~19。
根据第7实施方式,可以得到与第1实施方式相同的效果。
针对本发明的第8实施方式所述的氧化锆烧结体进行说明。
第8实施方式所述的氧化锆烧结体、预烧体和组合物可以含有0.007质量%~0.06质量%的着色剂B、以及0.01质量%~0.06质量%的着色剂D。
第8实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为64~71、a*为0~2、b*为7~13。
根据第8实施方式,可以得到与第1实施方式相同的效果。
针对本发明的第9实施方式所述的氧化锆烧结体进行说明。
第9实施方式所述的氧化锆烧结体、预烧体和组合物可以含有0.01质量%~0.04质量%的着色剂A、0.05质量%~0.07质量%的着色剂C、以及0.05质量%~0.08质量%的着色剂D。
第9实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为67~69、a*为-2~0、b*为17~18。
根据第9实施方式,可以得到与第1实施方式相同的效果。
针对本发明的第10实施方式所述的氧化锆烧结体进行说明。
第10实施方式所述的氧化锆烧结体、预烧体和组合物可以含有0.002质量%~0.3质量%的着色剂A、0.0005质量%~0.03质量%的着色剂B、0.005质量%~0.07质量%的着色剂C、以及0.004质量%~0.04质量%的着色剂D。
第10实施方式的氧化锆烧结体优选的是,L*a*b*表色系中的L*为65~74、a*为-2~3、b*为9~18。
根据第10实施方式,可以得到与第1实施方式相同的效果。
针对本发明的第11实施方式所述的齿科用制品进行说明。
齿科用制品包含上述实施方式所述的氧化锆烧结体或预烧体。齿科用制品可以进一步包含层叠在氧化锆烧结体上的烤瓷(例如玻璃材料)。烤瓷可以含有抗黄变材料。作为抗黄变材料,例如可以使用锑化合物。
齿科用制品例如包含陶瓷外框、全解剖式牙冠(Full Contour Zirconia Crown)等修补材料。齿科用修补材料优选具有齿冠形状。此外,齿科用制品例如包括牙齿矫正用制品(例如牙齿矫正用托架)、齿科人工牙根用制品(例如齿科人工牙根用桥基)。
实施例
制作添加有下述表中记载的着色剂的氧化锆烧结体,针对各试样测定色度。首先,向含有4mol%三氧化二钇作为稳定剂的部分稳定化氧化锆粉末中添加着色剂,并进行混合。接着,向直径约为18mm的圆柱状模具中投入混合物1.2g,在30kN的压力下进行成形,从而制作成形组合物。接着,将成形组合物以1500℃烧成2小时,从而制作圆板状的氧化锆烧结体。接着,对试样表面进行研磨加工,将表面精加工成镜面状(#2000以上),制作试样。并且,使用色度测定机(奥林巴斯公司制造的CE100-DC/US)和分析软件(Crystaleye),将背景设为黑色并测定各试样的色度。表1和表2示出所添加的着色剂的种类和量、以及色度的测定结果。
表1和表2中,着色剂A为岩谷产业株式会社制造的氧化铒(Er2O3)。着色剂B为岩月化矿株式会社制造的氧化镍(NiO)。着色剂C是属于锆和钒的复合氧化物((Zr,V)O2)的日陶颜料工业株式会社制造的“Z-300黄”。着色剂D为属于铁、钴和铬的复合氧化物((Co,Fe)(Fe,Cr)2O4)、锆和硅的复合氧化物(锆石(ZrSiO4))、二氧化硅(SiO2)、以及氧化镍(NiO)的混合物((Co,Fe)(Fe,Cr)2O4)/ZrSiO4/SiO2/NiO)的川村化学株式会社制造的“4555グレー”。着色剂E为属于锆、硅、钴和镍的复合氧化物((Co,Ni)O·ZrSiO4)的日陶颜料工业株式会社制造的“H-150グレー”。
此外,作为比较例,针对使用了氧化镨的试样,进行与实施例相同的测定。在比较例1~9中,着色剂A为氧化铒(Er2O3)。着色剂F为氧化铁(Fe2O3)。着色剂G为氧化镨(Pr6O11)。
实施例1~55中的任意试样均具有天然牙齿那样的颜色。此外,实施例1~55具有与比较例1~9相同的颜色。由此,即使不使用氧化镨和铁化合物作为着色剂,也能够显示出与天然牙齿相同的颜色。
通过目视来对比各试样的颜色时,实施例1~11所述的试样具有相同体系的颜色。实施例12~25所述的试样具有相同体系的颜色。实施例26~27所述的试样具有相同体系的颜色。实施例28~49所述的试样具有相同体系的颜色。实施例50~55所述的试样具有相同体系的颜色。因此,实施例1~55所述的试样根据颜色大致可分类成5个体系。应予说明,还可以根据颜色将实施例1~55的试样进一步细分。
[表1]
[表2]
[表3]
制作实施例9、实施例24、实施例32和比较例2所述的试样,对各试样烧结烤瓷,并测定颜色的变化。表4~表7示出测定结果。表4~表7所示的烤瓷1为KURARAY NORITAKEDENTAL INC.制造的セラビアンZRトランスルーセントTx。烤瓷2为KURARAY NORITAKEDENTAL INC.制造的セラビアンZRエクスターナルステインE Glaze。
按照各烤瓷的使用方法,在与实施例1~55同样制作的试样的一个表面上承载烤瓷。烤瓷1使用笔制备成厚度0.2mm±0.1mm。烤瓷2使用笔制备成厚度0.02mm±0.01mm。表4~表7中提及的烧成前是指承载烤瓷之前的试样。1次烧成是指承载烤瓷并进行了烧成的试样。2次~5次烧成是指将烧结有烤瓷的试样烧成该次数而得到的试样。若为2次烧成,则是将1次烧成的试样再次烧成而得到的试样。在承载有烤瓷1的情况下,试样在930℃下进行烧成。在承载有烤瓷2的情况下,试样在850℃下进行烧成。关于色度,将烤瓷面朝向测定装置并进行测定。关于式差ΔE,基于式1,算出烧成前的试样色度与烧结有烤瓷的试样色度之差。例如,将烧成前的试样色度记作(L* 1,a* 1,b* 1),并将1次烧成的试样色度记作(L* 2,a* 2,b* 2),可以算出式差ΔE。式差表示烧结烤瓷之前之后的颜色变化的大小。
式1
首先,若针对烤瓷1进行观察,则实施例9、24和实施例32中的式差低于2.5,与此相对,比较例2中的式差为8.5以上。若针对烤瓷2进行观察,则实施例9、24和实施例32中的式差低于3,与此相对,比较例2中的式差为5.5以上。因此,根据本发明,对于任意烤瓷而言,均能够抑制由烤瓷中的抗黄变材料导致的褪色。因而,根据本发明,能够抑制褪色,并且能够制作具有天然牙齿那样的颜色的氧化锆烧结体和齿科用制品。
[表4]
[表5]
[表6]
[表7]
作为参考,将实施例中使用的着色剂C、着色剂D和着色剂E的元素分析结果示于下表。表8示出着色剂C的分析结果,表9示出着色剂D的分析结果,表10示出着色剂E的分析结果。下述表中示出各元素的换算成氧化物的质量比例,但着色剂不一定是指在着色剂中以表所记载的氧化物的形态来含有各元素。
[表8]
[表9]
[表10]
将上述专利文献的各公开内容通过引用而援引至本说明书中。本发明的氧化锆组合物、氧化锆预烧体和氧化锆烧结体、以及齿科用制品基于上述实施方式进行了说明,但不限定于上述实施方式,可以在本发明的全部公开范围内且基于本发明的基本技术思想,对于各种公开要素(包括各权利要求的各要素、各实施方式~实施例的各要素、各附图的各要素等),可以涵盖各种变形、变更和改良是不言而喻的。此外,在本发明的全部公开范围内,可以进行各种公开要素(包括各权利要求的各要素、各实施方式~实施例的各要素、各附图的各要素等)的多种组合·置换~选择(包括排除~删除)。
根据包括权利要求书在内的本发明的全部公开事项,也可以明确本发明的进一步的课题、目的和展开方式。
针对本说明书中记载的数值范围,该范围内包含的任意数值~小范围在没有特别记载的情况下也应该解释为已经具体记载。
Claims (12)
1.氧化锆烧结体,其含有:
着色剂A:氧化铒;
着色剂B:氧化镍;以及
着色剂C:锆和钒的复合氧化物,
所述氧化锆烧结体含有:
0.002质量%~0.4质量%的所述着色剂A;
0.0002质量%~0.03质量%的所述着色剂B;以及
0.005质量%~0.1质量%的所述着色剂C,
所述氧化锆烧结体的主要结晶相是正方晶系和立方晶系中的至少一者。
2.氧化锆烧结体,其含有:
着色剂A:氧化铒;
着色剂B:氧化镍;
着色剂C:锆和钒的复合氧化物;以及
着色剂D:铁、钴和铬的复合氧化物、锆和硅的复合氧化物、二氧化硅、以及氧化镍的混合物,
所述氧化锆烧结体含有:
0.002质量%~0.3质量%的所述着色剂A;
0.0005质量%~0.03质量%的所述着色剂B;
0.005质量%~0.07质量%的所述着色剂C;以及
0.004质量%~0.04质量%的所述着色剂D,
所述氧化锆烧结体的主要结晶相是正方晶系和立方晶系中的至少一者。
3.组合物,其用于制备权利要求1所述的氧化锆烧结体,
所述组合物含有氧化锆、氧化钇和着色剂,
所述着色剂包含:
着色剂A:氧化铒
着色剂B:氧化镍;以及
着色剂C:锆和钒的复合氧化物,
所述组合物含有:
0.002质量%~0.4质量%的所述着色剂A;
0.0002质量%~0.03质量%的所述着色剂B;以及
0.005质量%~0.1质量%的所述着色剂C。
4.组合物,其用于制备权利要求2所述的氧化锆烧结体,
所述组合物含有氧化锆、氧化钇和着色剂,
所述着色剂包含:
着色剂A:氧化铒;
着色剂B:氧化镍;
着色剂C:锆和钒的复合氧化物;以及
着色剂D:铁、钴和铬的复合氧化物、锆和硅的复合氧化物、二氧化硅、以及氧化镍的混合物;
所述组合物含有:
0.002质量%~0.3质量%的所述着色剂A;
0.0005质量%~0.03质量%的所述着色剂B;
0.005质量%~0.07质量%的所述着色剂C;以及
0.004质量%~0.04质量%的所述着色剂D。
5.预烧体,其是将权利要求3或4所述的组合物在800℃~1200℃下进行烧成而制作的。
6.氧化锆烧结体,其是将权利要求3或4所述的组合物在1300℃~1600℃下进行烧成而制作的。
7.预烧体,其用于制备权利要求1所述的氧化锆烧结体,
所述预烧体含有氧化锆、氧化钇和着色剂,
所述着色剂包含:
着色剂A:氧化铒
着色剂B:氧化镍;以及
着色剂C:锆和钒的复合氧化物,
所述预烧体含有:
0.002质量%~0.4质量%的所述着色剂A;
0.0002质量%~0.03质量%的所述着色剂B;以及
0.005质量%~0.1质量%的所述着色剂C。
8.预烧体,其用于制备权利要求2所述的氧化锆烧结体,
所述预烧体含有氧化锆、氧化钇和着色剂,
所述着色剂包含:
着色剂A:氧化铒;
着色剂B:氧化镍;
着色剂C:锆和钒的复合氧化物;以及
着色剂D:铁、钴和铬的复合氧化物、锆和硅的复合氧化物、二氧化硅、以及氧化镍的混合物,
所述预烧体含有:
0.002质量%~0.3质量%的所述着色剂A;
0.0005质量%~0.03质量%的所述着色剂B;
0.005质量%~0.07质量%的所述着色剂C;以及
0.004质量%~0.04质量%的所述着色剂D。
9.氧化锆烧结体,其是将权利要求7或8所述的预烧体在1300℃~1600℃下进行烧成而制作的。
10.齿科用制品,其具备权利要求1或2所述的氧化锆烧结体。
11.根据权利要求10所述的齿科用制品,其还具备层叠于所述氧化锆烧结体的烤瓷层,
所述烤瓷层含有抗黄变材料。
12.根据权利要求11所述的齿科用制品,其中,所述抗黄变材料含有锑化合物和铈化合物之中的至少一者。
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