CN114436650B - Zirconia composition, zirconia sintered body, dental prosthesis and method for producing the same - Google Patents
Zirconia composition, zirconia sintered body, dental prosthesis and method for producing the same Download PDFInfo
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Abstract
The invention relates to a dental material, in particular to a zirconia composition, a zirconia sintered body, a dental restoration and a preparation method. Zirconium oxide composition comprising ZrO 2 Stabilizers and fluorescent agents; wherein the phosphor comprises SrO and CeO 2 . The zirconium oxide composition provided by the invention can enhance the fluorescence property of the restoration and realize that the restoration has the fluorescence property consistent with that of natural teeth.
Description
Technical Field
The invention relates to a dental material, in particular to a zirconia composition, a zirconia sintered body, a dental restoration and a preparation method.
Background
With the development of society, the requirements of patients on oral cavity restoration are not only the defects of restored teeth, but also the visual effects of the restoration and natural teeth are almost different. The zirconia restoration can be very close to natural teeth in color and permeability through the prior art, but the zirconia restoration can show a 'bad tooth' phenomenon under the irradiation of light at night or in a dark environment, namely, the zirconia restoration does not have a fluorescent effect. Thus, in addition to being the same in color and permeability as natural teeth, the zirconia restorations are also to have the same fluorescent properties as natural teeth.
At present, the commonly used fluorescent elements are rare earth elements, such as CN113105754A, and at least one of soluble salts of Sm, eu, dy, er, tb, ho, tm, yb, nd, gd and Ga is used as a fluorescent agent to endow zirconia with fluorescence. However, pure rare earth elements have poor fluorescence properties and cannot meet the requirements.
Disclosure of Invention
The invention provides a zirconium oxide composition, which can enhance the fluorescence property of a restoration and realize that the restoration has the fluorescence property consistent with that of natural teeth.
A zirconia composition comprising ZrO 2 Stabilizers and fluorescent agents; wherein the fluorescent agent comprises SrO and CeO 2 。
The invention surprisingly discovers that the fluorescent agent adopts SrO and CeO 2 The two components play a synergistic role, so that the fluorescence effect is enhanced, and the zirconia restoration body with the fluorescence performance consistent with that of the natural tooth is obtained. The zirconia sintered body made of the zirconia composition of the present invention emits blue fluorescence under the excitation of ultraviolet light having a wavelength of 299nm or more by adding a fluorescent agent containing strontium and cerium.
According to an embodiment of the invention, the stabilizer is selected from Y 2 O 3 、Yb 2 O 3 、Gd 2 O 3 And Tm 2 O 3 Any one or a combination of several thereof, preferably Y 2 O 3 。
In some embodiments, the phosphor consists of SrO and CeO 2 And (4) forming.
In some embodiments, the zirconia composition does not contain other than SrO and CeO 2 An external fluorescent agent.
According to an embodiment of the present invention, srO and CeO are contained in the phosphor 2 The mass ratio of (2-6) to (1-3), can be (2.4-5.8) to (1.1-2.9), or (3.9-5.7) to (1.9-2.5), or (4.5-5.7) to (2.2-2.5). Specifically for example, 2.
Research shows that SrO and CeO in the fluorescent agent 2 The fluorescence property of the natural tooth can be better consistent within the proportion range.
According to the examples of the present invention, zrO in the zirconia composition was calculated based on the mass of the zirconia composition 2 Is from 75wt% to 91.1wt%, optionally from 82wt% to 90wt%, or from 84wt% to 89wt%. Specific examples thereof include 75wt%, 84.6wt%, 84.7wt%, 85.1wt%, 85.2wt%, 85.5wt%, 85.6wt%, 84wt%, 86wt%, 86.2wt%, 86.3wt%,88wt％、88.6wt％、90wt％、91wt％、91.1wt％。
According to an embodiment of the present invention, a stabilizer (e.g., Y) is added to a zirconia composition based on the mass of the zirconia composition 2 O 3 ) Is 5 to 10wt%, preferably 7 to 9wt%. Specifically, for example, 5wt%, 7wt%, 7.1wt%, 7.4wt%, 7.5wt%, 7.7wt%, 7.9wt%, 8.2wt%, 8.4wt%, 8.5wt%, 8.6wt%, 9wt%, 10wt%.
According to an embodiment of the present invention, the mass proportion of SrO in the zirconia composition is in the range of 0.6wt% to 10wt%, preferably 2wt% to 6wt%, based on the mass of the zirconia composition. Specifically, for example, 0.6wt%, 1wt%, 2wt%, 2.4wt%, 2.5wt%, 2.7wt%, 3.5wt%, 3.9wt%, 4.3wt%, 4.5wt%, 5.3wt%, 5.7wt%, 5.8wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%.
According to an embodiment of the present invention, ceO is added to a zirconia composition based on the mass of the zirconia composition 2 Is 0.3 to 5wt%, preferably 1 to 3wt%. Specifically, for example, 0.3wt%, 1.1wt%, 1.5wt%, 1.6wt%, 1.9wt%, 2wt%, 2.2wt%, 2.5wt%, 2.8wt%, 2.9wt%, 3wt%, 4wt%, 5wt%.
According to the examples of the present invention, zrO in the zirconia composition was calculated based on the mass of the zirconia composition 2 Is 75wt% to 91.1wt%; stabilizers (e.g. Y) 2 O 3 ) 5wt% to 10wt%; the mass ratio of SrO is 0.6 to 10 weight percent; ceO (CeO) 2 Is 0.3wt% to 5wt%.
According to a preferred embodiment of the present invention, zrO in the zirconia composition is calculated based on the mass of the zirconia composition 2 The mass ratio of (A) is 82wt% to 90wt%; stabilizers (e.g. Y) 2 O 3 ) Is 7wt% to 9wt%; the mass ratio of SrO is 2-6 wt%; ceO (CeO) 2 Is 1wt% to 3wt%.
In order to further improve the permeability of the prosthesis, the invention also makes a big proposalAnd (4) carrying out quantitative study. As a result, it was found that by controlling the oxides of strontium and cerium (SrO and CeO) 2 ) The zirconia sintered body having good permeability was obtained. When the grain size of the oxides of strontium and cerium is large, the pore size in the zirconia restoration is increased, the permeability is reduced, when the oxides of strontium and cerium are too small, the number and the area of crystal boundaries in the zirconia restoration are increased, the reflection, the refraction and the scattering of light are increased, and the permeability is reduced. In order to ensure the permeability of the prosthesis, the grain diameter of SrO is within 50-60 nm, ceO 2 Has a particle diameter of 50 to 60nm.
According to an embodiment of the present invention, in the zirconia composition, the particle size of SrO may be 50nm, 55nm, or 60nm.
According to an embodiment of the invention, ceO is present in the zirconia composition 2 The particle size of (B) may be 50nm, 55nm or 60nm.
According to an embodiment of the present invention, in the zirconia composition, the particle size of SrO is 55nm; ceO (CeO) 2 Has a particle diameter of 50nm.
According to the embodiment of the invention, the transmittance of the fluorescent zirconia sintered body prepared from the zirconia composition is more than 40%.
According to the embodiment of the invention, the zirconia composition is powder.
According to an embodiment of the present invention, the zirconia composition is formed by mixing, preferably uniformly mixing, the components.
The invention also provides application of the zirconia composition in preparing a zirconia pre-sintered body, a zirconia sintered body or a dental restoration.
In another aspect of the present invention, there is provided a zirconia calcined body comprising the above zirconia composition.
According to the embodiment of the invention, the zirconia pre-sintered body is prepared by sintering the zirconia composition serving as a raw material, has fluorescence, is processed into a corresponding shape, and is subjected to secondary sintering to obtain the zirconia dental product.
In another aspect of the present invention, a method for preparing the zirconia pre-fired body is also provided, which comprises the following steps: and (3) preparing the zirconia composition into a blank by dry pressing and optional cold isostatic pressing, and pre-sintering the blank to obtain the zirconia pre-sintered body.
According to an embodiment of the invention, the pressure of the dry-pressing is 20 to 200MPa, preferably 30 to 120MPa.
According to an embodiment of the invention, the pressure of the cold isostatic pressing is between 100 and 400Mpa, preferably between 150 and 300Mpa.
According to an embodiment of the invention, the temperature of the pre-sintering is 800 to 1250 ℃, preferably 850 to 1150 ℃.
The present invention also provides a zirconia sintered body which is mainly obtained by sintering the zirconia composition of the present invention or the zirconia calcined body of the present invention.
According to an embodiment of the present invention, there is provided a zirconia sintered body prepared by secondary sintering of the above zirconia calcined body of the present invention.
According to an embodiment of the invention, the temperature of the secondary sintering is 1350 to 1600 ℃, preferably 1400 to 1500 ℃, e.g. 1460 ℃.
The introduction of the fluorescent agent enables the zirconia sintered body to emit blue fluorescence under the excitation of ultraviolet light with the wavelength of more than 299nm, and the fluorescence performance of the whole restoration body is enhanced through the synergistic effect of non-rare earth ion strontium and rare earth ion cerium. In the fluorescent agent-containing zirconium oxide, strontium and cerium form two cerium-oxygen bonds of Ce-O-Sr and Ce-O-Ce, the bond length of the former is shorter than that of the latter due to higher terminal oxygen electron density, so that charge migration is possible, and when the fluorescent layer absorbs energy from the outside, the outer layer P of the terminal oxygen in the Ce-O bond electronically jumps to Ce 4+ The empty orbitals form a charge transition state, and then electrons transition back to a ground state, radiating energy in the form of photons, which macroscopically appear as fluorescence.
The preparation method of the zirconia presintering body and the zirconia sintering body provided by the invention has the advantages of simple process, convenience in operation and low cost, and can realize batch production.
The invention also provides a dental prosthesis which is mainly formed by sintering the zirconia composition provided by the invention or the zirconia pre-sintered body provided by the invention.
According to an embodiment of the present invention, the dental prosthesis provided by the present invention is different from the zirconia sintered body provided by the present invention in that the dental prosthesis has a corresponding shape and structure.
According to the embodiment of the invention, in one scheme, the dental restoration is prepared by processing a zirconia pre-sintered body into the shape and the structure of a corresponding product and then performing secondary sintering.
According to the embodiment of the present invention, the process parameters regarding the secondary sintering are as described in the foregoing method for preparing the zirconia sintered body.
According to an embodiment of the invention, the dental restoration should not contain components that are harmful to the health of the patient and therefore not harmful and toxic components that can migrate out of the dental article.
In the present invention, the term "dental restoration" refers to any article to be used in the dental or orthodontic field, in particular for the preparation or use as dental restoration, dental model and parts thereof. Examples of dental articles include crowns (including single crowns), bridges, inlays, onlays, veneers, braces, crowns, bridge shells, crowns and bridge shells, implants, abutments, orthodontic appliances (e.g., brackets, buccal tubes, braces and buttons), dental mill pieces, and other parts. The tooth surface is not considered a dental restoration.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space. It is therefore contemplated to cover by the present invention, equivalents and modifications that fall within the scope of the invention, and that fall within the scope of the invention.
The zirconia composition provided by the embodiment of the invention contains zirconia of a non-rare earth fluorescent agent, and the fluorescent agent is CeO 2 And the SrO and the composite lead the prosthesis to have fluorescence performance under dark conditions under the combined action of the SrO and the composite lead the prosthesis to have fluorescence performance, so that the prosthesis has the fluorescence performance consistent with that of natural teeth. In some embodiments of the present invention, by additionally controlling the grain size of the phosphor,the problem of reduction of the permeability of the prosthesis after the fluorescent agent is introduced is avoided. In some embodiments, the fluorescent agent causes the zirconia sintered body to emit blue fluorescence under the irradiation of ultraviolet light with a wavelength of 299nm or more, so that the zirconia sintered body has fluorescence properties consistent with those of natural teeth, and the aesthetic effect of the zirconia sintered body in a dark environment is optimized.
Detailed Description
In order to facilitate understanding of those skilled in the art, the technical solutions provided by the present invention will be further described below with reference to examples and comparative examples.
Example 1
This example provides a zirconia composition comprising: 85.6wt% ZrO 2 7.5wt% of Y 2 O 3 5.8wt% SrO and 1.1wt% CeO 2 Wherein the grain size of SrO is 50nm, wherein CeO 2 Has a grain size of 55nm.
The zirconia composition of this example was a powder.
The embodiment also provides a fluorescent zirconia pre-sintered body, and the preparation method comprises the following steps:
the zirconia composition (powder) of this example was dry-pressed under a pressure of 35MPa, then isostatically pressed under 220MPa, and then sintered at 1020 ℃ to obtain a zirconia pre-sintered body.
The present embodiment also provides a fluorescent zirconia sintered body, which is prepared by the following steps:
the fluorescent zirconia calcined body of the present example was sintered at 1460 ℃ to obtain a fluorescent zirconia sintered body.
Example 2
This example provides a zirconia composition comprising: 85.5wt% of ZrO 2 9wt% of Y 2 O 3 3.5wt% SrO and 2wt% CeO 2 Wherein the grain size of SrO is 60nm, wherein CeO 2 Has a grain size of 55nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Example 3
This example provides a zirconia composition comprising: 85.1wt% ZrO 2 8.2wt% of Y 2 O 3 4.5wt% SrO and 2.2wt% CeO 2 Wherein the grain size of SrO is 55nm, wherein CeO 2 Has a grain size of 50nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Example 4
This example provides a zirconia composition comprising: 86wt% ZrO 2 8.5wt% of Y 2 O 3 2.7wt% SrO and 2.8wt% CeO 2 Wherein the grain size of SrO is 50nm, wherein CeO 2 Has a grain size of 60nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Example 5
This example provides a zirconia composition comprising: 84.7wt% of ZrO 2 7.1wt% of Y 2 O 3 5.7wt% SrO and 2.5wt% CeO 2 Wherein the grain size of SrO is 55nm, wherein CeO 2 Has a grain size of 50nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Example 6
This example provides a zirconia composition comprising: 86.2 wt.% ZrO 2 8.4wt% of Y 2 O 3 2.5wt% SrO and 2.9wt% CeO 2 Wherein the grain size of SrO is 60nm, wherein CeO 2 Has a grain size of 60nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Example 7
This example provides a zirconia composition comprising: 88.6 wt.% ZrO 2 7.4wt% of Y 2 O 3 2.4wt% SrO and 1.6wt% CeO 2 Wherein the grain size of SrO is 60nm, wherein CeO 2 Has a grain size of 55nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Example 8
This example provides a zirconia composition comprising: 86.3wt% ZrO 2 7.9wt% of Y 2 O 3 3.9wt% SrO and 1.9wt% CeO 2 Wherein the grain size of SrO is 50nm, wherein CeO 2 Has a grain size of 60nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as in example 1.
Example 9
This example provides a zirconia composition comprising: 84.6wt% ZrO 2 8.6wt% of Y 2 O 3 5.3wt% SrO and 1.5wt% CeO 2 Wherein the grain size of SrO is 50nm, wherein CeO 2 Has a grain size of 50nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Example 10
This example provides a zirconia composition comprising: 85.2wt% ZrO 2 7.7wt% of Y 2 O 3 4.3wt% SrO and 2.8wt% CeO 2 Wherein the grain size of SrO is 55nm, wherein CeO 2 Has a grain size of 60nm.
The zirconia composition of this example was a powder.
This example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which were prepared using the zirconia composition of this example. The specific preparation method is the same as that of example 1.
Comparative example 1
The present comparative example provides a zirconia composition comprising: 88.9wt% ZrO 2 8.1wt% of Y 2 O 3 And 3wt% of CeO 2 Wherein CeO is 2 Has a grain size of 55nm.
The zirconia composition of this comparative example was a powder.
The comparative example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which are prepared by adopting the zirconia composition of the comparative example. The specific preparation method is the same as that of example 1.
Comparative example 2
The present comparative example provides a zirconia composition comprising: 85.1wt% ZrO 2 8.2wt% of Y 2 O 3 4.5wt% SrO and 2.2wt% CeO 2 Wherein the grain size of SrO is 40nm, wherein CeO 2 Has a grain size of 45nm.
The zirconia composition of this comparative example was a powder.
The comparative example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which are prepared by adopting the zirconia composition of the comparative example. The specific preparation method is the same as that of example 1.
Comparative example 3
The present comparative example provides a zirconia composition comprising: 85.1wt% ZrO 2 8.2wt% of Y 2 O 3 4.5wt% SrO and 2.2wt% CeO 2 Wherein the grain size of SrO is 70nm, wherein CeO 2 Has a grain size of 70nm.
The zirconia composition of this comparative example was a powder.
The comparative example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which are prepared by adopting the zirconia composition of the comparative example. The specific preparation method is the same as that of example 1.
Comparative example 4
The present comparative example provides a zirconia composition comprising: 86.3wt% ZrO 2 8.5wt% of Y 2 O 3 And 5.2wt% SrO, wherein the grain size of SrO is 55nm.
The zirconia composition of this comparative example was a powder.
The comparative example also provides a fluorescent zirconia calcined body and a fluorescent zirconia sintered body, which are prepared by adopting the zirconia composition of the comparative example. The specific preparation method is the same as that of example 1.
Test example 1
The light transmittance of the fluorescent zirconia sintered bodies of examples 1 to 10 and comparative examples 1 to 4 was measured. The test method is that the sample is made into a sample wafer with phi 14 multiplied by 1.0, and an X-Rite color i7 desk type spectrophotometer is adopted to measure the full light transmittance of the sample. The light source of the instrument is a pulse xenon lamp, a calibration D65 light source is adopted, the spectral range is 360-750nm, and the wavelength interval is 10nm. The resolution of the photometry was 0.001%. The transmittance within the range of 6mm of the central diameter of each group of test pieces was measured, and the result was compared by selecting the value of the transmittance corresponding to the wavelength of 550nm multiplied by 1.19.
The fluorescence intensity was measured using the fluorescent zirconia sintered bodies obtained in examples 1 to 10 and comparative examples 1 to 4. The fluorescence intensity was measured by using a spectrofluorometer F-7000 manufactured by Hitachi high and New technology science, inc. and measuring the fluorescence spectrum with an excitation wavelength of 365nm in the fluorescence mode. Rhodamine B was used for correction of the fluorescence intensity spectrum between species. The fluorescence wavelength of the obtained spectrum in the range of 430 to 500nm shows the highest intensity as the maximum wavelength and the intensity of the maximum wavelength as the maximum intensity. The results of permeability and fluorescence properties are shown in Table 1.
TABLE 1 zirconia sintered body permeability and fluorescence Properties
As is clear from Table 1, the fluorescent properties of zirconia can be imparted by adding strontium oxide and cerium oxide to examples 1 to 10; compared with comparative example 1 and comparative example 4, the zirconium oxide restoration body can show satisfactory fluorescence performance under the synergistic action of strontium oxide and cerium oxide; and comparing with comparative example 2 and comparative example 3, it can be seen that when the grain size of the phosphor is within a certain range, excellent permeability can be maintained, more satisfying people's requirement for zirconia aesthetics.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (18)
1. A zirconia composition characterized by comprising ZrO 2 Stabilizers and fluorescent agents; wherein the fluorescent agent consists of SrO and CeO 2 Composition is carried out; srO and CeO in the fluorescent agent 2 The mass ratio of (2-6) to (1-3); the grain diameter of SrO is 50-60nm 2 Has a particle diameter of 50 to 60nm;
the stabilizer is selected from Y 2 O 3 、Yb 2 O 3 、Gd 2 O 3 And Tm 2 O 3 Any one or a combination of several of them;
in the zirconia composition, based on the mass of the zirconia composition,ZrO 2 is up to 75wt% to 91.1wt%; the mass proportion of the stabilizer is 5wt% to 10wt%; the mass ratio of SrO is 0.6 to 10 weight percent; ceO (CeO) 2 Is 0.3wt% to 5wt%.
2. The zirconia composition of claim 1 wherein the stabilizer is Y 2 O 3 。
3. The zirconia composition of claim 1 or 2 wherein the phosphor comprises SrO and CeO 2 The mass ratio of (2.4-5.8) to (1.1-2.9).
4. The zirconia composition of claim 1 or 2 wherein the phosphor comprises SrO and CeO 2 The mass ratio of (3.9-5.7) to (1.9-2.5).
5. Zirconia composition according to claim 1 or 2 wherein the fluorescer is SrO with CeO 2 The mass ratio of (4.5-5.7) to (2.2-2.5).
6. The zirconia composition of claim 1 or 2, wherein the ZrO in the zirconia composition is based on the mass of the zirconia composition 2 Is 82 to 90wt%; and/or the presence of a gas in the gas,
the mass of the stabilizer in the zirconia composition is 7-9 wt% based on the mass of the zirconia composition; and/or the presence of a gas in the gas,
the mass proportion of SrO in the zirconia composition is 2-6 wt% based on the mass of the zirconia composition; and/or the presence of a gas in the gas,
based on the mass of the zirconia composition, ceO in the zirconia composition 2 Is 1wt% to 3wt%.
7. The zirconia composition of claim 1 or 2, wherein in the zirconia composition, the particle size of SrO is 50nm, 55nm, or 60nm; and/or the presence of a gas in the gas,
CeO 2 has a particle diameter of 50nm, 55nm or 60nm.
8. A zirconia pre-fired body comprising the zirconia composition of any one of claims 1 to 7.
9. The method of preparing the zirconia pre-fired body of claim 8, comprising the steps of: and (3) preparing the zirconia composition into a blank by dry pressing and optional cold isostatic pressing, and pre-sintering the blank to obtain the zirconia pre-sintered body.
10. The method for producing the zirconia calcined body according to claim 9, wherein the pressure of the dry pressing is 20 to 200MPa;
the pressure of the cold isostatic pressing is 100-400 MPa;
the temperature of the pre-sintering is 800 to 1250 ℃.
11. The method for preparing the zirconia pre-sintered body according to claim 9, wherein the pressure of the dry pressing is 30 to 120MPa;
the pressure of the cold isostatic pressing is 150-300 MPa;
the temperature of the presintering is 850 to 1150 ℃.
12. A zirconia sintered body, which is obtained by sintering the zirconia calcined body according to claim 8.
13. The method of producing a zirconia sintered body according to claim 12, comprising preparing the zirconia calcined body by secondary sintering.
14. The method for producing a zirconia sintered body according to claim 13, wherein the temperature of the secondary sintering is 1350 to 1600 ℃.
15. The method for producing a zirconia sintered body according to claim 14, wherein the temperature of the secondary sintering is 1400 to 1500 ℃.
16. The method for producing a zirconia sintered body according to claim 14, wherein the temperature of the secondary sintering is 1460 ℃.
17. A dental prosthesis which is obtained by sintering the zirconia calcined body according to claim 8.
18. The dental prosthesis set forth in claim 17 wherein said dental prosthesis is produced by processing a pre-fired body of zirconia into a shape and configuration corresponding to the article and then by secondary sintering.
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