WO2013018728A1 - 着色透光性ジルコニア焼結体及びその用途 - Google Patents
着色透光性ジルコニア焼結体及びその用途 Download PDFInfo
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- WO2013018728A1 WO2013018728A1 PCT/JP2012/069232 JP2012069232W WO2013018728A1 WO 2013018728 A1 WO2013018728 A1 WO 2013018728A1 JP 2012069232 W JP2012069232 W JP 2012069232W WO 2013018728 A1 WO2013018728 A1 WO 2013018728A1
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- sintered body
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- A61C13/00—Dental prostheses; Making same
- A61C13/08—Artificial teeth; Making same
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- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
- A61C7/12—Brackets; Arch wires; Combinations thereof; Accessories therefor
- A61C7/14—Brackets; Fixing brackets to teeth
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Definitions
- the present invention relates to a zirconia sintered body having not only high strength but also aesthetic properties very close to teeth.
- the zirconia sintered body Since the zirconia sintered body has high strength, it is used as a dental material. When using a zirconia sintered body as a dental material, it is required to have not only high strength but also aesthetic properties similar to natural teeth. So far, in order to make the zirconia sintered body have the same aesthetics as natural teeth, other materials are laminated on the surface of the zirconia sintered body, and thereby a dental material in which the color tone is adjusted has been reported (for example, Patent Document 1). However, since the dental material is a composite material made of a glass material having a strength different from that of zirconia, the strength is not sufficient as the dental material.
- a zirconia sintered body for dental materials that has improved aesthetics while maintaining strength without laminating other materials has been studied.
- a zirconia sintered body having translucency similar to that of natural teeth by imparting translucency has been reported.
- Patent Documents 2 and 3 disclose zirconia sintered bodies having high strength and high translucency because they are directly used as dental materials.
- these zirconia sintered bodies have the same translucency as natural teeth, they exhibit a bright white tone inherent to zirconia that is different from natural teeth.
- a zirconia sintered body having an aesthetic property equivalent to that of a natural tooth, in particular a color tone and translucency equivalent to that of a natural tooth, and having high strength has not been obtained.
- the present inventors diligently studied the relationship between the strength and aesthetics of the zirconia sintered body. As a result, it has been found that a zirconia sintered body having a controlled composition, physical properties, and type of colorant has aesthetics and strength suitable for dental materials, and has completed the present invention.
- the gist of the present invention is as follows. (1) It contains an iron compound and 2 to 4 mol% yttria, has a lightness L * in the L * a * b * color system of 51 to 80 and a relative density of 99.80% or more. Colored translucent zirconia sintered body. (2) The colored translucent zirconia sintered body according to (1) above, wherein the lightness L * in the L * a * b * color system is 51 or more and 70 or less. (3) The colored translucent zirconia sintered body according to (1) above, wherein the lightness L * in the L * a * b * color system is more than 70 and 80 or less.
- the colored translucent zirconia sintered body of the present invention has the same color tone and translucency as natural teeth, and also has high strength. Therefore, the colored translucent zirconia sintered body of the present invention is a sintered body suitable for a dental material, and in particular, a sintered body suitable for a mill blank such as a denture material or an orthodontic bracket. .
- FIG. 6 is a graph showing the relationship between lightness L * and near-infrared transmittance (total light transmittance for light having a wavelength of 850 nm) in Examples 1 to 15 and Comparative Examples 1 to 3. It is a figure which shows the measurement wavelength dependence of the total light transmittance of Example 4 and 6. FIG. It is a figure which shows the measurement wavelength dependence of the total light transmittance of Example 3, 7 and 9. FIG. It is a figure which shows the measurement wavelength dependence comparison of the total light transmittance of Example 2 and a reference example.
- Example 6 is a graph showing lightness L * and total light transmittance (total light transmittance in a D65 light source) in Examples 16 to 25 and Comparative Examples 4 to 7. It is a figure which shows the lightness L * and the near-infrared transmittance (total light transmittance with respect to the light of wavelength 850nm) in Examples 16-25 and Comparative Examples 4-7. It is a figure which shows the measurement wavelength dependence of the total light transmittance in Example 17 and 19.
- the present invention is a colored translucent zirconia sintered body. Therefore, the sintered body of the present invention is a zirconia polycrystal having a color tone other than colorless and having translucency. Therefore, the colored translucent zirconia sintered body of the present invention is different from an opaque zirconia sintered body (hereinafter, opaque zirconia sintered body) or a zirconia single crystal.
- opaque zirconia sintered body here is, for example, a zirconia sintered body having a sample thickness of 1 mm and a total light transmittance of 10% or less in a D65 light source.
- the colored translucent zirconia sintered body of the present invention contains an iron compound.
- the iron compound functions as a colorant for coloring.
- the content of the iron compound is preferably less than 2000 ppm (0.2% by weight) in terms of Fe 2 O 3 . If the content of the iron compound is less than 2000 ppm, the color tone of the sintered body becomes a pale yellow color and tends to be a color tone closer to natural teeth. Furthermore, light absorption in the visible wavelength region is suppressed, and the translucency is unlikely to decrease. In the colored translucent zirconia sintered compact of this invention, it becomes a color tone close
- the colored translucent zirconia sintered body of the present invention contains an iron compound (that is, if the content of the iron compound exceeds 0 ppm in terms of Fe 2 O 3 ), the lower limit is There is no particular limitation. For example, if the content of the iron compound is 50 ppm (0.005% by weight) or more in terms of Fe 2 O 3 , the colored translucent zirconia sintered body of the present invention is naturally close to teeth with a relatively light color. It becomes a color tone.
- the content of the iron compound is the total weight of ZrO 2 and Y 2 O 3 of the colored translucent zirconia sintered body (when the colored translucent zirconia sintered body contains alumina, the colored translucent zirconia sintered body is It is the ratio of the iron compound in terms of Fe 2 O 3 relative to the total weight of ZrO 2 , Y 2 O 3 and Al 2 O 3 of the body.
- the colored translucent zirconia sintered body of the present invention may contain a compound that dissolves in zirconia in addition to the iron compound in order to finely adjust the color tone.
- a compound that dissolves in zirconia include, for example, Group 3a (Group 3), Group 5a (Group 5), Group 6a (Group 6), Group 7a (Group 7), Group 8 (Group 8-10) and One or more oxides of Group 3b (Group 13) can be mentioned (in parentheses are display methods by the International Pure Applied Chemical Association (IUPAC)).
- the colored translucent zirconia sintered body of the present invention contains 2 to 4 mol% yttria. If the yttria content is less than 2 mol%, the crystalline phase will contain monoclinic crystals, so that not only will the strength of the sintered body be reduced, but it will also be susceptible to hydrothermal degradation and when used for a long period of time. It becomes fragile. On the other hand, when the yttria content exceeds 4 mol%, the strength of the sintered body is lowered.
- the colored translucent zirconia sintered body of the present invention preferably contains alumina.
- the colored translucent zirconia sintered body contains alumina (that is, the content of alumina exceeds 0% by weight)
- the hydrothermal deterioration becomes difficult.
- the so-called “color loss” phenomenon is less likely to occur, and discoloration and decoloration are less likely to occur even after long-term use.
- the content of alumina is preferably less than 0.25% by weight, and more preferably 0.15% by weight or less. If the content of alumina is less than 0.25% by weight, a colored translucent zirconia sintered body having high translucency can be obtained.
- the alumina content is preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and further preferably 0.025% by weight or more. When the alumina content is 0.005% by weight or more, discoloration or decoloration is less likely to occur in an accelerated test such as when treated with hot water, etc. Changes are less likely to occur.
- the alumina content is the ratio of Al 2 O 3 to the total weight of ZrO 2 and Y 2 O 3 of the colored translucent zirconia sintered body.
- the relative density of the colored translucent zirconia sintered body of the present invention is 99.80% or more, preferably 99.85% or more, and more preferably 99.90% or more.
- the relative density is less than 99.80%, the translucency tends to be low, and the sintered body is inferior in aesthetics as a dental material.
- the colored translucent zirconia sintered body of the present invention has a lightness L * (hereinafter, simply referred to as “lightness L *” or “L *”) in the L * a * b * color system having an iron compound content. If it is less than 2000 ppm, it is preferably 51 or more. Moreover, if content of an iron compound is less than 500 ppm, it is preferable that it is 70 and 80 or less.
- the colored translucent zirconia sintered body of the present invention preferably has a lightness L * of 51 or more and 70 or less and an iron compound content of 500 ppm or more and less than 2000 ppm in terms of Fe 2 O 3 . Moreover, the colored translucent zirconia sintered body of the present invention preferably has a lightness L * of more than 70 and 80 or less, and an iron compound content of 50 ppm or more and less than 500 ppm in terms of Fe 2 O 3 .
- the colored translucent zirconia sintered body of the present invention has aesthetics equivalent to natural teeth because the lightness L * is within this range.
- the total light transmittance is likely to be lower as the value of the lightness L * is smaller.
- the colored translucent zirconia sintered body of the present invention has a hue a * (hereinafter simply referred to as “hue a *” or “a *”) in the L * a * b * color system of ⁇ 5 to 10 Preferably, it is -4 or more and 9 or less, more preferably -3 or more and 8 or less. Further, the hue a * is within this range, and the hue b * (hereinafter simply referred to as “hue b *” or “b *”) in the L * a * b * color system is 0 to 30. It is preferably 0 or more and 29 or less, more preferably 0 or more and 28 or less.
- the color tone of the colored translucent zirconia sintered body of the present invention is defined by lightness L *, hue a * and b *.
- the color tone in the colored translucent zirconia sintered body of the present invention is a value measured by collecting light transmitted through the sintered body and light reflected from the sintered body. Therefore, when the thickness or translucency of the sintered body changes, the color tone also changes.
- the color tone of the colored translucent zirconia sintered body of the present invention is the color tone of the opaque zirconia sintered body having no translucency, that is, the lightness L * obtained from only the reflected light on the surface of the sintered body, the hue a It is a value different from the value obtained by * and b *.
- total light transmittance is a lightness L * of 51 or more and less than 70, It is preferably 20% or more, more preferably 23% or more, and further preferably 25% or more.
- the total light transmittance is preferably 20% or more, more preferably 35% or more, and further preferably 40% or more.
- the lightness L * is within the scope of the present invention, and when the total light transmittance is 20% or more, it is likely to be aesthetic that can be widely used as a dental material.
- the total light transmittance need not be higher than necessary. For example, if the total light transmittance is 43% or less, the same degree of translucency as natural teeth can be obtained.
- the colored translucent zirconia sintered body of the present invention preferably has a total light transmittance (hereinafter referred to as “near infrared transmittance”) of 35% or more with respect to light having a wavelength of 850 nm at a sample thickness of 1 mm. 35.5% or more, more preferably 36% or more. If the near-infrared transmittance is 35% or more, the material is suitable not only for dental materials that require aesthetic translucency but also for protective layers of energy conversion materials (for example, solar cells).
- the colored translucent zirconia sintered body of the present invention has a high near infrared transmittance, and a sintered body having a near infrared transmittance of about 40% can be obtained.
- the colored translucent zirconia sintered body of the present invention preferably includes a tetragonal crystal phase, and preferably a tetragonal single phase. Thereby, mechanical strength tends to be high.
- the colored translucent zirconia sintered body of the present invention preferably has a three-point bending strength of 1000 MPa or more, more preferably 1100 MPa or more, and still more preferably 1200 MPa or more.
- the colored translucent zirconia sintered body of the present invention preferably has a crystal grain size of 0.2 ⁇ m or more and 0.45 ⁇ m or less, and more preferably 0.3 ⁇ m or more and 0.45 ⁇ m or less.
- the crystal grain size is 0.2 ⁇ m or more, pores hardly remain in the sintered body, and the relative density tends to increase.
- the crystal grain size is 0.45 ⁇ m or less, the hydrothermal deterioration of the sintered body is easily suppressed, and the dental material can withstand long-term use.
- the monoclinic phase transition depth after being immersed in hot water at 140 ° C. for 24 hours is preferably 20 ⁇ m or less, and preferably 10 ⁇ m or less. More preferred.
- the transition depth of the monoclinic phase can be used as an indicator of deterioration of the zirconia sintered body in a hydrothermal environment. That is, the small transition depth of the monoclinic phase is an indicator that it is difficult to deteriorate even when used as a dental material for a long time.
- the transition depth of the monoclinic phase is 20 ⁇ m or less, the hydrothermal deterioration of the sintered body is difficult to proceed, and the sintered body is not easily destroyed.
- the transition depth of the monoclinic phase the cross section of the sintered body can be observed with a scanning electron microscope (SEM) or the like.
- SEM scanning electron microscope
- the monoclinic phase transition depth after being immersed in hot water at 140 ° C. for 72 hours is preferably 20 ⁇ m or less, and is preferably 10 ⁇ m or less. It is more preferable.
- the colored translucent zirconia sintered body of the present invention preferably has a monoclinic phase ratio of 30% or less after being immersed in hot water at 140 ° C. for 24 hours, more preferably 15% or less. preferable. Further, the colored translucent zirconia sintered body of the present invention preferably has a monoclinic phase ratio of 80% or less after being immersed in hot water at 140 ° C. for 72 hours, and 60% or less. Is more preferable.
- the monoclinic phase ratio (also referred to as the M phase ratio) means that XRD measurement is performed on the mirror surface portion of the sintered body, and the (111) and (11-1) faces of the monoclinic phase, The diffraction intensities of the (111) plane and the (111) plane of the cubic phase are obtained, and the values calculated by the following formula 1 are used.
- the colored translucent zirconia sintered body of the present invention can be produced by molding and sintering a mixed powder of zirconia powder and iron compound.
- the zirconia powder preferably has a BET specific surface area of 10 m 2 / g or more and 15 m 2 / g or less, and more preferably 11 m 2 / g or more and 14 m 2 / g or less.
- the zirconia powder has a BET specific surface area of 10 m 2 / g or more, the powder is easily sintered even at a low temperature. Moreover, it becomes the powder by which aggregation between particle
- the average particle size of the zirconia powder is preferably 0.4 ⁇ m or more and 0.7 ⁇ m or less, and more preferably 0.4 ⁇ m or more and 0.6 ⁇ m or less.
- the average particle diameter of the zirconia powder is 0.4 ⁇ m or more, the number of fine particles that enhance the cohesiveness of the powder is reduced, and molding becomes easy.
- the average particle size is 0.7 ⁇ m or less, coarse particles containing hard agglomerated particles are reduced and molding becomes easy.
- the maximum particle size of the zirconia powder is preferably 2.0 ⁇ m or less, and preferably 1.5 ⁇ m or less. More preferred.
- the zirconia powder has a sintering shrinkage rate ( ⁇ / ⁇ T: g / cm 3 ⁇ ° C.) of 70% to 90% relative density in atmospheric pressure sintering at a heating rate of 300 ° C./hour in the atmosphere (hereinafter, It is preferable that the “sintering shrinkage rate” is 0.012 or more and 0.016 or less. Sintering shrinkage speed is an index of sinterability of zirconia powder. When the sintering shrinkage rate is within this range, the zirconia powder is excellent in sinterability.
- the sintering shrinkage rate is a measured value when the relative density is 70% or more.
- the sintering shrinkage rate is not affected by the variation in the density of the molded body. Furthermore, the rate of sintering shrinkage at a relative density of 70% to 90% is constant. Thus, since the shrinkage speed is a linear function of temperature and relative density, an accurate shrinkage speed can be obtained without using a special approximate calculation process.
- the zirconia powder is preferably a zirconia powder obtained by drying, calcining and pulverizing a hydrated zirconia sol obtained by hydrolysis of a zirconium salt aqueous solution.
- zirconium salt used in the production of the hydrated zirconia sol examples include at least one of zirconium oxychloride, zirconium nitrate, zirconium chloride, zirconium sulfate, and a mixture of zirconium hydroxide and an acid. Further, an alkali metal hydroxide, an alkaline earth metal hydroxide or both of them (hereinafter referred to as “alkali metal hydroxide etc.”) may be added to the zirconium salt aqueous solution. Examples of the alkali metal hydroxide include one or more hydroxides of lithium, sodium, potassium, magnesium, or calcium.
- the dried zirconia sol obtained above is dried and calcined to obtain a calcined zirconia powder.
- the calcination temperature is preferably 1000 ° C. or more and 1200 ° C. or less, and preferably 1050 ° C. or more and 1150 ° C. or less.
- zirconia powder can be obtained by pulverizing the zirconia calcined powder obtained above.
- the pulverization is not limited as long as the average particle size is 0.4 ⁇ m or more and 0.7 ⁇ m or less. It is preferable to pulverize by wet pulverization using zirconia balls.
- the colored translucent zirconia sintered body of the present invention is obtained by mixing a zirconia powder and an iron compound to obtain a mixed powder.
- the iron compound include water-soluble compounds such as iron chloride and iron nitrate, and water-insoluble compounds such as iron oxide and iron oxide hydroxide.
- water-soluble compounds such as iron chloride and iron nitrate
- water-insoluble compounds such as iron oxide and iron oxide hydroxide.
- the iron compound is 2000 ppm in terms of Fe 2 O 3 with respect to the total weight of ZrO 2 and Y 2 O 3 (when alumina is added, the total weight of ZrO 2 , Y 2 O 3 and Al 2 O 3 ). It is preferable to mix so that it may become less than 0.2 weight%), it is more preferable to mix so that it may become 1800 ppm (0.18 weight%) or less, and it may become 1600 ppm (0.16 weight%) or less More preferably, they are mixed.
- the colored translucent zirconia sintered body of the present invention contains alumina
- alumina source examples include one or more of alumina, hydrated alumina, alumina sol, aluminum hydroxide, aluminum chloride, aluminum nitrate, and aluminum sulfate.
- the alumina source is preferably a water-insoluble alumina compound, and more preferably alumina.
- a mixed powder is obtained by mixing zirconia powder, an iron compound and, if necessary, an alumina source.
- the composition of mixed powder and the composition of the colored translucent zirconia sintered compact which uses this as a raw material become equivalent.
- the zirconia powder or mixed powder it is preferable to use spray-granulated powder granules which are made into a slurry and then spray-dried. Thereby, the fluidity of the powder at the time of forming the molded body is increased, and pores are easily excluded from the molded body.
- Spray granulation powder granules the particle size is 30 ⁇ m or 80 ⁇ m or less and a loosed bulk density (Untamped density) is less than 1.10 g / cm 3 or more 1.40 g / cm 3.
- the colored translucent zirconia sintered body of the present invention can be manufactured by molding a mixed powder to obtain a molded body, and sintering the molded body.
- the molding method is not limited as long as the relative density of the molded body is about 50 ⁇ 5%.
- a method of performing cold isostatic pressing (hereinafter referred to as “CIP”) treatment after pressing the mixed powder as needed can be exemplified.
- CIP cold isostatic pressing
- the colored translucent zirconia sintered body of the present invention can be obtained by sintering the obtained molded body.
- the sintering method is preferably a sintering method performed under normal pressure, so-called normal pressure sintering.
- normal pressure sintering a sintering method performed under normal pressure
- the zirconia powder obtained by the above method is used, colored zirconia having high strength and translucency only by atmospheric pressure sintering without performing a hot isostatic pressing (hereinafter referred to as “HIP”) treatment.
- HIP hot isostatic pressing
- the sintering temperature is preferably 1350 ° C. or higher and 1450 ° C. or lower, more preferably 1400 ° C. or higher and 1450 ° C. or lower.
- the sintering temperature is 1350 ° C. or higher, the relative density tends to be as high as 99.80%.
- the sintering temperature is 1450 ° C. or lower, hydrothermal deterioration hardly occurs, and a sintered body that can withstand long-term use as a dental material can be obtained.
- the sintering atmosphere is preferably an atmosphere other than the reducing atmosphere, and is preferably an oxygen atmosphere or air. Since it is simple, it is preferable to sinter in the atmosphere.
- the sintering shrinkage rate of the mixed powder was measured as follows. The mixed powder was put into a mold and press-molded, and then CIP-treated at a pressure of 2 t / cm 2 to obtain a molded body having a relative density of 50 ⁇ 5%. The obtained compact was sintered up to 1500 ° C. under atmospheric pressure in the air at a temperature rising rate of 300 ° C./hour, and the heat shrinkage behavior was measured.
- a general-purpose thermal dilatometer manufactured by ULVAC-RIKO, model: DL9700 was used. From the obtained heat shrinkage behavior, the temperature at which the relative density changes from 70% to 90% was obtained, and the heat shrinkage rate was obtained.
- the average particle diameter of the zirconia powder was measured using a Microtrac particle size distribution meter (manufactured by Honeywell, model: 9320-HRA). The median value of the cumulative curve of the particle size distribution expressed on a volume basis (median diameter; the particle size corresponding to 50% of the cumulative curve) was taken as the average particle size. Prior to the measurement, the powder was suspended in distilled water and pretreated by dispersing for 3 minutes using an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho, model: US-150T).
- Measured density Measurement of density of molded body and sintered body (hereinafter referred to as “measured density”) ⁇ )
- the volume of the molded body was determined by measuring the size of the molded body with calipers, and the measured density of the molded body was determined from the obtained volume and the weight of the molded body.
- the measured density of the sintered body was determined by the Archimedes method.
- ⁇ 0 100 / [(X / ⁇ Al ) + (Y / ⁇ Fe ) + (100 ⁇ XY) / ⁇ Zr ] (2)
- X Alumina content
- wt% Y Fe 2 O 3 content
- wt% ⁇ Al Theoretical density of alumina
- 3.987 g / cm 3 ⁇ Zr Theoretical density of zirconia
- 6.0956 g / cm 3 ⁇ Fe Theoretical density of Fe 2 O 3 ; 5.24 g / cm 3 It is.
- the total light transmittance was measured according to JIS K7361 using a turbidimeter (Nippon Denshoku Industries Co., Ltd., model: NDH2000).
- the light source D65 was used as the light source.
- the sample used was a disk-shaped sample having a thickness of 1 mm obtained by polishing the sintered body on both sides.
- the near-infrared transmittance (total light transmittance with respect to light having a wavelength of 850 nm) was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO Corporation, model: V-650) with a 150 mm diameter integrating sphere unit (form: ILV-724) was attached and measured.
- the sample used was a disk-shaped sample having a thickness of 1 mm obtained by polishing the sintered body on both sides.
- a circle on a microscope image a circle such that the total number of particles N i spent in particle number n c and the circumference of the circle is 100 to 150, or In the case of an image of less than 100, a plurality of circles are drawn using images of a plurality of fields so that the total number of particles (n c + N i ) is 100 to 150, and crystallized by a planimetric method. The particle size was determined.
- the hydrothermal deterioration characteristic is determined by polishing one side of the obtained sintered body until it becomes a mirror surface and immersing it in hot water at 140 ° C. for 24 hours or 72 hours to form a monoclinic phase ratio (monoclinic phase).
- the phase ratio was evaluated by calculating.
- the monoclinic phase ratio (M phase ratio) was measured by XRD on the mirror surface of the immersed sintered body, and the (111) and (11-1) planes of the monoclinic phase and the (111) plane of the tetragonal phase , The diffraction intensity of the (111) plane of the cubic phase, respectively, and the value calculated by the following formula 1.
- the transition depth is obtained by cutting the immersed sintered body, observing the cross section with a scanning electron microscope (SEM), and observing the depth at which the crystal structure becomes rough from the mirror surface. It was.
- Example 1 Hydrated zirconia sol was obtained by hydrolysis after adding yttrium chloride to the zirconium oxychloride aqueous solution to adjust the Y 2 O 3 concentration to 3 mol%.
- the hydrated zirconia sol was dried and then calcined at 1100 ° C. for 2 hours to obtain a zirconia calcined powder containing 3 mol% yttria.
- the obtained zirconia calcined powder was washed with water, and ⁇ -alumina was mixed so that the alumina content was 0.05 wt% with respect to the zirconia calcined powder.
- iron oxide hydroxide FeOOH
- distilled water was added to form a slurry having a zirconia concentration of 45% by weight.
- the slurry was pulverized by a vibration mill using zirconia balls having a diameter of 3 mm for 24 hours to obtain a pulverized slurry.
- a part of the pulverized slurry was dried to measure the BET specific surface area to obtain a mixed powder.
- the average particle size of the particles in the pulverized slurry was 0.43 ⁇ m, the maximum particle size was 1.16 ⁇ m, and the BET specific surface area of the mixed powder was 12.5 m 2 / g. 3% by weight of an organic binder was added to the obtained pulverized slurry and spray-dried to obtain zirconia powder having an average granule diameter of 45 to 50 ⁇ m.
- the obtained zirconia powder was uniaxially pressed at a pressure of 19.6 MPa and then CIP-treated at a pressure of 196 MPa to obtain a molded body.
- the obtained molded body was heated to 1000 ° C.
- Example 2 A colored translucent zirconia sintered body was obtained in the same manner as in Example 1 except that the sintering temperature was 1450 ° C. The results are shown in Table 1.
- Example 2 The colored zirconia sintered body obtained in Example 2 was subjected to hot isostatic pressing (HIP) treatment at a treatment temperature of 1400 ° C. and a pressure of 150 MPa. There was almost no change in the relative density and L * value of the colored translucent zirconia sintered body before and after the HIP treatment. Thereby, it turned out that the colored translucent zirconia sintered compact of this invention is a sintered compact which has a characteristic equivalent to a HIP process, without performing a HIP process.
- HIP hot isostatic pressing
- Example 3 A colored translucent zirconia sintered body was obtained in the same manner as in Example 1 except that 1500 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 . The results are shown in Table 1.
- Example 4 A colored translucent zirconia sintered body was obtained in the same manner as in Example 1 except that 1500 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 and the sintering temperature was 1450 ° C. The results are shown in Table 1.
- Example 5 A colored translucent zirconia sintered body was obtained in the same manner as in Example 1 except that 750 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 . The results are shown in Table 1.
- Example 6 A colored translucent zirconia sintered body was obtained in the same manner as in Example 1 except that 750 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 and the sintering temperature was 1450 ° C. The results are shown in Table 1.
- Example 7 Example 1 except that 0.1% by weight of ⁇ -alumina was added in terms of alumina content, iron oxide hydroxide was added at 1500 ppm in terms of Fe 2 O 3 , and the sintering temperature was 1450 ° C.
- a colored translucent zirconia sintered body was obtained in the same manner. The results are shown in Table 1.
- Example 8 The colored translucent zirconia fired in the same manner as in Example 1 except that ⁇ -alumina was added in an amount of 0.1% by weight in terms of alumina content and iron oxide hydroxide was added in an amount of 750 ppm in terms of Fe 2 O 3. A ligature was obtained. The results are shown in Table 1.
- Example 9 Colored translucent zirconia baked in the same manner as in Example 1 except that ⁇ -alumina was added in an alumina content of 0.15% by weight and iron oxide hydroxide was added in an amount of 1500 ppm in terms of Fe 2 O 3. A ligature was obtained. The results are shown in Table 1.
- Example 10 Colored translucent zirconia baked in the same manner as in Example 1 except that ⁇ -alumina was added in an alumina content of 0.15 wt%, and iron oxide hydroxide was added in an amount of 750 ppm in terms of Fe 2 O 3. A ligature was obtained. The results are shown in Table 1.
- Example 11 A colored translucent zirconia sintered body was obtained in the same manner as in Example 1 except that 500 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 . The results are shown in Table 1.
- Example 12 A colored translucent zirconia sintered body was obtained in the same manner as in Example 1 except that 500 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 and the sintering temperature was 1450 ° C. The results are shown in Table 1.
- Comparative Example 1 The colored translucent light is transmitted in the same manner as in Example 1 except that ⁇ -alumina is not added, iron oxide hydroxide is added in an amount of 1500 ppm in terms of Fe 2 O 3 , and the sintering temperature is 1450 ° C. A sintered zirconia sintered body was obtained. The results are shown in Table 1. Comparative Example 2 Colored translucent zirconia baked in the same manner as in Example 1 except that ⁇ -alumina was added in an amount of 0.25% by weight in terms of alumina content, and iron oxide hydroxide was added in an amount of 2000 ppm in terms of Fe 2 O 3. A ligature was obtained. The results are shown in Table 1.
- Example 1 except that ⁇ -alumina was added at 0.25 wt% in terms of alumina content, iron oxide hydroxide was added at 2000 ppm in terms of Fe 2 O 3 , and the sintering temperature was 1450 ° C. A colored translucent zirconia sintered body was obtained in the same manner. The results are shown in Table 1.
- Example 13 A mixed powder was obtained in the same manner as in Example 1 except that 1350 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 .
- the obtained mixed powder was uniaxial press-molded at a pressure of 49.0 MPa, and then subjected to CIP treatment at a pressure of 196 MPa to obtain a molded body.
- the obtained molded body was heated to 1000 ° C. in the atmosphere at 50 ° C./hour, held for 1 hour to remove the binder, and then sintered in the atmosphere at a sintering temperature of 1400 ° C., a temperature increase rate of 400 ° C./hour and firing.
- a colored translucent zirconia sintered body was obtained by sintering at normal pressure with a holding time of 2 hours at the sintering temperature.
- the crystal phase of the obtained colored translucent zirconia sintered body was a tetragonal single phase.
- the results are shown in Table 1.
- Example 14 A colored translucent zirconia sintered body was obtained in the same manner as in Example 13 except that 700 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 . The results are shown in Table 1.
- Example 15 The mixed powder 41% obtained by adding 1700 ppm of iron oxide hydroxide in terms of Fe 2 O 3 obtained in Example 1 and the powder without adding iron oxide hydroxide in Example 1 (zirconia calcined powder + ⁇ Alumina) 59% was mixed in a plastic bottle to obtain a mixed powder of 700 ppm in terms of Fe 2 O 3 .
- the obtained mixed powder was uniaxial press-molded at a pressure of 49.0 MPa, and then subjected to CIP treatment at a pressure of 196 MPa to obtain a molded body.
- the obtained molded body was heated to 1000 ° C.
- a colored translucent zirconia sintered body was obtained by sintering at normal pressure with a holding time of 2 hours at the sintering temperature.
- the crystal phase of the obtained colored translucent zirconia sintered body was a tetragonal single phase. The results are shown in Table 1.
- Example 16 Hydrated zirconia sol was obtained by hydrolysis after adding yttrium chloride to the zirconium oxychloride aqueous solution to adjust the Y 2 O 3 concentration to 3 mol%.
- the hydrated zirconia sol was dried and then calcined at 1100 ° C. for 2 hours to obtain a zirconia calcined powder containing 3 mol% yttria.
- the obtained zirconia calcined powder was washed with water, and ⁇ -alumina was mixed so that the alumina content was 0.05 wt% with respect to the zirconia calcined powder.
- iron oxide hydroxide FeOOH
- distilled water was added to form a slurry having a zirconia concentration of 45% by weight.
- the slurry was pulverized by a vibration mill using zirconia balls having a diameter of 3 mm for 24 hours to obtain a pulverized slurry.
- a part of the pulverized slurry was dried to measure the BET specific surface area to obtain a mixed powder.
- the average particle size of the particles in the pulverized slurry was 0.44 ⁇ m, the maximum particle size was 1.38 ⁇ m, and the BET specific surface area of the mixed powder was 12.3 m 2 / g. 3% by weight of an organic binder was added to the obtained pulverized slurry and spray-dried to obtain zirconia powder having an average granule diameter of 45 to 50 ⁇ m.
- the obtained zirconia powder was uniaxially pressed at a pressure of 19.6 MPa and then CIP-treated at a pressure of 196 MPa to obtain a molded body.
- the obtained molded body was heated to 1000 ° C.
- a colored translucent zirconia sintered body was obtained by sintering at normal pressure with a holding time of 2 hours at the sintering temperature.
- the crystal phase of the obtained colored translucent zirconia sintered body was a tetragonal single phase. The results are shown in Table 1.
- Example 17 A colored translucent zirconia sintered body was obtained in the same manner as in Example 16 except that the sintering temperature was 1450 ° C. The results are shown in Table 1.
- Example 18 A colored translucent zirconia sintered body was obtained in the same manner as in Example 16 except that 80 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 . The results are shown in Table 1.
- Example 19 A colored translucent zirconia sintered body was obtained in the same manner as in Example 16 except that 80 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 and the sintering temperature was 1450 ° C. The results are shown in Table 1.
- Example 20 A colored translucent zirconia sintered body was obtained in the same manner as in Example 16, except that ⁇ -alumina was added in an alumina content of 0.1% by weight. The results are shown in Table 1.
- Example 21 A colored translucent zirconia sintered body was obtained in the same manner as in Example 16, except that ⁇ -alumina was added in an alumina content of 0.15% by weight. The results are shown in Table 1.
- Example 22 A colored translucent zirconia sintered body was obtained in the same manner as in Example 16 except that ⁇ -alumina was not added and the sintering temperature was 1450 ° C. The results are shown in Table 1.
- Comparative Example 4 Colored translucent zirconia baked in the same manner as in Example 16 except that ⁇ -alumina was added in an amount of 0.25 wt% in terms of alumina content, and iron oxide hydroxide was added in an amount of 1000 ppm in terms of Fe 2 O 3. A ligature was obtained. The results are shown in Table 1. Comparative Example 5 Colored translucent zirconia baked in the same manner as in Example 16 except that ⁇ -alumina was added in an amount of 0.25% by weight in terms of alumina content, and iron oxide hydroxide was added in an amount of 500 ppm in terms of Fe 2 O 3. A ligature was obtained. The results are shown in Table 1.
- Comparative Example 6 Example 16 except that ⁇ -alumina was added at 0.25 wt% in terms of alumina content, iron oxide hydroxide was added at 1000 ppm in terms of Fe 2 O 3 , and the sintering temperature was 1450 ° C. A colored translucent zirconia sintered body was obtained in the same manner. The results are shown in Table 1. Comparative Example 7 Example 16 except that ⁇ -alumina was added in an amount of 0.25 wt% in terms of alumina content, iron oxide hydroxide was added in an amount of 500 ppm in terms of Fe 2 O 3 , and the sintering temperature was 1450 ° C. A colored translucent zirconia sintered body was obtained in the same manner. The results are shown in Table 1.
- Example 23 A mixed powder was obtained in the same manner as in Example 16. The obtained mixed powder was uniaxial press-molded at a pressure of 49.0 MPa, and then subjected to CIP treatment at a pressure of 196 MPa to obtain a molded body. The obtained molded body was heated to 1000 ° C. in the atmosphere at 50 ° C./hour, held for 1 hour to remove the binder, and then sintered in the atmosphere at a sintering temperature of 1400 ° C., a temperature increase rate of 400 ° C./hour and firing. A colored translucent zirconia sintered body was obtained by sintering at normal pressure with a holding time of 2 hours at the sintering temperature.
- Example 24 A colored translucent zirconia sintered body was obtained in the same manner as in Example 23 except that 80 ppm of iron oxide hydroxide was added in terms of Fe 2 O 3 . The results are shown in Table 1.
- Example 25 12% of mixed powder obtained by adding 1700 ppm of iron oxide hydroxide obtained in Example 1 in terms of Fe 2 O 3 and powder not containing iron oxide hydroxide in Example 1 (zirconia calcined powder + ⁇ -alumina) ) 88% was mixed in a plastic bottle to obtain a mixed powder of 200 ppm in terms of Fe 2 O 3 .
- the obtained mixed powder was uniaxial press-molded at a pressure of 49.0 MPa, and then subjected to CIP treatment at a pressure of 196 MPa to obtain a molded body.
- the obtained molded body was heated to 1000 ° C.
- a colored translucent zirconia sintered body was obtained by sintering at normal pressure with a holding time of 2 hours at the sintering temperature.
- the crystal phase of the obtained colored translucent zirconia sintered body was a tetragonal single phase. The results are shown in Table 1.
- the colored translucent zirconia sintered body obtained in the examples has high relative density and total light transmittance. It is an excellent colored translucent zirconia sintered body and can be used as a dental material for mill blanks, orthodontic brackets and the like.
- the colored translucent zirconia sintered body of the present invention has high strength and has aesthetics very close to the color of the teeth. In particular, it has the same translucency and color tone as natural teeth. Therefore, it is particularly suitable for zirconia sintered bodies used in dental applications, mill blanks such as denture materials, and orthodontic brackets.
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Abstract
Description
これまで、ジルコニア焼結体を自然な歯と同様な審美性とするため、ジルコニア焼結体の表面に他の材料を積層し、これにより色調を調整した歯科材料が報告されている(例えば、特許文献1参照)。しかしながら、当該歯科材料では、ジルコニアと強度の異なるガラス材料からなる複合材料であるため、歯科材料としては強度が十分ではなかった。
例えば、透光性を付与することで、自然の歯と同様な透光性を有するジルコニア焼結体が報告されている。特許文献2及び3では、そのまま歯科材料で使用するため、高い強度及び高い透光性を有するジルコニア焼結体が開示されている。しかしながら、これらのジルコニア焼結体は自然な歯と同様な透光性を有するものの、自然な歯とは異なるジルコニア本来の明るい白色の色調を呈するものであった。
本発明では、上記の課題を解消し、強度が高いだけではなく、審美性にも優れるジルコニア焼結体を提供することを目的とする。
(1)鉄化合物及び2~4mol%のイットリアを含み、L*a*b*表色系における明度L*が51以上80以下であり、相対密度が99.80%以上であることを特徴とする着色透光性ジルコニア焼結体。
(2)L*a*b*表色系における明度L*が51以上70以下であることを特徴とする上記(1)に記載の着色透光性ジルコニア焼結体。
(3)L*a*b*表色系における明度L*が70を超え80以下であることを特徴とする上記(1)に記載の着色透光性ジルコニア焼結体。
(4)試料厚さ1mm、D65光源における全光線透過率が20%以上であることを特徴とする上記(1)乃至(3)のいずれかに記載の着色透光性ジルコニア焼結体。
(5)鉄化合物の含有量がFe2O3換算で2000ppm未満であることを特徴とする上記(1)乃至(4)のいずれかに記載の着色透光性ジルコニア焼結体。
(6)鉄化合物の含有量がFe2O3換算で500ppm以上であることを特徴とする上記(1)乃至(5)のいずれかに記載の着色透光性ジルコニア焼結体。
(7)鉄化合物の含有量がFe2O3換算で500ppm未満であることを特徴とする上記(1)乃至(5)のいずれかに記載の着色透光性ジルコニア焼結体。
(8)着色透光性ジルコニア焼結体が、更にアルミナを含むことを特徴とする上記(1)乃至(7)のいずれかに記載の着色透光性ジルコニア焼結体。
(9)アルミナの含有量が0.25重量%未満であることを特徴とする上記(8)に記載の着色透光性ジルコニア焼結体。
(10)140℃熱水中に24時間浸漬させた後の単斜晶相の転移深さが10μm以下であることを特徴とする上記(9)に記載の着色透光性ジルコニア焼結体。
(11)140℃熱水中に72時間浸漬させた後の単斜晶相の転移深さが10μm以下であることを特徴とする上記(10)に記載の着色透光性ジルコニア焼結体。
(12)上記(1)乃至(11)のいずれかに記載の着色透光性ジルコニア焼結体を用いてなる歯科材料。
(13)歯列矯正ブラケットである上記(12)に記載の歯科材料。
(14)義歯、義歯ミルブランク又はその両者である上記(12)に記載の歯科材料。
本発明は着色透光性ジルコニア焼結体である。そのため、本発明の焼結体は、無色以外の色調を有し、かつ、透光性を有するジルコニア多結晶体である。従って、本発明の着色透光性ジルコニア焼結体は、不透明のジルコニア焼結体(以下、不透明ジルコニア焼結体)、又はジルコニア単結晶とは異なる。なお、ここでいう不透明ジルコニア焼結体とは、例えば、D65光源において試料厚さ1mmの全光線透過率が10%以下のジルコニア焼結体である。
なお、アルミナ含有量は着色透光性ジルコニア焼結体のZrO2及びY2O3の合計重量に対するAl2O3の割合である。
さらに、本発明の着色透光性ジルコニア焼結体は、140℃の熱水中に72時間浸漬させた後の単斜晶相の転移深さが20μm以下であることが好ましく、10μm以下であることがより好ましい。
さらに、本発明の着色透光性ジルコニア焼結体は、140℃の熱水中に72時間浸漬させた後の単斜晶相率が80%以下であることが好ましく、60%以下であることがより好ましい。
本発明の着色透光性ジルコニア焼結体は、ジルコニア粉末及び鉄化合物の混合粉末を成形、焼結することで製造することができる。
鉄化合物の種類は、塩化鉄、硝酸鉄のような水に可溶性の化合物や酸化鉄、酸化水酸化鉄のような水に不溶性の化合物を例示できる。
水に不溶性の化合物を使用する場合、平均粒径が1μm以下の鉄化合物をジルコニア仮焼粉末の粉砕時に混合することが好ましい。これにより、水に不溶性の鉄化合物の凝集物がなくなり、得られる焼結体の色調が均一となりやすい。
ジルコニア粉末又は混合粉末は、これをスラリーとした後に噴霧乾燥した噴霧造粒粉末顆粒を用いることが好ましい。これにより、成形体を形成する際の粉末の流動性が高くなり、成形体から気孔が排除されやすくなる。
噴霧造粒粉末顆粒は、粒径は30μm以上80μm以下、軽装嵩密度(Untamped density)が1.10g/cm3以上1.40g/cm3以下であることが好ましい。
成形体は、その相対密度が50±5%程度となるようにすれば成形方法は限定されない。好ましい成形方法として混合粉末をプレス成形した後に、必要に応じて冷間静水圧プレス(以下、「CIP」とする)処理する方法を挙げることができる。
得られた成形体を焼結することで本発明の着色透光性ジルコニア焼結体を得ることができる。
(焼結収縮速度の測定)
混合粉末の焼結収縮速度は以下の様に測定した。混合粉末を金型に入れプレス成形した後、圧力2t/cm2でCIP処理し、相対密度50±5%の成形体とした。得られた成形体を常圧下、大気中、昇温速度300℃/時、1500℃まで焼結することで熱収縮挙動を測定した。測定には、汎用的な熱膨張計(アルバック理工製、型式:DL9700)を用いた。
得られた熱収縮挙動から、その相対密度が70%から90%に変化する温度を求め、熱収縮速度を求めた。
ジルコニア粉末の平均粒径は、マイクロトラック粒度分布計(Honeywell社製、型式:9320-HRA)を用いて測定した。体積基準で表される粒径分布の累積カーブの中央値(メディアン径;累積カーブの50%に対応する粒径)を平均粒径とした。
測定に先立ち、粉末を蒸留水に懸濁させ、超音波ホモジナイザー(日本精機製作所製,型式:US-150T)を用いて3分間分散させて前処理を行った。
(成形体及び焼結体の密度(以下、「実測密度」とする)ρの測定)
成形体のサイズをノギスで測定して体積を求め、得られた体積と成形体重量とから成形体の実測密度を求めた。また、焼結体の実測密度はアルキメデス法により求めた。
相対密度は、理論密度ρ0及び実測密度ρから以下の(1)式から求めた。
相対密度(%)=(ρ/ρ0)×100 ・・・(1)
また、理論密度ρ0は以下の(2)式から求めた。
ρ0=100/[(X/ρAl)+(Y/ρFe)+(100-X-Y)/ρZr] ・・・(2)
なお、
X :アルミナ含有量;重量%
Y :Fe2O3含有量;重量%
ρAl :アルミナの理論密度;3.987g/cm3
ρZr :ジルコニアの理論密度;6.0956g/cm3
ρFe :Fe2O3の理論密度;5.24g/cm3
である。
全光線透過率は、濁度計(日本電色工業(株)製、型式:NDH2000)を用いて、JIS K7361に準拠して測定した。光源としては光源D65を使用した。試料は焼結体を両面研磨した試料厚さ1mmの円板形状のものを用いた。
また、近赤外透過率(波長850nmの光に対する全光線透過率)は、紫外可視近赤外分光光度計(日本分光株式会社製、型式:V-650)に直径150mm積分球ユニット(形式:ILV-724)を取り付けて測定した。試料は焼結体を両面研磨した試料厚さ1mmの円板形状のものを用いた。
JIS Z8729に準拠して明度L*、色相a*及びb*を測定した。色調の測定に際し、試料は試料厚さ2.8mmの円板形状とし、片面を鏡面研磨した。測定は鏡面研磨をした面について行った。
(焼結体強度の測定)
焼結体強度をJIS R1601に準拠して、3点曲げ測定法で評価した。
(結晶粒径の測定)
ジルコニア焼結体の結晶粒径は、鏡面研磨した焼結体を熱エッチング処理し、走査型電子顕微鏡(SEM)観察した写真から、プラニメトリック法を用いて算出した。具体的には、顕微鏡画像上に円を描いたとき、円内の粒子数ncと円周にかかった粒子数Niの合計が100個~150個となるような円を描いて、または100個に満たない画像の場合には、粒子数の合計(nc+Ni)が100個~150個となるように複数視野の画像を用いて複数の円を描き、プラニメトリック法により結晶粒径を求めた。
水熱劣化特性は、得られた焼結体の片面を鏡面になるまで研磨して、140℃の熱水中に24時間又は72時間浸漬させ、生成する単斜晶相の率(単斜晶相率)を求めることによって評価した。単斜相率(M相率)は、浸漬処理した焼結体の鏡面部分についてXRD測定を行い、単斜晶相の(111)及び(11-1)面,正方晶相の(111)面,立方晶相の(111)面の回折強度をそれぞれ求めて、以下の数式1により算出された値をいう。
オキシ塩化ジルコニウム水溶液に塩化イットリウムを添加し、Y2O3濃度を3mol%としてから加水分解によって水和ジルコニアゾル得た。当該水和ジルコニアゾルを乾燥させた後、1100℃で2時間焼成し、3mol%のイットリアを含むジルコニア仮焼粉末を得た。
得られたジルコニア仮焼粉末を水洗した後、当該ジルコニア仮焼粉末に対してアルミナ含有量で0.05重量%となるように、α-アルミナを混合した。さらに、当該ジルコニア仮焼粉末及びα-アルミナの合計重量に対してFe2O3換算で1700ppmとなるように酸化水酸化鉄(FeOOH)を混合した。
これらの原料を混合後、蒸留水を添加してジルコニア濃度45重量%のスラリーにした。当該スラリーを直径3mmのジルコニアボールを用いた振動ミルで24時間粉砕して粉砕スラリーとした。又、粉砕スラリーの一部をBET比表面積の測定のために乾燥して混合粉末を得た。
得られた粉砕スラリーに有機バインダーを3重量%加えて、噴霧乾燥を行い平均顆粒径45~50μmのジルコニア粉末を得た。
得られたジルコニア粉末を19.6MPaの圧力で一軸プレス後、196MPaの圧力でCIP処理して成形体を得た。
得られた成形体を、大気中、1000℃まで50℃/時昇温し、1時間保持してバインダーを除去した後、大気中、焼結温度1400℃、昇温速度600℃/時及び焼結温度での保持時間2時間で常圧焼結して着色透光性ジルコニア焼結体を得た。得られた着色透光性ジルコニア焼結体の結晶相は正方晶の単相であった。結果を表1に示す。
実施例2
焼結温度を1450℃としたこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例2で得られた着色ジルコニア焼結体を処理温度1400℃、圧力150MPaで熱間静水圧プレス(HIP)処理した。
HIP処理前後で着色透光性ジルコニア焼結体の相対密度及びL*値の変化はほとんどなかった。これにより、本発明の着色透光性ジルコニア焼結体は、HIP処理をすることなく、HIP処理と同等の特性を有する焼結体であることが分かった。
酸化水酸化鉄をFe2O3換算で1500ppm添加したこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例4
酸化水酸化鉄をFe2O3換算で1500ppm添加したこと、及び、焼結温度を1450℃でしたこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例5
酸化水酸化鉄をFe2O3換算で750ppm添加したこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例6
酸化水酸化鉄をFe2O3換算で750ppm添加したこと、及び、焼結温度を1450℃でしたこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例7
α-アルミナをアルミナ含有量で0.1重量%添加したこと、酸化水酸化鉄をFe2O3換算で1500ppm添加したこと、及び、焼結温度を1450℃としたこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
α-アルミナをアルミナ含有量で0.1重量%添加したこと、及び、酸化水酸化鉄をFe2O3換算で750ppm添加したこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例9
α-アルミナをアルミナ含有量で0.15重量%添加したこと、及び、酸化水酸化鉄をFe2O3換算で1500ppm添加したこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例10
α-アルミナをアルミナ含有量で0.15重量%添加したこと、及び、酸化水酸化鉄をFe2O3換算で750ppm添加したこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例11
酸化水酸化鉄をFe2O3換算で500ppm添加したこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例12
酸化水酸化鉄をFe2O3換算で500ppm添加したこと、及び、焼結温度を1450℃としたこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
α-アルミナを添加しなかったこと、酸化水酸化鉄をFe2O3換算で1500ppm添加したこと、及び、焼結温度を1450℃としたこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
比較例2
α-アルミナをアルミナ含有量で0.25重量%添加したこと、及び、酸化水酸化鉄をFe2O3換算で2000ppm添加したこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
比較例3
α-アルミナをアルミナ含有量で0.25重量%添加したこと、酸化水酸化鉄をFe2O3換算で2000ppm添加したこと、及び、焼結温度を1450℃としたこと以外は実施例1と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
酸化水酸化鉄をFe2O3換算で1350ppm添加したこと以外は実施例1と同様な方法で混合粉末を得た。得られた混合粉末を49.0MPaの圧力で一軸プレス成形後、196MPaの圧力でCIP処理して成形体を得た。
得られた成形体を、大気中、1000℃まで50℃/時昇温し、1時間保持してバインダーを除去した後、大気中、焼結温度1400℃、昇温速度400℃/時及び焼結温度での保持時間2時間で常圧焼結して着色透光性ジルコニア焼結体を得た。得られた着色透光性ジルコニア焼結体の結晶相は正方晶の単相であった。結果を表1に示す。
実施例14
酸化水酸化鉄をFe2O3換算で700ppm添加したこと以外は実施例13と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例15
実施例1で得られた、酸化水酸化鉄をFe2O3換算で1700ppm添加した混合粉末41%と、実施例1において、酸化水酸化鉄を添加していない粉末(ジルコニア仮焼粉末+α-アルミナ)59%をポリ瓶の中で混合してFe2O3換算で700ppmの混合粉末を得た。
得られた混合粉末を49.0MPaの圧力で一軸プレス成形後、196MPaの圧力でCIP処理して成形体を得た。
得られた成形体を、大気中、1000℃まで50℃/時昇温し、1時間保持してバインダーを除去した後、大気中、焼結温度1400℃、昇温速度400℃/時及び焼結温度での保持時間2時間で常圧焼結して着色透光性ジルコニア焼結体を得た。得られた着色透光性ジルコニア焼結体の結晶相は正方晶の単相であった。結果を表1に示す。
オキシ塩化ジルコニウム水溶液に塩化イットリウムを添加し、Y2O3濃度を3mol%としてから加水分解によって水和ジルコニアゾル得た。当該水和ジルコニアゾルを乾燥させた後、1100℃で2時間焼成し、3mol%のイットリアを含むジルコニア仮焼粉末を得た。
得られたジルコニア仮焼粉末を水洗した後、当該ジルコニア仮焼粉末に対してアルミナ含有量で0.05重量%となるように、α-アルミナを混合した。さらに、当該ジルコニア仮焼粉末及びα-アルミナの合計重量に対してFe2O3換算で200ppmとなるように酸化水酸化鉄(FeOOH)を混合した。
これらの原料を混合後、蒸留水を添加してジルコニア濃度45重量%のスラリーにした。当該スラリーを直径3mmのジルコニアボールを用いた振動ミルで24時間粉砕して粉砕スラリーとした。又、粉砕スラリーの一部をBET比表面積の測定のために乾燥して混合粉末を得た。
得られた粉砕スラリーに有機バインダーを3重量%加えて、噴霧乾燥を行い平均顆粒径45~50μmのジルコニア粉末を得た。
得られたジルコニア粉末を19.6MPaの圧力で一軸プレス後、196MPaの圧力でCIP処理して成形体を得た。
得られた成形体を、大気中、1000℃まで50℃/時昇温し、1時間保持してバインダーを除去した後、大気中、焼結温度1400℃、昇温速度600℃/時及び焼結温度での保持時間2時間で常圧焼結して着色透光性ジルコニア焼結体を得た。得られた着色透光性ジルコニア焼結体の結晶相は正方晶の単相であった。結果を表1に示す。
焼結温度を1450℃としたこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例18
酸化水酸化鉄をFe2O3換算で80ppm添加したこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例19
酸化水酸化鉄をFe2O3換算で80ppm添加したこと、及び、焼結温度を1450℃でしたこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例20
α-アルミナをアルミナ含有量で0.1重量%添加したこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例21
α-アルミナをアルミナ含有量で0.15重量%添加したこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例22
α-アルミナを添加しなかったこと、及び、焼結温度を1450℃としたこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
α-アルミナをアルミナ含有量で0.25重量%添加したこと、及び、酸化水酸化鉄をFe2O3換算で1000ppm添加したこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
比較例5
α-アルミナをアルミナ含有量で0.25重量%添加したこと、及び、酸化水酸化鉄をFe2O3換算で500ppm添加したこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
比較例6
α-アルミナをアルミナ含有量で0.25重量%添加したこと、酸化水酸化鉄をFe2O3換算で1000ppm添加したこと、及び、焼結温度を1450℃としたこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
比較例7
α-アルミナをアルミナ含有量で0.25重量%添加したこと、酸化水酸化鉄をFe2O3換算で500ppm添加したこと、及び、焼結温度を1450℃としたこと以外は実施例16と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例16と同様な方法で混合粉末を得た。
得られた混合粉末を49.0MPaの圧力で一軸プレス成形後、196MPaの圧力でCIP処理して成形体を得た。
得られた成形体を、大気中、1000℃まで50℃/時昇温し、1時間保持してバインダーを除去した後、大気中、焼結温度1400℃、昇温速度400℃/時及び焼結温度での保持時間2時間で常圧焼結して着色透光性ジルコニア焼結体を得た。得られた着色透光性ジルコニア焼結体の結晶相は正方晶の単相であった。結果を表1に示す。
実施例24
酸化水酸化鉄をFe2O3換算で80ppm添加したこと以外は実施例23と同様な方法で着色透光性ジルコニア焼結体を得た。結果を表1に示す。
実施例1で得られた酸化水酸化鉄をFe2O3換算で1700ppm添加した混合粉末12%と、実施例1において、酸化水酸化鉄を添加していない粉末(ジルコニア仮焼粉末+α-アルミナ)88%をポリ瓶の中で混合してFe2O3換算で200ppmの混合粉末を得た。
得られた混合粉末を49.0MPaの圧力で一軸プレス成形後、196MPaの圧力でCIP処理して成形体を得た。
得られた成形体を、大気中、1000℃まで50℃/時昇温し、1時間保持してバインダーを除去した後、大気中、焼結温度1400℃、昇温速度400℃/時及び焼結温度での保持時間2時間で常圧焼結して着色透光性ジルコニア焼結体を得た。得られた着色透光性ジルコニア焼結体の結晶相は正方晶の単相であった。結果を表1に示す。
なお、2011年7月29日に出願された日本特許出願2011-166358号、及び2011年7月29日に出願された日本特許出願2011-166359号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- 鉄化合物及び2~4mol%のイットリアを含み、L*a*b*表色系における明度L*が51以上80以下であり、相対密度が99.80%以上であることを特徴とする着色透光性ジルコニア焼結体。
- L*a*b*表色系における明度L*が51以上70以下であることを特徴とする請求項1に記載の着色透光性ジルコニア焼結体。
- L*a*b*表色系における明度L*が70を超え80以下であることを特徴とする請求項1に記載の着色透光性ジルコニア焼結体。
- 試料厚さ1mm、D65光源における全光線透過率が20%以上であることを特徴とする請求項1乃至3のいずれかに記載の着色透光性ジルコニア焼結体。
- 鉄化合物の含有量がFe2O3換算で2000ppm未満であることを特徴とする請求項1乃至4のいずれかに記載の着色透光性ジルコニア焼結体。
- 鉄化合物の含有量がFe2O3換算で500ppm以上であることを特徴とする請求項1乃至5のいずれかに記載の着色透光性ジルコニア焼結体。
- 鉄化合物の含有量がFe2O3換算で500ppm未満であることを特徴とする請求項1乃至5のいずれかに記載の着色透光性ジルコニア焼結体。
- 着色透光性ジルコニア焼結体が、更にアルミナを含むことを特徴とする請求項1乃至7のいずれかに記載の着色透光性ジルコニア焼結体。
- アルミナの含有量が0.25重量%未満であることを特徴とする請求項8に記載の着色透光性ジルコニア焼結体。
- 140℃熱水中に24時間浸漬させた後の単斜晶相の転移深さが10μm以下であることを特徴とする請求項9に記載の着色透光性ジルコニア焼結体。
- 140℃熱水中に72時間浸漬させた後の単斜晶相の転移深さが10μm以下であることを特徴とする請求項10に記載の着色透光性ジルコニア焼結体。
- 請求項1乃至11のいずれかに記載の着色透光性ジルコニア焼結体を用いてなる歯科材料。
- 歯列矯正ブラケットである請求項12に記載の歯科材料。
- 義歯、義歯ミルブランク又はその両者である請求項12に記載の歯科材料。
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Also Published As
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KR101906628B1 (ko) | 2018-10-10 |
EP4011852A1 (en) | 2022-06-15 |
EP2738147B1 (en) | 2021-12-29 |
EP2738147A1 (en) | 2014-06-04 |
US9249056B2 (en) | 2016-02-02 |
US20140227654A1 (en) | 2014-08-14 |
KR20140056168A (ko) | 2014-05-09 |
CN103732559A (zh) | 2014-04-16 |
EP2738147A4 (en) | 2015-01-28 |
JP2013049616A (ja) | 2013-03-14 |
JP6079028B2 (ja) | 2017-02-15 |
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