WO2022220301A1 - ジルコニア成形体、ジルコニア仮焼体及びジルコニア焼結体並びにこれらの製造方法 - Google Patents

ジルコニア成形体、ジルコニア仮焼体及びジルコニア焼結体並びにこれらの製造方法 Download PDF

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Publication number
WO2022220301A1
WO2022220301A1 PCT/JP2022/017964 JP2022017964W WO2022220301A1 WO 2022220301 A1 WO2022220301 A1 WO 2022220301A1 JP 2022017964 W JP2022017964 W JP 2022017964W WO 2022220301 A1 WO2022220301 A1 WO 2022220301A1
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WIPO (PCT)
Prior art keywords
zirconia
sintered body
meth
less
mass
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Ceased
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PCT/JP2022/017964
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English (en)
French (fr)
Japanese (ja)
Inventor
恭敬 工藤
貴理博 中野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Noritake Dental Inc
Original Assignee
Kuraray Noritake Dental Inc
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Publication date
Application filed by Kuraray Noritake Dental Inc filed Critical Kuraray Noritake Dental Inc
Priority to US18/286,780 priority Critical patent/US20240199494A1/en
Priority to CN202280028846.9A priority patent/CN117157263A/zh
Priority to EP22788224.8A priority patent/EP4324807A4/en
Priority to JP2023514689A priority patent/JP7835737B2/ja
Priority to KR1020237038219A priority patent/KR20230169209A/ko
Publication of WO2022220301A1 publication Critical patent/WO2022220301A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9653—Translucent or transparent ceramics other than alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9661—Colour

Definitions

  • the present invention relates to zirconia moldings and the like. More specifically, the present invention provides a zirconia sintered body excellent in both mechanical strength and translucency, and a zirconia molding having a thickness of 10 mm or more, which contains a binder capable of providing such a zirconia sintered body.
  • the present invention relates to a body, a zirconia calcined body, and methods for producing these.
  • zirconia sintered bodies containing yttria have been used for dental materials such as dental prostheses.
  • these dental prostheses are made of zirconia having a desired shape such as a disk shape or a prism shape by press-molding zirconia particles or molding using a slurry or composition containing zirconia particles. It is produced by forming a molded body, then calcining it to obtain a calcined body (mill blank), cutting (milling) it into the shape of the intended dental prosthesis, and then sintering it. .
  • the obtained zirconia sintered body has not been able to have excellent mechanical strength and translucency.
  • An object of the present invention is to provide a zirconia sintered body excellent in both mechanical strength and translucency, to provide such a zirconia sintered body, and to form a zirconia molding containing a binder in an amount assuming a thickness of 10 mm or more.
  • An object of the present invention is to provide a body, a zirconia calcined body, and a method for producing these.
  • Another object of the present invention is to provide a zirconia sintered body excellent in both mechanical strength and translucency, a zirconia compact and a zirconia provisional which can provide the zirconia sintered body without using a HIP device. It is an object of the present invention to provide a method for manufacturing such a sintered body in a simple manner.
  • the present inventors have made intensive studies to achieve the above object, and found that the average primary particle diameter containing 2.0 to 9.0 mol% of yttria relative to the total number of moles of zirconium oxide and yttria is 60 nm or less.
  • a zirconia molded body containing zirconia particles, a polyol, and a binder attention was paid to the combustion start temperature and combustion end temperature of the polyol and the binder, and it was found that the above problems can be solved when these satisfy a specific relationship. .
  • a zirconia sintered body is particularly suitable as a dental material such as a dental prosthesis. It was found to be extremely useful as a dental prosthesis to be used. Based on these findings, the present inventors have further studied and completed the present invention.
  • the present invention includes the following inventions.
  • zirconia particles containing 2.0 to 9.0 mol% of yttria relative to the total number of moles of zirconium oxide and yttria and having an average primary particle size of 60 nm or less comprising a polyol and a binder;
  • X1 ⁇ Y1 ⁇ X2 ⁇ Y2 ⁇ 500°C (Wherein, X1 represents the combustion initiation temperature of the polyol, X2 represents the combustion termination temperature of the polyol, Y1 represents the combustion initiation temperature of the binder, Y2 represents the combustion termination temperature of the binder, and X1 and Y1 are heat Taking the weight before heating measured by gravimetry as 100%, represents the temperature at which 0.5% weight reduction is observed, and X2 and Y2 represent the temperature at which 99.5% weight reduction is observed.) [2] The zirconia molded article according to [1], which has a thickness of 10 mm or more.
  • the number of pores with a diameter of 50 nm or more per 28.5 ⁇ m 2 cross-sectional area after sintering at 900 to 1200 ° C. under normal pressure is 10 or less, according to any one of [1] to [8].
  • zirconia molded body [10] The zirconia molded article according to any one of [1] to [9], which has a ⁇ L * (WB) of 5 or more at a thickness of 1.5 mm after being calcined at 200 to 800°C.
  • [11] Contains 2.0 to 9.0 mol% of yttria relative to the total number of moles of zirconium oxide and yttria, has a ⁇ L * (WB) of 5 or more at a thickness of 1.5 mm, and A calcined zirconia body having 10 or less pores with a diameter of 50 nm or more per 28.5 ⁇ m 2 cross-sectional area after sintering and having a thickness of 10 mm or more.
  • a method for producing a calcined zirconia body comprising the step of calcining the zirconia molded body according to any one of [1] to [10] at 200 to 800°C.
  • [13] Contains 2.0 to 9.0 mol% of yttria with respect to the total number of moles of zirconium oxide and yttria, the number of pores with a diameter of 50 nm or more per 28.5 ⁇ m 2 cross-sectional area is 10 or less, and the thickness is 10 mm or more, a zirconia sintered body.
  • Zirconia sintering including a step of sintering the zirconia molded body according to any one of [1] to [10] or the zirconia calcined body according to [11] at 900 to 1200 ° C. under normal pressure. body manufacturing method.
  • a zirconia sintered body excellent in both mechanical strength and translucency such a zirconia sintered body can be provided, and a zirconia molding containing an amount of binder assuming a thickness of 10 mm or more. It is possible to provide a body, a zirconia calcined body, and a method for producing these. Further, according to the present invention, a zirconia sintered body excellent in both mechanical strength and translucency, a zirconia molded body capable of providing the zirconia sintered body, and a zirconia calcined body can be obtained without using a HIP apparatus. , can provide these manufacturing methods that can be manufactured easily.
  • the "zirconia molded body" in the present invention is a product formed by press molding, injection molding, stereolithography, etc., using zirconia in various forms such as powder, granules, paste, slurry, etc. as a main raw material. It means that it is in a calcined state and has not reached a sintered state. That is, the zirconia molded body is distinguished from the zirconia calcined body and the zirconia sintered body in that it is unfired after being formed into a molded body by molding.
  • the "calcined zirconia body” in the present invention is a precursor (intermediate product) of the zirconia sintered body, and means that the zirconia particles (powder) are not completely sintered (calcined state). do.
  • the “zirconia sintered body” in the present invention means zirconia particles (powder) in a sintered state.
  • the upper limit and lower limit of the numerical range content of each component, X1, Y1, X2, Y2 and values calculated therefrom, temperature range, physical properties, etc. can be combined as appropriate. .
  • the zirconia particles, zirconia molded body, zirconia calcined body, or zirconia sintered body of the present invention contains zirconium oxide and a stabilizer capable of suppressing the phase transition of zirconium oxide.
  • the stabilizer is preferably capable of forming partially stabilized zirconia.
  • the stabilizer examples include calcium oxide (CaO), magnesium oxide (MgO), yttrium oxide (Y 2 O 3 ), cerium oxide (CeO 2 ), scandium oxide (Sc 2 O 3 ), niobium oxide (Nb 2 O 5 ), lanthanum oxide (La 2 O 3 ), erbium oxide (Er 2 O 3 ), praseodymium oxide (Pr 2 O 3 , Pr 6 O 11 ), samarium oxide (Sm 2 O 3 ), europium oxide (Eu 2 O 3 ) and thulium oxide (Tm 2 O 3 ), with yttria being preferred.
  • the content of the stabilizer in the zirconia calcined body of the present invention and its sintered body can be measured by, for example, inductively coupled plasma (ICP) emission spectroscopic analysis, fluorescent X-ray analysis, or the like.
  • ICP inductively coupled plasma
  • the content of the stabilizer is 0.1 to 18 mol % is preferred, 1 to 15 mol % is more preferred, and 1.5 to 10 mol % is even more preferred.
  • the stabilizer is yttria (Y 2 O 3 ).
  • the present invention also includes those in which yttria is replaced with the stabilizing agent other than yttria.
  • the zirconia molded body of the present invention comprises zirconia particles containing 2.0 to 9.0 mol % of yttria relative to the total number of moles of zirconium oxide and yttria and having an average primary particle diameter of 60 nm or less, a polyol, and a binder. , wherein the polyol and the binder satisfy the following relational expression.
  • X1 ⁇ Y1 ⁇ X2 ⁇ Y2 ⁇ 500°C (Wherein, X1 represents the combustion initiation temperature of the polyol, X2 represents the combustion termination temperature of the polyol, Y1 represents the combustion initiation temperature of the binder, Y2 represents the combustion termination temperature of the binder, and X1 and Y1 are heat Taking the weight before heating measured by gravimetry as 100%, represents the temperature at which 0.5% weight reduction is observed, and X2 and Y2 represent the temperature at which 99.5% weight reduction is observed.)
  • zirconia sintering that is excellent in both mechanical strength and translucency despite being a zirconia molded body containing a binder (and a zirconia molded body having a thickness of 10 mm or more). you can get a body
  • yttria is contained in an amount of 2.0 to 9.0 mol% with respect to the total number of moles of zirconium oxide and yttria, and ⁇ L * (WB) at a thickness of 1.5 mm is 5 or more, the number of pores having a diameter of 50 nm or more after sintering at 900 to 1200° C. is 10 or less, and the thickness is 10 mm or more.
  • a zirconia sintered body excellent in both mechanical strength and translucency can also be obtained by using the zirconia calcined body.
  • zirconia means zirconium oxide containing yttrium oxide.
  • the "content of yttria" in the zirconia particles, zirconia molded body, zirconia calcined body, or zirconia sintered body is the ratio of the number of moles of yttrium oxide to the total number of moles of zirconium oxide and yttrium oxide. (mol%).
  • the yttria content in the zirconia molded body, calcined body, and sintered body thereof of the present invention can be measured, for example, by inductively coupled plasma (ICP) emission spectroscopic analysis, fluorescent X-ray analysis, or the like. .
  • the zirconia sintered body of the present invention contains 2.0 to 9.0 mol% of yttria relative to the total number of moles of zirconium oxide and yttria, and has 10 pores with a diameter of 50 nm or more per 28.5 ⁇ m 2 cross-sectional area. below and the thickness is 10 mm or more.
  • the thickness of the zirconia sintered body is preferably 12 mm or more, more preferably 15 mm or more.
  • the shape of the zirconia sintered body having a thickness of 10 mm or more is not particularly limited, and may be block-shaped (rectangular parallelepiped) or the like. In addition, the following description does not limit the present invention.
  • the zirconia sintered body of the present invention may contain a fluorescent agent. Since the zirconia sintered body contains a fluorescent agent, it has fluorescence.
  • the type of fluorescent agent is not particularly limited, and one or more of those capable of emitting fluorescence with light of any wavelength can be used. Examples of such fluorescent agents include those containing metal elements. Examples of the metal elements include Ga, Bi, Ce, Nd, Sm, Eu, Gd, Tb, Dy, and Tm.
  • the fluorescent agent may contain one of these metal elements alone, or may contain two or more of them. Among these metal elements, Ga, Bi, Eu, Gd, and Tm are preferred, and Bi and Eu are more preferred, because the effects of the present invention are exhibited more remarkably.
  • Examples of fluorescent agents used in producing the zirconia sintered body of the present invention include oxides, hydroxides, acetates, and nitrates of the above metal elements.
  • the fluorescent agents are Y2SiO5 :Ce, Y2SiO5 :Tb, ( Y,Gd,Eu) BO3 , Y2O3 :Eu, YAG:Ce, ZnGa2O4 :Zn , and BaMgAl10O . 17 :Eu or the like may be used.
  • the content of the fluorescent agent in the zirconia sintered body is not particularly limited, and can be appropriately adjusted according to the type of fluorescent agent or the application of the zirconia sintered body, but the viewpoint is that it can be preferably used as a dental prosthesis. Therefore, with respect to 100% by mass of zirconia contained in the zirconia sintered body, it is preferably 0.001% by mass or more in terms of oxide of the metal element contained in the fluorescent agent, and is 0.005% by mass or more.
  • the fluorescent property is not inferior to that of human natural teeth, and when the content is equal to or lower than the upper limit, translucency and mechanical strength are obtained. can be suppressed.
  • the zirconia sintered body of the present invention may contain a coloring agent.
  • a coloring agent When the zirconia sintered body contains a coloring agent, it becomes a colored zirconia sintered body.
  • the type of coloring agent is not particularly limited, and known pigments generally used for coloring ceramics, known dental liquid coloring agents, and the like can be used.
  • the coloring agent include those containing metal elements. Specifically, oxides containing metal elements such as iron, vanadium, praseodymium, erbium, chromium, nickel and manganese, their composite oxides, or their Examples include salt.
  • a commercially available coloring agent can also be used, for example, Prettau Color Liquid manufactured by Zirkon leopard can also be used.
  • the zirconia sintered body may contain one coloring agent, or may contain two or more coloring agents.
  • the content of the coloring agent in the zirconia sintered body is not particularly limited, and can be appropriately adjusted according to the type of coloring agent and the application of the zirconia sintered body, but it can be preferably used as a dental prosthesis. Therefore, it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, in terms of oxide of the metal element contained in the coloring agent, based on 100% by mass of zirconia contained in the zirconia sintered body. more preferably 0.01% by mass or more, preferably 5% by mass or less, more preferably 1% by mass or less, and 0.5% by mass or less is more preferable, and it may be 0.1% by mass or less, or even 0.05% by mass or less.
  • the zirconia sintered body of the present invention may contain a translucency adjusting agent.
  • Specific translucent modifiers include, for example, aluminum oxide, titanium oxide, silicon dioxide, zircon, lithium silicate, and lithium disilicate.
  • the zirconia sintered body may contain one translucency adjusting agent, or may contain two or more translucency adjusting agents.
  • the content of the translucency adjusting agent in the zirconia sintered body is not particularly limited, and can be appropriately adjusted according to the type of translucency adjusting agent and the application of the zirconia sintered body. From the viewpoint of being preferably used, it is preferably 0.1% by mass or less with respect to 100% by mass of zirconia contained in the zirconia sintered body.
  • the zirconia sintered body of the present invention contains 2.0 to 9.0 mol % of yttria with respect to the total number of moles of zirconium oxide and yttria. If the yttria content in the zirconia sintered body is less than 2.0 mol %, sufficient translucency cannot be obtained. Moreover, when the content of yttria in the zirconia sintered body exceeds 9.0 mol %, the mechanical strength is lowered.
  • the content of yttria in the zirconia sintered body is preferably 3.0 mol% or more, and is 3.5 mol% or more, because a zirconia sintered body having excellent translucency and mechanical strength can be obtained. More preferably 4.0 mol% or more, more preferably 8.0 mol% or less, more preferably 7.5 mol% or less, and 7.0 mol% or less is more preferred.
  • the crystal grain size in the zirconia sintered body of the present invention is preferably 180 nm or less. If the crystal grain size exceeds 180 nm, sufficient translucency may not be obtained. Since a zirconia sintered body having excellent translucency can be obtained, the crystal grain size is preferably 140 nm or less, more preferably 120 nm or less, even more preferably 110 nm or less, and 100 nm or less. There may be. Although the lower limit of the crystal grain size is not particularly limited, the crystal grain size can be, for example, 50 nm or more, and further 70 nm or more.
  • the crystal grain size of the zirconia sintered body is obtained by taking a field emission scanning electron microscope (FE-SEM) photograph of the cross section of the zirconia sintered body, selecting 100 arbitrary particles in the photographed image, and measuring each It can be obtained as an average value of equivalent circle diameters (diameters of perfect circles having the same area).
  • FE-SEM field emission scanning electron microscope
  • the zirconia sintered body of the present invention has excellent mechanical strength.
  • the three-point bending strength of the zirconia sintered body of the present invention is preferably 500 MPa or more, more preferably 600 MPa or more, further preferably 650 MPa or more, and particularly preferably 700 MPa or more. Most preferably, it is 800 MPa or more. Since the zirconia sintered body of the present invention has such a three-point bending strength, it is possible to suppress breakage in the oral cavity when used as a dental prosthesis, for example.
  • the upper limit of the 3-point bending strength is not particularly limited, the 3-point bending strength can be, for example, 1500 MPa or less, further 1000 MPa or less.
  • the 3-point bending strength of the zirconia sintered body can be measured according to ISO 6872:2015.
  • the zirconia sintered body of the present invention has excellent translucency.
  • the transmittance of light with a wavelength of 700 nm at a thickness of 0.5 mm is preferably 40% or more, more preferably 45% or more, 46% or more, 48% or more, It may be 50% or more, or even 52% or more.
  • the transmittance is within the above range, it becomes easier to satisfy the translucency required for the incisal portion when used as a dental prosthesis, for example.
  • the upper limit of the transmittance is not particularly limited, the transmittance can be, for example, 60% or less, further 57% or less.
  • the transmittance of light with a wavelength of 700 nm at a thickness of 0.5 mm of the zirconia sintered body may be measured using a spectrophotometer. Using the U-3900H type meter), the light generated by the light source is transmitted through the sample and scattered, and can be measured using an integrating sphere. In the measurement, the transmittance may be measured once in the wavelength range of 300 to 750 nm, and then the transmittance for light with a wavelength of 700 nm may be obtained.
  • a disk-shaped zirconia sintered body having a diameter of 15 mm and a thickness of 0.5 mm, both surfaces of which are mirror-polished, can be used as a sample for measurement.
  • the zirconia sintered body of the present invention has excellent linear light transmittance.
  • the zirconia sintered body of the present invention preferably has a linear light transmittance of 1% or more at a thickness of 1.0 mm, more preferably 3% or more, even more preferably 5% or more. % or more is particularly preferable, and may be 10% or more.
  • the linear light transmittance is within the above range, it becomes easier to satisfy the translucency required for the incisal portion when used as a dental prosthesis, for example.
  • the upper limit of the linear light transmittance is not particularly limited, the linear light transmittance can be, for example, 60% or less, further 50% or less.
  • the linear light transmittance at a thickness of 1.0 mm of the zirconia sintered body may be measured using a turbidity meter, for example, a turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., "Haze Meter NDH4000"). can be used to transmit and scatter the light generated by the light source to the sample, and can be measured using an integrating sphere.
  • the linear light transmittance is preferably measured according to ISO 13468-1: 1996 and JIS K 7361-1: 1997, and the haze is measured according to ISO 14782-1: 1999 and JIS K 7136: 2000. Measurement is preferred.
  • a disk-shaped zirconia sintered body having a diameter of 15 mm and a thickness of 1.0 mm, both surfaces of which are mirror-polished, can be used as a sample used for measurement.
  • the number of pores (pores) having a diameter of 50 nm or more per 28.5 ⁇ m 2 cross-sectional area contained in the zirconia sintered body of the present invention is 10 or less, preferably 8 or less, more preferably 6. It is below. If the number of pores with a diameter of 50 nm or more exceeds 10, the mechanical strength and translucency of the zirconia sintered body may be lowered when a block-shaped zirconia sintered body having a desired thickness is formed.
  • the number of pores with a diameter of 50 nm or more per 28.5 ⁇ m 2 cross-sectional area contained in the zirconia sintered body of the present invention is a field emission scanning electron microscope (FE-SEM) of a 28.5 ⁇ m 2 zirconia sintered body cross section. Photographs of 10 fields of view are taken, and the circle-equivalent diameter (diameter of a perfect circle with the same area) is obtained for each pore in the photographed image. The number of images obtained was totaled for 10 captured images, and the result was divided by 10 to obtain an arithmetic mean value.
  • FE-SEM field emission scanning electron microscope
  • the method for producing a zirconia sintered body of the present invention is characterized by using the zirconia molded body of the present invention, which will be described later.
  • a method for producing a zirconia sintered body is preferably a production method including a step of sintering the zirconia molded body at 900 to 1200° C. under normal pressure.
  • the zirconia calcined body of the present invention which will be described later, may be used, and a manufacturing method including a step of sintering the zirconia calcined body at 900 to 1200° C. under normal pressure is preferable.
  • the zirconia molded body of the present invention comprises zirconia particles containing 2.0 to 9.0 mol % of yttria relative to the total number of moles of zirconium oxide and yttria and having an average primary particle diameter of 60 nm or less, a polyol, and a binder. , wherein the polyol and the binder satisfy the following relational expression.
  • X1 ⁇ Y1 ⁇ X2 ⁇ Y2 ⁇ 500°C (Wherein, X1 represents the combustion initiation temperature of the polyol, X2 represents the combustion termination temperature of the polyol, Y1 represents the combustion initiation temperature of the binder, Y2 represents the combustion termination temperature of the binder, and X1 and Y1 are heat Taking the weight before heating measured by gravimetry as 100%, represents the temperature at which 0.5% weight loss is observed, and X2 and Y2 represent the temperature at which 99.5% weight loss is observed.)
  • the zirconia molded body although it is a zirconia molded body containing a binder (and a zirconia molded body having a thickness of 10 mm or more), both mechanical strength and translucency are excellent, and linear light transmission is improved. A zirconia sintered body having an excellent rate can be obtained. In addition, it is possible to achieve both moldability of the molded body and translucency of the sintered body.
  • the zirconia molded body of the present invention has high translucency, and a zirconia sintered body having a high linear light transmittance and a zirconia sintered body having a high linear light transmittance can be produced from such a zirconia molded body.
  • a calcined body can be produced.
  • the zirconia molded body of the present invention preferably has a ⁇ L * (W ⁇ B) at a thickness of 1.5 mm of 5 or more, more preferably 8 or more, and even more preferably 10 or more. Furthermore, it may be 11 or more, or 12 or more.
  • ⁇ L * (WB) is within the above range, when combined with a polyol and a binder that satisfy the above formula, zirconia sintering with high linear light transmittance when sintered under normal pressure you get a body
  • the upper limit of ⁇ L * (WB) is not particularly limited, it can be, for example, 30 or less, and further 25 or less.
  • ⁇ L * (W ⁇ B) at a thickness of 1.5 mm of the zirconia molded body can be measured using a spectrophotometer, for example, a spectrophotometer (manufactured by Konica Minolta Japan Co., Ltd., "CM-3610A").
  • ⁇ L * (WB) means the difference between the lightness (L * ) on a white background and the lightness (L * ) on a black background. Specifically, it means the difference between the L * value for a white background and the L * value for a black background of a zirconia molded body having a thickness of 1.5 mm.
  • the L * value is the L * value of chromaticity (color space) in the L * a * b * color system (JIS Z 8781-4:2013).
  • the white background means the white part of the hiding rate test paper described in JIS K 5600-4-1:1999, Part 4, Section 1, and the black background means the black part of the hiding rate test paper.
  • the raw material before sintering is preferably a zirconia molded body containing the fluorescent agent.
  • the content of the fluorescent agent in the zirconia compact containing the fluorescent agent can be appropriately adjusted according to the content of the fluorescent agent in the obtained zirconia sintered body.
  • the specific content of the fluorescent agent contained in the zirconia molded body is 0.001% by mass or more in terms of oxide of the metal element contained in the fluorescent agent with respect to 100% by mass of zirconia contained in the zirconia molded body. It is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 1% by mass or less, and 0.5% by mass or less. It is more preferable that the content is 0.1% by mass or less.
  • the raw material before sintering is preferably a zirconia molded body containing the coloring agent.
  • the content of the coloring agent in the zirconia molded body containing the coloring agent can be appropriately adjusted according to the content of the coloring agent in the resulting zirconia sintered body.
  • the specific content of the coloring agent contained in the zirconia molded body is 0.001% by mass or more in terms of the oxide of the metal element contained in the coloring agent with respect to 100% by mass of zirconia contained in the zirconia molded body. It is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 5% by mass or less, and 1% by mass or less. is more preferably 0.5% by mass or less, and may be 0.1% by mass or less, or even 0.05% by mass or less.
  • a zirconia molded body containing a translucency adjusting agent is suitably used as a raw material before sintering.
  • the content of the translucency adjusting agent in the zirconia molded body containing the translucency adjusting agent can be appropriately adjusted according to the content of the translucency adjusting agent in the obtained zirconia sintered body.
  • a specific content of the translucency adjusting agent contained in the zirconia molded body is preferably 0.1% by mass or less with respect to 100% by mass of zirconia contained in the zirconia molded body.
  • the yttria content in the zirconia molded body of the present invention is within the range of 2.0 to 9.0 mol% with respect to the total number of moles of zirconium oxide and yttria, and the yttria content in the obtained zirconia sintered body
  • the specific content of yttria in the zirconia compact is 2.0 mol% or more, preferably 3.0 mol% or more, more preferably 3.5 mol% or more. It is preferably 4.0 mol % or more, more preferably 8.0 mol % or less, more preferably 7.5 mol % or less, further preferably 7.0 mol % or less. .
  • the density of the zirconia molded body of the present invention is not particularly limited, and varies depending on the manufacturing method of the zirconia molded body, etc., but since a dense zirconia sintered body can be obtained, the density is 3.0 g/cm 3 . It is preferably at least 3.2 g/cm 3 , more preferably at least 3.4 g/cm 3 .
  • the upper limit of the density is not particularly limited, it can be, for example, 6.0 g/cm 3 or less, further 5.8 g/cm 3 or less.
  • the shape of the zirconia molded body of the present invention is not particularly limited, and it can be of any desired shape depending on the application. In consideration of the handling property when obtaining , a disk shape, a prism shape (rectangular parallelepiped shape, etc.) and the like are preferable. As will be described later, if a stereolithography method or the like is employed in the production of the zirconia molded body, it is possible to give the zirconia molded body a shape corresponding to the desired shape of the finally obtained zirconia sintered body. , the present invention also includes a zirconia molded body having such a desired shape.
  • the zirconia molded body may have a single-layer structure, or may have a multi-layer structure.
  • the finally obtained zirconia sintered body can have a multi-layer structure, and its physical properties such as translucency can be locally changed.
  • the zirconia molded body of the present invention preferably has a biaxial bending strength in the range of 2 to 10 MPa, more preferably in the range of 5 to 8 MPa, from the viewpoint of handleability.
  • the biaxial bending strength of the zirconia molded body can be measured according to JIS T 6526:2018.
  • the zirconia molded body of the present invention preferably has a crystal grain size of 180 nm or less after being sintered at 900 to 1200° C. for 2 hours under normal pressure (after being made into a zirconia sintered body). Thereby, the zirconia sintered body of the present invention having excellent translucency can be easily produced.
  • the crystal grain size is more preferably 140 nm or less, still more preferably 120 nm or less, particularly preferably 110 nm or less, particularly preferably 100 nm, because a zirconia sintered body having excellent translucency can be obtained. It may be below.
  • the crystal grain size can be, for example, 50 nm or more, further 70 nm or more.
  • the method for measuring the grain size is as described above for the grain size of the zirconia sintered body.
  • the zirconia molded body of the present invention preferably has a three-point bending strength of 500 MPa or more after sintering at 900 to 1200°C under normal pressure (after forming a zirconia sintered body).
  • the three-point bending strength is more preferably 600 MPa or more, still more preferably 650 MPa or more, and particularly preferably 700 MPa or more, because a zirconia sintered body having excellent mechanical strength can be obtained. , 800 MPa or more.
  • the upper limit of the 3-point bending strength is not particularly limited, the 3-point bending strength can be, for example, 1500 MPa or less, further 1000 MPa or less.
  • the method for measuring the three-point bending strength is as described above for the three-point bending strength of the zirconia sintered body.
  • the zirconia molded body of the present invention has a transmittance of 40% or more for light with a wavelength of 700 nm at a thickness of 0.5 mm after being sintered at 900° C. to 1200° C. under normal pressure (after being made into a zirconia sintered body). is preferred. Thereby, the zirconia sintered body of the present invention having excellent translucency can be easily produced. Since a zirconia sintered body having excellent translucency can be obtained, the transmittance is more preferably 45% or more, further preferably 46% or more, and particularly preferably 48% or more. It is preferably 50% or more, most preferably 52% or more.
  • the transmittance can be, for example, 60% or less, further 57% or less.
  • the method for measuring the transmittance is as described above for the transmittance of light with a wavelength of 700 nm in a zirconia sintered body having a thickness of 0.5 mm.
  • the zirconia molded body of the present invention preferably has a linear light transmittance of 1% or more at a thickness of 1.0 mm after being sintered at 900° C. to 1200° C. under normal pressure (after being made into a zirconia sintered body). , is more preferably 3% or more, further preferably 5% or more, particularly preferably 7% or more, and may be 10% or more.
  • the linear light transmittance is within the above range, it becomes easier to satisfy the translucency required for the incisal portion when used as a dental prosthesis, for example.
  • the upper limit of the linear light transmittance is not particularly limited, the linear light transmittance can be, for example, 60% or less, further 50% or less.
  • the method for measuring the linear light transmittance is as described above for the linear light transmittance at a thickness of 1.0 mm in the zirconia sintered body.
  • the number of pores with a diameter of 50 nm or more per 28.5 ⁇ m 2 cross-sectional area after sintering at 900 to 1200 ° C. under normal pressure is 10 or less. body.
  • a suitable range and measuring method for the number of pores are the same as those for the zirconia sintered body.
  • the method for producing the zirconia molded body of the present invention is not particularly limited as long as the effect of the present invention is exhibited. , a molding step of molding zirconia particles, a polyol and a binder to obtain a zirconia molding.
  • the combination of the polyol and the binder is not particularly limited as long as it satisfies the above relational expression, and specific materials are as described later.
  • the yttria content in the zirconia particles used is preferably the same as the yttria content in the obtained zirconia molded body, and thus in the zirconia calcined body and the zirconia sintered body.
  • the specific content of yttria in the zirconia particles is 2.0 mol% or more, preferably 3.0 mol% or more, more preferably 3.5 mol% or more, and 4.0 mol% or more. is more preferably 8.0 mol % or less, more preferably 7.5 mol % or less, and even more preferably 7.0 mol % or less.
  • the zirconia particles used have an average primary particle size of 60 nm or less.
  • the zirconia particles preferably have an average primary particle size of 60 nm or less, and preferably contain 0.5 mass % or less of zirconia particles having a particle size of more than 100 nm with respect to the total amount of the zirconia particles.
  • the average primary particle size of the zirconia particles is preferably 50 nm or less, more preferably 30 nm or less. It is more preferably 20 nm or less, and may be 10 nm or less, preferably 1 nm or more, and more preferably 5 nm or more. From the viewpoint of facilitating the production of the zirconia molded body of the present invention, as well as the zirconia calcined body and the zirconia sintered body of the present invention, and the desired linear light transmittance, the grain size is greater than 100 nm.
  • the content of zirconia particles is more preferably 0.3% by mass or less, more preferably 0.1% by mass or less, and may be 0.05% by mass or less.
  • the average primary particle size of the zirconia particles can be determined, for example, by photographing the zirconia particles (primary particles) with a transmission electron microscope (TEM), and the particle size of each particle for 100 arbitrary particles on the obtained image. (maximum diameter) can be measured and the average value thereof can be obtained.
  • the content of zirconia particles having a particle size exceeding 100 nm is measured on a volume basis using a laser diffraction/scattering particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.) after dispersing the zirconia particles in methanol. can.
  • zirconia particles There are no particular restrictions on the method of preparing zirconia particles, and for example, a breakdown process in which coarse particles are pulverized into fine powder, or a building-up process in which nuclei are formed and grown from atoms or ions can be adopted. Among these, the building-up process is preferred for obtaining fine zirconia particles of high purity.
  • the breakdown process can be performed, for example, by grinding with a ball mill, bead mill, or the like. At this time, it is preferable to use micro-sized grinding media, for example, it is preferable to use grinding media of 100 ⁇ m or less.
  • WB ⁇ L *
  • known methods and devices can be used, such as porous membranes (membrane filters having a pore size of 100 nm, etc.), classifiers (wet classifiers, dry classifiers), and the like.
  • a vapor-phase thermal decomposition method in which an oxate of a metal ion with a high vapor pressure or an organometallic compound is vaporized and thermally decomposed to deposit an oxide
  • Gas phase reaction method in which synthesis is carried out by gas phase chemical reaction between gas and reaction gas
  • Evaporative concentration method in which raw materials are heated and vaporized, and the vapor is condensed into fine particles by quenching in an inert gas at a predetermined pressure
  • Melt method in which a liquid is cooled and solidified as small droplets to form a powder
  • Solvent evaporation method in which the concentration in the liquid is increased by evaporating the solvent and precipitated in a supersaturated state
  • Precipitation methods are further divided into homogeneous precipitation methods in which a precipitant is generated in a solution through a chemical reaction to eliminate local unevenness in the concentration of the precipitant; Sedimentation method; hydrolysis method for obtaining oxides or hydroxides by hydrolysis from alcoholic solutions such as metal salt solutions and metal alkoxides; solvothermal synthesis method for obtaining oxides or hydroxides from high-temperature and high-pressure fluids.
  • the solvothermal synthesis method is further subdivided into a hydrothermal synthesis method using water as a solvent, a supercritical synthesis method using a supercritical fluid such as water or carbon dioxide as a solvent, and the like.
  • any building-up process it is preferred to increase the precipitation rate to obtain finer zirconia particles.
  • known methods and devices can be used, such as porous membranes (membrane filters having a pore size of 100 nm, etc.), classifiers (wet classifiers, dry classifiers), and the like.
  • zirconium source in the building-up process for example, nitrates, acetates, chlorides, alkoxides, etc. can be used, and specifically, zirconium oxychloride, zirconium acetate, zirconyl nitrate, etc. can be used.
  • yttria can be blended in the production process of the zirconia particles.
  • yttria may be solid-dissolved in the zirconia particles.
  • the yttrium source for example, nitrates, acetates, chlorides, alkoxides, etc. can be used, and specifically, yttrium chloride, yttrium acetate, yttrium nitrate, etc. can be used.
  • Zirconia particles if necessary, organic compounds having an acidic group; fatty acid amides such as saturated fatty acid amide, unsaturated fatty acid amide, saturated fatty acid bisamide, unsaturated fatty acid bisamide; silane coupling agent (organosilicon compound), organic titanium
  • a known surface treatment agent such as a chemical compound, an organic zirconium compound, an organic metal compound such as an organic aluminum compound, or the like.
  • the zirconia particles are surface-treated, when preparing a powder containing zirconia particles and a fluorescent agent using a slurry containing a liquid having a surface tension of 50 mN / m or less as a dispersion medium at 25 ° C., such a liquid is used as described later. or adjusting the miscibility with zirconia, or in the case of producing a zirconia molded body by a method having a step of polymerizing a composition containing zirconia particles, a fluorescent agent and a polymerizable monomer, as described later. The miscibility between the particles and the polymerizable monomer can be adjusted.
  • a zirconia molded article obtained by having excellent miscibility with a liquid having a surface tension of 50 mN/m or less at 25°C and by enhancing the chemical bonding between the zirconia particles and the polymerizable monomer.
  • An organic compound having an acidic group is preferred because it can improve the mechanical strength of the organic compound.
  • organic compounds having an acidic group examples include organic compounds having at least one acidic group such as a phosphoric acid group, a carboxylic acid group, a pyrophosphate group, a thiophosphoric acid group, a phosphonic acid group, and a sulfonic acid group.
  • a phosphoric acid group-containing organic compound having at least one phosphoric acid group and a carboxylic acid group-containing organic compound having at least one carboxylic acid group are preferable, and a phosphoric acid group-containing organic compound is more preferable.
  • the zirconia particles may be surface-treated with one surface treatment agent, or may be surface-treated with two or more surface treatment agents.
  • the surface treatment layer formed thereby may be a surface treatment layer of a mixture of two or more surface treatment agents, or a plurality of surface treatment layers.
  • the surface treatment layer may have a laminated multilayer structure.
  • Examples of phosphoric acid group-containing organic compounds include 2-ethylhexyl acid phosphate, stearyl acid phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth) acryloyloxypropyl dihydrogen phosphate, 4-( meth) acryloyloxybutyl dihydrogen phosphate, 5-(meth) acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8 -(meth) acryloyloxyoctyl dihydrogen phosphate, 9-(meth) acryloyloxy nonyl dihydrogen phosphate, 10-(meth) acryloyloxydecyl dihydrogen phosphate, 11-(meth) acryloyloxy undecyl dihydrogen P
  • carboxylic acid group-containing organic compounds examples include succinic acid, oxalic acid, octanoic acid, decanoic acid, stearic acid, polyacrylic acid, 4-methyloctanoic acid, neodecanoic acid, pivalic acid, 2,2-dimethylbutyric acid, 3 , 3-dimethylbutyric acid, 2,2-dimethylvaleric acid, 2,2-diethylbutyric acid, 3,3-diethylbutyric acid, naphthenic acid, cyclohexanedicarboxylic acid, (meth)acrylic acid, N-(meth)acryloylglycine, N -(meth)acryloyl aspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-amino
  • organic compounds having at least one acidic group other than the above such as a pyrophosphate group, a thiophosphate group, a phosphonic acid group, and a sulfonic acid group, include those described in International Publication No. 2012/042911. can be used.
  • saturated fatty acid amides include palmitic acid amide, stearic acid amide, and behenic acid amide.
  • unsaturated fatty acid amides include oleic acid amide and erucic acid amide.
  • Saturated fatty acid bisamides include, for example, ethylenebispalmitamide, ethylenebisstearic acid amide, hexamethylenebisstearic acid amide and the like.
  • unsaturated fatty acid bisamides include ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, and N,N'-dioleylsebacic acid amide.
  • Silane coupling agents include, for example, compounds represented by R 1 n SiX 4-n (wherein R 1 is a substituted or unsubstituted hydrocarbon having 1 to 12 carbon atoms). group, X is an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen atom or a hydrogen atom, and n is an integer of 0 to 3; , which may be the same or different).
  • silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, Diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3- trifluoropropyldimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane
  • a silane coupling agent having a functional group is preferable, and ⁇ -(meth)acryloyloxyalkyltrimethoxysilane [the number of carbon atoms between the (meth)acryloyloxy group and the silicon atom: 3 to 12], ⁇ - (Meth)acryloyloxyalkyltriethoxysilane [Number of carbon atoms between (meth)acryloyloxy group and silicon atom: 3 to 12], vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, ⁇ -glycid Xypropyltrimethoxysilane is more preferred.
  • organic titanium compounds examples include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, and tetra(2-ethylhexyl) titanate.
  • organic zirconium compounds include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, and zirconyl acetate.
  • organic aluminum compounds include aluminum acetylacetonate and aluminum organic acid salt chelate compounds.
  • the specific method of surface treatment is not particularly limited, and known methods can be employed.
  • a method of removing the solvent after dispersing or dissolving the surface treatment agent can be employed.
  • the solvent may be a dispersion medium containing a liquid having a surface tension of 50 mN/m or less at 25° C., as described later.
  • reflux or high-temperature and high-pressure treatment may be performed after dispersing or dissolving the zirconia particles and the surface treatment agent.
  • the polyol and binder used in the present invention when the polyol combustion start temperature (X1), the polyol combustion end temperature (X2), the binder combustion start temperature (Y1), and the binder combustion end temperature (Y2) , X1 ⁇ Y1 ⁇ X2 ⁇ Y2 ⁇ 500°C. It is thought that by selecting and combining substances that satisfy the above relationship, the polyol creates a route through which the binder burns out during sintering inside the zirconia molded body, and the binder easily escapes during sintering.
  • the average primary particle size of the zirconia particles contained in the zirconia compact is 60 nm or less
  • the fine particle size causes the particles to join together during heating (necking phenomenon), filling the voids between the particles
  • the binder tends to be unable to be completely removed by heating, but by using a combination of polyol and binder that satisfy the above relational expression, the polyol forms a route through which the binder burns out inside the zirconia compact during sintering. It is the one through which the binder can exit.
  • the zirconia molded body contains an amount of binder that assumes a thickness of 10 mm or more, the problem of the binder-containing zirconia molded body is solved, despite the fact that the binder is difficult to burn out.
  • the zirconia sintered body after sintering is excellent in both mechanical strength and translucency.
  • such a zirconia sintered body is also excellent in linear light transmittance.
  • the polyol combustion start temperature (X1), polyol combustion end temperature (X2), binder combustion start temperature (Y1), and binder combustion end temperature (Y2) can be measured by thermogravimetry (TG).
  • TG thermogravimetry
  • the weight before heating is defined as 100%
  • the temperatures at which 0.5% weight reduction is observed are X1 and Y1
  • the temperatures at which 99.5% weight reduction is observed are X2 and Y2.
  • Measurement conditions for thermogravimetry (TG) are as described in Examples below.
  • diols and triols can be used as polyols used in the present invention.
  • diols include ethylene glycol, propylene glycol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, 3-methyl-1,3-butanediol, and polyethylene glycol.
  • triols include glycerin, 1,2,3-butanediol and 1,2,4-butanediol.
  • Other polyols that can be used include, for example, polyglycerin and sugar.
  • a polyol may be used individually by 1 type, and may use 2 or more types together.
  • binders used in the present invention include polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, acrylic binders, wax binders, polyvinyl butyral, polymethyl methacrylate, and ethyl cellulose.
  • a binder may be used individually by 1 type, and may use 2 or more types together.
  • the type of binder is not particularly limited as long as it is selected so as to satisfy the above relational expression, and the effects of the present invention described above can be exhibited.
  • X1 is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 90°C or higher, and X1 is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.
  • X1 is 50° C. or higher, it is easy to control the outflow of polyol from the zirconia molded article, and the zirconia molded article is excellent in shape retention. Further, when X1 is 300° C. or less, the bonding between zirconia particles is not inhibited, and desired physical properties are easily obtained.
  • Y2 is 500°C or lower, preferably 480°C or lower, more preferably 460°C or lower, and even more preferably 440°C or lower. If Y2 exceeds 500° C., the bonded zirconia particles cannot withstand the pressure of the gas generated by burning the binder, and the calcined zirconia body may be destroyed.
  • the polyol burns out before the binder during sintering, so that a route for the binder to burn out is created inside the zirconia molded body, and the binder burns out before necking occurs.
  • >X1, and Y1-X1 is preferably 5°C or higher, more preferably 15°C or higher, and even more preferably 30°C or higher.
  • the polyol burns out before the binder during sintering, so that a route for the binder to burn out is created inside the zirconia molded body, and the binder burns out before necking occurs.
  • >X2 and Y2-X2 is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 45°C or higher.
  • the content of the polyol in the zirconia molded article of the present invention is not particularly limited, but is 8% by mass with respect to 100% by mass of zirconia. The following is preferable, 4% by mass or less is more preferable, and 1.5% by mass or less is even more preferable because the obtained zirconia sintered body has excellent translucency.
  • the polyol content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more.
  • the content of polyol and binder is the rate of external addition, and means % by mass with respect to 100% by mass of zirconia (zirconium oxide containing yttrium oxide).
  • the content of the binder in the zirconia molded body of the present invention is not particularly limited, but is 10% by mass with respect to 100% by mass of zirconia. Less than is preferable, 5 mass % or less is more preferable, and 3 mass % or less is still more preferable.
  • the content of the binder is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more.
  • the compounding ratio (mass ratio) between the binder and the polyol in the zirconia molded article of the present invention is not particularly limited, but the binder:polyol is preferably 10:1 to 1:10, more preferably 5:1 to 1:5. The ratio is more preferably 3:1 to 1:4, particularly preferably 2.5:1 to 1.1:1, because the resulting zirconia sintered body has excellent translucency.
  • the binder content is 0.05% by mass or more with respect to 100% by mass of zirconia,
  • the content of polyol with respect to 100% by mass of zirconia is 0.01% by mass or more
  • the polyol and the binder have the following relational expression: X1 ⁇ Y1 ⁇ X2 ⁇ Y2 ⁇ 500° C.
  • the polyol content is preferably less than or equal to the binder content, more preferably lower than the binder content, and preferably lower than the binder content by 0.1% by mass or more. More preferred.
  • the content of the binder, the content of the polyol, the zirconia particles, etc. can be appropriately set within the ranges described herein.
  • the binder content may be 0.2% by mass or more or 7% by mass or less with respect to 100% by mass of zirconia.
  • a preferred embodiment of the present invention includes a zirconia molded body having a thickness of 10 mm or more.
  • the thickness of the zirconia molded body is preferably 12 mm or more, more preferably 15 mm or more.
  • the shape of the zirconia molded body having a thickness of 10 mm or more is not particularly limited, and may be block-shaped (rectangular parallelepiped) or the like.
  • the type of the molding step is not particularly limited, but the zirconia molded body of the present invention, and thus the zirconia calcined body of the present invention.
  • the molding process is (i) slip casting a slurry comprising zirconia particles; (ii) gel casting a slurry containing zirconia particles; (iii) pressing a powder containing zirconia particles; (iv) molding a composition comprising zirconia particles and a resin; and (v) polymerizing a composition comprising zirconia particles and a polymerizable monomer; It is preferable that it is at least one of.
  • the method for preparing the slurry containing zirconia particles is not particularly limited. For example, it may be obtained through the above-described breakdown process or building-up process, or may be commercially available. good.
  • each of the binder and polyol is preferable to mix each of the binder and polyol with a slurry containing zirconia particles in a liquid state such as a solution or dispersion.
  • a slurry containing zirconia particles in a liquid state such as a solution or dispersion.
  • the slurry containing the zirconia particles and the fluorescent agent is added with such a coloring agent and/or Alternatively, a translucency adjusting agent may be included.
  • the coloring agent and/or the translucency adjusting agent are preferably mixed with the slurry containing the zirconia particles in a liquid state such as a solution or dispersion.
  • Powder containing zirconia particles There is no particular limitation on the preparation method of the powder containing zirconia particles, and since it is possible to obtain a zirconia sintered body that is more uniform and has excellent physical properties, it is possible to dry the slurry containing the above-described zirconia particles. is preferably obtained by The slurry to be dried here may further contain a fluorescent agent and/or a coloring agent and/or a translucency adjusting agent.
  • the drying method is not particularly limited, and for example, spray drying, supercritical drying, freeze drying, hot air drying, reduced pressure drying, etc. can be adopted.
  • spray drying, supercritical drying and freeze drying is preferable because aggregation of particles can be suppressed during drying and a denser zirconia sintered body can be obtained. and supercritical drying are more preferred, and spray drying is even more preferred.
  • the slurry containing zirconia particles to be dried may be a slurry in which water is used as a dispersion medium, but aggregation of the particles can be suppressed during drying to obtain a denser zirconia sintered body. It is preferably a slurry of a dispersion medium other than water, such as an organic solvent, because it can be used.
  • organic solvents examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-(2- ethoxyethoxy) ethanol, diethylene glycol monobutyl ether, alcohols such as glycerin; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether, diisopropyl ether, 1,4-dioxane, dimethoxyethane (propylene glycol monomethyl ether acetate (commonly known as ”) and other modified ethers (preferably ether-modified ethers and / or ester-modified ethers, more preferably ether-modified alkylene glycols and / or ester-modified alkylene glycols)); Esters; hydrocarbons such as hexane and to
  • organic solvents may be used individually by 1 type, and may use 2 or more types together.
  • the organic solvent is preferably a water-soluble organic solvent in consideration of both safety to the living body and ease of removal.
  • ethanol, 2-propanol, 2-methyl-2- More preferred are propanol, 2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, propylene glycol monomethyl ether acetate, acetone and tetrahydrofuran.
  • the dispersion medium of the slurry containing the zirconia particles and the fluorescent agent to be dried contains a liquid with a surface tension of 50 mN / m or less at 25 ° C.
  • the particles aggregate during drying. can be suppressed and a denser zirconia sintered body can be obtained.
  • the surface tension of the liquid is preferably 40 mN/m or less, more preferably 30 mN/m or less.
  • the surface tension at 25°C for example, the values described in Handbook of Chemistry and Physics can be used, and for liquids not described therein, the values described in International Publication No. 2014/126034 should be used. can be done. Liquids that are not described in any of these can be obtained by known measurement methods, such as the suspension ring method and the Wilhelmy method.
  • the surface tension at 25°C is preferably measured using an automatic surface tension meter "CBVP-Z" manufactured by Kyowa Interface Science Co., Ltd. or "SIGMA702" manufactured by KSV INSTRUMENTS LTD.
  • An organic solvent having the above surface tension can be used as the above liquid.
  • the organic solvent those having the above-mentioned surface tension can be used, and it is possible to suppress the aggregation of particles during drying and to obtain a denser zirconia sintered body.
  • methanol, ethanol, 2-methoxyethanol, 1,4-dioxane, 2-ethoxyethanol and 2-(2-ethoxyethoxy) ethanol is preferably at least one selected from the group consisting of methanol, ethanol, 2-ethoxyethanol and 2-(2-ethoxyethoxy)ethanol is more preferred.
  • the content of the liquid in the dispersion medium is preferably 50% by mass or more, and 80% by mass, because aggregation of particles can be suppressed during drying and a denser zirconia sintered body can be obtained. % or more, more preferably 95 mass % or more, and particularly preferably 99 mass % or more.
  • a slurry containing a dispersion medium other than water can be obtained by substituting the dispersion medium for a slurry containing water as the dispersion medium.
  • the method of replacing the dispersion medium is not particularly limited, and for example, a method of adding a dispersion medium other than water (such as an organic solvent) to a slurry containing water as the dispersion medium and then distilling off the water can be employed. In distilling off water, part or all of the dispersion medium other than water may be distilled off together. The addition of a dispersion medium other than water and the distillation of water may be repeated multiple times.
  • a method of precipitating dispersoids after adding a dispersion medium other than water to a slurry in which the dispersion medium is water can also be employed. Furthermore, for a slurry in which the dispersion medium is water, after replacing the dispersion medium with a specific organic solvent, the dispersion medium may be further replaced with another organic solvent.
  • the fluorescent agent may be added after replacing the dispersion medium, but it is preferable to add it before replacing the dispersion medium because it is possible to obtain a zirconia sintered body that is more uniform and has excellent physical properties. .
  • the slurry when the slurry contains a coloring agent and/or a translucency adjusting agent, it may be added after replacing the dispersion medium, but it is possible to obtain a zirconia sintered body that is more uniform and has excellent physical properties. It is preferable to add it before replacing the dispersion medium because it is possible.
  • the slurry containing zirconia particles to be dried may be subjected to dispersion treatment by heat or pressure such as reflux treatment or hydrothermal treatment.
  • the slurry containing zirconia particles to be subjected to the drying process is subjected to mechanical dispersion treatment using a roll mill, colloid mill, high-pressure jet disperser, ultrasonic disperser, vibration mill, planetary mill, bead mill, or the like. There may be. Only one of the above treatments may be employed, or two or more may be employed.
  • the slurry containing zirconia particles to be dried further contains one or more of other components such as dispersants, emulsifiers, antifoaming agents, pH adjusters, and lubricants, in addition to the binder and polyol. You can stay. By including such other components (especially dispersants, antifoaming agents, etc.) in addition to the binder, it is possible to suppress aggregation of particles during drying and obtain a more dense zirconia sintered body. Sometimes you can.
  • Dispersants include, for example, ammonium polycarboxylate (triammonium citrate, etc.), ammonium polyacrylate, acrylic copolymer resin, acrylic acid ester copolymer, polyacrylic acid, bentonite, carboxymethylcellulose, anionic surfactant agents (for example, polyoxyethylene alkyl ether phosphates such as polyoxyethylene lauryl ether phosphates, etc.), nonionic surfactants, olein glycerides, amine surfactants, oligosaccharide alcohols, and the like.
  • ammonium polycarboxylate triammonium citrate, etc.
  • ammonium polyacrylate acrylic copolymer resin
  • acrylic acid ester copolymer acrylic acid ester copolymer
  • polyacrylic acid bentonite
  • carboxymethylcellulose for example, polyoxyethylene alkyl ether phosphates such as polyoxyethylene lauryl ether phosphates, etc.
  • anionic surfactant agents for example, polyoxy
  • emulsifiers examples include alkyl ethers, phenyl ethers, sorbitan derivatives, and ammonium salts.
  • antifoaming agents examples include alcohol, polyether, polyethylene glycol, silicone, and wax.
  • pH adjusters examples include ammonia, ammonium salts (including ammonium hydroxide such as tetramethylammonium hydroxide), alkali metal salts, and alkaline earth metal salts.
  • lubricants examples include polyoxyethylene alkylate ethers and waxes.
  • the water content in the slurry containing the zirconia particles to be dried is 3% by mass or less because it is possible to suppress the aggregation of the particles during drying and to obtain a more dense zirconia sintered body. is preferred, 1% by mass or less is more preferred, and 0.1% by mass or less is even more preferred.
  • the water content can be measured using a Karl Fischer moisture meter.
  • the drying conditions in each of the above drying methods are not particularly limited, and known drying conditions can be appropriately adopted.
  • an organic solvent is used as a dispersion medium, it is preferable to dry in the presence of a non-flammable gas in order to reduce the risk of explosion during drying, and it is preferable to dry in the presence of nitrogen. more preferred.
  • the supercritical fluid in the case of supercritical drying, and for example, water, carbon dioxide, etc. can be used. It is preferable that the supercritical fluid is carbon dioxide.
  • composition containing zirconia particles and resin There is no particular limitation on the method for preparing the composition containing zirconia particles and resin.
  • composition containing zirconia particles and a polymerizable monomer The method for preparing a composition containing zirconia particles and a polymerizable monomer is not particularly limited. can be obtained by mixing
  • slip casting In the case of producing a zirconia molded body by a method having a step of slip casting a slurry containing zirconia particles, the specific method of slip casting is not particularly limited. It is possible to adopt a method of drying after pouring into.
  • the content of the dispersion medium in the slurry containing the zirconia particles used makes it easy to pour the slurry into the mold, prevents the drying from taking a long time, and increases the number of times the mold is used.
  • the content is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less.
  • the slurry may be poured into the mold under normal pressure, but it is preferable to perform it under pressurized conditions from the viewpoint of production efficiency.
  • the type of mold used for slip casting is not particularly limited, and for example, porous molds made of gypsum, resin, ceramics, etc. can be used. Porous molds made of resin or ceramics are excellent in terms of durability.
  • the slurry containing the zirconia particles used for slip casting contains, in addition to binders and polyols, one of the other ingredients such as dispersants, emulsifiers, defoamers, pH adjusters, lubricants, etc., as described above. Or it may further contain 2 or more types.
  • the content of the dispersion medium in the slurry containing the zirconia particles to be used is preferably 80% by mass or less because it is possible to prevent the drying from taking a long time and to suppress the occurrence of cracks during drying. It is more preferably 50% by mass or less, and even more preferably 20% by mass or less.
  • the gelling may be performed, for example, by adding a gelling agent, or by adding a polymerizable monomer and then polymerizing it.
  • the type of mold used is not particularly limited, and for example, porous molds made of gypsum, resin, ceramics, etc., and non-porous molds made of metal, resin, etc. can be used.
  • the type of gelling agent is not limited, and for example, a water-soluble gelling agent can be used. Specifically, agarose, gelatin, etc. can be preferably used. A gelling agent may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of suppressing cracks during sintering, the amount of the gelling agent used is preferably 10% by mass or less, and 5% by mass, based on the mass of the slurry after the gelling agent is added. % or less, more preferably 1% by mass or less.
  • polymerizable monomer examples include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate acrylates, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide and the like.
  • a polymerizable monomer may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polymerizable monomer used is 10% by mass or less based on the mass of the slurry after the polymerizable monomer is blended, from the viewpoint of suppressing crack generation during sintering. It is preferably 5% by mass or less, more preferably 1% by mass or less.
  • the polymerization is performed using a polymerization initiator.
  • a polymerization initiator is not particularly limited, a photopolymerization initiator is particularly preferred.
  • the photopolymerization initiator it is possible to appropriately select and use photopolymerization initiators used in general industry, and among them, photopolymerization initiators used for dental applications are preferable.
  • photopolymerization initiators include, for example, (bis)acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, ⁇ -diketones, and coumarins. , anthraquinones, benzoin alkyl ether compounds, ⁇ -aminoketone compounds, and the like.
  • a photoinitiator may be used individually by 1 type, and may use 2 or more types together.
  • polymerization can be performed in both the ultraviolet region (including the near-ultraviolet region) and the visible light region.
  • Polymerization (gelation) can be sufficiently carried out using any light source such as a lamp, a light emitting diode (LED), a mercury lamp, a fluorescent lamp, or the like.
  • acylphosphine oxides include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (commonly known as “TPO”), 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi (2,6-dimethylphenyl)phosphonate, sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, potassium salt of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Examples include ammoni
  • bisacylphosphine oxides include, for example, bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenyl Phosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis(2,3,6-trimethyl
  • ⁇ -diketones examples include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphthenequinone and the like. .
  • camphorquinone is preferable especially when a light source in the visible region is used.
  • the dispersant, emulsifier, antifoaming agent, pH adjuster, and lubricant are added as described above. It may further contain one or more of other ingredients such as agents.
  • drying method for drying the shaped wet body there are no particular restrictions on the drying method for drying the shaped wet body, and examples include natural drying, hot air drying, vacuum drying, dielectric heating drying, induction heating drying, constant temperature and constant humidity drying, and the like. Only one of these may be employed, or two or more may be employed. Among these, natural drying, dielectric heating drying, induction heating drying, and constant temperature and constant humidity drying are preferable because they can suppress the occurrence of cracks during drying.
  • (iii) Press molding In the case of producing a zirconia molded body by a method having a step of press molding a powder containing zirconia particles, the specific method of press molding is not particularly limited, and it is performed using a known press molding machine. be able to. Specific methods of press molding include, for example, uniaxial pressing. Moreover, in order to increase the density of the obtained zirconia molded body, it is preferable to further perform cold isostatic pressing (CIP) treatment after the uniaxial pressing.
  • CIP cold isostatic pressing
  • the powder containing the zirconia particles used for press molding contains, in addition to the binder and polyol, one or more of the other components such as dispersants, emulsifiers, antifoaming agents, pH adjusters, lubricants, etc. Two or more types may be further included. These ingredients may be blended when preparing the powder.
  • resin there are no particular restrictions on the type of resin described above, and those that can be used as raw materials for molding can be preferably used.
  • Specific examples of the resin include paraffin wax, polyvinyl alcohol, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polystyrene, atactic polypropylene, methacrylic resin, and fatty acids such as stearic acid. These resins may be used individually by 1 type, and may use 2 or more types together.
  • the composition containing the zirconia particles and the resin contains, in addition to the binder and polyol, one or two other components such as a dispersant, an emulsifier, an antifoaming agent, a pH adjuster, and a lubricant as described above. The above may be further included.
  • the stereolithography method may be suitable especially when the zirconia sintered body of the present invention is used as a dental material such as a dental prosthesis.
  • polymerizable monomer in the composition containing the zirconia particles and the polymerizable monomer, and monofunctional monomers such as monofunctional (meth)acrylates and monofunctional (meth)acrylamides
  • monofunctional monomers such as monofunctional (meth)acrylates and monofunctional (meth)acrylamides
  • Any of polymerizable monomers and polyfunctional polymerizable monomers such as bifunctional aromatic compounds, bifunctional aliphatic compounds, and trifunctional or higher compounds may be used.
  • One polymerizable monomer may be used alone, or two or more thereof may be used. Among these, it is preferable to use a polyfunctional polymerizable monomer, especially when stereolithography is employed.
  • Monofunctional (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6 - hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate having a hydroxyl group (meth) acrylate; methyl ( meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) Alkyl (meth
  • Monofunctional (meth)acrylamides include, for example, (meth)acrylamide, N-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N- Di-n-propyl (meth)acrylamide, N,N-di-n-butyl (meth)acrylamide, N,N-di-n-hexyl (meth)acrylamide, N,N-di-n-octyl (meth) acrylamide, N,N-di-2-ethylhexyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide and the like.
  • (meth)acrylamide is preferable in terms of excellent polymerizability, N-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N- Diethyl (meth)acrylamide is more preferred.
  • bifunctional aromatic compounds include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl ] Propane, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as “Bis-GMA”), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl) Propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth) ) acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryl
  • 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as “Bis-GMA”) is superior in terms of polymerizability and mechanical strength of the obtained zirconia molded article. ), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane are preferred.
  • 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propanes 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (the average number of added moles of ethoxy groups is 2.6 A compound (commonly known as "D-2.6E”) is preferred.
  • bifunctional aliphatic compounds include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate.
  • UDMA 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)e
  • triethylene glycol dimethacrylate (commonly known as "TEGDMA"), 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl), are excellent in terms of polymerizability and mechanical strength of the resulting zirconia molded article. Dimethacrylate is preferred.
  • trifunctional or higher compounds examples include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra( meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth)acrylate, 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane and the like.
  • N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3- diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane are preferred.
  • the composition is preferably polymerized using a polymerization initiator, and the composition preferably further contains a polymerization initiator.
  • a polymerization initiator is particularly preferred.
  • the photopolymerization initiator it is possible to appropriately select and use photopolymerization initiators used in general industry, and among them, photopolymerization initiators used for dental applications are preferable. Specific examples of the photopolymerization initiator are the same as those described above in the description of gel casting, and redundant description is omitted here.
  • the composition containing the zirconia particles and the polymerizable monomer contains, in addition to the binder and polyol, one of other components such as a dispersant, an emulsifier, an antifoaming agent, a pH adjuster, and a lubricant as described above.
  • a seed or two or more may be further included.
  • stereolithography In the case of producing a zirconia molded article by stereolithography using a composition containing zirconia particles and a polymerizable monomer, the specific method of stereolithography is not particularly limited, and stereolithography is performed by appropriately adopting a known method. can do. For example, a method of obtaining a desired zirconia molded body by sequentially forming each layer having a desired shape by photopolymerizing a liquid composition with ultraviolet light, a laser, etc., using a stereolithography device is adopted. be able to.
  • the content of zirconia particles in the composition containing zirconia particles and polymerizable monomers is preferably as large as possible from the viewpoint of subsequent sinterability.
  • the content of zirconia particles in the composition is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and 50% by mass. % or more is particularly preferable.
  • the viscosity of the composition is within a certain range from the principle of lamination molding.
  • the content of zirconia particles in the composition is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and 60% by mass or less. It is particularly preferred to have
  • the adjustment of the viscosity of the composition is performed by irradiating light from the bottom of the container through the bottom surface of the container to cure the layers and sequentially form the zirconia molded body layer by layer. , can be particularly important for raising the cured layer by one layer to allow the composition to form the next layer to flow smoothly between the underside of the cured layer and the bottom of the container. .
  • the viscosity at 25° C. is preferably 20,000 mPa s or less, more preferably 10,000 mPa s or less, and 5,000 mPa s or less. more preferably 100 mPa ⁇ s or more.
  • the higher the content of zirconia particles the higher the viscosity. Therefore, the balance between the speed during stereolithography and the accuracy of the resulting zirconia molded body should be adjusted according to the performance of the stereolithography device used. It is preferable to appropriately adjust the balance between the content of zirconia particles and the viscosity in the above composition, taking into consideration the above.
  • the viscosity can be measured using an E-type viscometer.
  • the zirconia molded body in order to further improve the density of the zirconia molded body, may be subjected to CIP treatment after being subjected to humidification treatment.
  • the press molding may be performed after subjecting the powder containing zirconia particles before press molding to a moisturizing treatment.
  • a known method can be used for the humidification treatment without any limitation, and the treatment may be performed by spraying water with a mist sprayer or the like, or by using a hygrostat or a constant temperature and hygrostat.
  • the amount of increase in water content due to humidification depends on the particle size of the zirconia particles contained, but it is preferably more than 2% by mass, more than 3% by mass, relative to the mass of the powder before wetting (powder before humidification) and the compact. %, more preferably 4% by mass, particularly preferably 5% by mass, preferably 15% by mass or less, and more preferably 13% by mass or less. , 11% by mass or less.
  • the amount of increase in water content due to humidification is obtained by subtracting the mass of the pre-wet powder and compact from the mass of the wet powder (powder after humidification) and the compact, divided by the mass of the pre-wet powder and compact. It can be obtained as a percentage by
  • yttria is contained in an amount of 2.0 to 9.0 mol% with respect to the total number of moles of zirconium oxide and yttria, and ⁇ L * (WB) at a thickness of 1.5 mm is 5 or more.
  • the zirconia calcined body By using the zirconia calcined body, it is possible to obtain a zirconia sintered body which is excellent in both mechanical strength and translucency, and which is excellent in linear light transmittance.
  • the definition of ⁇ L * (WB) is the same as for the zirconia compact.
  • the method for measuring the number of pores having a diameter of 50 nm or more is as described above for the number of pores having a diameter of 50 nm or more in the zirconia sintered body.
  • the thickness of the zirconia calcined body is preferably 12 mm or more, more preferably 15 mm or more.
  • the shape of the zirconia calcined body having a thickness of 10 mm or more is not particularly limited, and may be block-shaped (rectangular parallelepiped) or the like.
  • a calcined zirconia body containing a fluorescent agent is suitably used as the raw material before sintering.
  • the content of the fluorescent agent in the calcined zirconia body containing the fluorescent agent can be appropriately adjusted according to the content of the fluorescent agent in the resulting zirconia sintered body.
  • the specific content of the fluorescent agent contained in the zirconia calcined body is 0.001% by mass in terms of oxide of the metal element contained in the fluorescent agent with respect to 100% by mass of zirconia contained in the zirconia calcined body. It is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 1% by mass or less, and 0.5% by mass. It is more preferably 0.1% by mass or less, more preferably 0.1% by mass or less.
  • a zirconia calcined body containing a coloring agent is suitably used as a raw material before sintering.
  • the content of the coloring agent in the zirconia calcined body containing the coloring agent can be appropriately adjusted according to the content of the coloring agent in the obtained zirconia sintered body.
  • the specific content of the coloring agent contained in the zirconia calcined body is 0.001% by mass in terms of oxide of the metal element contained in the coloring agent with respect to 100% by mass of zirconia contained in the zirconia calcined body.
  • a calcined zirconia body containing a translucency adjusting agent is suitably used as a raw material before sintering.
  • the content of the translucency adjusting agent in the calcined zirconia body containing the translucency adjusting agent can be appropriately adjusted depending on the content of the translucency adjusting agent in the obtained zirconia sintered body.
  • a specific content of the translucency adjusting agent contained in the zirconia calcined body is preferably 0.1% by mass or less with respect to 100% by mass of zirconia contained in the zirconia calcined body.
  • the content of yttria contained in the zirconia calcined body of the present invention is within the range of 2.0 to 9.0 mol%, and may be the same as the yttria content in the obtained zirconia sintered body.
  • the specific content of yttria in the sintered body is 2.0 mol% or more, preferably 3.0 mol% or more, more preferably 3.5 mol% or more, and 4.0 mol% or more. is more preferably 8.0 mol % or less, more preferably 7.5 mol % or less, and even more preferably 7.0 mol % or less.
  • the density of the calcined zirconia body of the present invention is not particularly limited, and may be in the range of 3.0 to 6.0 g/m 3 , although it varies depending on the method of manufacturing the zirconia molded body used for its manufacture. Preferably, it is in the range of 3.2 to 5.8 g/m 3 .
  • the shape of the calcined zirconia body of the present invention is not particularly limited, and it can be of any desired shape depending on the application. Considering the properties and the like, a disk shape, prismatic shape (rectangular parallelepiped shape, etc.) and the like are preferable. As will be described later, before the zirconia calcined body is turned into a zirconia sintered body, it can be formed into a desired shape according to the application by cutting (milling). A zirconia calcined body having a later desired shape is also included. Moreover, the zirconia calcined body may have a single-layer structure, or may have a multi-layer structure. By forming a multi-layer structure, the finally obtained zirconia sintered body can have a multi-layer structure, and its physical properties such as translucency can be locally changed.
  • the three-point bending strength of the zirconia calcined body of the present invention is 10 from the viewpoint that the shape of the workpiece can be maintained during processing using a cutting machine and that the cutting itself can be easily performed. It is preferably in the range of ⁇ 70 MPa, more preferably in the range of 20-60 MPa.
  • the three-point bending strength of the zirconia calcined body was measured using a universal testing machine with a test piece of 5 mm ⁇ 40 mm ⁇ 10 mm under the conditions of a span length (distance between fulcrums) of 30 mm and a crosshead speed of 0.5 mm / min. can be measured.
  • the zirconia calcined body of the present invention preferably has a crystal grain size of 180 nm or less after being sintered at 900 to 1200° C. under normal pressure for 2 hours (after being made into a zirconia sintered body).
  • the crystal grain size is more preferably 140 nm or less, still more preferably 120 nm or less, and particularly preferably 115 nm or less, because a zirconia sintered body having excellent translucency can be obtained. It may be below.
  • the lower limit of the crystal grain size is not particularly limited, the crystal grain size can be, for example, 50 nm or more, further 100 nm or more.
  • the method for measuring the grain size is as described above for the grain size of the zirconia sintered body.
  • the calcined zirconia body of the present invention has a ⁇ L * (WB) at a thickness of 1.5 mm of 5 or more, preferably 7 or more, and may be 10 or more.
  • a zirconia sintered body having a high linear light transmittance can be obtained when sintered under normal pressure.
  • the upper limit of ⁇ L * (WB) is not particularly limited, it can be, for example, 30 or less, and further 25 or less.
  • ⁇ L * (WB) at a thickness of 1.5 mm of the zirconia calcined body was measured in the same manner as for the zirconia molded body, except that the measurement sample was changed from the zirconia molded body to the zirconia calcined body. can.
  • the zirconia calcined body of the present invention preferably has a three-point bending strength of 500 MPa or more after being sintered at 900 to 1200°C under normal pressure (after being made into a zirconia sintered body).
  • the three-point bending strength is more preferably 600 MPa or more, still more preferably 650 MPa or more, and particularly preferably 700 MPa or more, because a zirconia sintered body having excellent mechanical strength can be obtained. , 800 MPa or more.
  • the upper limit of the 3-point bending strength is not particularly limited, the 3-point bending strength can be, for example, 1500 MPa or less, further 1000 MPa or less.
  • the method for measuring the three-point bending strength is as described above for the three-point bending strength of the zirconia sintered body.
  • the zirconia calcined body of the present invention has a transmittance of 40% or more for light with a wavelength of 700 nm at a thickness of 0.5 mm after sintering at 900 to 1200 ° C. under normal pressure (after making a zirconia sintered body). is preferred. Thereby, the zirconia sintered body of the present invention having excellent translucency can be easily produced. Since a zirconia sintered body having excellent translucency can be obtained, the transmittance is more preferably 45% or more, further preferably 46% or more, and particularly preferably 48% or more. Preferably, it is 50% or more, most preferably 52% or more.
  • the transmittance can be, for example, 60% or less, further 57% or less.
  • the method for measuring the transmittance is as described above for the transmittance of light with a wavelength of 700 nm in a zirconia sintered body having a thickness of 0.5 mm.
  • the zirconia calcined body of the present invention preferably has a linear light transmittance of 1% or more at a thickness of 1.0 mm after sintering at 900 to 1200 ° C. under normal pressure (after making a zirconia sintered body). , is more preferably 3% or more, further preferably 5% or more, particularly preferably 7% or more, and may be 10% or more.
  • the linear light transmittance is within the above range, it becomes easier to satisfy the translucency required for the incisal portion when used as a dental prosthesis, for example.
  • the upper limit of the linear light transmittance is not particularly limited, the linear light transmittance can be, for example, 60% or less, further 50% or less.
  • the method for measuring the linear light transmittance is as described above for the linear light transmittance at a thickness of 1.0 mm in the zirconia sintered body.
  • the method for producing a calcined zirconia body of the present invention is characterized by using, for example, the zirconia molded body of the present invention.
  • a method for producing a calcined zirconia body is preferably a production method including a step of calcining the zirconia molded body at 200 to 800°C.
  • the method for producing a calcined zirconia body of the present invention may include a step of cutting the zirconia molded body of the present invention, and the cut zirconia molded body may be calcined.
  • the cutting method is not particularly limited, and known devices (for example, known milling devices) and methods can be used.
  • the calcining temperature is preferably 200° C. or higher, more preferably 250° C. or higher, and even more preferably 300° C. or higher, from the viewpoint of easily obtaining the desired zirconia calcined body. Also, the temperature is preferably 800° C. or lower, more preferably 700° C. or lower, and even more preferably 600° C. or lower. When the calcining temperature is equal to or higher than the above lower limit, it is possible to effectively suppress the generation of organic residue. In addition, when the calcining temperature is equal to or lower than the above upper limit, it is possible to prevent excessive progress of sintering and difficulty in cutting (milling) with a cutting machine.
  • the rate of temperature increase when calcining the zirconia molded body of the present invention is preferably 0.1° C./min or more, more preferably 0.2° C./min or more, and 0 It is more preferably 5°C/min or more, more preferably 50°C/min or less, more preferably 30°C/min or less, and even more preferably 20°C/min or less.
  • Productivity improves when the heating rate is equal to or higher than the above lower limit.
  • the heating rate is equal to or less than the above upper limit, the volume difference between the inside and the outside of the zirconia molded body or the zirconia calcined body can be suppressed, and when the zirconia molded body contains organic matter, the organic matter rapidly decomposes. can be suppressed, and cracks and breakage can be suppressed.
  • the calcining time for calcining the zirconia molded body of the present invention is not particularly limited, but the calcining time is set so that the desired zirconia calcined body can be efficiently and stably obtained with good productivity. , preferably 0.5 hours or more, more preferably 1 hour or more, further preferably 2 hours or more, preferably 10 hours or less, and preferably 8 hours or less. More preferably, it is 6 hours or less.
  • the calcination in the present invention can be performed using a calcination furnace.
  • the type of calcining furnace is not particularly limited, and for example, electric furnaces and degreasing furnaces used in general industry can be used.
  • the zirconia calcined body of the present invention can be formed into a desired shape according to the application by cutting (milling) before making it into a zirconia sintered body.
  • the zirconia sintered body of the present invention is particularly suitable as a dental material such as a dental prosthesis because it has excellent translucency and mechanical strength in spite of containing a fluorescent agent.
  • the zirconia calcined body can be cut (milled) into a corresponding shape.
  • a known milling device can be used.
  • the zirconia sintered body of the present invention can be produced by sintering the zirconia molded body of the present invention under normal pressure, and the zirconia calcined body of the present invention is sintered under normal pressure. It can also be manufactured by
  • the sintering temperature is determined from the viewpoint of easily obtaining the desired zirconia sintered body. Therefore, it is preferably 900° C. or higher, more preferably 1000° C. or higher, further preferably 1050° C. or higher, and preferably 1200° C. or lower, more preferably 1150° C. or lower. It is preferably 1120° C. or lower, and more preferably 1120° C. or lower.
  • the sintering temperature is equal to or higher than the above lower limit, sintering can be sufficiently advanced, and a dense sintered body can be easily obtained.
  • the sintering temperature is equal to or lower than the above upper limit, a zirconia sintered body having a crystal grain size within the preferred range of the present invention can be easily obtained, and deactivation of the fluorescent agent can be suppressed. can.
  • the sintering time is not particularly limited.
  • the sintering time is preferably 5 minutes or longer, more preferably 15 minutes or longer, and even more preferably 30 minutes or longer, since it can be obtained efficiently and stably. It is preferably 6 hours or less, more preferably 4 hours or less, and even more preferably 2 hours or less.
  • Sintering in the present invention can be performed using a sintering furnace.
  • the type of sintering furnace is not particularly limited, and for example, electric furnaces and degreasing furnaces used in general industry can be used. Especially when it is used for dental materials, a dental porcelain furnace with a relatively low sintering temperature can be used in addition to the conventional dental zirconia sintering furnace.
  • the zirconia sintered body of the present invention can be easily produced without HIP treatment, but it is possible to further improve translucency and mechanical strength by performing HIP treatment after sintering under normal pressure. .
  • the zirconia sintered body of the present invention is not particularly limited in use, but the zirconia sintered body of the present invention is excellent in both translucency and mechanical strength, and is excellent in linear light transmittance. Among others, it is extremely useful not only as a dental prosthesis used for the cervical region, but also as a dental prosthesis used for the occlusal surface of molars and anterior incisal ends.
  • the zirconia sintered body of the present invention is preferably used as a dental prosthesis particularly used for an anterior incisal edge.
  • the present invention will be described in detail below with examples and comparative examples, but the present invention is not limited to these examples.
  • the measuring method of each physical property is as follows.
  • Crystal grain size in the zirconia sintered body is obtained by taking a field emission scanning electron microscope (FE-SEM) photograph of the cross section of the zirconia sintered body and selecting 100 arbitrary particles in the photographed image. It was obtained as the average value of each equivalent circle diameter (diameter of a perfect circle with the same area).
  • FE-SEM field emission scanning electron microscope
  • This test piece is obtained by molding the powder containing zirconia particles obtained in the process of the example into a square bar shape of 40 mm ⁇ 6 mm ⁇ 5 mm with a uniaxial press, and cold isostatic pressing (CIP) treatment (pressure 170 MPa) to increase the density to obtain a zirconia compact, which was fired and then surface-polished.
  • CIP cold isostatic pressing
  • Light transmittance (wavelength 700 nm, thickness 0.5 mm)
  • the transmittance of light with a wavelength of 700 nm at a thickness of 0.5 mm of the zirconia sintered body was measured using a spectrophotometer (manufactured by Hitachi High-Technologies Co., Ltd., "Hitachi Spectrophotometer U-3900H"). was transmitted and scattered by the sample and measured using an integrating sphere. In the measurement, the transmittance was once measured in the wavelength range of 300 to 750 nm, and then the transmittance for light with a wavelength of 700 nm was obtained.
  • Linear light transmittance (1.0 mm thickness)
  • the linear light transmittance at a thickness of 1.0 mm of the zirconia sintered body was measured by using a turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., "Haze Meter NDH4000"), and transmitting and scattering the light generated from the light source to the sample. , was measured using an integrating sphere.
  • linear light transmittance shall be measured according to ISO 13468-1:1996 and JIS K 7361-1:1997
  • haze shall be measured according to ISO 14782-1:1999 and JIS K 7136:2000.
  • combustion start temperature and combustion end temperature of polyol and binder were measured by a thermal analysis device manufactured by Rigaku Corporation ("trade name : Thermo plus EVO2", differential heat-thermogravimetric simultaneous measurement device "TG-DTA8122”, analysis software: Thermo plus EVO ver2.086, sample pan: platinum, measurement atmosphere: Air (100 cc/min), heating rate: 10. 0° C./min, sampling interval: 1.0 sec).
  • Tables 1 and 2 show the types of polyols and binders used and the results of measurements of combustion start and end temperatures.
  • Example 1 1.0 L of mixed aqueous solution containing 0.62 mol/L of zirconium oxychloride and 0.038 mol/L of yttrium chloride and 0.5 L of 1.9 mol/L of sodium hydroxide aqueous solution were prepared. 1.0 L of pure water was poured into the sedimentation tank, and the mixed aqueous solution and the sodium hydroxide aqueous solution were simultaneously poured to coprecipitate zirconium oxychloride and yttrium chloride to obtain a slurry. After filtering and washing this, 22.2 g of acetic acid was added to the above slurry and hydrothermally treated at 200° C. for 3 hours.
  • Pure water was added so that the concentration of dissolved zirconia was 5.0% by mass, and a zirconia slurry from which coarse particles were removed was obtained.
  • the average primary particle size of the zirconia particles contained in this zirconia slurry was 17 nm, and the zirconia particles having a particle size of 100 nm or more accounted for 0.33% by mass.
  • the remaining water content of this methanol-substituted slurry was measured using a Karl Fischer moisture meter and found to be 0.08% by mass.
  • 1% by mass of glycerin relative to 100% by mass of zirconia and 2% by mass of an acrylic binder "KFE-124" relative to 100% by mass of zirconia were added, and ultrasonication was performed at 40 kHz for 1 hour.
  • ultrasonication was performed at 40 kHz for 1 hour.
  • an additive-containing slurry was obtained.
  • the obtained additive-containing slurry was supercritically dried by the following procedure using a supercritical drying apparatus.
  • the additive-containing slurry was placed in a pressure vessel, the pressure vessel was connected to a supercritical carbon dioxide extractor, and it was confirmed that there was no pressure leakage.
  • the pressure vessel and the preheating tube were immersed in a water bath heated to 60° C., heated to 80° C., pressurized to 25 MPa, and left for 10 minutes for stabilization.
  • carbon dioxide and methanol as an entrainer are introduced under predetermined conditions (temperature: 80° C., pressure: 25 MPa, flow rate of carbon dioxide: 10 mL/min, flow rate of entrainer (methanol): 1.5 mL/min). After 2 hours, the introduction of methanol was stopped, and the introduction of only carbon dioxide was continued.
  • the obtained powder was formed into a plate shape of 20 mm ⁇ 20 mm ⁇ 5 mm, a disc shape of 20 mm diameter ⁇ 2.5 mm thickness, and a block shape of 20 mm ⁇ 20 mm ⁇ 15 mm by a uniaxial press, and these were subjected to cold isostatic pressing.
  • a pressurization (CIP) treatment pressure of 170 MPa was performed to increase the density to obtain a zirconia molded body.
  • CIP pressurization
  • These zirconia molded bodies were calcined at 500° C. for 2 hours under normal pressure to obtain zirconia calcined bodies. Further, the non-block-shaped zirconia calcined body was sintered under normal pressure at 1100° C. for 2 hours to obtain a zirconia sintered body.
  • the obtained zirconia sintered body was white.
  • Table 3 Each measurement result is shown in Table 3.
  • a milling device (“Katana (registered trademark) H-18”, manufactured by Kuraray Noritake Dental Co., Ltd.) was used for the block-shaped zirconia calcined body to form a single crown shape of the upper central incisor and a lower first tooth.
  • the single crown-shaped zirconia calcined bodies of molar teeth were cut and sintered under normal pressure at 1100° C. for 2 hours to obtain crown-shaped dental prostheses.
  • Example 1 Glycerin was added to the methanol-substituted slurry prepared in Example 1 in an amount of 1% by mass with respect to 100% by mass of zirconia, and ultrasonically dispersed at 40 kHz for 1 hour to obtain an additive-containing slurry.
  • a powder containing zirconia particles, plate-like and disc-like zirconia molded bodies, zirconia calcined bodies, and zirconia sintered bodies were obtained in the same manner as in Example 1, except that the above slurry was used as the additive-containing slurry.
  • the obtained zirconia sintered body was white.
  • Table 3 Each measurement result is shown in Table 3.
  • the block-shaped zirconia molded body was broken when the pressure was released from the uniaxial press, and had insufficient mechanical strength. Therefore, a block-shaped zirconia calcined body and a block-shaped zirconia sintered body could not be produced.
  • Comparative Example 2 Powder containing zirconia particles, plate-shaped and disk-shaped zirconia compacts, and zirconia calcining were prepared in the same manner as in Comparative Example 1 except that the glycerin used in Comparative Example 1 was 2% by mass with respect to 100% by mass of zirconia. A body and a zirconia sintered body were obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 3. The block-shaped zirconia molded body was broken when the pressure was released from the uniaxial press, and had insufficient mechanical strength.
  • Example 3 Add 2% by mass of acrylic binder "KFE-124" to the methanol-substituted slurry prepared in Example 1 with respect to 100% by mass of zirconia, and ultrasonically disperse at 40 kHz for 1 hour to obtain an additive-containing slurry. got Powder containing zirconia particles, plate-shaped, disk-shaped, block-shaped zirconia compacts, zirconia calcined bodies, and zirconia sintered bodies were prepared in the same manner as in Example 1, except that the above slurry was used as the additive-containing slurry. Obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 3.
  • Example 4 A powder containing zirconia particles, plate-like, disk-like, and block-like zirconia molded bodies, zirconia calcined bodies, and zirconia sintered bodies were obtained in the same manner as in Example 1, except that the polyol was changed to dipentaerythritol. . The obtained zirconia sintered body was white. Each measurement result is shown in Table 3.
  • Example 2 A test was conducted in the same manner as in Example 1 except that 1.0 L of mixed aqueous solution containing 0.62 mol/L zirconium oxychloride and 0.066 mol/L yttrium chloride was used.
  • the zirconia particles contained in the zirconia slurry had an average primary particle size of 18 nm, and the zirconia particles having a particle size of 100 nm or more accounted for 0.35% by mass.
  • An additive-containing slurry containing a polyol and a binder was prepared in the same manner as in Example 1, except that the slurry obtained above was used. , disk-shaped and block-shaped zirconia molded bodies, zirconia calcined bodies, and zirconia sintered bodies were obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 4.
  • Example 3 The test was conducted in the same manner as in Example 1, except that 1.0 L of mixed aqueous solution containing 0.62 mol/L of zirconium oxychloride and 0.108 mol/L of yttrium chloride was used.
  • the zirconia particles contained in the zirconia slurry had an average primary particle size of 17 nm, and the zirconia particles having a particle size of 100 nm or more accounted for 0.15% by mass.
  • An additive-containing slurry containing a polyol and a binder was prepared in the same manner as in Example 1, except that the slurry obtained above was used. , disk-shaped and block-shaped zirconia molded bodies, zirconia calcined bodies, and zirconia sintered bodies were obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 4.
  • Example 4 A dilute nitric acid solution of bismuth nitrate was added to the zirconia slurry prepared in Example 2 (average primary particle size: 18 nm, zirconia particles having a particle size of 100 nm or more: 0.35% by mass), and bismuth was added to 100% by mass of zirconia. was added so that the content in terms of the oxide (Bi 2 O 3 ) of was 0.02% by mass to obtain a slurry containing zirconia particles and a fluorescent agent.
  • An additive-containing slurry containing a polyol and a binder was prepared in the same manner as in Example 1, except that the slurry obtained above was used. , disk-shaped and block-shaped zirconia molded bodies, zirconia calcined bodies, and zirconia sintered bodies were obtained. The obtained zirconia sintered body was white and had fluorescence. Each measurement result is shown in Table 4.
  • Example 5 An aqueous solution of nickel (II) nitrate was added to the zirconia slurry prepared in Example 2 (average primary particle size: 18 nm, 0.35% by mass for zirconia particles having a particle size of 100 nm or more), nickel for 100% by mass of zirconia (II) was added so that the content in terms of oxide (NiO) was 0.02% by mass to obtain a slurry containing zirconia particles and a colorant.
  • An additive-containing slurry containing a polyol and a binder was prepared in the same manner as in Example 1, except that the slurry obtained above was used. , disk-shaped and block-shaped zirconia molded bodies, zirconia calcined bodies, and zirconia sintered bodies were obtained. The obtained zirconia sintered body was colored red. Each measurement result is shown in Table 4.
  • Example 6 Powder, plate-shaped, disk-shaped, and block-shaped zirconia moldings containing zirconia particles in the same manner as in Example 2 except that polyethylene glycol "PEG-6000P” was used as the polyol and "KFA-440" was used as the binder. , a zirconia calcined body, and a zirconia sintered body were obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 5.
  • Example 7 Powder containing zirconia particles, plate-shaped, disk-shaped and block-shaped zirconia molded bodies, zirconia calcined bodies and zirconia sintered bodies were obtained in the same manner as in Example 2 except that propylene glycol was used as the polyol. The obtained zirconia sintered body was white. Each measurement result is shown in Table 5.
  • Example 8 Powder containing zirconia particles, plate-shaped, disk-shaped, block-shaped zirconia molded bodies, zirconia temporary A fired body and a zirconia sintered body were obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 5.
  • Example 9 Powder containing zirconia particles, plate-shaped, disk-shaped, block-shaped zirconia molded bodies, zirconia calcined bodies, zirconia sintered in the same manner as in Example 2 except that the acrylic binder "KFA-440" was used as the binder. got a body The obtained zirconia sintered body was white. Each measurement result is shown in Table 6.
  • Example 10 Powder containing zirconia particles, plate-shaped, disk-shaped, block-shaped zirconia molded bodies, zirconia calcined bodies, zirconia A sintered body was obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 6.
  • Example 11 Powder containing zirconia particles, plate-shaped, disk-shaped, block-shaped zirconia molded bodies, zirconia calcined bodies, zirconia A sintered body was obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 6.
  • Example 12 A powder containing zirconia particles, a plate-shaped, disk-shaped, block-shaped zirconia molded body, a zirconia calcined body, and a zirconia sintered body were prepared in the same manner as in Example 1, except that the content of the polyol was 2% by mass. Obtained. The obtained zirconia sintered body was white. Each measurement result is shown in Table 6.

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