WO2020262597A1 - Composite de zircone non cuit et son procédé de production, ébauche de fraisage dentaire et procédé de fabrication de prothèse dentaire - Google Patents

Composite de zircone non cuit et son procédé de production, ébauche de fraisage dentaire et procédé de fabrication de prothèse dentaire Download PDF

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Publication number
WO2020262597A1
WO2020262597A1 PCT/JP2020/025176 JP2020025176W WO2020262597A1 WO 2020262597 A1 WO2020262597 A1 WO 2020262597A1 JP 2020025176 W JP2020025176 W JP 2020025176W WO 2020262597 A1 WO2020262597 A1 WO 2020262597A1
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Prior art keywords
zirconia
unfired
molded product
zirconia composite
unfired zirconia
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PCT/JP2020/025176
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English (en)
Japanese (ja)
Inventor
紘之 坂本
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クラレノリタケデンタル株式会社
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Priority to JP2021527765A priority Critical patent/JPWO2020262597A1/ja
Publication of WO2020262597A1 publication Critical patent/WO2020262597A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • A61C13/083—Porcelain or ceramic teeth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C5/00—Filling or capping teeth
    • A61C5/70—Tooth crowns; Making thereof
    • A61C5/77—Methods or devices for making crowns

Definitions

  • the present invention relates to an uncalcined zirconia composite and a method for producing the same. More specifically, for example, inlays, onlays, veneers, crowns, bridges, abutment teeth, dental posts, dentures, denture bases, implant members (fixtures, abutments) by cutting with a dental CAD / CAM system.
  • the present invention relates to a dental mill blank preferably used for producing dental prostheses such as.
  • metal has often been used as a dental product (for example, a typical covering crown, crown, crown, prosthesis such as an insert tooth; orthodontic product, dental implant product).
  • a dental product for example, a typical covering crown, crown, crown, prosthesis such as an insert tooth; orthodontic product, dental implant product.
  • the color of metal is clearly different from that of natural teeth, and it has the disadvantage of lacking aesthetics, and it may cause allergies due to the elution of metal. Therefore, in order to solve the problems associated with the use of metal, ceramic materials such as aluminum oxide (alumina) and zirconium oxide (zirconia) have been used in dental products as alternative materials for metals.
  • zirconia is excellent in strength and relatively excellent in aesthetics, so demand is increasing especially in combination with the recent price reduction.
  • the zirconia sintered body depending on the type of product to which the zirconia sintered body is applied, high dimensional accuracy may be required.
  • the artificial tooth in the case of an artificial tooth used for dental treatment, the artificial tooth cannot be applied to a patient unless the shape and size of the artificial tooth and the size and shape of the abutment tooth of the patient whose data have been collected in advance match.
  • zirconia has been generally used as a material for mill blank, which is a material to be cut used in the system, because aesthetics are emphasized.
  • the zirconia mill blank is a porous calcined form (hereinafter, also referred to as calcined form) that has been calcined once at around 900 to 1200 ° C.
  • the zirconia mill blank needs to have a predetermined strength.
  • a calcining step is required in the above temperature range in order to impart physical properties such as the predetermined strength to the zirconia mill blank.
  • the zirconia mill blank which is a calcined body, is a brittle material with high hardness, the mill blank is chipped due to the impact of cutting and grinding, and the influence of the wet processing coolant using the coolant is used. There was a problem that the dental prosthesis that had been fired again after processing could not obtain the required translucency.
  • a mill blank made of a composite material containing a polymer resin and an inorganic filler has been studied, including a change in the material.
  • the composite mill blank has been processed into a dental prosthesis and has begun to be used clinically because it is excellent in machinability and grindability during processing.
  • Patent Document 1 a liquid resin is permeated into a porous support to cure the resin impregnated with the support, and a pressure exceeding about 30 MPa (300 bar) is applied to the resin to improve the strength. Although it has been examined, it has not been examined using zirconia.
  • Patent Document 2 is a mill characterized in that an inorganic filler molded product obtained by press-molding an inorganic filler is brought into contact with a polymerizable monomer-containing composition to polymerize and cure the polymerizable monomer.
  • blanks have been studied, they are mill blanks used without sintering and are not supposed to be sintered. That is, the problems peculiar to the zirconia mill blank as a zirconia calcined body have not been examined.
  • the present invention provides an unfired zirconia composite and a dental mill blank that do not require prior sintering work, can produce a dental prosthesis by one sintering work, and have appropriate strength to withstand machining.
  • the purpose is to do.
  • the present invention also provides an unfired zirconia composite and a dental mill blank that have a hydrophobic surface, are not affected by cooling water even in wet processing, and can be suitably used in wet processing. The purpose.
  • the present invention includes the following inventions.
  • An unfired zirconia composite composed of an unfired zirconia molded product and a resin, in which the resin is impregnated into the unfired zirconia molded product.
  • the composition In the case of infiltrating the composition containing the curable resin, the polymerizable monomer or the polymerizable monomer into the unfired zirconia molded product in the step (2), after the step (2), the composition The method for producing an unfired zirconia composite according to [9], which comprises a step (3) of curing the curable resin or the polymerizable monomer. [11] The method for producing an unfired zirconia composite according to [10], which is cured in a vacuum state in the step (3). [12] The method for producing an unfired zirconia composite according to [10], which is cured under atmospheric pressure in the step (3).
  • a method for producing a dental prosthesis which comprises the step (I) of processing the dental mill blank according to [18] or [19], and the step (II) of sintering an unbaked dental prosthesis.
  • the unfired zirconia composite of the present invention it is possible to manufacture a dental prosthesis made of zirconia ceramic to satisfy the aesthetic requirements of the dental prosthesis.
  • a dental prosthesis can be manufactured by a single sintering operation, and an unfired zirconia composite and a dental mill blank having appropriate strength to withstand machining can be manufactured. be able to.
  • the unfired zirconia composite of the present invention has strength enough to withstand machining, when it is used as a dental mill blank, it is possible to suppress the occurrence of cracking or chipping during cutting.
  • the unfired zirconia composite and the dental mill blank of the present invention have a hydrophobic surface and are not affected by the coolant even in the wet processing, and can be suitably used for the wet processing.
  • the unfired zirconia composite of the present invention is composed of an unfired zirconia molded product and a resin, and it is important that the resin is permeated into the unfired zirconia molded product.
  • the production method includes a step (1) of press-molding zirconia to obtain an unfired zirconia molded product, and a thermoplastic resin, a curable resin, a polymerizable monomer, or a polymerizable monomer or a polymerizable resin, a curable resin, or a polymerizable monomer on the obtained unfired zirconia molded product. It is characterized by comprising a step (2) of infiltrating a composition containing a polymerizable monomer.
  • a resin component thermoplastic resin or curable resin
  • a resin raw material component a polymerizable monomer or a composition containing a polymerizable monomer
  • zirconia for example, zirconia powder
  • a composition obtained by adding a binder to a slurry containing the above) may be press-molded to obtain an unfired zirconia molded product, but even in that case, a step of infiltrating the resin component or the resin raw material component into the molded product. is required.
  • unfired zirconia composite the unfired zirconia molded product after the resin has been impregnated is referred to as "unfired zirconia composite" to distinguish it from the “unfired zirconia molded product” before permeation. The details will be described below.
  • the unfired zirconia molded product in the present invention is an unfired, that is, a molded product made of unsintered zirconia.
  • "not sintered” refers to a state in which the contacting portions of the zirconia powder particles do not react with each other.
  • the unfired zirconia molded product in the present invention preferably contains a stabilizer in that it requires chipping resistance, crack resistance, and bending strength sufficient to withstand repeated chewing movements as a dental prosthesis. That is, it is preferable to include a stabilizer in the zirconia before firing.
  • the fired zirconia sintered body which is the base material of the dental prosthesis, can have at least one of partially stabilized zirconia and fully stabilized zirconia as a matrix phase.
  • the main crystal phase of zirconia is at least one of a tetragonal system and a cubic system, and may contain both a tetragonal system and a cubic system.
  • the zirconia sintered body does not substantially contain a monoclinic crystal system.
  • substantially free of monoclinic crystal system means that the content of the monoclinic crystal system in the zirconia sintered body is less than 5.0% by mass, preferably less than 1.0% by mass.
  • Zirconia partially stabilized by adding a stabilizer is called partially stabilized zirconia (PSZ; Partially Stabilized Zirconia), and completely stabilized zirconia is called fully stabilized zirconia.
  • PSZ partially stabilized zirconia
  • the unfired zirconia molded product in the present invention may be partially stabilized zirconia or fully stabilized zirconia.
  • the unfired zirconia molded product is composed of an unfired zirconia molded product and a resin, the resin is permeated into the unfired zirconia molded product, and the unfired zirconia molded product is stabilized by a stabilizer.
  • a stabilizer examples thereof include an uncalcined zirconia complex containing partially stabilized zirconia and the stabilizer being yttria.
  • the stabilizer examples include yttrium oxide (Y 2 O 3 ) (hereinafter referred to as “itria”), calcium oxide (calcia; CaO), magnesium oxide (magnesia; MgO), cerium oxide (ceria; CeO 2 ), and the like.
  • yttria is preferable as a stabilizer from the viewpoint of high translucency and improvement in strength. These may be used alone or in combination of two or more.
  • zirconia containing a stabilizer such as partially stabilized zirconia can withstand machining such as cutting even though it does not undergo a general calcining process.
  • a dental mill blank that has physical properties such as strength and can suppress the occurrence of cracks or chipping during machining such as cutting can be obtained, solving the problems of conventional zirconia calcined bodies. it can.
  • the content of yttria in the unfired zirconia molded product is preferably 2 to 8 mol%, more preferably 3 to 6 mol%, based on a total of 100 mol% of the zirconia and the stabilizer. .. With this content, the phase transition to monoclinic crystals can be suppressed and the transparency of the zirconia sintered body can be enhanced.
  • the content of calcium oxide is preferably 2 to 15 mol%, more preferably 2.1 to 12 mol%, based on a total of 100 mol% of zirconia and the stabilizer.
  • magnesium oxide When magnesium oxide is contained as a stabilizer, the content of magnesium oxide is preferably 2 to 12 mol%, more preferably 2.1 to 10 mol%, based on a total of 100 mol% of zirconia and the stabilizer.
  • cerium oxide When cerium oxide is contained as a stabilizer, the content of cerium oxide is preferably 2 to 18 mol%, more preferably 2.1 to 12 mol%, based on a total of 100 mol% of zirconia and the stabilizer.
  • the content of scandium oxide is preferably 0.1 to 1 mol%, preferably 0.1 to 0.3 mol%, based on a total of 100 mol% of zirconia and the stabilizer. More preferred.
  • the content of niobium oxide is preferably 0.1 to 10 mol%, more preferably 0.1 to 7 mol%, based on a total of 100 mol% of zirconia and the stabilizer. ..
  • the content of lanthanum oxide is preferably 1 to 10 mol%, more preferably 2 to 7 mol%, based on a total of 100 mol% of zirconia and the stabilizer.
  • the content of erbium oxide is preferably 0.1 to 1 mol%, preferably 0.1 to 0.3 mol%, based on a total of 100 mol% of zirconia and the stabilizer. More preferred.
  • the content of praseodymium oxide is preferably 0.1 to 1 mol%, preferably 0.1 to 0.3 mol%, based on a total of 100 mol% of zirconia and the stabilizer. More preferred.
  • the content of samarium oxide is preferably 0.1 to 1 mol%, preferably 0.1 to 0.3 mol%, based on a total of 100 mol% of zirconia and the stabilizer. More preferred.
  • the content of europium oxide is preferably 0.1 to 1 mol%, preferably 0.1 to 0.3 mol%, based on a total of 100 mol% of zirconia and the stabilizer. More preferred.
  • the content of thulium oxide is preferably 0.1 to 1 mol%, preferably 0.1 to 0.3 mol%, based on a total of 100 mol% of zirconia and the stabilizer. More preferable.
  • the content of the stabilizer in the zirconia 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 unfired zirconia molded article in the present invention preferably contains a colorant in order to imitate the color tone of natural teeth.
  • the colorant preferably contains an oxide.
  • the oxide for example, known pigments (inorganic pigments, composite pigments, fluorescent pigments, etc.) used for dental applications can be used.
  • the inorganic pigment include oxides such as nickel oxide, red iron oxide, chromium oxide, aluminum oxide, and titanium oxide.
  • the composite pigment include (Zr, V) O 2 , Fe (Fe, Cr) 2 O 4 , (Ni, Co, Fe) (Fe, Cr) 2 O 4 and ZrSiO 4 , (Co, Zn). ) Oxides such as Al 2 O 4 can be mentioned.
  • the fluorescent pigment examples include Y 2 SiO 5 : Ce, Y 2 SiO 5 : Tb, (Y, Gd, Eu) BO 3 , Y 2 O 3 : Eu, YAG: Ce, ZnGa 2 O 4 : Zn, BaMgAl. 10 O 17 : Oxides such as Eu can be mentioned.
  • the content of the oxide in the unfired zirconia molded product may be 0% by mass (excluding the oxide) as described above, but when the oxide is contained, 10.0 from the viewpoint of aesthetics. It is preferably mass% or less. More specifically, it is preferably 0.0001 to 10.0% by mass, more preferably 0.001 to 9.0% by mass, and further preferably 0.1 to 8.0% by mass. preferable.
  • the unfired zirconia molded product in the present invention can be produced by press-molding zirconia (preferably zirconia powder) as in step (1).
  • a method for press-molding the zirconia raw material a known method is used without limitation, and may include, for example, a uniaxial press molding step and / or a cold isotropic pressurization (CIP) step.
  • a uniaxial press forming step a method in which zirconia is filled in a pressing die (die) having a desired size and pressed by a uniaxial press using an upper punch and a lower punch is preferable.
  • the press pressure at this time is appropriately set to an optimum value in consideration of the size of the target molded product, the particle size of zirconia, and the like, and is usually 10 MPa or more.
  • the press pressure is low, the zirconia particles are not densely filled and the gaps between the zirconia particles are not sufficiently narrowed, so that the content of the zirconia particles per unit volume cannot be increased in the obtained mill blank.
  • the press pressure in the uniaxial press is usually 200 MPa or less, which is preferable.
  • the press time can be appropriately set according to the press pressure, but is usually 1 to 120 minutes.
  • CIP molding can usually apply a higher press pressure than a uniaxial press, and pressure can be evenly applied to the molded body from the three-dimensional direction. Therefore, by performing CIP molding, the inside of the molded body is preferred.
  • a mill blank having an extremely high content of zirconia particles can be obtained by eliminating the fine voids or the unevenness of the aggregated state of the zirconia particles and further increasing the compression density of the zirconia particles.
  • CIP molding when press molding with a uniaxial press, the CIP treatment can be performed after the press-molded body is left as it is or in a vacuum state.
  • a CIP device "Dr. CHEF” manufactured by Kobe Steel, Ltd. which can pressurize to about 980 MPa, can be used.
  • zirconia is filled in a highly elastic container such as silicone rubber or polyisoprene rubber without going through the process of uniaxial pressing with a die, and this is left as it is or in a vacuum state.
  • a press-molded product can also be obtained by performing CIP treatment after that. It is preferable that the pressing force during CIP molding is also high.
  • the pressing force during CIP molding is preferably high regardless of the presence or absence of a uniaxial press, but in consideration of productivity, for example, when performing a uniaxial press, it is preferably 30 MPa or more, more preferably 50 MPa or more, still more preferable. Is 100 MPa or more, preferably 500 MPa or less, more preferably 400 MPa or less, still more preferably 300 MPa or less. Further, 30 to 500 MPa is preferable, 50 to 400 MPa is more preferable, and 100 to 300 MPa is further preferable.
  • the CIP treatment When the CIP treatment is performed without performing the uniaxial press, it is preferably 30 MPa or more, more preferably 50 MPa or more, further preferably 100 MPa or more, preferably 1000 MPa or less, more preferably 800 MPa or less, still more preferably 700 MPa or less. Is within the range of.
  • the pressing force during CIP molding is preferably 30 to 1000 MPa, more preferably 50 to 800 MPa, and even more preferably 100 to 700 MPa.
  • the CIP molding time can be appropriately set according to the press pressure, but is usually 1 to 120 minutes.
  • step (1) two or more different types of zirconia powder may be stacked and press-molded, and the following methods can be mentioned.
  • a die for a uniaxial press fitted with a lower punch is filled with the first zirconia powder, and the upper punch is set in the die to press the powder.
  • the upper punch is removed, the second zirconia powder is filled on the pressed first zirconia powder agglomerate, the upper punch is set again, and the second zirconia powder is pressed.
  • the press-molded product it is possible to obtain a press-molded product in which the first zirconia particles and the second zirconia particles are layered.
  • the press pressure at the time of press molding is appropriately set to an optimum value in consideration of the type of zirconia particles used, the amount of the colorant contained, and the like, and the press pressure in each layer may be different or the same. Also, after filling the mold with the first zirconia powder, the surface is flattened and the second zirconia powder is filled on it without pressing, and the first zirconia powder and the second zirconia powder are filled. Zirconia powder can also be pressed together.
  • the size of the unfired zirconia molded product (and the unfired zirconia composite) in the present invention is not particularly limited because it can be processed into a dental mill blank having each shape described later.
  • the unfired zirconia molded product in the present invention may be a molded product obtained by press-molding the zirconia raw materials at once, or may be formed as a single molded product by laminating separately molded products and then press-molding. A single molded product may be formed by newly press-molding a zirconia raw material on a separately molded molded product.
  • the unfired zirconia molded product obtained in the step (1) is impregnated with a composition containing a thermoplastic resin, a curable resin, a polymerizable monomer or a polymerizable monomer, which will be described later (further, if necessary).
  • a composition containing a thermoplastic resin, a curable resin, a polymerizable monomer or a polymerizable monomer which will be described later (further, if necessary).
  • the resin penetrates into the gaps between the primary powder particles, and as a result, a composite having a structure in which the zirconia particles are extremely densely dispersed in the resin is obtained. Therefore, in the present invention, it is preferable to use the zirconia raw material as it is press-molded. That is, it is not preferable to obtain a porous body which is sintered and communicated as in Patent Document 1, and a molded body which is a highly densely packed body of zirconia powder is preferable.
  • the resin is infiltrated into the above-mentioned unfired zirconia molded product.
  • the resin is not limited as long as the effects of the present invention are exhibited, but is preferably a curable resin, a cured product or polymer of the curable resin, or a thermoplastic resin. Contaminated water or oil containing an inhibitory component that causes a decrease in the aesthetics and strength of the finished product after sintering (for example, a dental prosthesis such as a crown) due to the permeation of the resin into the unfired zirconia molded product. Furthermore, since it is possible to suppress the peeling of zirconia particles during processing during processing of the fine structure portion, the processing reproduction performance can be improved.
  • the thermoplastic resin includes low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polyethylene (PE) such as high-density polyethylene (HDPE), and a copolymer of ethylene and vinyl acetate.
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • PE polyethylene
  • HDPE high-density polyethylene
  • Polyethylene-based copolymer polyolefin-based resin such as polypropylene (PP); vinyl-based resin such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA); polystyrene (PS), acryliconitrile / styrene Polystyrene-based resin such as polymer (AS) and acrylonitrile-butadiene-styrene copolymer (ABS); acrylic resin such as polymethylmethacrylate (PMMA) and methacrylic-styrene copolymer (MS); polybutylene terephthalate (PBT) ), Polyethylene terephthalate (PET) and other polyester-based resins.
  • PP polypropylene
  • PVDC polyvinylidene chloride
  • PVA polyvinyl alcohol
  • PS polystyrene
  • PS acryliconitrile / styrene
  • AS polymer
  • ABS acryl
  • the curable resin includes epoxy resin (EP), phenol resin (PF), unsaturated polyester resin (UP), urea resin (UF), melamine resin (MF), diallyl phthalate resin (PDAP), and vinyl ester resin.
  • EP epoxy resin
  • PF phenol resin
  • UP unsaturated polyester resin
  • UF urea resin
  • MF melamine resin
  • PDAP diallyl phthalate resin
  • vinyl ester resin vinyl ester resin
  • Polyimide polyurethane
  • PU polyurethane
  • SI silicone resin
  • the cured product is placed in a crucible and heated in an electric furnace at a temperature of 575 ° C. for a predetermined time to incinerate the organic resin component, and the remaining zirconia remains. It can be calculated by measuring the mass of.
  • the applied surface-treating agent is calculated as an incinerated organic resin component.
  • the unfired zirconia molded product contains a curable resin, a polymerizable monomer, or a polymerizable monomer in the step (2).
  • the composition (hereinafter, the composition containing the polymerizable monomer and the polymerizable monomer may be collectively referred to as “polymerizable monomer-containing composition”) is infiltrated, and then the curable property is allowed. It is preferable to include the step (3) of curing the resin or the polymerizable monomer.
  • polymerizable monomer used in the present invention known polymerizable monomers used for dental composite resins and the like can be used without any limitation, but in general, radical polymerizable monomers are preferably used. ..
  • Specific examples of the radically polymerizable monomer include esters such as ⁇ -cyanoacrylic acid, (meth) acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid. Examples thereof include (meth) acrylamide, (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like.
  • (meth) acrylic acid ester and (meth) acrylamide derivative are preferable, and (meth) acrylic acid ester is more preferable.
  • the notation "(meth) acrylic” is used in the meaning which includes both methacrylic and acrylic. Examples of the (meth) acrylic acid ester-based and (meth) acrylamide derivative-based polymerizable monomers in the present invention are shown below.
  • Trifunctional or higher (meth) acrylate Trimethylolpropane Tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, N, N'-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propan-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2 , 2,6,6-tetraacryloyloxymethyl-4-oxaheptane and the like.
  • each of the above-mentioned polymerizable monomers may be used alone or in combination of two or more.
  • the polymerizable monomer used in the present invention is preferably in a liquid state, but it does not necessarily have to be in a liquid state at room temperature, and is a step of bringing the polymerizable monomer into contact with a press-molded body made of powder. It does not matter if it is a liquid in the environment. Further, even a solid polymerizable monomer can be mixed and dissolved with other liquid polymerizable monomers before use.
  • the viscosity range (25 ° C.) of the polymerizable monomer is preferably 10 Pa ⁇ s or less, more preferably 5 Pa ⁇ s or less, still more preferably 2 Pa ⁇ s or less, but two or more kinds of polymerizable monomers are mixed.
  • the individual polymerizable monomers need not be in the viscosity range, and in the state of the composition used by mixing and dissolving, it may be in the viscosity range. preferable.
  • the content of the polymerizable monomer with respect to the uncalcined zirconia molded product can be appropriately adjusted depending on the degree of contact of the polymerizable monomer-containing composition. Further, in the unfired zirconia composite of the present invention, the content of zirconia varies depending on the average particle size of the zirconia particles constituting the unfired zirconia molded product or the press molding method, so that the content of the polymerizable monomer is unconditional. Is not decided.
  • the polymer is permeated by polymerizing and curing the polymerizable monomer that has permeated into the gap inside the unfired zirconia molded body. Therefore, the polymerizable monomer-containing composition may contain a polymerization initiator in order to facilitate polymerization curing.
  • the polymerization initiator can be selected from the polymerization initiators used in the general industry, and among them, the polymerization initiator used for dental applications is preferably used, and the polymerization initiators for heat polymerization, photopolymerization and chemical polymerization are used. One type is preferably used alone or two or more types are appropriately combined.
  • heat polymerization initiator examples include organic peroxides and azo compounds.
  • organic peroxide used as the above-mentioned heat polymerization initiator examples include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate and the like.
  • hydroperoxide used as the heat polymerization initiator examples include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzenehydroperoxide, cumene hydroperoxide, t-butylhydroperoxide and 1,1,3,3-. Examples thereof include tetramethylbutylhydroperoxide.
  • diacyl peroxide used as the heat polymerization initiator examples include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoy peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. Can be mentioned.
  • dialkyl peroxide used as the heat polymerization initiator examples include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like.
  • dialkyl peroxide examples include 1,3-bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexine.
  • Examples of the peroxyketal used as the heat polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and 2,2. Examples thereof include -bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane and 4,4-bis (t-butylperoxy) balleric acid-n-butyl ester.
  • peroxy ester used as the heat polymerization initiator examples include ⁇ -cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, and 2,2,4-trimethylpentylperoxy-2.
  • peroxydicarbonate used as the heat polymerization initiator examples include di-3-methoxyperoxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and diisopropylperoxydicarbonate. , Di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, diallyl peroxydicarbonate and the like.
  • diacyl peroxide is preferably used from the viewpoint of overall balance of safety, storage stability and radical generation ability, and among them, benzoyl peroxide is more preferably used.
  • azo compound used as the heat polymerization initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and 4,4'-azobis (4-). Cyanovaleric acid), 1,1-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobis (isobutyrate), 2,2'-azobis (2-amidinopropane) dihydrochloride and the like.
  • photopolymerization initiator examples include (bis) acylphosphine oxides, ⁇ -diketones, coumarins and the like.
  • the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6.
  • bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6-dichlorobenzoyl)-.
  • Examples of coumarins used as the photopolymerization initiator are 3,3'-carbonylbis (7-diethylamino kumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoyl coumarin, 3-benzoyl-5.
  • 3,3'-carbonylbis (7-diethylaminocoumarin) and 3,3'-carbonylbis (7-dibutylaminocoumarin) are preferable.
  • At least one selected from the group consisting of (bis) acylphosphine oxides, ⁇ -diketones, and coumarins widely used in dental curable compositions should be used. Is preferable.
  • Such a photopolymerization initiator may be able to efficiently carry out photopolymerization in a shorter time by further adding a polymerization accelerator, if necessary.
  • Examples of the polymerization accelerator suitable for the photopolymerization initiator mainly include tertiary amines, aldehydes, compounds having a thiol group, sulfinic acid and salts thereof.
  • tertiary amines include, for example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N- Dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-Hydroxyethyl) -p-toluidine, N
  • aldehydes include dimethylaminobenzaldehyde, terephthalaldehyde and the like.
  • examples of compounds having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, thiobenzoic acid and the like.
  • sulfinic acid and salts thereof include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, p-toluenesulfinic acid, sodium p-toluenesulfinate, and p-toluene.
  • Sulfinic acid calcium p-toluenesulfinate, lithium p-toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfinate Potassium acid, calcium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, Potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, 2, , 4,6-Triisopropylbenzenesulfinate potassium, 2,4,6-triisopropyl
  • the chemical polymerization initiator a combination of an organic peroxide and a polymerization accelerator is preferably used.
  • the organic peroxide used as the chemical polymerization initiator is not particularly limited, and known ones can be used. Specific examples thereof include organic peroxides exemplified by the heat polymerization initiator.
  • diacyl peroxide is preferably used from the viewpoint of overall balance of safety, storage stability and radical generation ability, and among them, benzoyl peroxide is more preferably used.
  • the polymerization accelerator used as the chemical polymerization initiator can be selected from the polymerization accelerators used in the general industry, and among them, the polymerization accelerator used for dental applications is preferably used. In addition, the polymerization accelerator is used alone or in combination of two or more.
  • polymerization accelerator for the chemical polymerization initiator examples include amines, sulfinic acid and salts thereof, copper compounds, tin compounds and the like.
  • Mines used as polymerization accelerators are divided into aliphatic amines and aromatic amines.
  • the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethylmethacrylate, N-methyldiethanolaminedimethacrylate, N-ethyldiethanolaminedimethacrylate, triethanolamine monomethacrylate , Triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine and other tertiary aliphatic
  • aromatic amine examples include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-Hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropylaniline, N, N-bis (2-hydroxyethyl) -3, 5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-die
  • Examples of sulfinic acid and salts thereof used as a polymerization accelerator include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, and the like.
  • the copper compound used as the polymerization accelerator for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.
  • tin compound used as the polymerization accelerator examples include di-n-butyl tin dilaurate, di-n-octyl tin dimarate, di-n-octyl tin dilaurate, di-n-butyl tin dilaurate and the like.
  • suitable tin compounds are di-n-octyl tin dilaurate and di-n-butyl tin dilaurate.
  • a photopolymerization initiator and a heat polymerization initiator can also be used in combination.
  • a combination of (bis) acylphosphine oxides and diacyl peroxide is more preferable.
  • the content of the polymerization initiator in the polymerizable monomer-containing composition is not particularly limited, but from the viewpoint of curability and the like of the obtained composition, the polymerization initiator is added to 100 parts by mass of the polymerizable monomer. It is preferably contained in an amount of 0.001 to 30 parts by mass. When the content of the polymerization initiator is 0.001 part by mass or more, there is no possibility that the polymerization will proceed sufficiently and the mechanical strength will be lowered, and more preferably 0.05 part by mass or more, still more preferably 0. . 1 part by mass or more.
  • the content of the polymerization initiator is 30 parts by mass or less, sufficient mechanical strength can be obtained even when the polymerization performance of the polymerization initiator itself is low, and there is no possibility of causing precipitation from the composition.
  • the curable resin or polymerizable monomer-containing composition used in the present invention contains a pH adjuster, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, and a colorant (inorganic pigment), depending on the purpose.
  • a colorant inorganic pigment
  • antibacterial agents X-ray contrast agents, thickeners, and the like can be further added.
  • the colorant include those described as the colorant contained in the unfired zirconia molded product.
  • the method of infiltrating the curable resin or the polymerizable monomer-containing composition into the unfired zirconia molded product is that the curable resin or the polymerizable monomer-containing composition is formed in the gaps between the zirconia particles in the unfired zirconia molded product.
  • a simple and preferable method is to immerse the molded product in a curable resin or a composition containing a polymerizable monomer. By immersing, the curable resin or the polymerizable monomer can gradually permeate into the molded product (aggregate) due to the capillary phenomenon.
  • placing the surrounding environment in a reduced pressure atmosphere is a preferable means because it promotes the permeation of the liquid monomer.
  • repeating the operation of returning to normal pressure (decompression / normal pressure operation) a plurality of times after the depressurization operation shortens the time of the step of completely permeating the curable resin or the polymerizable monomer into the molded product. It is effective for.
  • the degree of decompression at this time is appropriately selected in consideration of the viscosity of the monomer or the particle size of the zirconia particles constituting the uncalcined zirconia molded product, but is usually 100 hPa (10 kPa) or less, preferably 50 to 0.
  • a method of feeding the curable resin or the polymerizable monomer-containing composition into the molded product in the mold by applying pressure as it is in the state of being press-molded by the mold can be considered. .. If this method is adopted, the subsequent curing step can be continuously performed in the mold as it is.
  • the pressurizing condition is preferably 2 MPa or more, more preferably 10 MPa or more, still more preferably 20 MPa or more.
  • an unfired zirconia composite in which the curable resin or the polymerizable monomer has apparently penetrated is used.
  • the pressurizing condition is preferably 20 MPa or more, more preferably 50 MPa or more, still more preferably 100 MPa or more. Further, it is more preferable to repeat the pressurization / normal pressure by releasing the pressurization, returning to the normal pressure, and pressurizing again.
  • the viscosity of the curable resin or the composition containing a polymerizable monomer affects the permeation rate into the unfired zirconia molded product, and usually, the lower the viscosity, the faster the permeation.
  • the preferable viscosity range (25 ° C.) is 10 Pa ⁇ s or less, more preferably 5 Pa ⁇ s or less, still more preferably 2 Pa ⁇ s or less, but the selection of the curable resin or the polymerizable monomer is not limited to the viscosity, but also mechanical. It is necessary to take into consideration the target strength or the refractive index.
  • a curable resin or a composition containing a polymerizable monomer may be diluted with a solvent and used, and the solvent may be distilled off by a subsequent decompression operation.
  • the curable resin or polymerizable monomer-containing composition is formed by raising the temperature to preferably 25 ° C. or higher, more preferably 30 ° C. or higher, preferably 70 ° C. or lower, and more preferably 60 ° C. or lower. It is also possible to reduce the viscosity of the material to accelerate its penetration.
  • the time for the curable resin or the composition containing the polymerizable monomer to permeate the unfired zirconia molded product is not unconditionally determined by the type of zirconia, the size of the molded product, the degree of permeation of the monomer, the contact method, and the like. , Can be adjusted as appropriate. For example, in the case of permeation by immersion, it is usually 1 to 120 hours, in the case of immersion under reduced pressure, it is usually 0.5 to 12 hours, and in the case of contact under pressure, it is usually 0.2 to 6 hours. It's time.
  • the curable resin or the polymerizable monomer is cured in a state where the curable resin or the polymerizable monomer has penetrated into the unfired zirconia molded product. ..
  • a curable resin When a curable resin is used, it can be softened and fluidized by heating and cured by a cross-linking reaction, or it can be cured by adding a curing accelerator, and when a polymerizable monomer-containing composition is used, it is heated. It can be carried out by polymerization, photopolymerization, or chemical polymerization, and the conditions can be carried out according to a known method. Among them, in the present invention, it is preferable to carry out heat polymerization from the viewpoint of increasing the polymerization rate of the polymerizable monomer to obtain a dental mill blank having higher mechanical strength.
  • the photopolymerization in the present invention may be carried out not only with visible light but also with UV light.
  • step (3) it may be cured under atmospheric pressure, it may be cured in a vacuum state, or it may be cured under a pressure of 50 MPa or more.
  • the press-molded product impregnated with the polymerizable monomer is polymerized in an inert atmosphere such as nitrogen gas or in a reduced pressure environment at the time of polymerization curing.
  • the polymerization rate can be increased and the mechanical strength can be further increased.
  • it is preferable from the viewpoint of productivity that the molded product impregnated with the polymerizable monomer is packed in a vacuum pack or the like and put into a vacuum state to perform the polymerization operation.
  • pressure-heating polymerization can also be performed using an autoclave or the like.
  • the polymerization curing can be performed while the unfired zirconia molded product in which the polymerizable monomer has permeated is under pressure.
  • pressure polymerization is one of the more preferable polymerization curing methods in the present invention. That is, by placing the unfired zirconia molded product impregnated with the polymerizable monomer under pressure conditions together with the polymerizable monomer, the polymerizable monomer can further penetrate into the minute gaps in the molded product. It can be formed or the residual minute bubbles can be eliminated. By polymerizing under pressurized conditions, the mechanical strength can be further increased.
  • Such conditions are preferably 20 MPa or more, more preferably 50 MPa or more, still more preferably 100 MPa or more.
  • a pressurizing device an autoclave, a CIP device, and a HIP (hot isotropic pressurizing) device are used.
  • a CIP device "Dr. CHEF" capable of pressurizing to about 980 MPa of Kobe Steel, Ltd. is also known.
  • heat polymerization which polymerizes by raising the temperature under pressurized conditions, it is also possible to polymerize by photopolymerization or chemical polymerization.
  • a more preferable pressure polymerization method there is a method in which a molded product impregnated with a polymerizable monomer is sealed in a plastic bag, a rubber tube or the like with a vacuum pack, and polymerized while being pressurized using a CIP device or the like.
  • the higher the pressure at this time the more preferable it is, preferably 50 MPa or more, and more preferably 200 MPa or more.
  • a method in which a molded product impregnated with a polymerizable monomer is sealed, placed in a CIP treatment chamber, a predetermined pressure is applied, and then the treatment chamber is heated to start polymerization under high pressure is mechanical. This is a more preferable polymerization method for increasing the strength.
  • the temperature is raised over a period of about 30 minutes to 24 hours, and the reached temperature is preferably 80 to 180 ° C.
  • the polymerization time and the ultimate temperature are set in consideration of the decomposition temperature of the polymerization initiator blended in the polymerizable monomer.
  • the polymerization temperature (reached temperature) may be, for example, 60 to 190 ° C.
  • the curing conditions can be set in the same manner as the conditions relating to the polymerizable monomer-containing composition.
  • the stress strain generated inside the cured product can be alleviated and damage during the cutting process of the dental prosthesis can be suppressed.
  • the resin constituting the unfired zirconia composite is a thermoplastic resin
  • the third component that can be added to the thermoplastic resin, the method of permeating into the uncalcined zirconia molded product, and the conditions for permeating are the same as when the above-mentioned polymerizable monomer is used.
  • a curable resin or a polymerizable monomer-containing composition is impregnated into an unfired zirconia molded product obtained by press-molding a zirconia raw material.
  • the curable resin or the polymerizable monomer is cured, or the unfired zirconia molded product is impregnated with the molten thermoplastic resin.
  • zirconia preferably zirconia powder
  • Such a molded product is, for example, one in which individual zirconia is closely packed.
  • the curable resin, the polymerizable monomer-containing composition, or the molten thermoplastic resin is impregnated into the molded product.
  • the curable resin, the polymerizable monomer-containing composition or the thermoplastic resin is impregnated into the gaps between the primary particles of zirconia constituting the molded product.
  • the content of zirconia in the unfired zirconia composite of the present invention varies depending on the particle size or shape of the zirconia powder used, but even if a zirconia powder having a small particle size is used, it is usually 60% by mass or more. It is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 82% by mass or more, particularly preferably 85% by mass or more, preferably 96% by mass or less, and more preferably 95% by mass or less.
  • the content of zirconia in the uncalcined zirconia composite of the present invention is preferably 60 to 96% by mass, more preferably 70 to 96% by mass, still more preferably 80 to 95% by mass, and particularly preferably 85 to 95% by mass. %.
  • the zirconia content can be measured by the strong heat residue of the uncalcined zirconia composite (cured product).
  • the polished smooth surface of the unfired zirconia composite of the present invention is observed under a microscope, it is possible to observe how the zirconia particles are packed extremely precisely. It is also possible to indirectly estimate the zirconia content by analyzing such a microscopic observation image by image processing and calculating the areas of the zirconia portion and the resin matrix portion.
  • image processing system for example, image analysis software (National Institutes of Health, Image J) can be used.
  • the average particle size of zirconia in the unfired zirconia composite of the present invention is preferably 0.001 to 10 ⁇ m, more preferably 0.005 to 5 ⁇ m, and further preferably 0.01 to 1 ⁇ m from the viewpoint of moldability and sinterability. preferable.
  • the particle size range of zirconia in the unfired zirconia composite of the present invention is preferably 0.0005 to 50 ⁇ m, more preferably 0.0005 to 10 ⁇ m, and preferably 0.0005 to 5 ⁇ m. More preferred.
  • the average particle size of zirconia means the particle size (average primary particle size) of the primary particles of zirconia particles.
  • the particle size range is a particle size range in which 95% or more of the particles of the population used for measurement are satisfied, and particles that do not satisfy the specified particle size range are unintentional. Even if it is contained, it is not particularly limited as long as it does not impair the effect of the present invention.
  • the method for measuring the average particle size and the particle size range can be obtained by the laser diffraction / scattering method.
  • the laser diffraction / scattering method can be specifically measured by using, for example, a laser diffraction type particle size distribution measuring device (SALD-2300: manufactured by Shimadzu Corporation) using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium. ..
  • the unfired zirconia composite of the present invention preferably has biaxial bending strength and Vickers hardness satisfying a specific range.
  • the biaxial bending strength is preferably 20 to 140 MPa, more preferably 40 to 90 MPa, and further preferably 50 to 80 MPa from the viewpoint of being more excellent in machinability and free-cutting property.
  • the Vickers hardness is preferably 5 to 140 Hv, more preferably 10 to 120 Hv, and even more preferably 20 to 100 Hv.
  • the fracture load is preferably 35 to 100 N, more preferably 40 to 95 N, and further preferably 45 to 90 N from the viewpoint of fine part reproducibility. preferable.
  • the material has physical properties such as strength that can withstand machining such as cutting, even though it does not undergo a general calcining process, and cracks or chipping during machining such as cutting. It is composed of an unfired zirconia molded product and a resin, and the resin is permeated into the unfired zirconia molded product, and the biaxial bending strength is 50 to 80 MPa, and the Vickers hardness is high. An uncalcined zirconia complex having a value of 80 to 120 Hv can be mentioned. Further, as the unfired zirconia composite in the preferred embodiment, it is particularly preferable that the unfired zirconia molded product contains 2 to 8 mol% of yttria. The details of the method for measuring the biaxial bending strength, Vickers hardness, and breaking load will be described in Examples described later.
  • a dental mill blank made of the unfired zirconia composite of the present invention is a dental mill blank made of the unfired zirconia composite of the present invention.
  • the unfired zirconia composite of the present invention can be suitably used for dental mill blanks.
  • the obtained dental mill blank is cut, cut, and surface-polished to a desired size as needed, and then shipped as a product.
  • the dental mill blank of the present invention has a high content of zirconia in the cured product, and although it does not undergo a general calcining step (more than 800 ° C and 1200 ° C or less), it is conventional general calcining. It will be about the same as the processing strength achieved by the dental mill blank that has undergone the process.
  • the unfired zirconia composite and the dental mill blank of the present invention preferably have a surface contact angle of 35 ° or more, preferably 35 to 100 °, in the Young-Laplace method. More preferably, it is more preferably 40 to 80 °.
  • the unfired zirconia composite and the dental mill blank of the present invention can satisfy the above range with respect to the contact angle of the surface.
  • the conventional zirconia calcined body or its processed body has fine pores inside, and the surface of the molded body itself is made hydrophilic by the action of the capillary phenomenon caused by the pores.
  • the pores are closed with a resin and the surface of the molded product or its processed product is coated to make it hydrophobic. Therefore, by having the structural characteristics, hydrophobicity can be imparted to the surfaces of the calcined zirconia composite and the dental mill blank regardless of the type of the permeated resin. Since the surfaces of the unfired zirconia composite and the dental mill blank of the present invention are hydrophobic, they are not affected by the coolant even in the wet processing using the coolant, and can be suitably used for the wet processing. The details of the method for measuring the contact angle will be described in Examples described later.
  • the size of the dental mill blank of the present invention is preferably processed to an appropriate size so that it can be set in a commercially available dental CAD / CAM system.
  • preferred sizes include, for example, a 40 mm ⁇ 20 mm ⁇ 15 mm prism suitable for producing a single tooth missing bridge, a 17 mm ⁇ 10 mm ⁇ 10 mm prism suitable for producing an inlay or onlay, and a full crown suitable for producing.
  • Examples thereof include a 14 mm ⁇ 18 mm ⁇ 20 mm prismatic shape, a long span bridge or a disk shape having a diameter of 100 mm and a thickness of 10 to 28 mm suitable for producing a denture base, but the size is not limited to these.
  • the method for producing a dental prosthesis of the present invention includes a step (I) of processing the dental mill blank of the present invention and a step (II) of sintering an unbaked dental prosthesis.
  • the sintering step (II) includes a step of degreasing the unfired dental prosthesis (burning the resin) and a step of firing the unfired dental prosthesis, and the unfired dental prosthesis is heated at a temperature of 800 ° C. or lower. It is preferable to degreas. The heating rate, mooring time, etc.
  • the degreasing step may be included in the heating step for raising the temperature from room temperature to the maximum temperature of firing, for example.
  • a general dental porcelain firing furnace can be used.
  • the dental porcelain firing furnace a commercially available product may be used. Examples of commercially available products include "Noritake Katana (registered trademark) F-1N" and “Noritake Katana (registered trademark) F-2" (above, SK Medical Electronics Co., Ltd.).
  • the mooring time held in the dental porcelain firing furnace is preferably 1 to 140 minutes.
  • the temperature at the time of sintering is preferably a maximum temperature of 1400 to 1600 ° C.
  • Dental prostheses manufactured from the dental mill blank of the present invention include, for example, crown restorations such as inlays, onlays, veneers, crowns and bridges, as well as abutment teeth, dental posts, dentures and denture bases. Implant members (fixtures, abutments) and the like can be mentioned. Further, the cutting process is preferably performed using, for example, a commercially available dental CAD / CAM system, and examples of such a CAD / CAM system include a CEREC system manufactured by DENTSPLY-Sirona Co., Ltd. and "Kuraray Noritake Dental Co., Ltd.” "Katana (registered trademark) system" can be mentioned.
  • the mill blank obtained in the present invention can be used for applications other than dental applications, for example, electronic material applications such as encapsulation materials and laminated plate molding materials, general-purpose composite material members, for example. It can also be used as a part for construction, electrical appliances, household goods, and toys.
  • the zirconia powder used in Examples and Comparative Examples described later was prepared as follows. Using zirconia powder and yttria powder, a mixture was prepared so that the yttria content was 6 mol%. Next, this mixture was added to water to prepare a slurry, which was then wet pulverized and mixed with a ball mill until the average particle size became 0.13 ⁇ m (particle size range: 0.110 ⁇ m to 0.133 ⁇ m). The pulverized slurry was dried with a spray dryer, and the obtained powder was calcined at 950 ° C. for 2 hours to prepare a primary powder.
  • the average particle size and particle size range can be measured by using a laser diffraction type particle size distribution measuring device (SALD-2300: manufactured by Shimadzu Corporation) using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium. it can.
  • SALD-2300 manufactured by Shimadzu Corporation
  • Polymerizable monomer 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (UDMA) ("HTM” manufactured by Kyoeisha Chemical Co., Ltd.) 2-Hydroxyethyl methacrylate (HEMA) (manufactured by Nippon Shokubai Co., Ltd.) Triethylene glycol dimethacrylate (3G) ("NK ester 3G” manufactured by Shin Nakamura Chemical Industry Co., Ltd.) Polyethylene Glycol # 600 Dimethacrylate (14G) (“NK Ester Polyethylene Glycol Methacrylate 14G” manufactured by Shin Nakamura Chemical Industry Co., Ltd.) Heat polymerization initiator: Benzoyl peroxide (purity 75% diluted with water) (BPO) (NOF CORPORATION "NOF CORPORATION (registered trademark) BW”) Antioxidant: 3,5-Di-t-Butyl-4-hydroxytoluene (BHT)
  • Example 1 Preparation of unfired zirconia molded article, unfired zirconia composite, dental prosthesis] (Example 1) 25.5 g of the 6 mol% yttria-containing zirconia powder obtained in Production Example 1 was filled in a mold having an inner size of 35 mm ⁇ 25 mm, the powder was smoothed by tapping, and then the press pressure was 68.6 MPa and the holding time was 3 minutes. A plate-shaped unfired zirconia molded product having a size of 35 mm ⁇ 25 mm ⁇ 14 mm was obtained.
  • the polymerizable monomer, the heat polymerization initiator, the antioxidant, and the photopolymerization initiator were placed in a beaker so as to have a total amount of 30 g so as to have the composition shown in Table 1, and mixed using a stirrer. Then, a composition containing a polymerizable monomer was prepared. Then, the uncalcined zirconia molded product was immersed in 15 g of the polymerizable monomer-containing composition, allowed to stand in a dark place at room temperature for 24 hours, and then the polymerizable monomer-containing composition adhering to the outside of the molded product was wiped off. , A molded product in which the polymerizable monomer-containing composition was infiltrated was obtained.
  • the obtained molded product was heat-treated at 80 ° C. for 120 minutes and 110 ° C. for 20 minutes under atmospheric pressure with a hot air dryer to obtain a target unfired zirconia composite.
  • the unfired zirconia composite was dry-cut using a commercially available CAD / CAM system "CEREC MC XL" (manufactured by DENTSPLY-Sirona Co., Ltd.), it was possible to visually confirm that there were no cracks or chipping, and the upper jaw.
  • the first molar crown could be made.
  • the produced crown was heated from room temperature using "Noritake Katana (registered trademark) F-1N" (SK Medical Electronics Co., Ltd.), sintered at a maximum temperature of 1550 ° C. and a mooring time of 90 minutes, and then dental prosthesis. I was able to get things.
  • Example 2 An unfired zirconia composite and a dental prosthesis without cracks and chipping were produced in the same manner as in Example 1 except that the polymerizable monomer-containing composition was changed to the composition as shown in Table 1. I was able to get.
  • Example 5 After uniaxial pressing, CIP treatment was performed under the conditions of 170 MPa and a holding time of 1 minute to obtain an unfired zirconia molded product, which was produced in the same manner as in Example 1 to obtain an unfired zirconia composite and cracks. And a dental prosthesis without chipping could be obtained.
  • Example 1 The unbaked zirconia molded product prepared in the same manner as in Example 5 was not impregnated with the polymerizable monomer-containing composition, and the maxillary first molar was used with a commercially available CAD / CAM system "CEREC MC XL" (manufactured by DENTSPLY-Sirona Co., Ltd.). When a first molar crown was produced, the unfired zirconia molded product cracked inside the device when it came into contact with the processing tool during processing, and a dental prosthesis could not be obtained.
  • All of the unfired zirconia composites of the present invention had a biaxial bending strength of 50 MPa or more and a Vickers hardness of 80 Hv or more.
  • none of the unfired zirconia composites of the present invention was cracked or chipped, and could be cut without any problem.
  • the contact angle was 37.7 ° to 44.5 °, and from the viewpoint of hydrophobicity, the result was that the wet processing was not affected by the cooling water during processing. Therefore, the unfired zirconia composite of the present invention can be suitably used as a dental mill blank.
  • Comparative Example 1 It is an unfired zirconia molded product that has not been impregnated with the polymerizable monomer-containing composition, has a low biaxial bending strength of 12 MPa, and the Vickers hardness cannot be measured because fracture occurred when the indenter was pushed into the sample. The result was that it did not have the strength and hardness that could be machined. The contact angle could not be measured because the ion-exchanged water immediately penetrated into the sample after it was brought into contact with the sample, resulting in the influence of the cooling water in the wet processing.

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Abstract

La présente invention concerne un composite de zircone non cuit et une ébauche de fraisage dentaire, au moyen desquels une prothèse dentaire peut être fabriquée en une seule opération de frittage sans opération de pré-frittage et qui ont une résistance appropriée pour supporter l'usinage. La présente invention concerne : un composite de zircone non cuit composé d'un corps moulé et d'une résine, la résine étant incorporée dans le corps moulé en zircone non cuit; et une ébauche de fraisage dentaire comprenant ledit composite de zircone non cuit.
PCT/JP2020/025176 2019-06-27 2020-06-26 Composite de zircone non cuit et son procédé de production, ébauche de fraisage dentaire et procédé de fabrication de prothèse dentaire WO2020262597A1 (fr)

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JP2019-120094 2019-06-27
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WO2020262597A1 true WO2020262597A1 (fr) 2020-12-30

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CN113101230A (zh) * 2021-03-03 2021-07-13 深圳爱尔创口腔技术有限公司 氧化锆组合物、荧光氧化锆及制备方法和氧化锆牙科制品

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JPS56130402A (en) * 1980-03-18 1981-10-13 Toshiba Corp Production of sintered parts
JP2013053353A (ja) * 2011-09-05 2013-03-21 Toyota Motor Corp 焼結品の製造方法
WO2014021343A1 (fr) * 2012-07-31 2014-02-06 クラレノリタケデンタル株式会社 Procédé pour la fabrication de ciment dentaire blanc broyé
JP2016540772A (ja) * 2013-12-04 2016-12-28 スリーエム イノベイティブ プロパティズ カンパニー 歯科用ミルブランク、その製造方法及び使用

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JPS56130402A (en) * 1980-03-18 1981-10-13 Toshiba Corp Production of sintered parts
JP2013053353A (ja) * 2011-09-05 2013-03-21 Toyota Motor Corp 焼結品の製造方法
WO2014021343A1 (fr) * 2012-07-31 2014-02-06 クラレノリタケデンタル株式会社 Procédé pour la fabrication de ciment dentaire blanc broyé
JP2016540772A (ja) * 2013-12-04 2016-12-28 スリーエム イノベイティブ プロパティズ カンパニー 歯科用ミルブランク、その製造方法及び使用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113101230A (zh) * 2021-03-03 2021-07-13 深圳爱尔创口腔技术有限公司 氧化锆组合物、荧光氧化锆及制备方法和氧化锆牙科制品

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