Composite bulk block for fabricating dental prostheses, its manufacturing method and prostheses manufactured therefrom

Abstract

The present invention provides a composite bulk block for fabricating dental prostheses, which comprises a glass ceramic matrix and a polymer, wherein the glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, the crystalline phase including at least one type of primary crystalline phase selected from the group consisting of a leucite crystalline phase and a lithium disilicate crystalline phase, the glass ceramic matrix having an average particle size of 3 to 10 μm, and the polymer being contained in an amount of 20 to 40 wt % based on the total weight of the bulk block, and which contains zwitterionic groups, a method for manufacturing the same, and a prosthesis manufactured therefrom, which allows for the machining of restorations having excellent mechanical properties and stain resistance.

Description

[Technical Field]

[0001] The present invention relates to a composite bulk block for use in fabricating dental prostheses, which has excellent mechanical strength and can be used to fabricate restorations that exhibit stain resistance, a method for manufacturing the same, and prostheses manufactured from the same. [Background technology]

[0002] As the dental industry develops, traditional prosthetic materials such as porcelain and metal have begun to show problems with their physical properties and dental aesthetics, gradually reducing their market share. To replace these materials, materials such as glass-ceramics and zirconia are increasingly gaining market share. Furthermore, hot-pressing, the traditional method for manufacturing prosthetics, takes a long time to produce, making it difficult to manufacture the one-day prosthetics currently popular in the dental market. This has led to a shift to CAD / CAM systems. Supporting this shift is the emerging utility of 1:1 processing materials, such as glass-ceramics, which can be implanted immediately after processing without additional heat treatment.

[0003] Of course, with the development of zirconia and crystallized glass, many materials that are aesthetically pleasing and have high physical properties are now in use, but in the case of most ceramic materials, they undergo a crystallization heat treatment process after processing, making them difficult to use as one-day prosthetics.

[0004] Additionally, in the case of ceramic materials currently processed in a 1:1 ratio, the processability is low due to the use of ceramic materials that have already undergone crystallization, and there is a problem of cracks appearing at the margins (the boundary between the prosthesis and the tooth).

[0005] To address these issues and meet the current demands of the dental market, composites, which contain both organic and inorganic materials, have been developed. Composites are complementary materials, with the organic material suppressing the brittleness, one of the drawbacks of inorganic materials, while the inorganic material enhances the low strength and other physical properties of organic materials. Furthermore, composites offer the advantage of being able to be processed 1:1, allowing them to be implanted in the mouth immediately after processing. Continuous technological developments are leading to the release of new composite products. Depending on the product currently on the market, composites have a strength of approximately 150-200 MPa and offer superior processability compared to conventional glass ceramics, which can be processed 1:1.

[0006] In relation to such composites, the present inventors have disclosed in Korean Patent No. 10-1682542 a method for manufacturing a dental block, which includes the steps of preparing a glass ceramic, porousifying the glass ceramic to form a ceramic porous body, placing the ceramic porous body in a vacuum chamber and primarily infiltrating a polymer into the ceramic porous body under vacuum conditions, and secondary infiltration of a polymer into the ceramic porous body for a second time before the primarily infiltrated polymer is completely hardened, and which is characterized by achieving a biaxial bending strength of 100 to 150 MPa.

[0007] The glass ceramic used here was a feldspar-based glass ceramic, specifically containing 2.0 to 6.0 wt% N2O, 60.0 to 65.0 wt% SiO2, 8.0 to 15.0 wt% K2O, 0.5 to 3.0 wt% CaO, 0.5 to 2.0 wt% BaO, 0.2 to 1.0 wt% CeO2, 0 to 0.5 wt% TiO2, 16.0 to 19.0 wt% Al2O3 to increase the glass transition temperature and softening point and improve the chemical durability of the glass-ceramics, and 0 to 1.0 wt% of a color-tuning component that affects color tuning such as brightness and saturation and exhibits fluorescence.

[0008] In addition, Patent Document 1: Korean Patent No. 10-1609291, there is a step of crushing glass and then melting it at a temperature of 1,400 to 1,800°C, a step of cooling the melted glass and crushing it, and then subjecting the crushed glass to a crystallization heat treatment at 875 to 970°C, a step of crushing the crystallized glass that has been subjected to the crystallization heat treatment again, and then subjecting the glass to a porous heat treatment at a temperature of 700 to 840°C, and a step of forming a porous body in the porous crystallized glass that has been subjected to the porous heat treatment. and infiltrating the glass melted at a temperature of 1,400 to 1,800°C with a polymer, wherein the glass contains 2.0 to 6.0 wt% N2O, 60 to 65.0 wt% SiO2, 8.0 to 15 wt% K2O, 0.5 to 3.0 wt% CaO, 0.5 to 2.0 wt% BaO, 0.2 to 1.0 wt% CeO2, more than 0.5 wt% TiO2, and 16.0 to 19.0 wt% Al2O3. Specifically, the glass used here is also a feldspar glass, and it is disclosed that the obtained block has a biaxial bending strength of about 100 to 150 MPa.

[0009] Meanwhile, Patent Document 2: Korean Patent No. 10-212202 discloses a method for manufacturing a composite using chemical bonding between inorganic and organic materials using a silane coupling agent. Specifically, the method proposes a method for manufacturing a composite, characterized by including the steps of adding a thermal initiator to a first mixture obtained by mixing at 20 to 70°C at least two types of organic materials having different viscosities; surface-treating the inorganic material with a second mixture obtained by mixing 10 to 14% by weight of an acrylic silane coupling agent in ethanol; mixing the first mixture to which the thermal initiator has been added with the inorganic material that has been surface-treated with the second mixture; and curing the resultant mixture by thermal polymerization at 100 to 150°C.

[0010] In addition, Patent Document 3: Korean Patent No. 10-2228118 proposed a dental composite composition containing crystallized glass and a hardenable organic substance, which can provide a dental composite having an average crystal size of 50 to 400 nm, a biaxial bending strength of 200 to 300 MPa, and a Vickers hardness of 270 to 300 Hv.

[0011] As another example, Patent Document 4 (U.S. Patent No. 7,807,227) discloses a composite material including a porous inorganic-nonmetallic matrix and a second substance, and a manufacturing method thereof. The manufacturing method of the composite material includes the steps of sintering an inorganic-nonmetallic starting material to obtain a sintered porous inorganic-nonmetallic matrix, coating the surface of the porous inorganic-nonmetallic matrix with a coupling agent to obtain a surface-modified product, infiltrating the surface-modified porous inorganic-nonmetallic matrix with an organic material, and solidifying the organic material, for obtaining an isotropic composite material. The isotropic composite material includes a porous inorganic-nonmetallic matrix having a flexural strength of 40 MPa or more as measured in accordance with ISO 6 872, and an organic material at least partially filling the voids of the porous inorganic-nonmetallic matrix. The isotropic composite material has an elastic modulus of 25 GPa or more as measured in accordance with ISO 10 477, and a bending strength of 100 MPa or more as measured in accordance with ISO 6 872.

[0012] Patent Document 5: Japanese Patent No. 4636514 describes a material that can maintain mechanical strength such as abrasion resistance and bending strength, color fastness, color fastness, and aesthetics for a long period of time, and has a high bending modulus (modulus of bending The paper also discloses an inexpensive dental material that is excellent in properties such as elasticity and impact strength, and is also suitable for processing using CAD / CAM systems, as well as a method for producing the same. This method for producing a dental material is comprised of porous ceramics impregnated with resin, and includes the steps of: (a) molding a mixture containing a ceramic powder having an average particle size of 3.0 to 50 μm, which contains a network-forming oxide, an intermediate oxide, and a network-modifying oxide, and a binder into a predetermined shape; (b) firing the molded mixture to obtain a porous ceramic block having interconnected pores; (c) infiltrating the interconnected pores of the porous ceramic block with at least one coupling agent selected from a silane coupling agent, a titanate coupling agent, and a zircoaluminate coupling agent under ultrasonic waves and / or reduced pressure to couple the surfaces of the interconnected pores; and (d) infiltrating the interconnected pores of the coupled-treated porous ceramic block with a monomer and / or oligomer containing at least an ethylenic double bond under ultrasonic waves and / or reduced pressure, followed by polymerization. As a specific example, the ceramic powder here is an aluminosilicate ceramic powder with SiO2 and BO3 as the network-forming oxides, Al2O3 as the intermediate oxide, and Na2O as the network-modifying oxide. By impregnating the interconnected pores of such porous ceramics with resin, the inorganic material filling rate can be increased, allowing for long-term maintenance of abrasion resistance, mechanical strength such as bending strength, discoloration resistance, stain resistance, and aesthetics. Furthermore, stress within the ceramic is alleviated, providing a dental material with excellent bending modulus and impact strength. This is also described as being suitable for CAD / CAM systems.

[0013] Meanwhile, it is known that zwitterionic substances (also called dipolar ionic substances or amphoteric substances) contribute to antifouling effects by blocking the adsorption of proteins and bacteria when used with various dental materials. One example is a dental polymerizable composition described in Patent Document 6 (JP 2007-217516 A) that contains a polymerizable monomer and an aggregate having a zwitterionic group in the side chain. This document demonstrates that the use of an aggregate having a zwitterionic group in the side chain is highly effective in suppressing the adsorption of proteins, plugs, and other substances.

[0014] Furthermore, Patent Document 7 (JP 2014-009219 A) discloses a dental adhesive composition that uses an aggregate having a zwitterionic group in the side chain in combination with water, and describes that such a dental adhesive composition is useful as a dental pretreatment material, adhesive, and adhesive composite resin.

[0015] Another technology disclosed in this publication relates to a dental implant made of titanium or a titanium alloy, which includes a step of removing contaminants adsorbed and stabilized on a titanium oxide film to expose a bioactive superhydrophilic titanium surface, and a method of forming a uniform coating film by applying a mixed solution containing a pH buffer and an organic amphoteric substance having a sulfonic group. The mixed solution contains i) an organic pH buffer and / or an inorganic pH buffer and ii) an organic amphoteric substance having a sulfonic group, on the rough surface that has been pretreated to remove contaminants (Patent Document 8: Korean Patent No. 10-1405859).

[0016] The inventors have been continuously searching for a method that not only realizes the appearance and functionality of teeth in a resin-ceramic composite, but also enables the prosthesis itself to inhibit adhesion of contaminants in the oral cavity, and have already filed a patent application for this (Patent Document 9: Korean Patent Application No. 10-2021-0055575). [Prior art documents] [Patent documents]

[0017] [Patent Document 1] Korean Patent No. 10-1609291 [Patent Document 2] Korean Patent No. 10-212202 [Patent Document 3] Korean Patent No. 10-2228118 [Patent Document 4] U.S. Patent No. 7,807,227 [Patent Document 5] Japanese Patent No. 4636514 [Patent Document 6] Japanese Patent Publication No. 2007-217516 [Patent Document 7] Japanese Patent Publication No. 2014-009219 [Patent Document 8] Korean Patent No. 10-1405859 [Patent Document 9] Korean Patent Application No. 10-2021-0055575 [Patent Document 10] Korean Patent No. 10-1682542 [Patent Document 11] Korean Patent No. 10-2122202 Summary of the Invention [Problem to be solved by the invention]

[0018] The object of the present invention is to provide a composite bulk block for fabricating dental prostheses that has improved mechanical strength and can be used not only for inlays and onlays but also for artificial molar teeth, and that can exhibit the ability to inhibit the adhesion of contaminants in the oral cavity.

[0019] Another object of the present invention is to provide a method for producing a composite bulk block for use in fabricating dental prostheses, which is capable of inhibiting adhesion of contaminants in the oral cavity. Another object of the present invention is to provide a prosthesis manufactured from the composite bulk block for fabricating a dental prosthesis having the above characteristics. [Means for solving the problem]

[0020] The present invention provides a composite bulk block for fabricating a dental prosthesis, comprising a glass ceramic matrix and a polymer, wherein the glass ceramic matrix comprises an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, the crystalline phase comprising at least one of a leucite crystalline phase and a lithium disilicate crystalline phase as a primary crystalline phase, the polymer being contained in an amount of 20 to 40 wt % based on the total weight of the bulk block, the glass ceramic matrix having an average particle size of 3 to 10 μm, and the polymer comprising an amphoteric ion group.

[0021] According to a preferred embodiment of the present invention, the zwitterionic group is selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine), sulfobetaine methacrylate (SBMA), DMPC (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine), DMSP (3-dimethylsulfoniopropanoate), trigonelline, ectoine, betaine, SPE (N-(2-methacryloyloxy)ethyl-N,N-dimethylammoniopropanesulfonate), SPP (N-(3-methacryloylimino)propyl-N,N-dimethylammoniopropanesulfonate), CBMA (carboxybetaine The zwitterionic group may be derived from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and SPV (3-(2'-vinyl-pyridinio)propanesulfonate), more preferably from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA), and most preferably from MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA).

[0022] In a preferred embodiment of the present invention, the zwitterionic groups may be derived from a mixture of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA) at 0.1 to 0.45 wt % of the total composite bulk block composition. In one embodiment of the present invention, the glass ceramic matrix may be present in an amount of 74.5 to 77.9 wt %.

[0023] In one embodiment of the present invention, the polymer may include a cured product of a curable organic material selected from (meth)acrylate monomers and oligomers containing unsaturated double bonds.

[0024] In a preferred embodiment, the curable organic material is selected from the group consisting of hydroxy ethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethane dimethacrylate (UDMA), urethane dimethacrylate (UDM), biphenyl dimethacrylate (BPDM), n-tolylglycine-glycidylmethacrylate (NTGE), polyethylene glycol dimethacrylate (PEG-DMA), and oligocarbonate dimethacrylic esters. The polyol may be at least one selected from the group consisting of: In one preferred embodiment, the composite bulk block for fabricating a dental prosthesis may have a biaxial flexural strength of 220 to 280 MPa.

[0025] In one embodiment of the present invention, the glass matrix may contain 69.0 to 75.0 wt% of SiO2, 12.0 to 14.0 wt% of Li2O, 2.5 to 3.5 wt% of Al2O3, 0.12 to 0.22 wt% of ZnO, 1.1 to 2.7 wt% of K2O, 0.1 to 0.3 wt% of Na2O, 2.0 to 6.0 wt% of P2O5, and a toning agent.

[0026] In one embodiment of the present invention, the glass ceramic matrix is ​​prepared by melting a glass composition containing 69.0 to 75.0 wt% of SiO, 12.0 to 14.0 wt% of LiO, 2.5 to 3.5 wt% of AlO, 0.12 to 0.22 wt% of ZnO, 1.1 to 2.7 wt% of KO, 0.1 to 0.3 wt% of NaO, 2.0 to 6.0 wt% of PO, and a toning agent, and then water-cooling the glass melt. The glass ceramic powder may be manufactured by a method including the steps of: (1) subjecting a glass molded body to primary pulverization to obtain a coarse-grained glass body, and (2) pulverizing the glass molded body to prepare a glass powder having a maximum average particle size of 300 μm or less; (3) subjecting the glass powder to a crystallization heat treatment in a furnace, starting from room temperature and increasing the temperature to a maximum temperature of 755 to 810°C, for 30 minutes to 6 hours; (4) pulverizing the crystallization heat-treated powder to produce a glass ceramic powder having an average particle size of 3 to 10 μm; and (5) forming the glass ceramic powder into a predetermined shape.

[0027] The present invention also provides a method for producing a composite bulk block for fabricating a dental prosthesis, which includes a glass ceramic matrix and a polymer, comprising the steps of: preparing a crystallizable glass powder having a maximum average particle size of 300 μm or less; crystallizing the crystallizable glass powder for 30 minutes to 6 hours, starting from room temperature and heating the furnace temperature to a maximum temperature of 755 to 810°C; pulverizing the crystallization-heat-treated powder to produce a glass ceramic powder having an average particle size of 3 to 10 μm; and molding the glass ceramic powder into a predetermined shape. In the method for producing a composite bulk block for fabricating a dental prosthesis according to the present invention, the polymer may be contained in an amount of 20 to 40% by weight based on the total weight of the composite bulk block.

[0028] In order to provide antifouling properties, in the method for producing a composite bulk block according to a preferred embodiment, the polymer may contain zwitterionic groups.

[0029] In a specific embodiment, the zwitterionic group is selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine (MPC), sulfobetaine methacrylate (SBMA), 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC), 3-dimethylsulfoniopropanoate (DMSP), trigonelline, ectoine, betaine, N-(2-methacryloyloxy)ethyl-N,N-dimethylammoniopropanesulfonate (SPE), N-(3-methacryloylimino)propyl-N,N-dimethylammoniopropanesulfonate (SPP), carboxybetaine (CBMA), and the like. The zwitterionic group may be derived from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and SPV (3-(2'-vinyl-pyridinio)propanesulfonate), more preferably from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA), and most preferably from MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA).

[0030] In one specific embodiment, the zwitterionic groups may be derived from a mixture of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA) at 0.1 to 0.45 wt % of the total composite bulk block composition. In the method for producing a composite bulk block according to the present invention, the glass ceramic matrix may be contained in an amount of 74.5 to 77.9% by weight.

[0031] In one embodiment of the present invention, the polymer may include a cured product of a curable organic material selected from (meth)acrylate monomers and oligomers containing unsaturated double bonds.

[0032] In a preferred embodiment, the curable organic material is selected from the group consisting of hydroxy ethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethane dimethacrylate (UDMA), urethane dimethacrylate (UDM), biphenyl dimethacrylate (BPDM), n-tolylglycine-glycidylmethacrylate (NTGE), polyethylene glycol dimethacrylate (PEG-DMA), and oligocarbonate dimethacrylic esters. The polyol may be at least one selected from the group consisting of:

[0033] In a method for producing a composite bulk block according to a preferred embodiment of the present invention, the crystallizable glass powder may be obtained from a glass composition containing 69.0 to 75.0 wt% of SiO2, 12.0 to 14.0 wt% of Li2O, 2.5 to 3.5 wt% of Al2O3, 0.12 to 0.22 wt% of ZnO, 1.1 to 2.7 wt% of K2O, 0.1 to 0.3 wt% of Na2O, 2.0 to 6.0 wt% of PO5, and a toning agent. More specifically, the crystallizable glass powder may be obtained by melting the glass composition, water-quenching the glass melt to obtain a glass molded body of coarse particle size, and subjecting this to primary pulverization.

[0034] Furthermore, another embodiment of the present invention provides a prosthesis processed from the composite bulk block according to the above embodiment, comprising a glass ceramic matrix and a polymer, wherein the glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, the crystalline phase having at least one primary crystalline phase selected from the group consisting of a leucite crystalline phase and a lithium disilicate crystalline phase, the polymer being contained in an amount of 20 to 40 wt % based on the total weight of the bulk block, the glass ceramic matrix having an average particle size of 3 to 10 μm, and the polymer containing a zwitterionic group. [Effects of the Invention]

[0035] The composite bulk block according to the present invention has improved mechanical strength and can be used not only as an inlay or onlay but also as an artificial tooth for the molar region, and can provide an artificial tooth that can inhibit the adhesion of contaminants in the oral cavity. [Brief explanation of the drawings]

[0036] [Figure 1] and [Figure 2] The results of evaluating the antifouling properties of the composite bulk block according to the present invention are shown in Figure 1, which is a graph showing the results of evaluating the CFU reduction rate for an experimental group of six composite bulk blocks according to the present invention compared to a control group, and Figure 2 is a photograph comparing two of the experimental groups with the control group. DETAILED DESCRIPTION OF THE INVENTION

[0037] The above and additional aspects of the present invention will become more apparent from the following detailed description of preferred embodiments thereof, which are given with reference to the accompanying drawings, in which:

[0038] The present invention provides a composite bulk block for fabricating a dental prosthesis, comprising a glass ceramic matrix and a polymer, wherein the glass ceramic matrix comprises an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, the crystalline phase comprising at least one type of crystalline phase selected from the group consisting of a leucite crystalline phase and a lithium disilicate crystalline phase as a primary crystalline phase, the glass ceramic matrix having an average particle size of 3 to 10 μm, and the polymer is contained in an amount of 20 to 40 wt % based on the total weight of the bulk block, and the polymer contains a zwitterionic group.

[0039] In the above and following descriptions, the term "main crystalline phase" is defined as a crystalline phase that accounts for at least 50% by weight of the total crystalline phase, and the term "additional crystalline phase" can be defined as the remaining crystalline phase of the total crystalline phase that is not the main crystalline phase.

[0040] The content of the crystalline phase can be calculated by X-ray diffraction analysis. For example, the ratio F of the crystalline phase a in a test piece consisting of two polymorphic phases a and b can be calculated as follows: a is quantitatively expressed by the following formula 1.

[0041] [Formula 1] Fa=1 / (1+K·Ib / Ia)

[0042] This value can be determined by measuring the intensity ratio of the two crystalline phases and obtaining an integer K, which is the absolute intensity ratio I of the two pure polymorphic forms. oa / I ob and is determined by measuring a standard substance. The term "main crystalline phase" used above and below can be defined as being set based on the content calculated by this method.

[0043] In the above and following descriptions, it goes without saying that the composite bulk block is not limited in shape and can include bulk bodies of various shapes, such as, for example, a block shape, a disk shape, an ingot shape, a cylinder shape, and the like.

[0044] The composite bulk block according to the present invention contains a glass ceramic as the ceramic, taking into account the difference in refractive index between the monomer material forming the polymer and the ceramic. In particular, a leucite-based glass ceramic or a lithium disilicate-based glass ceramic is preferred from the viewpoint of aesthetics, and a lithium disilicate-based glass ceramic may be most preferred.

[0045] In the composite bulk block according to the present invention, it is preferable that the glass ceramic matrix has an average grain size of 3 to 10 μm, preferably 3 to 5 μm, in order to improve mechanical properties. A composite bulk block containing a glass ceramic matrix having such an average grain size is preferable in that, when processed and applied as a prosthesis, it can exhibit mechanical properties that are suitable for use as an inlay or onlay as well as a molar crown.

[0046] The polymer content in the composite bulk block is preferably 20-40 wt% based on the total weight of the bulk block. However, if the polymer content is less than 20 wt% based on the total weight of the bulk block, it is disadvantageous in use due to poor processability caused by the brittleness of ceramics, while if the polymer content is more than 40 wt%, it may cause problems such as breakage and wear due to too poor mechanical properties. A composite bulk block according to a specific embodiment of the present invention may contain 74.5-77.9 wt% of a glass ceramic matrix. On the other hand, the composite bulk block according to the present invention may be one in which the polymer contains zwitterionic groups.

[0047] The amphoteric ion group can be defined as a functional group of an amphotric ion or zwitterion, which is a neutral molecule because it has both positive and negative electrons in chemistry. Examples of the amphoteric ion group of the present invention include MPC (2-methacryloyloxyethyl phosphorylcholine), sulfobetaine methacrylate (SB), DMPC (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine), DMSP (3-dimethylsulfoniopropanoate), trigonelline, ectoine, betaine, SPE (N-(2-methacryloyloxy)ethyl-N,N-dimethylammoniopropanesulfonate), SPP (N-(3-methacryloylimino)propyl-N,N-dimethylammoniopropanesulfonate), CBMA (carboxybetaine The polymer may be derived from at least one amphoteric compound selected from the group consisting of SPV (3-(2'-vinyl-pyridinio)propanesulfonate) and SPV (3-(2'-vinyl-pyridinio)propanesulfonate).

[0048] For example, MPC (2-methacryloyloxyethyl phosphorylcholine) is attracting attention as a biocompatible and environmentally friendly material that mimics the hydrophilic functional groups of phosphatidylcholine (PC), a component of biological bilayer phospholipids. Furthermore, MPC has high hydrophilicity due to the inclusion of the aforementioned hydrophilic functional groups, and can form a stable hydration shell, providing excellent anti-fouling properties.

[0049] SBMA (sulfobetaine methacrylate) is a zwitterion that contains both a sulfonate anion group and an ammonium cation group in a single molecule, making it biocompatible like MPC and highly applicable in vivo due to the sulfobetaine functional group that replaces the phosphate group of phosphatidylcholine. SBMA also has antifouling properties and can be synthesized more easily and simply than PC-based polymers, making it more readily applicable for commercial applications.

[0050] Although the zwitterionic groups of MPC and SBMA may differ to some extent, most amphoteric polymers can suppress nonspecific adsorption in aqueous solutions through hydrophobic or electrostatic attraction. Furthermore, adding zwitterionic substances as additives can suppress thermal and chemical denaturation of proteins. In particular, the aforementioned MPC and SBMA are more stably bioavailable by mimicking their in vivo constituents.

[0051] From this perspective, the zwitterionic group may be derived from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA).

[0052] Most preferably, the zwitterionic group may be derived from MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA).

[0053] When zwitterionic groups derived from MPC and SBMA are contained together, the weight ratio of MPC to SBMA can be set between 1:3 and 3:1. In this case, when two or more zwitterionic substances are contained in the specific ratios described above, the antifouling properties of the composite bulk block are further improved compared to when they are used alone. Most preferably, the weight ratio of MPC to SBMA is 1:1.

[0054] When introducing such zwitterionic groups into the composite bulk block, the content thereof is preferably within an appropriate range that allows the development of antifouling properties without impairing mechanical properties. The content may be 0.1 to 0.45 wt % based on the weight of the amphoteric compound in the entire composite bulk block composition, and preferably, a mixture of MPC and SBMA may be used in an amount of 0.15 wt % or more but less than 0.45 wt %. On the other hand, in the dental bulk block of the present invention, the polymer may be bonded to the glass ceramic matrix via a silane bond.

[0055] Such silane bonding can be achieved by surface treatment of the glass-ceramic matrix, specifically by treating the surface of the glass-ceramic with an organofunctional silane compound having an ethylenically unsaturated double bond and then bonding a polymer thereto.

[0056] More specifically, the organofunctional silane may be at least one selected from the group consisting of methacryloxyalkylene trialkoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-methacryloxypropyl triethoxysilane, but is not limited thereto.

[0057] Examples of such a treatment method include the method described in Patent Document 1: Korean Patent No. 10-1609291, Patent Document 10: Korean Patent No. 10-1682542, Patent Document 11: Korean Patent No. 10-2122202, and Patent Document 3: Korean Patent No. 10-2228118. Cut.

[0058] The polymer contained in the composite bulk block according to the present invention contains a zwitterionic group as described above, and may be a cured product of a curable organic material selected from (meth)acrylate monomers and oligomers containing an unsaturated double bond. Specific examples of the curable organic material include hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethane dimethacrylate (UDMA), and urethane dimethacrylate (UR). dimethacrylate (UDM), biphenyldimethacrylate (BPDM), n-tolylglycine-glycidylmethacrylate (NTGE), polyethylene glycol dimethacrylate (PEG-DMA), and oligocarbonate dimethacrylic esters.

[0059] Among such monomers and / or oligomers, for example, UDMA and Bis-GMA have high viscosity and can be mixed with TEGDMA, which has low viscosity, in a mass ratio of 5:5 to 6:4, but the present invention is not limited to this.

[0060] In the case of a curable organic material, shrinkage and hardening occur during the polymerization reaction, but the use of the above-mentioned organofunctional silane can also have the effect of minimizing changes in physical properties due to shrinkage and hardening.

[0061] It goes without saying that the surface treatment of the crystallized glass with such an organofunctional silane can be carried out using a solution of the organofunctional silane diluted in ethanol, taking into consideration the specificity of dental composites.

[0062] In this way, by treating the surface of glass ceramic with an organofunctional silane and then bonding it with a polymer to prepare a composite bulk block, the volume percentage of inorganic matter in the composite as a whole can be increased, thereby improving biaxial bending strength and hardness.

[0063] Meanwhile, an initiator may be included to crosslink and cure the curable organic material in the form of a polymer, and examples of the initiator include a photoinitiator and a thermal initiator. In the present invention, a preferred initiator is a thermal initiator, and a composite with better physical properties can be obtained by thermal polymerization using a thermal initiator compared to photopolymerization using a photoinitiator.

[0064] Various compounds known in the art can be used as thermal initiators, and examples include, but are not limited to, known peroxides such as benzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, or tert-butyl perbenzoate.

[0065] In obtaining the composite bulk block for fabricating a dental prosthesis according to the present invention, the glass matrix may preferably contain 69.0 to 75.0 wt % of SiO, 12.0 to 14.0 wt % of LiO, 2.5 to 3.5 wt % of AlO, 0.12 to 0.22 wt % of ZnO, 1.1 to 2.7 wt % of KO, 0.1 to 0.3 wt % of NaO, 2.0 to 6.0 wt % of PO, and a toning agent.

[0066] Such glass compositions undergo crystal nucleation and crystal growth heat treatments to precipitate a crystalline phase within an amorphous glass matrix. The temperatures at which crystal nucleation and crystal growth occur in the above-described glass matrix are between 500°C and 880°C. That is, crystal nuclei begin to form at a minimum of 500°C, and crystal growth occurs as the temperature rises. This crystal growth exhibits the lowest optical transparency for use in artificial teeth at a maximum of 880°C. Since optical transparency gradually decreases from the crystal growth temperature to a maximum of 880°C, focusing on this crystal growth, it is possible to grow crystals to a degree that satisfies both high strength and machinability, and this can be used as the glass-ceramic matrix for the composite bulk block according to the present invention.

[0067] From this viewpoint, the glass ceramic constituting the dental bulk block according to the present invention is prepared by melting a glass composition containing 69.0 to 75.0% by weight of SiO, 12.0 to 14.0% by weight of LiO, 2.5 to 3.5% by weight of AlO, 0.12 to 0.22% by weight of ZnO, 1.1 to 2.7% by weight of KO, 0.1 to 0.3% by weight of NaO, and 2.0 to 6.0% by weight of PO, and then water-cooling the glass melt. It is preferable that the glass ceramic powder can be obtained by the method including the steps of: (1) quenching a glass molded body to obtain a coarse-grained glass body, which is then primarily pulverized to prepare a glass powder having a maximum average particle size of 300 μm or less; (2) crystallizing the glass powder by heat-treating it in a furnace from room temperature to a maximum temperature of 755 to 810°C for 30 minutes to 6 hours; (3) pulverizing the crystallization-heat-treated powder to produce a glass ceramic powder having a size of 3 to 10 μm, preferably 3 to 5 μm; and (4) molding the glass ceramic powder into a predetermined shape.

[0068] In one specific embodiment for obtaining the glass ceramic constituting the composite bulk block of the present invention, first, a glass composition containing 69.0 to 75.0 wt% of SiO2, 12.0 to 14.0 wt% of Li2O, 2.5 to 3.5 wt% of Al2O3, 0.12 to 0.22 wt% of ZnO, 1.1 to 2.7 wt% of K2O, 0.1 to 0.3 wt% of Na2O, and 2.0 to 6.0 wt% of P2O5 is weighed and mixed.

[0069] Li2CO3 may be added to the glass composition instead of Li2O, and carbon dioxide (CO2), the carbon (C) component of Li2CO3, is released as a gas during the glass melting process. Also, K2CO3 and Na2CO3 may be added instead of K2O and Na2CO3, respectively, in the alkali oxides, and carbon dioxide (CO2), the carbon (C) component of K2CO3 and Na2CO3, is released as a gas during the glass melting process.

[0070] The mixing is performed using a dry mixing process, which may be a ball milling process. Specifically, the starting materials are loaded into a ball mill, which rotates at a constant speed to mechanically pulverize and uniformly mix the starting materials. The balls used in the ball mill may be made of ceramic materials such as zirconia or alumina, and may be all the same size or at least two different sizes. The ball size, milling time, and rotation speed of the ball mill are adjusted based on the desired particle size. For example, the ball size may be set to a range of approximately 1 mm to 30 mm, and the rotation speed of the ball mill may be set to a range of approximately 50 to 500 rpm. Ball milling is preferably performed for 1 to 48 hours, based on the desired particle size. Through ball milling, the starting materials are pulverized into fine particles with uniform particle size and uniform mixing.

[0071] The mixed starting materials are placed in a melting furnace, which is then heated to melt the starting materials. Melting refers to the process of converting the starting materials from a solid state to a viscous liquid state. The melting furnace is preferably made of a material that has a high melting point, high strength, and a low contact angle to prevent the molten material from sticking together. For this reason, the melting furnace is preferably made of a material such as platinum (Pt), diamond-like carbon (DLC), or chamotte, or is coated with a material such as platinum (Pt) or diamond-like carbon (DLC).

[0072] Melting is preferably carried out at 1400-2000°C under normal pressure for 1-12 hours. If the melting temperature is below 1400°C, the starting materials may not yet melt. If the melting temperature is above 2000°C, excessive energy consumption is required, which is uneconomical. Therefore, melting within the above-mentioned temperature range is preferred. Furthermore, if the melting time is too short, the starting materials may not melt sufficiently. If the melting time is too long, excessive energy consumption is required, which is uneconomical. The temperature rise rate of the melting furnace is preferably approximately 5°C / min to 50°C / min. However, if the temperature rise rate of the melting furnace is too slow, it takes too long and productivity is poor. If the temperature rise rate of the melting furnace is too fast, the amount of volatilization of the starting materials increases due to a sudden temperature rise, which can result in poor physical properties of the crystallized glass. Therefore, it is preferable to raise the temperature of the melting furnace at a rate within the above-mentioned range. Melting is preferably carried out in an oxidizing atmosphere such as oxygen (O2) or air.

[0073] In order to crush the glass melt into a desired shape and size, the glass melt is water quenched to obtain a glass molded body of coarse particle size, which is then crushed primarily to prepare glass powder having a maximum average particle size of 300 μm or less. The glass powder thus obtained is transferred to a crystallization heat treatment furnace to produce the desired crystallization heat treated powder.

[0074] In this case, the crystallization heat treatment is carried out for 30 minutes to 6 hours by starting the temperature inside the furnace from room temperature and raising it to a maximum temperature of 755 to 810°C, thereby obtaining a crystallization heat-treated powder containing only pure lithium disilicate as a crystalline phase, with the crystal size being 0.01 to 1.0 μm. Next, the powder that has been heat-treated for crystallization is pulverized to produce a glass ceramic powder having an average particle size of 3 to 10 μm, preferably 3 to 5 μm. Finally, the glass-ceramic powder is molded into a predetermined shape to obtain a glass-ceramic matrix.

[0075] Meanwhile, in the step of molding the glass ceramic powder into a predetermined shape, the mechanical properties may be affected depending on the molding conditions, but as the molding pressure increases and the heat treatment time increases, the mechanical properties may be improved.

[0076] However, if the molding pressure or heat treatment conditions are too high or too long, the glass ceramic matrix and the polymer may not mix well, resulting in a deterioration in mechanical properties. Taking this into consideration, the molding pressure is preferably 15 to 25 tons and the heat treatment time is preferably 5 to 7 hours. Of course, the molding pressure or heat treatment time can be adjusted within the above ranges depending on the shape or purpose of the desired composite bulk block.

[0077] Using the molded product thus obtained as a glass ceramic matrix, a composite bulk block for fabricating a dental prosthesis can be manufactured using a method such as that described in Patent Document 1 (Korean Patent No. 10-1609291), Patent Document 10 (Korean Patent No. 10-1682542), Patent Document 11 (Korean Patent No. 10-2122202), or Patent Document 3 (Korean Patent No. 10-2228118), which includes the glass ceramic matrix of the present invention and a polymer, wherein the glass ceramic matrix comprises an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, and the crystalline phase includes at least one primary crystalline phase selected from the group consisting of a leucite crystalline phase and a lithium disilicate crystalline phase, the glass ceramic matrix having an average particle size of 3 to 10 μm, and the polymer is included in an amount of 20 to 40 wt % based on the total weight of the bulk block, and which contains a zwitterion.

[0078] In some cases, additional vacuum can be applied to ensure uniform dispersion of the polymer within the composite bulk block. The degree of vacuum can also affect the mechanical properties. -2 torr~10 -3 A pressure of about torr is preferable from the viewpoint of mechanical properties, but is not limited to this.

[0079] Meanwhile, in manufacturing the composite bulk block, the curing temperature and time can be appropriately adjusted in consideration of the curing characteristics of the polymer. The curing time can also affect the mechanical properties, and the mechanical properties can be improved as the curing time is longer. The resulting composite bulk block can be machined into the desired shape, for example, by CAD-CAM processing as described above, to produce a prosthesis.

[0080] The machined prosthesis comprises a glass ceramic matrix and a polymer, the glass ceramic matrix being composed of an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, the crystalline phase comprising at least one of a leucite crystalline phase and a lithium disilicate crystalline phase as the main crystalline phase, the polymer being contained in an amount of 20 to 40 wt% based on the weight of the entire bulk block, the glass ceramic matrix having an average particle size of 3 to 10 μm, and the polymer containing a zwitterionic group, which has excellent mechanical properties and is therefore useful not only for inlays and onlays but also for molar crowns, and is capable of suppressing bacterial adhesion and preventing secondary caries caused by the prosthesis.

[0081] In relation to the composite bulk block for fabricating dental prostheses and its manufacturing method, the influence of the average particle size of the glass ceramic matrix on the mechanical properties of the composite bulk block was confirmed, and the results are shown in Table 1. The average particle size here is the average particle size of the glass ceramic powder forming the glass ceramic matrix, and was calculated using a SEM.

[0082] In this case, the composite bulk block is one that has the same composition and is manufactured through the same process into a composite bulk block.

[0083] [Table 1] TIFF2026502315000002.tif39166

[0084] In the above and following descriptions, the biaxial bending strength is defined as a value measured in accordance with ISO 4049. The three-point bending strength is defined as a value measured in accordance with ISO 6872.

[0085] From the information in Table 1, it can be seen that the mechanical properties of the composite bulk block vary depending on the size of the particles constituting the glass ceramic matrix, and that it is particularly preferable for the average particle size of the glass ceramic matrix to be 3 to 10 μm in order to further improve the mechanical properties of the composite block.

[0086] Until now, dental CAD / CAM hybrid products have been mainly used for inlays or onlays due to their insufficient mechanical properties, but the composite block of the present invention has excellent mechanical properties and is expected to be applicable to molar crowns as well.

[0087] As described above, the composite bulk block according to the present invention contains zwitterionic groups in the polymer. However, to determine whether the zwitterionic groups affect the mechanical properties of the composite bulk block, a control was performed by preparing a composite block without the zwitterionic groups, with all other compositions and processes remaining the same. As a result, as shown in Table 2, it was confirmed that the inclusion of zwitterionic groups in the composite bulk block does not negatively affect the mechanical properties. However, if the content is excessive, the mechanical properties may be reduced, making it difficult to achieve strength sufficient for use as a molar crown. Therefore, it is necessary to control the content of the zwitterionic group-derived compound in the composite block.

[0088] [Table 2] TIFF2026502315000003.tif39166

[0089] Meanwhile, an experiment was conducted to confirm the influence of the type and content of zwitterions on the development of antifouling properties of the composite block according to the present invention.

[0090] At this time, a composite block not containing zwitterions was prepared as a control group, as shown in test piece 2 in Table 5. As an experimental group, a composite block containing an amphoteric compound was prepared, as shown in test piece 2 in Table 1 and test piece 1 in Table 2. Specifically, six test pieces containing 0.15 wt % and 0.45 wt % of MPC alone, SBMA alone, and a composite bulk block containing a mixture of MPC and SBMA as the amphoteric compound, respectively, relative to the total composition of the composite bulk block, were prepared as composite block test pieces. The specific experimental groups are summarized in Table 3 below.

[0091] [Table 3] TIFF2026502315000004.tif51166

[0092] Note) MPC: 2-methacryloyloxyethyl phosphorylcholine, SBMA: sulfobetaine methacrylate The method for evaluating the antifouling property is a method for measuring the colony forming unit (CFU), and specifically, is as follows. 1) The surface of a rectangular test piece measuring 10 mm wide, 10 mm long, and 2 mm high is coated with artificial saliva containing mucin for 4 hours, taking into account clinical situations.

[0093] 2) 1 × 10 in all groups surface-treated with artificial saliva 6 CFU / mL of dental caries bacteria (Streptococcus mutans, S. mutans) is dispensed and cultured at 37°C for 72 hours. 3) After culturing at 37°C for 72 hours, all groups were washed three times with PBS solution, and the biofilm formed on the surface was separated by vortexing and sonication. 4)10 -5 The mixture is diluted 2:1 and spread onto a BHI agar plate, followed by incubation at 37°C for 24 hours. 5) Measure the CFU (Colony forming units) of bacteria produced on the agar plate after 24 hours of culture. 6) Calculate the percentage of CFU reduction in the experimental group compared to the control group.

[0094] The results are shown in Figure 1. A photograph of the culture medium is shown in Figure 2.

[0095] The results in Figure 1 show that all of the composite blocks according to the present invention containing zwitterionic groups exhibit antifouling properties. Specifically, from the perspective of CFU reduction rate alone, the best results were observed when SBMA was contained at 0.45 wt.%, but when considering the mechanical properties and economics of the composite bulk block, a combination of MPC and SBMA appears to be preferable. Furthermore, the most preferable results were observed when MPC and SBMA were contained in a combination of 0.15 wt.% of the total composition.

[0096] The composite block of the present invention according to the above-described embodiment specifically has the composition shown in Table 4 below, but it goes without saying that the present invention is not limited to these examples of compositions.

[0097] [Table 4] TIFF2026502315000005.tif45166

[0098] Note) UDMA: diurethanedimethacrylate, TEGDMA: triethylene glycol dimethacrylate, BPO: benzoyl peroxide

[0099] Although the present invention has been described with reference to one embodiment, this is by way of example only, and various modifications and equivalent alternative embodiments are possible for those skilled in the art. [Industrial Applicability]

[0100] The present invention relates to a composite bulk block for use in fabricating dental prostheses, which has excellent mechanical strength and can be used to fabricate restorations that exhibit stain resistance, a method for manufacturing the same, and prostheses manufactured from the same.

[0101] The composite bulk block according to the present invention has improved mechanical strength and can be used not only as an inlay or onlay but also as an artificial tooth for the molar region, and can provide an artificial tooth that can inhibit the adhesion of contaminants in the oral cavity.

Claims

1. a glass-ceramic matrix and a polymer; the glass-ceramic matrix comprises an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, the crystalline phase comprising at least one crystalline phase selected from a leucite crystalline phase and a lithium disilicate crystalline phase as a main crystalline phase, and the polymer is contained in an amount of 20 to 40 wt % based on the weight of the entire bulk block; The glass-ceramic matrix has an average grain size of 3 to 10 μm; The polymer contains amphoteric ion groups A composite bulk block for fabricating dental prostheses, characterized in that:

2. The zwitterionic group is MPC (2-methacryloyloxyethyl phosphorylcholine), sulfobetaine methacrylate (SBMA), DMPC (1,2-dimyristoyl-sn-glycero-3-phosphotidylcholine), DMSP (3-dimethylsulfoniopropanoate), trigonelline, ectoine, betaine, SPE (N-(2-methacryloyloxy)ethyl-N,N-dimethylammonium methyl ester), propanesulfonate), SPP (N-(3-methacryloyllimino)propyl-N,N-dimethylammonio propanesulfonate), CBMA (carboxybetaine methacrylate), and SPV (3-(2'-vinyl-pyridinio)propanesulfonate).

2. The composite bulk block for fabricating dental prostheses according to claim 1.

3. The zwitterionic group is derived from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA).

2. The composite bulk block for fabricating dental prostheses according to claim 1.

4. The zwitterionic groups are derived from MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA).

2. The composite bulk block for fabricating dental prostheses according to claim 1.

5. The zwitterionic groups are derived from a mixture of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA) at 0.1-0.45 wt % of the total composite bulk block composition.

5. A composite bulk block for fabricating dental prostheses according to claim 4.

6. The glass-ceramic matrix is ​​present in an amount of 74.5 to 77.9 wt. %.

2. The composite bulk block for fabricating dental prostheses according to claim 1.

7. The polymer contains a cured product of a curable organic material selected from (meth)acrylate monomers and oligomers containing unsaturated double bonds.

2. The composite bulk block for fabricating dental prostheses according to claim 1.

8. The curable organic materials include hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethane dimethacrylate (UDMA), and urethane dimethacrylate (urethane dimethacrylate (UDM), biphenyl dimethacrylate (BPDM), n-tolylglycine-glycidyl methacrylate (NTGE), polyethylene glycol dimethacrylate (PEG-DMA), and oligocarbonate dimethacrylate esters.

8. A composite bulk block for fabricating dental prostheses according to claim 7.

9. The composite bulk block for manufacturing dental prostheses has a biaxial bending strength of 220 to 280 MPa.

2. The composite bulk block for fabricating dental prostheses according to claim 1.

10. The glass matrix is ​​SiO ２ 69.0-75.0% by weight, Li ２ O12.0-14.0% by weight, Al ２ O ３ 2.5-3.5% by weight, ZnO 0.12-0.22% by weight, K ２ O1.1-2.7% by weight, Na ２ O0.1-0.3% by weight, P ２ O ５ 2.0 to 6.0% by weight, and a toning agent.

2. The composite bulk block for fabricating dental prostheses according to claim 1.

11. The glass ceramic matrix is ​​SiO ２ 69.0-75.0% by weight, Li ２ O12.0-14.0% by weight, Al ２ O ３ 2.5-3.5% by weight, ZnO 0.12-0.22% by weight, K ２ O1.1-2.7% by weight, Na ２ O0.1-0.3% by weight, P ２ O ５ The glass ceramic is manufactured by a method including the steps of: melting a glass composition containing 2.0 to 6.0 wt. % of a toning agent, water-quenching the glass melt to obtain a glass molded body with a coarse particle size, and primarily pulverizing the glass molded body to prepare a glass powder having a maximum average particle size of 300 μm or less; crystallizing the glass powder by heat-treating the glass powder in a furnace from room temperature to a maximum temperature of 755 to 810°C for 30 minutes to 6 hours; pulverizing the crystallization-heat-treated powder to produce a glass ceramic powder having an average particle size of 3 to 10 μm; and molding the glass ceramic powder into a predetermined shape.

2. The composite bulk block for fabricating dental prostheses according to claim 1.

12. 1. A method for producing a composite bulk block for fabricating a dental prosthesis, comprising: A step of preparing a crystallizable glass powder having a maximum average particle size of 300 μm or less; The crystallization heat treatment of the crystallizable glass powder is performed in a furnace at a temperature of 755 to 810°C starting from room temperature for 30 minutes to 6 hours. grinding the crystallization heat-treated powder to produce a glass ceramic powder with an average particle size of 3 to 10 μm; forming the glass-ceramic powder into a predetermined shape.

1. A method for manufacturing a composite bulk block for fabricating a dental prosthesis, comprising:

13. The polymer is contained in an amount of 20 to 40% by weight of the entire composite bulk block. A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 12.

14. The polymer contains zwitterionic groups A method for producing a composite bulk block for producing a dental prosthesis according to claim 12 or 13.

15. The zwitterionic group is MPC (2-methacryloyloxyethyl phosphorylcholine), sulfobetaine methacrylate (SBMA), DMPC (1,2-dimyristoyl-sn-glycero-3-phosphotidylcholine), DMSP (3-dimethylsulfoniopropanoate), trigonelline, ectoine, betaine, SPE (N-(2-methacryloyloxy)ethyl-N,N-dimethylammonium methyl ester), propanesulfonate), SPP (N-(3-methacryloyllimino)propyl-N,N-dimethylammonio propanesulfonate), CBMA (carboxybetaine methacrylate), and SPV (3-(2'-vinyl-pyridinio)propanesulfonate). A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 14.

16. The zwitterionic group is derived from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA). A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 14.

17. The zwitterionic groups are derived from MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA). A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 14.

18. The zwitterionic groups are derived from a mixture of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA) at 0.1-0.45 wt % of the total composite bulk block composition.

18. A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 17.

19. The glass-ceramic matrix is ​​present in an amount of 74.5 to 77.9 wt. %. A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 12.

20. The polymer contains a cured product of a curable organic material selected from (meth)acrylate monomers and oligomers containing unsaturated double bonds. A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 12.

21. The curable organic materials include hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethane dimethacrylate (UDMA), and urethane dimethacrylate (urethane dimethacrylate (UDM), biphenyl dimethacrylate (BPDM), n-tolylglycine-glycidyl methacrylate (NTGE), polyethylene glycol dimethacrylate (PEG-DMA), and oligocarbonate dimethacrylate esters.

21. A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 20.

22. The crystallizable glass powder is SiO ２ 69.0-75.0% by weight, Li ２ O12.0-14.0% by weight, Al ２ O ３ 2.5-3.5% by weight, ZnO 0.12-0.22% by weight, K ２ O1.1-2.7% by weight, Na ２ O0.1-0.3% by weight, P ２ O ５ 2.0 to 6.0 wt % of a glass composition containing a toning agent. A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 12.

23. The crystallizable glass powder is obtained by melting a glass composition, water-quenching the glass melt to obtain a glass molded body of coarse particle size, and then subjecting this to primary crushing.

23. A method for producing a composite bulk block for fabricating a dental prosthesis according to claim 22.

24. Fabricated from the composite bulk block of claim 1, a glass-ceramic matrix and a polymer; the glass-ceramic matrix comprises an amorphous glass matrix and a crystalline phase dispersed in the glass matrix, the crystalline phase comprising at least one crystalline phase selected from a leucite crystalline phase and a lithium disilicate crystalline phase as a main crystalline phase, and the polymer is contained in an amount of 20 to 40 wt % based on the weight of the entire bulk block; The glass-ceramic matrix has an average grain size of 3 to 10 μm; The polymer contains zwitterionic groups A prosthesis characterized by:

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