Composite bulk block for dental prosthesis fabrication, manufacturing method therefor, and prosthesis fabricated therefrom

Abstract

The present invention relates to a composite bulk block for dental prosthesis fabrication, a manufacturing method therefor, and a prosthesis fabricated therefrom. The composite bulk block for dental prosthesis fabrication comprises a glass ceramic matrix and a polymer, wherein the glass ceramic matrix consists of an amorphous glass matrix and crystalline phases dispersed therein and has an average particle size of 3 to 10 μm, the crystalline phase including at least one selected from a lucite crystal phase and a lithium disilicate crystal phase, and the polymer is included in an amount of 20 to 40 wt% on the basis of the total weight of the bulk block and contains amphoteric ionic groups. The present invention provides a composite bulk block for dental prosthesis fabrication which enables the fabrication of restorations that possess excellent mechanical properties and antifouling characteristics through machining.

Description

Composite bulk block for manufacturing dental prostheses, method for manufacturing the same, and prostheses manufactured therefrom

[0001] The present invention relates to a composite bulk block for manufacturing a dental prosthesis capable of processing a restoration having excellent mechanical strength and exhibiting anti-fouling properties, a method for manufacturing the same, and a prosthesis manufactured therefrom.

[0002] As the dental industry has developed, problems with the physical properties and aesthetics of teeth have emerged, leading to a gradual decline in market share for existing prosthetic materials such as porcelain and metal. To replace these, materials such as crystallized glass and zirconia are increasing their market share. Furthermore, the previously used hot pressing method for prosthetic manufacturing has the problem of taking a long time to produce the prosthesis, making it difficult to produce the one-day prosthesis currently promoted in the dental market. Consequently, a shift towards CAD / CAM systems is underway. To support this shift, the utility of 1:1 processing materials that can be processed and implanted immediately without additional heat treatment of crystallized glass is being highlighted.

[0003] Of course, with the development of zirconia and crystallized glass, many materials with good aesthetics and high physical properties are being used, but most ceramic materials undergo a crystallization heat treatment process after processing, making them difficult to use as one-day prosthetics.

[0004] In addition, in the case of ceramic materials currently being processed in a 1:1 ratio, there is a problem in that the processability is low due to the use of ceramic materials that have already undergone crystallization, and there is a problem in that breakage occurs in the margin area (the boundary area between the prosthesis and the tooth).

[0005] To address these issues and meet the demands of the current dental market, composites, which combine organic and inorganic materials, have been developed. Composites are complementary materials, with the organic material suppressing brittleness, a drawback of inorganic materials, and the inorganic material enhancing the organic material's properties, such as low strength. Furthermore, composites offer the advantage of 1:1 machining, allowing immediate implantation into the oral cavity. This is why new products are being released as the technology continues to develop. Currently, commercially available composites have a strength of approximately 150 to 200 MPa, and their machinability is superior to that of conventional 1:1 machinable glass ceramics.

[0006] The present inventors have disclosed, in relation to such a composite, in Korean Patent Registration No. 10-1682542, a method for manufacturing a dental block, which comprises the steps of: preparing a glass ceramic; forming a porous ceramic body by porousing the glass ceramic; a first infiltration step of first infiltrating a polymer into the ceramic porous body in a vacuum chamber under vacuum; and a second infiltration step of secondly infiltrating a polymer into the ceramic porous body before the first infiltrated polymer is completely cured, and is characterized in that it realizes a biaxial flexural strength of 100 to 150 MPa.

[0007] The glass ceramic here is a feldspathic glass ceramic, and specifically contains 2.0 to 6.0 wt% of N2O, 60.0 to 65.0 wt% of SiO2, 8.0 to 15.0 wt% of K2O, 0.5 to 3.0 wt% of CaO, 0.5 to 2.0 wt% of BaO, 0.2 to 1.0 wt% of CeO2, 0 to 0.5 wt% of TiO2, 16.0 to 19.0 wt% of Al2O3 to increase the glass transition temperature and softening point and to enhance the chemical durability of the crystallized glass, and 0 to 1.0 wt% of a coloring component that affects the coloring such as brightness and saturation and exhibits fluorescence.

[0008] In addition, Korean Patent Registration No. 10-1609291 discloses a method for producing a glass, comprising: 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, then crushing it, and performing a crystallization heat treatment on the crushed glass at a temperature of 875 to 970°C; a step of re-crushing the crystallized glass that has undergone the crystallization heat treatment, and then performing a porous heat treatment at a temperature of 700 to 840°C; A method for manufacturing a dental block is disclosed, comprising a step of infiltrating a polymer into a porous body formed in crystallized glass that has undergone the above porous heat treatment, wherein the glass melted at a temperature of 1,400 to 1,800°C comprises 2.0 to 6.0 wt% of N2O, 60 to 65.0 wt% of SiO2, 8.0 to 15 wt% of K2O, 0.5 to 3.0 wt% of CaO, 0.5 to 2.0 wt% of BaO, 0.2 to 1.0 wt% of CeO2, more than 0.5 wt% of TiO2O, and 16.0 to 19.0 wt% of Al2O3.

[0009] Specifically, the glass here was also feldspathic glass, and the resulting block was disclosed to have a biaxial flexural strength of approximately 100 to 150 MPa.

[0010] On the other hand, Korean Patent Registration No. 10-212202 discloses a method for manufacturing a composite using a chemical bond between an inorganic substance and an organic substance using a silane coupling agent. Specifically, the method comprises the steps of: adding a thermal initiator to a first mixture in which at least two or more organic substances having different viscosities are mixed at 20 to 70°C; surface-treating an inorganic substance using a second mixture in which 10 to 14 wt% of an acrylic silane coupling agent is mixed in ethanol; mixing the first mixture to which the thermal initiator has been added and the inorganic substance surface-treated by the second mixture; and curing using thermal polymerization at 100 to 150°C.

[0011] In addition, in Korean Patent Registration No. 10-2228118, a dental composite composition including crystallized glass and a curable organic material is proposed, wherein the crystallized glass has an average crystal size of 50 to 400 nm, and a biaxial flexural strength of 200 to 300 MPa and a Vickers hardness of 270 to 300 Hv, which can provide a dental composite composition.

[0012] As another example, U.S. Patent No. 7,807,227 discloses a composite material comprising a porous inorganic-nonmetallic matrix and a second material, and a method for producing the same, comprising the steps of: sintering an inorganic-nonmetallic starting material to obtain a porous inorganic-nonmetallic matrix sintered body; coating a coupling agent on the surface of the porous inorganic-nonmetallic matrix to obtain a surface-modified product; and infiltrating an organic material into the surface-modified porous inorganic-nonmetallic matrix. And a method for producing a composite material including a step of solidifying the organic material, which is for obtaining an isotropic composite material, the isotropic composite material comprising a porous inorganic-nonmetallic matrix having a flexural strength of at least 40 MPa measured according to ISO 6 872 and an organic material at least partially filling the pores of the porous inorganic-nonmetallic matrix, and the isotropic composite material is disclosed to have an elastic modulus of at least 25 GPa measured according to ISO 10 477 and a bending strength of at least 100 MPa measured according to ISO 6 872.

[0013] Japanese Patent Registration No. 4636514 discloses a dental material and a manufacturing method thereof that can maintain mechanical strength such as wear resistance and flexural strength, discoloration resistance, staining resistance, and aesthetics over a long period of time, and is excellent in modulus of bending elasticity and impact strength, and is also suitable for processing using an inexpensive CAD / CAM system, which is a manufacturing method of a dental material formed by impregnating a porous ceramic with a resin, comprising: (a) molding a mixture containing a ceramic powder containing a network-forming oxide, an intermediate oxide, and a network-modifying oxide and having an average particle size of 3.0 to 50 μm, and a binder, into a predetermined shape; (b) firing the molded mixture, and obtaining a porous ceramic block having interconnecting holes; (c) a coupling agent selected from a silane coupling agent, a titanate coupling agent, and a zircoaluminato coupling agent is permeated into the communicating hole of the porous ceramic block under ultrasonic waves and / or reduced pressure, thereby performing a coupling treatment on the surface of the communicating hole; and (d) a monomer and / or oligomer containing at least an ethylenic double bond is permeated into the communicating hole of the coupled-treated porous ceramic block under ultrasonic waves and / or reduced pressure, and then polymerized. As a specific example, the ceramic powder herein is an aluminosilicate ceramic powder in which the network-forming oxides are SiO2 and B2O3, the intermediate oxide is Al2O3, and the network-modifying oxide is Na2O, and by impregnating resin into the communicating pores of such porous ceramics, the filling ratio of the inorganic material can be increased, so that mechanical strength such as wear resistance and flexural strength, discoloration resistance, staining resistance, and aesthetics can be maintained over a long period of time, and also, since the stress within the ceramic is relaxed, a dental material excellent in flexural modulus, impact strength, etc. can be provided, and this is described as being suitable for a CAD / CAM system.

[0014] Meanwhile, it is known that zwitterionic substances (also called positively charged ionic substances or zwitterionic substances) contribute to the antifouling effect by blocking the adsorption of proteins and bacteria when used with various dental materials. For example, Japanese Patent Application Laid-Open No. 2007-217516 discloses a dental polymerizable composition comprising a polymerizable monomer and a group having a zwitterionic group as a side chain. This composition demonstrates a high effect in inhibiting the adsorption of proteins, plaque, and the like by utilizing a group having a zwitterionic group as a side chain.

[0015] In addition, Japanese Patent Publication No. 2014-009219 discloses a dental adhesive composition comprising a group having a zwitterionic group as a side chain and water, and describes that such a dental adhesive composition is useful as a dental pretreatment material, adhesive, and adhesive composite resin.

[0016] In addition, a technology is also disclosed for a dental implant made of titanium or a titanium alloy, which comprises 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, wherein a coating layer of a mixed solution containing i) an organic pH buffering substance and / or an inorganic pH buffering substance and ii) an organic amphoteric substance having a sulfonic group is formed on the rough surface pretreated to remove contaminants (Domestic Patent No. 10-1405859).

[0017] In addition to the appearance and functional implementation of teeth in a resin-ceramic composite, the inventors of the present invention have continuously sought a method for the prosthesis itself to exhibit adhesion inhibition properties against oral contaminants, and have previously applied for this (Domestic Patent Application No. 10-2021-0055575).

[0018] The purpose of the present invention is to provide a composite bulk block for manufacturing a dental prosthesis that 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 exhibit the ability to inhibit the adhesion of contaminants in the oral cavity.

[0019] In addition, the present invention aims to provide a method for manufacturing a composite bulk block for manufacturing a dental prosthesis that can additionally exhibit the ability to inhibit the adhesion of oral contaminants.

[0020] Furthermore, the present invention also aims to provide a prosthesis manufactured from a composite bulk block for manufacturing a dental prosthesis having the above characteristics.

[0021] The present invention provides a composite bulk block for manufacturing a dental prosthesis, comprising a glass ceramic matrix and a polymer, wherein the glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystal phase dispersed in the glass matrix, the crystal phase includes at least one selected from a leucite crystal phase and a lithium disilicate crystal phase as a main crystal phase, the polymer is included in an amount of 20 to 40 wt% based on the weight of the entire bulk block, the glass ceramic matrix has an average particle size of 3 to 10 μm, and the polymer includes an amphoteric ion group.

[0022] According to a preferred embodiment of the present invention, the zwitterionic group may be derived from at least one 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-dimethylammonio propanesulfonate), SPP (N-(3-methacryloylimino)propyl-N,N-dimethylammonio propanesulfonate), CBMA (carboxybetaine methacrylate) and SPV (3-(2'-vinyl-pyridinio)propanesulfonate), and more Preferably, the zwitterionic group is derived from at least one selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA), and most preferably, the zwitterionic group may be derived from 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA).

[0023] In a preferred embodiment of the present invention, the zwitterionic group 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.

[0024] In one embodiment of the present invention, the glass ceramic matrix may be included in an amount of 74.5 to 77.9 wt%.

[0025] 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.

[0026] 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-methacryloyloxy propoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethanedimethacrylate (UDMA), urethane dimethacrylate (UDM), biphenyldimethacrylate (BPDM), n-tolylglycine-glycidylmethacrylate (NTGE), polyethylene glycol It may be at least one selected from the group consisting of polyethylene glycol dimethacrylate (PEG-DMA) and oligocarbonate dimethacrylic esters.

[0027] In one embodiment of the present invention, the composite bulk block for manufacturing a dental prosthesis may have a biaxial flexural strength of 220 to 280 MPa.

[0028] In one embodiment of the present invention, the glass matrix may include 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 coloring agent.

[0029] In one embodiment of the present invention, a glass ceramic matrix is ​​formed by melting a glass composition including SiO2 69.0 to 75.0 wt%, Li2O 12.0 to 14.0 wt%, Al2O3 2.5 to 3.5 wt%, ZnO 0.12 to 0.22 wt%, K2O 1.1 to 2.7 wt%, Na2O 0.1 to 0.3 wt%, P2O5 2.0 to 6.0 wt% and a coloring agent, water quenching the glass melt to obtain a glass molded body of a granular size, and first crushing the glass powder to prepare a glass powder having a maximum average particle size of 300 ㎛ or less; and subjecting the glass powder to a crystallization heat treatment at a furnace temperature starting from room temperature to a maximum temperature of 755 to 810°C for 30 minutes to 6 hours. It may be manufactured by a method including a step of manufacturing a glass ceramic powder having an average particle size of 3 to 10 ㎛ by crushing a crystallized heat-treated powder; and a step of forming the glass ceramic powder into a predetermined shape.

[0030]

[0031] In addition, the present invention provides a method for manufacturing a composite bulk block for manufacturing a dental prosthesis, comprising a glass ceramic matrix and a polymer, the method comprising the steps of: preparing crystalline glass powder having a maximum average particle size of 300 ㎛ or less; subjecting the crystalline glass powder to a crystallization heat treatment at a furnace temperature starting 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 ㎛; and forming the glass ceramic powder into a predetermined shape.

[0032] In the method for manufacturing a composite bulk block for manufacturing a dental prosthesis according to the present invention, the polymer may be included in an amount of 20 to 40 wt% of the entire composite bulk block.

[0033] In a preferred embodiment of a method for manufacturing a composite bulk block in terms of providing antifouling properties, the polymer may include a zwitterionic group.

[0034] In a specific embodiment, the zwitterionic group may be derived from at least one 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-dimethylammonio propanesulfonate (SPE), N-(3-methacryloylimino)propyl-N,N-dimethylammonio propanesulfonate (SPP), carboxybetaine methacrylate (CBMA), and 3-(2'-vinyl-pyridinio)propanesulfonate (SPV), more preferably, the zwitterionic group may be derived from at least one 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-dimethylammonio propanesulfonate (SPE), N-(3-methacryloylimino)propyl-N,N-dimethylammonio propanesulfonate (SPP), carboxybetaine methacrylate (CBMA), and 3-(2'-vinyl-pyridinio)propanesulfonate (SPV), and more preferably, the zwitterionic group may be derived from at least one selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine (MPC), sulfobetaine methacrylate (SBMA), sulfobetaine methacrylate (SBMA), sulfobe The ionic group may be derived from at least one selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA), and most preferably, the zwitterionic group may be derived from 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA).

[0035] In a specific embodiment, the zwitterionic group 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.

[0036] In the method for manufacturing a composite bulk block according to the present invention, the glass ceramic matrix may be included in an amount of 74.5 to 77.9 wt%.

[0037] 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.

[0038] In a specific embodiment, the curable organic material is selected from the group consisting of hydroxy ethyl methacrylate (HEMA), 2,2-bis [4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethanedimethacrylate (UDMA), urethane dimethacrylate (UDM), biphenyldimethacrylate (BPDM), n-tolyglycine-glycidylmethacrylate (NTGE), polyethylene glycol It may be at least one selected from the group consisting of polyethylene glycol dimethacrylate (PEG-DMA) and oligocarbonate dimethacrylic esters.

[0039] In a method for manufacturing a composite bulk block according to a preferred embodiment of the present invention, the crystalline glass powder may be obtained from a glass composition comprising SiO2 69.0 to 75.0 wt%, Li2O 12.0 to 14.0 wt%, Al2O3 2.5 to 3.5 wt%, ZnO 0.12 to 0.22 wt%, K2O 1.1 to 2.7 wt%, Na2O 0.1 to 0.3 wt%, P2O5 2.0 to 6.0 wt% and a coloring agent, and more specifically, the crystalline glass powder may be obtained by melting a glass composition, water quenching the glass melt to obtain a glass molded body of an assembly size, and first crushing the same.

[0040]

[0041] Additionally, in another embodiment of the present invention, a prosthesis is provided, which is processed from a composite bulk block according to the above embodiments, and includes a glass ceramic matrix and a polymer, wherein the glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystal phase dispersed in the glass matrix, and the crystal phase includes at least one selected from a leucite crystal phase and a lithium disilicate crystal phase as a main crystal phase, and the polymer is included in an amount of 20 to 40 wt% based on the weight of the entire bulk block, and the glass ceramic matrix has an average particle diameter of 3 to 10 μm, and the polymer includes a zwitterionic group.

[0042] 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 capable of inhibiting adhesion of oral contaminants.

[0043] Figures 1 and 2 are results of evaluating the antifouling properties of a composite bulk block according to the present invention. Figure 1 is a graph showing the results of evaluating the CFU reduction rate compared to the control group for six experimental groups of composite bulk blocks according to the present invention, and Figure 2 is a photograph showing two of the experimental groups compared to the control group.

[0044] The aforementioned and additional aspects of the present invention will become more apparent through preferred embodiments described with reference to the accompanying drawings. Below, these embodiments of the present invention will be described in detail so that those skilled in the art can easily understand and reproduce them.

[0045] The present invention provides a composite bulk block for manufacturing a dental prosthesis, comprising a glass ceramic matrix and a polymer, wherein the glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystal phase dispersed in the glass matrix, the crystal phase includes at least one selected from a leucite crystal phase and a lithium disilicate crystal phase as a main crystal phase, the glass ceramic matrix has an average particle diameter of 3 to 10 µm, the polymer is included in an amount of 20 to 40 wt% based on the weight of the entire bulk block, and the polymer includes a zwitterionic group.

[0046] In the description above and below, the term “main crystal phase” is defined as a crystal phase that accounts for at least 50 wt% of the entire crystal phase, and the term “additional crystal phase” may be defined as the remaining crystal phase(s) other than the main crystal phase among the entire crystal phase.

[0047] The content of the crystal phase can be calculated through X-ray diffraction analysis, for example, the ratio F of crystal phase a in a specimen with two polymorphs a and b. a is quantitatively expressed by the following mathematical formula 1.

[0048]

[0049] This value can be obtained by measuring the intensity ratio of the two crystal phases and obtaining the integer K. K is the absolute intensity ratio I of the two pure polymorphs. oa / I ob , and is obtained by measuring standard substances.

[0050] In the descriptions above and below, the term "main crystal phase" may be defined as being established based on the content produced by this method.

[0051] In the description above and below, the composite bulk block has no shape limitation and may include various shapes of bulk bodies such as a block shape, a disk shape, an ingot shape, a cylinder shape, etc.

[0052] The composite bulk block according to the present invention includes a glass ceramic as a ceramic in consideration of the difference in refractive index between the monomer material forming the polymer and the ceramic, and in particular, a leucite-based glass ceramic or a lithium disilicate-based glass ceramic may be preferable in terms of aesthetics, and most preferably, a lithium disilicate-based glass ceramic may be preferable.

[0053] In the composite bulk block according to the present invention, it is preferable that the glass ceramic matrix has an average particle size of 3 to 10 ㎛, preferably 3 to 5 ㎛, in that it can improve mechanical properties. A composite bulk block including a glass ceramic matrix having an average particle size of such a degree can be processed and applied as a prosthesis, and it is preferable that it can exhibit mechanical properties that can be applied as an inlay or onlay as well as a molar crown.

[0054] Meanwhile, it may be preferable that the polymer present in the composite bulk block be included in an amount of 20 to 40 wt% based on the weight of the entire bulk block. However, if the polymer is included in an amount of less than 20 wt% based on the weight of the entire bulk block, it may be disadvantageous in use due to low processability caused by the brittleness of ceramics, and if it is included in an amount exceeding 40 wt%, problems such as fracture or wear may occur due to excessively low mechanical properties. A composite bulk block according to a specific embodiment of the present invention may include a glass ceramic matrix in an amount of 74.5 to 77.9 wt%.

[0055] Meanwhile, the composite bulk block according to the present invention may be a polymer containing a zwitterionic group.

[0056] A zwitterionic group can be defined as a functional group of an amphoteric ion or a zwitter ion, which refers to a molecule that is both electrically positive and negative in chemistry and is neutral. Examples of the present invention include MPC (2-methacryloyloxyethyl phosphorylcholine), sulfobetaine methacrylate (SB), DMPC (1,2-dimyristoylsn-glycero-3-phosphatidylcholine), DMSP (3-dimethylsulfoniopropanoate), trigonelline, ectoine, betaine, SPE (N-(2-methacryloyloxy)ethyl-N,N-dimethylammonio propanesulfonate), SPP (N-(3-methacryloylimino)propyl-N,N-dimethylammonio propanesulfonate), CBMA (carboxybetaine It may be derived from at least one amphoteric compound selected from the group consisting of methacrylate) and SPV (3-(2'-vinyl-pyridinio)propanesulfonate).

[0057] 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, by including the aforementioned hydrophilic functional groups, MPC possesses high hydrophilicity and can form a stable hydration shell, resulting in excellent anti-gouling properties.

[0058] SBMA (sulfobetaine methacrylate) contains sulfobetaine, which has a sulfonate functional group instead of the phosphate group of phosphatidylcholine. Like MPC, it is biocompatible and has high potential for in vivo applications. It is a zwitterionic polymer with both a sulfonic acid anion and an ammonium cation group in a single molecule. SBMA also has antifouling properties and, compared to PC-based polymers, is easier and more simple to synthesize, making it readily available for more commercial applications.

[0059] Although MPC and SBMA, which are derived from zwitterionic groups, may exhibit some differences, most zwitterionic polymers can suppress nonspecific adsorption in aqueous solutions through hydrophobic or electrostatic attraction. Furthermore, the addition of zwitterionic substances as additives can suppress thermal and chemical denaturation of proteins. In particular, the aforementioned MPC and SBMA mimic biological components, allowing for more stable in vivo use.

[0060] In this respect, the zwitterionic group may be derived from at least one selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA).

[0061] Ideally, the zwitterionic groups would be derived from 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA).

[0062] When zwitterionic groups derived from MPC and SBMA are included together, the weight ratio of MPC and SBMA can be set between 1:3 and 3:1. In this case, when two or more zwitterionic substances are included in the above-mentioned specific ratio, the antifouling properties of the composite bulk block are further improved compared to when used alone. The most preferable weight ratio of MPC and SBMA is 1:1.

[0063] When introducing such zwitterionic groups into the composite bulk block, it may be desirable that the content be included within an appropriate range that can exhibit antifouling properties without deteriorating mechanical properties. The content may be preferably 0.1 to 0.45 wt% of the total composite bulk block composition based on the weight of the zwitterionic compound, and preferably, a mixture of MPC and SBMA may be used in an amount of 0.15 wt% or more and less than 0.45 wt%.

[0064] Meanwhile, in the dental bulk block of the present invention, the polymer may be bonded to the glass ceramic matrix through a silane bond.

[0065] Such silane bonding can be achieved through surface treatment of the glass ceramic matrix, specifically by treating the surface of the glass ceramic with an organic functional silane compound having an ethylenically unsaturated double bond and bonding a polymer thereto.

[0066] More specifically, the organofunctional silane may be at least one selected from the group consisting of, but not limited to, methacryloxyalkylene trialkoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-methacryloxypropyl triethoxysilane.

[0067] Examples of such processing methods include the method described in Korean Patent No. 10-1609291, the method described in Korean Patent No. 10-1682542, the method described in Korean Patent No. 10-2122202, or the method described in Korean Patent No. 10-2228118.

[0068] The polymer included in the composite bulk block according to the present invention may be a cured product of a curable organic material selected from among (meth)acrylate monomers and oligomers containing an unsaturated double bond, which includes a zwitterionic group as described above. As a specific example, the curable organic material may be hydroxy ethyl methacrylate (HEMA), 2,2-bis [4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethane dimethacrylate (UDMA), urethane dimethacrylate (UDM), biphenyl It may be at least one selected from the group consisting of biphenyldimethacrylate (BPDM), n-tolyglycine-glycidylmethacrylate (NTGE), polyethylene glycol dimethacrylate (PEG-DMA), and oligocarbonate dimethacrylic esters.

[0069] Among these monomers and / or oligomers, for example, UDMA or Bis-GMA have high viscosity, so they can be mixed with TEGDMA, which has low viscosity, in a mass ratio of 5:5 to 6:4, but this is not a limitation.

[0070] In the case of curable organic materials, shrinkage hardening occurs during polymerization, but the effect of minimizing changes in physical properties through shrinkage hardening can also be obtained through the organic functional silane described above.

[0071] It goes without saying that surface treatment of crystallized glass using such organic functional silanes can be performed using a solution of the organic functional silane diluted in ethanol, taking into account the specificity of dental composites.

[0072] In this way, by treating the surface of a glass ceramic with an organic functional silane and combining it with a polymer to manufacture a composite bulk block, the volume % of inorganic matter in the composite as a whole is increased, thereby improving biaxial flexural strength and hardness.

[0073] Meanwhile, an initiator may be included to cure the curable organic material by cross-linking it into a polymer form. Types of initiators include photoinitiators and thermal initiators. In the present invention, a preferred initiator is a thermal initiator, and a composite having superior physical properties can be obtained when thermally polymerized by including a thermal initiator compared to when photopolymerization is performed by including a photoinitiator.

[0074] The thermal initiator may be a variety of compounds known in the art, including, but not limited to, known peroxides such as benzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, or tert-butyl perbenzoate.

[0075] In obtaining a composite bulk block for manufacturing a dental prosthesis according to the present invention as described above, it is preferable that the glass matrix include SiO2 69.0 to 75.0 wt%, Li2O 12.0 to 14.0 wt%, Al2O3 2.5 to 3.5 wt%, ZnO 0.12 to 0.22 wt%, K2O 1.1 to 2.7 wt%, Na2O 0.1 to 0.3 wt%, P2O5 2.0 to 6.0 wt% and a coloring agent.

[0076] This glass composition undergoes crystal nucleation and crystal growth heat treatment to precipitate a crystal phase within an amorphous glass matrix for crystallization. The temperature at which crystal nuclei and crystal growth occur in the above-mentioned glass matrix corresponds to 500°C to 880°C. That is, crystal nuclei begin to form from a minimum of 500°C and crystal growth occurs with increasing temperature, and this crystal growth exhibits the lowest light transmittance for use as an artificial tooth at a maximum of 880°C. That is, the light transmittance gradually decreases from the temperature at which crystals grow to a maximum of 880°C. When focusing on this crystal growth, crystal growth is performed to a degree that satisfies high strength while also satisfying machinability, and this can be useful as a glass ceramic matrix of a composite bulk block according to the present invention.

[0077] From this point of view, the glass ceramic constituting the dental composite block according to the present invention comprises the steps of: melting a glass composition including SiO2 69.0 to 75.0 wt%, Li2O 12.0 to 14.0 wt%, Al2O3 2.5 to 3.5 wt%, ZnO 0.12 to 0.22 wt%, K2O 1.1 to 2.7 wt%, Na2O 0.1 to 0.3 wt%, and P2O5 2.0 to 6.0 wt%, water quenching the glass melt to obtain a glass molded body of a granular size, and first crushing the same to prepare glass powder having a maximum average particle size of 300 ㎛ or less; performing a crystallization heat treatment on the glass powder at a furnace temperature starting from room temperature to a maximum temperature of 755 to 810°C for 30 minutes to 6 hours; It may be preferable to obtain a product including a step of producing a glass ceramic powder having a size of 3 to 10 ㎛, preferably 3 to 5 ㎛, by crushing a crystallized heat-treated powder; and a step of forming the glass ceramic powder into a predetermined shape.

[0078] A specific example for obtaining a glass ceramic constituting the composite bulk block of the present invention is as follows: First, a glass composition including 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.

[0079] Instead of Li2O, Li2CO3 can be added as a glass composition, and carbon dioxide (CO2), which is the carbon (C) component of Li2CO3, is emitted as a gas during the melting process of the glass and escapes. In addition, instead of K2O and Na2O in the alkali oxide, K2CO3 and Na2CO3 can be added, respectively, and carbon dioxide (CO2), which is the carbon (C) component of K2CO3 and Na2CO3, is emitted as a gas during the melting process of the glass and escapes.

[0080] Mixing is done using a dry mixing process, and a ball milling process can be used as a dry mixing process. Specifically, the ball milling process involves loading the starting raw materials into a ball mill, and rotating the ball mill at a constant speed to mechanically pulverize and uniformly mix the starting raw materials. The balls used in the ball milling machine can be made of ceramic materials such as zirconia or alumina, and the balls can be all the same size or have at least two different sizes. The ball size, milling time, and the rotation speed of the ball milling machine are adjusted in consideration of the target particle size. For example, the ball size can be set to a range of about 1 mm to 30 mm in consideration of the particle size, and the rotation speed of the ball milling machine can be set to a range of about 50 to 500 rpm. It is preferable to perform ball milling for 1 to 48 hours in consideration of the target particle size, etc. By ball milling, the starting materials are ground into fine particles, which have a uniform particle size and are uniformly mixed at the same time.

[0081] The mixed starting materials are placed in a melting furnace, and the melting furnace containing the starting materials is heated to melt the starting materials. Here, melting means that the starting materials change into a viscous liquid state rather than a solid state. It is preferable that the melting furnace be made of a material with a high melting point, high strength, and a low contact angle to suppress the phenomenon of the melt material sticking together. For this purpose, it is preferable that the melting furnace be made of a material such as platinum (Pt), diamond-like carbon (DLC), or chamotte, or a material whose surface is coated with a material such as platinum (Pt) or diamond-like carbon (DLC).

[0082] Melting is preferably performed at 1,400 to 2,000°C under normal pressure for 1 to 12 hours. If the melting temperature is lower than 1,400°C, the starting material may not fully melt, and if the melting temperature exceeds 2,000°C, excessive energy consumption is required, which is not economical. Therefore, it is preferable to melt at a temperature within the above-mentioned range. In addition, if the melting time is too short, the starting material may not sufficiently melt, and if the melting time is too long, excessive energy consumption is required, which is not economical. The heating rate of the melting furnace is preferably 5 to 50°C / min. If the heating rate of the melting furnace is too slow, it takes a long time, which reduces productivity, and if the heating rate of the melting furnace is too fast, the rapid temperature increase may cause a large amount of volatilization of the starting material, which may deteriorate the physical properties of the crystallized glass. Therefore, it is preferable to increase the temperature of the melting furnace at a heating rate within the above-mentioned range. Melting is preferably performed in an oxidizing atmosphere such as oxygen (O2) or air.

[0083] To crush the glass melt into a desired shape and size, the glass melt is water quenched to obtain a glass molded body of an assembly size, and this is first crushed to prepare glass powder having a maximum average particle size of 300 ㎛ or less.

[0084] The glass powder obtained in this manner is transferred to a crystallization heat treatment furnace to manufacture the desired crystallization heat treatment powder.

[0085] At this time, the crystallization heat treatment is performed by starting the temperature inside the furnace from room temperature and increasing it to a maximum temperature of 755 to 810°C for 30 minutes to 6 hours, thereby obtaining a crystallization heat treatment powder having only pure lithium disilicate as a crystal phase and including a crystal phase having a crystal size of 0.01 to 1.0 μm.

[0086] Next, the crystallized heat-treated powder is pulverized to produce a glass ceramic powder having an average particle size of 3 to 10 ㎛, preferably 3 to 5 ㎛.

[0087] Finally, a glass ceramic matrix can be obtained by shaping the glass ceramic powder into a predetermined shape.

[0088] Meanwhile, in the step of forming glass ceramic powder into a predetermined shape, the mechanical properties can be affected depending on the forming conditions. As the forming pressure increases and the heat treatment time increases, the mechanical properties can be improved.

[0089] However, if the molding pressure or heat treatment conditions are excessively high or prolonged, the glass ceramic matrix and polymer may not mix well, which may result in a deterioration in mechanical properties. Considering this, it is preferable that the molding pressure be 15 to 25 tons and the heat treatment time be 5 to 7 hours. Of course, the molding load or heat treatment time can be appropriately adjusted within the above range depending on the shape or area of ​​the intended composite bulk block.

[0090] By using the molded product obtained in this way as a glass ceramic matrix, a composite bulk block for manufacturing a dental prosthesis can be manufactured, which includes a glass ceramic matrix and a polymer according to the present invention, wherein the glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystal phase dispersed in the glass matrix, and the crystal phase includes at least one selected from a leucite crystal phase and a lithium disilicate crystal phase as a main crystal phase, the glass ceramic matrix has an average particle size of 3 to 10 ㎛, and the polymer is included in an amount of 20 to 40 wt% based on the weight of the entire bulk block, and includes a zwitterion.

[0091] In some cases, additional vacuum may be applied to ensure even dispersion of the polymer within the composite bulk block, and the degree of vacuum may also affect the mechanical properties. The vacuum pressure is 10 -2 torr to 10 -3 Although it may be desirable in terms of mechanical properties when the pressure is around torr, it is not limited to this.

[0092] Meanwhile, in the manufacture of composite bulk blocks, the curing temperature and time can be appropriately controlled by considering the curing characteristics of the polymer. The mechanical properties can also be affected depending on the curing time, and the mechanical properties can be improved as the curing time increases.

[0093] The obtained composite bulk block can be machined into a desired shape and manufactured into a prosthesis by processing using CAD-CAM, etc. as described above.

[0094] A machined prosthesis comprises a glass ceramic matrix and a polymer, wherein the glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystal phase dispersed in the glass matrix, wherein the crystal phase comprises at least one selected from a leucite crystal phase and a lithium disilicate crystal phase as a main crystal phase, and the polymer is contained in an amount of 20 to 40 wt% based on the weight of the entire bulk block, wherein the glass ceramic matrix has an average particle size of 3 to 10 μm, and the polymer contains a zwitterionic group, which has excellent mechanical properties and is useful as an inlay, an onlay, and a molar crown, and can exhibit an effect of inhibiting bacterial adhesion and preventing secondary caries caused by the prosthesis.

[0095] In relation to the composite bulk block for manufacturing dental prostheses and the manufacturing method thereof, the results of confirming the influence of the average particle diameter of the glass ceramic matrix on the mechanical properties of the composite bulk block are as shown in Table 1 below. The average particle diameter here is the average particle diameter of the glass ceramic powder forming the glass ceramic matrix, and this was calculated through SEM.

[0096] At this time, the composite bulk block is manufactured into a composite bulk block with the same composition and through the same process.

[0097] Average particle size of the glass ceramic matrix (㎛) Biaxial flexural strength of the composite block (MPa) Three-point flexural strength of the composite block (MPa) 112.8 20 7.66 ± 7.45 18 4.25 ± 3.45 24.6 25 1.78 ± 9.67 22 7.52 ± 1.24

[0098] In the descriptions above and below, the biaxial flexural strength is defined as a value measured in accordance with ISO 4049. In addition, the three-point flexural strength is defined as a value measured in accordance with ISO 6872.

[0099] From the description in Table 1 above, 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 in the composite bulk block, and in particular, it is preferable that the average particle size of the glass ceramic matrix be 3 to 10 ㎛, in that it further improves the mechanical properties of the composite block.

[0100] Until now, hybrid products for dental CAD / CAM have been mainly applied to inlays and onlays due to insufficient mechanical properties. However, it can be predicted that the composite block according to the present invention can be applied to molar crowns due to its excellent mechanical properties.

[0101] Meanwhile, as described above, the composite bulk block according to the present invention includes a zwitterionic group in the polymer. In order to determine whether the zwitterionic group affects the mechanical properties of the composite bulk block, a composite block was manufactured without including the zwitterionic group but with all other compositions and processes identical, and the result was compared. As a result, as shown in Table 2, it was confirmed that including the zwitterionic group in the composite bulk block does not have a negative effect on the mechanical properties. However, if the content is excessive, the mechanical properties may be lowered, making it difficult to express a level of strength that can be applied to a molar crown. Therefore, it can be seen that it is necessary to control the content of the compound derived from the zwitterionic group in the composite block in this respect.

[0102] Average particle size (㎛) of the glass ceramic matrix of the specimen Content of amphoteric compounds (wt%) in the composition Biaxial flexural strength of the composite block (MPa) Three-point flexural strength of the composite block (MPa) 14.6 0.15 25 1.78 ± 9.67 22 7.52 ± 1.24 24.60 25 3.81 ± 28.5 12 27.55 ± 5.08

[0103] Meanwhile, an experiment was conducted to confirm the effect of the type and content of amphoteric ions on the antifouling properties of the complex block according to the present invention.

[0104] At this time, the control group was prepared as a complex block not containing a zwitterion, as shown in Sample 2 of Table 5. As an experimental group, a complex block containing an zwitterion compound was prepared as shown in Sample 2 of Table 1 and Sample 1 of Table 2. Specifically, six complex block specimens were prepared, including specimens containing only MPC, only SBMA, and a mixed composite bulk block of MPC and SBMA as the zwitterion compound, in which the contents of the composite bulk block were 0.15 wt% and 0.45 wt%, respectively, of the total composition.

[0105] The specific experimental groups are summarized in Table 3 below.

[0106] Amphoteric compound Amphoteric compound content (wt%) G11MPC0.15G12MPC0.45G13SBMA0.15G14SBMA0.45G15MPC+SBMA0.15G16MPC+SBMA0.45

[0107] Note) MPC: 2-methacryloyloxyethyl phosphorylcholine, SBMA: sulfobetaine methacrylate

[0108] The antifouling evaluation method is a method that measures the colony forming unit (CFU) of bacteria, and is specifically as follows.

[0109] 1) The surface of a rectangular specimen measuring 10 mm in width, 10 mm in length, and 2 mm in height was coated with artificial saliva containing mucin for 4 hours, taking into account the clinical situation.

[0110] 2) 1 × 10 to all groups surface-treated with artificial saliva 6Dispense CFU / mL of cariogenic bacteria (Streptococcus mutans, S. mutans) and culture at 37°C for 72 hours.

[0111] 3) All groups that had been cultured at 37°C for 72 hours were washed three times with PBS solution and the biofilm formed on the surface was separated through vortexing and sonication.

[0112] 4) 10 -5 Dilute to double the amount, spread on a BHI Agar plate, and incubate at 37°C for 24 hours.

[0113] 5) Measure the colony forming units (CFU) of bacteria produced on the agar plate cultured for 24 hours.

[0114] 6) Calculate the CFU value of the experimental group as a % compared to the control group.

[0115] The results are as shown in Fig. 1. In addition, a photograph of the culture medium related thereto is shown in Fig. 2.

[0116] From the results of Fig. 1, it can be seen that all composite blocks according to the present invention including zwitterionic groups exhibit antifouling properties. Specifically, in terms of the CFU reduction rate, the case where SBMA alone was included at 0.45 wt% showed the best results, but considering the mechanical properties and economic feasibility of the composite bulk block, the case where MPC and SBMA were mixed is preferable, and in particular, the case where MPC and SBMA were mixed and included at 0.15 wt% of the total composition showed the most preferable results.

[0117] The composite block of the present invention according to the above-described examples specifically has a composition as shown in Table 4 below; however, it is to be understood that the present invention is not limited to these examples of composition.

[0118] Composition (weight %) Glass ceramic matrix 74.5 - 77.9 UDMA 12.3 - 14.5 TEGDMA 7.5 - 8.4 BPO 0.07 - 0.08 Zwitterionic 0.10 - 0.45

[0119] UDMA: diurethanedimethacrylate, TEGDMA: triethylene glycoldimethacrylate, BPO: benzoyl peroxide

[0120]

[0121] Although the present invention has been described with reference to an embodiment, this is merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom.

[0122] The present invention relates to a composite bulk block for manufacturing a dental prosthesis capable of processing a restoration having excellent mechanical strength and exhibiting anti-fouling properties, a method for manufacturing the same, and a prosthesis manufactured therefrom.

[0123] 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 capable of inhibiting adhesion of oral contaminants.

Claims

1. Contains a glass ceramic matrix and a polymer, The glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystal phase dispersed in the glass matrix, and the crystal phase includes at least one selected from a leucite crystal phase and a lithium disilicate crystal phase as the main crystal phase. 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 particle size of 3 to 10 ㎛. The polymer contains an amphoteric ion group. Composite bulk blocks for the manufacture of dental prosthetics.

2. In the first paragraph, the zwitterionic group is characterized in that it is derived from at least one 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-dimethylammonio propanesulfonate), SPP (N-(3-methacryloylimino)propyl-N,N-dimethylammonio propanesulfonate), CBMA (carboxybetaine methacrylate), and SPV (3-(2'-vinyl-pyridinio)propanesulfonate). Composite bulk blocks for the manufacture of dental prosthetics.

3. In the first paragraph, the zwitterionic group is characterized in that it is derived from at least one selected from the group consisting of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA). Composite bulk blocks for the manufacture of dental prosthetics.

4. In the first paragraph, the zwitterionic group is characterized in that it is derived from MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA). Composite bulk blocks for the manufacture of dental prosthetics.

5. In the fourth paragraph, the zwitterionic group is characterized in that it is derived from a mixture of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA) at 0.1 to 0.45 wt% of the total composite bulk block composition. Composite bulk blocks for the manufacture of dental prosthetics.

6. In the first paragraph, the glass ceramic matrix is ​​characterized in that it is included in an amount of 74.5 to 77.9 wt%. Composite bulk blocks for the manufacture of dental prosthetics.

7. In the first paragraph, the polymer is characterized in that it includes a cured product of a curable organic material selected from (meth)acrylate monomers and oligomers containing an unsaturated double bond. Composite bulk blocks for the manufacture of dental prosthetics.

8. In the 7th paragraph, the curable organic material is hydroxy ethyl methacrylate (HEMA), 2,2-bis [4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethanedimethacrylate (UDMA), urethane dimethacrylate (UDM), biphenyldimethacrylate (BPDM), n-tolyglycine-glycidylmethacrylate (NTGE), polyethylene glycol characterized by at least one selected from the group consisting of polyethylene glycol dimethacrylate (PEG-DMA) and oligocarbonate dimethacrylic esters. Composite bulk blocks for the manufacture of dental prosthetics.

9. In paragraph 1, The composite bulk block for manufacturing the above dental prosthesis is characterized by having a biaxial flexural strength of 220 to 280 MPa. Composite bulk blocks for the manufacture of dental prosthetics.

10. In the first paragraph, the glass matrix is ​​characterized by 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 P2O5, and a coloring agent. Composite bulk blocks for the manufacture of dental prosthetics.

11. In the first paragraph, the glass ceramic matrix comprises a step of melting a glass composition containing SiO2 69.0 to 75.0 wt%, Li2O 12.0 to 14.0 wt%, Al2O 3 2.5 to 3.5 wt%, ZnO 0.12 to 0.22 wt%, K2O 1.1 to 2.7 wt%, Na2O 0.1 to 0.3 wt%, P2O 5 2.0 to 6.0 wt% and a coloring agent, water quenching the glass melt to obtain a glass molded body of an aggregate size, and first crushing the glass molded body to prepare a glass powder having a maximum average particle size of 300 ㎛ or less; and a step of crystallizing the glass powder by heat-treating the temperature in a furnace starting from room temperature to a maximum temperature of 755 to 810°C for 30 minutes to 6 hours. A method characterized in that it is manufactured by a step of producing a glass ceramic powder having an average particle size of 3 to 10 ㎛ by crushing a crystallized heat-treated powder; and a step of forming the glass ceramic powder into a predetermined shape. Composite bulk blocks for the manufacture of dental prosthetics.

12. A method for manufacturing a composite bulk block for manufacturing a dental prosthesis comprising a glass ceramic matrix and a polymer, A step for preparing crystalline glass powder having a maximum average particle size of less than 300 ㎛; A step of crystallizing the above crystalline glass powder by heat-treating the furnace temperature starting from room temperature to a maximum temperature of 755 to 810°C for 30 minutes to 6 hours; A step of producing a glass ceramic powder having an average particle size of 3 to 10 ㎛ by crushing a crystallized heat-treated powder; and Characterized in that it includes a step of forming glass ceramic powder into a predetermined shape. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

13. In the 12th paragraph, the polymer is characterized in that it is included in 20 to 40 wt% of the entire composite bulk block. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

14. In claim 12 or 13, the polymer is characterized in that it contains a zwitterionic group. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

15. In the 14th paragraph, the zwitterionic group is characterized in that it is derived from at least one 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-dimethylammonio propanesulfonate), SPP (N-(3-methacryloylimino)propyl-N,N-dimethylammonio propanesulfonate), CBMA (carboxybetaine methacrylate), and SPV (3-(2'-vinyl-pyridinio)propanesulfonate). doing, A method for manufacturing a composite bulk block for manufacturing dental prosthetics.

16. In the 14th paragraph, the zwitterionic group is characterized in that it is derived from at least one selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine (MPC) and sulfobetaine methacrylate (SBMA). Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

17. In the 14th paragraph, the zwitterionic group is characterized in that it is derived from MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA). Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

18. In the 17th paragraph, the zwitterionic group is characterized in that it is derived from a mixture of MPC (2-methacryloyloxyethyl phosphorylcholine) and sulfobetaine methacrylate (SBMA) at 0.1 to 0.45 wt% of the total composite bulk block composition. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

19. In the 12th paragraph, the glass ceramic matrix is ​​characterized in that it is included in an amount of 74.5 to 77.9 wt%. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

20. In the 12th paragraph, the polymer is characterized in that it includes a cured product of a curable organic material selected from (meth)acrylate monomers and oligomers containing an unsaturated double bond. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

21. In the 20th paragraph, the curable organic material is hydroxy ethyl methacrylate (HEMA), 2,2-bis [4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), diurethanedimethacrylate (UDMA), urethane dimethacrylate (UDM), biphenyldimethacrylate (BPDM), n-tolyglycine-glycidylmethacrylate (NTGE), polyethylene glycol characterized by at least one selected from the group consisting of polyethylene glycol dimethacrylate (PEG-DMA) and oligocarbonate dimethacrylic esters. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

22. In the 12th paragraph, the crystalline glass powder is characterized in that it is obtained from a glass composition containing SiO2 69.0 to 75.0 wt%, Li2O 12.0 to 14.0 wt%, Al2O3 2.5 to 3.5 wt%, ZnO 0.12 to 0.22 wt%, K2O 1.1 to 2.7 wt%, Na2O 0.1 to 0.3 wt%, P2O5 2.0 to 6.0 wt% and a coloring agent. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

23. In the 22nd paragraph, the crystalline glass powder is characterized in that it is obtained by melting a glass composition, water quenching the glass melt to obtain a glass molded body of an assembly size, and first crushing the same. Method for manufacturing composite bulk blocks for manufacturing dental prostheses.

24. Processed from the composite bulk block of Article 1, Containing a glass ceramic matrix and a polymer, The glass ceramic matrix is ​​composed of an amorphous glass matrix and a crystal phase dispersed in the glass matrix, and the crystal phase includes at least one selected from a leucite crystal phase and a lithium disilicate crystal phase as the main crystal phase. 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 particle size of 3 to 10 ㎛. Polymers contain zwitterionic groups, Prosthesis.

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