Method for manufacturing patient-customized dental prosthesis by means of 3D printer

Abstract

The present invention provides a method for manufacturing a patient-customized dental prosthesis by means of a 3D printer, the method using a 3D printer to separately print patient-customized enamel and dentin shapes and joining same together to manufacture a prosthesis similar to an actual tooth, which can be used for prosthetic treatment. The prosthesis not only has an improved aesthetic appearance as described above, but also exhibits excellent mechanical strength. Thus, after prosthetic treatment, the prosthesis is not damaged by use.

Description

Method for manufacturing patient-specific dental prostheses using a 3D printer

[0001] The present invention relates to a method for manufacturing a patient-customized dental prosthesis using a 3D printer.

[0002] Recently, dental prosthetic materials are being replaced by zirconia, which has excellent biocompatibility, is similar in appearance to natural teeth, has superior aesthetics, and has high mechanical properties for improved durability.

[0003] Meanwhile, when manufacturing dental prosthetics using zirconia, the most important aspect is to enhance aesthetics by applying a color gradient to the zirconia to achieve a color corresponding to natural teeth.

[0004] Previously, color gradients were applied based on a color guide, and a process called zirconia coloring liquid was additionally included to induce a more natural color gradient. Here, zirconia coloring liquid refers to a method of applying different colors to different parts of a zirconia block.

[0005] The above-mentioned prior art includes a method in which a zirconia block is immersed in a plurality of color solutions prepared to induce a color gradient of the tooth from light to dark colors, and then heat is applied to cause the color solution to be absorbed. Another method involves introducing zirconia powder into each color solution of a different color, applying heat to cause the color solution to permeate the powder, removing the powder permeated with the color solution, drying it, and then injecting it into a pressurizing device based on a color guide to apply pressure, thereby producing a zirconia block having a color gradient.

[0006] Here, the disadvantage of the above conventional technology is that since all parts of the zirconia block are composed of the same moisture absorption rate, there was the inconvenience of having to replace the color solution for each part to color it.

[0007] It is practically impossible to reproduce the subtle color differences found in the enamel and dentin of teeth using zirconia blocks produced as described above. Furthermore, since there are individual differences in tooth enamel and dentin, even if a color similar to that of actual teeth is achieved using zirconia blocks, it is impossible to perfectly replicate the variations that exist between people.

[0008] To address these issues, there is a need to develop a method for manufacturing patient-specific dental prostheses that resemble real teeth, making them difficult to distinguish as prostheses even after treatment, thereby enhancing aesthetics.

[0009] [Prior Art Literature]

[0010] [Patent Literature]

[0011] (Patent Document 1) KR 10-1142805 B1

[0012] The objective of the present invention is to provide a method for manufacturing a patient-customized dental prosthesis using a 3D printer.

[0013] Another objective of the present invention is to provide a method for manufacturing a patient-specific dental prosthesis that can be used for prosthetic treatment by separately printing the shape of the patient-specific tooth enamel and tooth dentin using a 3D printer and joining them to manufacture a prosthesis that is almost identical to a real tooth.

[0014] Another objective of the present invention is to provide a method for manufacturing a patient-specific dental prosthesis that not only improves the aesthetics described above but also has excellent mechanical strength, so that no damage occurs to the prosthesis due to the use of the tooth after the prosthetic treatment is completed.

[0015] To achieve the above-mentioned objective, the present invention relates to a method for manufacturing a patient-specific dental prosthesis using a 3D printer, comprising the steps of: securing data for a tooth requiring prosthetic treatment; forming an image of the tooth requiring prosthetic treatment using the data; and printing using a 3D printer using the image of the tooth, wherein the tooth image is formed into a plurality of images according to the color difference of the tooth, and for each of the plurality of formed tooth images, a plurality of accessory prostheses are printed using a 3D printer, and the plurality of accessory prostheses are bonded to form a prosthesis.

[0016] In addition, the above plurality of accessory prostheses can have their surfaces treated to bond with each other, thereby increasing the bonding strength.

[0017] In addition, the surface treatment can increase the surface area of ​​the contact surface by sandblasting and / or air abrasion.

[0018] In addition, the above plurality of accessory prostheses can be bonded by applying resin cement after the contacting surfaces are surface-treated.

[0019] Additionally, the above prosthesis is printed using a 3D printer with a photocurable resin composition, wherein the photocurable resin composition comprises a photocurable resin composition for a 3D printer; and a surface-treated inorganic material, and the photocurable resin composition may comprise a photocurable oligomer represented by the following chemical formula 1, a reactive monomer, and a photoinitiator:

[0020] [Chemical Formula 1]

[0021]

[0022] [Chemical Formula 2]

[0023]

[0024] [Chemical Formula 3]

[0025]

[0026] [Chemical Formula 4]

[0027]

[0028] Here,

[0029] * indicates the part being combined,

[0030] R1 to R6 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 6 to 30 carbon atoms Selected from the group consisting of an arylamino group, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0031] L1 and L3 are identical or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 30 carbon atoms, and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms.

[0032] L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and

[0033] n and m are identical or different from each other, and each is independently an integer from 1 to 10, and

[0034] R7 to R 12 The groups are identical or different from one another and are each independently selected from the group consisting of hydrogen, deuterium, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms.

[0035] The above substituted alkylene group, substituted arylene group, substituted heteroarylene group, substituted cycloalkylene group, substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group, substituted heteroaryl group, substituted heteroarylalkyl group, substituted alkoxy group, substituted alkylamino group, substituted arylamino group, substituted aralkylamino group, substituted heteroarylamino group, substituted alkylsilyl group, substituted arylsilyl group, and substituted aryloxy group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, carbon number It is substituted with one or more substituents selected from the group consisting of 6 to 30 aryl groups, 5 to 60 nuclei, 6 to 30 heteroaryl alkyl groups, 1 to 30 alkoxy groups, 1 to 30 alkylamino groups, 6 to 30 arylamino groups, 6 to 30 aralkylamino groups, 2 to 24 heteroarylamino groups, 1 to 30 alkylsilyl groups, 6 to 30 arylsilyl groups, and 6 to 30 aryloxy groups, and when substituted with multiple substituents, these are identical or different from each other.

[0036] In addition, the above-mentioned mineral may be selected from the group consisting of alumina, zirconia, barium silicate, and mixtures thereof.

[0037] In addition, the above-mentioned inorganic material can be surface-treated using a silane coupling agent.

[0038] The present invention allows for the separate printing of patient-specific tooth enamel and tooth dentin shapes using a 3D printer, and by joining them, to manufacture a prosthesis that is nearly identical to a real tooth, which can then be utilized in prosthetic treatment.

[0039] In addition to the aforementioned improvement in aesthetics, the prosthesis exhibits excellent mechanical strength, ensuring that no damage occurs to the prosthesis due to tooth use after the prosthetic treatment is completed.

[0040] FIG. 1 is a drawing of a tooth structure according to one embodiment of the present invention.

[0041] FIG. 2 is a drawing of the enamel portion and the dentin portion of a dental prosthesis according to one embodiment of the present invention.

[0042] FIG. 3 relates to a method for testing the compressive strength of a prosthetic material according to one embodiment of the present invention.

[0043] Figure 4 is a photograph of a specimen after a compressive strength test on a prosthetic material according to one embodiment of the present invention.

[0044] Figure 5 is the result of a compressive strength test on a prosthetic material according to one embodiment of the present invention.

[0045] FIG. 6 is a method for measuring adhesive strength using a specimen according to one embodiment of the present invention.

[0046] Figure 7 is a test result for confirming the interfacial adhesion surface of a surface-treated specimen according to one embodiment of the present invention.

[0047] FIG. 8 is an image of a prosthesis manufactured to be the same color as a tooth according to one embodiment of the present invention.

[0048] The present invention relates to a method for manufacturing a patient-specific dental prosthesis using a 3D printer, comprising the steps of: securing data for a tooth requiring prosthetic treatment; forming an image of the tooth requiring prosthetic treatment using the data; and printing using a 3D printer using the image of the tooth, wherein the tooth image forms a plurality of images according to the color difference of the tooth, and for each of the plurality of formed tooth images, printing a plurality of accessory prostheses using a 3D printer, and bonding the plurality of accessory prostheses to form a prosthesis.

[0049] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0050] Generally, a normal person has a total of 32 teeth, consisting of 16 in the upper jaw and 16 in the lower jaw, and after the deciduous teeth formed during infancy are replaced by growth teeth as the child enters the growth stage, the child uses the growth teeth to perform oral activities throughout their life.

[0051] As mentioned above, after the formation of growing teeth, one or more teeth are damaged due to various oral diseases (such as cavities or gum disease). In such cases, smooth pronunciation or food grinding becomes impossible, leading to aesthetic distress and frequently hindering normal social life.

[0052] As one of the methods to restore or treat the damaged teeth as described above, dental prosthetics were applied to restore masticatory function, aesthetics, and normal pronunciation.

[0053] As described above, the types of prosthetics using dentures are classified into general prosthetics, which cover teeth weakened by excessive cavities or root canal treatments or restore areas where teeth are lost; aesthetic prosthetics, which are mainly used in the anterior region to improve tooth discoloration, abnormal shape, and gaps between teeth; and implant prosthetics, which involve removing healthy teeth on both sides to restore the lost area, implanting an artificial tooth root in the damaged area, and placing an artificial tooth on top of it to avoid the discomfort caused by using dentures.

[0054] Titanium, which possesses appropriate mechanical strength, biocompatibility, excellent corrosion resistance, and superior osseointegration ability, is the most widely used material for dental implants. Additionally, alumina, hydroxyapatite (HA), and zirconia ceramics have been studied as materials that can replace titanium.

[0055] Among the aforementioned materials, zirconia is a general term for zirconium oxide (ZrO2). It exhibits chemical and volumetric stability and possesses high flexural strength and fracture toughness by suppressing crack propagation caused by volumetric expansion resulting from the phase strengthening mechanism that occurs during phase transitions due to its polymorphic structure. Furthermore, it does not cause toxic reactions when implanted in the human body and offers excellent resistance to corrosion and wear.

[0056] However, conventional dental prosthetic materials such as titanium, alumina, hydroxyapatite (HA), and zirconia ceramics differ from the actual tooth color, so when dentures are applied through dental prosthetics, there is a problem of poor aesthetics.

[0057] Accordingly, in the present invention, an accessory prosthesis of a prosthesis is manufactured using a 3D printer, and the accessory prosthesis is manufactured by separating it by color identical to the patient's actual tooth color and bonding them together to form a single prosthesis, thereby making it possible to realize a shape identical to the actual patient's tooth.

[0058] Refer to FIG. 1 to illustrate the manufacture of a prosthesis according to one embodiment of the present invention. FIG. 1 is a drawing of a conventional tooth. According to FIG. 1, the tooth typically has a color difference between the enamel portion (100) and the dentin portion (200). This difference cannot be realized in a single output.

[0059] Accordingly, this is a process for manufacturing a prosthesis when, for example, prosthetic treatment is required for tooth No. 11 or No. 21. When tooth No. 11 or No. 21 is extracted or partially damaged and the external surface visible from the outside needs to be completely treated, the enamel and dentin of the tooth typically have a difference in color. Typically, the enamel exhibits a slightly more transparent color, while the dentin exhibits an opaque color. Accordingly, in the present invention, as shown in FIG. 2, an accessory prosthesis (100, 200) can be manufactured by using separate pigments to achieve the same color for the enamel portion (100) and the dentin portion (200) of the tooth. Subsequently, the accessory prosthesis (100) corresponding to the enamel portion and the accessory prosthesis (200) corresponding to the dentin portion, which exhibit different colors, can be bonded together to manufacture a single prosthesis.

[0060] By manufacturing the prosthesis (10) in the manner described above, it is possible to manufacture a tooth that has the same color as the patient's actual tooth.

[0061] As another example, in cases where the color of the tooth is distinguished into two or more colors or a color gradient appears, multiple accessory prostheses can be printed using pigments representing each color and bonded together to manufacture a single prosthesis.

[0062] By using the above method, compared to the case where the aforementioned zirconia is used, it is possible not only to achieve a color equivalent to or very similar to the actual tooth color, but also to produce a patient-customized prosthesis.

[0063] More specifically, in order to manufacture a dental prosthesis as described above, the present invention comprises the steps of: obtaining data for a tooth requiring prosthetic treatment; forming an image of the tooth requiring prosthetic treatment using the data; and printing using a 3D printer using the image of the tooth, wherein the tooth image forms a plurality of images according to the color difference of the tooth, and for each of the plurality of formed tooth images, a plurality of auxiliary prostheses are printed using a 3D printer, and the plurality of auxiliary prostheses can be bonded to form a prosthesis.

[0064] In order to print a prosthesis using the above 3D printer, the step of obtaining the patient's tooth data may utilize a method of obtaining images of the parts requiring prosthetic treatment by using an oral scanner, etc.

[0065] After securing tooth data as described above, an image of the tooth requiring prosthetic treatment can be formed. The image can be formed as a 3D image, and commonly used programs can be used for this purpose. That is, Dental CAD can be used, and 3shape, exocad, inlad, etc., can be used, but is not limited to the above examples; any software capable of forming a tooth image can be used without restriction.

[0066] Subsequently, the tooth image can be printed using a 3D printer. The 3D printing of the present invention refers to a process of manufacturing a three-dimensional object by layering materials using 3D digital data. Although this specification describes 3D printing technologies primarily focusing on DLP (Digital Light Processing), SLA (Stereo Lithography Apparatus), and PolyJet methods, it can be understood that other 3D printing technologies are also applicable.

[0067] The above prosthesis is printed using a 3D printer with a photocurable resin composition, wherein the photocurable resin composition comprises a photocurable resin composition for a 3D printer; and a surface-treated inorganic material, and the photocurable resin composition may comprise a photocurable oligomer represented by the following chemical formula 1, a reactive monomer, and a photoinitiator:

[0068] [Chemical Formula 1]

[0069]

[0070] [Chemical Formula 2]

[0071]

[0072] [Chemical Formula 3]

[0073]

[0074] [Chemical Formula 4]

[0075]

[0076] Here,

[0077] * indicates the part being combined,

[0078] R1 to R6 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 6 to 30 carbon atoms Selected from the group consisting of an arylamino group, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0079] L1 and L3 are identical or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 30 carbon atoms, and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms.

[0080] L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and

[0081] n and m are identical or different from each other, and each is independently an integer from 1 to 10, and

[0082] R7 to R 12The groups are identical or different from one another and are each independently selected from the group consisting of hydrogen, deuterium, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms.

[0083] The above substituted alkylene group, substituted arylene group, substituted heteroarylene group, substituted cycloalkylene group, substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group, substituted heteroaryl group, substituted heteroarylalkyl group, substituted alkoxy group, substituted alkylamino group, substituted arylamino group, substituted aralkylamino group, substituted heteroarylamino group, substituted alkylsilyl group, substituted arylsilyl group, and substituted aryloxy group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, carbon number It is substituted with one or more substituents selected from the group consisting of 6 to 30 aryl groups, 5 to 60 nuclei, 6 to 30 heteroaryl alkyl groups, 1 to 30 alkoxy groups, 1 to 30 alkylamino groups, 6 to 30 arylamino groups, 6 to 30 aralkylamino groups, 2 to 24 heteroarylamino groups, 1 to 30 alkylsilyl groups, 6 to 30 arylsilyl groups, and 6 to 30 aryloxy groups, and when substituted with multiple substituents, these are identical or different from each other.

[0084] The above inorganic material may be selected from the group consisting of alumina, zirconia, barium silicate, and mixtures thereof, and the above inorganic material may be surface-treated using a silane coupling agent.

[0085] More specifically, the above inorganic material may be included as alumina and zirconia, as zirconia and barium silicate, as alumina and barium silicate, as alumina, zirconia and barium silicate, as alumina, as zirconia, and as barium silicate.

[0086] However, the above-mentioned inorganic material is surface-treated with a silane coupling agent and, upon mixing with the aforementioned photocurable resin composition, exhibits excellent water resistance so that deformation does not occur in the oral environment and physical properties are improved, making it highly suitable for use as a prosthetic material compared to existing photocurable materials.

[0087] The above silane coupling agent may be selected more specifically from the group consisting of vinyltrimethoxysilane, (3-glycidoxypropyl)trimethoxysilane, [3-(methacryloxy]propyl]trimethoxysilane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, (3-chloropropyl)trimethoxysilane, (3-mercaptopropyl)trimethoxysilane, and mixtures thereof.

[0088] As described above, when an inorganic material surface-treated with a silane coupling agent is mixed with the aforementioned photocurable resin composition, it can increase interfacial affinity and improve dispersibility, thereby allowing the inorganic material to be uniformly dispersed within the printed object when printed with a 3D printer, which not only improves water resistance but also improves physical properties.

[0089] The above surface-treated inorganic material can be manufactured through the steps of: preparing a base solution by adding a silane coupling agent to a solvent and mixing; preparing a mixed solution containing the inorganic material by adding the inorganic material to the base solution and grinding the inorganic material in the mixed solution into a fine powder; heat-treating the mixed solution containing the powdered inorganic material; and performing a post-treatment step of vacuum drying.

[0090] The solvent for preparing the above mixed solution may include ethanol and ultrapure water. The above mixed solution may include 40 to 50 weight% of inorganic material, 40 to 50 weight% of ethanol, 4 to 5 weight% of a silane coupling agent, and 4 to 5 weight% of ultrapure water. When mixed within the above range, the inorganic material is appropriately surface-treated by the silane coupling agent, so that when mixed with the photocurable resin composition, interfacial affinity can be increased and dispersibility improved, allowing the inorganic material to be uniformly dispersed within the printed object when printed with a 3D printer, thereby improving not only water resistance but also physical properties.

[0091] The mixed solution containing the above inorganic material was finely powdered using methods such as ball milling, 3-roll milling, and tip sonication. Specifically, the ball milling process can be carried out for 24 hours.

[0092] After the above-mentioned fine powdering, a heat treatment process is carried out, wherein the heat treatment process is performed by hydrothermal treatment at 90°C to 110°C for 1 to 5 hours. Through the above-mentioned heat treatment process, a silane coupling agent can be coated on the surface of the finely powdered inorganic material to perform surface treatment.

[0093] After the heat treatment process above, a post-treatment process can be carried out by vacuum drying for 20 to 30 hours. Through the post-treatment process, the bonding of the silane coupling agent coated on the inorganic material can be stabilized, and residual organic solvent can be completely removed. If the post-treatment process is not carried out, residual organic solvent may affect the dispersibility when the surface-treated inorganic material is mixed with a photocurable resin composition.

[0094] The above photocurable resin composition may include a photocurable oligomer represented by the following chemical formula 1, an alumina dispersion, a reactive monomer, and a photoinitiator:

[0095] [Chemical Formula 1]

[0096]

[0097] [Chemical Formula 2]

[0098]

[0099] [Chemical Formula 3]

[0100]

[0101] [Chemical Formula 4]

[0102]

[0103] Here,

[0104] * indicates the part being combined,

[0105] R1 to R6 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 6 to 30 carbon atoms Selected from the group consisting of an arylamino group, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.

[0106] L1 and L3 are identical or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 30 carbon atoms, and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms.

[0107] L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and

[0108] n and m are identical or different from each other, and each is independently an integer from 1 to 10, and

[0109] R7 to R 12The groups are identical or different from one another and are each independently selected from the group consisting of hydrogen, deuterium, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms.

[0110] The above substituted alkylene group, substituted arylene group, substituted heteroarylene group, substituted cycloalkylene group, substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group, substituted heteroaryl group, substituted heteroarylalkyl group, substituted alkoxy group, substituted alkylamino group, substituted arylamino group, substituted aralkylamino group, substituted heteroarylamino group, substituted alkylsilyl group, substituted arylsilyl group, and substituted aryloxy group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, carbon number It is substituted with one or more substituents selected from the group consisting of 6 to 30 aryl groups, 5 to 60 nuclei, 6 to 30 heteroaryl alkyl groups, 1 to 30 alkoxy groups, 1 to 30 alkylamino groups, 6 to 30 arylamino groups, 6 to 30 aralkylamino groups, 2 to 24 heteroarylamino groups, 1 to 30 alkylsilyl groups, 6 to 30 arylsilyl groups, and 6 to 30 aryloxy groups, and when substituted with multiple substituents, these are identical or different from each other.

[0111] The above R1 and R6 may be compounds represented by the following chemical formula 5:

[0112] [Chemical Formula 5]

[0113]

[0114] Here,

[0115] * indicates the part being combined,

[0116] R 13 It is selected from the group consisting of hydrogen, deuterium, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms.

[0117] The above substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group, and substituted heteroaryl group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 5 to 60 nuclei, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, aralkylamino group having 6 to 30 carbon atoms, carbon number It is substituted with one or more substituents selected from the group consisting of 2 to 24 heteroarylamino groups, 1 to 30 carbon atom alkylsilyl groups, 6 to 30 carbon atom arylsilyl groups, and 6 to 30 carbon atom aryloxy groups, and when substituted with multiple substituents, these are identical or different from each other.

[0118] The above L1 and L3 may be identical or different from each other and may each be independently selected from the group consisting of compounds represented by the following chemical formulas 6 to 10:

[0119] [Chemical Formula 6]

[0120]

[0121] [Chemical Formula 7]

[0122]

[0123] [Chemical Formula 8]

[0124]

[0125] [Chemical Formula 9]

[0126]

[0127] [Chemical Formula 10]

[0128]

[0129] Here,

[0130] * indicates the part being combined,

[0131] p and r are identical or different from each other, and each is independently an integer from 0 to 4, and

[0132] q is an integer from 1 to 10, and

[0133] L4 and L5 are identical or different from each other, and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 30 carbon atoms, and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms.

[0134] R 14 to R 17 The groups are identical or different from one another and are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms.

[0135] The above substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group, and substituted heteroaryl group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 5 to 60 nuclei, heteroarylalkyl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, aralkylamino group having 6 to 30 carbon atoms, carbon number It is substituted with one or more substituents selected from the group consisting of 2 to 24 heteroarylamino groups, 1 to 30 carbon atom alkylsilyl groups, 6 to 30 carbon atom arylsilyl groups, and 6 to 30 carbon atom aryloxy groups, and when substituted with multiple substituents, these are identical or different from each other.

[0136] The above photocurable resin composition may include a ceramic material. The ceramic material generally refers to an inorganic or non-metallic solid material and may include, for example, alumina, silica, zirconia, etc., but is not limited to the above examples.

[0137] The photocurable resin composition of the present invention may include a reactive monomer together with the aforementioned oligomer component. The reactive monomer may improve workability by controlling the viscosity of the resin composition, or may become part of the cured structure through crosslinking or addition polymerization as a curing reaction agent.

[0138] Specific examples of the reactive monomer that can be used in one embodiment of the present invention may include one or more selected from the group consisting of acrylic monomers, urethane-based acrylate monomers, epoxy acrylate monomers, and vinyl monomers, and specifically, monofunctional or polyfunctional acrylates may be used as the reactive monomer, but are not limited thereto.

[0139] The above monofunctional or polyfunctional acrylate may be appropriately selected from among alkyl acrylate esters; aryl (meth)acrylate esters; (poly)alkylene glycol mono(meth)acrylate, (meth)acrylate alkoxyalkyl esters; heterocyclic (meth)acrylates; and polyfunctional acrylates, taking into account the purpose of the reaction. More specifically, examples of reactive monomers include acryloylmorpholine, isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, stearyl acrylate, caprolactone acrylate, tripropyleneglycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and pentaerythritol. It is selected from the group consisting of pentaerythritol triacrylate and dipentaerythritol hexaacrylate, but is not limited to the examples above.

[0140] The content of the reactive monomer included in the photocurable resin composition may be 20% to 40% by weight relative to the total weight of the composition. It is preferable that the content of the reactive monomer be 20% by weight or more in terms of securing viscosity favorable for printability during 3D printing, and 40% by weight or less in terms of ensuring the quality of the final printed product (preventing cracks from occurring, etc.).

[0141] In addition, the above photopolymerization initiator may be any photopolymerization initiator known in the field, in addition to the photopolymerization initiator exemplified above, without any particular limitation. As the above photopolymerization initiator, one or more compounds such as benzoin ethers, acetophenones, anthraquinones, thioxantones, ketals, and benzophenones may be used.

[0142] More specifically, benzoin ether compounds may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and benzoin phenyl ether, and acetophenone compounds may be selected from the group consisting of acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 1-hydroxycyclohexyl phenyl ketone, but are not limited to the above examples.

[0143] In addition, anthraquinone compounds include 2-methyl anthraquinone and 2-amyl anthraquinone, thioxantone compounds include 2,4-dimethyl thioxantone, 2,4-diethyl thioxantone, 2-chlorothioxantone, 2,4-diisopropyl thioxantone, and 1-chloro-4-propoxy thioxantone, and ketal compounds may include acetophenone dimethyl ketal and benzyl dimethyl ketal.

[0144] Benzophenone compounds may include benzophenone, diethylaminobenzophenone, 4,4'-bis-diethylaminobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, and 3,3',4,4'-tetra-(t-butylperoxycarbonyl)benzophenone, and furthermore, 4-benzoyl-4'-methyl diphenyl sulfido, xanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, etc.

[0145] Preferred photoinitiators are phosphine oxide photoinitiators and camphorquinone. Examples of such initiators include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Omirad 819), and camphorquinone (CQ).

[0146] In addition, the photocurable resin used in the present invention may further include various additives known in the art in addition to the reactive oligomer, reactive monomer, and photopolymerization initiator, and may include, for example, photopolymerization promoters or sensitizers such as p-dimethylaminobenzoic acid isoamyl ester and 2-dimethylaminoethyl benzoate.

[0147] In another embodiment of the present invention, the photocurable resin may include a light stabilizer and an antifoaming agent in addition to a photocurable oligomer, a reactive monomer, a photoinitiator, and a ceramic material. In a photocurable resin composition according to one embodiment of the present invention, the light stabilizer added is not particularly limited, and, for example, a hindered amine-based light stabilizer may be used. In particular, in terms of simultaneously improving the durability and wear resistance of the molded article, it is preferable to include a high molecular weight hindered amine-based light stabilizer having a number average molecular weight of 10,000 to 50,000.

[0148] The above-mentioned defoaming agent serves to remove bubbles present in the composition, and one or more selected from the group consisting of silicones, ethanol, octaol, cyclohexanol, ethylene glycol, and higher alcohols may be used.

[0149] An accessory prosthesis can be manufactured using the above photocurable composition, and the surface of the plurality of accessory prostheses that bond to each other can be surface-treated to increase the adhesive strength.

[0150] The above surface treatment can increase the surface area of ​​the contact surface by sandblasting and / or air abrasion. The above surface treatment method is not limited to the method described above, and any surface treatment method that increases the surface area can be used without limitation.

[0151] The above plurality of accessory prostheses can be bonded by applying resin cement and / or monomer after the contacting surfaces are surface-treated. Preferably, both the resin cement and primer typically used for bonding are applied to achieve an excellent bonding effect.

[0152] Any dental primer may be used as the primer, but preferably, Brident’s MKZ primer may be used, though it is not limited to the examples above. The MKZ primer may be a zirconia primer.

[0153] The above adhesive process can be fully bonded by a post-treatment process. Specifically, the post-treatment process involves UV irradiation; specifically, after completely blocking oxygen under a nitrogen atmosphere, a first UV irradiation was performed for 20 to 30 minutes. Subsequently, the material was immersed in a bath containing glycerol and subjected to a second UV irradiation for 20 to 30 minutes. Afterward, the post-curing process was completed by treating with hot water at 80 to 100°C.

[0154] Through the post-processing process described above, the accessory prostheses can be completely bonded together to be manufactured as a single prosthesis.

[0155] The effects of the present invention will be explained more specifically through the following exemplary embodiments illustrating the technical concept.

[0156] Preparation Example

[0157] Preparation of a photocurable resin composition

[0158] A photocurable resin composition was obtained by adding 40 g of a photocurable oligomer represented by the following chemical formula 1, 30 g of a reactive monomer (isobornyl acrylate), and 1 g each of TPO (diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide) and Phenylbis-(2,4,6-trimentylbenzoyl)phosphine oxide (OMNIRAD 819, IGM resin) as photoinitiators:

[0159] [Chemical Formula 1]

[0160]

[0161] [Chemical Formula 4]

[0162]

[0163] [Chemical Formula 11]

[0164]

[0165] [Chemical Formula 12]

[0166]

[0167] Here,

[0168] * indicates the part being combined,

[0169] L2 is selected by the above chemical formula 4, and

[0170] m is an integer from 10 to 100, and

[0171] R 11 and R 12 is hydrogen, and

[0172] L1 is selected by the above chemical formula 11, and L3 can be selected by the chemical formula 12.

[0173] Manufacture of surface-treated inorganic materials

[0174] A base solution was prepared by mixing ethanol, ultrapure water, and (3-glycidoxypropyl)trimethoxysilane, a silane coupling agent. Aluminum(III) oxide with a particle size of 300 nm and a density of 3.987 g / cm³ and 3-YSZ (3 mol% Yttria stabilized Tetragonal Zirconia Polycrystalline) with a particle size of 90 nm and a density of 6.03 g / cm³ were mixed in a 1:1 weight ratio and added to the base solution to prepare a mixed solution.

[0175] The above mixed solution was ball-milled for 24 hours to finely pulverize the inorganic material in the mixed solution. Subsequently, the material was hydrothermally treated at 100°C for 3 hours and vacuum-dried for 24 hours to remove the organic solvent, thereby producing a surface-treated inorganic material.

[0176] To produce the above surface-treated inorganic material, a mixed inorganic material comprising aluminum (III) oxide and 3-YSZ mixed in a weight ratio of 1:1, ethanol, ultrapure water, and a silane coupling agent were used in amounts of 45.45 wt%, 45.45 wt%, 4.55 wt%, and 4.55 wt%, respectively.

[0177] The above surface-treated inorganic material was mixed with the above photocurable resin composition in the ratio shown in Table 1 below to prepare a photocurable resin composition.

[0178] R-190 R-191 R-192 R-193 Surface-treated inorganic material 10155560 Photocurable resin composition 90854540

[0179] (Unit: Weight%)

[0180] Test example

[0181] Using the above R-191, a specimen in the shape of a tooth was printed using a 3D printer, and the compressive strength was evaluated.

[0182] The equipment used to measure compressive strength was the QM100™ (QMESYS). Five specimens were measured, and the average of the measured values ​​was used. As a control group, a tooth was used with an inner surface made of R-191 and an outer surface made of enamel. The test procedure is shown in Fig. 3, and a photograph of the specimen after fracture is shown in Fig. 4.

[0183] The test results are as shown in Figure 5. Specifically, when the tooth shape was printed using only R-191, the maximum load (kgf) was 351.73d, and when the tooth was made with an inner surface of R-191 and an outer surface of enamel, the maximum load (kgf) was 350.07, confirming that there was no significant difference.

[0184] In light of the above results, it was confirmed that R-191 alone exhibits a compressive strength sufficient to be used as a prosthetic material when manufactured into a tooth shape. Accordingly, the difference in compressive strength according to the inorganic content in Table 1 above was confirmed through testing.

[0185] It was confirmed that the maximum load (kgf) measured according to the same test for R-190 was 211.6, for R-192 was 322.6, and for R-193 was 121.0. Based on the above experimental results, it can be said that the materials used as prosthetic materials correspond to R-191 and R-192.

[0186] Evaluation of adhesive strength

[0187] Specimens were printed using a 3D printer with the above R-191, and shear bond stress was measured for a group with an untreated surface (Non treated), a sandblasted group, and a group that was sandblasted and coated with a dental primer (MKZ Brident).

[0188] The test method is as shown in Fig. 6. Dental resin cement was applied to the three groups above, and titanium specimens were bonded. Then, a shear force was applied to each specimen at a cross head speed of 1.0 mm / min using a universal testing machine (Shimadzu Universal Testing Machine EZ-S; Shimadzu, Kyoto, Japan). The maximum load at which the titanium specimen detached was measured in kgf using a Trapezium program connected to a computer, and this was converted to MPa by dividing it by the contact area of ​​the tooth-composite resin.

[0189] The test results are as shown in Table 2 below:

[0190] Resin Cement Type Results (MPa) Fujicem 2 Non-treated 49.2 Sandblast (110㎛ Alumina) 55.5 Sandblast + Primer 90.8 G-Cem Non-treated 258.2 Sandblast (110㎛ Alumina) 386.8 Sandblast + Primer 489.8

[0191] The results of verifying the interfacial adhesion surfaces for the three groups mentioned above are shown in Figure 7. According to the test results, among the three treatment groups, the group in which the specimen was surface-treated and both resin cement and primer were applied showed excellent adhesion performance. This confirmed that, regardless of the type of resin cement available on the market, the group treated with surface treatment + resin cement + primer showed excellent adhesion performance.

[0192] A prosthesis was manufactured using the photocurable composition of the present invention, and an accessory prosthesis identical in color to a tooth was manufactured using different pigments, and the two were bonded to produce a prosthesis as shown in FIG. 8. It can be confirmed that the prosthesis according to FIG. 8 is very similar in color to a tooth.

[0193] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims also fall within the scope of the present invention.

[0194] The present invention relates to a method for manufacturing a patient-customized dental prosthesis using a 3D printer.

Claims

1. Step of securing data on teeth requiring prosthetic treatment; A step of forming an image of a tooth requiring prosthetic treatment using the above data; and It includes the step of printing using a 3D printer with the image of the tooth above, and The above tooth image forms multiple images depending on the color difference of the tooth, and For each of the plurality of tooth images formed above, a plurality of accessory prostheses are printed using a 3D printer, and the plurality of accessory prostheses are bonded to form a prosthesis. Method for manufacturing patient-specific dental prostheses using a 3D printer.

2. In Paragraph 1, The plurality of above-mentioned accessory prostheses have surface treatments on the bonding surfaces between the accessory prostheses to increase the bonding strength. Method for manufacturing patient-specific dental prostheses using a 3D printer.

3. In Paragraph 2, The above surface treatment increases the surface area of ​​the contacting surface by the sandblasting method and / or air abrasion. Method for manufacturing patient-specific dental prostheses using a 3D printer.

4. In Paragraph 2, The above plurality of accessory prostheses are bonded by applying resin cement and / or monomer after the contacting surfaces are surface-treated. Method for manufacturing patient-specific dental prostheses using a 3D printer.

5. In Paragraph 1, The above-mentioned prosthesis is printed using a 3D printer with a photocurable resin composition, and The above photocurable resin composition is, Photocurable resin composition for 3D printers; and It includes surface-treated inorganic materials, The above photocurable resin composition comprises a photocurable oligomer represented by the following chemical formula 1, a reactive monomer, and a photoinitiator. Method for manufacturing patient-specific dental prostheses using a 3D printer: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] Here, * indicates the part being combined, R1 to R6 are identical or different from one another and each independently hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group having 6 to 30 carbon atoms Selected from the group consisting of an arylamino group, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. L1 and L3 are identical or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 30 carbon atoms, and a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms. L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and n and m are identical or different from each other, and each is independently an integer from 1 to 10, and R7 to R 12 The groups are identical or different from one another and are each independently selected from the group consisting of hydrogen, deuterium, halogen group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms. The above substituted alkylene group, substituted arylene group, substituted heteroarylene group, substituted cycloalkylene group, substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted alkynyl group, substituted aralkyl group, substituted aryl group, substituted heteroaryl group, substituted heteroarylalkyl group, substituted alkoxy group, substituted alkylamino group, substituted arylamino group, substituted aralkylamino group, substituted heteroarylamino group, substituted alkylsilyl group, substituted arylsilyl group, and substituted aryloxy group are hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, carbon number It is substituted with one or more substituents selected from the group consisting of 6 to 30 aryl groups, 5 to 60 nuclei, 6 to 30 heteroaryl alkyl groups, 1 to 30 alkoxy groups, 1 to 30 alkylamino groups, 6 to 30 arylamino groups, 6 to 30 aralkylamino groups, 2 to 24 heteroarylamino groups, 1 to 30 alkylsilyl groups, 6 to 30 arylsilyl groups, and 6 to 30 aryloxy groups, and when substituted with multiple substituents, these are identical or different from each other.

6. In Paragraph 5, The above inorganic material is selected from the group consisting of alumina, zirconia, barium silicate, and mixtures thereof. Method for manufacturing patient-specific dental prostheses using a 3D printer.

7. In Paragraph 6, The above inorganic material is surface-treated using a silane coupling agent. Method for manufacturing patient-specific dental prostheses using a 3D printer.

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