Novel dental prosthetic material and patient-customized dental prosthesis comprising same

Abstract

The present invention relates to a novel dental prosthetic material and a patient-customized dental prosthesis comprising same, the material improving water resistance, reproducing a color similar to an actual tooth, and thus improving the aesthetic appearance even after prosthetic treatment. In addition, patient-customized prosthetic treatment can be performed using a 3D printer on a tooth requiring prosthetic treatment. The material exhibits enhanced physical properties compared to existing photocurable resin compositions and has excellent adhesive strength, thereby preventing a dental prosthesis from detaching after treatment.

Description

Novel prosthetic material for teeth and patient-customized dental prosthetics including the same

[0001] The present invention relates to a novel dental prosthetic material and a patient-customized dental prosthesis comprising the same.

[0002] 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.

[0003] 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.

[0004] 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.

[0005] 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.

[0006] 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.

[0007] 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.

[0008] 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.

[0009]

[0010] In addition, since conventional prosthetic treatment cannot be custom-made for each patient, discomfort may occur due to a foreign body sensation inside the tooth for a considerable period after treatment.

[0011] To resolve the aforementioned problems, the development of new prosthetic materials is necessary.

[0012] [Prior Art Literature]

[0013] [Patent Literature]

[0014] KR 10-2013-0162904 A1

[0015] The objective of the present invention is to provide a novel prosthetic material for teeth and a patient-customized dental prosthesis comprising the same.

[0016] Another objective of the present invention is to provide a novel prosthetic material that enhances water resistance and achieves a color similar to real teeth, thereby improving aesthetics even after prosthetic treatment.

[0017] Another objective of the present invention is to provide a patient-customized dental prosthesis that enables patient-customized prosthetic treatment on teeth requiring prosthetic treatment through a 3D printer, exhibits enhanced physical properties compared to existing photocurable resin compositions, and has excellent adhesion to prevent the problem of detachment after treatment.

[0018] To achieve the above-mentioned objective, the present invention relates to a novel prosthetic material for teeth comprising a photocurable resin composition for a 3D printer and a surface-treated inorganic material, wherein the photocurable resin composition comprises a photocurable oligomer represented by the following chemical formula 1, an alumina dispersion, a reactive monomer, and a photoinitiator.

[0019] [Chemical Formula 1]

[0020]

[0021] [Chemical Formula 2]

[0022]

[0023] [Chemical Formula 3]

[0024]

[0025] [Chemical Formula 4]

[0026]

[0027] Here,

[0028] * indicates the part being combined,

[0029] 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.

[0030] 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.

[0031] L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and

[0032] n and m are identical or different from each other, and each is independently an integer from 1 to 10, and

[0033] 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.

[0034] 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.

[0035] In addition, the above-mentioned mineral may be selected from the group consisting of alumina, zirconia, barium silicate, and mixtures thereof.

[0036] In addition, the above-mentioned inorganic material can be surface-treated using a silane coupling agent.

[0037] In addition, the reactive monomer may be selected from the group consisting of keryl-based monomers, urethane-based acrylate-based monomers, epoxy acrylate-based monomers, vinyl-based monomers, and mixtures thereof.

[0038] In addition, the alumina dispersion may contain 0.1 to 5 weight percent of alumina particles having an average particle size of 50 nm to 60 nm relative to the total weight of the photocurable resin composition for a 3D printer.

[0039] In addition, the photoinitiator may be selected from the group consisting of benzoin ethers, acetophenones, anthraquinones, thioxantones, ketals, benzophenones, and mixtures thereof.

[0040] In addition, the above photocurable resin composition may further include a light stabilizer and an antifoaming agent.

[0041] In addition, the novel prosthetic material may contain 10% to 55% by weight of surface-treated inorganic material relative to the total weight.

[0042] Another invention for achieving the above-mentioned purpose relates to a patient-customized dental prosthesis comprising the novel dental prosthetic material described above.

[0043] In addition, the dental prosthesis may be produced by printing the novel dental prosthetic material using a 3D printer.

[0044] In addition, the above dental prosthetics can be used for inlay treatment, onlay treatment, crown treatment, implants, bridges, and dentures.

[0045] The present invention provides a novel prosthetic material that can enhance aesthetics even after prosthetic treatment by realizing a color similar to that of real teeth.

[0046] Another objective of the present invention is to provide a patient-customized dental prosthesis that enables patient-customized prosthetic treatment on teeth requiring prosthetic treatment through a 3D printer, exhibits enhanced physical properties compared to existing photocurable resin compositions, and has excellent adhesion to prevent the problem of detachment after treatment.

[0047] FIG. 1 relates to a method for testing the compressive strength of a prosthetic material according to one embodiment of the present invention.

[0048] Figure 2 is a photograph of a specimen after a compressive strength test on a prosthetic material according to one embodiment of the present invention.

[0049] Figure 3 is the result of a compressive strength test on a prosthetic material according to one embodiment of the present invention.

[0050] FIG. 4 is a photograph of a tooth shape printed using a photocurable resin composition according to one embodiment of the present invention.

[0051] The present invention relates to a novel prosthetic material for teeth comprising a photocurable resin composition for a 3D printer; and a surface-treated inorganic material, wherein the photocurable resin composition comprises a photocurable oligomer represented by the following chemical formula 1, a reactive monomer, and a photoinitiator:

[0052] [Chemical Formula 1]

[0053]

[0054] [Chemical Formula 2]

[0055]

[0056] [Chemical Formula 3]

[0057]

[0058] [Chemical Formula 4]

[0059]

[0060] Here,

[0061] * indicates the part being combined,

[0062] 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.

[0063] 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.

[0064] L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and

[0065] n and m are identical or different from each other, and each is independently an integer from 1 to 10, and

[0066] 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.

[0067] 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.

[0068] 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.

[0069] Prosthetic treatment refers to a procedure that artificially creates teeth when they are lost, extracted, or partially lost. The causes are diverse, including loss due to wisdom teeth, gum disease, accidents, and cavities. In everyday language, this is commonly expressed as "filling / crowning" or "putting in a tooth."

[0070] Prosthetic treatment is commonly performed during cavity treatment. The reason prosthetic treatment is carried out during cavity treatment is due to concerns about the recurrence of cavities or infection. In other words, when a cavity develops, the contaminated tooth is ground down; however, this process can make the tooth surface uneven and potentially expose the nerve. Therefore, prosthetic treatment may be performed to protect the damaged tooth and prevent the recurrence of cavities.

[0071] In addition, prosthetic treatment is available when teeth are lost. Since both the tooth and the gum bone are lost when a tooth is removed, failure to provide timely prosthetic treatment can make the process more complex, as it may require procedures such as gum bone grafting.

[0072] Common types of prosthetic treatment include resin, inlays / onlays, crowns, bridges, and implants. Among the above treatments, resin and inlays / onlays can utilize ceramic materials, which, while exhibiting a color similar to that of teeth, may discolor and may cause problems such as breakage or detachment with prolonged use.

[0073] Therefore, it is necessary to develop patient-customized prosthetic materials to enable appropriate prosthetic treatment based on the patient's dental condition.

[0074] The present invention aims to provide a novel prosthetic material that can be used as a printed product for prosthetic treatment of a patient using a 3D printer.

[0075] Specifically, the present invention may relate to a novel prosthetic material for teeth comprising a photocurable resin composition for a 3D printer; and a surface-treated inorganic material, wherein the photocurable resin composition comprises a photocurable oligomer represented by the following chemical formula 1, an alumina dispersion, a reactive monomer, and a photoinitiator.

[0076] [Chemical Formula 1]

[0077]

[0078] [Chemical Formula 2]

[0079]

[0080] [Chemical Formula 3]

[0081]

[0082] [Chemical Formula 4]

[0083]

[0084] Here,

[0085] * indicates the part being combined,

[0086] 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.

[0087] 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.

[0088] L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and

[0089] n and m are identical or different from each other, and each is independently an integer from 1 to 10, and

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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:

[0103] [Chemical Formula 1]

[0104]

[0105] [Chemical Formula 2]

[0106]

[0107] [Chemical Formula 3]

[0108]

[0109] [Chemical Formula 4]

[0110]

[0111] Here,

[0112] * indicates the part being combined,

[0113] 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.

[0114] 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.

[0115] L2 is selected from the group consisting of compounds represented by the above chemical formulas 2 to 4, and

[0116] n and m are identical or different from each other, and each is independently an integer from 1 to 10, and

[0117] 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.

[0118] 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.

[0119] The above R1 and R6 may be compounds represented by the following chemical formula 5:

[0120] [Chemical Formula 5]

[0121]

[0122] Here,

[0123] * indicates the part being combined,

[0124] 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.

[0125] 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.

[0126] 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:

[0127] [Chemical Formula 6]

[0128]

[0129] [Chemical Formula 7]

[0130]

[0131] [Chemical Formula 8]

[0132]

[0133] [Chemical Formula 9]

[0134]

[0135] [Chemical Formula 10]

[0136]

[0137] Here,

[0138] * indicates the part being combined,

[0139] p and r are identical or different from each other, and each is independently an integer from 0 to 4, and

[0140] q is an integer from 1 to 10, and

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.).

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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).

[0154] 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.

[0155] 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.

[0156] 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.

[0157] The effects of the present invention will be explained more specifically through the following exemplary embodiments illustrating the technical concept.

[0158] Preparation Example

[0159] Preparation of a photocurable resin composition

[0160] 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:

[0161] [Chemical Formula 1]

[0162]

[0163] [Chemical Formula 4]

[0164]

[0165] [Chemical Formula 11]

[0166]

[0167] [Chemical Formula 12]

[0168]

[0169] Here,

[0170] * indicates the part being combined,

[0171] L2 is selected by the above chemical formula 4, and

[0172] m is an integer from 10 to 100, and

[0173] R 11 and R 12 is hydrogen, and

[0174] L1 is selected by the above chemical formula 11, and L3 can be selected by the chemical formula 12.

[0175] Manufacture of surface-treated inorganic materials

[0176] 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.

[0177] 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.

[0178] 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.

[0179]

[0180] 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.

[0181] R-190 R-191 R-192 R-193 Surface-treated inorganic material 10155560 Photocurable resin composition 90854540

[0182] (Unit: Weight%)

[0183] Test example

[0184] 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.

[0185] 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. 1, and a photograph of the specimen after fracture is shown in Fig. 2.

[0186] The test results are as shown in Figure 3. 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.

[0187] 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.

[0188] 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.

[0189] Figure 4 shows a photograph of a product printed using a 3D printer with a shape identical to a tooth using the above R-191.

[0190] 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.

[0191] The present invention relates to a novel dental prosthetic material and a patient-customized dental prosthesis comprising the same.

Claims

1. 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. New prosthetic material for teeth. [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, 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. 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.

2. In Paragraph 1, The above inorganic material is selected from the group consisting of alumina, zirconia, barium silicate, and mixtures thereof. New prosthetic material for teeth.

3. In Paragraph 1, The above inorganic material is surface-treated using a silane coupling agent. New prosthetic material for teeth.

4. In Paragraph 1, The above reactive monomer is selected from the group consisting of chlorine-based monomers, urethane-based acrylate-based monomers, epoxy acrylate-based monomers, vinyl-based monomers, and mixtures thereof. New prosthetic material for teeth.

5. In Paragraph 1, The above photoinitiator is selected from the group consisting of benzoin ethers, acetophenones, anthraquinones, thioxantones, ketals, benzophenones, and mixtures thereof. New prosthetic material for teeth.

6. In Paragraph 1, The above photocurable resin composition further comprises a light stabilizer and an antifoaming agent. New prosthetic material for teeth.

7. In Paragraph 1, The novel prosthetic material described above comprises 10% to 55% by weight of surface-treated inorganic material relative to the total weight. New prosthetic material for teeth.

8. A novel prosthetic material for teeth according to paragraphs 1 through 7 Patient-customized dental prosthetics.

9. In Paragraph 8, The above dental prosthesis is produced by printing the above novel dental prosthetic material using a 3D printer. Patient-customized dental prosthetics.

10. In Paragraph 8, The above dental prosthetics are used for inlay treatment, onlay treatment, crown treatment, implants, bridges, and dentures. Patient-customized dental prosthetics.

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