Method for manufacturing transparent orthodontic device having excellent biocompatibility

Abstract

The present invention relates to a method for manufacturing a transparent orthodontic device having excellent biocompatibility. Due to a coating layer being formed on the surface of the transparent orthodontic device by using the coating composition, biocompatibility of the transparent orthodontic device can be increased, thus reducing inflammation and improving compatibility with body tissues. In addition, it is possible to prevent the attachment of microbial organisms to the surface of the transparent orthodontic device on which the coating layer is formed by the coating composition, and the formation of biofilms that can cause infection and complications.

Description

Method for manufacturing a transparent orthodontic device with excellent biocompatibility

[0001] The present invention relates to a method for manufacturing a transparent orthodontic device having excellent biocompatibility.

[0002] In line with the current trend of prioritizing quality of life regardless of age, the orthodontic market for improving facial aesthetics is rapidly growing, with most removable orthodontic devices being manufactured with PMMA. The global orthodontic market is projected to grow at an annual rate of 8.9%, from $4.32 billion in 2018 to $6.63 billion by 2023. Within this trend, the development of premium PMMA source technology for therapeutic use is expected to create significant market expansion and growth opportunities.

[0003] However, most of the PMMA used in dentistry is imported entirely from companies such as Ivoclar Vivadent (Principality of Liechtenstein) and Lang (USA).

[0004] Research and development of antimicrobial biomaterials to secure global competitiveness is ongoing both domestically and internationally, but due to various limitations, they have not been developed into products. In particular, there are no therapeutic PMMA products that have the effect of inhibiting the adhesion of biofilms and oral bacteria.

[0005] Oral biofilms are implicated as a cause of not only localized oral diseases such as salivary proteins, dental caries, periodontitis, periapical inflammation, and peri-implantitis, but also infectious systemic diseases including those of the digestive and cardiovascular systems.

[0006] To address these issues, antibacterial agents or antibiotics are commonly used. However, these solutions can be toxic, destroying not only bacteria but also normal cells, and can lead to resistance.

[0007] Because orthodontic devices are worn for extended periods of time, bacterial growth and tartar buildup frequently occur. Even cleaning orthodontic devices with a brush or other cleaning tool can damage the device's surface and shorten its lifespan.

[0008] There is a need to develop solutions to address these issues.

[0009] [Prior Art Literature]

[0010] [Patent Document]

[0011] KR 10-2114824 B1

[0012] The purpose of the present invention is to provide a method for manufacturing a transparent orthodontic device having excellent biocompatibility.

[0013] Another object of the present invention is to provide a manufacturing method capable of increasing the biocompatibility of a transparent orthodontic device by forming a coating layer on the surface of the transparent orthodontic device using the coating composition, thereby reducing inflammation and improving compatibility with body tissues.

[0014] Another object of the present invention is to provide a transparent orthodontic device capable of preventing the attachment of microbial organisms to the surface of the transparent orthodontic device on which a coating layer is formed by the coating composition and the formation of a biofilm that may cause infection and complications.

[0015] In order to achieve the above object, the present invention relates to a method for manufacturing a transparent orthodontic device having a surface coated with a coating composition containing a zwitterionic ion, comprising the steps of: dissolving a zwitterionic ion and a photocurable monomer in a solvent to prepare a mixture containing the zwitterionic ion; mixing a photocurable oligomer into the mixture to prepare a coating composition containing the zwitterionic ion; applying the coating composition containing the zwitterionic ion to a 3D printed transparent orthodontic device to form a coating layer; And a step of post-curing the transparent orthodontic device on which the coating layer is formed, wherein the zwitterionic ion may be a monomer selected from the group consisting of sulfobetaine methacrylate (SBMA), carboxybetaine methacrylate (CBMA), carboxybetaine acrylamide (CBAA), 2-methacryloyloxyethyl phosphorylcholine (MPC), and combinations thereof.

[0016] The coating composition including the above-mentioned amphoteric ion may be manufactured by placing the above-mentioned amphoteric ion and the photocurable monomer in a solvent, ultrasonically dispersing for 1 to 5 seconds, and resting for 1 to 5 seconds, and then repeating the process for 30 to 90 minutes.

[0017] The above photocurable oligomer may be a compound represented by the following chemical formula 1:

[0018] [Chemical Formula 1]

[0019]

[0020] [Chemical Formula 2]

[0021]

[0022] [Chemical Formula 3]

[0023]

[0024] [Chemical Formula 4]

[0025]

[0026] [Chemical Formula 5]

[0027]

[0028] [Chemical Formula 6]

[0029]

[0030] Here,

[0031] n is an integer from 1 to 100,

[0032] m is an integer from 1 to 50,

[0033] A, B, C and D are the same or different from each other and are repeating units each independently selected from the group consisting of compounds represented by chemical formulas 2 to 6,

[0034] a, b, c and d are the same or different and are each independently an integer from 1 to 30,

[0035] R1 and R2 are the same or different, and can each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

[0036] The viscosity of the above coating composition may be 500 to 5,000 cps.

[0037] The above transparent orthodontic device can be printed using a 3D printer using a photocurable composition containing an oligomer represented by the following chemical formula 1:

[0038] [Chemical Formula 1]

[0039]

[0040] [Chemical Formula 2]

[0041]

[0042] [Chemical Formula 3]

[0043]

[0044] [Chemical Formula 4]

[0045]

[0046] [Chemical Formula 5]

[0047]

[0048] [Chemical Formula 6]

[0049]

[0050] Here,

[0051] n is an integer from 1 to 100,

[0052] m is an integer from 1 to 50,

[0053] A, B, C and D are the same or different from each other and are repeating units each independently selected from the group consisting of compounds represented by chemical formulas 2 to 6,

[0054] a, b, c and d are the same or different and are each independently an integer from 1 to 30,

[0055] R1 and R2 are the same or different, and can each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

[0056] The step of post-curing the transparent orthodontic device having the coating layer formed thereon can increase the conversion rate of unreacted monomers in the 3D printed transparent orthodontic device by irradiating the transparent orthodontic device having the coating layer formed thereon with UV under an inert gas atmosphere, and at the same time, increase the bonding strength between the coating layer and the transparent orthodontic device.

[0057] According to another embodiment of the present invention, a transparent orthodontic device coated with a coating composition containing a zwitterionic agent can be manufactured by the above manufacturing method.

[0058] The present invention can increase the biocompatibility of a transparent orthodontic device by forming a coating layer on the surface of the transparent orthodontic device using a coating composition containing a zwitterionic compound, thereby reducing inflammation and improving compatibility with body tissues.

[0059] In addition, the coating composition can prevent the attachment of microbial organisms to the surface of a transparent orthodontic device having a coating layer formed thereon and the formation of a biofilm that can cause infection and complications.

[0060] Figure 1 is a flowchart illustrating a process for manufacturing a photocurable oligomer according to one embodiment of the present invention.

[0061] Figure 2 shows the GPC measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0062] Figure 3 shows the NMR measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0063] Figure 4 shows the GPC measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0064] Figure 5 shows the NMR measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0065] Figure 6 shows the GPC measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0066] Figure 7 shows the NMR measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0067] Figure 8 shows the GPC measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0068] Figure 9 shows the NMR measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0069] Figure 10 shows the GPC measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0070] Figure 11 shows the NMR measurement results for a photocurable oligomer according to one embodiment of the present invention.

[0071] FIG. 12 is a photograph of a specimen manufactured using a photocurable composition according to one embodiment of the present invention.

[0072] FIG. 13 is a photograph of dipping a specimen into a coating composition according to one embodiment of the present invention.

[0073] Figure 14 is a photograph of a specimen on which a coating layer is formed according to one embodiment of the present invention.

[0074] Figure 15 shows the results of protein adsorption performance evaluation for a specimen including a coating layer according to one embodiment of the present invention.

[0075] Figure 16 shows the results of protein adsorption performance evaluation for a specimen including a coating layer according to one embodiment of the present invention.

[0076] The present invention relates to a method for manufacturing a transparent orthodontic device with excellent biocompatibility, comprising the steps of: dissolving a zwitterion and a photocurable monomer in a solvent to prepare a mixture containing the zwitterion; mixing a photocurable oligomer into the mixture to prepare a coating composition containing the zwitterion; applying the coating composition containing the zwitterion to a 3D printed transparent orthodontic device to form a coating layer; and post-curing the transparent orthodontic device having the coating layer formed thereon, wherein the zwitterion is a monomer selected from the group consisting of sulfobetaine methacrylate (SBMA), carboxybetaine methacrylate (CBMA), carboxybetaine acrylamide (CBAA), 2-methacryloyloxyethyl phosphorylcholine (MPC), and combinations thereof.

[0077] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0078] The 3D printing of the present invention refers to a process of manufacturing a three-dimensional object by layering materials using 3D digital data. This specification focuses on 3D printing technologies such as DLP (Distal Light Processing), SLA (Stereo Lithography Apparatus), and PolyJet, but it should be understood that the technology can be applied to other 3D printing technologies as well.

[0079] The photocurable composition of the present invention refers to a polymer that is crosslinked and polymerized into a polymer network structure, and is a material that is cured by light irradiation. While the present specification focuses on UV light, the present invention is not limited to UV light and can be applied to other types of light.

[0080] Orthodontic treatment utilizes the ability of teeth to move when subjected to a certain force. The most common method for orthodontic treatment is fixed braces, which attach brackets to teeth and use elasticity, such as orthodontic wires and elastic bands, to move the teeth. Brackets are typically made of metal, but they have the disadvantage of being noticeable during treatment.

[0081] To address these shortcomings, transparent orthodontics was proposed. This procedure involves creating transparent orthodontic brackets that gradually change from the initial state of the teeth to the desired state, and then replacing them on the teeth to correct the alignment.

[0082] Specifically, the treatment using a transparent aligner was developed in 1997, and is a dental aligner developed by the American company "Align Technology, Inc." under the name "Invisalign System." The technical details of this device are disclosed in U.S. Patent Nos. 5,975,893 and 6,217,325.

[0083] The "Invisalign System" uses a special program to cut out each tooth on a computer using three-dimensional scan data of the teeth, and then creates 20 to 30 pairs of models step by step through virtual simulations to determine where the teeth should ultimately move. Then, a transparent plastic mold that allows teeth to be moved is made for each model and distributed to the patient.

[0084] The "Invisalign System" features a series of prepared plastic frame-type orthodontic devices that are gradually inserted into the teeth to gradually move the teeth to the final target point. Since the plastic frames are made of a transparent material and are not easily visible from the outside, they can be of great help in the daily social life of orthodontic patients. In addition, patients can put on and take off the orthodontic devices as needed.

[0085] The present invention relates to a method for manufacturing a patient-tailored transparent orthodontic device that can be used for the above-described teeth correction, and unlike conventional transparent orthodontic devices, the surface is coated with a coating composition containing zwitterionic ions, so that it can exhibit effects such as reduction in the thickness and biomass of saliva-derived biofilm, reduction in antifouling ability and viability due to adhesion resistance to fungi and bacteria, and prevention of protein adsorption.

[0086] Specifically, a method for manufacturing a transparent orthodontic device having a surface coated with a coating composition containing a zwitterionic ion according to one embodiment of the present invention comprises the steps of: dissolving a zwitterionic ion and a photocurable monomer in a solvent to prepare a mixture containing the zwitterionic ion; mixing a photocurable oligomer into the mixture to prepare a coating composition containing the zwitterionic ion; applying the coating composition containing the zwitterionic ion to a 3D printed transparent orthodontic device to form a coating layer; And a step of post-curing the transparent orthodontic device on which the coating layer is formed, wherein the zwitterionic ion may be a monomer selected from the group consisting of sulfobetaine methacrylate (SBMA), carboxybetaine methacrylate (CBMA), carboxybetaine acrylamide (CBAA), 2-methacryloyloxyethyl phosphorylcholine (MPC), and combinations thereof.

[0087] The coating composition comprises a zwitterionic monomer and a photocurable monomer, wherein the zwitterionic monomer may be a monomer selected from the group consisting of sulfobetaine methacrylate (SBMA), carboxybetaine methacrylate (CBMA), carboxybetaine acrylamide (CBAA), 2-methacryloyloxyethyl phosphorylcholine (MPC), and combinations thereof.

[0088] The above photocurable monomer may be an acrylate monomer and may be selected from the group consisting of the following chemical formulas 7 to 13:

[0089] [Chemical Formula 7]

[0090]

[0091] [Chemical Formula 8]

[0092]

[0093] [Chemical Formula 9]

[0094]

[0095] [Chemical Formula 10]

[0096]

[0097] [Chemical Formula 11]

[0098]

[0099] [Chemical Formula 12]

[0100]

[0101] [Chemical Formula 13]

[0102]

[0103] In order to prepare a coating composition containing the above-described zwitterionic ion, a mixture containing the zwitterionic ion is first prepared, wherein the zwitterionic ion and the photocurable monomer are placed in a solvent, and the mixture is dispersed for 30 to 90 minutes by repeating the steps of ultrasonic dispersion for 1 to 5 seconds and resting for 1 to 5 seconds. Preferably, the mixture is dispersed for 50 to 70 minutes by repeating the steps of ultrasonic dispersion for 1 to 2 seconds and resting for 1 to 2 seconds.

[0104] As described above, in order to prepare a mixture containing zwitterionic ions, when ultrasonic dispersion is performed so that the photocurable monomer and zwitterionic ions are uniformly dispersed in the solvent, the temperature rises to 50°C to 100°C. This is because the temperature increases as the photocurable monomer and zwitterionic ions are uniformly dispersed in the solvent by ultrasonic dispersion.

[0105] The solvent for preparing the above coating composition may be distilled water, but is not limited to the above examples and any solvent capable of preparing the coating composition may be used without limitation.

[0106] After preparing a mixture containing the above-mentioned amphoteric ions, a photocurable oligomer can be mixed into the mixture to prepare a coating composition.

[0107] The coating composition containing the above zwitterionic ion comprises 0.1 to 0.5 parts by weight of the zwitterionic ion and 0.1 to 100 parts by weight of the photocurable oligomer, relative to 100 parts by weight of the photocurable monomer, and preferably comprises 0.2 to 0.3 parts by weight of the zwitterionic ion and 90 to 100 parts by weight of the photocurable oligomer, relative to 100 parts by weight of the photocurable monomer. Within the above mixing range, when manufactured as a coating composition, it can be excellently bonded to the surface of a dental orthodontic device, and can exhibit excellent antifouling ability, effects such as reduction in viability and prevention of protein adsorption.

[0108] The above photocurable oligomer may be a compound represented by the following chemical formula 1, and the synthesis method for the above oligomer is as described below:

[0109] [Chemical Formula 1]

[0110]

[0111] [Chemical Formula 2]

[0112]

[0113] [Chemical Formula 3]

[0114]

[0115] [Chemical Formula 4]

[0116]

[0117] [Chemical Formula 5]

[0118]

[0119] [Chemical Formula 6]

[0120]

[0121] Here,

[0122] n is an integer from 1 to 100,

[0123] m is an integer from 1 to 50,

[0124] A, B, C and D are the same or different from each other and are repeating units each independently selected from the group consisting of compounds represented by chemical formulas 2 to 6,

[0125] a, b, c and d are the same or different and are each independently an integer from 1 to 30,

[0126] R1 and R2 are the same or different, and can each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

[0127] The viscosity of the coating composition may be 500 to 5,000 cps. When preparing the coating composition as described above, the viscosity of the coating composition can be increased by mixing a high molecular weight polymer compound, and by preparing the composition with increased viscosity as described above, the convenience of work can be improved when coating a transparent orthodontic device.

[0128] When the above-described coating composition is prepared, it can be applied to a 3D printed transparent orthodontic device to form a coating layer.

[0129] The method for forming the above coating layer may involve applying the coating composition by spraying or dipping. The application method is not limited to the examples described above, and any method capable of uniformly applying the coating composition to the surface of a transparent orthodontic device may be used.

[0130] The above 3D printed transparent orthodontic device is, unlike the conventional transparent orthodontic device described above, manufactured to be customized for the patient and printed using a photocurable composition as described below. Unlike the conventional transparent orthodontic device, the transparent orthodontic device printed using the photocurable composition can precisely reproduce even the curved surface of the teeth and has high adhesion to the teeth, resulting in an excellent orthodontic effect.

[0131] The transparent orthodontic device of the present invention is manufactured by acquiring data on the patient's tooth structure and outputting the data, and can be manufactured with almost no difference in the deviation from the tooth structure of 50 to 80㎛, whereas the conventional transparent orthodontic device has a deviation from the patient's teeth of 200 to 300㎛, and thus cannot adhere closely, resulting in poor orthodontic effect. However, the transparent orthodontic device of the present invention is manufactured to be customized for the patient using 3D printing, and thus has a very small deviation from the patient's tooth structure, and thus can exhibit excellent orthodontic effects.

[0132] In addition, the transparent orthodontic device of the present invention is heated to 40°C or higher, and then fitted onto the patient's teeth to form a shape that is in close contact with the teeth, and the transparent orthodontic device in close contact with the teeth is restored to its original shape by body temperature, thereby correcting the teeth.

[0133] The transparent orthodontic device of the present invention is characterized in that it returns to its original shape when placed in heated water and then taken out. Specifically, the transparent orthodontic device of the present invention exhibits flexibility for a certain period of time when heat is applied, enabling shape deformation. By utilizing this property, before fitting the transparent orthodontic device to a patient's teeth, the device is immersed in water at 60 to 100°C, taken out, fitted to the teeth, and then simply pressed by hand, thereby causing the device to be deformed into a shape that adheres closely to the teeth.

[0134] Afterwards, when heat is supplied to the transparent orthodontic device by the body temperature in the oral cavity, restoration to the original output shape occurs.

[0135] That is, after being immersed in water of 60 to 100℃, fitted to the teeth, and then transformed into the same shape as the teeth, the transparent teeth orthodontic device of the present invention is transformed into a shape that matches the current tooth structure of the patient, and then when heat is supplied by body temperature, it is slowly restored to its original output shape, and at this time, the transparent teeth orthodontic device moves the teeth to the position to be corrected by the force that restores them to their original shape.

[0136] In other words, conventional orthodontic devices are manufactured as transparent orthodontic devices that are gradually adjusted to the position of the teeth to be corrected based on information obtained from the patient's dental structure. These devices are then fitted to the teeth and move the teeth based on the properties of the hard material. As explained above, conventional transparent orthodontic devices move teeth based on the properties of the material, and thus do not provide uniform force within the teeth, resulting in poor orthodontic effectiveness.

[0137] On the other hand, the transparent orthodontic device of the present invention, as described above, is in a state where it is deformed to the same state as the structure of the teeth when the transparent orthodontic device is first used, but when heat is provided by body temperature, the transparent orthodontic device is restored to its original shape and force is transmitted to the teeth. Since the force transmitted to the teeth is not a force due to the material of the orthodontic device, but is generated and transmitted by restoration of shape, a uniform force is provided to the entire teeth, and the teeth can move as a whole.

[0138] The transparent orthodontic device of the present invention exhibits the characteristics described above because it is manufactured by printing using a 3D printer using the photocurable composition described below.

[0139] The photocurable composition may include an oligomer represented by the following chemical formula 1:

[0140] [Chemical Formula 1]

[0141]

[0142] [Chemical Formula 2]

[0143]

[0144] [Chemical Formula 3]

[0145]

[0146] [Chemical Formula 4]

[0147]

[0148] [Chemical Formula 5]

[0149]

[0150] [Chemical Formula 6]

[0151]

[0152] Here,

[0153] n is an integer from 1 to 100,

[0154] m is an integer from 1 to 50,

[0155] A, B, C and D are the same or different from each other and are repeating units each independently selected from the group consisting of compounds represented by chemical formulas 2 to 6,

[0156] a, b, c and d are the same or different and are each independently an integer from 1 to 30,

[0157] R1 and R2 are the same or different, and can each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

[0158] The above photocurable oligomer is characterized by including a urethane acrylate structure as a main chain, a photocurable functional group bonded to the urethane structure, and including a soft functional group and a hard functional group in the compound.

[0159] The output exhibits flexible properties due to the soft functional group included in the photocurable composition, and can also exhibit heat resistance due to the hard functional group.

[0160] That is, by combining a photocurable functional group with a photocurable oligomer and utilizing a soft functional group and a hard functional group, a flexible effect can be exhibited by utilizing a carbon skeleton having a soft property at room temperature, and heat-resistant properties can also be exhibited by utilizing a carbon skeleton having a hard property at room temperature.

[0161] Since the above photocurable oligomer includes a carbon skeleton having hard properties, it can produce a 3D printing output that has excellent physical properties such as thermal properties, strength, elastic modulus, and tensile elongation, and can be restored to its original shape by heat.

[0162] In addition, since the photocurable oligomer contains a carbon skeleton with soft properties, its shape can be deformed by an external force after heat is provided.

[0163] In general, a composition for a 3D printer may include a photocurable oligomer for 3D printing; a monomer; a photoinitiator; and a stabilizer, as described below. The oligomer, monomer, photoinitiator, and stabilizer included in the composition all affect the physical properties of the output, but the oligomer has the greatest effect. Accordingly, in general, in order to improve the physical properties of a 3D output, only a carbon skeleton having a hard property is included, which can improve the physical properties of the output, but conversely, if the shape is deformed due to use, the shape cannot be restored, which is a problem in that it cannot be used multiple times.

[0164] The composition for a 3D printer of the present invention includes a carbon skeleton having a hard property and a carbon skeleton having a soft property, so that not only is it excellent in physical properties such as thermal properties, strength, elasticity, and tensile elongation, but also the flexible property of the soft functional group can be utilized together, so that when the shape is deformed by an external force in a state where heat is provided, it can be fixed in the deformed shape, and when heat is provided again, it can be restored to the original shape.

[0165] The above A, B and D are the same or different from each other, and may be repeating units independently selected from compounds represented by chemical formula 2 or 3.

[0166] The above C may be a repeating unit selected from the group consisting of compounds represented by chemical formulas 4 to 6.

[0167] Specifically, the photocurable oligomer represented by the above chemical formula 1 can be manufactured by a method for synthesizing a urethane acrylate series. Basically, it proceeds through a stepwise polymerization reaction of a diol and a diisocyanate, and in order to prevent gelation of the material due to an increase in molecular weight during the polymerization process of the material, an acrylic monomer without a reaction site is used as a suspension. The monomer used in the synthesis of the oligomer of the present invention as an available acrylic monomer may be Isobornyl acrylate, Cyclic Trimethylolpropane Formal Acrylate, Lauryl acrylate, Lauryl methacrylate, 3,5,3-trimethelhexyl acrylate, Tetrahydrofurfuryl acrylate, Tetrahydrofurfuryl methacrylate, Benzyl methacrylate, etc.

[0168] More specifically, diol was pre-introduced into the monomer base used as the primary monomer to stabilize it, and then diisocyanate was added. As the urethane reaction progressed, heat of reaction was generated, the urethane chain lengthened, and the molecular weight increased.

[0169] As the molecular weight increases, the viscosity of the material may also increase. If the above-mentioned increase in molecular weight proceeds rapidly, the temperature rises rapidly, which also causes the urethane reaction to proceed more quickly, and as a result, the oligomer gels before reaching a sufficient molecular weight, making it unusable as a material. Therefore, in the present invention, in order to prevent this reaction, a solvent selected from the group consisting of Isobornyl acrylate, Cyclic Trimethylolpropane Formal Acrylate, Lauryl acrylate, Lauryl methacrylate, 3,5,3-trimethelhexyl acrylate, Tetrahydrofurfuryl acrylate, Tetrahydrofurfuryl methacrylate, Benzyl methacrylate, and mixtures thereof is used as a solvent for introducing the diol. The solvent does not participate in the reaction, and is used to control the reaction speed of the material and prevent a rapid increase in viscosity due to an increase in molecular weight. Additionally, the monomers used to synthesize the oligomer of the present invention must be free of functional groups capable of reactive urethane reactions, such as hydroxyl groups or urethane groups. Under the above conditions, the present invention can produce oligomers with excellent mass production and process stability.

[0170] In addition, the equivalent ratio of diol and diisocyanate was set to a state where the equivalent of diisocyanate was higher than that of diol, so that the oligomer terminal exists as an isocyanate group. A reaction catalyst including a Zn-based catalyst can be used during the reaction process. The catalyst may or may not be included. The catalyst is included to proceed the reaction more quickly, and the reaction can proceed even if it is not necessarily included, but even if it is included, the reaction can proceed with a very small amount added.

[0171] After the temperature increase was stopped due to the completion of the urethane reaction, 2-hydroxy acrylate and 2-hydroxy methacrylate were added dropwise to end-cap the ends of the oligomers.

[0172] The diols used for the preparation of the above oligomers are as follows:

[0173]

[0174]

[0175] In addition, the diisocyanate for reacting with the above diol is as follows:

[0176]

[0177]

[0178] Additionally, monomers that may be included to terminate the urethane reaction or increase the molecular weight are as follows:

[0179]

[0180]

[0181]

[0182]

[0183] The compound represented by the above chemical formula 1 manufactured by the above manufacturing method can be selected from the group consisting of the following compounds:

[0184]

[0185]

[0186]

[0187]

[0188]

[0189] Here, p, p', p", q, q', q", r, s, t, u and v are integers from 1 to 100.

[0190] The photocurable oligomer may have a number average molecular weight (Mn) of 1,500 to 6,000, 1,500 to 5,500, or 1,600 to 5,000. The photocurable oligomer may have a weight average molecular weight (Mw) of 2,500 to 9,000, 3,000 to 8,500, or 3,500 to 8,000.

[0191] When a photocurable composition for 3D printing, described below, is manufactured using an oligomer having a number average molecular weight and a weight average molecular weight within the above range, and a transparent orthodontic device is manufactured using the same, the transparent orthodontic device can be printed in a manner customized to the patient's oral structure, and the orthodontic force can be increased using the same. In addition, when the transparent orthodontic device is immersed in water at 50 to 100°C and then deformed, the shape changes to the deformed shape, but when used while fitted on a tooth, the orthodontic device, which has been deformed by body temperature, gradually returns to its original shape, thereby exhibiting orthodontic force.

[0192] That is, conventional transparent orthodontic devices are manufactured from transparent plastic materials and can transmit sufficient force for correcting teeth. However, as described above, the transparent orthodontic devices are printed in accordance with the gradual movement state of the teeth, and are different from the current tooth structure of the patient. Therefore, they are not easy to wear when fitted to the teeth and can cause great pain even after wearing them.

[0193] On the other hand, when using the photocurable composition for 3D printing of the present invention, if the printed transparent orthodontic device is immersed in water at 50 to 100°C before use and then positioned on the patient's teeth to change its shape to fit the current, the shape of the orthodontic device gradually changes due to body temperature, so that it can exert a large orthodontic force without the patient feeling great pain.

[0194] The above photocurable oligomer may have a viscosity of 2,000 psi to 3,500 psi, 2,100 psi to 3,200 psi, or 2,200 psi to 3,000 psi. When a photocurable composition is manufactured using an oligomer having a viscosity within the above range, it can be provided with a viscosity suitable for use in a 3D printer.

[0195] The above nano clay is characterized as being sepiolite, but the nano clay is not limited to sepiolite, and any nano clay that can enhance mechanical properties by being included in a photocurable composition for a 3D printer can be used without limitation.

[0196] Polymer composite technology can be applied to overcome the mechanical strength limitations of 3D printing materials. However, applying these composite materials to 3D printing poses several challenges. The most critical issue is the size of the additives used in the composite material. As the additive size increases, the printing gap also increases, potentially resulting in lower printing resolution.

[0197] To avoid the above problems, nano-sized materials can be used as additives. Conventional nano-sized materials, such as graphene and carbon nanotubes (CNTs), can be price-competitive. On the other hand, nano-clays are more suitable for industrial applications due to their reasonable price. Among nano-clays, sepiolite is Mg8Si. 12 O 30 It is a hydrated magnesium silicate with a half unit cell formula of (OH)4·12H2O.

[0198] The above sepiolite has a chemical structure as shown in the cross-section of Fig. 2 and a lattice crystal form as shown in Fig. 3. More specifically, it has a needle-like or fiber-like form composed of multiple blocks and tunnels parallel to the fiber direction. Each structural block contains a central octahedral magnesium (MgOH6) sheet sandwiched between two tetrahedral silica (SiO4) sheets. A single sepiolite fiber is 0.2 to 4 µm in length, 10 to 30 nm in width, and 5 to 10 nm in thickness.

[0199] Incorporating sepiolite into nanoclay can maintain a viscosity that allows 3D printing within a photocurable composition and exhibit high mechanical strength for the printed output.

[0200] That is, when a large amount of nano clay is included, the viscosity of the photocurable composition increases, and when the viscosity increases, there is a problem in that the composition cannot be manufactured into an output product through a 3D printer. When a certain amount of nano clay is included or more, the mechanical strength of the output product may increase, but because a composition with a high viscosity cannot be used for 3D printing, it is desirable that the viscosity of the photocurable composition be included within a certain range.

[0201] Accordingly, the photocurable composition may include 0.5 to 5 parts by weight of nano clay and 1 part by weight of a photoinitiator per 100 parts by weight of UV resin. The UV resin includes a photocurable oligomer and a reactive oligomer. When mixed and used within the above range, not only can it be manufactured into an output product using a 3D printer, but the manufactured output product can exhibit excellent mechanical strength. The UV resin may include the photocurable oligomer and the reactive monomer. The 3D printer is a DLP-type 3D printer.

[0202] The above monomer is a reactive monomer, and may specifically be an acrylate monomer.

[0203] More specifically, the acrylate monomer may be selected from the group consisting of a compound represented by the following chemical formula 7, a compound represented by the following chemical formula 8, and a mixture thereof:

[0204] [Chemical Formula 7]

[0205]

[0206] [Chemical Formula 8]

[0207]

[0208] The photoinitiator may be BP, TPO, DCP, BPO, DPPO, etc., and preferably DPPO (2-hydroxy-2-methylpropiophenone) may be used. However, the present invention is not limited to the above examples, and any photoinitiator capable of producing a photocurable composition may be used without limitation.

[0209] The above stabilizer may be selected from the group consisting of tertiary amines such as diethylethanolamine and trihexylamine, hindered amines, organic phosphates, and hindered phenols, but is not limited to the above examples, and any stabilizer capable of producing a photocurable composition may be used without limitation.

[0210] In addition to the above photoinitiator and stabilizer, other additives may be additionally included.

[0211] The above additives may include conventional additives such as leveling agents, slip agents or stabilizers to improve thermal and oxidation stability, storage stability, surface properties, flow properties and process properties.

[0212] The above UV resin comprises a photocurable oligomer of the present invention and a monomer, and more specifically, may comprise a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 7, and a compound represented by the following chemical formula 8 in a weight ratio of 1:1:1 to 2:1:1.

[0213] The coating composition containing the zwitterionic ions can be applied to the 3D printed transparent orthodontic device and centrifuged to evenly apply the coating composition containing the zwitterionic ions to the surface of the transparent orthodontic device.

[0214] The step of post-curing the transparent orthodontic device having the coating layer formed thereon can increase the conversion rate of unreacted monomers in the 3D printed transparent orthodontic device by irradiating the transparent orthodontic device having the coating layer formed thereon with UV under an inert gas atmosphere, and at the same time, increase the bonding strength between the coating layer and the transparent orthodontic device.

[0215] The above coating composition contains a zwitterionic ion and a photocurable monomer as described above. In addition, in the case of a transparent orthodontic device printed by a 3D printer, the above-described photocurable composition is cured and manufactured in the form of a orthodontic device. However, the transparent orthodontic device printed by the 3D printer contains an unreacted monomer, and the unreacted monomer contains an acrylic group, as the photocurable composition is not completely cured and generally shows a conversion rate of about 50 to 70%. As the coating composition is applied, the acrylic group chemically bonds with the zwitterionic ion and the photocurable monomer in the coating composition, and a more solid bond occurs through the above-described post-curing step.

[0216] The above post-curing step specifically irradiates UV light on a transparent orthodontic device having a coating layer formed in an inert gas environment to promote curing, thereby preventing deformation of the transparent orthodontic device, improving strength, preventing damage caused by external force, and increasing the bonding strength of the coating layer.

[0217] By carrying out the curing process in an inert gas environment, not only does the curing speed of the transparent orthodontic device increase, but its strength is also improved, preventing deformation and detachment of the coating layer even under high levels of impact.

[0218] In other words, when the curing process is performed using UV irradiation in an inert gas environment, the curing speed is accelerated by the inert gas, and the strength of the transparent orthodontic device can be improved. Furthermore, when the post-curing process is performed in an inert gas environment, the transparency of the transparent orthodontic device is further improved.

[0219] When a 3D printer using a DLP or SLA method is used to manufacture an orthodontic device, a transparent output is obtained. However, as described above, when a 3D printer using a DLP or SLA method is used to manufacture an output, unreacted monomers remain in the output. These unreacted monomers require additional curing. However, when the orthodontic device is exposed to the air during the post-curing process to cure these unreacted monomers, the photoinitiator in the orthodontic device comes into contact with oxygen to generate radicals, and the photocuring behavior is suppressed by the scavenging of the generated radicals.

[0220] That is, it is necessary to prevent the orthodontic device from contacting oxygen, and for this purpose, when performing the post-curing process in the present invention, post-curing is performed by irradiating UV in an inert gas environment, thereby blocking contact with oxygen.

[0221] When the above transparent orthodontic device is manufactured as a personalized output using 3D printing and used as an orthodontic device, if the transparency is not excellent and there is even a slight yellow tint, there is a risk of the user mistaking it for a poor dental condition, which could have a negative impact on the user's appearance.

[0222] To avoid these problems, the 3D printed object itself must be able to exhibit a degree of complete transparency.

[0223] When a conventional DLP or SLA printer is used to produce an output and then a product is manufactured through a post-curing process, some differences may occur depending on the type of photocurable polymer resin, but it usually has a yellowish tint, making it impossible to provide a completely transparent orthodontic device.

[0224] On the other hand, as in the present invention, when UV is irradiated in an inactive environment during the post-curing process, the curing speed is improved and the strength is improved by the UV irradiation, and the transparency of the transparent orthodontic device is improved.

[0225] That is, when a post-curing process such as that of the present invention is performed, it is possible to provide a completely transparent orthodontic device.

[0226] When a post-curing process is performed using UV in an inert gas environment, the curing speed is improved, which improves the production speed of the final product, and the strength is excellent, making it less susceptible to deformation due to external force.

[0227] The above inert gas is selected from the group consisting of nitrogen, argon, helium, krypton, neon and mixtures thereof, preferably nitrogen, but is not limited to the above examples, and any gas capable of blocking contact with oxygen as an inert gas can be used without limitation.

[0228] According to another embodiment of the present invention, a transparent orthodontic device is characterized by having a coating layer formed by a coating composition containing zwitterionic ions. The transparent orthodontic device is manufactured using the above-described manufacturing method, and the coating layer is formed on the surface, thereby exhibiting excellent anti-fouling properties, anti-reduction of viability, and anti-protein adsorption effects.

[0229] In addition, as described above, the post-curing process is performed in an inert gas environment, and thus, it is characterized by excellent transparency.

[0230]

[0231] Although the 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 made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

[0232] Manufacturing example

[0233] Preparation of photocurable compositions

[0234] Manufacturing Example 1 (Example 1)

[0235] Isobornyl acrylate was used as a solvent, and polypropylene glycol, cyclohexanedimethanol, and BHT were added, and stirred at 10 to 200 rpm at 10 to 50°C. Isophorone diisocyanate was added, and stirring was performed under the same temperature conditions while changing the stirring speed from 50 to 200 rpm. Afterwards, HEMA was added, and stirring was performed at 150 to 500 rpm at 50 to 250°C to produce an oligomer.

[0236] The intermediate compounds produced by the above reaction are as follows:

[0237]

[0238] The oligomer finally produced by reacting the above intermediate compounds is as follows:

[0239]

[0240] The sequence of the manufacturing method of the above Example 1 is as shown in Fig. 1.

[0241] The GPC analysis results for the oligomer of Example 1 are as shown in Fig. 2. In addition, the NMR analysis results are as shown in Fig. 3.

[0242] Example 2

[0243] Oligomers were prepared using the same method as in Example 1, but the monomers used in the reaction were different. The prepared oligomers are as follows:

[0244]

[0245] The GPC analysis results for the oligomer of Example 2 are as shown in Fig. 4. In addition, the NMR analysis results are as shown in Fig. 5.

[0246] Example 3

[0247] Oligomers were prepared using the same method as in Example 1, but the monomers used in the reaction were different. The prepared oligomers are as follows:

[0248]

[0249] The GPC analysis results for the oligomer of Example 2 are as shown in Fig. 6. In addition, the NMR analysis results are as shown in Fig. 7.

[0250] Example 4

[0251] Oligomers were prepared using the same method as in Example 1, but the monomers used in the reaction were different. The prepared oligomers are as follows:

[0252]

[0253] The GPC analysis results for the oligomer of Example 2 are as shown in Fig. 8. In addition, the NMR analysis results are as shown in Fig. 9.

[0254] Example 5

[0255] Oligomers were prepared using the same method as in Example 1, but the monomers used in the reaction were different. The prepared oligomers are as follows:

[0256]

[0257] The GPC analysis results for the oligomer of Example 2 are as shown in Fig. 10. In addition, the NMR analysis results are as shown in Fig. 11.

[0258]

[0259] The results of the analysis of the oligomers of Examples 1 to 5 are summarized in Table 1 below:

[0260] Example 1 Example 2 Example 3 Example 4 Example 5GPCMn41794102166347672691Mw69446763785575913703PDI1.681.651.681.591.38NMRA(6.44)OOOOOB(5.89)OOOOOC(5.61)O(39.0)O(39.3)O(9.3)O(22.1)XD(4.91)O(87.9)O(89.6)O(77.6)O(86.4)O(61.0)E(6.48)XXO(16.1)XO(22.3)F(6.49)XXOXOG(3.41)OOOOO

[0261] Manufacturing Example 2

[0262] The monomers represented by the following chemical formulas 7 and 8 were mixed in a weight ratio of 1:1, sepiolite was added, and then the mixture was ground and dispersed for 1 minute at 750 W using a tip ultrasonic processor. Then, the oligomer of Example 1 was heated in an oven at 60°C for 12 hours and added to the mixture. Afterwards, DPPO was mixed as a photoinitiator, and the mixture was mixed and defoamed using a paste mixer.

[0263] [Chemical Formula 7]

[0264]

[0265] [Chemical Formula 8]

[0266]

[0267] The weight ratio for the above photocurable composition is as follows:

[0268] Composition sample specification Sepiolite Example 1 UV resin photoinitiator 1001DLP Sep-00DLP Sep-0.50.5DLP Sep-11DLP Sep-22DLP Sep-33DLP Sep-55

[0269] (Unit weight part) Here, the UV resin contains the oligomer of Example 1, the compound represented by the above chemical formula 7, and the compound represented by the above chemical formula 8 in a weight ratio of 2:1:1.

[0270] Storage stability assessment

[0271] To evaluate the storage stability by dispersion of monomer and sepiolite, a solution containing a mixture of sepiolite and monomer was stored for 3 days to check whether layer separation occurred.

[0272] It can be confirmed that DLP Sep-0.5, DLP Sep-1, DLP Sep-2, DLP Sep-3, and DLP Sep-5 all remain stable without layer separation even after 3 days.

[0273] In addition, in the case of a photocurable composition prepared by replacing the oligomer of Example 1 with the oligomer of Examples 2 to 5 and then mixing it with sepiolite in the same manner, the composition remained stable without layer separation even after 3 days.

[0274] Sepiolite, a type of clay, is difficult to disperse with monomers and has poor storage stability even after dispersion. However, using tip-sonic equipment for the grinding and dispersion process as described in the present invention not only ensures uniform dispersion, but also demonstrates excellent stability even during long-term storage.

[0275] Preparation of coating composition

[0276] Example 6

[0277] 2-methacryloyloxyethyl phosphorylcholine (MPC) and a compound represented by the following chemical formula 7 were added to distilled water, and a mixture was prepared by dispersing the mixture for 1 second at 750 W output using a tip ultrasonic processor, followed by pausing for 1 second, repeating this process for 1 hour:

[0278] [Chemical Formula 7]

[0279]

[0280] Afterwards, the photocurable oligomer of Example 1 was mixed to prepare a coating composition.

[0281] The contents of the components of the coating compositions of Examples 6 to 10 are as shown in Table 3 below. In addition, the viscosity of the coating compositions was measured using a viscometer:

[0282] MPC Chemical Formula 7 Photocurable Oligomer Viscosity Example 60.2 100 100 4 200 cps Example 70.2 4 100 100 4 210 cps Example 80.1 100 100 4 190 cps Example 90.3 100 100 4 220 cps

[0283] (unit weight)

[0284] Experimental example

[0285] The photocurable composition manufactured in the above Manufacturing Example 2 was placed in a 3D printer, and a specimen was manufactured as in Fig. 12. Then, it was placed in the coating composition of the above Manufacturing Example 3 (Example 6) as in Fig. 13, and centrifuged.

[0286] Afterwards, the specimen was placed in a complete nitrogen atmosphere inside the curing machine and post-cured by UV irradiation for 25 minutes. The specimen with the formed coating layer is shown in Fig. 14.

[0287] A coating layer was formed on the specimen in the same manner using the coating compositions of Examples 7 to 9 above.

[0288] Results of protein adsorption prevention experiment

[0289] The specimens prepared in the above experimental examples were immersed in fresh phosphate-buffered saline (PBS, Gibco) at room temperature for 1 hour. Each sample was then immersed in bovine serum albumin (BSA; Pierce Biotechnology) broth (2 mg of protein / mL in PBS, 100 μL). After incubation for 4 hours at 37°C in 5% CO2, unbound proteins were removed by washing twice with PBS. Afterwards, the amount of protein bound to the specimens was measured using micro-bicinchoninic acid (200 μL; Micro BCATM Protein Assay Kit, Pierce Biotechnology), and the specimens were incubated at 37°C for 30 minutes. The amount of surface-adsorbed protein was quantified based on the optical density (OD) at 562 nm measured using a microplate reader (Epoch, BioTek Instruments). The experimental results are shown in Figure 15.

[0290] As a control, a photocurable composition manufactured in Manufacturing Example 2 was manufactured into a specimen, and then a specimen without forming a separate coating layer was used. As a result of the experiment, it was confirmed that a large amount of protein was adsorbed in the control specimen. On the other hand, in the case of a specimen in which a coating layer was formed with a coating composition containing a zwitterion within the scope of the present invention, it was confirmed that the amount of adsorbed protein was significantly less, confirming that the effect of preventing protein adsorption was excellent.

[0291] Bacterial adsorption prevention experiment

[0292] Before conducting the bacterial adsorption inhibition experiment, all specimens were sterilized by ultraviolet irradiation. Actinomyces naeslundii (A. naeslundii) was cultured under anaerobic conditions using 3.8% BHI supplemented with 0.5% yeast extract (Becton Dickinson and Co. Sparks, MD, USA), 4 μg / mL resazurin (Sigma-Aldrich, St. Louis, MO, USA), 5 μg / mL hemin (Sigma-Aldrich, St. Louis, MO, USA), 0.05% L-cysteine ​​(Sigma-Aldrich, St. Louis, MO, USA), and 2 μg / mL vitamin K (Sigma-Aldrich, St. Louis, MO, USA).

[0293] After sufficient bacterial growth, 1 mL (108 cells / mL) of bacterial suspension was added to each sample in a 24-well plate and incubated at 37°C for 24 h. After incubation, the samples were gently washed twice with PBS to remove non-adherent bacteria. To assess bacterial colony forming units (CFU), attached bacteria were harvested by sonication (SH-2100, Saehan Ultrasonic, Seoul, Korea) in 1 mL of BHI for 5 min. 100 μL of this bacterial suspension was spread on an agar plate, incubated at 37°C for 24 h, and then colonies were counted.

[0294] The bacterial culture was centrifuged, and the bacterial pellet was resuspended in fresh medium until the optical density (OD) reached 0.55 (measured at a wavelength of 600 nm). The specimens were individually placed into each well of a 24-well plate containing 1 mL of medium and the bacterial cell suspension (OD = 0.55) and incubated for 24 h in a humidified atmosphere at 36°C. After incubation, each specimen was washed three times with Dulbecco's PBS (DBPS, Gibco BRL, USA) to remove loosely attached bacteria. Bacteria that were firmly attached to the substrate were fixed by passing the bottom of the sample over the flame of a Bunsen burner. The fixed sample was placed in 1 mL of a 0.1% gram crystal violet solution (Sigma-Aldrich, USA) and incubated at room temperature for 10 minutes. After the staining step, each sample was washed twice with 1 mL of DPBS and then placed in 1 mL of 95% ethanol to dissolve the crystal violet stain on the surface. 100 μL of the crystal violet solution dissolved for 10 minutes was added to each well of a 96-well plate, and the absorbance of the sample was measured at 570 nm using a microplate reader.

[0295] The experimental results are shown in Fig. 16. The experimental results confirm that a large amount of bacteria were adsorbed in the control group. Conversely, in the case of a specimen in which a coating layer was formed using a coating composition containing a zwitterionic compound within the scope of the present invention, the amount of adsorbed bacteria was significantly reduced, confirming the excellent effect of preventing bacterial adsorption.

[0296] Although the 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 made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

[0297] The present invention relates to a method for manufacturing a transparent orthodontic device having excellent biocompatibility.

Claims

1. A step of preparing a mixture containing a zwitterionic ion by dissolving a zwitterionic ion and a photocurable monomer in a solvent; A step of preparing a coating composition containing a zwitterionic compound by mixing a photocurable oligomer into the above mixture; A step of forming a coating layer by applying a coating composition containing the above-described amphoteric ions to a 3D printed transparent orthodontic device; and It includes a step of post-curing the transparent orthodontic device on which the above coating layer is formed. The above zwitterion is a monomer selected from the group consisting of sulfobetaine methacrylate (SBMA), carboxybetaine methacrylate (CBMA), carboxybetaine acrylamide (CBAA), 2-methacryloyloxyethyl phosphorylcholine (MPC), and combinations thereof. A method for manufacturing a transparent orthodontic device with excellent biocompatibility.

2. In paragraph 1, The coating composition containing the above-mentioned amphoteric ion is prepared by placing the above-mentioned amphoteric ion and the photocurable monomer in a solvent, and dispersing the mixture by ultrasonic dispersion for 1 to 5 seconds, and resting for 1 to 5 seconds, and then dispersing the mixture for 30 to 90 minutes. A method for manufacturing a transparent orthodontic device with excellent biocompatibility.

3. In paragraph 1, The above photocurable oligomer is a compound represented by the following chemical formula 1. Method for manufacturing a transparent orthodontic device with excellent biocompatibility: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] Here, n is an integer from 1 to 100, m is an integer from 1 to 50, A, B, C and D are the same or different from each other and are repeating units each independently selected from the group consisting of compounds represented by chemical formulas 2 to 6, a, b, c and d are the same or different and are each independently an integer from 1 to 30, R1 and R2 are the same or different, and can each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

4. In paragraph 1, The viscosity of the above coating composition is 500 to 5,000 cps. A method for manufacturing a transparent orthodontic device with excellent biocompatibility.

5. In paragraph 1, The above transparent orthodontic device is printed using a 3D printer using a photocurable composition containing an oligomer represented by the following chemical formula 1. Method for manufacturing a transparent orthodontic device with excellent biocompatibility: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] Here, n is an integer from 1 to 100, m is an integer from 1 to 50, A, B, C and D are the same or different from each other and are repeating units each independently selected from the group consisting of compounds represented by chemical formulas 2 to 6, a, b, c and d are the same or different and are each independently an integer from 1 to 30, R1 and R2 are the same or different, and can each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

6. In paragraph 1, The step of post-curing the transparent orthodontic device having the coating layer formed thereon is to irradiate the transparent orthodontic device having the coating layer formed thereon with UV under an inert gas atmosphere to increase the conversion rate of unreacted monomers in the 3D printed transparent orthodontic device, and at the same time, to increase the bonding strength between the coating layer and the transparent orthodontic device. A method for manufacturing a transparent orthodontic device with excellent biocompatibility.

7. Manufactured by a manufacturing method according to any one of Articles 1 to 6. A transparent orthodontic device with excellent biocompatibility coated with a coating composition containing zwitterionic ions.

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