Composite resin for esthetic restoration with improved antibacterial property and polymerization depth, antimicrobial and antiviral 3D printing denture base resin composition, and manufacturing method therefor

Abstract

The present invention relates to a composite resin for esthetic restorations with improved antimicrobial properties and polymerization depth, and a manufacturing method therefor, wherein the compositive resin comprises urethane dimethacrylate (UDMA), bisphenol A-glycidyl methacrylate (BIS-GMA), bisphenol A dimethacrylate ethoxylated (BIS-EMA), triethylene glycol dimethacrylate (TEGDMA), a photoinitiator, a co-photoinitiator, a filler, barium glass, an accelerator, an antioxidant, a discoloration inhibitor, and an antimicrobial agent in addition to lysozyme. With the enhanced polymerization depth, the resin can be applied as a bulk-fill resin, and the excellent antimicrobial properties thereof provide resistance against bacteria and viruses. After polymerization, the resin exhibits a flexural strength exceeding 80 MPa, which is a level required by the Korean Ministry of Food and Drug Safety.

Description

Composite resin compositions for aesthetic restoration with improved antibacterial properties and polymerization depth, and resin compositions for antibacterial and antiviral 3D printed denture bases, and methods for manufacturing the same

[0001] The present invention relates to a composite resin for aesthetic restoration used in dental treatment, characterized by enhanced antibacterial properties and polymerization depth. Furthermore, the present invention relates to a resin composition for denture bases that can be used through a 3D printing process, characterized by excellent antibacterial and antiviral properties.

[0002] Generally, when teeth are lost due to caries, fracture, or damage, problems with pronunciation, chewing, and aesthetics arise. In addition, when adjacent teeth move into the empty space where the tooth was missing, the normal alignment of the teeth begins to shift, causing food to become lodged between the teeth, resulting in secondary cavities or periodontitis, and problems such as bad breath.

[0003] To solve these problems and maintain and restore oral function, dental restoration is performed using dental restorative resin to replace part or all of the lost teeth.

[0004] Various materials have been used for dental restorative resins. Initially, mercury amalgam was primarily used due to its ease of use, wear resistance, and excellent mechanical strength. However, amalgam is known to have a distinct color difference from natural teeth, poor adhesion to tooth tissue, and mercury gradually leaks over time after restoration, potentially posing long-term health risks.

[0005] Accordingly, development of new materials to replace them has been ongoing, and recently, polymer materials have been receiving the most attention. The first polymer composite resin for dental restorative purposes was developed by Kulzer in Germany in 1942 by mixing PMMA powder with methyl methacrylate (MMA) monomer, and has been in clinical use ever since. Acrylic resins have been used for a long time since then.

[0006] While these organic polymers have advantages such as aesthetics, ease of procedure, and low biohazard, they do not have sufficient hardness, strength, and wear resistance to withstand masticatory pressure, etc. with their own physical properties. Therefore, composite resins containing inorganic fillers have been developed. Commercial dental restorative composite resins were first developed by Brown in 1962 using chemical initiation, and after the development of photopolymerization using ultraviolet light in the 1970s and visible light photopolymerization by ICI in the UK in 1980, the use of these dental restorative composite resins has been increasing as they replace existing amalgams. Recently, fluoride has been introduced into dental restorative composite resins to prevent secondary caries after restoration. Resins containing fluoride prevent secondary caries to some extent due to the antibacterial properties of fluoride, but fluoride-releasing materials have the problem of inhibiting the adhesive strength of the resin.

[0007] Meanwhile, dentures or false teeth are a type of removable prosthesis that replaces the lost teeth and their surrounding tissues when all natural teeth of the upper or lower jaw are lost. Unlike partial dentures, they function in the mouth only with the help of the alveolar ridge, so they have the problem of lacking retention (the force to not fall out of the mouth), support (the force by which the oral tissues support the complete denture), and stability (the degree to which the complete denture does not shake when chewing or speaking).

[0008] Typically, heat-curing or self-curing resins made primarily of PMMA (polymethyl methacrylate) and MMA (methyl methacrylate) are used as raw materials for denture bases. However, while these existing resin compositions for denture bases offer excellent transparency and high glass transition temperatures, resulting in superior mechanical properties, they also suffer from low impact strength, making them susceptible to damage from external forces. Furthermore, their low surface hardness and abrasion resistance make them susceptible to surface scratches and wear.

[0009] Meanwhile, with the recent expansion of the 3D printing market, 3D printing has been adopted by dentistry, enabling the production of denture bases optimized for individual oral structures. Denture base resins suitable for 3D printing must meet a range of requirements, including mechanical properties, wear resistance, and transparency. However, due to the nature of 3D printing, which involves layering 3D ink to create a product, securing these mechanical properties presents challenges.

[0010] In addition, due to the nature of being worn in the mouth for a long period of time, the surface of the denture is easily exposed to various harmful bacteria and viruses, which can cause problems such as infection or inflammation or secondary infection.

[0011] The present invention provides a composite resin for aesthetic restoration with improved antibacterial properties and polymerization depth, and a method for manufacturing the same. Furthermore, the present invention provides a resin composition for a 3D-printed denture base, applicable to 3D printing and possessing antibacterial and antiviral properties, and a method for manufacturing the same.

[0012] One embodiment of the present invention for achieving the above-described purpose includes an aesthetic restorative composite resin comprising UDMA (urethane dimethacrylate), BIS-GMA (bisphenol A glycidyl methacrylate), BIS-EMA (bisphenol A dimethacrylate ethoxylated), TEGDMA (triethylene glycol dimethacrylate), a photoinitiator, a photoinitiator assistant, a filler, barium glass, an accelerator, an antioxidant, an anti-discoloration agent, and an antibacterial agent, and has the effect of improving antibacterial properties and polymerization depth.

[0013] The above-mentioned aesthetic restorative composite resin may include 2-5 parts by weight of a filler, 4-6 parts by weight of an antibacterial agent, and 40-45 parts by weight of barium glass, based on 100 parts by weight of a base composition including 5-20 wt% of UDMA, 40-70 wt% of BIS-GMA, 15-30 wt% of BIS-EMA, 3-6 wt% of TEGDMA, 0.5-2.5 wt% of a photoinitiator, 0.02-0.2 wt% of a photoinitiator assistant, 0.2-1 wt% of an accelerator, 0.05-0.5 wt% of an antioxidant, and 0.05-0.5 wt% of an anti-discoloration agent. In addition, the antibacterial agent may include or be lysozyme.

[0014] Another embodiment of the present invention provides a method for producing an aesthetic restorative composite resin, comprising: a first step of preparing a polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA, and TEGDMA; a second step of preparing a base composition by mixing the polymer mixture with a photoinitiator, a photoinitiation assistant, an accelerator, an antioxidant, and a discoloration inhibitor; and a third step of preparing a composite resin by mixing the base composition with an antibacterial agent, a filler, and barium glass. The method has the effect of improving antibacterial properties and polymerization depth. In addition, the antibacterial agent may include or be lysozyme.

[0015] The composite resin manufactured through the third step may include 2 to 5 parts by weight of a filler, 4 to 6 parts by weight of an antibacterial agent, and 40 to 45 parts by weight of barium glass, based on 100 parts by weight of a base composition including 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 6 wt% of TEGDMA, 0.5 to 2.5 wt% of a photoinitiator, 0.02 to 0.2 wt% of a photoinitiator assistant, 0.2 to 1 wt% of an accelerator, 0.05 to 0.5 wt% of an antioxidant, and 0.05 to 0.5 wt% of an anti-discoloration agent.

[0016] The above lysozyme may be a modified lysozyme that has undergone a modification process, and the modification process may include a purification step of purifying the surface of the lysozyme with ethanol; and a surface modification step of mixing the surface-purified lysozyme with PEGDMA.

[0017]

[0018] Another embodiment of the present invention includes an antibacterial and antiviral 3D printing denture base resin composition comprising UDMA, BIS-GMA, BIS-EMA, TEGDMA, a photoinitiator, a photoinitiator assistant, a filler, an accelerator, an antioxidant, an anti-discoloration agent, and an antibacterial agent.

[0019] Specifically, the antibacterial and antiviral 3D printing denture base resin composition may include 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 5 wt% of TEGDMA, 0.5 to 2.5 wt% of photoinitiator, 0.02 to 0.2 wt% of photoinitiator assistant, 2 to 6 wt% of filler, 0.2 to 1 wt% of accelerator, 0.05 to 0.5 wt% of antioxidant, 0.05 to 0.5 wt% of discoloration inhibitor, and 1 to 3 wt% of antibacterial agent, wherein the antibacterial agent may include pectin and / or protamine.

[0020] Another embodiment of the present invention comprises a method for preparing an antibacterial and antiviral 3D printing denture base resin composition, comprising: a step a of preparing a second polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA, and TEGDMA; a step b of preparing a second base composition by mixing the second polymer mixture with a photoinitiator, a photoinitiator assistant, an accelerator, an antioxidant, and a discoloration inhibitor; and a step c of preparing a resin composition by mixing the first base composition with an antibacterial substance and a filler.

[0021] The resin composition manufactured through the above step c may include 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 5 wt% of TEGDMA, 0.5 to 2.5 wt% of photoinitiator, 0.02 to 0.2 wt% of photoinitiator assistant, 2 to 6 wt% of filler, 0.2 to 1 wt% of accelerator, 0.05 to 0.5 wt% of antioxidant, 0.05 to 0.5 wt% of discoloration inhibitor, and 1 to 3 wt% of antibacterial agent. The antibacterial agent used here may be pectin and / or protamine.

[0022] The aesthetic restorative composite resin of the present invention possesses excellent antibacterial properties, ensuring resistance to bacteria and viruses. Furthermore, its enhanced polymerization depth allows it to be applied as a bulk-fill resin, thereby reducing the number of layers required during treatment, thereby preventing secondary caries at the layer interface and shortening treatment time.

[0023] In addition, the resin composition for a 3D printed denture base according to the present invention can achieve a flexural strength of 65 MPa or more, which is the flexural strength of a resin used for a denture base when applied to 3D printing, and has antibacterial and antiviral properties, so that resistance to bacterial or viral contamination of a denture base that is repeatedly attached and detached from the oral cavity can be secured.

[0024] Figure 1 shows the results of an antibacterial test of composite resins for aesthetic restoration according to one embodiment of the present invention.

[0025] Figure 2 shows the results of an antibacterial evaluation for each 3D printing denture base resin composition according to another embodiment of the present invention.

[0026] Hereinafter, a preferred embodiment of the present invention will be described in detail.

[0027] Throughout this specification, whenever a part is said to “include” a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise stated.

[0028] Throughout this specification, “%” used to indicate the concentration of a specific substance means (weight / weight)% for solid / solid, (weight / volume)% for solid / liquid, and (volume / volume)% for liquid / liquid, unless otherwise stated.

[0029] One embodiment of the present invention relates to an aesthetic restorative composite resin with improved antibacterial properties and polymerization depth, and a method for manufacturing the same. The aesthetic restorative composite resin of the present invention comprises lysozyme. This provides antibacterial and antiviral properties, enabling it to fight against various harmful bacteria and viruses. In addition, since it does not contain a fluorine-containing material as an antibacterial agent, it can prevent a decrease in the adhesiveness of the resin due to the addition of an antibacterial agent.

[0030] In addition, since the thickness of the laminate can be formed thicker during restoration due to the increase in the polymerization depth, the area of ​​the laminate interface can be reduced, so secondary tooth caries at the laminate interface can be prevented, and the convenience of the procedure can be improved by shortening the procedure time.

[0031] According to one embodiment of the present invention, an aesthetic restorative composite resin having improved antibacterial properties and polymerization depth comprises UDMA, BIS-GMA, BIS-EMA, TEGDMA, a photoinitiator, a photoinitiator assistant, a filler, barium glass, an accelerator, an antioxidant, an anti-discoloration agent, and an antibacterial agent.

[0032] Specifically, for 100 parts by weight of a base composition including 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 6 wt% of TEGDMA, 0.5 to 2.5 wt% of a photoinitiator, 0.02 to 0.2 wt% of a photoinitiator assistant, 0.2 to 1 wt% of an accelerator, 0.05 to 0.5 wt% of an antioxidant, and 0.05 to 0.5 wt% of an anti-discoloration agent, 2 to 5 parts by weight of a filler, 4 to 6 parts by weight of an antibacterial agent, and 40 to 45 parts by weight of barium glass may be included.

[0033] The above UDMA, BIS-GMA, BIS-EMA and TEGDMA are polymer materials that form the basic structure of a restoration formed with a composite resin, the photoinitiator and photoinitiator assistant are materials that initiate photocuring of these polymers, and the filler, barium glass, accelerator, antioxidant, discoloration inhibitor and antibacterial agent are a type of additives that are added to improve the physical and chemical properties of a restoration manufactured using a composite resin.

[0034] The above UDMA (urethane dimethacrylate) is added to reduce polymerization shrinkage and improve elasticity and toughness, and can be included in the composite resin at 5 to 20 wt%. If the content of UDMA is below the above range, it is difficult to obtain the above-described effect of UDMA, and if the content of UDMA exceeds the above range, the content of BIS-GMA is relatively reduced, making it difficult to secure sufficient flexural strength. Therefore, it is preferable to include it within the above-described weight range.

[0035] The above BIS-GMA (bisphenol A glycidyl methacrylate) contains two hydrophobic methacrylic groups, and is characterized by low volatility and polymerization shrinkage, rapid curing, large molecular weight, and high stability, making it suitable as a matrix resin. However, due to its high viscosity, it is difficult to mix uniformly with other components and has poor workability, so it is used together with BIS-EMA to lower the viscosity.

[0036] The above BIS-GMA may be pure BIS-GMA, modified BIS-GMA, or a mixture containing both, wherein the modified BIS-GMA may contain at least one of DMBIS-GMA (2,2-bis[3-methyl, 4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane) and TMBIS-GMA (2,2-bis[3-methyl, 4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane). In particular, in order to secure the strength of the restoration, it is preferable to use modified BIS-GMA, which has significantly higher strength after curing, and most preferably, it is preferable to use DMBIS-GMA to secure further improved strength.

[0037] BIS-GMA can be included in the entire composition at 40 to 70 wt%. If it is included in less than the above weight range, it is difficult to secure sufficient strength, and if it is included in excess of the above weight range, it is difficult to perform a uniform stirring process due to excessively high viscosity. Therefore, it is preferable to include it within the above weight range.

[0038] The above BIS-EMA (Bisphenol A dimethacrylate ethoxylated) is added to lower the viscosity due to the use of BIS-GMA, and can be included in the composite resin at 15 to 30 wt%. If it is included below the above weight range, sufficient viscosity reduction for uniform stirring is not achieved, and if it is included above the above weight range, it is difficult to secure sufficient strength after curing, and the formulation may become difficult to perform with a desired thickness during restorative treatment due to excessive viscosity reduction, so it is preferable to include it within the above-mentioned weight range.

[0039] The above TEGDMA (triethylene glycol dimethacrylate) is added as a viscosity modifier and may be included in an amount of 3 to 6 wt% in the entire composition. If TEGDMA is included in an amount less than the above weight range, the viscosity characteristics required for restorative treatment may not be satisfied, and if TEGDMA is included in an amount exceeding the above weight range, defects due to excessive polymerization shrinkage may occur. Therefore, it is preferable to include TEGDMA within the above weight range.

[0040] The above photoinitiator is a material having the characteristic of being activated by light irradiation to form radicals, and the radicals thus formed can initiate a photopolymerization reaction of BIS-GMA, BIS-EMA, UDMA, and TEGDMA, thereby causing a curing reaction of the composite resin. The photoinitiator is preferably included in the entire composition at 0.5 to 2.5 wt% to cause a sufficient photocuring reaction.

[0041] Such photoinitiators include, for example, hardeners for dental curing materials, such as camphorquinone and TPO (2.4.6-trimethyl benzoyl-diphenylphosphine oxide), and any photoinitiator that can be applied to a cured material for dental equipment or materials is applicable to the present invention without being limited to the types listed above. In particular, in order to secure desirable curing properties and safety, at least one of camphorquinone and TPO may be used, and more preferably, a mixture of these may be used.

[0042] The above photoinitiator is added to assist photoinitiation by the photoinitiator. For example, DIFP (diphenyliodonium hexafluorophosphate) may be used, but is not limited thereto, and may be included in the entire composition at 0.02 to 0.2 wt%.

[0043] The above accelerator may be added to promote photoinitiation by increasing the radical generation efficiency of the photoinitiator by light irradiation. As such an accelerator, for example, at least one selected from the group consisting of EDMAB (ethyl (4-dimethyl amino) benzoate), DMABA (4-(dimethylamino) benzoic acid), DMABZR (4-(dimethylamino) benzaldehyde), DMAEMA (2-(dimethylamino) ethyl methacrylate), DMAEA (2-(dimethylamino) ethyl acrylate), DEAEMA (2-(diethylamino) ethyl methacrylate), and DEAEA (2-(diethylamino) ethyl acrylate) may be used, but is not limited thereto. The accelerator may be included in an amount of 0.2 to 1 wt% in the entire composition.

[0044] The above antioxidant is added to prevent oxidation-induced degeneration of the composite resin or restoration, and may be, but is not limited to, BHT (butylated hydroxy toluene) or commercial products such as Iganox, and may be included in the entire composition in a range of 0.05 to 0.5 wt%.

[0045] The above discoloration inhibitor is added to prevent discoloration of composite resin or restoration parts due to ultraviolet rays, and is traded under the name Tinuvin. ® , Tinopal ® A discoloration inhibitor such as may be used. It is preferable that the discoloration inhibitor be included in the composite resin at 0.05 to 0.5 wt% to obtain a discoloration prevention effect while preventing deterioration of the physical properties of the restoration.

[0046] Meanwhile, a composite resin for aesthetic restoration according to one embodiment of the present invention may include 2 to 5 parts by weight of a filler, 4 to 6 parts by weight of an antibacterial agent, and 40 to 45 parts by weight of barium glass, based on 100 parts by weight of a base composition including 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 6 wt% of TEGDMA, 0.5 to 2.5 wt% of a photoinitiator, 0.02 to 0.2 wt% of a photoinitiator assistant, 0.2 to 1 wt% of an accelerator, 0.05 to 0.5 wt% of an antioxidant, and 0.05 to 0.5 wt% of an anti-discoloration agent.

[0047] The above filler is added to improve the physical strength and wear resistance of the restoration, and may be included in an amount of 2 to 5 parts by weight based on 100 parts by weight of the base composition. In order to obtain the effect of improving strength and durability by the filler while preventing problems such as filler detachment or reduced bonding strength due to an increase in the amount of filler, it is preferable to include it within the weight range described above.

[0048] Examples of such fillers that can be used include silica, strontium aluminum silicate, barium aluminum silicate, kaolin, talc, radiopaque glass powder, and zirconia compounds, and the types of fillers that can be applied to the present embodiment are not limited thereto.

[0049] Preferably, silica surface-treated with a silane coupling agent may be used to improve miscibility with hydrophobic polymerization monomers. Since the method for modifying the surface of silica with a silane coupling agent and the specific type of silane coupling agent used for surface treatment are known in the art, a detailed description thereof will be omitted.

[0050] Furthermore, it is preferable to use fillers whose particle size has been adjusted to 50㎛ or less through a microsizing process. When the particle size is within this range, filler agglomeration is prevented and the space between filler particles is reduced. Consequently, when microcracks occur in the repaired part, the effective path for crack extension is lengthened, making it less susceptible to destruction even when microcracks occur, thereby enhancing the durability of the repaired part.

[0051] The above antibacterial agent may be added to the composite resin to provide antibacterial and antiviral functions. The antibacterial agent may be included in an amount of 4 to 6 parts by weight per 100 parts by weight of the base composition. If included in an amount less than the above range, the antibacterial and antiviral performance is not guaranteed. If included in an amount exceeding the above range, the content of other components may be relatively reduced, resulting in a decline in function. In particular, the barium glass content may be reduced, thereby hindering the suitability of radiopacity required by the Ministry of Food and Drug Safety. Therefore, it is preferable to include the antibacterial agent within the above-mentioned weight range.

[0052] The above antibacterial agent may include lysozyme. Lysozyme is a substance contained in egg white, animal tissues, body fluids, etc., and has an antibacterial effect by hydrolyzing the beta bonds of some polysaccharides among the cell wall components of bacteria, thereby destroying the cell wall. Lysozyme is included in the composite resin of the present invention, and plays a role in imparting antibacterial properties to the restoration part to which the composite resin is applied.

[0053] Lysozyme, which has not been separately treated, is highly hygroscopic and can promote changes in physical properties, such as discoloration of the resin due to food and contaminants in the oral cavity. Therefore, it is preferable to use modified lysozyme that has undergone a modification process as the antibacterial agent for the composite resin according to the present invention. In addition, lysozyme that has undergone a modification process, which will be described later, can improve the polymerization depth of the composite resin, allowing it to be utilized as a bulk-fill composite resin.

[0054] The modification process for manufacturing modified lysozyme may include a purification step of purifying the surface of lysozyme with ethanol; and a surface modification step of mixing the purified lysozyme with PEGDMA (Polyethylene glycol dimethacrylate); and the specific method is described in detail in the specific examples related to the manufacturing method described below.

[0055] The above barium glass is added to ensure radiopacity suitability of the restoration, and may be included in an amount of 40 to 45 parts by weight per 100 parts by weight of the base composition.

[0056] Meanwhile, another embodiment of the present invention includes a method for manufacturing a composite resin for aesthetic restoration with improved antibacterial properties and polymerization depth. Since the composite resin for aesthetic restoration with improved antibacterial properties and polymerization depth described above can be manufactured according to this embodiment, some overlapping descriptions will be omitted.

[0057] A method for manufacturing an aesthetic restorative composite resin with improved antibacterial properties and polymerization depth according to another embodiment of the present invention comprises: a first step of preparing a polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA, and TEGDMA; a second step of preparing a base composition by mixing the polymer mixture with a photoinitiator, a photoinitiation assistant, an accelerator, an antioxidant, and a discoloration inhibitor; and a third step of preparing a composite resin by mixing the base composition with an antibacterial agent, a filler, and barium glass.

[0058] The above first, second and third steps are steps for sequentially mixing raw materials, respectively. In each mixing step, mixing can be performed at a stirring speed of 5 to 15 rpm at 30 to 60°C, and can be performed under reduced pressure conditions with a vacuum gauge pressure of 0.05 to 0.2 MPa to prevent bubble formation during stirring.

[0059] The above first step is a step of preparing a polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA, and TEGDMA.

[0060] This step is a step of mixing 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, and 3 to 6 wt% of TEGDMA, wherein the composition ratio refers to a weight ratio in a base composition including UDMA, BIS-GMA, BIS-EMA, TEGDMA, a photoinitiator, a photoinitiator assistant, an accelerator, an antioxidant, and a discoloration inhibitor. In this step, stirring can be performed for 30 to 100 minutes, and the stirring time can vary depending on the season, and within the stirring time range, stirring can be performed for a short time in summer and for a long time in winter.

[0061] Additionally, the first step may be performed under light irradiation, wherein the wavelength of the light source may be 330 to 510 nm, which may vary depending on the absorption wavelength of the photoinitiator. For example, when camphorquinone is used as the photoinitiator, light of 450 to 480 nm may be irradiated, and when TPO is used, light of 350 to 430 nm may be irradiated.

[0062] In addition, as described above, since a vacuum is applied during the stirring process, bubble formation is prevented, which reduces light bending caused by bubbles and increases the exposure area of ​​the raw material mixture to the light source, enabling more efficient and effective light irradiation.

[0063] As the first step is performed under light irradiation conditions for a polymer mixture that does not contain a photoinitiator, the polymer mixture undergoes photoreactive modification, and the polymer is activated by light more quickly and effectively during subsequent photocuring, thereby improving the quality of the cured body, which is the repaired part.

[0064] The second step is a step of preparing a base composition by mixing the polymer mixture with a photoinitiator, a photoinitiator assistant, an accelerator, an antioxidant, and a discoloration inhibitor. These components are the same as those described in the above-described embodiment of the present invention, and each raw material can be mixed in this step so that the base composition contains 0.5 to 2.5 wt% of the photoinitiator, 0.02 to 0.2 wt% of the photoinitiator assistant, 0.2 to 1 wt% of the accelerator, 0.05 to 0.5 wt% of the antioxidant, and 0.05 to 0.5 wt% of the discoloration inhibitor.

[0065] The third step is a step of manufacturing a composite resin by mixing the base composition, an antibacterial agent, and a filler. Specifically, it may be a step of mixing 100 parts by weight of the base composition, 2 to 5 parts by weight of the filler, 4 to 6 parts by weight of the antibacterial agent, and 40 to 45 parts by weight of barium glass, and then maturing the mixture at 31.5 to 65°C for 48 hours or more. Through such maturation, the surfaces of the activated filler and barium glass are stabilized, the basic properties of the polymer damaged during the stirring process are partially restored, and the cross-linking between the polymer and the filler is strengthened, thereby stabilizing the properties of the composite resin.

[0066] The composite resin manufactured through this step may include 2 to 5 parts by weight of a filler, 4 to 6 parts by weight of an antibacterial agent, and 40 to 45 parts by weight of barium glass, based on 100 parts by weight of a base composition including 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 6 wt% of TEGDMA, 0.5 to 2.5 wt% of a photoinitiator, 0.02 to 0.2 wt% of a photoinitiator assistant, 0.2 to 1 wt% of an accelerator, 0.05 to 0.5 wt% of an antioxidant, and 0.05 to 0.5 wt% of an anti-discoloration agent.

[0067] The above antibacterial agent may include lysozyme, and the lysozyme may be modified lysozyme that has undergone a modification process. Lysozyme that has not been separately treated is highly hygroscopic and may promote changes in physical properties, such as discoloration of the resin due to food and contaminants in the oral cavity. Therefore, it is preferable to use modified lysozyme that has undergone a modification process as the antibacterial agent for composite resins.

[0068] The modification process for manufacturing modified lysozyme may include a purification step of purifying the surface of lysozyme with ethanol; and a surface modification step of mixing the purified lysozyme with PEGDMA (Polyethylene glycol dimethacrylate).

[0069] The above purification step is a step of purifying lysozyme by removing oil from the surface of lysozyme particles, and includes a first step of mixing lysozyme and ethanol and stirring them in a sealed container; and a second step of opening the sealed container and stirring them to evaporate ethanol.

[0070] The first step is a step of mixing lysozyme and ethanol and stirring them in a sealed container. The ethanol used in this step may be a 90-99% aqueous solution, and the mixture may be mixed in a ratio of 20-30 wt% of lysozyme and 70-80 wt% of ethanol, and stirring may be performed at 4-5 rpm for 4-8 hours. Through this step, impurities such as oil on the surface of lysozyme may be dissolved in ethanol.

[0071] The second step may be a step of opening a sealed container containing lysozyme and ethanol that have undergone the first step, and stirring the mixture of lysozyme and ethanol to evaporate the ethanol. This step may be performed by opening the sealed container and stirring the mixture at 2 to 3 rpm until the ethanol evaporates.

[0072] This purification step can be performed once or repeated two or three times.

[0073] Next, a surface modification step is performed in which the surface-purified lysozyme obtained through the above purification step is mixed with PEGDMA (Polyethylene glycol dimethacrylate). This step may be a step in which 65 to 70 wt% of purified lysozyme and 30 to 35 wt% of PEGDMA are mixed, and the lysozyme and PEGDMA mixture is stirred at 3 to 4 rpm under reduced pressure conditions with a vacuum gauge pressure of 0.05 to 0.2 MPa and a temperature of 30 to 40°C, and the stirring may be performed for 10 to 18 hours.

[0074] The modified lysozyme obtained through this process has lost its hygroscopic properties, so it can prevent discoloration and degeneration of the repaired area due to hygroscopicity.

[0075] In this way, the aesthetic restorative composite resin containing lysozyme with improved antibacterial properties and polymerization depth according to an embodiment of the present invention can be applied as a bulk-fill resin due to its improved polymerization depth, and has excellent antibacterial properties to ensure resistance to bacteria and viruses, and can implement a flexural strength after polymerization exceeding 80 MPa, which is the level required by the Ministry of Food and Drug Safety.

[0076]

[0077] Another embodiment of the present invention includes an antibacterial and antiviral 3D printing denture base resin composition and a method for manufacturing the same. A denture base manufactured with the 3D printing denture base resin composition according to the present invention has the advantage of having antibacterial and antiviral performance while satisfying the flexural strength standard of 65 MPa for 3D printing denture base resin required by the Ministry of Food and Drug Safety.

[0078] The resin composition for a 3D printed denture base according to the present invention comprises UDMA, BIS-GMA, BIS-EMA, TEGDMA, a photoinitiator, a photoinitiation assistant, a filler, an accelerator, an antioxidant, an anti-discoloration agent, and an antibacterial substance.

[0079] Specifically, it may include 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 5 wt% of TEGDMA, 0.5 to 2.5 wt% of photoinitiator, 0.02 to 0.2 wt% of photoinitiator assistant, 2 to 6 wt% of filler, 0.2 to 1 wt% of accelerator, 0.05 to 0.5 wt% of antioxidant, 0.05 to 0.5 wt% of discoloration inhibitor, and 1 to 3 wt% of antibacterial agent.

[0080] The above UDMA, BIS-GMA, BIS-EMA and TEGDMA are polymer materials forming the basic structure of a denture base manufactured using a resin composition, the photoinitiator and photoinitiator assistant are materials that initiate photocuring of these polymers, and the filler, accelerator, antioxidant, discoloration inhibitor and antibacterial material are a type of additive added to improve the physical and chemical properties of a denture base manufactured using a resin composition.

[0081] The above UDMA (urethane dimethacrylate) is added to reduce polymerization shrinkage and improve elasticity and toughness, and may be included in the resin composition at 5 to 20 wt%. If the content of UDMA is less than the above range, it is difficult to obtain the above-described effect of UDMA, and if the content of UDMA exceeds the above range, the content of BIS-GMA is relatively reduced, making it difficult to secure sufficient flexural strength. Therefore, it is preferable to include it within the above-described weight range.

[0082] The above BIS-GMA (bisphenol A-glycidyl methacrylate) contains two hydrophobic methacrylic groups, and is characterized by low volatility and polymerization shrinkage, rapid curing, large molecular weight, and high stability, making it suitable as a matrix resin. However, due to its high viscosity, it is difficult to mix uniformly with other components and has poor workability, so it is used together with BIS-EMA to lower the viscosity.

[0083] The above BIS-GMA may be pure BIS-GMA, modified BIS-GMA, or a mixture containing both, wherein the modified BIS-GMA may contain at least one of DMBIS-GMA (2,2-bis[3-methyl, 4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane) and TMBIS-GMA (2,2-bis[3-methyl, 4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane). In particular, in order to secure the strength of the denture base, it is preferable to use modified BIS-GMA, which has significantly higher strength after curing, and most preferably, it is preferable to use DMBIS-GMA to secure further improved strength.

[0084] BIS-GMA can be included in the entire composition at 40 to 70 wt%. If it is included in a weight range below the above, it is difficult to secure sufficient strength, and if it is included in a weight range exceeding the above, it is difficult to perform a uniform stirring process due to excessively high viscosity. Therefore, it is preferable to include it within the weight range described above.

[0085] The above BIS-EMA (Bisphenol A dimethacrylate ethoxylated) is added to lower the viscosity due to the use of BIS-GMA, and can be included in the resin composition at 15 to 30 wt%. If it is included in an amount less than the above weight range, sufficient viscosity reduction for uniform stirring is not achieved, and if it is included in an amount exceeding the above weight range, it is difficult to secure sufficient strength after curing, and the formulation may become difficult to apply to 3D printing due to excessive viscosity reduction, so it is preferable to include it within the above-mentioned weight range.

[0086] The above TEGDMA (triethylene glycol dimethacrylate) is added as a viscosity modifier for application in 3D printing, and may be included in an amount of 3 to 5 wt% in the entire composition. If TEGDMA is included in an amount less than the above weight range, the viscosity characteristics required for 3D printing are not satisfied, and if TEGDMA is included in an amount exceeding the above weight range, there is a possibility of defects occurring due to excessive polymerization shrinkage. Therefore, it is preferable that TEGDMA be included within the above weight range.

[0087] The above photoinitiator is a material having the characteristic of being activated by light irradiation to form radicals, and the radicals thus formed can initiate a photopolymerization reaction of BIS-GMA, BIS-EMA, UDMA, and TEGDMA, thereby causing a curing reaction of the resin composition. The photoinitiator is preferably included in the entire composition at 0.5 to 2.5 wt% to cause a sufficient photocuring reaction.

[0088] Such photoinitiators include, for example, hardeners for dental curing materials, such as camphorquinone and TPO (2.4.6-trimethyl benzoyl-diphenylphosphine oxide), and any photoinitiator that can be applied to a cured material for dental equipment or materials is applicable to the present invention without being limited to the types listed above. In particular, in order to secure desirable curing properties and safety, at least one of camphorquinone and TPO may be used, and more preferably, a mixture of these may be used.

[0089] The above photoinitiator is added to assist photoinitiation by the photoinitiator. For example, DIFP (diphenyliodonium hexafluorophosphate) may be used, but is not limited thereto, and may be included in the entire composition at 0.02 to 0.2 wt%.

[0090] The above filler is added to improve the physical strength and wear resistance of the denture base, and may be included in a weight range of 2 to 6 wt% in the entire composition. In order to obtain the effect of improving strength and durability by the filler while preventing problems such as filler detachment or reduced bonding strength due to an increase in the amount of filler, it is preferable to include it within the weight range described above.

[0091] Examples of such fillers that can be used include silica, strontium aluminum silicate, barium aluminum silicate, barium glass, kaolin, talc, radiopaque glass powder, and zirconia compounds, and the types of fillers that can be applied in this embodiment are not limited thereto.

[0092] Preferably, silica surface-treated with a silane coupling agent may be used to improve miscibility with hydrophobic polymerization monomers. Since the method for modifying the surface of silica with a silane coupling agent and the specific type of silane coupling agent used for surface treatment are known in the art, a detailed description thereof will be omitted.

[0093] Furthermore, it is preferable to use fillers whose particle size has been adjusted to 50㎛ or less through a microsizing process. When the particle size is within this range, filler agglomeration is prevented and the space between filler particles is reduced. Consequently, when microcracks occur in the denture base, the effective path for crack extension is lengthened, making them less susceptible to fracture even when they do occur, thereby enhancing the durability of the denture base.

[0094] The above accelerator may be added to promote photoinitiation by increasing the radical generation efficiency of the photoinitiator by light irradiation. As such an accelerator, for example, at least one selected from the group consisting of EDMAB (ethyl (4-dimethyl amino) benzoate), DMABA (4-(dimethylamino) benzoic acid), DMABZR (4-(dimethylamino) benzaldehyde), DMAEMA (2-(dimethylamino) ethyl methacrylate), DMAEA (2-(dimethylamino) ethyl acrylate), DEAEMA (2-(diethylamino) ethyl methacrylate), and DEAEA (2-(diethylamino) ethyl acrylate) may be used, but is not limited thereto. The accelerator may be included in an amount of 0.2 to 1 wt% in the entire composition.

[0095] The above antioxidant is added to prevent degeneration due to oxidation of the denture base resin composition or the denture base, and may be BHT (butylated hydroxy toluene) or commercial products such as Iganox, but is not limited thereto, and may be included in the entire composition at 0.05 to 0.5 wt%.

[0096] The above discoloration prevention agent is added to prevent discoloration due to ultraviolet rays of the denture base resin composition or the denture base formed by 3D printing it, and is a product name Tinuvin. ® , Tinopal ® A discoloration inhibitor such as the above may be used. The discoloration inhibitor is preferably included in the resin composition at 0.05 to 0.5 wt% to obtain a discoloration prevention effect while preventing deterioration of the physical properties of the denture base.

[0097] The above antibacterial substance may be added to a denture base resin composition to provide antibacterial and antiviral functions. The antibacterial substance may be included in the resin composition at 1 to 3 wt%. If the antibacterial substance is included in an amount less than the above range, the antibacterial and antiviral performance is not guaranteed. If the antibacterial substance is included in an amount exceeding the above range, the strength of the denture base may be reduced, and in particular, the flexural strength of the 3D printed denture base resin may be lower than 65 MPa, which is the flexural strength standard for 3D printed denture base resin required by the Ministry of Food and Drug Safety. Therefore, it is preferable to include the antibacterial substance within the above-mentioned weight range.

[0098] The antibacterial agent may include at least one of pectin and protamine, preferably encapsulated pectin and protamine.

[0099] The above pectin is a component containing at least one of pectin and a pectin hydrolyzate, and the pectin hydrolyzate may be a pectin hydrolyzate obtained by decomposing pectin with an enzyme (pectinase). This pectin hydrolyzate has a bactericidal effect and an effect of inhibiting the growth of bacteria or viruses, which is due to the action of oligomers and polymers of galacturonic acid contained in the pectin hydrolyzate.

[0100] The above protamine has antibacterial properties against bacteria, mold, yeast, and other fungi, and antiviral properties against viruses.

[0101] Pectin and protamine, which have antibacterial and antiviral properties, are included in a resin composition to exhibit antibacterial and antiviral properties. However, if they are included in a resin composition without a separate treatment process such as encapsulation, damage or migration of the antibacterial agent may occur during the manufacturing process or use of the denture base, resulting in a decrease in the antibacterial and antiviral properties or a shortened shelf life. Therefore, it is preferable to encapsulate pectin and protamine for use.

[0102] Encapsulated pectin and protamine can be obtained through an encapsulation method including the steps of: preparing a first precursor by mixing pectin, protamine, and collagen and then freeze-drying; preparing a second precursor by thawing, stirring, and freeze-drying the first precursor; preparing a third precursor by mixing the second precursor and phospholipid and then freeze-drying; and thawing the third precursor. The specific method will be described later through another embodiment of the present invention.

[0103]

[0104] Meanwhile, another embodiment of the present invention includes a method for manufacturing an antibacterial and antiviral 3D printing denture base resin composition. Since the antibacterial and antiviral 3D printing denture base resin composition described above can be manufactured according to this embodiment, some overlapping descriptions are omitted.

[0105] The method for manufacturing an antibacterial and antiviral 3D printing denture base resin composition according to the present embodiment comprises: a step a of preparing a second polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA, and TEGDMA; a step b of preparing a second base composition by mixing the second polymer mixture with a photoinitiator, a photoinitiation assistant, an accelerator, an antioxidant, and a discoloration inhibitor; and a step c of preparing a resin composition by mixing the second base composition with an antibacterial substance and a filler.

[0106] The above steps a, b, and c are steps for sequentially mixing raw materials, respectively. In each mixing step, mixing can be performed at a stirring speed of 5 to 15 rpm at 30 to 60°C, and can be performed under reduced pressure conditions with a vacuum gauge pressure of 0.05 to 0.2 MPa to prevent bubble formation during stirring.

[0107] The above step a is a step for preparing a second polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA, and TEGDMA. This step is a step for mixing 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, and 3 to 5 wt% of TEGDMA, and the composition ratio refers to the weight ratio in the final resin composition. In this step, stirring can be performed for 30 to 100 minutes, and the stirring time can vary depending on the season, and within the stirring time range, stirring can be performed for a short time in summer and for a long time in winter.

[0108] In addition, the above step a can be performed under light irradiation, and at this time, the wavelength of the light source can be 330 to 510 nm, which can vary depending on the absorption wavelength of the photoinitiator. For example, when camphorquinone is used as the photoinitiator, light of 450 to 480 nm can be irradiated, and when TPO is used, light of 350 to 430 nm can be irradiated. In addition, as described above, since a vacuum is applied during the stirring process, bubble generation is prevented, thereby reducing light bending due to bubbles and increasing the exposure area of ​​the raw material mixture to the light source, so that more efficient and effective light irradiation can be achieved.

[0109] As the step a is performed under light irradiation conditions for the second polymer mixture that does not contain a photoinitiator, the second polymer mixture undergoes photoreactive modification, and the polymer is activated by light more quickly and effectively during subsequent photocuring, thereby improving the quality of the denture base, which is a hardened body.

[0110] The above step b is a step of preparing a second base composition by mixing the polymer mixture with a photoinitiator, a photoinitiator assistant, an accelerator, an antioxidant, and a discoloration inhibitor. These components are the same as described above, and each raw material can be mixed in this step so that the final resin composition contains 0.5 to 2.5 wt% of the photoinitiator, 0.02 to 0.2 wt% of the photoinitiator assistant, 2 to 6 wt% of the filler, 0.2 to 1 wt% of the accelerator, 0.05 to 0.5 wt% of the antioxidant, and 0.05 to 0.5 wt% of the discoloration inhibitor.

[0111] The above step c is a step of preparing a resin composition by mixing the second base composition with an antimicrobial agent and a filler. Specifically, this step may be a step of mixing the base composition with an antimicrobial agent and a filler, and then maturing the mixture at 31.5 to 65°C for 48 hours or more. Through this maturation, the surface of the activated filler is stabilized, the basic properties of the polymer damaged during the stirring process are partially restored, and the cross-linking between the polymer and the filler is strengthened, thereby stabilizing the properties of the resin composition.

[0112] The resin composition manufactured through this step may be a 3D printing denture base resin composition according to one embodiment of the present invention, which comprises UDMA 5 to 20 wt%, BIS-GMA 40 to 70 wt%, BIS-EMA 15 to 30 wt%, TEGDMA 3 to 5 wt%, photoinitiator 0.5 to 2.5 wt%, photoinitiator 0.02 to 0.2 wt%, filler 2 to 6 wt%, accelerator 0.2 to 1 wt%, antioxidant 0.05 to 0.5 wt%, discoloration inhibitor 0.05 to 0.5 wt%, and antibacterial agent 1 to 3 wt%.

[0113] The above antibacterial substance may include pectin and protamine, and preferably may include encapsulated pectin and protamine.

[0114] The above pectin is a component containing at least one of pectin and a pectin hydrolyzate, and the pectin hydrolyzate may be a pectin hydrolyzate obtained by decomposing pectin with an enzyme (pectinase). This pectin hydrolyzate has a bactericidal effect and an effect of inhibiting the growth of bacteria or viruses, which is due to the action of oligomers and polymers of galacturonic acid contained in the pectin hydrolyzate.

[0115] The above protamine has antibacterial properties against bacteria, mold, yeast, and other fungi, and antiviral properties against viruses.

[0116] Pectin and protamine, which have antibacterial and antiviral properties, are included in a resin composition to exhibit antibacterial and antiviral properties. However, if they are included in a resin composition without a separate treatment process such as encapsulation, damage or migration of the antibacterial agent may occur during the manufacturing process or use of the denture base, resulting in a decrease in the antibacterial and antiviral properties or a shortened shelf life. Therefore, it is preferable to encapsulate pectin and protamine for use.

[0117] Encapsulated pectin and protamine can be obtained through an encapsulation method comprising the steps of: preparing a first precursor by mixing pectin, protamine, and collagen and then freeze-drying; preparing a second precursor by thawing, stirring, and freeze-drying the first precursor; preparing a third precursor by mixing the second precursor and a phospholipid and then freeze-drying; and thawing the third precursor.

[0118] First, the step of preparing the first precursor is a step of preparing the first precursor by mixing pectin, protamine, and collagen and then freeze-drying them. This step may be a step of mixing pectin, protamine, and collagen in a weight ratio of 1:1 to 7:0.9 to 4, preferably in a weight ratio of 1:1.3 to 6:1 to 3, and then freeze-drying them.

[0119] At this stage, mixing can be performed under vacuum, and stirring can be performed at a stirring speed of 4 to 5 rpm at 57 to 65°C for 5 to 7 hours to ensure uniform stirring. Additionally, freeze-drying at this stage can be performed at 0°C or lower for 10 to 17 hours.

[0120] Next, the step of preparing the second precursor is to naturally thaw the first precursor at room temperature, stir it, and then freeze-dry it again to prepare the second precursor. In this step, stirring can be performed at a stirring speed of 3 to 4 rpm in a vacuum and an environment of 67 to 74°C for 10 to 15 hours, and then freeze-drying can be performed at 0°C or lower for 20 to 30 hours to prepare the second precursor.

[0121] Next, a step for preparing a third precursor is performed. This step involves mixing the second precursor and the phospholipid, followed by lyophilization to achieve actual encapsulation. The second precursor and the phospholipid may be mixed at a weight ratio of 1:0.8 to 1.5. At this time, stirring may be performed for 10 to 15 hours at a stirring speed of 3 to 4 rpm under vacuum and 65 to 75°C to ensure uniform mixing. The mixture obtained through this step may be lyophilized at 0°C or lower for 20 to 30 hours to prepare the third precursor.

[0122] The third precursor thus prepared can be thawed to obtain encapsulated pectin and protamine.

[0123] In this way, in the process of repeating the cycle of freeze-drying, thawing, and mixing, the functional substances pectin and protamine with antibacterial and antiviral properties are effectively encapsulated, and when mixed into the resin composition, manufactured into a denture base, and used, damage and migration of the antibacterial substances are prevented, so that the antibacterial properties of these functional substances can be maintained for a long period of time.

[0124] In this way, the resin composition for a 3D printed denture base according to an embodiment of the present invention can be cured into the shape of a denture base by being irradiated with light during the 3D printing process or after completion of 3D printing, and after curing, can achieve a flexural strength of 65 MPa or more, which is the denture base required by the Ministry of Food and Drug Safety.

[0125] Additionally, since it has antibacterial and antiviral properties, it can ensure resistance to bacterial or viral contamination of dentures that are repeatedly removed from the oral cavity, and secondary infections resulting from such contamination.

[0126] Below, specific examples of the present invention will be used to explain the specific functions and effects of the present invention. However, these examples are presented as preferred examples of the present invention, and the scope of the present invention is not limited by the examples.

[0127]

[0128] [Manufacturing Example 1]

[0129] First, UDMA, BIS-GMA, BIS-EMA, and TEGDMA were placed in a vacuum mixer and stirred at 45°C, 10 rpm, and a vacuum gauge pressure of 0.07 MPa to prepare a polymer mixture. Then, a photoinitiator (camphorquinone), a photoinitiator (DIFP), an accelerator (EDMAB), an antioxidant (BHT), and a discoloration inhibitor (Tinuvin) were added thereto, and stirred at the same temperature, stirring speed, and under vacuum to prepare a base composition. The composition of the base composition thus prepared is shown in Table 1.

[0130] Next, 4 parts by weight of an antibacterial agent, 4 parts by weight of a filler (silica), and 40 parts by weight of barium glass were added to 100 parts by weight of the base composition in a vacuum mixer containing the base composition, stirred under the same conditions to prepare a uniform composition, and then aged at 33°C for 50 hours to prepare an aesthetic restorative composite resin with improved antibacterial properties and polymerization depth.

[0131] The above antibacterial agent used was modified lysozyme that had undergone purification and surface modification steps. The purification step was performed by mixing lysozyme powder with a 95% ethanol aqueous solution at a weight ratio of 25:75, placing the mixture in a sealed container, mixing at 5 rpm for 6 hours at room temperature, then opening the container and mixing again at 2 rpm to evaporate the ethanol. The purification step was performed twice in total. The surface modification step was performed by mixing lysozyme and PEGDMA that had undergone the purification step at a weight ratio of 65:35, and stirring at 3 rpm for 12 hours under a vacuum of 0.05 MPa and a temperature of 35°C.

[0132] Raw material name Content (wt%) UDMA 7.9 BIS-GMA 60.5 BIS-EMA 24.8 TEGDMA 4.3 Photoinitiator 1.3 Photoinitiator 0.1 Accelerator 0.6 Antioxidant 0.3 Anti-discoloration agent 0.2 Total 100

[0133]

[0134] [Experimental Example 1]

[0135] Composite resins were manufactured using the same method as Manufacturing Example 1, but the content of the antibacterial agent in the composite resin was changed from 1 to 5 parts by weight per 100 parts by weight of the base composition, thereby manufacturing composite resins of various compositions. Afterwards, each composite resin was manufactured into a size of 64 mm × 10 mm × 3.3 mm and then light-cured to manufacture five specimens each.

[0136] Each specimen was mounted on a universal testing machine and bent at a speed of 5 mm / min until fracture, and the load at fracture (F) was recorded. The thickness (h) and width (b) of the specimen were measured, and the flexural strength (σ) was calculated using the following [Formula 1]. B ) was calculated. In [Formula 1], “l” represents the distance between the supports of the universal testing machine. Five specimens were manufactured for each sample, and the experiment was performed. The flexural strength was calculated, and the results and average values ​​are shown in Table 2.

[0137] [Formula 1]

[0138]

[0139] Antibacterial content (weight parts) 12345 Flexural strength (MPa) 101.2 102.4 103.298.3 105.398.297.5 101.1110.1102.197.5 103.297.3114.6 102.6 101.3101.299.5 100.2101.492.397.5 103.5 105.2 109.2 Average 98.1 100.4 100.9 105.7 104.1

[0140] According to the results in Table 2 above, all specimens met the Ministry of Food and Drug Safety's flexural strength requirement of 80 MPa or higher for aesthetic restorative composite resins, demonstrating a flexural strength significantly higher than the required standard. Furthermore, a slight increase in flexural strength was observed with increasing antimicrobial agent content.

[0141]

[0142] [Experimental Example 2]

[0143] As in Experimental Example 1, specimens were manufactured with the content of the antimicrobial agent adjusted to 1 to 5 parts by weight relative to 100 parts by weight of the base composition, and an experiment was conducted to measure the polymerization depth of each specimen in accordance with ISO 4049:2019(E), Dentistry-polymer-based restorative materials, clauses 7 and 10, and the results are shown in Table 3.

[0144] Antibacterial content (weight parts) 12345 Polymerization depth (mm) 1.5 1.8 2.3 3.0 3.11 8 1.7 2.13 23.11 7 1.5 2.4 3.13 21.8 1.6 2.9 3.3 3.4 1.6 1.9 2.7 3.2 3.5 Average 1.6 8 1.7 0 2.4 8 3.16 3.26

[0145] According to the experimental results in Table 3 above, the antimicrobial agent content and polymerization depth were found to be proportional, and it is predicted that the antimicrobial agent content and polymerization depth will remain proportional even when the antimicrobial agent content exceeds 5 parts by weight. Therefore, it was confirmed that it is desirable to increase the antimicrobial agent content to improve the polymerization depth, and in particular, it was confirmed that it is desirable to add 4 parts by weight or more of the antimicrobial agent to ensure a polymerization depth of 3 mm or more, which is the recognized range of polymerization depth for bulk-fill resins.

[0146]

[0147] [Experimental Example 3]

[0148] Composite resin samples were prepared using modified lysozyme and a fluorine compound (NaF) as antibacterial agents, respectively, and the adhesive strength according to the antibacterial agent content per 100 parts by weight of the base composition of each sample was evaluated, and the results are shown in Table 4.

[0149] The bonding strength was evaluated by embedding a tooth in a composite resin block to manufacture a specimen block, fixing the composite resin block with a holder, and applying tensile force until the tooth fell off, and the tensile force at the point of tooth falling off was evaluated as the bonding strength.

[0150] Lysozyme content (parts by weight)Fluorine content (parts by weight)124124Adhesive strength (MPa)101.2102.498.394.592.471.598.297.5110.188.888.572.997.5103.2114.687.582.874.2101.3101.2100.288.984.575.892.397.5105.291.583.273.1Average98.10100.36105.6890.2486.2873.50

[0151] As confirmed by the results in Table 4 above, when modified lysozyme is used as an antimicrobial agent, the adhesive strength is shown to be improved more than when fluorine compounds are used. Furthermore, while adhesive strength decreases as the content of fluorine compounds increases, in the case of modified lysozyme, adhesive strength slightly increases as the content increases.

[0152] Therefore, it was confirmed that it is desirable to use modified lysozyme rather than fluorine compounds as an antibacterial agent for dental resins in order to enhance antibacterial activity and prevent a decrease in adhesive strength due to the use of antibacterial agents.

[0153]

[0154] [Experimental Example 4]

[0155] The antibacterial activity of each composite resin manufactured by varying the content of antibacterial agent to 1 to 6 parts by weight per 100 parts by weight of the base composition in the same manner as Experimental Example 1 was evaluated, and the results are shown in Fig. 1. Specifically, the cured sample was added to a liquid medium, the sample strain was inoculated, and the culture was cultured for 24 hours. The turbidity of the culture solution was measured to evaluate the antibacterial activity. In addition, the turbidity of the medium to which no composite resin sample was added (Control Group 1) was set to 100%, and the turbidity of each sample was calculated as a relative value to the control group and is shown in Fig. 1.

[0156] The turbidity of the culture solution after culture is higher as the strain proliferation is active. As a result of the experiment, the turbidity of samples 1 to 3 did not decrease significantly compared to the control group, but the turbidity of samples 4 to 6 was very low at around 30%, and the turbidity difference between them was not large, so it was confirmed that samples 4 to 6 had the best antibacterial properties.

[0157] Therefore, as a result of this experiment, it was confirmed that when using lysozyme as an antibacterial agent, it is preferable to include the antibacterial agent in an amount of 4 to 6 parts by weight per 100 parts by weight of the base composition.

[0158]

[0159] [Manufacturing Example 2]

[0160] UDMA, BIS-GMA, BIS-EMA, and TEGDMA were placed in a vacuum mixer and stirred at 45°C, 10 rpm, and a vacuum gauge pressure of 0.07 MPa to prepare a polymer mixture. A photoinitiator (camphorquinone), a photoinitiator (DIFP), an accelerator (EDMAB), an antioxidant (BHT), and a discoloration inhibitor (Tinuvin) were added thereto, and stirred at the same temperature, stirring speed, and vacuum to prepare a base composition. Subsequently, an antibacterial substance and a filler (silica) were added to the vacuum mixer containing the base composition, and stirred under the same conditions to prepare a uniform composition, which was then aged at 33°C for 50 hours to prepare an antibacterial and antiviral 3D printed denture base resin composition. The composition of the resin composition thus prepared is shown in Table 5.

[0161] The above antibacterial substance was prepared by: a step of preparing a first precursor by stirring pectin, protamine, and collagen in a weight ratio of 3:4:3 at 60°C with a stirring speed of 4 rpm for 6 hours, and then freeze-drying for 12 hours; a step of naturally thawing the first precursor at room temperature, stirring it at 70°C with a stirring speed of 4 rpm for 12 hours, and then freeze-drying for 24 hours to prepare a second precursor; a step of mixing the second precursor and phospholipid in a weight ratio of 1:1, stirring it at 70°C with a stirring speed of 3 rpm for 12 hours, and then freeze-drying for 24 hours to prepare a third precursor; and then naturally thawing the third precursor obtained through the above process was used. The process in which stirring was performed throughout the entire process was performed under a vacuum of a vacuum gauge pressure of 0.07 MPa.

[0162] Raw material name Content (wt%) UDMA 7.6 BIS-GMA 5 5.4 BIS-EMA 2 3.3 TEGDMA 4.2 Photoinitiator 1.3 Photoinitiator 0.1 Filler 4.0 Accelerator 0.6 Antioxidant 0.3 Discoloration inhibitor 0.2 Antibacterial substance 3.0 Total 100.0

[0163] [Experimental Example 5]

[0164] Resin compositions were manufactured using the same method as in Manufacturing Example 2, but the content of the antibacterial substance included in the entire composition was changed from 1 to 5 wt% to manufacture resin compositions of various compositions. At this time, the total content of the remaining mixture excluding the antibacterial substance was changed according to the increase or decrease in the content of the antibacterial substance, thereby offsetting the increase or decrease in the content of the antibacterial substance. Afterwards, each resin composition was 3D printed into a size of 64 mm × 10 mm × 3.3 mm and then photocured to manufacture five specimens each.

[0165] Each specimen was mounted on a universal testing machine and bent at a speed of 5 mm / min until fracture, and the load at fracture (F) was recorded. The thickness (h) and width (b) of the specimen were measured, and the flexural strength (σ) was calculated using the following [Formula 1]. B ) was calculated. In [Formula 1], “l” refers to the distance between the supports of the universal material testing machine. Five specimens were manufactured for each antimicrobial agent content, and an experiment was performed on each specimen. The flexural strength was calculated, and the results and average values ​​are shown in Table 6.

[0166] [Formula 1]

[0167]

[0168] Antibacterial substance content (wt%) 12345 Flexural strength (MPa) 82807867628379797063848475716582827963618181756463

[0169] As a result of the experiment, when the content of antimicrobial substances was 1 to 3 wt%, the flexural strength of all specimens was 65 MPa or higher, which is the standard required by the Ministry of Food and Drug Safety. However, when the content of antimicrobial substances was 4 wt%, only some specimens met this standard, and when the content of antimicrobial substances was 5 wt%, most specimens did not meet the standard. Therefore, it was confirmed that in order to form a uniform quality with a flexural strength of 65 MPa or higher for each denture base, it is desirable to include the antimicrobial substance in the entire resin composition at 1 to 3 wt%.

[0170]

[0171] [Experimental Example 6]

[0172] When manufacturing an antibacterial substance, the content ratio of pectin, protamine, and collagen was varied as shown in Table 7, and the antibacterial substance was manufactured using the same method as in Manufacturing Example 2. Then, the content of the antibacterial substance in the resin composition was fixed at 3 wt%, and the resin composition was manufactured using the same method as in Manufacturing Example. Then, the same flexural strength evaluation as in Experimental Example 5 was performed, and the results are shown in Table 8.

[0173] Pectin (A) Protamine (B) Collagen (C) A : B : C Weight ratio Sample 111060301 : 6.0 : 3.0 Sample 122050301 : 2.5 : 1.5 Sample 133040301 : 1.3 : 1.0 Sample 144030301 : 0.75 : 0.75 Sample 155020301 : 0.4 : 0.6 Sample 166010301 : 0.17 : 0.5

[0174] Flexural strength (MPa) Sample 117175706970 Sample 127072747675 Sample 137879757975 Sample 146872736971 Sample 156770706766 Sample 166563626761

[0175] As a result of the experiment, it was found that all samples 11 to 15 satisfied the standard value of 65 MPa or more when the flexural strength was measured five times, but some specimens of sample 16 showed a flexural strength below the standard. Therefore, in order to secure stable flexural strength for each individual, the pectin, protamine, and collagen included in the antibacterial substance are preferably included in a weight ratio of 1:0.3~7.0:0.55~4.0, and more preferably, they can be included in a weight ratio of 1:0.4~6.0:0.6~3.0.

[0176]

[0177] [Experimental Example 7]

[0178] The antibacterial activity of each resin composition manufactured in Experimental Example 6 was evaluated, and the results are shown in Fig. 2. Specifically, the cured sample was added to a liquid medium, the sample strain was inoculated, and the culture was cultured for 24 hours. The turbidity of the culture solution was measured to evaluate the antibacterial activity. In addition, the turbidity of the medium to which no resin composition sample was added (Control Group 2) was set to 100%, and the turbidity of each sample was calculated as a relative value to the control group, and is shown in Fig. 2.

[0179] After cultivation, the turbidity of the culture solution increases as the strain proliferation becomes more active. As a result of the experiment, the turbidity of samples 11 to 13 was maintained at a consistently low level of around 35%, but the turbidity of samples 14 to 16 increased more than this. In particular, each sample had a fixed collagen content and changed the weight ratio of pectin and protamine. As the pectin content increased and the protamine content decreased, the turbidity increased, confirming that the antibacterial activity decreased.

[0180] Therefore, in order to secure high antibacterial properties, it was confirmed that it is desirable to use pectin, protamine, and collagen included in the antibacterial agent in a weight ratio of 1:1~7:0.9~4, and preferably in a weight ratio of 1:1.3~6:1~3.

[0181] The aesthetic restorative composite resin containing lysozyme, which has improved antibacterial properties and polymerization depth according to the present invention, comprises 2 to 5 parts by weight of a filler, 4 to 6 parts by weight of an antibacterial agent, and 40 to 45 parts by weight of barium glass, based on 100 parts by weight of a base composition, wherein the antibacterial agent is a modified lysozyme, and has excellent antibacterial properties, thereby ensuring high resistance to bacteria and viruses, and since the polymerization depth is improved, it can be applied as a bulk-fill resin, so that the number of layers is reduced during treatment, thereby preventing secondary caries due to the layered interface, and shortening the treatment time, and thus has industrial applicability.

Claims

1. A base composition containing 100 parts by weight of UDMA (urethane dimethacrylate), BIS-GMA (bisphenol A-glycidyl methacrylate), BIS-EMA (bisphenol A dimethacrylate ethoxylated), TEGDMA (triethylene glycol dimethacrylate), a photoinitiator, a photoinitiator assistant, an accelerator, an antioxidant and a discoloration inhibitor, contains 2 to 5 parts by weight of a filler, 4 to 6 parts by weight of an antibacterial agent and 40 to 45 parts by weight of barium glass. The above antibacterial agent is modified lysozyme, An aesthetic restorative composite resin with improved antibacterial properties and polymerization depth, characterized in that the modification of lysozyme is performed by a purification step of purifying the surface of lysozyme with ethanol; and a surface modification step of mixing the purified lysozyme with PEGDMA (polyethylene glycol dimethacrylate).

2. In paragraph 1, The above base composition comprises UDMA at 5 to 20 wt%, BIS-GMA at 40 to 70 wt%, BIS-EMA at 15 to 30 wt%, TEGDMA at 3 to 6 wt%, photoinitiator at 0.5 to 2.5 wt%, photoinitiator at 0.02 to 0.2 wt%, accelerator at 0.2 to 1 wt%, antioxidant at 0.05 to 0.5 wt%, and anti-discoloration agent at 0.05 to 0.5 wt%, which is an aesthetic restorative composite resin having improved antibacterial properties and polymerization depth.

3. The first step is to prepare a polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA and TEGDMA; A second step of preparing a base composition by mixing the polymer mixture and a photoinitiator, a photoinitiator assistant, an accelerator, an antioxidant and a discoloration inhibitor; and A third step of manufacturing a composite resin by mixing the base composition, an antibacterial agent, a filler, and barium glass; The above antibacterial agent is a modified lysozyme that has undergone a modification process and is included in an amount of 4 to 6 parts by weight based on 100 parts by weight of the base composition. A method for manufacturing an aesthetic restorative composite resin with improved antibacterial properties and polymerization depth, the above modification process comprising: a purification step of purifying the surface of lysozyme with ethanol; and a surface modification step of mixing lysozyme, the surface of which has been purified, with PEGDMA.

4. In paragraph 3, A method for manufacturing an aesthetic restorative composite resin having improved antibacterial properties and polymerization depth, characterized in that the composite resin manufactured through the third step comprises 100 parts by weight of a base composition including 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 6 wt% of TEGDMA, 0.5 to 2.5 wt% of a photoinitiator, 0.02 to 0.2 wt% of a photoinitiator assistant, 0.2 to 1 wt% of an accelerator, 0.05 to 0.5 wt% of an antioxidant, and 0.05 to 0.5 wt% of an anti-discoloration agent, and further comprises 2 to 5 parts by weight of a filler, 4 to 6 parts by weight of an antibacterial agent, and 40 to 45 parts by weight of barium glass. 5.An antibacterial and antiviral 3D printing denture base resin composition comprising UDMA, BIS-GMA, BIS-EMA, TEGDMA, a photoinitiator, a photoinitiator assistant, a filler, an accelerator, an antioxidant, an anti-discoloration agent, and an antibacterial agent.

6. In paragraph 5, An antibacterial and antiviral 3D printing denture base resin composition comprising 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 5 wt% of TEGDMA, 0.5 to 2.5 wt% of photoinitiator, 0.02 to 0.2 wt% of photoinitiator assistant, 2 to 6 wt% of filler, 0.2 to 1 wt% of accelerator, 0.05 to 0.5 wt% of antioxidant, 0.05 to 0.5 wt% of anti-discoloration agent, and 1 to 3 wt% of antibacterial agent.

7. In paragraph 5, An antibacterial and antiviral 3D printing denture base resin composition, characterized in that the antibacterial substance is pectin and / or protamine.

8. Step a: preparing a second polymer mixture by mixing UDMA, BIS-GMA, BIS-EMA, and TEGDMA; Step b of preparing a second base composition by mixing the second polymer mixture with a photoinitiator, a photoinitiator assistant, an accelerator, an antioxidant, and a discoloration inhibitor; and A method for producing an antibacterial and antiviral 3D printing denture base resin composition, comprising: a step c of producing a resin composition by mixing the second base composition with an antibacterial substance and a filler.

9. In paragraph 8, A method for producing an antibacterial and antiviral 3D printing denture base resin composition, characterized in that the resin composition manufactured through the above step c contains 5 to 20 wt% of UDMA, 40 to 70 wt% of BIS-GMA, 15 to 30 wt% of BIS-EMA, 3 to 5 wt% of TEGDMA, 0.5 to 2.5 wt% of a photoinitiator, 0.02 to 0.2 wt% of a photoinitiator assistant, 2 to 6 wt% of a filler, 0.2 to 1 wt% of an accelerator, 0.05 to 0.5 wt% of an antioxidant, 0.05 to 0.5 wt% of a discoloration inhibitor, and 1 to 3 wt% of an antibacterial agent.

10. In paragraph 8, A method for producing an antibacterial and antiviral 3D printing denture base resin composition, characterized in that the antibacterial substance is encapsulated pectin and / or protamine.

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