3D printing resin composition for transparent structure, fluorescent implant guide, and manufacturing method for composition and guide

Abstract

The present invention relates to: a 3D printing resin composition comprising bisphenol A-glycidyl methacrylate (BIS-GMA), ethoxylated bisphenol A dimethacrylate (BIS-EMA), urethane dimethacrylate (UDMA), a photoinitiator, an additive, a coloring aid, a filler, a viscosity modifier, and a fluorescent colorant; a fluorescent implant guide manufactured by using same; and a manufacturing method for the composition and the guide. An implant guide or a dental structure manufactured through 3D printing using the 3D printing resin composition according to the present invention emits fluorescence during light irradiation, thereby having the effect and benefit of enabling more efficient recognition of the implantation position, direction, depth, and the like of the dental structure during various dental procedures.

Description

3D printing resin composition for transparent structures and fluorescent implant guides and methods for manufacturing them

[0001] This invention relates to a 3D printing resin composition having fluorescent properties and a method for producing the same, and a fluorescent implant guide produced using the same and a method for producing the same. The fluorescent implant guide produced using the 3D printing resin composition according to this invention can more effectively guide the implantation position, direction, depth, etc. of the implant due to the fluorescent 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 shift into the empty space where the tooth was, the normal alignment of the teeth begins to misalign, and food gets stuck between the teeth, causing cavities, periodontitis, or bad breath.

[0003] To solve this problem, when a patient loses part or all of their teeth, all of the natural teeth and the associated gum area of ​​the dental arch are replaced with artificial objects to maintain or restore the function of the oral cavity, and a dental restorative resin is applied to the area where the teeth are lost.

[0004] Various dental structures, including these dental restorative resins, must be strong enough to allow the practitioner (dentist) to easily and accurately check the location of the dental structure and to avoid damage during drilling or punching.

[0005] Therefore, research and development are needed on a 3D printing resin composition that can manufacture restorative resins or dental structures in a patient-specific manner, while simultaneously increasing the convenience of the practitioner and minimizing side effects such as bleeding, swelling, and infection in the early stages of the procedure as well as detachment, fracture, and nerve damage after the procedure.

[0006] Meanwhile, the implant guide is intended to plan the implantation location of a dental implant to be applied to a patient during implant surgery and guide the implantation location, direction, angle, depth, etc. based on the results. It is configured to include a guide body that negatively corresponds to the patient's oral structure during dental implant surgery and a guide hole that guides the implantation location.

[0007] Since the drilling, punching, and implant placement processes for implant placement are guided by these guide holes, implant surgery can be performed at the originally designed implantation location and angle, and dependence on surgical skill can be reduced.

[0008] Accordingly, in the dental field, the development of devices and instruments for accurately placing implants in the planned location during dental implant surgery based on the patient's oral information acquired through oral scanners, etc., is becoming active, and accordingly, the market for implant guides manufactured using 3D printers is also growing rapidly.

[0009] To perform their role safely, implant guides must allow the dentist to easily identify the location of the guide hole and must be sufficiently strong to avoid damage during drilling or punching. However, due to recent rapid market growth, there has been an increase in the production and distribution of implant guides with inconsistent physical properties or cytotoxicity, which are inadequate for their intended purpose. The use of these defective guides has resulted in adverse effects such as bleeding, swelling, and infection during the initial procedure, as well as implant detachment, fracture, and nerve damage after the procedure.

[0010] Due to these problems, there is a need for a safe implant guide product that can faithfully perform the role of an implant guide.

[0011] This invention relates to a 3D printing resin composition and a method for manufacturing the same, and by providing a 3D printing resin composition having fluorescent properties and a method for manufacturing the same, it is possible to impart fluorescent properties to dental structures such as implant guides or resins for dental restoration, so that a practitioner can more effectively recognize the implantation position, direction, depth, etc. of dental structures, while at the same time ensuring sufficient physical and mechanical strength.

[0012] In addition, the invention includes an implant guide having fluorescent properties that can be manufactured by a method such as 3D printing using the above resin composition, and a method for manufacturing the same, and aims to provide a fluorescent implant guide that can effectively guide the implantation position, direction, depth, etc. of an implant when used in a dental implant procedure.

[0013] This 3D printing resin composition according to one embodiment of the invention includes bisphenol A glycidyl methacrylate (BIS-GMA), bisphenol A dimethacrylate ethoxylated (BIS-EMA), urethane dimethacrylate (UDMA), a photoinitiator, an additive, a color developer, a filler, a viscosity regulator, and a fluorescent developer.

[0014] The fluorescent colorant is preferably DAPI (4',6-Diamidino-2-phenylindole dihydrochloride), and is more preferably included in a range of 0.2 wt% or more and less than 1.6 wt%. In addition, the additive may be at least one of an accelerator, an antioxidant, and a photoinitiator.

[0015] Another embodiment of the invention provides a method for producing a 3D printing resin composition, comprising: a first mixing step of mixing and stirring BIS-GMA, BIS-EMA, and UDMA to produce a first mixture; a second mixing step of adding a photoinitiator and an additive to the first mixture and stirring the mixture to produce a second mixture; a third mixing step of adding a color developer mixture to the second mixture and stirring the mixture to produce a third mixture; a fourth mixing step of adding a filler to the third mixture and stirring the mixture to produce a fourth mixture; and a fifth mixing step of adding a viscosity modifier to the fourth mixture and stirring the mixture to produce a composition for an implant guide.

[0016] The above-mentioned color developer mixture is a mixture of UDMA, a fluorescent color developer, and a color developer, and it is preferable that the fluorescent color developer is DAPI (4',6-Diamidino-2-phenylindole dihydrochloride), and it is more preferable that the fluorescent color developer is included in a range of 0.2 wt% or more to less than 1.6 wt%.

[0017] In another embodiment of the invention, there is provided an implant guide including a guide body having at least one hole formed therein, wherein the guide body can be formed by curing a composition for an implant guide including BIS-GMA, BIS-EMA, UDMA, a photoinitiator, an additive, a color developer, a filler, a viscosity regulator, and a fluorescent developer.

[0018] It is preferable that the fluorescent agent is DAPI (4',6-Diamidino-2-phenylindole dihydrochloride), and it is more preferable that the content of the fluorescent agent included in the composition for the implant guide is 0.2 wt% or more and less than 1.6 wt%.

[0019] The composition for the implant guide may include 30 to 60 wt% of BIS-GMA, 10 to 30 wt% of BIS-EMA, 5 to 30 wt% of UDMA, 1 to 10 wt% of a photoinitiator, 0.01 to 5 wt% of an additive, 0.1 to 5 wt% of a color-developing agent, 0.5 to 8 wt% of a filler, 1 to 25 wt% of a viscosity modifier, and 0.2 wt% or more and less than 1.6 wt% of a fluorescent color-developing agent.

[0020] The above fluorescent implant guide can be manufactured through a guide design step of designing the shape of the implant guide from the patient's oral information; an implant guide composition manufacturing step of manufacturing a composition for the implant guide by mixing BIS-GMA, BIS-EMA, UDMA, a photoinitiator, an additive, a color development assistant, a filler, a viscosity modifier, and a fluorescent coloring agent; and an implant guide manufacturing step of manufacturing a patient-customized fluorescent implant guide by 3D printing the implant guide composition in the shape of the implant guide designed in the guide design step.

[0021] At this time, the step of preparing the composition for the implant guide may include a first mixing step of mixing and stirring BIS-GMA, BIS-EMA, and UDMA to prepare a first mixture; a second mixing step of adding a photoinitiator and an additive to the first mixture and stirring the mixture to prepare a second mixture; a third mixing step of adding a color developer mixture to the second mixture and stirring the mixture to prepare a third mixture; a fourth mixing step of adding a filler to the third mixture and stirring the mixture to prepare a fourth mixture; and a fifth mixing step of adding a viscosity modifier to the fourth mixture and stirring the mixture to prepare a composition for the implant guide; wherein the color developer mixture is preferably a mixture of UDMA, a fluorescent color developer, and a color developer.

[0022] It is preferable that the above fluorescent colorant is DAPI (4',6-Diamidino-2-phenylindole dihydrochloride).

[0023] The resin composition for 3D printing according to the present invention not only enables the manufacture of dental structures such as dental implant guides with excellent mechanical strength through 3D printing, but also has the advantage of emitting fluorescence when irradiated with light, thereby more efficiently guiding the implantation position, direction, depth, etc. of dental structures during various dental procedures.

[0024] Figure 1 is a photograph observing the results of a fluorescence development experiment of Experimental Example 3 of the invention.

[0025] Below, preferred embodiments of this invention are described in detail. Before proceeding, it should be noted that the terms and words used in the specification and claims of this invention are not limited to their conventional or dictionary meanings, but should be interpreted in their meanings and concepts consistent with the technical spirit of this invention.

[0026] Throughout the 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.

[0027] Additionally, throughout this specification, “%” used to indicate the concentration of a particular substance means (weight / weight)% for solid / solid, (weight / volume)% for solid / liquid, and (volume / volume)% for liquid / liquid, unless otherwise stated.

[0028] The identifiers used in each step are for convenience of explanation and do not indicate the order of the steps. The steps may be performed in a different order than stated, unless the context clearly dictates otherwise. In other words, the steps may be performed in the same order as stated, substantially simultaneously, or in the opposite order.

[0029] Below, we will examine specific embodiments of this invention. However, the scope of this invention is not limited to the preferred embodiments described below. Furthermore, anyone with common knowledge at the time of filing of the application would be able to implement various modified forms of the invention within the scope of protection described in the specification.

[0030] First, the 3D printing resin composition according to the invention is a composition that can manufacture a dental structure such as a dental fluorescent implant guide or a dental restorative resin through 3D printing. When the composition is used to manufacture a dental structure such as an implant guide or a dental resin, since it emits fluorescence when irradiated with light, it can accurately guide the position, angle, direction, depth, etc., of perforation or drilling or implant placement during a dental procedure, thereby preventing side effects such as perforation or implantation position errors, abnormal bleeding, swelling, infection, and nerve damage in advance and enabling safer and more accurate dental procedures.

[0031] According to one embodiment of the invention, a 3D printing resin composition comprises BIS-GMA, BIS-EM, UDMA, a photoinitiator, an additive, a color-developing agent, a filler, a viscosity modifier, and a fluorescent color-developing agent, and when the resin composition is cured after 3D printing, a dental structure such as a fluorescent implant guide can be formed.

[0032] More specifically, the 3D printing resin composition may include 30 to 60 wt% of BIS-GMA, 10 to 30 wt% of BIS-EMA, 5 to 30 wt% of UDMA, 1 to 10 wt% of a photoinitiator, 0.01 to 5 wt% of an additive, 0.1 to 5 wt% of a color developer, 0.5 to 8 wt% of a filler, 1 to 25 wt% of a viscosity modifier, and 0.2 wt% or more and less than 1.6 wt% of a fluorescent developer.

[0033] The above BIS-GMA, BIS-EMA and UDMA form the basic skeleton of dental structures, and are suitable for use as dental structures such as implant guides and orthodontic devices because they are transparent after hardening, and can be clearly colored without inhibiting color development by fluorescent dyes or color development aids.

[0034] Among these, BIS-GMA contains two hydrophobic methacrylic groups, has low volatility and polymerization shrinkage, cures quickly, has a large molecular weight, and possesses high stability, making it suitable as a matrix resin. However, its high viscosity makes it difficult to mix uniformly with other components and results in poor workability. Therefore, it is recommended to use it in combination with BIS-EMA to lower the viscosity.

[0035] The above BIS-GMA may be pure BIS-GMA, modified BIS-GMA, or a mixture including both, wherein the modified BIS-GMA may include 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).

[0036] In particular, it is desirable to use modified BIS-GMA, which has significantly higher strength after hardening, so that it can sufficiently withstand the force applied to the implant guide during perforation work, and it is even more desirable to use DMBIS-GMA, which is a modified BIS-GMA, to secure further improved strength.

[0037] BIS-GMA can be included in the entire composition at 30 to 60 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] BIS-EMA can be included in the entire composition at 10 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. 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 be difficult to apply to 3D printing due to excessive viscosity reduction. Therefore, it is preferable to include it within the above weight range.

[0039] The above UDMA is added to reduce polymerization shrinkage, improve elasticity and toughness, and ensure uniform dispersion of fluorescent dyes or coloring aids, and may be included in an amount of 5 to 30 wt% within the entire composition. If the content of UDMA is below the above range, it is difficult to obtain the effects described above with 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.

[0040] The above photoinitiator is a component that is activated by light irradiation to form radicals, and the radicals thus formed can induce a photopolymerization reaction of BIS-GMA, BIS-EMA, and UDMA, thereby inducing a curing reaction of a dental 3D printing resin composition.

[0041] Such photoinitiators are preferably included in the entire composition at 1 to 10 wt% to cause sufficient photocuring reaction, and specific photoinitiators, for example, can be used curing agents for dental curing materials, such as camphorquinone and TPO (2.4.6-trimethyl benzoyl-diphenylphosphine oxide). However, the photoinitiator components are not necessarily limited to these, and any photoinitiator that can be applied to a cured material for dental equipment or materials can be applied to the invention. In particular, in order to secure desirable curing characteristics and safety, at least one of camphorquinone and TPO can be used, and more preferably, a mixture of these can be used.

[0042] The above additive is added to improve the curing characteristics or physical and chemical properties of the dental 3D printing resin composition. As the additive, at least one of an accelerator, an antioxidant, and a photoinitiator may be used, and it is preferable that it be included in a weight ratio of 0.01 to 5 wt% in the entire composition.

[0043] An accelerator may be added to promote photoinitiation by increasing the radical generation efficiency of a photoinitiator by light irradiation. Such an accelerator may include, 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), but is not necessarily limited thereto, and may be included in an amount of 0.05 to 2 wt% in the entire composition of the 3D printing resin.

[0044] Antioxidants are added to prevent oxidation-induced deterioration of 3D printing resin compositions or 3D printed dental structures using the same. Antioxidants such as butylated hydroxy toluene (BHT) or commercially available products such as Iganox can be used. However, they are not necessarily limited to these, and can be included in the entire composition of the dental 3D printing resin in a range of 0.05 to 2 wt%.

[0045] The 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 in a range of 0.01 to 1 wt%.

[0046] The above-mentioned color-developing auxiliary agent is added to assist in the fluorescence development and color implementation of a dental structure or structure printed with a resin composition according to the present invention, and may be included in the range of 0.1 to 5 wt% in the entire resin composition.

[0047] Food coloring can be used as a coloring auxiliary agent, and for example, azo pigments such as Red No. 2, Yellow No. 4, Yellow No. 5, Red No. 40, and Red No. 102, xanthan pigments such as Red No. 3, triphenylmethane pigments such as Green No. 3 and Blue No. 1, and indigoid pigments such as Blue No. 2 can be used, but are not particularly limited thereto. Since these coloring auxiliary agents are composed of food coloring, they can ensure human safety for the use of the coloring agent while assisting the fluorescent emission characteristics of the fluorescent coloring agent to enable more vivid coloration and emission.

[0048] The above filler is added to improve the physical strength and wear resistance of a dental structure 3D printed with a resin composition according to the present invention, and may be included in a weight range of 0.5 to 8 wt% in the entire composition. In order to obtain the effect of improving strength and durability due to 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 the filler within the above-described weight range.

[0049] 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.

[0050] Preferably, silica surface-treated with a silane coupling agent can be used to improve compatibility with hydrophobic polymer monomers, and it is preferable to use a filler whose particle size is adjusted to 50㎛ or less through a micro-sizing process.

[0051] When the particle size is within this range, filler agglomeration is prevented, the space between filler particles is reduced, and thus the effective path length for crack extension when microcracks occur in the fluorescent implant guide is lengthened.

[0052] Therefore, even if microcracks occur, it is not easily destroyed, so the durability of the dental structure or structure printed with the resin composition according to the invention can be effectively improved.

[0053] The above viscosity modifier is added to control the viscosity of the resin composition according to the present invention, and TEGDMA (triethylene glycol dimethacrylate) may be used, but is not necessarily limited thereto.

[0054] The viscosity modifier may be included in the entire composition at 1 to 25 wt%, and when included within the above weight range, the stirring characteristics and viscosity characteristics required for 3D printing are satisfied, so it is preferably included within the above weight range. In particular, when using TEGDMA as a viscosity modifier, there is a possibility of defects occurring due to excessive polymerization shrinkage when the above range is exceeded, so it is preferable not to use it in an amount exceeding the above weight range.

[0055] The above fluorescent coloring agent is a substance that absorbs energy applied upon light irradiation, switches to an excited state, and then switches back to a ground state to emit fluorescence. This can improve visibility during dental procedures by imparting fluorescent properties to a dental structure or structure printed with the resin composition according to the invention. Accordingly, the location, angle, direction, depth, etc. during perforation or implant placement during dental procedures can be recognized more clearly and accurately, and side effects such as damage, bleeding, swelling, and infection due to incorrect positioning during dental procedures can be prevented in advance, and safe and efficient dental procedures that can satisfy both patients and practitioners can be enabled.

[0056] As a fluorescent dye, DAPI (4',6-Diamidino-2-phenylindole dihydrochloride) can be used as a biocompatible material that is safe for the human body and has excellent fluorescent properties. This material has the advantage of emitting sufficient fluorescence even with a small amount and not being cytotoxic at low concentrations.

[0057] The fluorescent coloring agent may be used in an amount of 0.2 wt% or more to less than 1.6 wt%, or 0.5 wt% or more to less than 1.6 wt%, or 0.8 wt% or more to less than 1.6 wt% within the entire composition. If the content of the fluorescent coloring agent is less than the above range, sufficient fluorescence is not emitted with the illuminance of the lighting installed in a general dental unit chair, so there is little effect of improving visibility. If it is included in an amount of 1.6 wt% or more, it is difficult to use it as a dental material due to cytotoxicity. Therefore, it is preferable to include it in the dental 3D printing resin composition in an amount that satisfies the above-described weight range. In addition, considering both fluorescent coloring and cytotoxicity, it is particularly more preferable to include it in an amount of 0.5 to 1.2 wt%.

[0058] Meanwhile, another embodiment of the invention includes a method for manufacturing a 3D printing resin composition.

[0059] A method for manufacturing a 3D printing resin composition according to a specific embodiment includes steps of mixing BIS-GMA, BIS-EMA, UDMA, a photoinitiator, an additive, a color development assistant, a filler, a viscosity modifier, and a fluorescent color developer. Any content that overlaps or is identical to the content of the 3D printing resin composition described above will be omitted, and the description herein will focus on the manufacturing process.

[0060] Specifically, the method for manufacturing a 3D printing resin composition according to the present invention includes a first mixing step of mixing and stirring BIS-GMA, BIS-EMA, and UDMA to prepare a first mixture; a second mixing step of adding a photoinitiator and an additive to the first mixture and stirring the mixture to prepare a second mixture; a third mixing step of adding a color developer mixture to the second mixture and stirring the mixture to prepare a third mixture; a fourth mixing step of adding a filler to the third mixture and stirring the mixture to prepare a fourth mixture; and a fifth mixing step of adding a viscosity modifier to the fourth mixture and stirring the mixture to prepare a 3D printing resin composition. At this time, the color developer mixture mixed in the third mixing step may be a mixture of UDMA, a fluorescent color developer, and a color developer assistant.

[0061] Each mixing step can be performed at room temperature of 10 to 25°C, the stirring speed can be 5 to 12 RPM, and under reduced pressure conditions with a vacuum gauge pressure of 0.05 to 0.15 MPa to prevent bubble formation during stirring.

[0062] The first mixing step is a step of mixing and stirring BIS-GMA, BIS-EMA, and UDMA to prepare a first mixture. In this step, 30 to 60 wt% of BIS-GMA, 10 to 30 wt% of BIS-EMA, and 3 to 18 wt% of UDMA can be mixed based on the final composition, and the compositions of the raw material components mentioned in the following steps are all based on the final composition, and refer to the weight range included in the final composition.

[0063] Here, since some of the UDMA is additionally mixed in the third mixing step described below, only a portion of the total weight may be mixed in this step. In this step, stirring may be performed for 150 to 300 minutes, preferably 180 to 240 minutes, and the stirring time may vary depending on the season, and within the above stirring time range, stirring may be performed for a short time in summer and for a long time in winter.

[0064] The second mixing step is a step of adding a photoinitiator and an additive to the first mixture and stirring to prepare a second mixture. Here, the photoinitiator may be added in an amount of 1 to 10 wt% and the additive may be added in an amount of 0.01 to 5 wt%. In this step, stirring may be performed for 150 to 300 minutes, preferably 180 to 240 minutes, and the stirring time may vary depending on the season. Within the stirring time range, stirring may be performed for a short time in the summer and for a long time in the winter.

[0065] The third mixing step is a step of adding a coloring agent mixture to the second mixture and stirring to prepare a third mixture. The coloring agent mixture is a mixture of UDMA, a fluorescent coloring agent, and a coloring assistant. When the coloring agents are added in the form of a coloring agent mixture in which UDMA, a fluorescent coloring agent, and a coloring assistant are mixed in advance rather than adding each raw material individually in the third mixing step, the coloring materials can be more uniformly dispersed and mixed stably. In this step, UDMA can be added in a weight range of 2 to 12 wt%, the coloring agent can be added in a weight range of 0.1 to 5 wt%, and the fluorescent coloring agent can be added in a weight range of 0.2 wt% or more and less than 1.6 wt%.

[0066] The fourth mixing step is a step of adding a filler to the third mixture and stirring to prepare a fourth mixture. The filler may be added at 0.5 to 8 wt% and stirred.

[0067] In the third mixing step and the fourth mixing step, stirring can be performed for 300 minutes or more, preferably 360 minutes or more, and in cases where the temperature is low, such as in winter, it is preferable to perform stirring for at least 480 minutes or more.

[0068] The fifth mixing step is a step of adding a viscosity modifier to the fourth mixture and stirring to prepare a composition for an implant guide. The viscosity modifier may be included in an amount of 1 to 25 wt%. The stirring may be performed for 150 to 300 minutes, preferably 180 to 240 minutes. Within this stirring time range, the stirring time may vary depending on the season, with stirring being performed for a shorter time in summer and for a longer time in winter.

[0069] After the fifth mixing step, an additional bubble removal step may be performed to remove bubbles in the composition for the implant guide, and in this bubble removal step, a bubble removal process such as vacuum defoaming or low-temperature aging (0 to 15°C) may be performed.

[0070] A step of manufacturing a dental structure used in dental implant procedures, such as an implant guide, through a 3D printing process can be performed using the 3D printing resin composition manufactured in this manner.

[0071] The fluorescent dental structure manufactured through 3D printing can be hardened through additional light irradiation, and the fluorescent dental structure manufactured through this step can be manufactured to a patient-specific manner, thereby increasing the accuracy of dental procedures, and can emit fluorescence through light irradiation from the lighting installed in the dental unit chair, thereby enabling more accurate and safe procedures.

[0072]

[0073] Next, another embodiment of the present invention, a fluorescent implant guide and a method for manufacturing the same, will be described. The fluorescent implant guide according to the present invention emits fluorescence when irradiated with light, so that it can accurately guide the position, angle, direction, depth, etc. of perforation, drilling, and implant placement during the implant procedure, thereby preventing side effects such as perforation or implant position errors, abnormal bleeding, swelling, infection, and nerve damage in advance, and enabling safer and more accurate implant procedures.

[0074] According to one embodiment of the present invention, a fluorescent implant guide includes a guide body having at least one hole formed therein. The guide body is supported by a tooth or gum to fix the position of the fluorescent implant guide, and the holes are provided to guide the entry position, angle, direction, depth, etc. of a drill or implant during drilling or implantation. Since such a fluorescent implant guide is manufactured to be customized for a patient, its shape is not particularly limited as long as the guide body or the holes are formed in a shape that can achieve the above-described purpose.

[0075] The above guide body can be formed by curing a composition for an implant guide including BIS-GMA, BIS-EMA, UDMA, a photoinitiator, an additive, a color developer, a filler, a viscosity regulator, and a fluorescent developer.

[0076] As the composition for the above implant guide, a 3D printing resin composition according to the embodiment described above may be used, and overlapping content is omitted to avoid repetition of the same material.

[0077] The fluorescent implant guide formed by curing the composition for such an implant guide has a flexural strength of 65 MPa or more, which is the flexural strength required by the Ministry of Food and Drug Safety, and can provide stable support against pressure and distortion applied during drilling for perforation. In addition, it fluoresces under a light source of 8,000 lux or more, which is slightly lower than the average illuminance of general dental unit chair lighting (approximately 9,500 lux), so that the practitioner can more easily and accurately check the perforation or implantation location. In addition, it is made of biocompatible materials, so it has the advantage of being safe without any human toxicity.

[0078] Specifically, the dental 3D printing resin composition, which is a composition for an implant guide used in the manufacture of the fluorescent implant guide, may include 30 to 60 wt% of BIS-GMA, 10 to 30 wt% of BIS-EMA, 5 to 30 wt% of UDMA, 1 to 10 wt% of a photoinitiator, 0.01 to 5 wt% of an additive, 0.1 to 5 wt% of a color developer, 0.5 to 8 wt% of a filler, 1 to 25 wt% of a viscosity modifier, and 0.2 wt% or more and less than 1.6 wt% of a fluorescent developer.

[0079] The above filler is added to improve the physical strength and wear resistance of the fluorescent implant guide, and may be included in a weight range of 0.5 to 8 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 above-described weight range.

[0080] Preferably, silica surface-treated with a silane coupling agent can be used to improve compatibility with hydrophobic polymer monomers, and it is preferable to use a filler whose particle size is adjusted to 50㎛ or less through a micro-sizing process.

[0081] When the particle size is within this range, filler agglomeration is prevented, and the space between filler particles is reduced, so that when microcracks occur in the fluorescent implant guide, the effective path length for the cracks to extend is lengthened, so that even when microcracks occur, the fluorescent implant guide is not easily destroyed, and thus the durability of the fluorescent implant guide can be improved.

[0082] A viscosity modifier is added to control the viscosity of a composition for an implant guide, and TEGDMA (triethylene glycol dimethacrylate) can be used. The viscosity modifier can be included in a 3D printing resin composition, which is a composition for an implant guide, at 1 to 25 wt%. When included within the above weight range, the stirring characteristics and viscosity characteristics required for 3D printing are satisfied, and therefore, it is preferable to include the viscosity modifier within the above weight range. In particular, when TEGDMA is used as a viscosity modifier, there is a possibility of defects occurring due to excessive polymerization shrinkage when the above range is exceeded, and therefore, it is preferable not to use it in an amount exceeding the above weight range.

[0083] The above fluorescent agent is a substance that absorbs energy applied when irradiated with light, switches to an excited state, and then switches back to a ground state to emit fluorescence. By imparting fluorescent properties to the fluorescent implant guide, the visibility of the implant guide can be improved during implant surgery. Accordingly, the location, angle, direction, depth, etc. during the perforation and implant placement process can be guided more clearly and accurately, and side effects such as damage, bleeding, swelling, and infection due to incorrect positioning during implant surgery can be prevented in advance, and safe and efficient implant surgery that satisfies both patients and surgeons can be enabled.

[0084] As a fluorescent dye, DAPI (4',6-Diamidino-2-phenylindole dihydrochloride) can be used as a biocompatible material that is safe for the human body and has excellent fluorescent properties. This material has the advantage of emitting sufficient fluorescence even with a small amount and not being cytotoxic at low concentrations.

[0085] The fluorescent coloring agent may be used in a dental 3D printing resin composition for implant guides in an amount of 0.2 wt% or more and less than 1.6 wt%, or 0.5 wt% or more and less than 1.6 wt%, or 0.8 wt% or more and less than 1.6 wt%. If the content of the fluorescent coloring agent is less than the above range, sufficient fluorescence is not emitted with the illuminance of the lighting installed in a general dental unit chair, so that the effect of improving visibility is almost non-existent.

[0086] Conversely, since it is difficult to use as a dental material due to cytotoxicity when included at a concentration of 1.6 wt% or more, it is preferable to include it in the implant guide composition in a content satisfying the above-described weight range. Furthermore, considering both fluorescence development and cytotoxicity, it is particularly more preferable to include it at 0.5 to 1.2 wt%.

[0087]

[0088] Meanwhile, another embodiment of the present invention relates to a method for manufacturing a fluorescent implant guide. Specifically, the method for manufacturing a fluorescent implant guide includes: a guide design step for designing a shape of an implant guide based on information about a patient's oral cavity; an implant guide composition manufacturing step for manufacturing a composition for an implant guide by mixing BIS-GMA, BIS-EMA, UDMA, a photoinitiator, an additive, a color development assistant, a filler, a viscosity modifier, and a fluorescent color developer; and an implant guide manufacturing step for manufacturing a patient-specific fluorescent implant guide by 3D printing the implant guide composition in the shape of an implant guide designed in the guide design step.

[0089] The above guide design step is a step for designing the shape of the implant guide based on the patient's oral information. The patient's oral information may include one or more of the following: oral information obtained by scanning the patient's oral cavity using a 3D scanner; oral information obtained by scanning a plaster model modeled after the patient's oral cavity using a 3D scanner; and oral information obtained by CT scanning. The patient's oral information can be input into an implant guide design program to design the shape of the implant guide. Through this step, the location, direction, angle, and depth of the perforation and implant placement during implant surgery can be set.

[0090] The above step of manufacturing a composition for an implant guide is a step of manufacturing a composition for an implant guide by mixing BIS-GMA, BIS-EMA, UDMA, a photoinitiator, an additive, a color development assistant, a filler, a viscosity modifier, and a fluorescent color developer. The composition for an implant guide manufactured through this step may be identical to the dental 3D printing resin composition described in one embodiment of the present invention, and therefore, some overlapping descriptions are omitted.

[0091] Specifically, the manufacturing step of the 3D printing resin composition, which is a composition for an implant guide, includes a first mixing step of mixing and stirring BIS-GMA, BIS-EMA, and UDMA to prepare a first mixture; a second mixing step of adding a photoinitiator and an additive to the first mixture and stirring the mixture to prepare a second mixture; a third mixing step of adding a color developer mixture to the second mixture and stirring the mixture to prepare a third mixture; a fourth mixing step of adding a filler to the third mixture and stirring the mixture to prepare a fourth mixture; and a fifth mixing step of adding a viscosity modifier to the fourth mixture and stirring the mixture to prepare a composition for an implant guide. At this time, the color developer mixture mixed in the third mixing step may be a mixture of UDMA, a fluorescent color developer, and a color developer.

[0092] Next, a step of manufacturing a fluorescent implant guide using a 3D printing process is performed. During 3D printing, an implant guide composition may be used as ink, and 3D printing may be performed using the implant guide composition as a design drawing in the shape of the implant guide designed in the guide design step.

[0093] The fluorescent implant guide manufactured through 3D printing can be additionally hardened through light irradiation, and the fluorescent implant guide manufactured through this step can be manufactured to a patient-specific manner, thereby increasing the accuracy of implant surgery, and can emit fluorescence through light irradiation from the lighting installed in the dental unit chair, thereby enabling more accurate and safe surgery.

[0094] 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.

[0095]

[0096] [Manufacturing Example 1]

[0097] A first mixture was prepared by mixing 40 g of DMBIS-GMA, 27 g of BIS-EMA, and 7 g of UDMA and stirring for 200 minutes. Then, 0.8 g of camphorquinone as a photoinitiator, 2.7 g of TPO, and 0.3 g of accelerator (EDMAB), 0.6 g of antioxidant (BHT), and 0.1 g of photoinitiator (DIFP) as additives were added, and stirring was performed for 200 minutes to prepare a second mixture. A color developer mixture was prepared by mixing 4.6 g of UDMA, 0.8 g of DAPI as a fluorescent color developer, 0.2 g of food coloring blue No. 1 as a color developer assistant, and 0.2 g of food coloring red No. 40, and then the entire amount was added to the second mixture and stirred for 320 minutes to prepare a third mixture. To this, 5 g of silane-modified silica (particle size of 50 μm or less) as a filler was added and stirred for 300 minutes to prepare a fourth mixture.

[0098] Next, 10.8 g of TEGDMA, a viscosity modifier, was added to the fourth mixture, stirred for 200 minutes, and aged at 5°C for 24 hours to remove air bubbles, thereby manufacturing a dental 3D printing resin composition of Example 1.

[0099]

[0100] [Experimental Example 1]

[0101] Using the same method as Manufacturing Example 1, which is a method for manufacturing a dental 3D printing resin composition of Example 1, a composition for implant guide of Comparative Example 1 was manufactured using pure BIS-GMA instead of DMBIS-GMA, which is a modified BIS-GMA, and the compositions of Example 1 and Comparative Example 1 were printed with a 3D printer in a size of 64 mm × 10 mm × 33 mm and cured to manufacture 5 specimens each.

[0102] Next, the specimen was mounted on a universal testing machine and bent at a speed of 5 mm / min until fracture, and the load (F) at fracture was recorded. The thickness (h) and width (b) of the specimen were measured, and the flexural strength (σ) was calculated using the following equation (1). B) was calculated. In Equation (1), "l" means the distance between the supports of the universal material testing machine. Five specimens were manufactured for each of Example 1 and Comparative Example 1, and an experiment was performed on each specimen, and the flexural strength was calculated. The results and average values ​​are shown in Table 1.

[0103] (Formula 1)

[0104] Example 1 Comparative Example 1 Flexural strength (MPa) 1 time 95.37 5.32 times 101.87 0.03 times 106.27 3.14 times 101.47 6.25 times 98.57 2.5 Average 100.67 3.4

[0105] Referring to the experimental results in Table 1 above, it was found that the flexural strength of the specimen of Example 1 to which modified BIS-GMA was applied was significantly higher than that of Comparative Example 1 to which non-modified BIS-GMA was applied. It was confirmed that both Example 1 and Comparative Example 1 had a flexural strength of 65 MPa or more, which is the flexural strength required for implant perforation surgery. However, considering the dental structure or the pressure or distortion applied to the dental structure, the higher the flexural strength, the more stable it is, and therefore, it is more preferable to use the dental 3D printing resin composition of Example 1.

[0106]

[0107] [Experimental Example 2]

[0108] A composition for an implant guide of Comparative Example 2 was manufactured using the same method as Manufacturing Example 1, which is a method for manufacturing a composition for an implant guide of Example 1, but the content of the fluorescent coloring agent was increased to 1.6 g and the content of DMBIS-GMA was lowered by the amount increased.

[0109] Example 1 and Comparative Example 2 were manufactured into film specimens measuring 20×20×2 mm, and the Korea Construction & Living Testing & Research Institute was commissioned to perform a cytotoxicity test on mouse fibroblasts (L-929) using three specimens each. The results are shown in Table 2. The test results were evaluated using a 5-point scale, where 0 indicates no reaction and 4 indicates a reaction to the extent that the cell layer is almost destroyed.

[0110] Psalm number Example 1 Comparative example 2 #104 #204 #304

[0111] Referring to the experimental results in Table 2 above, in the case of Example 1, no cytotoxicity was observed at all, but in the case of Comparative Example 2, a cytotoxic reaction was observed. Therefore, as a result of this experiment, it was confirmed that it is preferable for the fluorescent coloring agent to be included within a range that does not include 0.8 wt% and 1.6 wt%.

[0112] In particular, considering cytotoxicity, it is desirable to include less than 1.6 wt%, and considering that toxicity increases as the content of the fluorescent agent increases, it can be predicted that it is desirable to include less than 1.2 wt% in order to satisfy cytotoxicity level 2 corresponding to class 2 medical devices.

[0113] In addition, in the case of a fluorescent coloring agent, when included in an amount of 0.5 wt% or more, coloring occurs to a degree that can be easily observed with the naked eye. Therefore, considering these factors, it can be seen that the desirable content of the fluorescent coloring agent is 0.5 to 1.2 wt%.

[0114]

[0115] [Experimental Example 3]

[0116] A composition for implant guide was manufactured using the same method as Manufacturing Example 1, but the contents of fluorescent dye (DAPI), food coloring (Blue No. 1 and Red No. 40), and UDMA included in the coloring agent mixture were changed as shown in Table 3 to manufacture dental 3D printing resin compositions of Examples 2, 3, and Comparative Example 3.

[0117] Next, using Examples 2, 3 and Comparative Example 3, a dental structure, an implant guide model, was manufactured through 3D printing, and then photographed by irradiating with light, and the results are presented in Fig. 1. The content of each raw material in Table 3 refers to the content within the entire dental 3D printing resin composition.

[0118] (Unit: wt%) Example 2 Example 3 Comparative Example 3 UDMA6.36.37.1 Fluorescent color developer 0.80.8-Blue No. 1-0.2-Red No. 400.2-0.2

[0119] Referring to the results of Fig. 1, Comparative Example 3, which did not contain a fluorescent coloring agent, only displayed color due to the pigment, whereas Examples 2 and 3, which contained 0.8 wt% of the fluorescent coloring agent, were found to emit fluorescence. Although the fluorescence was not clearly visible in the photograph, strong fluorescence could be confirmed when observed with the naked eye.

[0120] Therefore, from the results of this experiment, it was confirmed that when the fluorescent dye is included at 0.8 wt%, sufficiently strong fluorescence is emitted to improve visibility during implant surgery. Furthermore, since fluorescence intensity is directly proportional to the content of the fluorescent dye, it can be predicted that sufficient fluorescence to improve visibility will be emitted even at a content slightly lower than 0.8 wt%, for example, 0.5 wt%.

[0121] This dental 3D printing resin composition according to the invention comprises BIS-GMA (bisphenol A-glycidyl methacrylate), BIS-EMA (ethoxylated bisphenol A dimethacrylate), UDMA (urethane dimethacrylate), a photoinitiator, an additive, a color-developing agent, a filler, a viscosity modifier, and a fluorescent coloring agent, and can impart fluorescent properties to dental structures such as implant guides manufactured using the same or dental restorative resins, thereby enabling a practitioner to more effectively recognize the implantation position, direction, depth, etc. of dental structures, while at the same time ensuring sufficient physical and mechanical strength, and therefore has industrial applicability.

Claims

1. In the 3D printing resin composition, A 3D printing resin composition comprising BIS-GMA (bisphenol A-glycidyl methacrylate), BIS-EMA (ethoxylated bisphenol A dimethacrylate), UDMA (urethane dimethacrylate), a photoinitiator, an additive, a color developer, a filler, a viscosity modifier, and a fluorescent developer.

2. In paragraph 1, A 3D printing resin composition, characterized in that the fluorescent colorant is DAPI (4',6-Diamidino-2-phenylindole dihydrochloride).

3. In paragraph 1, A 3D printing resin composition, characterized in that the fluorescent coloring agent is included in a range of 0.2 wt% or more and less than 1.6 wt%.

4. In paragraph 1, A 3D printing resin composition, characterized in that the additive is at least one of an accelerator, an antioxidant, and a photoinitiator.

5. In a method for manufacturing a 3D printing resin composition, A first mixing step of preparing a first mixture by mixing and stirring BIS-GMA, BIS-EMA and UDMA; A second mixing step of adding a photoinitiator and an additive to the first mixture and stirring to prepare a second mixture; A third mixing step of adding a coloring agent mixture to the second mixture and stirring to prepare a third mixture; A fourth mixing step of adding a filler to the third mixture and stirring to prepare a fourth mixture; and A fifth mixing step of adding a viscosity modifier to the fourth mixture and stirring to prepare a composition for an implant guide; A method for manufacturing a 3D printing resin composition, characterized in that the above-mentioned color developer mixture is a mixture of UDMA, a fluorescent color developer, and a color developer.

6. In paragraph 5, A method for manufacturing a 3D printing resin composition, characterized in that the fluorescent coloring agent is DAPI (4',6-Diamidino-2-phenylindole dihydrochloride).

7. In paragraph 5, A method for producing a 3D printing resin composition, characterized in that the fluorescent coloring agent is included in a range of 0.2 wt% or more to less than 1.6 wt%.

8. In an implant guide including a guide body in which at least one hole is formed, A fluorescent implant guide, characterized in that the guide body is formed by curing a composition for an implant guide including BIS-GMA (bisphenol A-glycidyl methacrylate), BIS-EMA (ethoxylated bisphenol A dimethacrylate), UDMA (urethane dimethacrylate), a photoinitiator, an additive, a color development aid, a filler, a viscosity control agent, and a fluorescent color development agent.

9. In paragraph 8, A fluorescent implant guide, characterized in that the fluorescent coloring agent is DAPI (4',6-Diamidino-2-phenylindole dihydrochloride).

10. In paragraph 8, A fluorescent implant guide, characterized in that the content of a fluorescent coloring agent included in the composition for the implant guide is 0.2 wt% or more and less than 1.6 wt%.

11. In paragraph 8, The composition for the above implant guide is, A fluorescent implant guide characterized by comprising 30 to 60 wt% of bisphenol A-glycidyl methacrylate (BIS-GMA), 10 to 30 wt% of ethoxylated bisphenol A dimethacrylate (BIS-EMA), 5 to 30 wt% of urethane dimethacrylate (UDMA), 1 to 10 wt% of a photoinitiator, 0.01 to 5 wt% of an additive, 0.1 to 5 wt% of a color developer, 0.5 to 8 wt% of a filler, 1 to 25 wt% of a viscosity modifier, and 0.2 wt% or more and less than 1.6 wt% of a fluorescent developer.

12. Guide design step for designing the shape of the implant guide based on the patient's oral information; A step for preparing a composition for an implant guide by mixing BIS-GMA, BIS-EMA, UDMA, a photoinitiator, an additive, a color developer, a filler, a viscosity regulator, and a fluorescent developer; and A method for manufacturing a fluorescent implant guide, comprising: an implant guide manufacturing step of manufacturing a patient-customized fluorescent implant guide by 3D printing the implant guide composition in the form of an implant guide designed in the guide design step; 13. In paragraph 12, The above step of manufacturing a composition for implant guide is: A first mixing step of preparing a first mixture by mixing and stirring BIS-GMA, BIS-EMA and UDMA; A second mixing step of adding a photoinitiator and an additive to the first mixture and stirring to prepare a second mixture; A third mixing step of adding a coloring agent mixture to the second mixture and stirring to prepare a third mixture; A fourth mixing step of adding a filler to the third mixture and stirring to prepare a fourth mixture; and A fifth mixing step of adding a viscosity modifier to the fourth mixture and stirring to prepare a composition for an implant guide; A method for manufacturing a fluorescent implant guide, characterized in that the above-mentioned color-developing agent mixture is a mixture of UDMA, a fluorescent color-developing agent, and a color-developing auxiliary agent.

14. In paragraph 12, A method for manufacturing a fluorescent implant guide, characterized in that the fluorescent coloring agent is DAPI (4',6-Diamidino-2-phenylindole dihydrochloride).

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