KR20240003496A - Method for manufacturing a medical resin filler having fluorescence - Google Patents

Abstract

The present invention relates to a method of manufacturing a medical resin filler with fluorescence, and more specifically, to a method of manufacturing a medical resin filler that is biocompatible and prevents the fluorescent dye from directly combining with the polymer composite material when manufacturing dental or medical moldings such as implant guide devices containing a fluorescent dye. The present invention relates to a method of manufacturing a medical resin filler having fluorescence that can maintain good mechanical strength.

Description

Method for manufacturing a medical resin filler having fluorescence}

The present invention relates to a method of manufacturing a medical resin filler with fluorescence, and more specifically, to a method of manufacturing a medical resin filler that is biocompatible and prevents the fluorescent dye from directly combining with the polymer composite material when manufacturing dental or medical moldings such as implant guide devices containing a fluorescent dye. The present invention relates to a method of manufacturing a medical resin filler having fluorescence that can maintain good mechanical strength.

Dental implants not only restore single missing teeth, but also improve the function of dentures for partially edentulous and completely edentulous patients, improve the aesthetics of dental prosthetic restorations, and further distribute excessive stress applied to the surrounding supporting bone tissue. It also helps stabilize the dentition.

Typically, during implant surgery, the gingiva is incised to expose the alveolar bone and then perforation is performed directly on top of it using a drill, etc. Since it is difficult to accurately determine the exact location and direction in which to perform the perforation work, an assistant called an implant guide is usually used. The instrument is being used.

Meanwhile, an implant guide is an auxiliary device manufactured to plan the placement location of dental implants to be applied to a patient using CT or CBCT during implant surgery and guide the direction, depth, and location of placement based on the results. It includes a guide body that negatively corresponds to the extracted oral structure, and a hole is formed in the guide body to guide the installation position of the implant and the installation guide.

These implant guides produce color (fluorescence) above a certain level of illumination when the unit chair lights used in dentistry are turned on, which not only guides the optimal implant placement by more easily and accurately indicating the location to the operator, but also provides the best treatment for both the operator and the patient. It has the advantage of having excellent treatment outcomes.

However, for color development, when manufacturing an implant guide, a polymer composite material and a fluorescent dye are mixed together to manufacture the guide, but fluorescent dyes have the problem of causing cytotoxicity depending on the type.

In addition, these fluorescent dyes cause inflammation when part of the implant guide is pulverized during the implant procedure and the fine particle powder containing the fluorescent dye comes in contact with the gums, and the solvent used to combine with the polymer composite material reduces mechanical strength. There is a problem of physical performance deterioration.

The present invention was created to solve the above-mentioned problems. The present invention minimizes the use of solvents when manufacturing dental or medical molded products containing fluorescent dyes, such as implant guides, and maintains good mechanical strength, including gums. The aim is to provide a fluorescent resin filler that can prevent inflammation from occurring when crushed fluorescent dye directly touches the surgical site during the processing or grinding of a molded product within the surgical site, and a method for manufacturing the same.

Meanwhile, the purposes of the present invention are not limited to the purposes mentioned above, other purposes not mentioned are not limited to the purposes mentioned above, and other purposes not mentioned are known to those skilled in the art from the description below. can be clearly understood.

In order to solve the above-described problem, the present invention includes a first process of preparing a first mixture by mixing and stirring a fluorescent dye, an inorganic filler, and ethanol; A second process of mixing and stirring an acrylate-based monomer to which a photoinitiator is added to the first mixture to prepare a second mixture; A third process of stirring the second mixture in a vacuum state; a fourth process of preparing a polymer by stirring the second mixture in a vacuum state while irradiating the second mixture stirred in a vacuum state with a light source having a wavelength at which the photoinitiator is activated; and a fifth step of removing unpolymerized portions of the polymer by mixing and stirring the polymer with volatile alcohol.

In a preferred embodiment, in the first process, 0.05% to 0.5% by weight of the fluorescent dye and 5% to 7% by weight of the ethanol are mixed relative to the weight of the inorganic filler.

In a preferred embodiment, the fluorescent dye includes one or more selected from DAPI (4,6-diamidino-2-phenylindole), food coloring Blue No. 1, and food coloring Red No. 40.

In a preferred embodiment, the inorganic filler is silica (SiO ₂ ) or barium glass.

In a preferred embodiment, the concentration of ethanol is 95% to 99%.

In a preferred embodiment, the first process and the second process are performed for 120 minutes at a stirring speed of 1 RPM to 5 RPM and a stirring temperature of 25°C to 45°C, while minimizing the temperature difference between the inside and outside of the mixer performing the stirring. This prevents the generation of water vapor inside the mixer.

In a preferred embodiment, the photoinitiator is camphorquinone, 2-(Dimethylamino methacrylates), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Phenylbis( It includes one or more selected from 2,4,6-trimethylbenzoyl)phosphine oxide and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

In a preferred embodiment, the acrylate monomer is bisphenol A-glycidyl methacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (TGDMA), ethoxyl Late bisphenol A dimethacrylate (Bis-EMA), urethane dimethacrylate (UDMA), dipentaerythritol pentacrylate monophosphate (PENTA), 2-hydroxyethyl methacrylate ( 2-hydroxyethyl methacrylate (HEMA), polyalkenic acid, biphenyl dimethacrylate (BPDM), glycerol phosphate dimethacrylate (GPDM), and 1,6-hexanediol It is at least one selected from the group consisting of diacrylate (1,6-Hexanediol diacrylate).

In a preferred embodiment, in the second process, the photoinitiator is included in an amount of 0.08% to 0.8% by weight relative to the weight of the acrylate-based monomer, and the acrylate-based monomer is included in an amount of 20% to 30% by weight relative to the weight of the first mixture. Weight percentages are mixed.

In a preferred embodiment, the third process is performed by stirring for 60 minutes at a stirring speed of 1 RPM to 5 RPM at a vacuum pressure of 0.05 mpa or more.

In a preferred embodiment, the fourth process is performed by stirring for 120 minutes at a stirring speed of 1 RPM to 5 RPM at a vacuum pressure of 0.05 mpa or more.

In a preferred embodiment, the volatile alcohol is isopropyl alcohol, and in the fifth process, 5% to 10% by weight of the volatile alcohol is mixed relative to the weight of the polymer and stirred at a stirring speed of 1 RPM to 5 RPM.

The present invention has the following excellent effects.

According to the method for producing a fluorescent medical resin filler of the present invention, a coating film is formed by mixing and stirring acrylate monomers with a fluorescent dye adsorbed on the surface of the inorganic filler, thereby forming a polymer composite when manufacturing dental or medical molded products. By preventing the material from combining with the fluorescent dye and minimizing the use of solvents, it is possible to prevent deterioration in physical performance and maintain stable strength, and the coating film can block the fluorescent dye from directly reaching the surgical site. It can prevent inflammation within the surgical area.

1 is a flowchart illustrating a method of manufacturing a fluorescent medical resin filler according to an embodiment of the present invention;
Figure 2 is a diagram showing the results of comparing the fluorescence intensity of a resin filler in which a repeated process was performed according to an embodiment of the present invention.

The terms used in the present invention are general terms that are currently widely used as much as possible. However, in certain cases, there are terms arbitrarily selected by the applicant, and in this case, the meaning described or used in the detailed description of the invention rather than the simple name of the term is considered. Therefore, its meaning must be understood.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to preferred embodiments shown in the attached drawings.

However, the present invention is not limited to the one embodiment described herein and may be embodied in other forms. Like reference numerals refer to like elements throughout the specification.

1 is a flowchart showing a method of manufacturing a medical resin filler with fluorescence according to an embodiment of the present invention.

Referring to FIG. 1, a method of manufacturing a medical resin filler with fluorescence according to an embodiment of the present invention relates to a resin filler in which a coating film is formed with an acrylate-based monomer on a mixture of a fluorescent dye adsorbed on an inorganic filler. A first process of adsorbing a fluorescent dye to the surface (S1000), a second process of forming a coating film on the mixture of the first process (S2000), a third process of adhering the coating film to the mixture (S3000), the coating film It includes a fourth process of polymerizing (S4000) and a fifth process of removing unpolymerized portions of the coating film (S5000).

In addition, the resin filler of the present invention can be used for dental purposes, but can also be used in various medical fields that require color development.

In addition, the stirring operation performed in the resin filler manufacturing method of the present invention is performed by a mixer, and the mixer includes a function of irradiating a light source inside where stirring is performed and controlling vacuum pressure.

Hereinafter, a method for manufacturing a resin filler according to an embodiment of the present invention will be described in detail.

The first process (S1000) is a process of preparing a first mixture in which a fluorescent dye is adsorbed on the surface of an inorganic filler. The first mixture is prepared by mixing and stirring the fluorescent dye, an inorganic filler, and ethanol.

At this time, the fluorescent dye may be mixed in an amount of 0.05% to 0.5% by weight based on the weight of the inorganic filler, and the ethanol may be mixed in an amount of 5% to 7% by weight compared to the weight of the inorganic filler.

In addition, the first process (S1000) is preferably performed at a stirring speed of 1 RPM to 5 RPM and a stirring temperature of 25°C to 45°C for 120 minutes.

Meanwhile, stirring is performed by limiting the stirring speed to 5 RPM or less, because if it exceeds 5 RPM, the fluorescent dye is not properly adsorbed to the inorganic filler, thereby reducing efficiency.

In addition, when performing stirring, it is desirable to control the stirring temperature or the external temperature of the mixer to minimize the temperature difference between the inside and outside of the mixer.

This is because when the temperature difference is high, water vapor is generated inside the mixer, which interferes with the formation of an ionic bond film due to surface friction between the inorganic filler and the fluorescent dye and the hydroxyl reaction of ethanol, preventing the fluorescent dye from being properly adsorbed on the inorganic filler. am.

The fluorescent dye may be a type of fluorescent dye with low cytotoxicity, for example, DAPI (4,6-diamidino-2-phenylindole), food coloring blue No. 1 or food coloring red No. 40, These can be used in combination.

The ethanol preferably has a low moisture content so that the fluorescent dye is adsorbed to the inorganic filler with high efficiency. For example, ethanol having a concentration of 95% to 99% may be used.

The inorganic filler may be a variety of known inorganic fillers, preferably silica (SiO ₂ ) or barium glass.

The second process (S2000) is a process of preparing a second mixture by mixing and stirring an acrylate-based monomer to which a photoinitiator has been added to the first mixture, and is a process of forming a coating film on the first mixture.

At this time, the photoinitiator may include 0.08% to 0.8% by weight based on the weight of the acrylate-based monomer, and the acrylate-based monomer may be mixed in an amount of 20% to 30% by weight based on the weight of the first mixture.

In addition, the second process (S2000) is preferably performed under the same conditions as the first process (S1000), stirring speed, stirring temperature, and time.

This is to evenly coat the first mixture with the acrylate-based monomer to which the photoinitiator has been added.

The photoinitiator may be a variety of known photoinitiators, for example, camphorquinone, 2-(dimethylamino methacrylates), phenylbis(2,4,6- Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide One of them can be selected and used.

The acrylate-based monomer may be a variety of known monomers, such as phenol A-glycidyl methacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), and ethylene glycol dimethacrylate. Methacrylate (TGDMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA), urethane dimethacrylate (UDMA), dipentaerythritol pentacrylate monophosphate (PENTA), 2-hydroxyethyl methacrylate (HEMA), polyalkenic acid, biphenyl dimethacrylate (BPDM), glycerol phosphate dimethacrylate One of GPDM) and 1,6-hexanediol diacrylate may be selected and used, and urethane dimethacrylate (UDMA) may be preferably used.

The third process (S3000) is a process for adhering the acrylate-based monomer of the second mixture to the inorganic filler and fluorescent dye, and is a process to increase the efficiency of the polymerization reaction to be performed below.

In addition, the third process (S3000) is performed in a vacuum, and stirring can be performed for 60 minutes at a vacuum pressure of 0.05 mpa or more and a stirring speed of 1 RPM to 5 RPM. In this process, vacuum pressure is applied to the second mixture. By adding it, the acrylate-based monomer can efficiently adhere to the inorganic filler and fluorescent dye.

The fourth process (S4000) is a process of preparing a polymer by polymerizing the second mixture in which the third process was performed, and stirring is performed while a light source is irradiated for the polymerization.

Additionally, in the fourth process (S4000), stirring may be performed for 120 minutes at a vacuum pressure of 0.05 mpa or more and 1 RPM to 5 RPM while a light source is irradiated to the second mixture.

At this time, the light source may cause a polymerization reaction of the second mixture by irradiating a wavelength at which the photoinitiator added to the acrylate-based monomer is activated.

That is, the polymerization reaction is initiated through the fourth process (S4000), the acrylate-based monomer is cured, and coating film formation is completed.

On the other hand, in the case of the above polymer, some areas may not be properly polymerized and remain as unpolymerized areas. If this is used as is to manufacture resin, mechanical strength may decrease and changes in physical properties such as discoloration may occur, resulting in unpolymerized areas. Removal of polymerization sites is essential.

Accordingly, the fifth process (S5000) is a process for removing unpolymerized formation sites of the polymer, and the polymer is stirred with volatile alcohol.

In addition, the fifth process (S5000) may be performed by mixing 5% to 10% by weight of the volatile alcohol with the polymer and stirring at a stirring speed of 1 RPM to 5 RPM.

Additionally, various types of known volatile alcohols may be used as the volatile alcohol, and isopropyl alcohol is preferably used.

Meanwhile, the fluorescent resin manufacturing method of the present invention is a process of repeatedly performing the second process (S2000) to the fifth process (S5000) to improve the color development of the resin filler manufactured through the above-described process processes ( Hereinafter, referred to as 'repeated process') may be performed.

Figure 2 is a diagram showing the results of comparing the fluorescence intensity of a resin filler in which a repeated process was performed according to an embodiment of the present invention. Referring to Figure 2, the repeated process may be performed multiple times, but the fluorescence intensity in the first time is While it was improved to 20% to 30%, it was confirmed that no significant change in fluorescence intensity was observed when performed the second time. Therefore, it is preferable to perform the repeat process about once.

In addition, in the method of producing a fluorescent resin of the present invention, after the fifth process or the repetitive process, a process of powdering or sphericalizing the resin filler into various sizes may be further performed depending on the purpose and use.

[Experimental example] Flexural strength comparison test

For a comparative test of flexural strength between a resin composition prepared by mixing a fluorescent dye with a polymer composite material and a resin composition prepared by mixing a medical resin filler of the present invention, a resin composition was prepared with the composition shown in Tables 1 and 2 below.

polymer photoinitiator Initiation aid filler fluorescent dye solvent Comparative example 86% 0.2% 0.2% 13% 0.05% 0.55%

polymer photoinitiator Initiation aid Medical resin filler with fluorescence Example 86% 0.2% 0.2% 13.6%

Here, the polymer of each comparative example and example contained urethane dimethacrylate (UDMA), and since the polymer must be dissolved in order to mix the fluorescent dye and the polymer in the comparative example, a solvent was used.

Meanwhile, the flexural strength comparative test was performed in accordance with the flexural strength measurement method of the Ministry of Food and Drug Safety's "3D Printing Dental Implant Guide", and the flexural strength test results of the comparative examples and examples are shown in Table 3 below.

Psalm 1 Psalm 2 Psalm 3 Psalm 4 Psalm 5 Comparative example 45.4 MPa 40.8 MPa 43.4Mpa 42.8Mpa 46.9Mpa Example 71.3 MPa 67.8 MPa 68.9 MPa 71.7 MPa 67.5 MPa

Looking at Table 3, it was confirmed that the average flexural strength of the Examples was 69.44 Mpa, which was significantly superior to that of the Comparative Examples, which were 43.86 Mpa on average.

Therefore, according to the method for manufacturing a medical resin filler with fluorescence of the present invention, a coating film is formed by mixing and stirring acrylate monomers with a fluorescent dye adsorbed on the surface of the inorganic filler, thereby making it possible to manufacture dental or medical molded articles. By preventing the polymer composite material from combining with the fluorescent dye and minimizing the use of solvents, it is possible to prevent deterioration in physical performance and maintain stable strength.

In addition, by coating an acrylate monomer on a mixture containing an inorganic filler and a fluorescent dye to form a coating film, direct contact of the fluorescent dye to the surgical site can be blocked by the coating film, thereby preventing inflammation within the surgical site.

As discussed above, the present invention has been illustrated and described with reference to preferred embodiments, but it is not limited to the above-described embodiments and is intended to be used by those skilled in the art without departing from the spirit of the invention. Various changes and modifications will be possible.

Claims (12)

A first process of preparing a first mixture by mixing and stirring a fluorescent dye, an inorganic filler, and ethanol;
A second process of mixing and stirring an acrylate-based monomer to which a photoinitiator is added to the first mixture to prepare a second mixture;
A third process of stirring the second mixture in a vacuum state;
a fourth process of preparing a polymer by stirring the second mixture in a vacuum state while irradiating the second mixture stirred in a vacuum state with a light source having a wavelength at which the photoinitiator is activated; and
A method for manufacturing a medical resin filler having fluorescence, comprising a fifth step of removing unpolymerized portions of the polymer by mixing and stirring volatile alcohol with the polymer. According to claim 1,
The first process is a method of manufacturing a medical resin filler with fluorescence, characterized in that 0.05% to 0.5% by weight of the fluorescent dye and 5% to 7% by weight of the ethanol are mixed relative to the weight of the inorganic filler. According to claim 2,
The fluorescent dye is a method of manufacturing a medical resin filler having fluorescence, characterized in that it includes one or more selected from DAPI (4,6-diamidino-2-phenylindole), food coloring blue No. 1, and food coloring red No. 40. According to claim 3,
A method of manufacturing a medical resin filler with fluorescence, wherein the inorganic filler is silica (SiO ₂ ) or barium glass. According to claim 4,
Method for producing a medical resin filler with fluorescence, characterized in that the concentration of ethanol is 95% to 99%. According to claim 1,
The first and second processes are performed for 120 minutes at a stirring speed of 1 RPM to 5 RPM and a stirring temperature of 25°C to 45°C,
A method of manufacturing a fluorescent medical resin filler, characterized in that the temperature difference between the inside and outside of the mixer performing stirring is minimized to prevent the generation of water vapor inside the mixer. According to claim 1,
The photoinitiator includes Camphorquinone, 2-(Dimethylamino methacrylates), and Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. A medical product having fluorescence, characterized in that it contains at least one selected from trimethylbenzoyl)phosphine oxide and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Resin filler manufacturing method According to claim 7,
The acrylate monomers include bisphenol A-glycidyl methacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (TGDMA), and ethoxylate bisphenol A dimethacrylate. Bis-EMA, urethane dimethacrylate (UDMA), dipentaerythritol pentacrylate monophosphate (PENTA), 2-hydroxyethyl methacrylate (HEMA) ), polyalkenic acid, biphenyl dimethacrylate (BPDM), glycerol phosphate dimethacrylate (GPDM), and 1,6-hexanediol diacrylate (1, 6-Hexanediol diacrylate) A method of manufacturing a medical resin filler having fluorescence, characterized in that it is at least one selected from the group consisting of According to claim 8,
In the second process,
The photoinitiator includes 0.08% by weight to 0.8% by weight based on the weight of the acrylate monomer,
A method of manufacturing a medical resin filler with fluorescence, characterized in that the acrylate-based monomer is mixed in an amount of 20% to 30% by weight based on the weight of the first mixture. According to claim 1,
The third process is a method of manufacturing a medical resin filler with fluorescence, characterized in that stirring is performed for 60 minutes at a stirring speed of 1 RPM to 5 RPM at a vacuum pressure of 0.05 mpa or more. According to claim 1,
The fourth process is a method of manufacturing a medical resin filler with fluorescence, characterized in that stirring is performed for 120 minutes at a stirring speed of 1 RPM to 5 RPM at a vacuum pressure of 0.05 mpa or more. According to clause 9,
The volatile alcohol is isopropyl alcohol,
The fifth process is a method of producing a medical resin filler with fluorescence, characterized in that the volatile alcohol is mixed at 5% by weight to 10% by weight relative to the weight of the polymer and stirred at a stirring speed of 1 RPM to 5 RPM.