WO2023080303A1 - Method for preparing dental and total medical resins for 3d printing by utilizing xylitol and propolis - Google Patents

Abstract

The present invention relates to a method for preparing dental and total medical resins for 3D printing by utilizing xylitol and propolis and, more particularly, to a method for preparing, by utilizing xylitol and propolis, dental and total medical resins for 3D printing that can improve antibacterial effects by using natural materials, xylitol and propolis, replacing fluoride ions conventionally used for antibacterial effects, and furthermore can provide stable and excellent mechanical properties.

Description

Manufacturing method of dental and total medical 3D printing resin using xylitol and propolis

The present invention relates to a method for manufacturing dental and total medical 3D printing resins using xylitol and propolis, and more specifically, to a method for manufacturing xylitol and By using propolis, it relates to a method for manufacturing dental and total medical 3D printing resins using xylitol and propolis capable of providing stable and excellent mechanical properties as well as increasing antibacterial effects.

Dental caries, commonly called tooth decay, is a phenomenon in which components such as calcium and phosphorus on the surface of teeth are melted by acid to form holes in the teeth. Such dental caries can cause problems with pronunciation, chewing, and aesthetics. Problems such as damage to the gums may also occur, and when dental caries is intensified due to failure to recognize the invention at an early stage, a problem of removing damaged teeth may occur.

Therefore, when dental caries occurs, a procedure for maintaining or restoring the function of the oral cavity is performed by replacing the damaged part or the whole of the tooth with a dental restorative resin.

Since ancient times, mercury amalgam has been widely used because of its easy operation and excellent abrasion resistance and mechanical strength. Recently, polymeric materials that can compensate for these disadvantages are in the limelight.

Conventionally, dental restorative resin compositions are composed of inorganic fillers, PP polymers, diluents, photoinitiators, and other additives, and have mechanical strength that can withstand high occlusal pressure generated when chewing food, thermal expansion similar to natural teeth, and polymerization. Requirements such as having the same appearance and texture as natural teeth, as well as physical properties of low polymerization shrinkage to prevent separation from teeth during curing, must be met.

However, such a dental restorative resin composition has a problem of causing dental caries in the repaired area again due to shrinkage and microcracks generated during curing, thereby minimizing shrinkage and microcracks and preventing the recurrence of dental caries The development of resins with

Accordingly, conventionally, products that add and release fluorine (F) ions for antibacterial properties and prevention of dental caries have been developed. There is a problem that the resin is dropped and causes a bigger problem.

On the other hand, as the 3D printing market grows, 3D printing is being introduced to the dental world, and is currently being applied and used to various products such as temporary crowns, splints, surgical guides, and dentures.

Saliva exists in the oral cavity, there is a temperature difference depending on the food eaten, masticatory pressure is continuously applied, and abnormal forces such as bruxism and clenching are applied. It should be non-toxic.

In the case of dentures, as prostheses that are continuously positioned in the oral cavity at least during the week, all of the above-mentioned properties are required, and general denture base resins for 3D printing are difficult to use due to low mechanical properties and aesthetic problems.

Therefore, in order to solve the above-mentioned problems, it is necessary to develop a resin material that can replace conventional fluorine ion-emitting materials and exhibits excellent mechanical properties and aesthetics and can be used for 3D printing.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a resin material that can be used not only for dental purposes but also for general medical 3D printing resin materials, and has excellent mechanical properties, aesthetics, and antibacterial properties. is to provide

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

In order to achieve the above objects, the present invention provides 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane ( Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA), a pretreatment step of performing surface modification by irradiation with urethane dimethacrylate (UDMA); preparing a first mixed solution by adding xylitol to the triethylene glycol dimethacrylate (TEGDMA) and then stirring; 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA) and urethane dimetha Preparing a second mixed solution by mixing and stirring acrylate (UDMA); preparing a third mixed solution by mixing and then stirring the first mixed solution and the second mixed solution; Preparing a fourth mixed solution by adding nano fillers to the third mixed solution and then stirring; preparing a fifth mixed solution by adding a flavonoid-containing material to the fourth mixed solution and then stirring; preparing a sixth mixed solution by adding the photoinitiator and other additives to the fifth mixed solution and stirring; and aging the sixth mixed solution at room temperature or in a lukewarm environment.

In a preferred embodiment, in the pretreatment step, stirring is performed in a vacuum atmosphere, and stirring is performed for 60 minutes at a light intensity of 600mW/cm ² to 1,000mW/cm ² at a temperature of 60° C. to 80° C.

In a preferred embodiment, after the step of preparing the fourth mixed solution, a post-treatment step of performing surface modification by irradiating the fourth mixed solution with light corresponding to a wavelength range capable of being absorbed by the photoinitiator; further comprising, In the post-treatment step, stirring is performed in a vacuum atmosphere for the same temperature and time as the pre-treatment step, but the agitation is performed at a light intensity higher than that of the pre-treatment step.

In a preferred embodiment, the light intensity in the post-processing step is 1000mW/cm ² to 2,000mW/cm ² .

In a preferred embodiment, in the step of preparing the fifth mixture, stirring is performed in a vacuum atmosphere for 6 hours or more, but stirring is performed at room temperature in the summer season and at a temperature of 50 ° C to 60 ° C in the winter season.

In a preferred embodiment, in the aging step, the sixth mixed solution is aged at a temperature of 32° C. to 36° C. for 48 hours or longer.

In a preferred embodiment, the first mixed solution contains 2% to 10% by weight of xylitol.

In a preferred embodiment, the fifth mixed solution contains 0.2% to 3.5% by weight of the propolis compared to the fourth mixed solution.

In a preferred embodiment, the material containing the flavonoids is propolis.

The present invention has the following excellent effects.

According to the resin manufacturing method of the present invention, the surface of xylitol is coated with a glycol substrate of triethylene glycol dimethacrylate (TEGDMA) and then mixed with each monomer to prepare a resin, so that xylitol has reduced antibacterial properties due to the phospahte substrate. By minimizing and further using propolis, a material containing flavonoids, it is possible to provide a resin with excellent antibacterial and mechanical properties.

In addition, according to the resin manufacturing method of the present invention, the surface of each monomer or mixture is modified by irradiating light of a wavelength capable of being absorbed by the photoinitiator used in the manufacture in the same environment as the temperature generated during the resin polymerization process of 3D printing, It is possible to provide a resin having excellent photopolymerization efficiency and suitable mechanical properties as a resin material for 3D printing that can produce dental and total medical products as well as general dental restoration.

1 is a flow chart of a resin manufacturing method according to an embodiment of the present invention.

The terms used in the present invention have been selected from general terms that are currently widely used as much as possible, but in certain cases, there are terms arbitrarily selected by the applicant. should be taken into account to understand its meaning.

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

1 relates to a resin manufacturing method according to an embodiment of the present invention. Referring to FIG. 1, the resin manufacturing method according to an embodiment of the present invention has an antibacterial function usable as a dental restorative and medical 3D printing resin material. It relates to a method for manufacturing a resin having a pretreatment step (S1000) for monomers to be used in the manufacture, a first mixture solution preparation step (S2000), a second mixture solution preparation step (S3000), a third mixture solution preparation step (S4000), and a fourth mixture solution preparation step (S4000). It includes a mixture solution preparation step (S5000), a post-processing step (S6000), a fifth mixture solution preparation step (S7000), a sixth mixture solution preparation step (S8000), and a aging step (S9000).

First, in the resin manufacturing method of the present invention, pretreatment is performed to modify the surface of monomers (S1000).

In detail, each monomer performs surface modification by irradiating light in a wavelength range capable of being absorbed by the photoinitiator according to the photoinitiator to be used for preparing the resin.

More specifically, when the photoinitiator to be used in resin production is 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), the wavelength range that can be absorbed by the 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) The surface modification may be performed by irradiation with light having a wavelength of 350 nm to 420 nm, and light having a wavelength of 370 nm to 450 nm in the case of 1-phenyl-1,2-propanedione (PPD) and 420 nm to 420 nm in the case of camphorquinone (CQ). Surface modification may be performed by irradiating light with a wavelength of 540 nm.

On the other hand, when light-curing resin is polymerized in the air, oxygen in the air is combined with radicals to generate unpolymerized parts. These unpolymerized parts not only lower the physical properties of the resin but also leak into the oral cavity, causing cytotoxicity and allergy. can cause a reaction.

Accordingly, in the present invention, a pretreatment process of modifying the surface of the monomer is performed in order to minimize the unpolymerized portion of the resin.

To this end, the surface of the monomer is irradiated with light of a wavelength capable of being absorbed by the photoinitiator to be used in preparing the resin to perform surface modification, and the surface hydrophilicity of the surface-modified monomer is improved.

In particular, surface hydrophilicity for light of a wavelength capable of being absorbed by the photoinitiator is improved, thereby minimizing unpolymerized sites during resin polymerization.

In addition, the pretreatment process (S1000) is preferably performed in a vacuum atmosphere, and for this purpose, a vacuum mixer capable of irradiating a light source and generating a vacuum pressure may be used.

On the other hand, when stirring is performed in a vacuum atmosphere, the generation of bubbles generated during the stirring process can be minimized, and through this, light bending can be minimized to maximize the efficiency of surface modification by a light source.

In addition, in the pretreatment process (S1000), stirring may be performed for 60 minutes at a light intensity of 600mW to 1,000mw/cm ² depending on the wavelength.

In addition, the pretreatment process (S1000) may be performed at a vacuum pressure of 0.05mpa to 0.2mpa, and at a stirring speed of 5 RPM to 15 RPM.

In addition, the pretreatment process (S1000) may be performed at a temperature of 60 ℃ to 80 ℃.

On the other hand, the pretreatment process (S1000) is performed at a temperature of 60 ° C to 80 ° C because the efficiency of surface modification is excellent when performed under the same conditions as the exothermic temperature generated during polymerization in the resin printing process.

The monomers are compounds having an unsaturated double bond, 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA), ethylene glycol dimethacrylate (EGDMA) ), ethylene glycol diacrylate (EDGA), triethylene glycol dimethacrylate (TEGDMA), triethylene glycol diacrylate (TEGDA), ethoxylate bisphenol A dimethacrylate (Bis-EMA), urethane dimetha Acrylates (UDMA), polyurethane diacrylate (PUDA), dipentaerythritol pentaacrylate monophosphate (PENTA), 2-hydroxyethyl methacrylate (HEMA), poly and polyalkenoic acid, biphenyl dimethacrylate (BPDM), biphenyl diacrylate BPDA, or glycerol phosphate dimethacrylate (GPDM). ,

In the present invention, 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), and Toxylate bisphenol A dimethacrylate (Bis-EMA) and urethane dimethacrylate (UDMA) were used, and the remaining monomers except for the triethylene glycol dimethacrylate (TEGDMA) were single compounds having an unsaturated double bond. Or two or more types may be used together.

On the other hand, in the present invention, not only the pretreatment process (S1000), but also all the manufacturing processes in which agitation to be described below are performed in a vacuum atmosphere, thereby minimizing the generation of bubbles during the agitation process to have excellent mechanical properties and surface conditions Resin can be provided.

Next, xylitol is added to the triethylene glycol dimethacrylate (TEGDMA) and stirred to prepare a first mixed solution (S2000).

Here, the xylitol is a non-cariogenic and anti-cariogenic material, and is a natural material that is more effective in preventing caries than sorbitol or other sugar alcohols. In the present invention, xylitol, which is stably used as a food and medicine, was used as an effective material for preventing caries, and a resin having excellent antibacterial properties and mechanical properties compared to conventional fluorine-containing materials was prepared.

In addition, in the process of preparing the first mixed solution (S2000), it is preferable that 2% to 10% by weight of xylitol is added compared to the first mixed solution, which reduces the degree of polymerization by reducing the light transmission efficiency when the xylitol is added in excess. because it drops

In addition, the process of preparing the first mixed solution (S2000) is prepared by mixing and stirring the triethylene glycol dimethacrylate (TEGDMA) and xylitol in a vacuum atmosphere, vacuum pressure 0.05 mpa to 0.2 mpa, temperature 40 ° C to 50 ° C, It can be carried out for 120 minutes at a stirring speed of 5 RPM to 10 RPM.

Next, the 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA) and urethane Dimethacrylate (UDMA) is mixed and stirred to prepare a second mixed solution (S3000).

In the preparation of the second mixed solution (S3000), 30% to 50% by weight of the 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA) compared to the second mixed solution It is prepared by mixing 10 to 25% by weight of ethoxylate bisphenol A dimethacrylate (Bis-EMA) and 10 to 25% by weight of urethane dimethacrylate (UDMA).

In addition, the second mixed solution preparation process (S3000) is prepared by mixing and stirring in a vacuum atmosphere, vacuum pressure 0.05mpa to 0.2mpa, temperature 40 ℃ to 50 ℃, stirring speed 5 RPM to 10 RPM for 60 minutes. can

Next, a third mixed solution is prepared by mixing and stirring the first mixed solution and the second mixed solution (S4000).

At this time, in the process of preparing the third mixed solution (S4000), it is preferable to mix and stir the first mixed solution in an amount of 10% to 20% by weight relative to the third mixed solution with the second mixed solution.

In addition, the third mixture preparation process (S4000) is prepared by mixing and stirring in a vacuum atmosphere, vacuum pressure 0.05mpa to 0.2mpa, temperature 40 ℃ to 50 ℃, stirring speed 5 RPM to 10 RPM for 120 minutes. can

On the other hand, the 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), ethoxylate bisphenol A Mixing dimethacrylate (Bis-EMA) and urethane dimethacrylate (UDMA) and the xylitol at the same time does not perform stirring, which is a phosphate substrate of the remaining monomers except for triethylene glycol dimethacrylate (TEGDMA). This is because the problem of deterioration of antimicrobial properties of xylitol occurs, and in the present invention, the xylitol is mixed with the triethylene glycol dimethacrylate (TEGDMA) to form a glycol substrate of the triethylene glycol dimethacrylate (TEGDA). A film was first covered on the surface of the xylitol to protect it, and then mixing with the rest of the monomers was performed.

Next, a fourth mixed solution is prepared by mixing the nano-filler with the prepared third mixed solution and then stirring (S5000).

The nano-filler means a filler of nano-sized particles, and various known organic/inorganic fillers for improving wear resistance and mechanical strength of a resin may be manufactured and used in nano-size.

The fourth mixed solution manufacturing process (S5000) is prepared by mixing and stirring 2 to 10% by weight of the nano-filler with 90 to 98% by weight of the third mixed solution compared to the fourth mixed solution.

In addition, the fourth mixture preparation process (S5000) is prepared by mixing and stirring in a vacuum atmosphere, vacuum pressure of 0.05 mpa to 0.2 mpa, temperature of 40 ℃ to 50 ℃, stirring speed 10 RPM to 25 RPM for 240 minutes or more can

Next, a material having a flavonoid component is added to the fourth mixed solution to prepare a fifth mixed solution (S6000).

Here, the flavonoid is a component having antibacterial, antiviral, and antiallergic effects, and propolis, vitamin P, hesperadin, anthocyanidin, naringenin, isoflavone, etc. may be used as a substance having the flavonoid component, It is preferable to use the propolis.

In addition, in the fifth mixture preparation process (S6000), when propolis is used as a substance having the flavonoid component, it is prepared by adding 0.2% to 3.5% by weight compared to the fourth mixture, and the propolis is added in excess. In this case, the durability and shape sustainability of the product may be significantly reduced due to the decrease in moldability of the resin.

In addition, the fifth mixture preparation process (S6000) is prepared by mixing and stirring in a vacuum atmosphere, the vacuum pressure is 0.05 mpa to 0.2 mpa, the temperature is room temperature to 60 ° C, and the stirring speed is 5 RPM to 15 RPM for 360 minutes or more can be performed

On the other hand, the manufacturing process of the fifth mixed solution (S6000) may be prepared by varying the temperature according to the summer season and the winter season.

For example, the process of preparing the fifth mixed solution (S6000) may be performed at room temperature in summer and at a temperature of 50° C. to 60° C. in winter. This is because dew condensation and moisture in the chamber can occur due to the difference in temperature between the outside and the inside of the chamber of the vacuum mixer that performs stirring, which can cause product quality deterioration and contamination, as well as an obstacle to maintaining polymer softening during the mixing process. am.

Next, in order to optimize the light source polymerization reaction of the resin, the fifth mixture is irradiated with light in a wavelength range that can be absorbed by the photoinitiator to perform post-treatment for surface modification (S7000).

For the same reason as the pretreatment (S1000), the post-treatment process (S7000) performs surface modification by irradiating light in a wavelength range capable of being absorbed by the photoinitiator to be used for manufacturing, but with higher light intensity than in the pre-treatment process (S1000). is performed with

Specifically, the post-processing process (S7000) is performed in a vacuum atmosphere at a light intensity of 1,000 mW/cm ² to 2,000 mW/cm ² depending on the wavelength for 60 minutes, a vacuum pressure of 0.05 mpa to 0.2 mpa, a temperature of 60 °C to 80 °C, and Agitation may be performed at a speed of 5 RPM to 15 RPM.

On the other hand, the reason for performing the surface modification with a higher light intensity than in the pre-treatment process (S1000) in the post-treatment process (S7000) is to increase the light transmission efficiency because the fifth mixture is mixed with nano-fillers, and furthermore, the resin This is to maximize the surface modification of the monomers before polymerization of

Next, a photoinitiator and other additives are mixed with the fifth mixed solution and stirred to prepare a sixth mixed solution (S8000).

Here, as the other additives, a pigment for adjusting the color tone of the fissure sealant, a reaction accelerator, a diluent, and the like may be used.

In addition, the photoinitiator is 2,4,6-trimethyl benzoyl diphenyl phosphine (2,4,6-trimethyl benzoyl diphenyl phosphine, TPO), 1-phenyl-1,2-propane dione (1-phenyl-1 ,2-propanedione, PPD), and camphorquinone (Camphorquinoe, CQ) can be selected and used.

In addition, the sixth mixed solution is prepared by mixing and stirring in a vacuum atmosphere, and may be performed at a vacuum pressure of 0.05 mpa to 0.2 mpa, a temperature of 40 ° C to 50 ° C, and a stirring speed of 5 RPM to 15 RPM for 240 minutes or more.

Next, the prepared sixth mixed solution is aged in a room temperature or lukewarm environment (S9000).

On the other hand, when the sixth mixed solution is aged at a refrigerating temperature, adhesion between materials contained in the sixth mixed solution is not properly achieved, and the propolis is precipitated, resulting in a decrease in mechanical properties and durability of the resin. there is.

Accordingly, in the present invention, the sixth mixed solution is aged in a room temperature or lukewarm environment, and in detail, naturally aged at a temperature of 32 ° C to 36 ° C for 48 hours or more.

Through this aging process, the surface of the activated nano-filler can be deposited to make resin discharge smooth, and the mechanical properties of monomers damaged by stirring can be restored in the process of making mixed solutions, and furthermore, the cross-linking of xylitol and propolis can be strengthened. It has the advantage of increasing functionality as well as mechanical properties.

Hereinafter, effects of the resin prepared according to an embodiment of the present invention will be described in detail.

<Examples 1 to 4>

1. Pretreatment process

2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), ethoxylate bisphenol A dimethacryl After adding late (Bis-EMA) and urethane dimethacrylate (UDMA) to a vacuum mixer, at a temperature of 60 ° C, a stirring speed of 15 RPM, a vacuum pressure of 0.2 mpa, corresponding to the absorption wavelength of camphorquinone (CQ), a photoinitiator to be used for manufacturing The mixture was stirred for 60 minutes while irradiated with light having a wavelength of 400 nm at a light intensity of 1,500 mw/cm ² .

2. Preparation of the first mixed solution

1.1 g, 2.2 g, 4.4 g, and 11 g of xylitol were added to each 200 g of the pretreated triethylene glycol dimethacrylate (TEGDMA) in a vacuum mixer, and then the temperature was 50 ° C, the stirring speed was 15 RPM, and the vacuum pressure was 0.2 mpa. The mixture was stirred for 4 minutes to prepare a first mixed solution.

3. Preparation of the second mixed solution

440 g of pretreated 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA), 240 g of ethoxylated bisphenol A dimethacrylate (Bis-EMA), After adding 200 g of urethane dimethacrylate (UDMA) to a vacuum mixer, the mixture was stirred at a temperature of 50° C., a stirring speed of 15 RPM, and a vacuum pressure of 0.2 mpa for 120 minutes to prepare a second mixed solution for 4 times.

4. Preparation of the third mixed solution

After mixing 9.2g of the first mixture having a different mixing ratio with each of the prepared second mixture, it was prepared by stirring in a vacuum mixer at a temperature of 50 ° C., a stirring speed of 15 RPM, and a vacuum pressure of 0.2 mpa for 120 minutes.

5. Preparation of the 4th Mixed Solution

After adding 20 g of silica nano filler (100 nm) to each of the prepared third mixed solutions, the mixture was prepared by stirring in a vacuum mixer at a temperature of 50 ° C., a stirring speed of 25 RPM, and a vacuum pressure of 0.2 mpa for 24 hours.

5. Post-processing process

Each of the prepared fourth mixed solutions was heated in a vacuum mixer at a temperature of 60° C., a stirring speed of 15 RPM, a vacuum pressure of 0.2 mpa, and a light intensity of 400 nm corresponding to the absorption wavelength of camphorquinone (CQ), a photoinitiator to be used for the preparation, at an optical intensity of 2,000 mw/ It was stirred for 60 minutes in a state irradiated with cm ² .

6. Preparation of the fifth mixed solution

5 g of propolis was added to each post-treated fourth mixture, and then stirred in a vacuum mixer at a temperature of 50 ° C., a stirring speed of 15 RPM, and a vacuum pressure of 0.2 mpa for 6 hours.

7. Preparation of the 6th mixed solution

1 g of camphorquinone (CQ) as a photoinitiator and 2 g of ethyl 4-dimethylaminobenzoate (EDMAB) as a reaction accelerator were added to each of the prepared fifth mixtures, and then in a vacuum mixer at a temperature of 50 ° C and a stirring speed It was prepared by stirring for 12 hours at 15 RPM and vacuum pressure of 0.2 mpa.

8. Maturation Process

By naturally aging each of the prepared sixth mixed solutions at a temperature of 36° C. for 48 hours without stirring, the preparation of the resin was finally completed.

At this time, it can be classified into Examples 1 to 4 according to the content (concentration) of the composition contained in the prepared resin, and the content of each composition is shown in Table 1 below.

	Bis-GMA	Bis-EMA	UDMA	TEGDMA	xylitol	propolis	Nano filler	CQ	EDMAB
Example 1	44%	24%	20%	9.15%	0.05%	0.5%	2%	0.1%	0.2%
Example 2	44%	24%	20%	9.1%	0.1%	0.5%	2%	0.1%	0.2%
Example 3	44%	24%	20%	9.0%	0.2%	0.5%	2%	0.1%	0.2%
Example 4	44%	24%	20%	8.7%	0.5%	0.5%	2%	0.1%	0.2%

<Comparative Examples 1 to 4>

A resin was prepared in the same manner as in Example, but in the process of preparing the first mixed solution, fluorine was added instead of xylitol to prepare the resin.

At this time, it can be classified into Comparative Examples 1 to 4 according to the content (concentration) of the composition contained in the prepared resin, and the content of each composition is shown in Table 2 below.

	Bis-GMA	Bis-EMA	UDMA	TEGDMA	fluoride	propolis	Nano filler	CQ	EDMAB
Comparative Example 1	44%	24%	20%	9.15%	0.05%	0.5%	2%	0.1%	0.2%
Comparative Example 2	44%	24%	20%	9.1%	0.1%	0.5%	2%	0.1%	0.2%
Comparative Example 3	44%	24%	20%	9.0%	0.2%	0.5%	2%	0.1%	0.2%
Comparative Example 4	44%	24%	20%	8.7%	0.5%	0.5%	2%	0.1%	0.2%

<Experimental Example 1> Flexural strength test

Experiments were conducted on the flexural strength of the resins according to the xylitol content of Examples and the fluorine content of Comparative Examples. Specimens were made using a mold of 30x100x2mm for each prepared resin, and the same test was performed according to the ISO 4049 flexural strength test method.

A flexural strength test was performed by making five specimens each of Examples and Comparative Examples. The wavelength of light was 500 nm and the light intensity was 1,500 mw/cm ² , and photopolymerization was performed by irradiating twice for 25 seconds.

	Psalm 1 flexural strength	Psalm 2 flexural strength	Psalm 3 flexural strength	Psalm 4 flexural strength	Psalm 5 flexural strength	average flexural strength
Example 1	120MPa	116 MPa	117 MPa	125 MPa	124 MPa	120.40mmPa
Example 2	124 MPa	125 MPa	119 MPa	112 MPa	113 MPa	118.60 MPa
Example 3	119 MPa	125 MPa	121 MPa	122 MPa	116 MPa	120.60MPa
Example 4	116 MPa	124 MPa	125 MPa	119 MPa	123 MPa	121.40 MPa
Comparative Example 1	102 MPa	99MPa	97 MPa	95 MPa	108 MPa	100.20 MPa
Comparative Example 2	95 MPa	90 MPa	92MPa	94MPa	89 MPa	92.00 MPa
Comparative Example 3	89 MPa	82MPa	81 MPa	79 MPa	83 MPa	82.80 MPa
Comparative Example 4	69 MPa	75 MPa	77 MPa	75 MPa	69 MPa	73.00 MPa

As a result of the flexural strength test, referring to Table 3, it was found that Examples 1 to 4 in which xylitol was added had generally higher flexural strength than Comparative Examples 1 to 4 in which fluorine was added. In the case of Examples 1 to 4, xylitol It can be seen that the flexural strength gradually decreases as the fluorine content increases in the case of Comparative Examples 1 to 4, while the flexural strength change increases little by little even when the content is increased.

<Experimental Example 2> Adhesion strength test

The adhesive strength test of the resin according to the xylitol content of the examples and the fluorine content of the comparative example was performed, and each prepared resin was tested by making specimens using a 20x100x4mm mold.

A pair of specimens were made in each of Examples and Comparative Examples, and the pair of specimens were overlapped by 5 mm in the longitudinal direction, and dentin adhesive was applied uniformly to the overlapping area, and then bonded.

Then, using a universal tester, the top and bottom of the bonded specimen was fixed in a jig, and the tensile pressure was applied at a rate of 10 mm/min to measure the adhesive strength. Photopolymerization was performed by irradiation.

	Psalm 1 adhesive strength	Psalm 2 adhesive strength	Psalm 3 adhesive strength	Psalm 4 adhesive strength	Psalm 5 adhesive strength	average adhesive strength
Example 1	11.7 MPa	12.4MPa	12.3MPa	11.7 MPa	12.0 MPa	12.02 MPa
Example 2	11.4 MPa	12.6MPa	12.2MPa	13.2MPa	11.7 MPa	12.22MPa
Example 3	10.9 MPa	11.3 MPa	11.5 MPa	11.9 MPa	12.5 MPa	11.62 MPa
Example 4	11.5 MPa	12.3MPa	12.2MPa	12.3MPa	11.7 MPa	12.00 MPa
Comparative Example 1	9 MPa	9.7 MPa	9.5MPa	9.5MPa	9.7 MPa	9.48MPa
Comparative Example 2	8.1MPa	9.6MPa	7.9 MPa	8.2MPa	8.4MPa	8.24MPa
Comparative Example 3	8.0 MPa	7.6 MPa	7.7 MPa	7.4 MPa	7.6 MPa	7.66MPa
Comparative Example 4	7.2MPa	7.1 MPa	6.8 MPa	6.9 MPa	6.8 MPa	6.96MPa

As a result of the adhesive strength test, referring to Table 4, it was found that Examples 1 to 4 in which xylitol was added had generally higher adhesive strength than Comparative Examples 1 to 4 in which fluorine was added, and in the case of Examples 1 to 4, xylitol was added. While the change in adhesive strength is small even if the content is increased, in the case of Comparative Examples 1 to 4, it can be seen that the adhesive strength gradually decreases as the fluorine content increases.

<Experimental Example 3> Measurement of polymerization depth

Based on the content of each composition in Example 4, a prototype resin was prepared and the depth of polymerization was measured. In the case of not performing both the pre- and post-treatment processes during the manufacturing process, only the pre-treatment process, and the post-treatment process The depth of polymerization was measured when only the polymerization was performed and when the pretreatment and posttreatment processes were performed together.

The test method for measuring the depth of polymerization was carried out in accordance with the ISO 4049 depth of polymerization test method. In each case, 5 prototype resins were manufactured. When manufacturing the prototype resin, the wavelength of light was 500 nm and the light intensity was 1,500 mw/cm2 for 25 seconds. Photopolymerization was performed by irradiation twice.

	not implemented	Conduct pretreatment	post-processing	Conducting pre- and post-processing
Psalm 1 polymerization depth	1.2mm	2.2mm	2.1mm	2.8mm
Psalm 2 polymerization depth	1.4mm	2.1mm	2.2mm	2.7mm
Psalm 3 polymerization depth	1.3mm	2.5mm	2.2mm	2.8mm
Psalm 4 polymerization depth	1.1mm	2.4mm	2.1mm	2.6mm
Psalm 5 polymerization depth	1.2mm	2.2mm	2.0mm	2.7mm
average polymerization depth	1.24mm	2.28mm	2.12mm	2.72mm

Referring to Table 5 of the results of the polymerization depth experiment, the polymerization depth was significantly greater when the pre-treatment or post-treatment process was performed, or when both the pre-treatment process and the post-treatment process were performed than when the pre-treatment process and the post-treatment process were not performed. In particular, it can be confirmed that when the pre-treatment process and the flushing process are performed together, the polymerization depth is more than twice as high as when the pre-treatment process and the post-treatment process are not performed, compared to the case where only the pre-treatment process or the post-treatment process is performed. there is.

<Experimental Example 4> Antimicrobial measurement test

2,2-bis[4-(2-hydroxy-3 -methacryloxypropoxy)phenyl]propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA) and urethane dimethacrylate (UDMA) A circular specimen of the resin (Comparative Example 5) prepared by simultaneously mixing was produced.

Five circular specimens of Example 4 and Comparative Example 5 were each produced with a size of 20x20x2mm, and Streptococcus mutans (S.mutans, ATCC 25175) was used to 'JIS Z 2801: 2006 Antimicrobial products Test for antimicrobial activity and efficacy' Antimicrobial activity was evaluated accordingly.

When producing a circular specimen, the wavelength of light was 500 nm and the light intensity was 1,500 mw/cm ² , and photopolymerization was performed by irradiating twice for 25 seconds.

	Psalm 1 antibacterial	Psalm 2 antibacterial	Psalm 3 antibacterial	Psalm 4 antibacterial	Psalm 5 antibacterial	antibacterial average
Example 1	95%	94.3%	95.2%	93.7%	95.6%	94.6%
Comparative Example 5	68.4%	67.2%	70.1%	65.9%	66.5%	67.6%

As a result of the antibacterial test, referring to Table 6, 2,2-bis[4-(2-hydroxy-3-methacrylic acid) was added to the first mixture obtained by mixing xylitol and triethylene glycol dimethacrylate (TEGDMA) first. Example prepared by mixing and stirring a second mixed solution in which oxypropoxy) phenyl] propane (Bis-GMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA) and urethane dimethacrylate (UDMA) are mixed It can be confirmed that the antibacterial properties of Example 4 exhibit better antibacterial properties than those of Comparative Example 5. Therefore, the resin prepared by the resin manufacturing method of the present invention shows excellent antibacterial properties of 94% or more because xylitol and propolis are used together, and further It has the advantage of being usable as a resin material for 3D printing that can produce not only dental products but also various medical products, as it exhibits excellent mechanical properties such as flexural strength of 112 MPa or more, adhesive strength of 11.3 MPa or more, and polymerization depth of 2.1 mm or more.

As described above, the present invention has been shown and described with preferred embodiments, but is not limited to the above embodiments, and those skilled in the art to which the present invention pertains within the scope of not departing from the spirit of the present invention Various changes and modifications will be possible.

In addition to being used as a dental material such as a dental restorative resin, the present invention can also be used industrially as a medical 3D printing resin material.

Claims (9)

1. 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA), triethylene glycol dimethate A pretreatment step of performing surface modification by irradiating acrylate (TEGDMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA), and urethane dimethacrylate (UDMA);

   preparing a first mixed solution by adding xylitol to the triethylene glycol dimethacrylate (TEGDMA) and then stirring;

   2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (Bis-GMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA) and urethane dimetha Preparing a second mixed solution by mixing and stirring acrylate (UDMA);

   preparing a third mixed solution by mixing and then stirring the first mixed solution and the second mixed solution;

   Preparing a fourth mixed solution by adding nano fillers to the third mixed solution and then stirring;

   Preparing a fifth mixed solution by adding a flavonoid-containing material to the fourth mixed solution and then stirring the mixture:

   preparing a sixth mixed solution by adding the photoinitiator and other additives to the fifth mixed solution and stirring; and

   3D printing resin manufacturing method for dental and total medical use, comprising the step of aging the sixth mixed solution in a room temperature or lukewarm environment.
2. According to claim 1,

   In the pretreatment step, stirring is performed in a vacuum atmosphere, at a temperature of 60 ° C to 80 ° C, a light intensity of 600 mW / cm ² to 1,000 mW / cm ² Dental and total medical 3D printing, characterized in that performing stirring for 60 minutes Resin manufacturing method
3. According to claim 2,

   After the step of preparing the fourth mixed solution,

   Further comprising:

   In the post-treatment step, stirring is performed in a vacuum atmosphere for the same temperature and time as the pre-treatment step, but the light intensity is higher than the light intensity of the dental and total medical 3D printing resin manufacturing method, characterized in that the stirring is performed
4. According to claim 3,

   The light intensity in the post-processing step is 1000mW/cm ² to 2,000mW/cm ² Dental and total medical 3D printing resin manufacturing method, characterized in that
5. According to claim 1,

   In the step of preparing the fifth mixed solution, stirring is performed in a vacuum atmosphere for 6 hours or more, for dental and total medical purposes, characterized in that stirring is performed at room temperature in the summer season and at a temperature of 50 ° C to 60 ° C in the winter season. 3D printing resin manufacturing method
6. According to claim 1,

   The aging step is a method for manufacturing dental and total medical 3D printing resin, characterized in that for aging the sixth mixed solution at a temperature of 32 ° C to 36 ° C for 48 hours or more
7. According to claim 1,

   3D printing resin manufacturing method for dental and total medical use, characterized in that the first mixture contains 2% to 10% by weight of xylitol
8. According to claim 7,

   3D printing resin manufacturing method for dental and total medical use, characterized in that the fifth mixture contains 0.2% to 3.5% by weight of the flavonoid-containing material compared to the fourth mixture
9. According to claim 1,

   3D printing resin manufacturing method for dental and total medical use, characterized in that the material containing the flavonoid is propolis

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