KR102146960B1 - Manufacturing method of composite resin compositions comprising DIFP for dental restoration and composite resin manufactured by the same method - Google Patents

Abstract

The present invention relates to a method of manufacturing a fluorine-releasing dental restoration composite resin containing DIFP (Diphenyliodonium hexafluorophosphate) and a dental restoration composite resin prepared through the same, and such a dental restoration composite resin has excellent physical strength and , Uniform fluoride ions are released throughout the composite resin, and fluoride ions are released stably for a long time, which is effective in preventing dental caries.

Description

Manufacturing method of composite resin compositions comprising DIFP for dental restoration and composite resin manufactured by the same method}

The present invention relates to a method for preparing a fluorine-releasing dental restoration composite resin containing DIFP (Diphenyliodonium hexafluorophosphate), and a dental restoration composite resin prepared therethrough, and more particularly, to a stable fluorine for a long period of time by including DIFP. The present invention relates to a method for manufacturing a fluorine-releasing type dental restoration composite resin that can be released to prevent dental caries, and a dental restoration composite resin manufactured through the method.

Dental caries, commonly referred to as caries, is a phenomenon in which a hole is formed in the tooth by dissolving ingredients such as calcium and phosphorus on the surface of the tooth by acid, and problems of pronunciation, mastication, and aesthetics may occur due to such caries, pain, aching, Problems such as damage to the gums may also occur, and if dental caries is intensified due to the initial failure to recognize the onset, the problem of removing the damaged tooth 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 entire tooth with a dental restoration resin.

Various materials have been used as dental restoration resins, and mercury amalgam, which is easy to perform and has excellent abrasion resistance and mechanical strength, has been widely used since ancient times, but the color difference with natural teeth is distinct, and adhesion with tooth tissue is poor. , Since mercury is leaked over a long period of time and is known to be harmful to the human body, polymer materials that can compensate for these shortcomings are in the spotlight.

Typically, a resin composition for dental restoration is composed of inorganic fillers, prepolymers, diluents, photoinitiators, and other additives, and has mechanical strength that can withstand high occlusal pressure generated when chewing food, a thermal expansion rate similar to that of natural teeth, polymerization and hardening. In addition to physical properties such as a low polymerization contraction rate to prevent detachment from the tooth, it must meet requirements such as having the same appearance and texture as natural teeth.

Bisphenol A glycidyl methacrylate (bisphenol A glycidyl methacrylate) is commonly used as a prepolymer for dental restoration resin compositions, and Bis-GMA has the advantages of low volatility and polymerization shrinkage, and excellent strength of a polymer using the same, as a matrix resin. Is being used.

However, such a dental restoration resin composition has a problem of causing dental caries again at the restoration site due to shrinkage and microcracks occurring during curing.

Accordingly, there is an increasing demand for the development of dental materials that can minimize contractions and microcracks that occur during hardening and prevent recurrence of dental caries.

Registered Patent No. 10-1519581 (registered on May 6, 2015) Registered Patent No. 10-1728461 (registered on April 13, 2017)

An object of the present invention is to provide a method of manufacturing a fluoride-releasing type dental restoration composite resin capable of stably releasing fluorine for a long period of time and preventing dental caries by including DIFP, and a dental restoration composite resin manufactured through the method.

One embodiment of the present invention for achieving the object as described above, a first mixture preparation step of preparing a first mixture by stirring a plurality of monomers causing a crosslinking reaction; A second stirring step of preparing a second mixture by stirring UDMA (Urethane dimethacrylate) and DIFP (Diphenyliodonium hexafluorophosphate); A third stirring step of stirring the first mixture and the second mixture to prepare a third mixture; A fourth stirring step of preparing a fourth mixture by adding a filler to the third mixture and mixing the filler material; A fifth stirring step of adding a pigment and a polymerization initiator to the fourth mixture and mixing them to prepare a fifth mixture; And a aging step of stirring and aging the fifth mixture. It relates to a method for manufacturing a fluorine-releasing type dental restoration composite resin comprising DIFP.

The aging step may include a refrigerated aging step of refrigerating and aging the fifth mixture; and a aging and then stirring step of vacuum stirring the refrigerated-aged fifth mixture.

The first stirring step, the second stirring step, the third stirring step, the fourth stirring step, the fifth stirring step, and the stirring step after aging are preferably performed in a vacuum atmosphere.

The vacuum pressure in the stirring step after aging in the aging step is preferably higher than the vacuum pressure in the first stirring step, the second stirring step, the third stirring step, the fourth stirring step and the fifth stirring step.

The plurality of monomers that cause the crosslinking half are bis-GMA (Bisphenol A glycidyl methacrylate), TGDMA (Ethyleneglycol dimethacrylate), TEGDMA (Triethyleneglycol dimethacrylate), bis-EMA (Etoxylated bisphenol A dimethacrylate), PENTA (Dipentaerythritol pentaacrylate monophosphate), It may include at least three or more selected from the group consisting of 2-hydrozyethyl methacrylate (HEMA), Biphenyl dimethacrylate (BPDM), Glycerol phosphate dimethacrylate (GPDM), Urethane dimethacrylate (UDMA), and polyalkenoic acid.

The content of DIFP contained in the fifth mixture may be 0.01 to 0.05 wt%.

On the other hand, another embodiment of the present invention relates to a fluorine-releasing type dental restoration composite resin containing DIFP, manufactured by the above method.

The dental restoration composite resin manufactured by the method of manufacturing a fluorine-releasing dental restoration composite resin containing DIFP (Diphenyliodonium hexafluorophosphate) according to the present invention has excellent physical strength, and uniform fluorine ions are released throughout the composite resin. , Fluorine ions are stably released for a long period of time, which is effective in preventing dental caries.

Before describing in detail through preferred embodiments of the present invention, terms or words used in the present specification and claims should not be construed as being limited to a conventional or dictionary meaning, but a meaning consistent with the technical idea of the present invention. And should be interpreted as a concept.

Throughout this specification, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

As described above, tooth areas damaged by dental caries can be restored similarly to natural teeth by using dental restoration resin. Even if a resin composition with a low polymerization contraction rate is used, the resin shrinkage and shrinkage in the step of curing the resin However, there is a problem that dental caries easily recurs at the restoration site because microcracks occur due to the difference in contraction rate.

In the present invention, diphenyliodonium hexafluorophosphate (DIFP), which is a component that releases fluorine ions after curing, is added to the dental restoration resin composition to solve the above-described problem, thereby preventing recurrence of dental caries at the restoration site.

An embodiment of the present invention relates to a fluorine-releasing type dental restoration composite resin containing DIFP, comprising: a first mixture preparation step of preparing a first mixture by stirring a plurality of monomers causing a crosslinking reaction; A second stirring step of preparing a second mixture by stirring UDMA (Urethane dimethacrylate) and DIFP (Diphenyliodonium hexafluorophosphate); A third stirring step of stirring the first mixture and the second mixture to prepare a third mixture; A fourth stirring step of preparing a fourth mixture by adding a filler to the third mixture and mixing the filler material; A fifth stirring step of adding a pigment and a polymerization initiator to the fourth mixture and mixing them to prepare a fifth mixture; And a aging step of stirring and aging the fifth mixture.

Each step, that is, the first stirring step, the second stirring step, the third stirring step, the fourth stirring step, the fifth stirring step and the aging step may be performed in a vacuum atmosphere, and in particular, the vacuum pressure in the aging step is It is preferably higher than the vacuum pressure in the first stirring step, the second stirring step, the third stirring step, the fourth stirring step and the fifth stirring step.

In general, when the composition is stirred, each component contained in the composition is homogeneously dispersed, while external air is contained in the composition during stirring, or a reaction product is generated through a reaction that occurs due to mixing of each component of the composition. This may cause air bubbles in the composition. The generated bubbles have a buffering effect on the shrinkage stress of the composition, and the polymerization reaction does not proceed rapidly during the curing process of the composition, and the stress is dispersed and cured, so there is a problem that the physical properties to be obtained through the polymerization reaction of the composition decrease. .

In particular, in the case of a composite resin for dental restoration, as a medical composition, it must not only be cured within a short time when cured through polymerization, but also must have a certain level of strength so that the cured resin is not damaged even by mastication. The generation of air bubbles in the manufacturing process should be minimized.

In general, in order to reduce the occurrence of air bubbles or to reduce the generated air bubbles, an antifoaming agent is added to the composition and agitated.In the case of a composite resin for dental restoration, since it directly contacts the body, it should not be toxic and must have biocompatibility. Cannot be used. In addition, since the composite resin for dental restoration must have a predetermined viscosity for the convenience of the procedure, a defoaming process for removing air bubbles after the composite resin is manufactured cannot be performed. Therefore, it is necessary to minimize the occurrence of air bubbles in the composition in the process of manufacturing the composite resin for dental restoration.

Thus, in the present invention, by performing each step in a vacuum atmosphere lower than normal pressure as described above, it is possible to minimize the occurrence of bubbles due to stirring or reaction. At this time, if the applied vacuum pressure is too low, it is difficult to expect a bubble generation reduction effect, and if an excessively high vacuum pressure is applied, the effect of reducing bubble generation due to the added vacuum pressure is insignificant or absent. The economic feasibility of wasting energy for giving may be lowered. In this way, a preferred vacuum pressure for maximizing the bubble generation reduction effect and preventing a decrease in economic efficiency may be 0.05 to 0.15 MPa. At this time, the vacuum pressure means a value obtained by subtracting the absolute pressure from the atmospheric pressure.

However, in the aging step, a sufficient bubble removal effect cannot be obtained with the vacuum pressure applied in each stirring step, so a vacuum pressure higher than the vacuum pressure applied in each stirring step must be applied to remove the bubbles generated in the aging step. A sufficient bubble removal effect can be obtained. A preferred vacuum pressure in the aging step for obtaining this effect may be 0.15 to 0.3 MPa.

On the other hand, the first stirring step is a step of mixing and stirring a plurality of monomers causing a crosslinking reaction to prepare a first mixture in which a plurality of monomers are uniformly dispersed. In general, as a dental material, mechanical strength can be exhibited. , If it is polymerizable, it is not particularly limited and may be used as a monomer, and preferably a monomer containing an unsaturated double bond may be used.

The plurality of monomers causing the crosslinking reaction are bis-GMA (Bisphenol A glycidyl methacrylate), TGDMA (Ethyleneglycol dimethacrylate), TEGDMA (Triethyleneglycol dimethacrylate), bis-EMA (Etoxylated bisphenol A dimethacrylate), PENTA (Dipentaerythritol pentaacrylate monophosphate), HEMA (2-hydrozyethyl methacrylate), BPDM (Biphenyl dimethacrylate), GPDM (Glycerol phosphate dimethacrylate), UDMA (Urethane dimethacrylate), and at least three selected from the group consisting of polyalkenoic acid may be included.

Among them, bis-GMA contains two hydrophobic methacrylic groups, has low volatility and polymerization shrinkage, fast curing, high molecular weight, and high stability, so it is suitable as a matrix resin. However, it is difficult to uniformly stir with other components due to high viscosity, and workability is poor, so it is preferable to be used together with TEGDMA to lower the viscosity.

However, when TEGDMA is used to lower the viscosity, the number of double bonds per unit weight increases, so that polymerization shrinkage increases, and moisture affinity increases, which makes it vulnerable to coloring.Thus, bis-EMA is used to prevent this. By using them together, it is possible to improve viscosity and polymerization shrinkage, and to lower moisture affinity, so it is preferable to use bis-GMA, bis-EMA and TEGDMA as a plurality of monomers causing a crosslinking reaction in the first stirring step.

The composition and content of the plurality of monomers included in the first stirring step not only play an important role in the dispersion degree of the composition during the subsequent polymerization reaction, but also play a role in the treatment and physical properties of the cured product formed after the dental procedure using the same. Because of the influence, the composite resin for dental restoration may be appropriately adjusted to a preferable composition and content depending on the method used, the location to be applied, and the purpose of use.

For example, when bis-GMA, bis-EMA, and TEGDMA are used as a plurality of monomers, the preferred content in the entire composite resin composition, that is, the fifth mixture, is 10 to 15 wt% bis-GMA, 6 to bis-EMA It is preferable to be 11 wt% and TEGDMA 1 to 2 wt%, and if the content of each monomer is outside the above-described range, the effect of each of the aforementioned monomers may not be obtained, or a problem may arise because opposite characteristics are expressed. Therefore, it is preferable to be included within the above-described range.

In particular, when TEGDMA is contained in excess of 2 wt%, the water absorption and polymerization shrinkage rate increase after curing the composite resin, resulting in increased crack incidence between the composite resin and the tooth surface and other physical properties. Therefore, the content of TEGDMA is preferably 1 to 2 wt%.

In the first stirring step, agitation of a plurality of monomers may be performed at 40° C. to 50° C. at 15 to 25 RPM for 20 to 40 minutes. When the stirring temperature, stirring speed, and stirring time are less than the above-described range, sufficient dispersion of each monomer may not be made, so that workability and physical properties after curing may be deteriorated in the future, and when the stirring temperature and stirring time exceed the above-described ranges There is a problem that energy is wasted because the stirring effect obtained is insignificant compared to the additional energy consumed.If the stirring speed exceeds the above range, the generation of bubbles increases rapidly and the physical properties of the composite resin after curing due to bubbles may be deteriorated. Therefore, it is preferable that the stirring is performed within the range of the above-described process conditions.

Next, the second stirring step is a step of preparing a second mixture by mixing and stirring DIFP (Diphenyliodonium hexafluorophosphate) emitting fluorine ions and UDMA (Urethane dimethacrylate) causing a crosslinking reaction with a plurality of monomers of the first mixture. As, the stirring may be performed at room temperature for 20 to 30 minutes at 15 to 25 RPM.

Since DIFP contains a phosphate group in its molecular structure, when it directly contacts a plurality of monomers included in the first mixture, there is a problem of rapidly deteriorating the physical performance of the cured product after curing. In particular, when TEGDMA is included as a plurality of monomers and DIFP directly contacts TEGDMA, the phosphate group of DIFP is dissolved in TEGDMA, and the physical performance of bis-GMA, which is the basis of the physical properties of the cured product, can be reduced.

Therefore, in the present invention, in order to prevent such a problem, the second mixture in which DIFP is dispersed in UDMA can be mixed with the first mixture without mixing DIFP in the first mixture. When DIFP is first dispersed in UDMA as described above, since the phosphate group of DIFP is surrounded and protected by the urethane group of UDMA, even if it is mixed with the first mixture, the effect of preventing degradation of physical properties due to the reaction of the phosphate group and the first mixture is obtained. have.

When DIFP is included, fluorine ions are gradually released from the cured composite resin after tooth restoration, which has the effect of preventing secondary caries at the treatment site of the composite resin. However, if DIFP is included in an excessive amount, the composite resin and teeth Since the adhesive force of the resin may be significantly reduced and the resin may fall off, an appropriate amount of DIFP should be included in the entire composite resin composition.

In this way, the content of DIFP that does not cause a problem of lowering adhesion to teeth while obtaining the secondary caries prevention effect is preferably contained in an amount of 0.01 to 0.05 wt% in the entire composite resin composition, that is, the fifth mixture. If it is less than 0.01 wt%, the effect of preventing secondary caries due to the release of fluorine ions is insignificant, and the period for obtaining this effect is short, and if it exceeds 0.05 wt%, the adhesion of the composite resin to the teeth is lowered. Since it can be made, it is preferable to be included within the above-described range.

In addition, as described above, in order to prevent the deterioration of the physical properties of the cured product due to the phosphate group of DIFP, UDMA and DIFP should be mixed at an appropriate weight ratio in the second stirring step, preferably, UDMA in the second mixture is 100 of DIFP. To 1000 times may be included.

At this time, when UDMA is contained less than 100 times for DIFP, the phosphate group of DIFP directly exposed to the first mixture may increase to reduce physical properties, and when it exceeds 1000 times, relatively the entire composite resin composition Since there is a problem that the content of UDMA in the UDMA increases, the physical strength decreases and the degree of polymerization shrinkage increases, it is preferable to mix them in the weight ratio described above.

In addition, the step of mixing DIFP is preferably before particulate matter such as a filler or pigment, which will be described later, is mixed. When DIFP is mixed in a mixture in which such particulate matter is first mixed, the particulate matter prevents dispersion of DIFP. This is because there is a problem in which DIFP is distributed unevenly in the final product, the composite resin.

When DIFP is distributed unevenly, the concentration of fluoride ions released for a predetermined period is excessively low, preventing dental caries from being prevented, or excessively high, resulting in a problem of lowering the safety of the human body, and teeth obtained during each procedure. Since the caries preventing effect is different, the reliability of the dental caries preventing effect of the composite resin may be lowered. Therefore, DIFP is preferably mixed before the particulate matter such as a filler or pigment is mixed.

Next, the third stirring step is a step of preparing a third mixture by mixing and stirring the first mixture in which a plurality of monomers are mixed and the second mixture in which DIFP and UDMA are mixed, and the stirring in this step is 40°C~ It can be performed for 20 to 40 minutes at 15 to 25 RPM at 50 °C.

Next, the fourth stirring step is a step of preparing a fourth mixture by adding a filler to the third mixture and mixing the mixture, and may be performed for 90 to 120 minutes at 25 to 35 RPM at room temperature. .

In particular, since reaction heat and frictional heat are generated when the third mixture and the filler are stirred, it is preferable to stir at room temperature without applying separate heat, and the stirring time is due to the temperature change according to the season, and the stirring time is reduced in the summer. , In winter, the stirring time can be increased.

The filler added in the fourth stirring step is to improve the wear resistance and physical strength of the composite resin, and the filler may be an inorganic filler, an organic filler, a stabilizer, or a mixed filler containing at least two or more of them.

The inorganic filler is not particularly limited and may be used as long as it is a known inorganic filler generally used for dental resin. For example, silica, amorphous synthetic silica, crystalline natural silica, barium aluminum silicate, barium glass, kaolin, talc, radioactive glass powder (strontium aluminum silicate, etc.), zirconia compounds, or other acid-reactive fillers, etc. A mixture of two or more may be used, preferably silica and barium glass.

In general, since inorganic fillers are chemically hydrophilic, they have low miscibility with a plurality of hydrophobic monomers, and the inorganic fillers are surface-treated with a binder or silane coupling agent that can further improve binding properties in the third stirring step. Thus, the binding properties with a plurality of monomers can be improved. As described above, a method of surface treatment of an inorganic filler with a silane coupling agent and specific examples of a silane coupling agent used for surface treatment are known in the art, and thus a detailed description thereof will be omitted.

The organic filler can be used as granulated by synthesizing a monomer constituting a matrix or a monomer compatible with it by bulk polymerization, emulsion polymerization, suspension polymerization, etc., and then prepared in a powder form when curing a dental restoration composite resin. have.

The stabilizer is a material capable of chemically and physically stabilizing the mixture or the dental restoration composite resin, and preferably a phenolic and/or phosphoric acid stabilizer may be used.

Next, the fifth stirring step is a step of preparing a fifth mixture by adding and mixing a pigment and a polymerization initiator to the fourth mixture, and mixing, that is, stirring, is performed at room temperature for 90 to 120 minutes at 20 to 30 RPM. It can be carried out, and in winter it is preferable to stir for a longer time than in summer.

The pigment may be added to improve the aesthetics of the user by minimizing the sense of heterogeneity with the natural teeth since the composite resin has the same color or similar to the natural teeth. For example, yellow, dark blue (black) and red iron oxide-based inorganic pigments or titanium dioxide inorganic pigments may be used, but are not limited thereto, and may be used regardless of the type as long as it is commonly used for dental resins. And can be used in an appropriate amount to maximize aesthetics.

The polymerization initiator is an initiator for polymerization reaction of a plurality of monomers, and may proceed with a cation formation mechanism, an anion formation mechanism, a radical formation mechanism, etc., depending on the type of catalyst used in the polymerization reaction, but generally a radical formation mechanism is used. And, the polymerization reaction may proceed through a photopolymerization reaction, a thermal polymerization reaction, or the like through cations, anions, and radicals generated through the polymerization initiator.

In the case of the fluorine-emitting dental restoration composite resin containing DIFP of the present invention, it is preferable to cure it through a photopolymerization reaction in which a polymerization reaction of a monomer is performed by being activated by a light source having a specific wavelength. The initiator may be a photopolymerization initiator that initiates a photopolymerization reaction.

Therefore, a light source having a specific wavelength, preferably harmless to the human body after applying or filling in the damaged area of the tooth using a fluorine-releasing type dental restoration composite resin containing DIFP prepared according to an embodiment of the present invention When exposed to a light source in the light ray region, a photopolymerization initiator and a catalyst generate radicals, and a polymerization reaction between a plurality of monomers and UDMA is initiated and cured by the generated radicals, thereby repairing teeth.

As such a photoinitiator, an α-diketone-based carbonyl compound or an acylphosphine oxide-based may be used, and more preferably, a tertiary amine compound as a hydrogen donor is further included as a reaction accelerator in the fifth mixture in the fifth stirring step. I can.

More preferably, as the photopolymerization initiator, camphorquinone (CQ), one of the α-diketone-based carbonyl compounds, may be used, and N,N-dimethylaminoethyl methacrylic as the tertiary amine compound as a reaction accelerator. Rate (N,N-dimethylaminoethyl methacrylate) or ethyl-4-dimethylamino benzoate (EDMAB) may be used.

The diluent is to increase chemical stability by reducing the viscosity of the fifth mixture and thereby improve storage properties, preferably methyl methacrylate, ethylene glycol dimethacrylate, diethylene Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, 1,4-Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Crylate (1,6-Hexanediol dimethacrylate), 1-methyl-1,3-propanediol dimethacrylate, bis-GMA (bisphenol A-glycidyl methacrylate), etc. Can be used.

Finally, a aging step for improving stability may be performed by sufficiently bringing the composition included in the fifth mixture, particularly various monomers into close contact with the surface of the filler included in the fifth mixture.

The aging step is a refrigeration aging step of aging the fifth mixture at 3 to 5° C. for 20 to 27 hours; And, after aging the fifth mixture refrigerated and aging at room temperature for 60 to 90 minutes with vacuum stirring at 10 to 20 RPM Stirring step; includes.

In the refrigeration aging step, when refrigeration aging is performed under conditions outside the limited refrigeration aging temperature and time range as described above, the filler and each component are not sufficiently adhered to each other, so that the strength or durability of the cured composite resin decreases, or the restoration Since a problem of detachment from the tooth may occur afterwards, it is preferable to perform refrigeration aging under conditions that satisfy the above temperature and time range.

On the other hand, the vacuum pressure during vacuum stirring in the stirring step after aging is preferably 0.15 to 0.3 MPa, and more preferably, when a vacuum pressure higher than the vacuum pressure applied in the first to fifth stirring steps is applied, Air bubbles generated during aging in the refrigerated aging step can be more effectively removed.

Through the stirring step after the refrigeration aging step, not only can some of the physical properties of each component be restored, but also the cured body of the composite resin restored to the teeth by applying tension to the pigment included in the fifth stirring step Color stability can be improved.

On the other hand, another embodiment of the present invention relates to a fluorine-releasing type dental restoration composite resin including DIFP, which is prepared according to the method of an embodiment of the present invention described above, and the composite resin has an adhesive strength with natural teeth. It is excellent and has excellent physical strength and properties, so it not only exhibits excellent functions as an artificial tooth, but also contains DIFP so that fluoride ions are gradually released from the cured composite resin after tooth restoration to prevent secondary caries at the treatment site of the composite resin. There is an effect.

In addition, since the photopolymerization reaction of the composite resin exposed to light during the procedure is accelerated and curing proceeds rapidly using such a composite resin, there is an advantage of improving the convenience of the procedure. The formation of gaps between the resins can be minimized or prevented.

Hereinafter, an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art may implement various modified forms of the contents described in the present specification within the scope of the present invention.

[Production Example 1]

First, bis-GMA. Bis-EMA and TEGDMA were stirred for 30 minutes at 20 RPM under a temperature of 42°C and a vacuum pressure of 0.1 MPa to prepare a first mixture, and UDMA and DIFP were mixed at room temperature (20°C) and a vacuum pressure of 0.1 MPa for 30 minutes at 20 RPM. Stirring to prepare a second mixture. At this time, each component was mixed so that the weights of bis-GMA, bis-EMA, and TEGDMA in the entire dental restoration composite resin composition that went through until the final aging step were 13.2wt%, 9.7wt%, and 1.4wt%, respectively.

Next, the first mixture and the second mixture were mixed and stirred at 20 RPM for 30 minutes under a temperature of 45° C. and a vacuum pressure of 0.1 MPa to prepare a third mixture.

After adding appropriate amounts of silica and barium glass as fillers to the third mixture, a fourth mixture was prepared by stirring for 100 minutes at 28 RPM under vacuum pressure of 0.1 MPa at room temperature (20° C.), and a pigment, a polymerization initiator, campoquinone. , After adding appropriate amounts of ethyl-4-dimethylamino benzoate and a diluent as a reaction accelerator, a fifth mixture was prepared by stirring at room temperature (20° C.) and a vacuum pressure of 0.1 MPa at 25 RPM for 110 minutes.

Finally, the fifth mixture was refrigerated and aged at 4° C. for 24 hours, and then stirred at room temperature (20° C.) under vacuum pressure of 0.22 MPa for 75 minutes at 15 RPM to prepare a final product, a composite resin for dental restoration.

At this time, the used bis-GMA,. The weights of Bis-EMA, TEGDMA, UDMA and DIFP were prepared differently as described in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 UDMA (wt%) 7.7 7.7 7.7 7.7 7.7 4.5 DIFP(wt%) 0.010 0.030 0.048 0.007 0.053 0.048 UDMA for DIFP
Weight ratio 770 257 160 1100 145 94

[Experimental Example 1]

After performing a flexural strength test, an adhesive strength test, and a fluorine ion leak test using each dental restoration composite resin prepared in Preparation Example 1, the results are shown in Table 2. Each experiment was performed in the following manner.

(1) Flexural strength test

A specimen (25×2×2mm) of each dental restoration composite resin prepared in Preparation Example 1 was prepared, stored in distilled water at 37°C for 24 hours, and then a cross of 0.75±0.25 mm/sec using a universal testing machine. A flexural strength test was performed by applying force at the head speed until the specimen fractured, and the results are shown in Table 2.

(2) Adhesion strength test

After washing and drying the prepared uchichi, each dental restoration composite resin prepared in Preparation Example 1 was applied, and the bracket was adhered and stored for 20 minutes in water at 37°C, then 0.75±0.30 mm/min using a universal testing machine. A load was applied until the bracket was removed at a crosshead speed of, and the adhesive strength test was performed, and the results are also shown in Table 2.

(3) Fluoride ion leak test

Cylindrical specimens of the same size prepared using each dental restoration composite resin composition prepared in Preparation Example 1 were each sealed by immersing in distilled water, stored for 500 hours in a thermostat at 37°C, and then spilled into distilled water. The concentration of ions was measured. The concentration of fluoride ion leakage, which is known to be effective in preventing dental caries in clinical practice, is 0.1~0.9ppm.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Flexural strength (MPa) 98.8 96.1 93.7 99.4 91.2 83.6 Adhesive strength (MPa) 16.6 16.2 15.3 13.8 9.5 13.5 Fluoride ion after 500 hours
Effluent concentration (ppm) 0.14 0.37 0.51 0.05 0.55 0.52

Looking at the experimental results in Table 2, it can be seen that Example 1, Example 2, and Example 3 exhibit excellent values in all test items.

However, in the case of Comparative Example 1, it was confirmed that the effluent concentration of fluorine ions after 500 hours was significantly less than the clinically suggested 0.1 ppm, which was a result of insufficient DIFP content contained in Comparative Example 1. Confirmed as. Looking at Comparative Example 1 and Examples 1 to 3 together, it was confirmed that the DIFP content is preferably included in the total composite resin composition at least 0.01 wt% or more.

In addition, looking at Comparative Example 2 together with other Examples, it can be seen that the adhesive strength of Comparative Example 2 is particularly low, which is excessively high in the content of DIFP contained in Comparative Example 2, Since it was confirmed as the result shown because it inhibited the adhesion, it was found that it is preferable that DIFP is contained in a maximum of 0.05 wt% or less.

On the other hand, in the case of Comparative Example 3, the content of UDMA was lower than that of DIFP, and the flexural strength was significantly lower than that of other specimens.

Therefore, through the results of this experiment, it was confirmed that the content of DIFP is preferably included in 0.01 to 0.05 wt% in the total composite resin composition, and the content of UDMA is preferably at least 100 times that of DIFP, and more preferably , It was found that it is preferable to be included in the range of 100 to 1000 times the DIFP content.

[Production Example 2]

To prepare a composite resin having the same composition ratio as the composite resin for dental restoration of Example 2, bis-GMA. The first mixture of bis-EMA and TEGDMA and the second mixture of UDMA and DIFP were not mixed, and bis-GMA. Bis-EMA, TEGDMA, UDMA, and DIFP were mixed at once to prepare a third mixture, and thereafter, a composite resin for dental restoration of Comparative Example 4 was prepared using the same method as in Example 2.

In addition, a composite resin having the same composition ratio as that of the dental restoration composite resin of Example 2 was prepared, but DIFP was not added when preparing the second mixture, and DIFP was added to the fifth mixture in which fillers and pigments were mixed. After inputting in the same amount as in Example 2, a composite resin for dental restoration of Comparative Example 5 was prepared through the same aging step as in Example 2.

[Experimental Example 2]

Experimental example 2-1: Example 2, Comparative example 4, flexural strength test

The same flexural strength test as in Experimental Example 1 was performed 5 times using the dental restoration composite resins of Example 2 and Comparative Example 4, and the results are shown in Table 3.

Flexural strength (MPa) Average flexural strength (MPa) Example 2 96.1 88.9 91.2 92.3 89.2 91.5 Comparative Example 4 78.8 75.3 81.5 82.7 79.1 79.5

Experimental example 2-2: Example 2, Comparative example 5, fluorine ion leak test

In addition, the same fluorine ion leakage test as in Experimental Example 1 was performed using the dental restoration composite resin of Example 2 and Comparative Example 5, but three specimens of each of Example 2 and Comparative Example 5 were prepared, and for 3 days. The test results performed are shown in Table 4.

Concentration of fluoride ion leakage after 72 hours Standard Deviation Example 2 0.75 0.63 0.49 0.11 Comparative Example 5 0.76 1.61 0.29 0.55

First, looking at the flexural strength test results of Example 2 and Comparative Example 4 of Experimental Example 2-1, in the average of the test results and results of individual specimens, the flexural strength of Comparative Example 4 was significantly lower than that of Example 2. Can be confirmed.

This, in Comparative Example 4, did not go through the step of mixing a mixture of DIFP and UDMA previously mixed with a plurality of other monomers, the phosphate group of DIFP is dissolved in the monomers of the first mixture, especially TEGDMA, the final product It is confirmed by the results shown because it lowers the physical strength of the composite resin.

Therefore, through Experimental Example 2-1, a first mixture, which is a mixture of a plurality of monomers, and a second mixture, which is a mixture of DIFP and UDMA, was prepared, and then the first mixture and the second mixture were mixed. It was confirmed that only when the resin was prepared, a fluorine-releasing type dental restoration composite resin having excellent performance could be manufactured without a separate physical performance degradation due to DIFP.

Next, referring to the results of Experimental Example 2-2, in the case of Example 2, after 72 hours, it was found that all three specimens had similar values of the fluorine ion outflow concentration, and the standard deviation for each result was 0.11. , It was confirmed to be good.

However, it was found that the standard deviation of Comparative Example 5 was 0.55 and the degree of dispersion of the result was significantly higher than that of Example 2. In addition, the minimum effluent concentration was found to be about 5 times more than the maximum effluent concentration, and it was confirmed that non-uniform concentrations of fluorine ions were effluent for each specimen, and thus the reliability of the effect of preventing dental caries due to fluoride ion leakage was reduced.

In particular, Comparative Example 5 did not satisfy the clinically recommended condition of'within 0.9 ppm for 500 hours', and there was a specimen in which a high concentration of fluorine ions was leaked, so that not only the reliability of the composite resin but also the safety of the human body was reduced. Appeared.

This is, as in Comparative Example 5, when DIFP is mixed after the particulate filler or pigment is first mixed, it is judged as a problem that appeared because these particulate materials interfere with the uniform dispersion of DIFP, so before these particulate materials are mixed It was confirmed that it is preferable to perform the step of mixing DIFP.

The present invention is not limited to the specific embodiments and description described above, and any person having ordinary knowledge in the technical field to which the present invention pertains without departing from the gist of the present invention claimed in the claims can implement various modifications. And, such modifications are within the scope of protection of the present invention.

Claims (7)

A first mixture preparation step of stirring a plurality of monomers causing a crosslinking reaction to prepare a first mixture;
A second stirring step in which UDMA (Urethane dimethacrylate) and DIFP (Diphenyliodonium hexafluorophosphate) are stirred to prepare a second mixture, wherein UDMA in the second mixture is included in a weight ratio of 100 to 1000 times that of DIFP;
A third stirring step of stirring the first mixture and the second mixture to prepare a third mixture;
A fourth stirring step of preparing a fourth mixture by adding a filler to the third mixture and mixing the filler material;
A fifth stirring step of adding a pigment and a polymerization initiator to the fourth mixture and mixing them to prepare a fifth mixture; And
Including; a aging step of stirring and aging the fifth mixture,
The content of DIFP contained in the fifth mixture is, characterized in that 0.01 ~ 0.05wt%, the method of manufacturing a fluorine-releasing type dental restoration composite resin containing DIFP. The method of claim 1,
The aging step comprises: a refrigerated aging step of refrigerating and aging the fifth mixture; and a aging and then stirring step of vacuum stirring the refrigerated-aged fifth mixture; characterized in that it includes, fluorine-releasing dental water containing DIFP Method of manufacturing a composite resin to be taken. The method of claim 2,
The first mixture preparation step, the second stirring step, the third stirring step, the fourth stirring step, the fifth stirring step, and the stirring step after aging are performed in a vacuum atmosphere. Manufacturing method of composite resin for restoration. The method of claim 2,
DIFP, characterized in that the vacuum pressure in the stirring step after aging in the aging step is higher than the vacuum pressure in the first stirring step, the second stirring step, the third stirring step, the fourth stirring step and the fifth stirring step. Method for producing a fluorine-releasing type dental restoration composite resin containing. The method of claim 1,
The plurality of monomers causing the crosslinking reaction are bis-GMA (Bisphenol A glycidyl methacrylate), TGDMA (Ethyleneglycol dimethacrylate), TEGDMA (Triethyleneglycol dimethacrylate), bis-EMA (Etoxylated bisphenol A dimethacrylate), PENTA (Dipentaerythritol pentaacrylate monophosphate), HEMA (2-hydrozyethyl methacrylate), BPDM (Biphenyl dimethacrylate), GPDM (Glycerol phosphate dimethacrylate), UDMA (Urethane dimethacrylate), characterized in that it comprises at least three or more selected from the group consisting of polyalkenoic acid, including DIFP Method for producing a fluorine-releasing type dental restoration composite resin delete A fluorine-releasing dental restoration composite resin containing DIFP, prepared by the method according to any one of claims 1 to 5.