TWI472351B - Dental composite resin for fitting natural teeth and its preparation method - Google Patents

Description

Dental composite resin for fitting natural teeth and preparation method thereof

The invention relates to a dental composite resin, in particular to a dental composite resin which fits the fluorescence emission spectrum of natural teeth and a preparation method thereof.

Due to the development of modern aesthetic dentistry, dental ceramics and composite resins are widely used in artificial crowns and complex filling materials, and the resin composite materials used in clinical practice usually contain various compositions. Among them, the main components are resin matrix and inorganic filler particles, and other additives are used to cause polymerization reaction, enhance the clinical operation characteristics of the material or durability, and are called composite resins. In addition to the improvement in mechanical and physical properties, it also allows the composite resin to match the color of the teeth through the blending of colorants to achieve aesthetic requirements.

In 2010, Dr. Lin Xinyi, MD, from the Institute of Clinical Dentistry, National Taiwan University, found that the excitation spectrum of natural teeth is between 300 and 450 nm, and the peak is about 390. Nano, the emission spectrum is about 410~600 nm, and the peak is about 470 nm. It is known that dental composite resin matrix and filler molecules do not emit fluorescence, and fluorescent substances must be added to compare with natural dental fluorescence, while elements similar to natural dental fluorescence belong to III, IV, and V in the periodic table. The elements are generally inferred to be rare earth oxides or organic molecules such as europium (Eu), cerium (Cerium, Ce), and ytterbium (Ytterbium, Yb). However, the raw materials and ratios of commercially available composite resin fluorescent materials are all trade secrets. The fluorescent light after mixing of the rare earth elements exhibits a complex non-single fluorescent addition, and its fluorescent performance and matrix material have Off, when the matrix material changes, the fluorescence performance will also change.

Fluorescent substances of different brands have individual excitation and emission spectra, and under ultraviolet light, they also emit fluorescent light of different colors and intensity. In general, the excitation spectrum of natural teeth is wider, the peak width of the excitation spectrum of the commercially available composite resin is narrower, and the intensity of the band is reduced after 430 nm.

Dental composite materials must have good stability for use in environments where the humidity and temperature difference in the mouth are large. According to Takahashi, MK et al., "Fluorescence intensity of resin composites and dental tissues before and after acceleration aging: a comparative study" published in 2008, which is a commercially available composite resin of six brands by Xenon arc illumination and aging cycle test. This test method has photo-oxidation ability and can break the carbon bond of the resin matrix. Since the resin is added to the phosphor or can be attached to the matrix or bonded to the matrix polymer chain by carbon bonds, after the aging cycle test, the fluorescence intensity of the six brands is weakened, and the fluorescent substance in the composite resin can be inferred. The stability is not good.

In the past, there has been a technique of adding a cadmium selenide (CdSe) quantum dot to a dental composite resin as a fluorescent substance. The quantum dot system uses a core-shell nanocrystal structure of cadmium selenide/zinc sulfide (CdSe/ZnS), and the diameter of the crystal is 3.7 nm, and the outer layer is composed of polymethylmethacrylate (PMMA). Coated. When the user incorporates different proportions of quantum dots into a commercially available composite resin at room temperature, the emission spectrum peak of the composite resin having a cadmium selenide/zinc sulfide core-shell nanocrystal structure will fall at 608. Nano is not the main range of natural dental fluorescence emission spectra. Furthermore, cadmium selenide quantum dots are highly biotoxic, and their application to dental composite resins poses a great risk to the health of users, so it is not suitable for biomedical materials.

In view of this, the present invention proposes a dental composite resin for fitting natural teeth and a preparation method thereof to overcome the disadvantages.

The main object of the present invention is to provide a dental composite resin for fitting natural teeth and a preparation method thereof, which comprises mixing a phosphorus-containing quantum dot with a dental composite resin having a fluorescent expression to make a fluorescence emission spectrum and a natural tooth. Spectral fitting, so its appearance will be closer to the true texture of natural teeth.

Another object of the present invention is to provide a dental composite resin for fitting natural teeth and a preparation method thereof, wherein the phosphorus-containing quantum dots used are not biologically toxic and do not contain cadmium metal, thereby causing no health hazard to the living body. It is environmentally friendly.

A further object of the present invention is to provide a dental composite resin for fitting natural teeth and a preparation method thereof, wherein the fluorescence of the phosphorus-containing quantum dots used is relatively stable and has industrial application value.

In order to achieve the above object, the present invention discloses a dental composite resin for fitting natural teeth and a preparation method thereof. The content of the dental composite resin is coated in a resin matrix to coat a plurality of first indium phosphide quantum dots and a plurality a second indium phosphide quantum dot, wherein the first first indium phosphide quantum dots have a first light-emitting wavelength of 527 nm, and the second plurality of indium phosphide quantum dots are second-emitting. The wavelength is 553 nm.

1‧‧‧ Dental Composite Resin

11‧‧‧First Indium Phosphide Quantum Dots

12‧‧‧Second indium phosphide quantum dots

13‧‧‧Inorganic filler particles

14‧‧‧Resin matrix

The first drawing is a schematic view of a composition of a preferred embodiment of the present invention; the second drawing is a flow chart of the preparation method of a preferred embodiment of the present invention; The second comparative map of indium phosphide quantum dots, resin and natural teeth is shown in the invention; the fourth figure is a comparison chart of the first indium phosphide quantum dots, the resin and the natural tooth release spectrum of the invention; Figure: is a comparison chart of the emission spectrum of a preferred embodiment of the present invention; Figure 6 is a comparison diagram of chromaticity coordinates of a preferred embodiment of the present invention; Figure 7 is a comparison chart of results of an aging test according to a preferred embodiment of the present invention; and an eighth figure: It is a comparison chart of the results of the biocompatibility test of a preferred embodiment of the present invention.

In order to give the review board members a better understanding and understanding of the features and effects of the present invention, the preferred embodiment and the detailed description are as follows: due to the poor stability of the past dental composite resin or It is a cadmium-containing metal, which is not a good practical material. Therefore, the present invention provides a dental composite resin for fitting natural teeth, particularly a fluorescence emission spectrum thereof, and a preparation method thereof, which is good for this disadvantage. Performance, stability and non-toxicity replace the past products.

First, referring to the first figure, the dental composite resin 1 of the present invention has a resin matrix 14 as a coating material, and a plurality of first indium phosphide quantum dots 11 and a plurality of second indium phosphide quantum dots 12 are evenly packaged. Covered in it. The main function of the resin matrix 14 is to bond the various components of the composite resin together, thereby imparting plasticity, curing properties and strength, and the material is usually urethane dimethacrylate mixed with low viscosity. Diethylene glycol dimethacrylate, however, is not limited thereto.

The first indium phosphide quantum dot 11 has a particle diameter of about 2 to 5 nm, and the material is, as the name suggests, indium phosphide (InP), which has a first light-emitting wavelength of 527 nm. Green; the second indium phosphide quantum dot 12 is also composed of indium phosphide, and has a second light-emitting wavelength of 553 nm, which is yellow. This plurality is mixed with resin The indium phosphide quantum dots in the matrix 14 can be fitted to the fluorescence emission spectrum close to the natural teeth, so that the appearance of the dental composite resin 1 can be approximated to the natural teeth.

In addition to the light-emitting indium phosphide quantum dots, a plurality of inorganic filler particles 13 are further mixed in the dental composite resin 1. The plurality of inorganic filler particles 13 can affect the properties of the dental composite resin 1, such as abrasion resistance, toughness, hardness or polishability, etc., so that the composite resin has excellent physicochemical properties. The inorganic filler particles 13 used in the present invention contain silicate or zirconia (ZrO ₂ ).

In the present invention, for the preparation method of the dental composite resin 1 for fitting the fluorescence emission spectrum of the natural tooth, please refer to the second figure; as shown in the figure, the steps include: Step S1: using indium chloride ( Preparing a plurality of indium phosphide quantum dots by using InCl ₃ ), Tris (dimethylamino)phosphine and Dodecylamine; Step S2: centrifuging the plurality of indium phosphide quantum dots to obtain a plurality of first indium phosphide quantum dots and a plurality of second indium phosphide quantum dots; and step S3: mixing or doping the plurality of first indium phosphide quantum dots and the plurality of second indium phosphide quantum dots A dental composite resin is obtained in a resin matrix.

As described above, the first indium phosphide quantum dots 11 and the second indium phosphide quantum dots 12 mixed in the resin matrix 14 in these steps have a first light-emitting wavelength and a second light-emitting wavelength, respectively. The wavelength is sequentially 527 nm and 553 nm, and the resin matrix 14 is also coated with inorganic filler particles 13 such as citrate or zirconia.

The following is a detailed practical preparation and testing procedure of the dental composite resin for fitting natural teeth of the present invention; wherein, the light-emitting wavelength codes of the third to seventh figures are as follows:

[Preparation of Indium Phosphide Quantum Dots]

Using indium chloride (InCl ₃ ), tris (dimethylamino) phosphine and dodecylamine as precursors, solvothermal method (Solvothermal Method), through centrifugation step The quantum dots are separated into particle sizes of different sizes, and the luminous efficiency of the indium phosphide quantum dots is increased by a photoetching step and dispersed in chloroform (CHCl ₃ ).

[Mixed Indium Phosphide Quantum Dots on Resin Matrix Test Pieces]

Select weaker fluorescence intensity than the natural tooth resin ^{Filtek TM Z350 XT (3M ESPE,} USA) and mixed. The indium phosphide quantum dots dispersed in chloroform at a wavelength of 553 nm and 527 nm were dispersed, and after drying, a scale of 0.3 mg was mixed with an appropriate amount of the resin matrix. After uniformly mixing the two, put them into a plastic mold, cover them with a cover glass, and gently press the coverslip so that the resin and the cover glass fit closely to make the surface of the test piece flat. The front and back sides were evenly irradiated with a polymer light source (LED Curing Light, output light intensity of 500-700 mW/cm 2 ) for 40 seconds to prepare a circular test piece having a diameter of 10 mm and a thickness of 2 mm, and stored at room temperature. .

[Xenon test chamber aging test]

A test piece made of the above-mentioned circular test piece and a non-fluorescent reaction Polofil Supra (VOCO GmbH, Cuxhaven, Germany) composite resin mixed with an indium phosphide quantum dot having a wavelength of 620 nm, 0.5 mg, each set Three pieces were stored at 37 ° C and 100% humidity for 24 hours.

The aging test was carried out by the Materials and Engineering Laboratory of Taiwan Inspection Technology Co., Ltd. According to the American Society for Testing Materials (ASTM) Standard Practice for Operating Xenon Arc Light Apparatus for Exposure of Non-Metallic Materials (G155), Q is used. -SUN Xe-1-S test chamber is cycled one (cycle 1), the condition environment is set to xenon arc lamp through the daylight filter, the irradiation wavelength is set to 340 nm, the light intensity is 0.35 W/m 2 , and the temperature is 63 ° C ± 2 ° C. The test cycle was once for 120 minutes, irradiated in a 50% humidity environment for 102 minutes and sprinkled with water, and then irradiated for 18 minutes for a total of 60 cycles for 120 hours. After the test, the test piece was placed in an environment of 100% humidity.

[Biocompatibility test]

The indium phosphide quantum dots with a wavelength of 620 nm are taken, and the indium phosphide quantum dots are treated by first washing the dried indium phosphide quantum dots with anhydrous alcohol to remove chloroform, and repeating three times. A 1.0 mg indium phosphide quantum dot was mixed with an appropriate amount of a non-fluorescent reaction composite resin Polofil Supra (VOCO GmbH, Cuxhaven, Germany) to prepare an experimental group. This biocompatibility test is carried out in accordance with the instructions of Section 12 of the International Standard for Biocompatibility of Medical Devices (ISO 10993-1:2007). After mixing uniformly, a circular test piece having a diameter of 8 mm and a thickness of 1.2 mm was prepared, and the total surface area per test piece was 4.62 cm 2 . During the test, Polofil Supra, a composite resin without adding indium phosphate quantum dots, was used as a positive control group, and was immersed in 10 ml of medium; The medium in which any sample was soaked was a negative control group. The sample medium was placed in an environment of 37 ° C and 5% carbon dioxide for 24 hours, and then filtered with a Syringe-driven filter (pore size 0.22 μm) as a test medium. A five-day cell viability assay was performed according to the instructions in Section 5 of the International Standard for Biocompatibility of Medical Devices (ISO 10993-1:2009).

[Plastic composite resin test piece of mixed indium phosphide quantum dots]

The third graph Filtek ^TM Z350 XT mixed resin of reproducing light having a wavelength of 553 nm InP quantum dots with other conditions comparing shine radiation spectrum; fourth graph Filtek ^TM Z350 XT hybrid resin having a wavelength of 527 nm shine The radiation spectroscopy spectrum of indium phosphide quantum dots compared with other conditions; the fifth diagram is a radiation spectroscopy spectrum which is compared with other conditions in which phosphide quantum dots having a wavelength of 553 and 527 nm are simultaneously mixed. By comparison, when the second indium phosphide quantum dot with a wavelength of 553 nm is added, the radiation peak is the same as that of the unjoined test piece, but its intensity is decreased, and there is also a peak at 553 nm; After the first indium phosphide quantum dot of 527 nm, the peak intensity also decreased. Although there was no obvious peak at 527 nm, the waveform was observed to be flat, and the emission wavelengths of 553 nm and 527 Nai were simultaneously added. After the indium phosphide quantum dots, the waveform becomes more flat.

The sixth figure is to convert the data of the emission spectrum into the chromaticity coordinates represented by the resin test pieces by the formula of the Chromaticity diagram set by the International Commission on Illumination in 1931, namely: InP-553 ( 0.2729, 0.2998), InP-527 (0.2406, 0.2456) and InP-553+InP527 (0.2763, 0.3128), the mixed test piece can be found, and the closer the chromaticity coordinates are to the white light region.

[Results of aging test of xenon lamp test chamber]

The radiation spectrum before and after the aging test is as shown in the seventh figure, and the radiation spectrum is observed. After the aging test of the commercially available composite resin, the fluorescence intensity is reduced to 50 to 70% before aging. The peak wavelength is changed to a red shift of 11 to 28 nm. The resin with mixed indium phosphate quantum dots has a peak wavelength of about 615-619 nm before the aging test. After the aging test, the peak wavelength changes to a blue shift of 589-597 nm; its fluorescence intensity can be maintained at 5 ~30%.

[Results of biocompatibility test]

On the fifth day, the cell survival test results are shown in the eighth figure. The cell survival rate is analyzed by one-way analysis of variance. The average number of tests is the same, the significant level is 0.05, and the calculated result is p<0.0001. Group survival rates were not statistically significantly different. Further, the Tukey's studentized range test was compared, and the test conditions of the mixed indium phosphide quantum dots showed no statistically significant difference in cell survival compared with the control group.

According to the dental composite resin for fitting natural teeth disclosed in the present invention and a preparation method thereof, the dental composite resin formed by mixing the phosphorus-containing quantum dots having a light-emitting wavelength of 527 nm and 553 nm in the resin matrix can Fitted with the spectrum of natural teeth, the appearance will be closer to the true texture of natural teeth, and based on the cadmium-free, it can meet the health and environmental requirements, and has substantial economic benefits.

The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the variations, modifications, and modifications of the shapes, structures, features, and spirits described in the claims of the present invention. All should be included in the scope of the patent application of the present invention.

1‧‧‧ Dental Composite Resin

11‧‧‧First Indium Phosphide Quantum Dots

12‧‧‧Second indium phosphide quantum dots

13‧‧‧Inorganic filler particles

14‧‧‧Resin matrix

Claims (12)

A composite resin comprising: a resin matrix having a plurality of first indium phosphide (InP) quantum dots and a plurality of second indium phosphide quantum dots; wherein the plurality of first indium phosphide The quantum dot has a first light-emitting wavelength, and the plurality of second indium phosphide quantum dots have a second light-emitting wavelength. The composite resin according to claim 1, wherein the first light-emitting wavelength is 527 nm. The composite resin according to claim 1, wherein the second light-emitting wavelength is 553 nm. The composite resin according to claim 1, wherein the plurality of first indium phosphide quantum dots have a particle size of 2 to 5 nm. The composite resin according to claim 1, which comprises a plurality of inorganic filler particles. The composite resin according to claim 5, wherein the plurality of inorganic filler particles comprise silicate or zirconia. A composite resin preparation method, the method comprising: preparing a plurality of indium phosphide quantum dots; centrifuging the plurality of indium phosphide quantum dots to obtain a plurality of first indium phosphide quantum dots and a plurality of second indium phosphide quantum dots And mixing or doping the plurality of first indium phosphide quantum dots and the plurality of second indium phosphide quantum dots in a resin matrix; The plurality of first indium phosphide quantum dots have a first light emission wavelength, and the plurality of second indium phosphide quantum dots have a second light emission wavelength. The method for preparing a composite resin according to claim 7, wherein a plurality of indium phosphide quantum dots are prepared by using indium chloride (InCl ₃ ), tris (dimethylamino) phosphine, and Dodecylamine. The method for preparing a composite resin according to claim 7, wherein the first light-emitting wavelength is 527 nm. The method for preparing a composite resin according to claim 7, wherein the second light-emitting wavelength is 553 nm. The method for preparing a composite resin according to claim 7, wherein the step further comprises: mixing a plurality of inorganic filler particles in the resin matrix. The method for producing a composite resin according to claim 11, wherein the plurality of inorganic filler particles comprise citrate or zirconia.