KR102558011B1 - Silicate composition having luminescence properties similar to natural teeth and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a silicate-based phosphor composition having a luminescent property similar to that of natural teeth of a person to be treated by doping a host material with divalent cations of rare earth elements (REE) in a specific ratio, and a method for producing the same. By providing a phosphor composition having luminescent properties similar to natural teeth of a person to be treated, it is possible to improve aesthetic effects on tooth appearance.

Description

Silicate-based composition having luminescent properties similar to natural teeth and method for preparing the same

The present invention relates to a silicate-based phosphor composition and a method for producing the same, and more specifically, to a host material by doping rare earth elements (REE) metal divalent cations in a specific ratio to a silicate-based phosphor composition having light emitting characteristics similar to those of natural teeth of a person to be treated, and a method for producing the same.

In general, when a tooth is lost due to damage or loss due to caries or fracture, a great obstacle occurs in pronunciation, chewing, and aesthetics. In addition, when adjacent teeth move into an empty space where there are no teeth, and the normal arrangement of the teeth starts to shift, food gets caught between the teeth, resulting in tooth decay or tooth decay and bad breath. In particular, damage or missing molars can cause malnutrition because they cannot eat properly. In addition, damage or deficiency of the front teeth not only causes aesthetic problems, but also increases the probability of secondary caries occurring in the damaged or missing area.

Therefore, for patients with such damage or loss of teeth, chewing and aesthetic treatment such as dental restoration, which is a tooth replacement treatment, is performed.

Due to the special environment in the oral cavity, dental restorative materials require various properties, such as occlusal pressure, biological tissue intimacy, and hypersensitivity reactions, unlike general materials. In recent years, color harmony with hemorrhoids should also be considered, reflecting the increase in individual aesthetic desires due to the development of mass media.

In 1991, Studel confirmed that natural teeth exhibit strong blue fluorescence under irradiation with an ultraviolet beam. These properties make natural teeth appear whiter and brighter in daylight. In addition, it was confirmed by Clark that this characteristic is due to fluorescence appearing on teeth in the oral cavity. After this, many researchers observed that the fluorescence spectrum of natural teeth shows the widest band at a wavelength of about 410 nm to 420 nm, which is characteristic of blue mauve, and gradually decreases to 680 nm.

When these natural teeth are exposed to ultraviolet radiation (ultraviolet radiation) in the oral cavity, various fluorescence appears from a single tooth or between teeth. The fluorescence of natural teeth has a great effect on the length and area of the teeth. Western teeth are larger than Asians in length and area, so they are close to bluish-white, and in the case of Asians, reddish from the gums. It is close to yellowish-white.

Therefore, it is necessary to develop a phosphor composition that is similar to natural teeth in light emitting characteristics and can satisfy different aesthetic needs.

Accordingly, the present inventors prepared a silicate-based phosphor composition containing divalent cations of rare earth metals, and the composition according to the present invention adjusts the doping concentration of divalent cations of rare earth metals, thereby confirming that natural teeth can exhibit light emitting properties similar to those.

Accordingly, an object of the present invention is to provide a silicate-based phosphor composition.

Another object of the present invention is to provide a method for preparing a silicate-based phosphor composition.

Another object of the present invention is to provide a dental composition comprising a silicate-based phosphor composition.

Another object of the present invention relates to a method of applying a silicate-based phosphor composition.

The present invention relates to a silicate-based phosphor composition and a method for producing the same, and more specifically, to a silicate-based phosphor composition having light-emitting characteristics similar to natural teeth of a person to be treated by adjusting the doping ratio of a rare earth element (REE) metal divalent cation in a host material, and a method for manufacturing the same.

Hereinafter, the present invention will be described in more detail.

An example of the present invention relates to a silicate-based phosphor composition represented by Chemical Formula 1.

[Formula 1]

(AE _1-xy REE1 _x REE2 _y )Al ₂ Si ₂ O ₈

In the present invention, the term “mother crystal material” may mean Al ₂ Si ₂ O ₈ .

In the present invention, AE may mean an alkaline earth element selected from the group consisting of barium (Ba), strontium (Sr), calcium (Ca), etc., for example, may be calcium, but is not limited thereto.

In the present invention, the alkaline earth metal may mean a Group 2 element group on the periodic table of elements.

In the present invention, REE1 is lanthanum (La), gadolinium (Gd), yttrium (Y), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (T m) may be any rare earth metal (rare earth elements, REE) selected from the group consisting of, for example, europium, but is not limited thereto.

In the present invention, REE2 is lanthanum (La), gadolinium (Gd), yttrium (Y), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (T m) may be any one rare earth metal (rare earth elements, REE) selected from the group consisting of, for example, terbium, but is not limited thereto.

In the present invention, the term “rare earth elements (REE)” may mean a metal belonging to the group of atomic numbers 57 to 71 on the periodic table of elements.

In the present invention, x may be 0<x≤0.15, which means that x does not include 0 and includes 0.15, but has a value between 0 and 0.15.

In the present invention, the element ratio of the chemical formula is generally described as an integer, but if the ratio of elements contained in one molecule such as alloys or special minerals is complicated, it is simpler to describe as a decimal rather than as an integer.

In the present invention, x is the ratio of the rare earth metal REE2 doped at the site of the rare earth metal REE1 of the parent crystal in the chemical formula, and can be expressed as wt% or mol% depending on the synthesis method such as the solid phase method and the liquid phase method. For example, in the case of 5 wt% or 5 mol%, x may be 0.05.

In the present invention, x may be 0.01 to 0.15, 0.01 to 0.13, 0.01 to 0.11, 0.01 to 0.09, 0.03 to 0.15, 0.03 to 0.13, 0.03 to 0.11 or 0.03 to 0.09, for example, 0.03 to 0.09. However, it is not limited thereto.

In the present invention, y may be 0≤y≤0.15, which means that y includes 0 and 0.15, but has a value between 0 and 0.15.

In the present invention, y may be 0 to 0.05, 0 to 0.04, 0.01 to 0.05, or 0.01 to 0.04, for example, 0.01 to 0.03, but is not limited thereto.

y may represent the mol% concentration of the rare earth metal as a decimal number in the aqueous solution, and for example, when the concentration of the rare earth metal in the aqueous solution is 1 mol%, y may be 0.01.

In the present invention, the term "doping" may refer to an act of improving or reforming the properties of a parent crystal material by adding a small amount of another material to the parent crystal material in the field of metallurgy.

In one embodiment of the present invention, the silicate-based composition represented by Chemical Formula 1 may be (Ca _0.95 Eu _0.05 )Al ₂ Si ₂ O ₈ .

In one embodiment of the present invention, the silicate-based composition represented by Formula 1 may be (Ca _0.85 Eu _0.12 Tb _0.03 )Al ₂ Si ₂ O ₈ .

In one embodiment of the present invention, the silicate-based composition represented by Chemical Formula 1 may be (Ca _0.87 Eu _0.12 Tb _0.01 )Al ₂ Si ₂ O ₈ .

In the present invention, the average particle diameter of the phosphor composition is 0.01 to 10 um, 0.01 to 8 um, 0.01 to 6 um, 0.01 to 4 um, 0.1 to 10 um, 0.1 to 8 um, 0.1 to 6 um, 0.1 to 4 um, 1 to 10 um, 1 to 8 um, 1 to 6 um , 1 to 4 um, 2 to 10 um, 2 to 8 um, 2 to 6 um, 2 to 4 um, 3 to 10 um, 3 to 8 um, 3 to 6 um, or 3 to 4 um, for example, It may be 3 um, but is not limited thereto.

In the present invention, the emission wavelength of the phosphor composition is 420 to 600 nm, 420 to 590 nm, 420 to 580 nm, 420 to 570 nm, 420 to 560 nm, 420 to 550 nm, 420 to 540 nm, 420 to 530 nm, 420 to 520 nm, 420 to 510 nm, 430 to 600 nm, 430 to 590 nm, 430 to 580 nm, 430 to 570 nm, 430 to 560 nm, 430 to 550 nm, 430 to 540 nm, 430 to 530 nm, 430 to 520 nm, 430 to 510 nm, 440 to 600 nm, 44 0 to 590 nm, 440 to 580 nm, 440 to 570 nm, 440 to 560 nm, 440 to 550 nm, 440 to 540 nm, 440 to 530 nm, 440 to 520 nm, 440 to 510 nm, 450 to 600 nm, 450 to 590 nm, 450 to 580 nm, 450 to 570 nm, 450 to 560 nm, 450 to 550 nm, 450 to 540 nm, 450 to 530 nm, 450 to 520 nm, 450 to 510 nm, 460 to 600 nm, 460 to 590 nm, 460 to 580 nm, 460 to 5 70 nm, 460 to 560 nm, 460 to 550 nm, 460 to 540 nm, 460 to 530 nm, 460 to 520 nm, 460 to 510 nm, 470 to 600 nm, 470 to 590 nm, 470 to 580 nm, 470 to 570 nm, 470 to 560 nm, 470 to 550 nm, 470 to 540 nm, 470 to 530 nm, 470 to 520 nm, 470 to 510 nm, 480 to 600 nm, 480 to 590 nm, 480 to 580 nm, 480 to 570 nm, 480 to 560 nm, 480 to 550 nm, It may be 480 to 540 nm, 480 to 530 nm, 480 to 520 nm, or 480 to 510 nm, for example, 480 to 510 nm, but is not limited thereto.

Another example of the present invention relates to a method for preparing a silicate-based phosphor composition comprising the following steps:

Calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), silicon oxide (Silicon Dioxide, SiO ₂ ) and europium oxide [Europium(III) oxide, Eu ₂ O ₃ ] A preparation step of preparing a melt by dissolving in a solvent;

a drying step of drying the lysate to obtain a dry mixture;

a first calcination step of heat-treating the dry mixture under air conditions to obtain a first calcination mixture; and

A second calcination step of heat-treating the first calcination mixture under a mixed gas condition to obtain a second calcination mixture.

In the present invention, the preparation step is calcium carbonate (Calcium carbonate, CaCO ₃ ), aluminum oxide (Aluminium oxide, Al ₂ O ₃ ), silicon oxide (Silicon Dioxide, SiO ₂ ) and europium oxide [Europium (III) oxide, Eu ₂ O ₃ ] may be dry mixed and dissolved in a solvent to prepare a melt.

In the present invention, the solvent may be any one selected from the group consisting of distilled water, sulfuric acid aqueous solution, nitric acid aqueous solution, and hydrochloric acid aqueous solution, for example, distilled water, but is not limited thereto.

In the present invention, the phase of the lysate may be an aqueous solution, but is not limited thereto.

In the present invention, the drying step may be performed under a temperature condition of 100 to 200 ° C, 100 to 180 ° C, 100 to 160 ° C, 120 to 200 ° C, 120 to 180 ° C or 120 to 160 ° C, for example, It may be carried out under a temperature condition of 150 ° C, but is not limited thereto.

In the present invention, the drying step may be performed for 12 to 72 hours, 12 to 60 hours, 12 to 48 hours, 12 to 36 hours, or 12 to 24 hours, for example, it may be performed for 12 hours, but is not limited thereto.

If the drying step is performed for less than 12 hours, the solvent included in the melt may not be sufficiently evaporated, and the solvent may remain, contaminating the phosphor composition.

In the present invention, the first calcination step may be to heat-treat the dry mixture subjected to the drying step to obtain the first calcination mixture.

In the present invention, the first calcination step is 700 to 1100 ℃ 700 to 1050 ℃ 700 to 1000 ℃ 700 to 950 ℃, 700 to 900 ℃ 750 to 1100 ℃ 750 to 1050 ℃ 750 to 1000 ℃ under temperature conditions of 750 to 950 ℃ or 750 to 900 ℃ It may be performed, for example, it may be performed under a temperature condition of 750 to 900 ℃, but is not limited thereto.

In the present invention, the first calcination step may be performed for 6 to 24 hours, 6 to 20 hours, 6 to 16 hours, 6 to 12 hours, or 6 to 8 hours, for example, 6 to 8 hours. It may be performed, but is not limited thereto.

In the present invention, the second calcination step may be a step of obtaining a second calcination mixture by calcination of the first calcination mixture.

In the present invention, the second calcination step is 700 to 1100 ℃ 700 to 1050 ℃ 700 to 1000 ℃ 750 to 1100 ℃ 750 to 1050 ℃ 750 to 1000 ℃ 800 to 1100 ℃, 800 to 1050 ℃, 800 to 1000 ℃, 900 to 1100 ℃, 900 to 1050 ℃ or may be carried out under a temperature condition of 900 to 1000 ℃, for example, it may be carried out under a temperature condition of 900 to 1000 ℃, but is not limited thereto.

In the present invention, the second calcination step may be performed for 6 to 24 hours, 6 to 20 hours, 6 to 16 hours, 8 to 24 hours, 8 to 20 hours, 8 to 16 hours, 10 to 24 hours, 10 to 20 hours or 10 to 16 hours, for example, it may be performed for 10 to 16 hours, but is not limited thereto.

In one embodiment of the present invention, the second calcination step may be performed under a mixed gas condition including H ₂ and N ₂ gases for reducing doped rare earth metal ions and not including other types of gases.

In the present invention, the mixed gas may contain 5 to 10%, 5 to 9%, 5 to 8%, 5 to 7%, or 5 to 6% of H ₂ gas based on the molar gas fraction of the total gas, For example, it may contain 5%, but is not limited thereto.

In the present invention, the mixed gas may contain 90 to 95%, 91 to 95%, 92 to 95%, 93 to 95%, or 94 to 95% of N ₂ gas based on the molar gas fraction of the total gas, for example, it may contain 95%, but is not limited thereto.

In the present invention, the phosphor manufacturing method may further include a pulverization step of pulverizing the second calcination mixture after the second calcination step is completed.

In the present invention, the pulverization step may be pulverization of the calcined mixture with any one of a fine pulverizer or an ultra pulverizer, but is not limited thereto.

In the present invention, the pulverizer may be any one selected from the group consisting of a ball mill, a vibration mill, a roller mill, a jet mill, and a planetary mill, and may be, for example, a ball mill, but is not limited thereto.

In the present invention, the grinding step may be performed for 6 to 24 hours, 6 to 20 hours, 6 to 16 hours, 6 to 12 hours, or 6 to 8 hours, for example, it may be performed for 6 hours, but is not limited thereto.

In the present invention, when the pulverization step is performed for less than 6 hours, the borate-based phosphor composition is not sufficiently pulverized, and the uniformity of the pulverized powder is reduced, so it may be difficult to implement a smooth surface when applied (applied) to teeth.

Another example of the present invention is to provide a dental composition comprising the silicate-based phosphor composition represented by Formula 1.

[Formula 1]

(AE _1-xy REE1 _x REE2 _y )Al ₂ Si ₂ O ₈

In the present invention, the formulation of the dental composition may be any one or more selected from the group consisting of dental restorations, dental prostheses, and dental prosthesis surface treatment agents, but is not limited thereto.

In the present invention, teeth may mean natural teeth and/or artificial teeth.

Another example of the present invention relates to a method of applying a phosphor composition comprising the following steps:

A mixing step of preparing a coating material by mixing a powder mixture including the phosphor composition represented by Formula 1 and the powder, and a binder;

an application step of applying the application material to a target object; and

A heat treatment step of raising the temperature of the coating material applied to the object to a temperature condition of 300 to 900 ° C. at a heating rate of 40 to 60 ° C./min and maintaining it in an isothermal state for 20 to 40 minutes.

[Formula 1]

(AE _1-xy REE1 _x REE2 _y )Al ₂ Si ₂ O ₈

In the present invention, the powder is a dental glaze powder, which may mean a dental material for giving gloss to artificial teeth to cause aesthetics, but is not limited thereto.

In the present invention, the powder mixture may include the phosphor composition represented by Formula 1 and the powder, but is not limited thereto.

In the present invention, the weight ratio (w/w%) of the phosphor composition and the powder included in the powder mixture may be 2:8, but is not limited thereto.

In the present invention, the binder may be propylene glycol (propylene glycol), but is not limited thereto, and a suitable binder may be used to facilitate moldability of the silicate-based phosphor composition.

In the present invention, the weight ratio (w / w%) of the powder mixture included in the coating may be 50 to 70% by weight, 50 to 65% by weight, 50 to 60% by weight, 55 to 70% by weight, 55 to 65% by weight or 55 to 60% by weight, but is not limited thereto.

In the present invention, the weight ratio (w / w%) of the binder included in the coating is 30 to 50% by weight, 30 to 45% by weight, 35 to 50% by weight, 35 to 45% by weight, 40 to 50% by weight or 40 to 45% by weight, but is not limited thereto.

In the present invention, the coating material may be a mixture of a powder mixture and a binder so as to have a viscosity to be properly applied to the target object, but is not limited thereto.

In the present invention, the temperature increase rate of the heat treatment step is 40 to 60 °C/min, 40 to 58 °C/min, 40 to 56 °C/min, 40 to 54 °C/min, 40 to 52 °C/min, 42 to 60 °C/min, 42 to 58 °C/min, 42 to 56 °C/min, 42 to 54 °C/min, 42 to 52 °C/min, 44 to 60 ℃/min, 44 to 58 ℃/min, 44 to 56 ℃/min, 44 to 54 ℃/min, 44 to 52 ℃/min, 46 to 60 ℃/min, 46 to 58 ℃/min, 46 to 56 ℃/min, 46 to 54 ℃/min, 46 to 52 ℃/min, 48 to 60 ℃/min, 4 It may be 8 to 58 °C/min, 48 to 56 °C/min, 48 to 54 °C/min or 48 to 52 °C/min, for example, 48 to 52 °C/min, but is not limited thereto.

In the present invention, the heat treatment step is 300 to 900 ℃, 300 to 800 ℃, 300 to 700 ℃, 300 to 600 ℃, 400 to 900 ℃, 400 to 800 ℃, 400 to 700 ℃, 400 to 600 ℃, 500 to 900 ℃, 500 to 800 ℃, 500 to 700 °C or 500 to 600 °C, but may be performed at a temperature condition of, for example, 500 to 600 °C, but is not limited thereto.

In the present invention, the heat treatment step may be to maintain an isothermal state for 20 to 40 minutes, 20 to 35 minutes, 25 to 40 minutes, or 25 to 30 minutes, for example, 25 to 30 minutes It may be to maintain an isothermal state, but is not limited thereto.

The present invention relates to a silicate-based phosphor composition having light emitting properties similar to natural teeth of a person to be treated by doping a host material with divalent cations of rare earth elements (REE) in a specific ratio, and a method for producing the same. Since the luminescent properties of the phosphor composition can be adjusted by adjusting the doping concentration ratio of the rare earth metal divalent cations, it is possible to improve the aesthetic effect of the teeth of the person to be treated.

1 is a graph showing emission characteristics (PL/PLE) of a silicate-based phosphor composition according to an experimental example of the present invention.
Figure 2 is a graph analyzing the XRD pattern of the silicate-based phosphor composition of the present invention.
FIG. 3 is a photograph taken to analyze the apparent light emission characteristics by applying a silicate-based phosphor composition to a substrate according to an experimental example of the present invention.
4 is a graph analyzing apparent light emission characteristics (PL/PLE) when a silicate-based phosphor composition is applied according to an experimental example of the present invention.

Terms used in this specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, terms such as “include” or “have” are intended to indicate that the features, components, etc. described in the specification exist, but one or more other features or components do not exist or cannot be added.

Unless otherwise defined herein, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined herein, they are not interpreted in an ideal or excessively formal meaning.

As used herein, the terms "about", "substantially", and the like are used at or in the vicinity of a numerical value when manufacturing and material tolerances inherent in the stated meaning are given, and accurate or absolute figures are used to aid understanding of the present invention and to prevent unscrupulous infringers from unfairly using the stated disclosure. Also, in the present specification, “step of” or “step of” does not mean “step for”.

In the present invention, the term “excitation wavelength” may refer to a wavelength of light that excites electrons of a phosphor composition to have a high energy level, and in general, an excitation spectrum may match an absorption spectrum.

In the present invention, the term "emission wavelength" may mean the wavelength of light emitted by the phosphor composition when electrons excited to have a high energy level lose energy and return to the energy level before excitation.

Hereinafter, the present invention will be described in more detail through preparation examples and examples. These preparation examples and examples are only for explaining the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these preparation examples and examples according to the gist of the present invention.

manufacturing example. Preparation of silicate-based phosphor composition using WASSR method (Water assisted solid state reaction)

Calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), silicon oxide (Silicon Dioxide, SiO ₂ ), and europium oxide (Europium(III) oxide, Eu ₂ O ₃ ) were dry mixed and mixed with 10% by weight of water based on the total weight of the mixture to prepare a mixture.

Table 1 shows the mol% ratios of Ca ²⁺ ions, Eu ²⁺ ions, and Tb ²⁺ ions included in the mixtures of Examples 1 to 3.

ingredient Example 1 Example 2 Example 3 Ca (mol%) 95 85 87 Eu (mol%) 5 12 12 Tb (mol%) - 3 One Sum 100 100 100

The mixtures of Examples 1 to 3 were sufficiently dried at a temperature of 80° C. for 12 hours to obtain a dried product. The obtained dried material was subjected to a first heat treatment (first calcination step) under air conditions at a temperature of 800° C. for 6 hours to obtain a first calcination mixture (first calcination mixture). A second calcination mixture (second calcination mixture) was obtained by subjecting the first calcination mixture to a second heat treatment (second calcination step) under a mixed gas condition containing 95% N ₂ and 5% H ₂ based on the molar gas fraction of the total gas at a temperature of 950 ° C. for 12 hours.

The second calcined mixture was ground for 6 hours using a ball mill so that the average particle diameter of the mixture was 10 um or less, and the silicate-based phosphor composition of Examples 1 to 3 having a white (or ivory) body color [(AE _1-xy REE1 _x REE2 _y )Al ₂ Si ₂ O ₈ ] was prepared.

Experimental Example 1. PL/PLE analysis of silicate-based phosphor composition

The silicate-based phosphor compositions of Examples 1 to 3 were analyzed for photoluminescence and excitation wavelength using a spectrofluorometer at room temperature.

When the silicate-based phosphor composition is irradiated with a light source having a wavelength (λ _ex ) of 365 to 405 nm, emission characteristics of the composition are shown in FIG. 1 and Table 2.

Example 1 Example 2 Example 3 Emission wavelength (nm) 505 550 550 Luminous intensity (a.u.) 2150 2500 2010

Experimental Example 2. XRD pattern analysis of silicate-based phosphor composition

The result of analyzing the XRD pattern of the silicate-based phosphor composition of Example 1 using X-ray diffraction (XRD) is shown in FIG. 2 .

As can be seen in FIG. 2, the single phase of the control group (CaAl ₂ Si ₂ O ₈ ) was well displayed, and other impurities were not detected in the silicate-based phosphor composition of Example 1 [(Ca _0.95 Eu _0.05 ) Al ₂ Si ₂ O ₈ ].

Experimental Example 3. Luminescence characteristics upon application of silicate-based phosphor composition

A powder mixture was prepared by mixing the silicate-based phosphor composition and IPS e.max Ceram Glaze powder at a ratio of 2:8 (w/w%). A paste (applied product) was prepared by mixing the powder mixture and a binder (propylene glycol) at a ratio of 7:3 to 5:5 (w/w%), and then applied to a glass ceramic block (e.max CAD block, Ivoclar vivadent). Heat treatment was performed for a total of 30 minutes while heating at a rate of 50 °C/min from room temperature to a temperature condition of 300 to 700 °C.

According to Table 3, the pastes of Examples 1 and 4 without heat treatment, 300 ° C. of Example 5, 400 ° C. of Example 6, 500 ° C. of Example 7, 600 ° C. of Example 8 or 700 ° C. of Example 8 Pastes subjected to heat treatment at a temperature in the temperature range were prepared.

Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Ca (mol%) 95 95 95 95 95 95 Eu (mol%) 5 5 5 5 5 5 Heat treatment temperature (℃) not implemented 300 400 500 600 700

When the substrates coated with Examples 1 and 4 to 9 are irradiated with ultraviolet light of a wavelength of 365 nm, a photograph of the appearance of the light-emitting paste is shown in FIG. 3 .

PL/PLE graphs analyzing the emission characteristics of the applied phosphor composition and paste are shown in FIG. 4 and Table 4. The phosphor compositions of Examples 1 and 4 to 9 showed the emission intensity and emission wavelength in Table 5, and after correcting the emission intensity to show a constant emission intensity in order to effectively compare the emission wavelengths, they are shown in FIG. 4 .

Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Emission wavelength (nm) 470 446 448 448 452 449 Luminous intensity (a.u.) 775 559 940 1452 2590 2444

As can be seen from FIG. 4 and Table 4, even after mixing the phosphor composition with the binder and heat-treating, the phosphor composition maintained light emission.

In general, when a phosphor composition is heat treated at a high temperature, the phosphor composition interacts with the binder and the light emission disappears, whereas the phosphor composition is subjected to a very high-speed heat treatment to minimize the interaction and damage between the binder and the phosphor, thereby maintaining light emission.

Claims (15)

delete delete delete delete delete A method for preparing a dental composition comprising a silicate-based phosphor composition comprising the following steps:
Calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), silicon oxide (Silicon Dioxide, SiO ₂ ), and europium oxide (Europium(III) oxide, Eu ₂ O ₃ ) were dry-mixed so that the mol% ratio of Ca ²⁺ ions and Eu ²⁺ ions was 95:5, and mixed with 10% by weight of water based on the total weight of the mixture to obtain a mixture. preparation stage;
drying the mixture to obtain a dry mixture;
heat-treating the dry mixture under air conditions at a temperature of 800° C. for 6 hours to obtain a first calcined mixture;
heat-treating the first calcination mixture at a temperature of 950° C. for 12 hours under a mixed gas condition containing 95% N ₂ and 5% H ₂ based on the molar gas fraction of the total gas to obtain a second calcination mixture; and
Grinding using a ball mill so that the average particle diameter of the second calcined mixture is 10 μm or less. The method of claim 6, wherein the drying step is performed under a temperature condition of 100 to 200 °C. The method of claim 6, wherein the drying step is performed for 12 to 72 hours. delete delete delete delete delete delete delete