WO2022114396A1

WO2022114396A1 - Phosphor composition having similar luminescence characteristics to natural teeth and preparation method therefor

Info

Publication number: WO2022114396A1
Application number: PCT/KR2021/001746
Authority: WO
Inventors: 김원호; 조성찬; 김혜인; 김선욱; 정규진; 강태욱
Original assignee: 주식회사 메디파이브; 한국세라믹기술원
Priority date: 2020-11-26
Filing date: 2021-02-09
Publication date: 2022-06-02

Abstract

The present invention relates to a phosphor composition and a preparation method therefor and, specifically, to silicate-based, phosphate-based, and borate-based phosphor compositions and preparation methods therefor, wherein the compositions have similar luminescence characteristics to natural teeth of a subject to be treated, by doping a host material with metal cations of rare earth elements (REE) at a predetermined ratio.

Description

Phosphor composition having luminescent properties similar to natural tooth and method for preparing same

This patent application is based on the Korean Patent Application Nos. 10-2020-0161388 and 10-2020-0161389 submitted to the Korean Intellectual Property Office on November 26, 2020, and the Korean Patent Application filed with the Korean Intellectual Property Office on January 15, 2021. Priority is claimed to Application No. 10-2021-0005977, the disclosure of which is incorporated herein by reference.

The present invention relates to a phosphor composition and a method for manufacturing the same, and more specifically, by doping a host material with rare earth elements (REE) metal cations in a specific ratio, similar to the natural teeth of the person being treated. The present invention relates to a silicate-based, phosphate-based and borate-based phosphor composition having light-emitting properties and a method for preparing the same.

In general, when a tooth is lost due to damage or loss due to caries or fracture, a major impairment in pronunciation, mastication, and esthetics occurs. Also, when adjacent teeth move to an empty space without teeth, and the normal arrangement of the teeth starts to deviate, food gets caught between the teeth, causing cavities or bad breath, and bad breath occurs. In particular, damage or missing molars can lead to malnutrition because they can't eat properly. In addition, damage or loss of incisors not only causes aesthetic problems, but also increases the probability of secondary caries occurring in the damaged or missing area rapidly.

Therefore, masticatory and esthetic treatment such as dental restoration, which is a replacement treatment for teeth, is performed for patients who have suffered such damage or loss of teeth. It refers to sealing the cavity formed by cutting out the affected part of the required tooth with a tooth replacement material, and the tooth replacement material used at this time is a dental restoration material.

Different from general materials due to the special environment in the oral cavity, dental restorative materials require various characteristics such as occlusal pressure, intimacy with living tissue, and whether or not hypersensitivity reaction is caused. In recent years, with the development of mass media, individual aesthetic needs are increasing, and color harmony with hemorrhoids should be considered.

In 1991, Studel confirmed that natural teeth exhibit strong blue fluorescence under irradiation with an ultraviolet beam. This property makes natural teeth appear whiter and brighter in daylight. In addition, it has been confirmed by Clark that this characteristic is due to the fluorescence that appears on the teeth inside the oral cavity. After that, by many researchers, the fluorescence spectrum of the natural tooth showed the largest band at the wavelength of about 410 nm to 420 nm, which is a characteristic of the blue mauve, and gradually increased to 680 nm. was observed to decrease.

When these natural teeth are exposed to intraoral ultraviolet (ultraviolet radiation), various fluorescence appears from a single tooth or between teeth, although there is a difference from person to person, but the color is blue-white to yellowish-white. see. The fluorescence of natural teeth has a great influence on the length and area of teeth. Western teeth are closer to blue-white because they are larger than Asians in length and area, and in the case of Asians, yellow-wish white color ( yellowish-white).

Accordingly, there is a need to develop a phosphor composition that is similar to the luminescent properties of natural teeth and can satisfy different aesthetic needs.

Accordingly, the present inventors prepared silicate-based, phosphate-based and borate-based phosphor compositions containing cations of rare earth metals, and the composition according to the present invention adjusts the doping concentration of the rare earth metal cations, so that the luminescent properties of natural teeth are similar to those of natural teeth. It was confirmed that luminescent properties could be exhibited.

Accordingly, it is an object of the present invention 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.

Another object of the present invention is to provide a phosphate-based phosphor composition.

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

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

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

Another object of the present invention is to provide a borate-based phosphor composition.

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

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

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

The present invention relates to a phosphor composition and a method for preparing the same, and more particularly, by controlling the doping ratio of rare earth elements (REE) metal cations in a host material, similar to the natural teeth of the recipient. The present invention relates to a silicate-based, phosphate-based and borate-based phosphor composition having light-emitting properties and a method for preparing 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 the formula (1).

[Formula 1]

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

In the silicate-based phosphor composition of the present invention, the term “mother crystal material” may mean Al ₂ Si ₂ O ₈ .

In the present invention, AE may mean any one of alkaline earth elements selected from the group consisting of barium (Ba), strontium (Sr), and calcium (Ca), for example, calcium may be, 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 (Tm) may be any one selected from the group consisting of rare earth elements (REE), for example, For example, it may be 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 (Tm) may be any one selected from the group consisting of rare earth elements (REE), for example, For example, it may be 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 may mean that x does not include 0 but 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 included in one molecule, such as an alloy or special mineral, is complicated, and writing as a decimal is simpler than writing as an integer, it is a decimal It can also be written as

In the present invention, x in Formula 1 is the ratio of the rare earth metal REE2 doped to the REE1 site of the parent crystal in the formula, and can be expressed in wt% or mol% according to synthesis methods such as solid phase method and liquid phase method. For example, in the case of 5 wt% or 5 mol%, x may be 0.05.

In the present invention, x in Formula 1 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 It may be 0.09, but is not limited thereto.

In the present invention, y in Formula 1 may be 0≤y≤0.15, which may mean that y includes 0 and 0.15, but has a value between 0 and 0.15.

In the present invention, y in Formula 1 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.

In Formula 1, y may represent the mol% concentration of the rare earth metal in the aqueous solution as a decimal number. 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 action of improving or reforming the properties of the parent crystal material by adding a trace 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 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 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, It may be 3 to 6 um or 3 to 4 um, for example, 3 um, but is not limited thereto.

In the present invention, the emission wavelength of the silicate-based 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, 420-520 nm, 420-510 nm, 430-600 nm, 430-590 nm, 430-580 nm, 430-570 nm, 430-560 nm, 430-550 nm, 430-540 nm, 430-530 nm, 430-520 nm, 430-510 nm, 440-600 nm, 440-590 nm, 440-580 nm, 440-570 nm, 440-560 nm, 440-550 nm, 440-540 nm, 440-530 nm, 440-520 nm, 440-510 nm, 450-600 nm, 450-590 nm, 450-580 nm, 450-570 nm, 450-560 nm, 450-550 nm, 450-540 nm, 450-530 nm, 450-520 nm, 450-510 nm, 460-600 nm, 460-590 nm, 460-580 nm, 460-570 nm, 460-560 nm, 460-550 nm, 460-540 nm, 460-530 nm, 460-520 nm, 460-510 nm, 470-600 nm, 470-590 nm, 470-580 nm, 470-570 nm, 470-560 nm, 470-550 nm, 470-540 nm, 470-530 nm, 470-520 nm, 470-510 nm, 480-600 nm, 480-590 nm, 480-580 nm, 480-570 nm, 480- 560 nm, 480 to 550 nm, 480 to 540 nm, 480 to 530 nm, 480 to 520 nm, or 480 to 510 nm, for example, may be 480 to 510 nm, but is not limited thereto.

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

Calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), silicon dioxide (SiO ₂ ) and europium oxide [Europium(III) oxide, Eu ₂ O ₃ ] are dissolved in a solvent a silicate-based lysate preparation step of preparing a silicate-based lysate;

a silicate-based melt drying step of drying the silicate-based melt to obtain a silicate-based dry mixture;

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

A second silicate-based calcination step of heat-treating the first silicate-based calcined mixture under mixed gas conditions to obtain a second silicate-based calcined mixture.

In the present invention, the silicate-based melt 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 silicate-based lysate.

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 phase, but is not limited thereto.

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

In the present invention, the silicate-based melt 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, performed for 12 hours. may be, but is not limited thereto.

When the silicate-based melt drying step is performed for less than 12 hours, the solvent contained in the silicate-based melt may not sufficiently evaporate, and the solvent may remain, thereby contaminating the silicate-based phosphor composition.

In the present invention, the first silicate-based calcination step may be to obtain a first silicate-based calcination mixture by heat-treating the silicate-based dry mixture that has been subjected to the silicate-based melt drying step.

In the present invention, the first silicate-based calcination step is 700 to 1100 °C, 700 to 1050 °C, 700 to 1000 °C, 700 to 950 °C, 700 to 900 °C, 750 to 1100 °C, 750 to 1050 °C, 750 to 1000 °C , 750 to 950 ° C., or may be carried out under a temperature condition of 750 to 900 ° C. For example, it may be carried out under a temperature condition of 750 to 900 ° C., but is not limited thereto.

In the present invention, the first silicate-based 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 during, but is not limited thereto.

In the present invention, the second silicate-based calcination step may be a step of calcining the first silicate-based calcination mixture to obtain a second silicate-based calcination mixture.

In the present invention, the second silicate-based calcination step is 700 to 1100 °C, 700 to 1050 °C, 700 to 1000 °C, 750 to 1100 °C, 750 to 1050 °C, 750 to 1000 °C, 800 to 1100 °C, 800 to 1050 °C , 800 to 1000 ° C, 900 to 1100 ° C, 900 to 1050 ° C, or 900 to 1000 ° C. It is not limited.

In the present invention, the second silicate-based calcination step is 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. Alternatively, it may be performed for 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 silicate-based calcination step includes H ₂ and N ₂ gas for the reduction of doped rare earth metal ions, and is performed under a mixed gas condition that does not include other types of gases. it could be

In the present invention, the mixed gas may include 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 include 5%, but is not limited thereto.

In the present invention, the mixed gas may include 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 include 95%, but is not limited thereto.

In the present invention, the method for producing a silicate-based phosphor may further include a pulverization step of pulverizing the second silicate-based calcination mixture after the second silicate-based calcination step is completed.

In the present invention, the pulverizing step may be pulverizing the calcined mixture using either a fine pulverizer or an ultra pulverizer, but is not limited thereto.

In the present invention, the pulverizer is any one selected from the group consisting of a ball mill, a vibration mill, a roller mill, a jet mill, and a planetary mill. may be, for example, may be 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 silicate-based phosphor composition is not pulverized sufficiently, and the uniformity of the pulverized powder of the composition is lowered, so it may be difficult to implement a smooth surface when applied (applied) to the teeth. .

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

[Formula 1]

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

The formulation of the dental composition in the present invention may be any one or more selected from the group consisting of a dental restoration, a dental prosthesis, and a surface treatment agent for a dental prosthesis, but is not limited thereto.

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

Another embodiment of the present invention relates to a method of applying a silicate-based phosphor composition comprising the steps of:

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

a silicate-based coating material application step of applying the silicate-based coating material to an object; and

A silicate-based coating heat treatment step of raising the temperature of the silicate-based coating applied to the object to a temperature condition of 300 to 900°C at a temperature increase rate of 40 to 60°C/min and maintaining the isothermal state for 20 to 40 minutes.

[Formula 1]

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

In the present invention, the powder is a dental glaze powder, and may mean a dental material for giving an artificial tooth a gloss to create an aesthetic feeling, but is not limited thereto.

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

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

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

In the present invention, the weight ratio (w/w%) of the silicate-based powder mixture contained in the silicate-based coating material is 50 to 70% by weight, 50 to 65% by weight, 50 to 60% by weight, 55 to 70% by weight, 55 to It may be 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 contained in the silicate-based coating material is 30 to 50 wt%, 30 to 45 wt%, 35 to 50 wt%, 35 to 45 wt%, 40 to 50 wt% Or it may be 40 to 45% by weight, but is not limited thereto.

In the present invention, the silicate-based coating material may be a mixture of a silicate-based powder mixture and a binder to have a viscosity to be properly applied to an object, but is not limited thereto.

In the present invention, the temperature increase rate of the silicate-based coating 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 °C/min, 44 to 58 °C/min, 44 to 56 °C/min, 44 to 54 °C/min, 44 to 52 °C/min, 46 to 60 °C/min, 46 to 58 °C/min, 46 to 56 °C/min, 46 to 54 °C/min, 46 to 52 °C/min, 48 to 60 °C/min, 48 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. It may be °C / min, but is not limited thereto.

In the present invention, the silicate-based 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 ℃, or may be carried out at a temperature condition of 500 to 600 ℃, for example, it may be carried out at a temperature condition of 500 to 600 ℃, but limited thereto it is not

In the present invention, the silicate-based 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, isothermal state for 25 to 30 minutes. may be to maintain, but is not limited thereto.

Another embodiment of the present invention relates to a phosphate-based phosphor composition represented by the formula (2).

[Formula 2]

Rb(AE _1-x REE3 _x )PO ₄

In the phosphate-based phosphor composition of the present invention, the term “mother crystalline material” may mean rubidium carbonate (RbCO ₃ ).

In the present invention, REE3 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 (Tm) may be any one selected from the group consisting of rare earth elements (REE), for example, For example, it may be europium, but is not limited thereto.

In the present invention, x in Formula 2 is the ratio of the rare earth metal REE3 doped to the metal AE site of the parent crystal in the formula, and can be expressed as wt% or mol% according to synthesis methods such as solid-phase method and liquid-phase method. For example, in the case of 5 wt% or 5 mol%, x may be 0.05.

In the present invention, x in Formula 2 is 0.01 to 0.15, 0.01 to 0.14, 0.01 to 0.13, 0.01 to 0.12, 0.01 to 0.11, 0.01 to 0.10, 0.01 to 0.09, 0.01 to 0.08, 0.01 to 0.07, 0.01 to 0.06, 0.01 to 0.05, 0.01 to 0.04, or 0.01 to 0.03, for example, may be 0.03, but is not limited thereto.

In one embodiment of the present invention, the phosphate-based phosphor composition represented by Formula 2 may be Rb(Ca _0.99 Eu _0.01 )PO ₄ .

In one embodiment of the present invention, the phosphate-based phosphor composition represented by Formula 2 may be Rb(Ca _0.97 Eu _0.03 )PO ₄ .

In one embodiment of the present invention, the phosphate-based phosphor composition represented by Formula 2 may be Rb(Ca _0.95 Eu _0.05 )PO ₄ .

In one embodiment of the present invention, the phosphate-based phosphor composition represented by Formula 2 may be Rb(Ca _0.93 Eu _0.07 )PO ₄ .

In one embodiment of the present invention, the phosphate-based phosphor composition represented by Formula 2 may be Rb(Ca _0.90 Eu _0.10 )PO ₄ .

In one embodiment of the present invention, the phosphate-based phosphor composition represented by Formula 2 may be Rb(Ca _0.87 Eu _0.13 )PO ₄ .

In one embodiment of the present invention, the phosphate-based phosphor composition represented by Formula 2 may be Rb(Ca _0.85 Eu _0.15 )PO ₄ .

In the present invention, the emission wavelength of the phosphate-based phosphor composition is 410 to 600 nm, 410 to 590 nm, 410 to 580 nm, 410 to 570 nm, 410 to 560 nm, 410 to 550 nm, 410 to 540 nm, 410 to 530 nm, 410-520 nm, 420-600 nm, 420-590 nm, 420-580 nm, 420-570 nm, 420-560 nm, 420-550 nm, 420-540 nm, 420-530 nm, 420-520 nm, 430-600 nm, 430-590 nm, 430-580 nm, 430-570 nm, 430-560 nm, 430-550 nm, 430-540 nm, 430-530 nm, 430-520 nm, 440-600 nm, 440-590 nm, 440-580 nm, 440-570 nm, 440-560 nm, 440-550 nm, 440-540 nm, 440-530 nm, 440-520 nm, 450-600 nm, 450-590 nm, 450-580 nm, 450-570 nm, 450-560 nm, 450-550 nm, 450-540 nm, 450-530 nm, 450-520 nm, 460-600 nm, 460-590 nm, 460-580 nm, 460-570 nm, 460-560 nm, 460-550 nm, 460-540 nm, 460-530 nm, 460-520 nm, 470-600 nm, 470-590 nm, 470-580 nm, 470-570 nm, 470-560 nm, 470-550 nm, 470-540 nm, 470-530 nm, 470-520 nm, 480-600 nm, 480- 590 nm, 480-580 nm, 480-570 nm, 480-560 nm, 480-550 nm, 480-540 nm, 480-530 nm or 480-520 nm, for example, 480-510 nm However, the present invention is not limited thereto.

Another embodiment of the present invention relates to a method for preparing a phosphate-based phosphor composition comprising the steps of:

Rubidium carbonate (Rb ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), phosphorus pentoxide (P ₂ O ₅ ) and europium oxide [Europium(III) oxide, Eu ₂ O ₃ ] as a solvent A phosphate-based lysate preparation step of dissolving in to prepare a phosphate-based lysate;

a phosphate-based melt drying step of drying the phosphate-based melt to obtain a phosphate-based dry mixture;

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

A second phosphate-based calcination step of heat-treating the first phosphate-based calcined mixture under mixed gas conditions to obtain a second phosphate-based calcined mixture.

In the present invention, the phosphate-based lysate preparation step is rubidium carbonate (Rb ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), phosphorus pentoxide (P ₂ O ₅ ) and europium oxide [Europium ( III) oxide, Eu ₂ O ₃ ] may be prepared by dissolving a phosphate-based lysate in a solvent.

In the present invention, the phosphate-based melt drying step may be carried out under a temperature condition of 100 to 200 ℃, 100 to 180 ℃, 100 to 160 ℃, 120 to 200 ℃, 120 to 180 ℃, or 120 to 160 ℃, , for example, may be carried out under a temperature condition of 150 ℃, but is not limited thereto.

In the present invention, the drying step of the phosphate-based lysate 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 is performed for 12 hours. may be, but is not limited thereto.

If the phosphate-based melt drying step is performed for less than 12 hours, the solvent contained in the melt may not sufficiently evaporate, and the solvent may remain, thereby contaminating the phosphate-based phosphor composition.

In the present invention, the first phosphate-based calcination step may be to obtain a first phosphate-based calcination mixture by heat-treating the phosphate-based dry mixture in which the phosphate-based melt drying step has been performed.

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

In the present invention, the first phosphate-based 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, performed for 6 hours may be, but is not limited thereto.

In the present invention, the second phosphate-based calcination step may be a step of heat-treating the first phosphate-based calcination mixture to obtain a second phosphate-based calcination mixture.

In the present invention, the second phosphate-based calcination step is 700 to 1100 °C, 700 to 1000 °C, 750 to 1100 °C, 750 to 1000 °C, 800 to 1100 °C, 800 to 1000 °C, 900 to 1100 °C, or 900 to 1000 °C. It may be carried out under a temperature condition of ℃, for example, it may be carried out under a temperature condition of 950 ℃, but is not limited thereto.

In the present invention, the second phosphate-based calcination step may be performed for 6 to 24 hours, 6 to 20 hours, 6 to 16 hours, or 6 to 12 hours, for example, it may be carried out for 12 hours, The present invention is not limited thereto.

In one embodiment of the present invention, the second phosphate-based calcination step includes H ₂ and N ₂ gas for the reduction of doped rare earth metal ions, and other types of gases are not included. It is performed under a mixed gas condition. it could be

In the present invention, the method for producing a phosphate-based phosphor may further include a pulverization step of pulverizing the second phosphate-based calcination mixture after the second phosphate-based calcination step is completed.

Another embodiment of the present invention is to provide a dental composition comprising a phosphate-based phosphor composition represented by Chemical Formula 2.

[Formula 2]

Rb(AE _1-x REE3 _x )PO ₄

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

Another embodiment of the present invention relates to a method for applying a phosphate-based phosphor composition comprising the steps of:

A phosphate-based mixing step of preparing a phosphate-based coating material by mixing a phosphate-based powder mixture comprising a phosphor composition represented by Formula 2 and a powder, and a binder;

a phosphate-based coating material application step of applying the phosphate-based coating material to an object; and

A phosphate-based coating heat treatment step of raising the temperature of the phosphate-based coating applied to the object to a temperature condition of 650 to 750° C. at a temperature increase rate of 40 to 60° C./min and maintaining the isothermal state for 10 to 40 minutes.

[Formula 2]

Rb(AE _1-x REE3 _x )PO ₄

In the present invention, the phosphate-based powder mixture may include the phosphor composition represented by Formula 2 and the powder, but is not limited thereto.

In the present invention, the weight ratio (w/w%) of the phosphate-based phosphor composition and the powder included in the phosphate-based powder mixture may be 1:9, but is not limited thereto.

In the present invention, the binder may be butanediol, propylene glycol, or a combination thereof, but is not limited thereto, and an appropriate binder may be used to facilitate moldability of the phosphate-based phosphor composition.

In the present invention, the weight ratio (w/w%) of the phosphate-based powder mixture contained in the phosphate-based coating material is 50 to 70% by weight, 50 to 65% by weight, 50 to 60% by weight, 55 to 70% by weight, 55 to It may be 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 phosphate-based coating material is 30 to 50 wt%, 30 to 45 wt%, 35 to 50 wt%, 35 to 45 wt%, 40 to 50 wt% Or it may be 40 to 45% by weight, but is not limited thereto.

In the present invention, the phosphate-based coating material may be a mixture of a phosphate-based powder mixture and a binder to have a viscosity to be properly applied to an object, but is not limited thereto.

In the present invention, the temperature increase rate of the phosphate-based 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 °C/min, 44 to 58 °C/min, 44 to 56 °C/min, 44-54 °C/min, 44-52 °C/min, 46-60 °C/min, 46-58 °C/min, 46-56 °C/min, 46-54 °C/min, 46-52 °C /min, 48 to 60 °C/min, 48 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. minutes, but is not limited thereto.

In the present invention, the phosphate-based heat treatment step is 650 to 850 °C, 650 to 825 °C, 650 to 800 °C, 650 to 775 °C, 700 to 850 °C, 700 to 825 °C, 700 to 800 °C, 700 to 775 °C, It may be carried out at a temperature condition of 725 to 850 °C, 725 to 800 °C, and 725 to 775 °C, for example, it may be carried out at a temperature condition of 725 to 775 °C, but is not limited thereto.

In the present invention, the phosphate-based 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, isothermal state for 25 to 30 minutes. may be to maintain, but is not limited thereto.

Another example of the present invention relates to a borate-based phosphor composition represented by the formula (3).

[Formula 3]

AE ₃ (REE4 _1-xy REE5 _x REE6 _y ) ₂ (BO ₃ ) ₄

In the borate-based phosphor composition of the present invention, the term “maternal crystal material” may mean AE ₃ (REE1) ₂ (BO ₃ ) ₄ .

In the present invention, REE4 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho) , erbium (Er) and thulium (Tm) may be one selected from the group consisting of rare earth elements (REE), for example, may be lanthanum, but is not limited thereto.

In the present invention, REE5 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho) , erbium (Er) and thulium (Tm) may be one selected from the group consisting of rare earth elements (REE), for example, cerium, but is not limited thereto.

In the present invention, x in Formula 3 may be 0<x≤0.15, which may mean that x does not include 0 but includes 0.15, but has a value between 0 and 0.15.

In the present invention, x in Formula 3 is the ratio of the rare earth metal REE5 doped to the REE4 site of the parent crystal in the formula, and can be expressed as wt% or mol% according to synthesis methods such as solid phase method and liquid phase method. For example, when the wt% of REE5 is 5 wt% or 5 mol%, x may be 0.05.

In the present invention, x in Formula 3 may be 0.01 to 0.15, 0.01 to 0.14, 0.01 to 0.13, 0.03 to 0.15, 0.03 to 0.14, 0.03 to 0.13, 0.05 to 0.15, 0.05 to 0.14 or 0.05 to 0.13, for example, For example, it may be 0.05 to 0.13, but is not limited thereto.

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.99 Ce _0.01 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.97 Ce _0.03 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.95 Ce _0.05 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.93 Ce _0.07 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.90 Ce _0.10 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.87 Ce _0.13 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.85 Ce _0.15 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.99 Tb _0.01 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.97 Tb _0.03 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.95 Tb _0.05 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.93 Tb _0.07 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.90 Tb _0.10 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.87 Tb _0.13 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.85 Tb _0.15 ) ₂ (BO ₃ ) ₄ .

In the present invention, REE6 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho) , erbium (Er) and thulium (Tm) may be one selected from the group consisting of rare earth elements (REE), for example, terbium, but is not limited thereto.

In the present invention, y in Formula 3 is the ratio of the rare earth metal REE6 doped to the REE4 site of the parent crystal in the formula, and can be expressed in wt% or mol% according to synthesis methods such as solid phase method and liquid phase method. For example, when the wt% or mol% of REE6 is 10 wt% or 10 mol%, y may be 0.07.

In the present invention, y in Formula 3 may be 0≤y≤0.15, which may mean that y includes 0 and 0.15 and has a value between 0 and 0.15.

In the present invention, y in Formula 3 is 0.01 to 0.15, 0.01 to 0.14, 0.01 to 0.13, 0.03 to 0.15, 0.03 to 0.14, 0.03 to 0.13, 0.05 to 0.15, 0.05 to 0.14, 0.05 to 0.13, 0.07 to 0.15, 0.07 to 0.14 or 0.07 to 0.13, for example, may be 0.07 to 0.13, but is not limited thereto.

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.92 Ce _0.07 Tb _0.01 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.90 Ce _0.07 Tb _0.03 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.88 Ce _0.07 Tb _0.05 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.86 Ce _0.07 Tb _0.07 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.83 Ce _0.07 Tb _0.10 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.80 Ce _0.07 Tb _0.13 ) ₂ (BO ₃ ) ₄ .

In one embodiment of the present invention, the borate-based phosphor composition represented by Formula 3 may be Ba ₃ (La _0.78 Ce _0.07 Tb _0.15 ) ₂ (BO ₃ ) ₄ .

In the present invention, the light emission wavelength of the borate-based phosphor composition is 410 to 600 nm, 410 to 590 nm, 410 to 580 nm, 410 to 570 nm, 410 to 560 nm, 410 to 550 nm, 410 to 540 nm, 410 to 530 nm, 410-520 nm, 420-600 nm, 420-590 nm, 420-580 nm, 420-570 nm, 420-560 nm, 420-550 nm, 420-540 nm, 420-530 nm, 420-520 nm, 430-600 nm, 430-590 nm, 430-580 nm, 430-570 nm, 430-560 nm, 430-550 nm, 430-540 nm, 430-530 nm, 430-520 nm, 440-600 nm, 440-590 nm, 440-580 nm, 440-570 nm, 440-560 nm, 440-550 nm, 440-540 nm, 440-530 nm, 440-520 nm, 450-600 nm, 450-590 nm, 450-580 nm, 450-570 nm, 450-560 nm, 450-550 nm, 450-540 nm, 450-530 nm, 450-520 nm, 460-600 nm, 460-590 nm, 460-580 nm, 460-570 nm, 460-560 nm, 460-550 nm, 460-540 nm, 460-530 nm, 460-520 nm, 470-600 nm, 470-590 nm, 470-580 nm, 470-570 nm, 470-560 nm, 470-550 nm, 470-540 nm, 470-530 nm, 470-520 nm, 480-600 nm, 480-5 90 nm, 480-580 nm, 480-570 nm, 480-560 nm, 480-550 nm, 480-540 nm, 480-530 nm or 480-520 nm, for example, 480-510 nm However, the present invention is not limited thereto.

Another embodiment of the present invention relates to a method for preparing a borate-based phosphor composition comprising the steps of:

Barium nitrate [Barium nitrate, Ba(NO ₃ ) ₂ ], Lanthanum nitrate [Lanthanum nitrate, La(NO ₃ ) ₃ ], Cerium nitrate [Cerium nitrate, Ce(NO ₃ ) ₃ ], and Hydrogen borate, HBO ₃ ) by dissolving in a solvent to prepare a borate-based lysate preparing a borate-based lysate;

drying the borate-based lysate to obtain a borate-based dry mixture by drying the borate-based lysate; and

A borate-based calcination step of heat-treating the borate-based dry mixture under a mixed gas condition comprising H ₂ and N ₂ gas to obtain a borate-based calcination mixture.

In the present invention, the borate-based melt preparation step is barium nitrate [Barium nitrate, Ba(NO ₃ ) ₂ ], lanthanum nitrate [Lanthanum nitrate, La(NO ₃ ) ₃ ], cerium nitrate [Cerium nitrate, Ce(NO ₃ ) ) ₃ ] and boric acid (Hydrogen borate, HBO ₃ ) may be dissolved in a solvent to prepare a borate-based lysate.

In the present invention, the borate-based lysate preparation step may be to prepare a borate-based lysate by further dissolving terbium nitrate [Terbium nitrate, Tb(NO3)3] in a solvent.

In the present invention, the borate-based melt drying step is performed under a temperature condition of 80 to 150 ℃, 80 to 140 ℃, 80 to 130 ℃, 80 to 120 ℃, 80 to 110 ℃, 80 to 100 ℃, or 80 to 90 ℃. It may be carried out, for example, it may be carried out under a temperature condition of 80 to 90 ℃, but is not limited thereto.

In the present invention, the borate-based lysate 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 is performed for 12 hours. may be, but is not limited thereto.

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

In the present invention, the borate-based calcination step may be to obtain a borate-based calcination mixture by heat-treating the borate-based dry mixture that has been subjected to the borate-based melt drying step.

In the present invention, the borate-based calcination step may be carried out at a temperature condition of 900 to 1300 ° C, 900 to 1200 ° C, 1000 to 1300 ° C, 1000 to 1200 ° C, 1100 to 1300 ° C, or 1100 to 1200 ° C. For example, it may be carried out at a temperature condition of 1100 to 1200 ℃, but is not limited thereto.

In the present invention, the borate-based 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, to be performed for 6 hours. However, the present invention is not limited thereto.

When the borate-based calcination step is performed for less than 6 hours, some of Ba(NO ₃ ) ₂ , La(NO ₃ ) ₃ , Tb(NO ₃ ) ₃ , Ce(NO ₃ ) ₃ , and HBO ₃ are added to the borate-based phosphor composition Since it cannot be synthesized as an impurity or residue, the yield of the borate-based phosphor composition may be lowered.

In one embodiment of the present invention, the borate-based calcination step includes H ₂ and N ₂ gas for the reduction of doped rare earth metal ions, and may be performed under a mixed gas condition that does not include other types of gases. have.

In the present invention, the borate-based calcination step may further include a grinding step of pulverizing the borate-based calcination mixture.

Another example of the present invention is to provide a dental composition comprising a borate-based phosphor composition represented by Chemical Formula 3.

[Formula 3]

AE ₃ (REE4 _1-xy REE5 _x REE6 _y ) ₂ (BO ₃ ) ₄

In the present invention, the dental composition may be at least one selected from the group consisting of a dental restoration, a dental prosthesis, and a surface treatment agent for a dental prosthesis, but is not limited thereto.

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

Another example of the present invention relates to a method for applying a borate-based phosphor composition comprising the steps of:

a borate-based mixing step of preparing a borate-based coating material by mixing a borate-based powder mixture comprising a phosphor composition represented by Formula 3 and a powder, and a binder;

a borate-based coating material application step of applying the borate-based coating material to an object; and

A borate-based heat treatment step of raising the temperature of the borate-based coating applied to the object to a temperature condition of 650 to 750°C at a temperature increase rate of 40 to 60°C/min and maintaining the isothermal state for 20 to 40 minutes.

[Formula 3]

AE ₃ (REE4 _1-xy REE5 _x REE6 _y ) ₂ (BO ₃ ) ₄

In the present invention, the borate-based powder mixture may include the borate-based phosphor composition and powder represented by Formula 3, but is not limited thereto.

In the present invention, the weight ratio (w/w%) of the borate-based phosphor composition and the powder included in the borate-based powder mixture may be 1:9, but is not limited thereto.

In the present invention, the binder may be butanediol, propylene glycol, or a combination thereof, but is not limited thereto, and an appropriate binder may be used to facilitate moldability of the borate-based phosphor composition.

In the present invention, the weight ratio (w/w%) of the borate-based powder mixture contained in the borate-based coating material is 50 to 70% by weight, 50 to 65% by weight, 50 to 60% by weight, 55 to 70% by weight, 55 to It may be 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 borate-based coating material is 30 to 50 wt%, 30 to 45 wt%, 35 to 50 wt%, 35 to 45 wt%, 40 to 50 wt% Or it may be 40 to 45% by weight, but is not limited thereto.

In the present invention, the object may be a natural tooth, an artificial tooth, or a dental composition, but is not limited thereto.

In the present invention, the borate-based coating material may be a mixture of a borate-based powder mixture and a binder to have a viscosity to be properly applied to an object, but is not limited thereto.

In the present invention, the temperature increase rate of the borate-based 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 °C/min, 44 to 58 °C/min, 44 to 56 °C/min, 44-54 °C/min, 44-52 °C/min, 46-60 °C/min, 46-58 °C/min, 46-56 °C/min, 46-54 °C/min, 46-52 °C /min, 48 to 60 °C/min, 48 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. minutes, but is not limited thereto.

In the present invention, the borate-based heat treatment step is 250 to 750 ℃, 250 to 700 ℃, 250 to 650 ℃, 250 to 600 ℃, 250 to 550 ℃, 250 to 500 ℃, 300 to 750 ℃, 300 to 700 ℃, 300 to 650 °C, 300 to 600 °C, 300 to 550 °C, 300 to 500 °C, 350 to 750 °C, 350 to 700 °C, 350 to 650 °C, 350 to 600 °C, 350 to 550 °C, 350 to 500 °C, 400 to 750 ° C, 400 to 700 ° C, 400 to 650 ° C, 400 to 600 ° C, 400 to 550 ° C, or 400 to 500 ° C. It may be to raise the temperature to, but is not limited thereto.

In the present invention, the borate-based 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, isothermal state for 25 to 30 minutes. may be to maintain, but is not limited thereto.

The present invention provides a silicate-based, phosphate-based and borate-based phosphor composition having a luminescent property similar to that of the natural teeth of a person to be treated by doping a host material with rare earth elements (REE) metal cations in a specific ratio. , and a method for manufacturing the same, and by controlling the doping concentration ratio of the rare-earth metal cation, the luminescent property of the phosphor composition can be controlled, so that the aesthetic effect on the appearance of the teeth of the recipient can be improved.

1 is a graph showing the luminescence characteristics (PL/PLE) of a silicate-based phosphor composition according to an experimental example of the present invention.

2 is a graph analyzing the XRD pattern of the silicate-based phosphor composition of the present invention.

3 is a photograph taken in order to analyze the apparent luminescence 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 the apparent luminescence characteristics (PL/PLE) when a silicate-based phosphor composition is applied according to an experimental example of the present invention.

5 is a phosphate-based phosphor composition (a) of a comparative group having a gray body color without performing the first calcination step and phosphate having a white or ivory body color after performing the first calcination step of the present invention It is a photograph taken by comparing the external color of the phosphor composition (b).

6 is a graph showing luminescence characteristics (PL/PLE) of phosphate-based phosphor compositions having different alkaline earth metals.

7 is a graph analyzing the emission characteristics of the phosphate-based phosphor composition according to the Eu 2+ doping concentration.

8 is a graph analyzing XRD patterns according to Eu 2+ doping concentration of a phosphate-based phosphor composition that has undergone a first calcination step according to an experimental example of the present invention.

9 is a graph analyzing the XRD pattern of a phosphate-based phosphor composition in which the first calcination step is not performed according to an experimental example of the present invention.

10 is a photograph taken after the phosphate-based phosphor composition is applied to a substrate according to an experimental example of the present invention.

11 is a graph comparing and analyzing the luminescence characteristics before the phosphate-based phosphor composition of the present invention is applied to the substrate and the luminescence characteristics after the phosphate-based phosphor composition is applied to the substrate and subjected to a heat treatment process.

12 is a microscopic view of a particle diameter of a borate-based phosphor composition according to an embodiment of the present invention. (Scale bar: 10 um)

13A to 13C are graphs showing XRD patterns of borate-based phosphor compositions according to an experimental example of the present invention.

14A and 14B are graphs showing PL/PLE of a borate-based phosphor composition (lanthanum-cerium-terbium) according to an experimental example of the present invention.

15A and 15B are graphs showing PL/PLE of a borate-based phosphor composition (lanthanum-cerium) according to an experimental example of the present invention.

16A and 16B are graphs showing PL/PLE of a borate-based phosphor composition (lanthanum-terbium) according to an experimental example of the present invention.

17 shows the appearance of a borate-based phosphor composition applied to a substrate and subjected to heat treatment at 300° C., 400° C., ° C. and 700° C. according to an experimental example of the present invention, and the borate-based phosphor composition emits light when irradiated with ultraviolet rays It's a picture of what you're doing.

18 is a graph comparing and analyzing the luminescence characteristics before the borate-based phosphor composition is applied to the substrate and the luminescence characteristics after the borate phosphor composition is applied to the substrate and subjected to a heat treatment process.

A phosphor composition represented by Formula 1.

[Formula 1]

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

here,

wherein x is 0<x≤0.15,

Wherein y is 0≤y≤0.15,

The AE is any one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

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 any one selected from the group consisting of thulium (Tm),

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 any one selected from the group consisting of thulium (Tm).

The terminology used herein is used only to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise.

In this specification, terms such as “include” or “have” are intended to designate that the features, components, etc. described in the specification are present, and one or more other features or components are not present or cannot be added. does not mean

Unless defined otherwise 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 this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present specification. does not

As used herein, the terms "about", "substantially" and the like are used in or close to the numerical value when manufacturing and material tolerances inherent in the stated meaning are presented, and are used to enhance the understanding of the present invention. To help, precise or absolute figures are used to prevent unfair use by unconscionable infringers of the stated disclosure. In addition, in the present specification, “step of doing” or “step of” does not mean “step for”.

In the present invention, the term “excitation wavelength” may mean a wavelength of light that excites electrons of the phosphor composition to have a high energy level, and in general, the excitation spectrum is one that matches the absorption spectrum can

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

Hereinafter, the present invention will be described in more detail through Preparation Examples and Examples. These Preparations and Examples are only for explaining the present invention in more detail, and it is common knowledge in the art that the scope of the present invention is not limited by these Preparations and Examples according to the gist of the present invention. It will be self-evident in person.

제조예 1. WASSR법 (Water assisted solid state reaction)을 이용한 실리케이트계 형광체 조성물의 제조Preparation Example 1. Preparation of silicate-based phosphor composition using WASSR method (Water assisted solid state reaction)

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

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

성분ingredient	실시예 1Example 1	실시예 2Example 2	실시예 3Example 3
Ca (mol%)Ca (mol%)	9595	8585	8787
Eu (mol%)Eu (mol%)	55	1212	1212
Tb (mol%)Tb (mol%)	--	33	1One
합계Sum	100100	100100	100100

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 product was subjected to primary heat treatment (first silicate-based calcination step) under air conditions for 6 hours at a temperature of 800° C. to obtain a primary calcination mixture (first silicate-based calcination mixture). The primary silicate-based calcined mixture was subjected to a secondary heat treatment under a mixed gas condition containing 95% N ₂ and 5% H ₂ based on the molar gas fraction of the total gas for 12 hours at a temperature condition of 950° C. (second silicate-based mixture) calcination step) to obtain a secondary silicate-based calcination mixture (second silicate-based calcination mixture).

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

실험예 1. 실리케이트계 형광체 조성물의 PL/PLE 분석Experimental Example 1. PL/PLE analysis of silicate-based phosphor composition

For the silicate-based phosphor compositions of Examples 1 to 3, photoluminescence and excitation wavelength were analyzed under a temperature condition of room temperature using a spectrofluorometer.

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

	실시예 1Example 1	실시예 2Example 2	실시예 3Example 3
발광 파장 (nm)Emission wavelength (nm)	505505	550550	550550
발광 세기(a.u.)Luminescence intensity (a.u.)	21502150	25002500	20102010

실험예 2. 실리케이트계 형광체 조성물의 XRD 패턴 분석Experimental 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 , a single phase of the control (CaAl ₂ Si ₂ O ₈ ) was well observed, and the silicate-based phosphor composition of Example 1 [(Ca _0.95 Eu _0.05 ) Al ₂ Si ₂ O ₈ ] was other impurities. This was not detected.

실험예 3. 실리케이트계 형광체 조성물의 도포시 발광 특성Experimental Example 3. Light emitting properties upon application of silicate-based phosphor composition

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

According to Table 3, the paste not subjected to the elevated temperature heat treatment of Example 1 or Example 4, 300° C. of Example 5, 400° C. of Example 6, 500° C. of Example 7, 600° C. of Example 8, or A paste was prepared which was subjected to a temperature increase heat treatment in the temperature range of 700° C. of Example 8.

	실시예 4Example 4	실시예 5Example 5	실시예 6Example 6	실시예 7Example 7	실시예 8Example 8	실시예 9Example 9
Ca (mol%)Ca (mol%)	9595	9595	9595	9595	9595	9595
Eu (mol%)Eu (mol%)	55	55	55	55	55	55
승온 열 처리 온도 (℃)Elevated heat treatment temperature (℃)	미실시not done	300300	400400	500500	600600	700700

3 shows pictures of the appearance of the paste emitting light when the substrates coated with Examples 1 and 4 to 9 are irradiated with ultraviolet light having a wavelength of 365 nm.

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

	실시예 4Example 4	실시예 5Example 5	실시예 6Example 6	실시예 7Example 7	실시예 8Example 8	실시예 9Example 9
발광 파장 (nm)Emission wavelength (nm)	470470	446446	448448	448448	452452	449449
발광 세기(a.u.)Luminescence intensity (a.u.)	775775	559559	940940	14521452	25902590	24442444

As can be seen from FIG. 4 and Table 4, the light emission of the phosphor composition was maintained even after heat treatment by mixing the silicate-based phosphor composition with a binder.

In general, when the phosphor composition is subjected to high-temperature heat treatment, the phosphor composition interacts with the binder and light emission disappears, whereas the interaction and damage between the binder and the silicate-based phosphor is reduced through very fast and high-temperature heat treatment for the silicate-based phosphor composition. It was possible to maintain the luminescence by minimizing it.

제조예 2. WASSR법 (Water assisted solid state reaction)을 이용한 유로퓸 포스페이트계 형광체 조성물의 제조Preparation Example 2. Preparation of europium phosphate-based phosphor composition using WASSR method (Water assisted solid state reaction)

Rubidium carbonate (Rb ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), phosphorus pentoxide (P ₂ O ₅ ) and europium oxide [Europium(III) oxide, Eu ₂ O ₃ ] were dried After mixing to prepare a dry mixture, the mixture of Examples 10 to 16 was prepared by mixing with water in an amount of 10% by weight based on the total weight of the mixture.

The mol% ratios of Ca ²⁺ ions and Eu ²⁺ ions included in the mixtures of Examples 10 to 16 are shown in Table 5.

성분 (mol%)Component (mol%)	실시예 10Example 10	실시예 11Example 11	실시예 12Example 12	실시예 13Example 13	실시예 14Example 14	실시예 15Example 15	실시예 16Example 16
Ca²⁺ Ca ²⁺	9999	9797	9595	9393	9090	8787	8585
Eu²⁺ Eu ²⁺	1One	33	55	77	1010	1313	1515
합계Sum	100100	100100	100100	100100	100100	100100	100100

The mixture of Examples 10 to 16 was sufficiently dried for 12 hours at a temperature of 80° C. to obtain a phosphate-based dried product. The obtained phosphate-based dried product was subjected to primary heat treatment (first phosphate-based calcination step) under atmospheric conditions for 4 hours at a temperature of 800° C. to obtain a primary calcination mixture (first phosphate-based calcination mixture). .

The primary phosphate-based calcined mixture was subjected to a secondary heat treatment under a mixed gas condition containing 95% N ₂ and 5% H ₂ based on the molar gas fraction of the total gas for 12 hours at a temperature condition of 950° C. (second phosphate-based calcination mixture) calcination step) to obtain a second calcination mixture (second phosphate-based calcination mixture).

The secondary phosphate-based calcined mixture was pulverized for 6 hours using a ball mill so that the average particle diameter was 10 μm or less, and the phosphate-based phosphor compositions of Examples 1 to 7 having a white (or ivory) body color [Rb(Ca _1-x Eu _x )PO ₄ ] was prepared.

In Preparation Example 2, the appearance of the phosphor composition prepared by omitting the primary heat treatment is shown in FIG. 5A, and the appearance of the phosphor composition prepared in Preparation Example 2 is shown in FIG. 5B. 5B is a photograph taken by arranging the appearance of the phosphor compositions from Examples 10 to 16 from left to right.

As can be seen from a and b of FIG. 5 , the phosphor compositions of Examples 10 to 16 had a body color closer to black as the concentration of Eu ²⁺ increased, and closer to white as the concentration of Eu ²⁺ decreased.

실험예 4. 알칼리 토금속이 다른 포스페이트계 형광체 조성물의 PL/PLE 분석Experimental Example 4. PL/PLE Analysis of Phosphate-Based Phosphor Compositions Different from Alkaline Earth Metals

For the phosphate-based phosphor composition having a difference in alkaline earth metal, photoluminescence and excitation wavelength were analyzed under a temperature condition of room temperature using a spectrofluorometer.

The components and contents of the phosphate-based phosphor composition having a difference in the alkaline earth metal are shown in Example 10 and Comparative Examples 1 and 2 of Table 6.

성분ingredient	실시예 10Example 10	비교예 1Comparative Example 1	비교예 2Comparative Example 2
Ca (mol%)Ca (mol%)	9999	--	--
Sr (mol%)Sr (mol%)	--	9999	--
Ba (mol%)Ba (mol%)	--	--	9999
Eu (mol%)Eu (mol%)	1One	1One	1One
합계Sum	100100	100100	100100

6 and Table 7 show the luminescence characteristics when irradiated with a light source having a wavelength (λ _ex ) of 365 to 405 nm to a phosphor composition having a difference in alkaline earth metal.

	실시예 10Example 10	비교예 1Comparative Example 1	비교예 2Comparative Example 2
발광 파장 (nm)Emission wavelength (nm)	470470	455455	440440
발광 세기(a.u.)Luminescence intensity (a.u.)	770770	11701170	15401540

As can be seen from FIGS. 6 and 7, in the phosphate-based phosphor compositions of Example 10 and Comparative Examples 1 and 2, the alkaline earth metal is converted from barium to strontium and calcium, that is, as the radius of the ion decreases, the emission peak is It was red-shifted toward the infrared wavelength by about 15 nm.

Ca _0.99 Eu _0.01 RbPO ₄ of Example 10 exhibited cyan light emission, and Comparative Examples 1 and 2 exhibited blue light emission.

실험예 5. 포스페이트계 형광체 조성물의 PL/PLE 분석Experimental Example 5. PL/PLE analysis of phosphate-based phosphor composition

For the phosphate-based phosphor compositions of Examples 10 to 16, using a spectrofluorometer, photoluminescence and excitation wavelength were analyzed under room temperature conditions.

When the phosphor composition is irradiated with a light source having a wavelength (λ _ex ) of 365 nm, the luminescence characteristics of the phosphor composition are shown in FIGS. 7 and 8 . The phosphor compositions of Examples 10 to 16 showed the emission intensity and emission wavelength of Table 8, and after correcting the emission intensity to show a constant emission intensity in order to effectively compare the emission wavelengths, it is shown in FIG. 7 .

	실시예 10Example 10	실시예 11Example 11	실시예 12Example 12	실시예 13Example 13	실시예 14Example 14	실시예 15Example 15	실시예 16Example 16
발광 파장 (nm)Emission wavelength (nm)	462462	471471	492492	510510	512512	495495	512512
발광 세기(a.u.)Luminescence intensity (a.u.)	1973219732	1983719837	1994719947	1996019960	82578257	1003610036	78307830

As can be seen from FIGS. 7 and 8, the emission wavelength was changed according to the concentration of Eu ²⁺ , and the emission peak was red-shifted toward the infrared wavelength.

실험예 6. 포스페이트계 형광체 조성물의 XRD 패턴 분석Experimental Example 6. XRD pattern analysis of phosphate-based phosphor composition

6-1. 실시예 11 내지 실시예 16의 형광체 조성물6-1. Phosphor compositions of Examples 11 to 16

The results of XRD pattern analysis of the phosphor compositions of Examples 11 to 16 using X-ray diffraction (XRD) are shown in FIG. 8 .

As can be seen in FIG. 8 , the crystal structure of the parent phosphor composition was not affected as the Eu ions at various concentrations were substituted.

6-2. 제1 포스페이트계 하소 단계를 생략하여 제조한 실시예 11의 형광체 조성물6-2. The phosphor composition of Example 11 prepared by omitting the first phosphate-based calcination step

When the phosphor composition of Example 11 was prepared by omitting the heat treatment process (the first phosphate-based calcination step) under air atmospheric conditions for 4 hours at a temperature of 800° C., the XRD pattern was analyzed, and the result is shown in FIG. 9 shown in

As can be seen in FIG. 9 , if the first phosphate-based calcination step of heat treatment under air atmospheric conditions is omitted, only a part of the phosphate-based phosphor composition is synthesized and the remaining part is present as unreacted substances and impurities.

실험예 7. 포스페이트계 형광체 조성물의 도포시 발광 특성Experimental Example 7. Luminescence characteristics when phosphate-based phosphor composition is applied

The phosphor composition of Example 11 (Ca _0.97 Eu _0.03 RbPO ₄ ), Comparative Example 3 (Ca _0.95 Eu _0.05 Al ₂ Si ₂ O ₈ ) or Comparative Example 4 (Ca _0.87 Eu _0.12 Tb _0.01 Al ₂ Si ₂ O ₈ ) and IPS e.max Ceram Glaze powder were mixed in a ratio of 1:9 (w/w%) to prepare a phosphate-based powder mixture. A paste (phosphate-based coating material) was prepared by mixing the phosphate-based powder mixture and the binder propylene glycol at 6:4 (w/w%), and then applied to a glass ceramic block (e.max CAD Block, Ivoclar vivadent) at room temperature. The heat treatment was performed for a total of 30 minutes while heating at a high speed to a temperature condition of 750° C. at a temperature increase rate of 50° C./min, and the appearance thereof is shown in FIG.

In addition, a PL/PLE graph in which the light emission characteristics of the coated phosphor composition of Example 11 were analyzed is shown in FIG. 11 .

As can be seen from FIG. 11 , the phosphor composition of Example 11 maintained light emission even after heat treatment after mixing with the binder.

In general, when the phosphor composition is subjected to high-temperature heat treatment, the interaction and damage between the binder and the phosphate-based phosphor is reduced through very fast and high-temperature heat treatment for the phosphate-based phosphor composition, compared to that the phosphor composition interacts with the binder to extinguish light emission. It was possible to maintain the emission wavelength by minimizing it.

제조예 3. 보레이트계 형광체 조성물의 제조 (란타넘-세륨-터븀)Preparation Example 3. Preparation of borate-based phosphor composition (lanthanum-cerium-terbium)

as a starting material Barium nitrate [Barium nitrate, Ba(NO ₃ ) ₂ ], Lanthanum nitrate [Lanthanum nitrate, La(NO ₃ ) ₃ ], Terbium nitrate [Terbium nitrate, Tb(NO ₃ ) ₃ ], Cerium nitrate [Cerium nitrate, Ce (NO ₃ ) ₃ ] and boric acid (Hydrogen borate, HBO ₃ ) were dry mixed, and a mixture was prepared by mixing with 10% by weight of water based on the total weight of the mixture. Ammonia water (NH ₄ OH) was further added to the mixture to adjust the pH to 9.

The mol% of La, Ce ³⁺ and Tb ³⁺ contained in the mixtures of Examples 17 to 23 are shown in Table 9.

원소 (mol%)element (mol%)	실시예 17Example 17	실시예 18Example 18	실시예 19Example 19	실시예 20Example 20	실시예 21Example 21	실시예 22Example 22	실시예 23Example 23
La(mol%)La(mol%)	9292	9090	8888	8686	8383	8080	7878
Ce(mol%)Ce(mol%)	77	77	77	77	77	77	77
Tb(mol%)Tb(mol%)	1One	33	55	77	1010	1313	1515
합계Sum	100100	100100	100100	100100	100100	100100	100100

The mixture whose pH was controlled to 9 was stirred at 60° C. for 2 hours using a stirrer. Using a centrifuge, the stirred mixture was dried under a temperature condition of 80° C. for 12 hours to obtain a borate-based dried product. A borate-based calcination mixture was obtained by heat-treating the obtained borate-based dried material at a temperature of 1200° C. for 6 hours under mixed gas conditions containing 95% N ₂ and 5% H ₂ based on the molar gas fraction of the total gas. did

The borate-based phosphor compositions of Examples 17 to 23 were prepared by grinding for 6 hours using a ball mill so that the average particle diameter of the borate-based calcination mixture was 3 μm or less, and the particle diameter of the borate-based phosphor composition was confirmed. Thus, it is shown in FIG. 12 .

제조예 4. 보레이트계 형광체 조성물의 제조 (란타넘-세륨)Preparation Example 4. Preparation of borate-based phosphor composition (lanthanum-cerium)

As a starting material, barium nitrate [Barium nitrate, Ba(NO ₃ ) ₂ ], lanthanum nitrate [Lanthanum nitrate, La(NO ₃ ) ₃ ], Cerium nitrate [Cerium nitrate, Ce(NO ₃ ) ₃ ] and boric acid (Hydrogen borate, HBO ₃ ) were dry mixed, and a mixture was prepared by mixing with 10% by weight of water based on the total weight of the mixture. Ammonia water (NH ₄ OH) was further added to the mixture to adjust the pH to 9.

The mol% ratios of La and Ce contained in the mixtures of Examples 24 to 30 are shown in Table 10.

원소 (mol%)element (mol%)	실시예 24Example 24	실시예 25Example 25	실시예 26Example 26	실시예 27Example 27	실시예 28Example 28	실시예 29Example 29	실시예 30Example 30
La (mol%)La (mol%)	9999	9797	9595	9393	9090	8787	8585
Ce (mol%)Ce (mol%)	1One	33	55	77	1010	1313	1515
합계Sum	100100	100100	100100	100100	100100	100100	100100

제조예 5. 보레이트계 형광체 조성물의 제조 (란타넘-터븀) Preparation 5. Preparation of borate-based phosphor composition (lanthanum-terbium)

As starting materials, barium nitrate [Barium nitrate, Ba(NO ₃ ) ₂ ], lanthanum nitrate [Lanthanum nitrate, La(NO ₃ ) ₃ ], terbium nitrate [Terbium nitrate, Tb(NO ₃ ) ₃ ] and boric acid (Hydrogen borate) , HBO ₃ ) was dry mixed, and a mixture was prepared by mixing with 10% by weight of water based on the total weight of the mixture. Ammonia water (NH ₄ OH) was further added to the mixture to adjust the pH to 9.

The mol% ratios of La and Tb contained in the mixtures of Examples 24 to 30 are shown in Table 11.

원소 (mol%)element (mol%)	실시예 31Example 31	실시예 32Example 32	실시예 33Example 33	실시예 34Example 34	실시예 35Example 35	실시예 36Example 36	실시예 37Example 37
La (mol%)La (mol%)	9999	9797	9595	9393	9090	8787	8585
Tb (mol%)Tb (mol%)	1One	33	55	77	1010	1313	1515
합계Sum	100100	100100	100100	100100	100100	100100	100100

실험예 8. 보레이트계 형광체 조성물의 XRD 패턴 분석Experimental Example 8. XRD pattern analysis of borate-based phosphor composition

As a result of analyzing the XRD patterns of the borate-based phosphor compositions of Examples 17 to 37 using X-ray diffraction (XRD), Examples 17 to 23 are shown in FIG. 13A Examples 24 to 30 are shown in FIG. 13B, and Examples 31 to 27 are shown in FIG. 13C.

13A to 13C, in the borate-based phosphor compositions of Examples 17 to 37, no impurities or unreacted substances were detected even when the concentrations of Tb ³⁺ ions and Ce ³⁺ ions were increased, and the peak was a single phase. was measured as

In addition, as the concentration of Tb ³⁺ ions and Ce ³⁺ ions increased, the Ba ₃ La ₂ (BO ₃ ) ₄ crystal lattice contracted, so it was confirmed that the position of the XRD peak shifted to a higher angle, through which Tb ³ It was determined that ⁺ ions and Ce ³⁺ ions were successfully substituted for La ³⁺ ions in the Ba ₃ La ₂ (BO ₃ ) ₄ crystal lattice.

실험예 9. 보레이트계 형광체 조성물의 PL/PLE 분석Experimental Example 9. PL/PLE analysis of borate-based phosphor composition

9-1. 란타넘-터븀-세륨 형광체 조성물9-1. Lanthanum-terbium-cerium phosphor composition

For the borate-based phosphor compositions of Examples 17 to 23, using a spectrofluorometer, photoluminescence and excitation wavelength were analyzed under a temperature condition of room temperature.

When the borate-based phosphor compositions of Examples 17 to 23 were irradiated with a light source having a light source wavelength (λ _ex ) of 365 to 405 nm, light emission characteristics are shown in FIGS. 14A, 14B and Table 12.

	실시예 17Example 17	실시예 18Example 18	실시예 19Example 19	실시예 20Example 20	실시예 21Example 21	실시예 22Example 22	실시예 23Example 23
발광 파장 (λ_em)emission wavelength (λ _em )	546546	546546	546546	546546	546546	546546	546546
여기 파장 (λ_ex)excitation wavelength (λ _ex )	329329	324324	320320	324324	320320	324324	330330
발광 세기 (a.u.)Luminescence intensity (a.u.)	360360	1,2471,247	1,6281,628	2,2202,220	4,5204,520	3,8703,870	3,1343,134

14A and Table 12, when the light source wavelength was 365 to 405 nm, the phosphor composition of Example 21 having 7% Ce and 10% Tb exhibited the strongest intensity of luminescence. In Figure 14a, each peak was measured to be Ex _{365 nm} = 490 nm, 545 nm, 585 nm, and 623 nm.

The borate-based phosphor composition containing 7 mol% of Ce and 10 mol% of Tb has the strongest PL intensity, and when Ce 7 mol% contains more than 10 mol% of Tb, the luminescence intensity is rather decreased. confirmed to be.

As can be seen in FIG. 14B and Table 12, it was measured that the minimum excitation wavelength was 320 nm and the maximum excitation wavelength was 329 nm. The phosphor composition was not excited when the light source wavelength was 405 nm, so that the excitation wavelength was hardly measured.

9-2. 란타넘-세륨 형광체 조성물9-2. Lanthanum-cerium phosphor composition

For the borate-based phosphor compositions of Examples 24 to 30, using a spectrofluorometer, photoluminescence and excitation wavelength were analyzed under room temperature conditions.

When the phosphor compositions of Examples 24 to 30 were irradiated with a light source having a light source wavelength (λ _ex ) of 365 to 405 nm, light emission characteristics are shown in FIGS. 15A, 15B and Table 13.

	실시예 24Example 24	실시예 25Example 25	실시예 26Example 26	실시예 27Example 27	실시예 28Example 28	실시예 29Example 29	실시예 30Example 30
발광 파장(λ_em)emission wavelength (λ _em )	473473	473473	473473	472472	482482	475475	489489
여기 파장(λ_ex)excitation wavelength (λ _ex )	323323	320320	320320	320320	329329	324324	323323
발광 세기(a.u.)Luminescence intensity (a.u.)	404404	495495	466466	652652	421421	515515	447447

As can be seen in FIGS. 15A, 15B and Table 13, when the light source wavelength was 365 nm, the phosphor composition of Example 27 of Ce ³⁺ 7 mol% was 652 au, showing the strongest intensity of luminescence. . When the phosphor composition contained 10 mol% or more of Ce ³⁺ , concentration quenching occurred. It was determined that the minimum excitation wavelength was 320 nm and the maximum excitation wavelength was 329 nm.

9-3. 란타넘-터븀 형광체 조성물9-3. Lanthanum-terbium phosphor composition

For the borate-based phosphor compositions of Examples 31 to 37, photoluminescence and excitation wavelength were analyzed under a temperature condition of room temperature using a spectrofluorometer.

When the phosphor compositions of Examples 31 to 37 were irradiated with a light source having a light source wavelength (λ _ex ) of 365 to 405 nm, light emission characteristics are shown in FIGS. 16A, 16B and Table 14.

	실시예 31Example 31	실시예 32Example 32	실시예 33Example 33	실시예 34Example 34	실시예 35Example 35	실시예 36Example 36	실시예 37Example 37
발광 파장(λ_em)emission wavelength (λ _em )	546546	546546	546546	546546	546546	546546	546546
여기 파장(λ_ex)excitation wavelength (λ _ex )	245245	245245	246246	250250	251251	251251	251251
발광 세기(a.u.)Luminescence intensity (a.u.)	403403	498498	733733	1,2721,272	1,3241,324	1,2701,270	669669

As can be seen in FIGS. 16a, 16b and Table 14, when the light source wavelength was 365 nm, the phosphor composition of Example 35 having Tb ³⁺ 10 mol% was 1,324 au, indicating the strongest intensity of luminescence. . When the phosphor composition contained 13 mol% or more of Tb ³⁺ , it was confirmed that the luminescence intensity was rather decreased, resulting in concentration quenching. It was determined that the minimum excitation wavelength was 245 nm and the maximum excitation wavelength was 251 nm.

In summary, in the case of the phosphor composition containing Ce ³⁺ 7 mol% and Tb ³⁺ 0 mol% (Example 27), cyan blue emission was exhibited at 473 nm, which is the shortest emission wavelength, and Ce ³⁺ 7 In the case of the phosphor composition containing mol% and Tb ³⁺ 10 mol% (Example 21), yellowish-white light emission of 547 nm, which is the longest emission wavelength, was exhibited. Yellow-wish-white emission refers to emission of the sum of all emission wavelengths in the visible region.

In the phosphor composition of the present invention, by adjusting the mol% concentration of Ce ³⁺ and Tb ³⁺ with reference to the fluorescence properties of natural teeth, the emission wavelength of the phosphor composition can be adjusted in the range of 473 to 547 nm. It is possible to adjust the light emission characteristics according to the

실험예 10. 보레이트계 형광체 조성물의 도포시 발광 특성Experimental Example 10. Luminescence properties of borate-based phosphor composition

A borate-based powder mixture was prepared by mixing the phosphor composition of Example 21 (Ce 7%, Tb 10%) and IPS e.max Ceram Glaze powder at 2:8 (w/w%). A paste (borate-based coating material) was prepared by mixing a borate-based powder mixture and a binder (propylene glycol) in a ratio of 7:3 (w/w%), and then applied to a substrate at a temperature increase rate of 300 to 50°C from room temperature. Heat treatment was performed for a total of 30 minutes while heating at high speed to a temperature condition of 700° C., and the appearance thereof is shown in FIG. 16 .

In addition, PL/PLE graphs comparing and analyzing the light emission characteristics of the phosphor composition applied to the substrate at each temperature increase are shown in FIG. 17 and Table 15.

	PastePaste	300℃300℃	400℃400℃	500℃500℃		600℃600℃	700℃700℃
발광 파장 (nm)Emission wavelength (nm)	545545	545545	545545		545545	545545	545545
발광 세기(a.u.)Luminescence intensity (a.u.)	4,0004,000	2,2552,255	1,2101,210		792792	957957	683683

17 and Table 15, when the phosphor composition of Example 21 was mixed with a binder and heat-treated, the light emission intensity was decreased, but the emission wavelength was maintained.

In general, when the phosphor composition is subjected to high-temperature heat treatment, the phosphor composition interacts with the binder and light emission disappears, whereas the interaction between the binder and the borate-based phosphor and It was possible to maintain the emission wavelength by minimizing the damage.

The present invention relates to a silicate-based, phosphate-based and borate-based phosphor composition, and a method for preparing the same, and specifically, by doping a host material with rare earth elements (REE) metal cations in a specific ratio. The present invention relates to a phosphor composition having luminescent properties similar to natural teeth of a person to be treated, and a method for preparing the same.

Claims

A phosphor composition represented by the formula (1):

[Formula 1]

(AE 1-xy REE1 x REE2 y ) 2 Al 2 Si 2 O 8

here,

wherein x is 0<x≤0.15,

Wherein y is 0≤y≤0.15,

The AE is any one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

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 any one selected from the group consisting of thulium (Tm),

The 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 any one selected from the group consisting of thulium (Tm).
The phosphor composition of claim 1, wherein x is 0.03≤x≤0.09, and y is 0≤y≤0.05.
The phosphor composition of claim 1, wherein AE is calcium (Ca).
The phosphor composition of claim 1, wherein REE1 is europium (Eu), and REE2 is terbium (Tb).
The silicate-based phosphor composition according to claim 1, wherein the phosphor composition has an average particle diameter of 0.01 to 10 um.
A method for preparing a phosphor composition comprising the steps of:

Calcium carbonate (CaCO 3 ), aluminum oxide (Al 2 O 3 ), silicon dioxide (SiO 2 ) and europium oxide [Europium(III) oxide, Eu 2 O 3 ] are dissolved in a solvent a silicate-based lysate preparation step of preparing a silicate-based lysate;

a silicate-based melt drying step of drying the silicate-based melt to obtain a silicate-based dry mixture;

a first silicate-based calcination step of heat-treating the silicate-based dry mixture under an air condition to obtain a first silicate-based calcination mixture; and

A second silicate-based calcination step of heat-treating the first silicate-based calcined mixture under mixed gas conditions to obtain a second silicate-based calcined mixture.
The method of claim 6, wherein the drying of the silicate-based melt is performed under a temperature condition of 100 to 200°C.
The method of claim 6, wherein the drying of the silicate-based melt is performed for 12 to 72 hours.
The method of claim 6, wherein the first silicate-based calcination step is performed under a temperature condition of 700 to 1100°C.
The method of claim 6, wherein the first silicate-based calcination step is performed for 6 to 24 hours.
The method of claim 6, wherein the second silicate-based calcination step is performed under a temperature condition of 700 to 1100°C.
The method of claim 6, wherein the second silicate-based calcination step is performed for 6 to 24 hours.
A dental composition comprising a silicate-based phosphor composition represented by Formula 1:

[Formula 1]

(AE 1-xy REE1 x REE2 y ) 2 Al 2 Si 2 O 8

here,

wherein x is 0<x≤0.15,

Wherein y is 0≤y≤0.15,

The AE is any one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

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 any one selected from the group consisting of thulium (Tm),

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 any one selected from the group consisting of thulium (Tm).
The dental composition of claim 13, wherein the dental composition is at least one selected from the group consisting of a dental restoration, a dental prosthesis, and a dental prosthesis surface treatment agent.
A method of applying a silicate-based phosphor composition comprising the steps of:

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

a silicate-based coating material application step of applying the silicate-based coating material to an object; and

A silicate-based coating heat treatment step of raising the temperature of the silicate-based coating applied to the object to a temperature condition of 300 to 900°C at a temperature increase rate of 40 to 60°C/min and maintaining the isothermal state for 20 to 40 minutes.

[Formula 1]

(AE 1-xy REE1 x REE2 y ) 2 Al 2 Si 2 O 8

here,

wherein x is 0<x≤0.15,

Wherein y is 0≤y≤0.15,

The AE is any one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

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 any one selected from the group consisting of thulium (Tm),

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 any one selected from the group consisting of thulium (Tm).
A phosphor composition represented by the formula (2):

[Formula 2]

Rb(AE 1-x REE3 x )PO 4

here,

wherein x is 0<x≤0.15,

The AE is any one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

The REE3 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 any one selected from the group consisting of thulium (Tm).
The phosphor composition of claim 16, wherein x is 0.01≤x≤0.05.
The phosphor composition of claim 16, wherein AE is calcium (Ca).
The phosphor composition of claim 16, wherein the REE is europium (Eu).
The phosphor composition of claim 16, wherein the REE is a divalent cation.
The phosphor composition according to claim 16, wherein the average particle diameter of the phosphor composition is 0.01 to 10 um.
A method for preparing a phosphor composition comprising the steps of:

Rubidium carbonate (Rb 2 CO 3 ), calcium carbonate (CaCO 3 ), phosphorus pentoxide (P 2 O 5 ) and europium oxide [Europium(III) oxide, Eu 2 O 3 ] as a solvent A phosphate-based lysate preparation step of dissolving in to prepare a phosphate-based lysate;

a phosphate-based melt drying step of drying the phosphate-based melt to obtain a phosphate-based dry mixture;

a first phosphate-based calcination step of heat-treating the phosphate-based dry mixture under an air condition to obtain a first phosphate-based calcination mixture; and

A second phosphate-based calcination step of heat-treating the first phosphate-based calcined mixture under a mixed gas condition to obtain a second phosphate-based calcined mixture.
The method of claim 22, wherein the phosphate-based drying step is performed under a temperature condition of 100 to 200°C.
The method of claim 22, wherein the phosphate-based drying step is performed for 12 to 72 hours.
The method of claim 22, wherein the first phosphate-based calcination step is performed under a temperature condition of 700 to 1100°C.
The method of claim 22, wherein the first phosphate-based calcination step is performed for 6 to 24 hours.
The method of claim 22, wherein the second phosphate-based calcination step is performed under a temperature condition of 700 to 1100°C.
The method of claim 22, wherein the second phosphate-based calcination step is performed for 6 to 24 hours.
A dental composition comprising a phosphor composition represented by Formula 2:

[Formula 2]

Rb(AE 1-x REE3 x )PO 4

here,

wherein x is 0<x≤0.15,

The AE is any one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

The REE3 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 any one selected from the group consisting of thulium (Tm).
The dental composition of claim 29, wherein the dental composition is at least one selected from the group consisting of a dental restoration, a dental prosthesis, and a surface treatment agent for a dental prosthesis.
A method of applying a phosphor composition comprising the steps of:

A phosphate-based phosphor composition mixing step of preparing a phosphate-based coating material by mixing a phosphate-based powder mixture comprising a phosphor composition represented by Formula 2 and a powder, and a binder;

a phosphate-based coating material application step of applying the phosphate-based coating material to an object; and

A phosphate-based heat treatment step in which the phosphate-based coating material applied to the object is heated to a temperature condition of 650 to 750° C. at a temperature increase rate of 40 to 60° C./min and maintained in an isothermal state for 10 to 40 minutes.

[Formula 2]

Rb(AE 1-x REE3 x )PO 4

here,

wherein x is 0<x≤0.15,

The AE is any one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

The REE3 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 any one selected from the group consisting of thulium (Tm).
A phosphor composition represented by the formula (3):

[Formula 3]

AE 3 (REE4 1-xy REE5 x REE6 y ) 2 (BO 3 ) 4

here,

wherein x is 0<x≤0.15,

Wherein y is 0≤y≤0.15,

The AE is one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

The REE4 is one selected from the group consisting of lanthanum (La), gadolinium (Gd) and yttrium (Y),

The REE5 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium ( Er) and one selected from the group consisting of thulium (Tm),

The REE6 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium ( Er) and thulium (Tm) is one selected from the group consisting of.
The phosphor composition of claim 32, wherein REE2 is cerium (Ce).
The phosphor composition of claim 33, wherein x is 0.05≤x≤0.13.
The phosphor composition of claim 32, wherein the REE3 is terbium (Tb).
The phosphor composition of claim 35, wherein y is 0.07≤y≤0.13.
The phosphor composition according to claim 32, wherein the average particle diameter of the phosphor composition is 0.01 to 10 um.
A method for preparing a phosphor composition comprising the steps of:

Barium nitrate [Barium nitrate, Ba(NO 3 ) 2 ], Lanthanum nitrate [Lanthanum nitrate, La(NO 3 ) 3 ], Cerium nitrate [Cerium nitrate, Ce(NO 3 ) 3 ], and Hydrogen borate, HBO 3 ) by dissolving in a solvent to prepare a borate-based lysate preparing a borate-based lysate;

drying the borate-based lysate to obtain a borate-based dry mixture by drying the borate-based lysate;

A borate-based calcination step of heat-treating the borate-based dry mixture under a mixed gas condition comprising H 2 and N 2 gas to obtain a borate-based calcination mixture.
The method of claim 38, wherein the preparing of the borate-based solution comprises dissolving terbium nitrate [Terbium nitrate, Tb(NO 3 ) 3 ] in a solvent in a solvent.
The method of claim 38, wherein the drying of the borate-based melt is performed under a temperature condition of 80 to 150°C.
The method of claim 38, wherein the drying of the borate-based lysate is performed for 12 to 72 hours.
The method of claim 38, wherein the borate-based calcination step is performed under a temperature condition of 900 to 1300°C.
The method of claim 38, wherein the borate-based calcination step is performed for 6 to 24 hours.
A dental composition comprising a phosphor composition represented by Formula 3:

[Formula 3]

AE 3 (REE4 1-xy REE5 x REE6 y ) 2 (BO 3 ) 4

here,

wherein x is 0<x≤0.15,

Wherein y is 0≤y≤0.15,

The AE is one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

The REE4 is one selected from the group consisting of lanthanum (La), gadolinium (Gd) and yttrium (Y),

The REE5 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium ( Er) and one selected from the group consisting of thulium (Tm),

The REE6 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium ( Er) and thulium (Tm) is one selected from the group consisting of.
The dental composition of claim 44, wherein the dental composition is at least one selected from the group consisting of dental restorations, dental prostheses, and dental prosthesis surface treatment agents.
A method of applying a phosphor composition comprising the steps of:

A borate-based phosphor composition mixing step of preparing a borate-based coating material by mixing a borate-based powder mixture comprising the phosphor composition and powder represented by Formula 3, and a binder;

a borate-based coating material application step of applying the borate-based coating material to an object; and

A borate-based coating heat treatment step of raising the temperature of the borate-based coating applied to the object to a temperature condition of 250 to 750°C at a temperature increase rate of 40 to 60°C/min and maintaining the isothermal state for 20 to 40 minutes.

[Formula 3]

AE 3 (REE4 1-xy REE5 x REE6 y ) 2 (BO 3 ) 4

here,

wherein x is 0<x≤0.15,

Wherein y is 0≤y≤0.15,

The AE is one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca),

The REE4 is one selected from the group consisting of lanthanum (La), gadolinium (Gd) and yttrium (Y),

The REE5 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium ( Er) and one selected from the group consisting of thulium (Tm),

The REE6 is cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium ( Er) and thulium (Tm) is one selected from the group consisting of.