KR20220103408A - Borate composition having luminescence properties similar to natural teeth and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a borate-based fluorescent substance composition and a method for manufacturing the same, wherein the composition has light emitting properties similar to the natural teeth of a person to be treated by doping trivalent rear earth element (REE) metal positive ions to a main body determining material (host material) at a specific ratio. Since the light emitting properties of the fluorescent substance composition can be controlled by adjusting the doping concentration ratio of trivalent rare earth element metal, it is possible to improve the aesthetic effect on the tooth appearance of the person to be treated.

Description

BORATE COMPOSITION HAVING LUMINESCENCE PROPERTIES SIMILAR TO NATURAL TEETH AND METHOD FOR MANUFACTURING THE SAME

The present invention relates to a borate-based phosphor composition and a method for preparing the same, and more particularly, by doping a host material with rare earth elements (REE) metal trivalent cations in a specific ratio to obtain natural values It relates to a borate-based phosphor composition having luminescent properties similar to those of natural teeth 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. In addition, 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 tooth decay or bad breath, and bad breath occurs. In particular, damage or missing molars can cause nutritional deficiencies because they cannot 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 in 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 hypersensitivity reaction is caused. In recent years, with the development of mass media, the individual's aesthetic needs have increased, 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, the fluorescence spectrum of natural teeth showed the largest band at a wavelength of about 410 nm to 420 nm, which is a characteristic of blue mauve, and gradually increased to 680 nm by many researchers. was observed to decrease.

When these natural teeth are exposed to ultraviolet (ultraviolet) radiation in the oral cavity, various fluorescence appears from a single tooth or between teeth. 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 Asians, yellow-wish white color (reddish) from the gums. yellowish-white).

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

Accordingly, the present inventors prepared a borate-based phosphor composition containing a trivalent cation of a rare earth metal, and the composition according to the present invention adjusts the doping concentration of the trivalent cation of the rare earth metal, thereby improving individual natural teeth It was confirmed that luminescence characteristics similar to luminescence characteristics can be exhibited.

Accordingly, it is an object of the present invention 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 borate-based phosphor composition and a method for preparing the same, and more particularly, by controlling the doping ratio of rare earth elements (REE) metal trivalent cations in a host material, [0001] The present invention relates to a borate-based phosphor composition having luminescent properties similar to those of natural teeth 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 borate-based phosphor composition represented by Formula 1:

[Formula 1]

AE ₃ (REE1 _1-xy REE2 _x REE3 _y ) ₂ (BO ₃ ) ₄

In the present invention, the term “maternal crystalline material” may mean AE ₃ (REE1) ₂ (BO ₃ ) ₄ .

In the present invention, AE may mean one kind of alkaline earth elements selected from the group consisting of barium (Ba), strontium (Sr), and calcium (Ca), for example, barium However, the present invention 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 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, REE2 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, 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, and 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 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 as wt% or mol% according to synthesis methods such as solid phase method and liquid phase method. For example, when the wt% of REE2 is 5 wt% or 5 mol%, x may be 0.05.

In the present invention, x may be 0.01 to 0.15, 0.01 to 0.14, 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, 0.05 to 0.13, but is not limited thereto.

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 borate-based phosphor composition represented by Formula 1 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 1 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 1 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 1 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 1 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 1 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 1 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 1 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 1 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 1 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 1 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 1 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 1 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 1 may be Ba ₃ (La _0.85 Tb _0.15 ) ₂ (BO ₃ ) ₄ .

In the present invention, REE3 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 kind of rare earth metal (REE) selected from the group consisting of, for example, terbium, but is not limited thereto.

In the present invention, y is the ratio of the rare earth metal REE3 doped to the REE1 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% or mol% of REE3 is 10 wt% or 10 mol%, y may be 0.07.

In the present invention, y 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 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 It may be 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 1 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 1 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 1 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 1 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 1 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 1 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 1 may be Ba ₃ (La _0.78 Ce _0.07 Tb _0.15 ) ₂ (BO ₃ ) ₄ .

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, may be 3 um, but is not limited thereto.

In the present invention, the emission wavelength of the 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 to 580 nm, 480 to 570 nm, 480 to 560 nm, 480 to 550 nm, 480 to 540 nm, 480 to 530 nm or 480 to 520 nm may be, for example, 480 to 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 following steps:

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 lysate;

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

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

In the present invention, the 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 It may be to prepare a lysate by dissolving boric acid (Hydrogen borate, HBO ₃ ) in a solvent.

In the present invention, the preparation step may be to prepare a lysate by further dissolving terbium nitrate [Terbium nitrate, Tb(NO ₃ ) ₃ ] in a solvent.

In the present invention, the solvent may be one selected from the group consisting of distilled water, nitric acid aqueous solution, hydrochloric acid aqueous solution, acetone and ethanol, 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 drying step may be 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 ℃, and , for example, may be carried out under a temperature condition of 80 to 90 ℃, but is not limited thereto.

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

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

In the present invention, the calcination step may be to obtain a calcined mixture by heat-treating the dried mixture subjected to the drying step.

In the present invention, the calcination step may be carried out at a temperature of 900 to 1300 ℃ 900 to 1200 ℃ 1000 to 1300 ℃ 1000 to 1200 ℃ 1100 to 1300 ℃ or 1100 to 1200 ℃, for example, 1100 to 1200 ℃ It may be carried out under the temperature conditions of, but is not limited thereto.

In the present invention, the 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, it may be performed for 6 hours. , but is not limited thereto.

When the 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 cannot be synthesized into the phosphor composition. Therefore, the yield of the borate-based phosphor composition may be lowered as impurities or residues remain.

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

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 be one containing 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 calcination step may further include a pulverization step of pulverizing the calcination mixture.

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

In the present invention, the fine pulverizer is 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, to be performed for 6 to 8 hours. However, the present invention is not limited thereto.

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

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

[Formula 1]

AE ₃ (REE1 _1-xy REE2 _x REE3 _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 dental prosthesis surface treatment agent, 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 phosphor composition comprising the steps of:

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

an application step of applying the coating material to an object; and

A heat treatment step of raising the temperature of the coating material 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 1]

AE ₃ (REE1 _1-xy REE2 _x REE3 _y ) ₂ (BO ₃ ) ₄

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

In the present invention, the weight ratio (w/w%) of the phosphor composition and the powder included in the powder mixture may be 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 powder mixture contained in the 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 65% by weight or It may be 55 to 60% by weight, but is not limited thereto.

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

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

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

The temperature increase rate of the heat treatment step in the present invention is 40 to 60 ℃ / min, 40 to 58 ℃ / min, 40 to 56 ℃ / min, 40 to 54 ℃ / min, 40 to 52 ℃ / min, 42 to 60 ℃ /min, 42-58 °C/min, 42-56 °C/min, 42-54 °C/min, 42-52 °C/min, 44-60 °C/min, 44-58 °C/min, 44-56 °C/min 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. However, the present invention is not limited thereto.

In the present invention, the heat treatment step is 250 to 750 °C 250 to 700 °C, 250 to 650 °C, 250 to 600 °C, 250 to 550 °C, 250 to 500 °C, 300 to 750 °C, 300 to 700 °C, 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 ℃, 400 to 700 ℃, 400 to 650 ℃, 400 to 600 ℃, 400 to 550 ℃ or 400 to 500 ℃ may be to raise the temperature to a temperature condition of, for example, to a temperature condition of 400 to 500 ℃ to increase the temperature However, the present invention is not limited thereto.

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

The present invention relates to a borate-based phosphor composition and a method for preparing the same, by doping a host material with a rare earth element (REE) metal trivalent cation in a specific ratio to have luminescent properties similar to the natural teeth of a person to be treated In this regard, since the luminescent property of the phosphor composition can be controlled by adjusting the ratio of the rare earth metal trivalent doping concentration, it is possible to improve the aesthetic effect on the appearance of the teeth of the recipient.

1 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)
2a to 2c are graphs showing XRD patterns of borate-based phosphor compositions according to an experimental example of the present invention.
3A and 3B are graphs showing PL/PLE of a borate-based phosphor composition (lanthanum-cerium-terbium) according to an experimental example of the present invention.
4A and 4B are graphs showing PL/PLE of a borate-based phosphor composition (lanthanum-cerium) according to an experimental example of the present invention.
5A and 5B are graphs showing PL/PLE of a borate-based phosphor composition (lanthanum-terbium) according to an experimental example of the present invention.
6 shows the appearance of a borate-based phosphor composition applied to a substrate according to an experimental example of the present invention and subjected to heat treatment at 300° C., 400° C., 500° C., 600° C. and 700° C., and a borate-based phosphor upon UV irradiation. It is a photograph of the state that the composition emits light.
7 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-based phosphor composition is applied to the substrate and subjected to a heat treatment process.

The terms used herein are used only to describe specific embodiments, and are 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 cannot be present or 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 intended to enhance the understanding of the present invention. To help, precise or absolute figures are used to prevent unfair use by unscrupulous infringers of the stated disclosure. Also, in the present specification, “step of” or “step of” does not mean “step for”.

In the present invention, the term “excitation wavelength” may 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 according to the gist of the present invention, it is common knowledge in the art that the scope of the present invention is not limited by these preparations and examples. It will be self-evident in person.

Preparation Example 1. 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 1 to 7 are shown in Table 1.

element (mol%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 La (mol%) 92 90 88 86 83 80 78 Ce (mol%) 7 7 7 7 7 7 7 Tb (mol%) One 3 5 7 10 13 15 Sum 100 100 100 100 100 100 100

The mixture whose pH was controlled to 9 was stirred at 60° C. for 2 hours using a stirrer. The stirred mixture using a centrifuge was dried for 12 hours under a temperature condition of 80° C. to obtain a dry product. A calcination mixture was obtained by heat-treating the obtained dried product 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.

The borate-based phosphor compositions of Examples 1 to 7 were prepared by pulverizing for 6 hours using a ball mill so that the average particle diameter of the calcined mixture was 3 μm or less, and the particle diameter of the borate-based phosphor composition was confirmed. 1 is shown.

Preparation Example 2. 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 8 to 14 are shown in Table 2.

element (mol%) Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 La (mol%) 99 97 95 93 90 87 85 Ce (mol%) One 3 5 7 10 13 15 Sum 100 100 100 100 100 100 100

Preparation Example 3. 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 15 to 21 are shown in Table 3.

element (mol%) Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 La (mol%) 99 97 95 93 90 87 85 Tb (mol%) One 3 5 7 10 13 15 Sum 100 100 100 100 100 100 100

Experimental Example 1. XRD pattern analysis of borate-based phosphor composition

As a result of analyzing the XRD patterns of the borate-based phosphor compositions of Examples 1 to 21 using X-ray diffraction (XRD), Examples 1 to 7 are shown in FIG. 2A Examples 8 to 14 are shown in FIG. 2B, and Examples 15 to 21 are shown in FIG. 2C.

As can be seen from FIGS. 2A to 2C , in the borate-based phosphor compositions of Examples 1 to 21, 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.

Experimental Example 2. PL/PLE analysis of borate-based phosphor composition

2-1. Lanthanum-terbium-cerium phosphor composition

For the borate-based phosphor compositions of Examples 1 to 7, photoluminescence and excitation wavelength were analyzed under a temperature condition of room temperature using a spectrofluorometer.

When the borate-based phosphor compositions of Examples 1 to 7 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. 3A, 3B and Table 4.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 emission wavelength (λ _em ) 546 546 546 546 546 546 546 excitation wavelength (λ _ex ) 329 324 320 324 320 324 330 Luminescence intensity (a.u.) 360 1,247 1,628 2,220 4,520 3,870 3,134

As can be seen in FIGS. 3A and 4 , when the light source wavelength was 365 to 405 nm, the phosphor composition of Example 5 having 7% Ce and 10% Tb exhibited the strongest intensity of luminescence. In Figure 3a, each peak was measured to be Ex _{365 nm} = 490 nm, 545 nm, 585 nm, and 623 nm.

The phosphor composition including 7 mol% of Ce and 10 mol% of Tb was measured to have the strongest PL intensity. Confirmed.

As can be seen in FIG. 3B and Table 4, 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.

2-2. Lanthanum-cerium phosphor composition

For the borate-based phosphor compositions of Examples 8 to 14, photoluminescence and excitation wavelength were analyzed under a temperature condition of room temperature using a spectrofluorometer.

When the phosphor compositions of Examples 8 to 14 were irradiated with a light source having a light source wavelength (λ _ex ) of 365 to 405 nm, emission characteristics are shown in FIGS. 4A, 4B and Table 5.

Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 emission wavelength (λ _em ) 473 473 473 472 482 475 489 excitation wavelength (λ _ex ) 323 320 320 320 329 324 323 Luminescence intensity (a.u.) 404 495 466 652 421 515 447

As can be seen in FIGS. 4A, 4B and Table 5, when the light source wavelength was 365 nm, the phosphor composition of Example 11 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.

2-3. Lanthanum-terbium phosphor composition

For the borate-based phosphor compositions of Examples 15 to 21, photoluminescence and excitation wavelength were analyzed under a temperature condition of room temperature using a spectrofluorometer.

When the phosphor compositions of Examples 15 to 21 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. 5A, 5B and Table 6 .

Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 emission wavelength (λ _em ) 546 546 546 546 546 546 546 excitation wavelength (λ _ex ) 245 245 246 250 251 251 251 Luminescence intensity (a.u.) 403 498 733 1,272 1,324 1,270 669

As can be seen in FIGS. 5A, 5B and Table 6, when the light source wavelength was 365 nm, the phosphor composition of Example 19 with Tb ³⁺ 10 mol% exhibited the strongest intensity of luminescence at 1,324 au. . 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 11), cyan blue light emission at 473 nm, which is the shortest emission wavelength, was exhibited, and Ce ³⁺ 7 In the case of the phosphor composition including mol% and Tb ³⁺ 10 mol% (Example 5), yellowish-white light emission of 547 nm, which is the longest emission wavelength, was exhibited. Yellow-wish-white emission refers to emission of all emission wavelengths in the visible region.

The phosphor composition of the present invention can control the emission wavelength of the phosphor composition in the range of 473 to 547 nm by adjusting the mol% concentration of Ce ³⁺ and Tb ³⁺ with reference to the fluorescence properties of natural teeth, so that the aesthetic properties of natural teeth The light emission characteristics can be adjusted accordingly.

Experimental Example 3. Luminescence properties of borate-based phosphor composition

A powder mixture was prepared by mixing the phosphor composition of Example 5 (Ce 7%, Tb 10%) and IPS e.max Ceram Glaze powder at 2:8 (w/w%). After mixing the powder mixture and the binder (propylene glycol) at 7:3 (w/w%) to prepare a paste (coating material), it is applied to a substrate and heated from room temperature to 50°C/min at a temperature increase rate of 300 to 700°C. Heat treatment was performed for a total of 30 minutes while heating at high speed to the temperature condition, and the appearance thereof is shown in FIG. 6 .

7 and Table 7 show PL/PLE graphs comparing and analyzing the luminescence characteristics of the phosphor composition applied to the substrate for each temperature rise temperature.

Paste 300 ℃ 400 ℃ 500 ℃ 600 ℃ 700 ℃ Emission wavelength (nm) 545 545 545 545 545 545 Luminescence intensity (a.u.) 4,000 2,255 1,210 792 957 683

As can be seen in FIGS. 7 and 7, when the phosphor composition of Example 5 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 is extinguished, whereas the interaction and damage between the binder and the phosphor is minimized through a very fast and high-speed heat treatment for the phosphor composition. The emission wavelength could be maintained.

Claims (15)

A phosphor composition represented by the formula (1):
[Formula 1]
AE ₃ (REE1 _1-xy REE2 _x REE3 _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 REE1 is one selected from the group consisting of lanthanum (La), gadolinium (Gd) and yttrium (Y),
The REE2 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 REE3 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 1, wherein the REE2 is cerium (Ce). The phosphor composition according to claim 2, wherein x is 0.05≤x≤0.13. The phosphor composition of claim 1, wherein the REE3 is terbium (Tb). The phosphor composition of claim 4, wherein y is 0.07≤y≤0.13. The phosphor composition according to claim 1, 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 lysate;
a drying step of drying the lysate to obtain a dry mixture; and
A calcination step of heat-treating the dried mixture under a mixed gas condition comprising H ₂ and N ₂ gas to obtain a calcined mixture. The method of claim 7, wherein the preparation step further dissolves terbium nitrate [Terbium nitrate, Tb(NO ₃ ) ₃ ] in a solvent in a solvent. The method of claim 7, wherein the drying step is performed under a temperature condition of 80 to 150°C. The method of claim 7, wherein the drying step is performed for 12 to 72 hours. The method of claim 7, wherein the calcination step is performed under a temperature condition of 900 to 1300 °C. The method of claim 7, wherein the calcination step is performed for 6 to 24 hours. A dental composition comprising a phosphor composition represented by Formula 1.
[Formula 1]
AE ₃ (REE1 _1-xy REE2 _x REE3 _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 REE1 is one selected from the group consisting of lanthanum (La), gadolinium (Gd) and yttrium (Y),
The REE2 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 REE3 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 according to claim 13, 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 mixing step of preparing a coating material by mixing a powder mixture comprising the phosphor composition represented by Formula 1 and a powder, and a binder;
an application step of applying the coating material to an object; and
A heat treatment step of raising the temperature of the coating material 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 1]
AE ₃ (REE1 _1-xy REE2 _x REE3 _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 REE1 is one selected from the group consisting of lanthanum (La), gadolinium (Gd) and yttrium (Y),
The REE2 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 REE3 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.

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