KR102523822B1 - Borate composition having luminescence properties similar to natural teeth and method for manufacturing the same - Google Patents

Abstract

The present invention is a borate-based phosphor composition having light emitting characteristics similar to natural teeth of a person to be treated by doping a host material with rare earth elements (REE) metal trivalent cations in a specific ratio, and Regarding the manufacturing method thereof, since the light emitting characteristics of the phosphor composition can be adjusted by adjusting the doping concentration ratio of rare earth metal trivalent, it is possible to improve the aesthetic effect on the tooth appearance of the person to be treated.

Description

Borate-based phosphor composition having luminescent 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 producing the same, and specifically, by doping a host material with rare earth elements (REE) metal trivalent cations in a specific ratio, the natural tooth of a person to be treated It relates to a borate-based phosphor composition having light emitting characteristics 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 great obstacle occurs in pronunciation, chewing, and aesthetics. In addition, when adjacent teeth move into an empty space where there are no teeth, and the normal arrangement of the teeth starts to shift, food gets caught between the teeth, resulting in tooth decay or tooth decay and bad breath. In particular, damage or missing molars can cause malnutrition because they cannot eat properly. In addition, damage or deficiency of the front teeth not only causes aesthetic problems, but also increases the probability of secondary caries occurring in the damaged or missing area.

Therefore, for patients with such damage or loss of teeth, chewing and aesthetic treatment such as dental restoration, which is a replacement treatment for teeth, is performed. It refers to sealing the cavity formed by cutting out the affected tooth with a tooth replacement material, and the tooth replacement material used at this time is a dental restorative material.

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

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

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

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

Accordingly, the inventors of the present invention prepared a borate-based phosphor composition containing trivalent cations of rare earth metals, and the composition according to the present invention adjusts the doping concentration of trivalent cations of rare earth metals to improve natural teeth of individuals. It was confirmed that luminescence characteristics similar to luminescence characteristics could be exhibited.

Accordingly, an 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 producing 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 manufacturing the same, and specifically, by adjusting the doping ratio of rare earth elements (REE) metal trivalent cations to a host material, thereby adjusting the natural tooth of the person to be treated It relates to a borate-based phosphor composition having light emitting characteristics 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 crystal material” may mean AE ₃ (REE1) ₂ (BO ₃ ) ₄ .

In the present invention, AE may mean an alkaline earth element selected from the group consisting of barium (Ba), strontium (Sr), and calcium (Ca), and for example, may be barium However, it 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), yttrium (Y), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium ( It may be a rare earth element (REE) selected from the group consisting of Tb), dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (Tm), for example, it may be lanthanum However, it 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), and may be one type of rare earth metal (rare earth elements, REE) selected from the group consisting of, for example, it may be 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 means that x does not include 0 and includes 0.15, but has a value between 0 and 0.15.

In the present invention, the element ratio of the chemical formula is generally described as an integer, but when the ratio of elements included in one molecule such as alloys or special minerals is complicated, it is simpler to describe as a decimal than to describe as an integer. can also be written as

In the present invention, x is the ratio of the rare earth metal REE2 doped at the site of the rare earth metal REE1 of the parent crystal in the chemical formula, and can be expressed as wt% or mol% depending on the synthesis method such as the solid phase method and the liquid phase method. For example, 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 act of improving or reforming the properties of a parent crystal material by adding a small amount of another material to the parent crystal material in the field of metallurgy.

In one embodiment of the present invention, the borate-based phosphor composition represented by Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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), and may be one type of rare earth metal (rare earth elements, REE) selected from the group consisting of, for example, terbium, but is not limited thereto.

In the present invention, y is the ratio of the rare earth metal REE3 doped at the site of the rare earth metal REE1 of the parent crystal in the chemical formula, and can be expressed in wt% or mol% depending on the synthesis method such as the solid phase method and the 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 means 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 0.17, or 0.15 It may be 0.07 to 0.13, for example, 0.07 to 0.13, but is not limited thereto.

In one embodiment of the present invention, the borate-based phosphor composition represented by Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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 Chemical 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, 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 to 520 nm, 420 to 600 nm, 420 to 590 nm, 420 to 580 nm, 420 to 570 nm, 420 to 560 nm, 420 to 550 nm, 420 to 540 nm, 420 to 530 nm, 420 to 520 nm, 430 to 600 nm, 430 to 590 nm, 430 to 580 nm, 430 to 570 nm, 430 to 560 nm, 430 to 550 nm, 430 to 540 nm, 430 to 530 nm, 430 to 520 nm, 440 to 600 nm, 440 to 590 nm, 440 to 580 nm, 440 to 570 nm, 440 to 560 nm, 440 to 550 nm, 440 to 540 nm, 440 to 530 nm, 440 to 520 nm, 450 to 600 nm, 450 to 590 nm, 450 to 580 nm, 450 to 570 nm, 450 to 560 nm, 450 to 550 nm, 450 to 540 nm, 450 to 530 nm, 450 to 520 nm, 460 to 600 nm, 460 to 590 nm, 460 to 580 nm, 460 to 570 nm, 460 to 560 nm, 460 to 550 nm, 460 to 540 nm, 460 to 530 nm, 460 to 520 nm, 470 to 600 nm, 470 to 590 nm, 470 to 580 nm, 470 to 570 nm, 470 to 560 nm, 470 to 550 nm, 470 to 540 nm, 470 to 530 nm, 470 to 520 nm, 480 to 600 nm, 480 to 590 nm, 480 to 580 nm, 480 to 570 nm, 480 to 560 nm, It may be 480 to 550 nm, 480 to 540 nm, 480 to 530 nm, or 480 to 520 nm, for example, 480 to 510 nm, but is not limited thereto.

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

Barium nitrate, Ba(NO ₃ ) ₂ ], lanthanum nitrate, La(NO ₃ ) ₃ ], cerium nitrate, Ce(NO ₃ ) ₃ ] and boric acid (Hydrogen borate, HBO ₃ ) in a solvent to prepare a lysate;

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

A calcination step of subjecting the dried mixture to heat treatment under a mixed gas condition containing H ₂ and N ₂ gas to obtain a calcination 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 Boric acid (Hydrogen borate, HBO ₃ ) may be dissolved in a solvent to prepare a lysate.

In the present invention, the preparation step may be to prepare a lysate by 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 solution, but is not limited thereto.

In the present invention, the drying step may be carried out under temperature conditions of 80 to 150 ° C, 80 to 140 ° C, 80 to 130 ° C, 80 to 120 ° C, 80 to 110 ° C, 80 to 100 ° C or 80 to 90 ° C, , For example, it may be performed 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 included in the melt may not be sufficiently evaporated, and the solvent may remain, contaminating the phosphor composition.

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

In the present invention, the calcination step may be performed 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, 1100 to 1200 °C It may be performed at a temperature condition 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 reduced by remaining as impurities or residues.

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

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

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

In the present invention, the 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 pulverizer or an ultra pulverizer, but is not limited thereto.

In the present invention, the 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. It may be, for example, a ball mill, but is not limited thereto.

In the present invention, the crushing 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 It may, but is not limited thereto.

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

Another example of the present invention is to provide a dental composition comprising 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 dental restorations, dental prostheses, and surface treatment agents for dental prostheses, but is not limited thereto.

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

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

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

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

A heat treatment step of raising the temperature of the coating material applied to the object to a temperature condition of 650 to 750 ° C. at a heating rate of 40 to 60 ° C./min and maintaining the temperature in an 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, which may mean a dental material for giving gloss to artificial teeth to cause aesthetics, but is not limited thereto.

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

In the present invention, the weight ratio (w/w%) of the phosphor composition and the powder included in the powder mixture may be 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 a suitable 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 included in the coating 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% by weight. to 45% by weight, but is not limited thereto.

In the present invention, the subject 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 so as to have a viscosity to be properly applied to the target object, but is not limited thereto.

In the present invention, the heating rate of the heat treatment step is 40 to 60 °C/min, 40 to 58 °C/min, 40 to 56 °C/min, 40 to 54 °C/min, 40 to 52 °C/min, 42 to 60 °C /min, 42 to 58 °C/min, 42 to 56 °C/min, 42 to 54 °C/min, 42 to 52 °C/min, 44 to 60 °C/min, 44 to 58 °C/min, 44 to 56 °C/min 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 . However, it is not limited thereto.

In the present invention, the 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 ℃, 300 to 600 ℃, 300 to 550 ℃, 300 to 500 ℃, 350 to 750 ℃, 350 to 700 ℃, 350 to 650 ℃, 350 to 600 ℃, 350 to 550 ℃, 350 to 500 ℃, 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 may be raised to a temperature condition, for example, to be heated to a temperature condition of 400 to 500 °C It may, but is not limited thereto.

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

The present invention is a borate-based phosphor composition having light emitting characteristics similar to natural teeth of a subject by doping Rare earth elements (REE) metal trivalent cations in a specific ratio in a host material and a method for manufacturing the same Regarding, since it is possible to adjust the light emitting characteristics of the phosphor composition by adjusting the doping concentration ratio of rare earth metal trivalent, it is possible to improve the aesthetic effect on the tooth appearance of the person to be treated.

1 is a photograph of a particle diameter of a borate-based phosphor composition according to an embodiment of the present invention observed under a microscope. (Scale bar: 10um)
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.
Figure 6 shows the appearance after a borate-based phosphor composition is applied to a substrate and subjected to heat treatment at 300 ° C, 400 ° C, 500 ° C, 600 ° C and 700 ° C according to an experimental example of the present invention, and a borate-based phosphor when irradiated with ultraviolet rays This is a photograph taken of the composition emitting light.
7 is a graph comparing and analyzing luminescence characteristics before a borate-based phosphor composition is applied to a substrate and luminescence characteristics after being applied to a substrate and subjected to a heat treatment process.

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

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

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

As used herein, the terms "about", "substantially" and the like are used at or close to the value when manufacturing and material tolerances inherent in the stated meaning are given, and are intended to convey an understanding of the present invention. Accurate or absolute figures are used to help prevent exploitation by unscrupulous infringers of the disclosed 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 a phosphor composition to have a high energy level, and in general, the excitation spectrum coincides with the absorption spectrum. can

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

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

Preparation Example 1. Preparation of borate-based phosphor composition (lanthanum-cerium-terbium)

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

Table 1 shows the mol% of La, Ce ³⁺ and Tb ³⁺ contained in the mixtures of Examples 1 to 7.

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 was dried for 12 hours under a temperature condition of 80 °C using a centrifugal separator to obtain a dried product. A calcined mixture was obtained by heat-treating the obtained dried material at a temperature of 1200° C. for 6 hours under a mixed gas condition 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 grinding for 6 hours using a ball mill so that the calcined mixture had an average particle diameter of 3 μm or less, and the particle diameter of the borate-based phosphor composition was confirmed. 1.

Preparation Example 2. Preparation of borate-based phosphor composition (lanthanum-cerium)

As starting materials, barium nitrate [Barium nitrate, Ba(NO ₃ ) ₂ ], lanthanum nitrate [Lanthanum nitrate, La(NO ₃ ) ₃ ], A mixture was prepared by dry mixing cerium nitrate (Ce(NO ₃ ) ₃ ) and boric acid (Hydrogen borate, HBO ₃ ) and 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 control the pH to 9.

The mol% ratios of La and Ce included 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, Ba(NO ₃ ) ₂ ], lanthanum nitrate, La(NO ₃ ) ₃ ], terbium nitrate, Tb(NO ₃ ) ₃ ] and boric acid (Hydrogen borate , HBO ₃ ) was dry mixed and mixed with 10% by weight of water based on the total weight of the mixture to prepare a mixture. Ammonia water (NH ₄ OH) was further added to the mixture to control the pH to 9.

The mol% ratios of La and Tb included 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 in 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 increased, and the peaks were single phase. was measured as

In addition, since the Ba ₃ La ₂ (BO ₃ ) ₄ crystal lattice contracted as the concentrations of Tb ³⁺ and Ce ³⁺ ions increased, it was confirmed that the position of the XRD peak shifted to a higher angle. Through this, it was confirmed that the 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

The borate-based phosphor compositions of Examples 1 to 7 were analyzed for photoluminescence and excitation wavelength using a spectrofluorometer at room temperature.

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, emission characteristics are shown in FIGS. 3a and 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 Luminous intensity (a.u.) 360 1,247 1,628 2,220 4,520 3,870 3,134

As can be seen in FIG. 3a and Table 4, when the wavelength of the light source is 365 to 405 nm, the phosphor composition of Example 5 containing 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, 623 nm.

The phosphor composition containing 7 mol% of Ce and 10 mol% of Tb was measured to have the strongest luminescence intensity (PL intensity), and when the 7 mol% of Ce and 10 mol% of Tb were included, the luminescence intensity rather decreased. Confirmed.

As can be seen in Figure 3b and Table 4, the minimum excitation wavelength was measured to be 320 nm and the maximum excitation wavelength to be 329 nm. The phosphor composition was not excited when the light source wavelength was 405 nm, so the excitation wavelength was hardly measured.

2-2. Lanthanum-cerium phosphor composition

The borate-based phosphor compositions of Examples 8 to 14 were analyzed for photoluminescence and excitation wavelength using a spectrofluorometer at room temperature.

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 and 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 Luminous intensity (a.u.) 404 495 466 652 421 515 447

As can be seen in Figures 4a, 4b and Table 5, when the light source wavelength is 365 nm, the phosphor composition of Example 11 with Ce ^{3 +} 7 mol% showed the strongest intensity of luminescence with 652 au. . 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

The borate-based phosphor compositions of Examples 15 to 21 were analyzed for photoluminescence and excitation wavelength using a spectrofluorometer at room temperature.

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, emission characteristics are shown in FIGS. 5a and 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 Luminous intensity (a.u.) 403 498 733 1,272 1,324 1,270 669

As can be seen in Figures 5a, 5b and Table 6, when the light source wavelength is 365 nm, the phosphor composition of Example 19 with Tb ^{3 +} 10 mol% showed the strongest intensity of luminescence with 1,324 au. . When the phosphor composition contained 13 mol% or more of Tb ³⁺ , it was confirmed that concentration quenching appeared due to a decrease in emission intensity. The minimum excitation wavelength was determined to be 245 nm and the maximum excitation wavelength to be 251 nm.

In summary, in the case of the phosphor composition (Example 11) containing Ce ³⁺ 7 mol% and Tb ³⁺ 0 mol%, cyan blue emission of 473 nm, which is the shortest emission wavelength, was exhibited, and Ce ³⁺ 7 In the case of the phosphor composition (Example 5) including mol% and Tb ³⁺ 10 mol%, yellowish-white emission of 547 nm, which is the longest emission wavelength, was exhibited. Yellow wish-white light emission means light emission obtained by summing all light emission wavelengths in the visible light region.

In the phosphor composition of the present invention, the emission wavelength of the phosphor composition can be controlled in the range of 473 to 547 nm by adjusting the mol% concentrations of Ce ³⁺ and Tb ³⁺ with reference to the fluorescence characteristics of natural teeth, thereby improving aesthetic properties of natural teeth. The luminous properties can be adjusted accordingly.

Experimental Example 3. Luminescence characteristics upon application 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 a ratio of 2:8 (w/w%). After preparing a paste (coating product) by mixing the powder mixture and a binder (propylene glycol) at a ratio of 7:3 (w/w%), it is applied to a substrate and heated from room temperature to 300 to 700 ℃ at a heating rate of 50 ℃/min. The heat treatment was performed for a total of 30 minutes while heating at high speed to the temperature condition, and the appearance is shown in FIG. 6 .

7 and Table 7 show PL/PLE graphs comparing and analyzing the emission characteristics of the phosphor composition applied to the substrate at each heating temperature.

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

As can be seen from FIG. 7 and Table 7, when the phosphor composition of Example 5 was mixed with a binder and subjected to heat treatment, the emission intensity decreased but the emission wavelength was maintained.

In general, when a phosphor composition is subjected to high-temperature heat treatment, the phosphor composition interacts with the binder and the light emission disappears, whereas the phosphor composition is subjected to a very high-speed heating heat treatment to minimize the interaction and damage between the binder and the phosphor. The emission wavelength could be maintained.

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Claims (15)

A dental composition comprising a phosphor 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). The dental composition according to claim 1, wherein REE2 is cerium (Ce). The dental composition according to claim 2, wherein x is 0.05≤x≤0.13. The dental composition according to claim 1, wherein REE3 is terbium (Tb). The dental composition according to claim 4, wherein y is 0.07≤y≤0.13. The dental composition according to claim 1, wherein the dental composition has an average particle diameter of 0.01 to 10 um. delete delete delete delete delete delete delete According to claim 1, wherein the dental composition is at least one member selected from the group consisting of dental restorations, dental prosthesis and dental prosthesis surface treatment agent, the dental composition. A method of applying a dental composition comprising the following steps:
A mixing step of preparing a coating material by mixing a powder mixture including the phosphor composition represented by Formula 1 and the powder, and a binder;
an application step of applying the application material to a target object; and
A heat treatment step of raising the temperature of the coating material applied to the object to a temperature condition of 250 to 750 ° C. at a heating rate of 40 to 60 ° C./min and maintaining it in an isothermal state for 20 to 40 minutes.
[Formula 1]
AE 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).

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