KR101885880B1 - Composition for toothpaste containing β-tricalcium phosphate and preparing method for thereof - Google Patents

Abstract

The present invention relates to a preparing method of a toothpaste composition which includes a step of producing β-tricalcium phosphate by reacting a calcium aqueous solution and a phosphoric acid aqueous solution at pH 4.8 to 5.5. Accordingly, nanosized water-soluble β-tricalcium phosphate which is produced in a specific condition is added to the toothpaste composition, so that the β-tricalcium phosphate can be dissolved by saliva or water from the oral cavity when users brush their teeth with toothpaste, and calcium ions can react to teeth and the root surface of the teeth, for improving functions of the toothpaste for regenerating bones of the teeth, removing plaque, whitening the teeth, stopping blood, regenerating gums, and controlling bad breath.

Description

The present invention relates to a dentifrice composition containing β-tricalcium phosphate and a preparation method thereof.

The present invention relates to a dentifrice composition comprising? -Tricalcium phosphate and a process for preparing the same, and more particularly to a dentifrice composition which comprises a nano-sized water-soluble? -Tricalcium phosphate in a dentifrice composition to remove dental calculus, whitening, Tricarboxylic acid, and the like, and a method for producing the same.

A commonly used dentifrice composition is prepared by appropriately adding a wetting and moisturizing agent, a surfactant, a binder, a foaming agent and a sweetener, a preservative, a pigment, a flavor, a stabilizer, and other necessary components, as a main ingredient of a tooth abrasive and a fluoride preparation. However, such a conventional dentifrice composition is focused on the plaque removal and the effect of inhibiting bacteria in the oral cavity caused by fluorine, so that the cleaning of the oral cavity is limited to the tooth itself. Therefore, the oral care such as the gum occupying the tooth or the mucous skin inside the oral cavity Only a slight effect could be provided.

Typical abrasives used as dentifrice components are calcium monohydrogenphosphate, light calcium carbonate, heavy calcium carbonate, precipitated silica, silica gel, hydrated alumina, zirconium silicate, calcium anhydrous calcium phosphate, calcium pyrophosphate, hydroxyapatite, Phosphate, and aluminum silicate. All abrasives, except heavy calcium carbonate, are made by chemical synthesis and have their advantages and disadvantages depending on the type.

For example, calcium fluoride, light calcium carbonate, heavy calcium carbonate, hydrated alumina, calcium pyrophosphate and hydroxyapatite have poor compatibility with the fluorine components, which are basic active ingredients in toothpastes, Zirconium silicate, anhydrous calcium phosphate monohydrate, insoluble metaphosphate, and aluminum silicate have good usability with the elapse of time with fluorine. However, since the hardness of the raw material itself is high, it damages the surface of the tooth or when the toothpaste using such abrasive is used for a long time, And may become an irritable tooth.

In particular, heavy calcium carbonate is a natural raw material of the existing abrasive, but as described above, it has a poor fluorine compatibility with time and crushed calcite formed for hundreds of millions of years, and therefore has high self-hardness and high possibility of containing impurities such as heavy metals.

Accordingly, a dentifrice composition capable of improving the effects of removing dental calculus, whitening, deodorization, and gum restoration while minimizing the tooth damage caused by the use of the abrasive, and suppressing unnecessary reaction with fluorine during storage of the toothpaste, Is required.

Korean Patent No. 10-0313225 Korean Patent Publication No. 10-2004-0059030

It is an object of the present invention to provide a method for producing a dentifrice composition comprising a nano-sized water-soluble beta -triccium phosphate which is cost effective and easy to mass-produce through a simple industrial process.

Another object of the present invention is to provide a dentifrice composition containing nano-sized water-soluble beta -tricalcium phosphate prepared under specific conditions, which is dissolved in saliva or moisture in the oral cavity when toothpaste is used to cause calcium ions to react with the root surface Thereby improving dental plaque removal, whitening, bleeding, gum regeneration, and bad breath suppression.

Another object of the present invention is to coat the surface of water-soluble? -Tricalcium phosphate with an organic material to inhibit the reaction of calcium and fluorine of? -Tricalcium phosphate during toothpaste storage, so that when using toothpaste, Which can improve tooth recrystallization and tooth corrosion prevention function.

According to one aspect of the present invention,

There is provided a method for producing a dentifrice composition comprising reacting an aqueous calcium solution and an aqueous phosphoric acid solution at a pH of 4.8 to 5.5 to prepare? -Tricalcium phosphate.

The reaction may be carried out in a carbon dioxide-free atmosphere.

The reaction may be carried out in a nitrogen atmosphere or in a vacuum.

The reaction may be carried out at a temperature of from 20 to 125 캜.

The aqueous calcium solution may be supersaturated with calcium ions (Ca ^< ^{2 + &} gt ^; ).

The concentration of calcium ion (Ca ^{2 +} ) in the aqueous calcium solution may be 7 to 10 mM.

(A) calcining calcium carbonate (CaCO ₃ ) to produce calcium oxide (CaO); (b) hydrating a calcium oxide (CaO) to produce calcium hydroxide (Ca (OH) ₂ ); And (c) adding water to the calcium hydroxide (Ca (OH) ₂ ) and stirring to generate calcium ions (Ca ^{2 +} ).

The calcination of step (a) can be carried out at 1000 to 1200 ° C for 1 hour to 3 hours.

Step (b) can be carried out in a nitrogen atmosphere or in a vacuum.

The stirring of step (c) may be carried out for 5 to 10 hours.

The aqueous phosphoric acid solution can be prepared by dissolving phosphoric acid (H ₃ PO ₄ ) in water in a carbon dioxide-free atmosphere.

The calcium phosphate slurry obtained according to the above reaction may be allowed to stand at 60 to 90 DEG C for 0.5 to 3 days.

The step of drying the calcium phosphate slurry after the above-mentioned standing can be further performed.

The drying can be carried out in a carbon dioxide free atmosphere and at a temperature of 20 to 125 캜 for 2 to 48 hours.

The product obtained according to the drying may further be heat-treated at a temperature of 700 to 900 DEG C for 0.5 to 12 hours.

The step of milling the β-tricalcium phosphate prepared in the above step with an organic material to form a coating film on the surface of β-tricalcium phosphate particles may be further performed.

The organic material may be at least one selected from a copolymer of polyoxyethylene polyoxypropylene, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, and gelatin.

According to another aspect of the present invention,

There is provided a dentifrice composition comprising [beta] -tricalcium phosphate prepared according to any one of the above.

The? -Tricalcium phosphate is a? -Tricalcium phosphate particle having a particle diameter of 1 to 50 nm; Or rectangular? -Tricalcium phosphate particles having a width of 20 to 50 nm and a length of 20 to 200 nm.

The? -Tricalcium phosphate may be water-soluble.

The dentifrice composition may further include at least one member selected from calcium hydroxide (CaOH) and dicalcium phosphate dihydrate (CaHPO ₄ .2H ₂ O, DCPD).

The dentifrice composition may be from pH 7.5 to pH 8.0.

The? -Tricalcium phosphate may be a particle having a coating film of an organic material formed on its surface.

The organic material may be at least one selected from a copolymer of polyoxyethylene polyoxypropylene, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, and gelatin.

The dentifrice composition may further comprise fluorine.

The method of manufacturing the dentifrice composition of the present invention can be cost-effective and simple to produce nano-sized water-soluble beta -triccium phosphate by mass production through a simple industrial process.

The dentifrice composition of the present invention contains nano-sized water-soluble beta -tricalcium phosphate prepared under specific conditions in a dentifrice composition so that it is dissolved in saliva or water in the oral cavity when toothpaste is used to cause calcium ions to react with the root surface It is possible not only to regenerate the tooth bone but also to improve the function of removing tartar, whitening, hemostasis, gum restoration and bad breath suppression.

In addition, the dentifrice composition of the present invention inhibits the reaction of calcium and fluorine of? -Tricalcium phosphate during toothpaste storage by coating the surface of water-soluble? -Tricalcium phosphate with an organic material so that calcium ions and fluorine ions It is possible to improve tooth recrystallization and tooth corrosion prevention function.

FIG. 1 is a graph showing the phase equilibrium of substances which change depending on the pH environment and the calcium concentration environment when an aqueous solution of calcium is reacted with phosphoric acid.
2 is a partially enlarged graph of FIG.
FIG. 3 is an exemplary conceptual diagram of a drying process in a manufacturing method according to an embodiment of the present invention.
4 is a conceptual diagram showing a manufacturing method according to an embodiment and a comparative example of the present invention.
FIG. 5 is an exemplary conceptual diagram of a method of forming CO ₂ -free air, according to one embodiment of the present invention.
6 is an image of apparatuses used in the manufacturing method according to an embodiment of the present invention.
FIG. 7 is an exemplary conceptual diagram of components that a dentifrice composition according to an embodiment of the present invention may include.
8 is an X-ray diffraction pattern graph of an embodiment of the present invention.
9 is an X-ray diffraction pattern graph of an embodiment of the present invention.
10 is an X-ray diffraction pattern graph of an embodiment of the present invention.
11 is a scanning electron microscope image of Preparation Example 3 particles.
12 is a scanning electron microscope image of Preparation Example 4 particles.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, the dentifrice composition of the present invention will be described.

The dentifrice composition of the present invention is a dentifrice composition comprising β-tricalcium phosphate (hereinafter abbreviated as β-TCP) particle having a particle diameter of 1 to 50 nm or a rectangular β-TCP having a width of 20 to 50 nm and a length of 20 to 200 nm Particles.

The β-TCP is characterized in that it is water-soluble.

The dentifrice composition may further include at least one member selected from calcium hydroxide (CaOH) and dicalcium phosphate dihydrate (CaHPO ₄ .2H ₂ O, DCPD).

Since the β-TCP is weakly acidic at pH 5 to pH 6 and the calcium hydroxide is a strong base at pH 11, it is preferable to mix the β-TCP and calcium hydroxide to adjust the acidity of the dentifrice composition to pH 7.5 to pH 8.0.

If necessary, the β-TCP may be a particle on which a coating film of an organic material is formed on the surface.

The organic material may be a surfactant component such as a copolymer of polyoxyethylene polyoxypropylene, a polyoxyethylene hydrogenated castor oil, a polyoxyethylene sorbitan fatty acid ester, gelatin, etc. However, the scope of the present invention is not limited thereto and β-TCP to prevent unnecessary reaction with other components, thereby improving stability over time. When the toothpaste is used, the coating component can be dissolved and any harmless components to the human body can be applied.

The dentifrice composition preferably further comprises fluorine.

The dentifrice composition of the present invention may comprise an excipient component commonly used in a dentifrice composition, and may include an abrasive, a wetting agent, a binder, and a foaming agent as an excipient. Usually, the wetting agent may be concentrated glycerin, a sorbitol liquid, a foaming agent may be sodium lauryl sulfate, a binder may be sodium carboxymethyl cellulose, a polishing agent may be precipitated silica, precipitated calcium carbonate, or the like.

In addition, sweeteners, fragrances, pigments, and the like may be further used to improve the feeling of use of the dentifrice composition. As the sweetener, xylitol, menthol and fragrance can be used as edible fragrances, such as peppermint oil, spearmint oil, and fruit extract. The sweetener may be sodium saccharin or the like.

Hereinafter, a method of producing the dentifrice composition of the present invention will be described.

The dentifrice composition of the present invention may include a step of reacting an aqueous calcium solution and an aqueous phosphoric acid solution in a pH of 4.8 to 5.5 to prepare beta -triccium phosphate. Such a chemical process is an essential condition for practicing the present invention, and the inventor of the present invention has conducted the above-mentioned conditions through numerous tests and studies. This process is remarkably advanced compared to the prior art, which premises the firing at an ultra-high temperature (1300 to 1400 ° C) and does not realize nano-sized particles.

1 and 2 (a partially enlarged view of FIG. 1) show a graph of supersaturation concentration of calcium and a reaction phase balance with phosphoric acid, which changes with pH conditions. As shown, the materials produced in phase equilibrium in accordance with various pH conditions change together. (CaHPO ₄ .2H ₂ O, DCPD) is formed as the most stable phase at a pH of 4.2 or lower, and hydroxyapatite (HAp) is formed in the most stable state at a pH of 5.5 or higher, A mixed phase of β-TCP, HAp, octacalcium phosphate (OCP), α-tricalcium phosphate (α-TCP) and tetracalcium phosphate (TTCP) is formed in the range of 4.2 to 4.8. Also, when the pH environment is set to 4.8 to 5.5 according to the present invention, a large amount of? -TCP is formed and supersaturated after supersaturation. This pH range can be set by closely controlling the amount of phosphoric acid added, but this can easily be achieved with manual capacity in a massive process.

The mixing of the aqueous calcium solution and the aqueous phosphoric acid solution causes an exothermic reaction. Although the present invention can be carried out without using an additional temperature-forming device, it is preferable to maintain a temperature environment of 20 to 125 캜 in order to obtain β-TCP as a moderate environment, more preferably 60 to 95 캜 Maintaining the temperature condition is advantageous in terms of solubility, reaction and yield of precipitation. That is, when the temperature environment is higher than 125 ° C, the solubility of β-TCP to be formed becomes too high and it is difficult to obtain satisfactory results, and at a temperature lower than 20 ° C., sufficient reaction between the aqueous calcium solution and phosphoric acid is difficult to achieve. Through these results and several additional tests, the present inventors have calculated an optimum yield range at a temperature of 60 to 95 ° C.

The calcium aqueous solution used in the reaction may be a solution in which calcium ions are supersaturated depending on pH and temperature environment. The expression " supersaturated " means that the solute has been added in an amount exceeding the limit that can be dissolved in the aqueous solution, as is known in the art. The supersaturated calcium ions can react with phosphate ions to precipitate products containing β-TCP. In the above-mentioned pH or temperature environment (20 to 125 ° C), the concentration of dissolved supersaturated calcium ions may be 7 to 10 mM, and in a more preferred range (temperature environment 60 to 95 ° C), 7.8 to 10 mM .

It is also preferable that the above reaction is carried out in a carbon dioxide-free atmosphere in which contact with carbon dioxide is blocked. Ca ^{2 +,} or Ca compounds is due to act as a disturbance of the β-TCP crystallization can be made after a carbon group having jinyeotneun a property of easily reacting with the CO ₂ in the environment, thereby generating. Therefore, those who wish to embody or reproduce the present invention should preferably block this ancillary reaction by creating a nitrogen atmosphere or a vacuum environment. Ar is also sufficient for carrying out the present invention. However, in consideration of cost efficiency and convenience, the present invention has set the N ₂ environment as an exemplary environment of the following embodiments. In the same manner, considering the characteristics of the reaction presupposing the aqueous solution environment, the water used as the solvent is also preferably filtered several times and deionized water or carbonic acid-depleted distilled water is used.

The calcium phosphate slurry obtained according to the above reaction is allowed to stand at 60 to 90 DEG C for 0.5 to 3 days.

Thereafter, it can be used in powder form through an additional drying step (Fig. 3), and a further refined form of the composition consisting of only β-TCP by further heat treating the dried composition may be used. The drying is preferably carried out in a carbon dioxide-free atmosphere and at a temperature of 20 to 125 ° C for 2 to 48 hours. The recommended environment is only an example, and the reaction solvent is not contacted with carbon dioxide Any process that can evaporate is applicable.

Thereafter, an additional heat treatment is carried out to add the ancillary components (anhydrous calcium phosphate (CaHPO ₄ , DCPA), tetracalcium dihydrogenphosphate (Ca ₄ H ₂ P ₆ O ₂₀ , TCHP), hydroxyapatite ) Or dicalcium phosphate dihydrate (CaHPO ₄ .2H ₂ O, DCPD)) can be converted into β-TCP. It is sintered by heat treatment, and grain growth occurs, so that the particle diameters of the components contained in the composition can be increased to a certain extent. The heat treatment is preferably performed at a temperature of 700 to 900 ° C for 0.5 to 12 hours. However, such a recommended environment is only an example, and if the process is capable of converting all the components included in the reaction into β-TCP Anything can be applied. As a feature of the above-described process, TCP contained in the dentifrice composition prepared through drying and heat treatment may be expressed as being composed of pure? -TCP with a particle diameter of 1 to 200 nm.

The aqueous calcium solution can be prepared according to the following method.

First, calcium carbonate (CaCO ₃ ) is calcined to produce calcium oxide (CaO) (step a).

The calcination is preferably performed at 1000 to 1200 ° C for 1 to 3 hours.

Thereafter, the calcium oxide (CaO) is hydrated to produce calcium hydroxide (Ca (OH) ₂ ) (step b).

Step (b) is preferably carried out in a nitrogen atmosphere or in a vacuum.

Next, the calcium hydroxide by stirring the (Ca (OH) ₂₎ adding water to generate calcium ions (Ca ^{2 +)} (Step c).

The stirring is preferably performed for 5 to 10 hours.

The aqueous phosphoric acid solution can be prepared by dissolving phosphoric acid (H ₃ PO ₄ ) in water in a carbon dioxide-free atmosphere.

The β-TCP produced according to the above method may be further milled with an organic material to form a coating film on the surface of β-TCP particles.

The organic material may be a copolymer of polyoxyethylene polyoxypropylene, polyoxyethylene hardened castor oil, polyoxyethylene sorbitan fatty acid ester, gelatin, and the like, but the scope of the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent to those skilled in the art, however, that these examples are provided to further illustrate the present invention, and the scope of the present invention is not limited thereto.

[Example]

Manufacturing example  1: Preparation of aqueous calcium solution

CaCO ₃ was calcined in air at 1050 ° C for 2 hours or more to obtain CaO powder. The mixture was cooled to 300 DEG C, transferred to a three-necked flask containing no carbon dioxide, and kneaded using a stir bar and a stirrer chamber. Secondary distilled water was slowly added thereto. The internal temperature of the reactor varied according to the time lapse of the intense exothermic reaction and the amount and rate of distilled water added. Two hours before the execution of the embodiment, the calcium oxide decomposition reaction proceeded to prepare a calcium aqueous solution in which sufficient amounts of Ca ^{2 +} free ions and OH ^- free ions were dissolved.

The carbon dioxide-free atmosphere of the three-necked flask consisted of purging N ₂ gas and introducing decarboxylated air through KOH. That is, CaO was transferred to a three-necked flask, and the rubber stopper was immediately closed. Then, the hose connected to the cap and the Schlenk line were purged with nitrogen gas 3 times or more, and then the air passed through the KOH flask was supplied.

Manufacturing example  2: Preparation of aqueous phosphoric acid solution

In another three-necked flask vessel, an appropriate amount of H ₃ PO ₄ solution was charged and filled with ultrapure water. Then, the connected air hose was purged with nitrogen as described above and connected to the hose through which the air passed through the KOH flask was supplied. Since the pH will be controlled later, the concentration of phosphoric acid was not measured.

Manufacturing example  3: β- TCP  Including Particle Manufacturing

Fig. 4 shows a schematic diagram of a manufacturing process according to an embodiment of the invention, and Fig. 6 shows an image of the substrates used in this manufacturing process. As shown in the figure, the main reaction vessel connected to the stirling chamber and filled with CO ₂ -free air after nitrogen purge was connected to a vessel containing an aqueous calcium solution and a vessel containing phosphoric acid, and these solutions were connected to a Masterflex pump and a silicone tube Were mixed in the main reaction vessel. The pH of these mixed phases is adjusted to 5.0, and the precipitation reaction proceeds while controlling the temperature to 60 to 95 占 폚. A fine nano-precipitate was formed by the precipitation reaction, and when the aqueous calcium or phosphorous acid was consumed, the main reaction vessel was dried at 60 to 95 ° C. In this case, since the CO ₂ -free air is continuously supplied to the main reaction vessel while being heated (FIG. 5), the moisture is discharged out of the vessel through the hose at a high internal pressure, thereby drying. After complete drying for 24 hours, the lid of the main reaction vessel was opened to remove the generated powder.

Manufacturing example  4: β- TCP  Including Particle Manufacturing

The particles prepared according to Preparation Example 3 were heat-treated at 800 ° C for 1 hour and cooled to obtain powders.

Comparative Manufacturing Example  1: β- TCP  Particle manufacturing

The cleaned egg shells were calcined at 800 ° C for 1 hour at atmospheric pressure. Phosphoric acid was added to the calcined egg shell. At this time, the mixing ratio of the egg shell and phosphoric acid was changed from 1: 1.0 to 1: 1.7 by weight, and isopropyl alcohol was used as a solvent. The mixture was ball milled with zirconia (Y-TZP) balls for 12 hours to prevent agglomeration of the mixture and to homogeneously mix. Polyethylene glycol (PEG, MW 2000) was added to the ball-milled mixture so that the weight ratio of the total metal ion: PEG was 3: 1, and the mixture was dried. In the mixed solution of the sol state, the isopropyl alcohol is evaporated due to the drying, and the viscosity is also increased due to the evaporation, resulting in a gel state which is likely to be crumbled. The dried gel was calcined at 900 < 0 > C for 1 hour at atmospheric pressure. The calcined β-TCP was ball-milled with zirconia balls under an isopropyl alcohol solvent. The wet milling was performed for 6 hours, and the ball milled powder was uniaxially pressurized at 10 MPa at atmospheric pressure, molded and sintered at 1300 ° C for 1 hour to obtain β-TCP particles.

Example  1: Preparation of dentifrice composition

20% by weight of particles of Preparation Example 3, 10% by weight of precipitated silica, 25% by weight of sorbitol solution, 10% by weight of concentrated glycerin, 2% by weight of sodium lauryl sulfate, 1% by weight of carboxymethylcellulose sodium, 0.6% by weight of xylitol, The dentifrice composition was prepared by mixing.

Example  2: Preparation of dentifrice composition

A dentifrice composition was prepared in the same amount as in Example 1, except that 10% by weight was included instead of 20% by weight of the particles of Preparation Example 3.

Example  3: Preparation of dentifrice composition

A dentifrice composition was prepared in the same amount as in Example 1, except that 5% by weight was included instead of 20% by weight of the particles of Preparation Example 3.

Example  4: Preparation of dentifrice composition

A dentifrice composition was prepared in the same proportions as in Example 1 except that 15% by weight was substituted for 20% by weight of the particles of Preparation Example 3 and 5% by weight of calcium hydroxide was further contained.

Example  5: Preparation of dentifrice composition

A dentifrice composition was prepared in the same amount as in Example 4, except that 1.5% by weight of a fluorine component (Na ₂ SiF ₆ ) was further contained in the dentifrice composition of Example 4.

Example  6: Preparation of dentifrice composition

A dentifrice composition was prepared in the same amount as in Example 1, except that particles prepared according to Preparation Example 4 were used instead of Preparation Example 3.

[Comparative Example]

Comparative Example  1: β- TCP  Preparation of no-dentifrice composition

A dentifrice composition was prepared in the same proportions as in Example 1, except that particles of Preparation Example 3 were not used and 15% by weight of calcium hydroxide was included.

Comparative Example  2: β- TCP  Preparation of no-dentifrice composition

A dentifrice composition was prepared in the same amount as in Example 1, except that particles of Preparation Example 3 were not used and 8 weight% of calcium hydroxide was included.

Comparative Example  3: β- TCP  Preparation of no-dentifrice composition

A dentifrice composition was prepared in the same amount as in Example 1, except that particles of Preparation Example 3 were not used but 4% by weight of calcium hydroxide was included.

Comparative Example  4: Conventional β- TCP  Preparation of dentifrice composition containing

A dentifrice composition was prepared in the same amount as in Example 1, except that particles of Comparative Preparation Example 1 were used instead of the particles of Preparation Example 3.

Comparative Example  5: Conventional β- TCP  Preparation of dentifrice composition containing

A dentifrice composition was prepared in the same amount as in Example 4, except that the particles of Comparative Preparation Example 1 were used instead of the particles of Preparation Example 3.

[Test Example]

Test Example  One: XRD  analysis

Figs. 8 and 9 show X-ray diffraction (XRD) patterns of Comparative Examples prepared with the same environment as Production Example 3 and Production Example 3 and with various compositions (aqueous calcium solution and phosphoric acid). As shown in the figure, it can be confirmed that Production Example 3 is composed of a calcium phosphate compound complex such as TCP, TCHP, DCPA or DCPD. In particular, the red arrows shown in the figure indicate peaks of? -TCP. The homogeneous reaction between the free ions Ca ^{2 +} and PO ₄ ^3- proceeded at high speed agitation, resulting in nanocrystalline TCP crystals (α, β or σ phase), Ca (OH) ₂ And CaHPO ₄ , The heterogeneous reaction occurs, indicating that TCHP, DCPA or DCPD is mixed. The schematic components of Production Example 3 are shown in the conceptual view of FIG.

FIG. 10 shows an X-ray diffraction (XRD) pattern of Production Example 4. As shown in the figure, it can be confirmed that Production Example 4 is composed of almost pure β-TCP crystals. Compared with the results of Production Example 3, all the impurities contained in Production Example 3 were converted into β-TCP by heat treatment. Further, in the subsequent measurement results, it was confirmed that the particles of Production Example 3 formed a particle size distribution of 1 to 50 nm, while the particles of Production Example 4 formed a particle size distribution of 1 to 200 nm. This is larger than the particles of Production Example 3, but still small particles as compared with conventional ones, and has excellent compactness and strength characteristics.

Test Example  2: SEM  image

Fig. 11 shows an image of a particle of Production Example 3 taken by a scanning electron microscope. As shown, Production Example 3 contains particles of 1 to 50 nm in particle size, and also includes rectangular beta -tricalcium phosphate particles of 20 to 50 nm in width and 20 to 170 nm in length.

Fig. 12 shows an image of particles of Production Example 4 taken by scanning electron microscope. As can be seen, in Production Example 4, particles of Production Example 3 were found to have achieved grain growth.

Test Example  3: Analysis of the effect of tartar removal

In order to confirm the effect of removing the calculus, the scaled calculus was finely pulverized and dried in the dental clinic. Then, using a dentifrice composition prepared according to Examples 1 to 6 and Comparative Examples 1 to 3, a dentifrice composition of a dentifrice composition: water = 1: 4 was prepared and centrifuged, and 10 ml of the supernatant was taken. After the dental calculus was soaked, the dental calculus was filtered and dried, and the weight of the dental calculus was calculated and summarized in Table 1 below.

division Preparation of TPC-Containing Particles TPC-containing particles (% by weight) Ca (OH) ₂ (% by weight) Fluoride (Na ₂ SiF ₆₎ (% by weight) Dental removal rate (%) Example 1 Production Example 3 20 0 0 35 Example 2 Production Example 3 10 0 0 23 Example 3 Production Example 3 5 0 0 15 Example 4 Production Example 3 15 5 0 39 Example 5 Production Example 3 15 5 0.5 42 Example 6 Production Example 4 20 0 0 36 Comparative Example 1 Production Example 3 0 15 0 17 Comparative Example 2 Production Example 3 0 8 0 8 Comparative Example 3 Production Example 3 0 4 0 3 Comparative Example 4 Comparative Preparation Example 1 20 0 0 15 Comparative Example 5 Comparative Preparation Example 1 15 5 0 18

According to Table 1, the dentifrice compositions prepared according to Examples 4 and 5 of the present invention showed the highest dental calculus removal rate, and these results show that the dentifrice composition containing both β-TCP and calcium hydroxide The dentifrice composition containing β-TCP of Comparative Preparation Example 1 produced according to the conventional method was effective even when the same amount was included, but the dental plaque removal effect was relatively low. In addition, the particle size of β-TCP did not significantly affect the dental plaque removal effect.

Experimental Example  4: Analysis of tooth whitening effect

A gel was prepared by mixing coffee, tea, sugar, and calcium, and an extracted human tooth sample was prepared. The gel was attached to the prepared tooth for 5 days to form a stain, followed by drying. Thereafter, the teeth formed with the irregularities were fixed on the polishing apparatus specially designed for the test, and the bristles were fixed on the axis of motion, so as to be able to friction with the tooth specimens. At this time, 1.5 g of the dentifrice compositions prepared according to the above Examples 1 to 6 and Comparative Examples 1 to 3 were placed on the bristles in the same manner, and the toothbrush was operated for 20 minutes so as to be reciprocated 70 times per minute, ), Whiteness after brushing (b) was measured with a color difference meter [CR10-Plus, Nonica Minolta Japan]. As a result, the degree of increase (? L, b-a) of whiteness is shown in Table 2 below.

division Preparation of TPC-Containing Particles TPC-containing particles (% by weight) Ca (OH) ₂ (% by weight) Fluoride (Na ₂ SiF ₆₎ (% by weight) ΔL Example 1 Production Example 3 20 0 0 68 Example 2 Production Example 3 10 0 0 43 Example 3 Production Example 3 5 0 0 26 Example 4 Production Example 3 15 5 0 71 Example 5 Production Example 3 15 5 0.5 75 Example 6 Production Example 4 20 0 0 67 Comparative Example 1 Production Example 3 0 15 0 23 Comparative Example 2 Production Example 3 0 8 0 15 Comparative Example 3 Production Example 3 0 4 0 14 Comparative Example 4 Comparative Preparation Example 1 20 0 0 22 Comparative Example 5 Comparative Preparation Example 1 15 5 0 24

According to Table 2, the dentifrice compositions prepared according to Examples 4 and 5 of the present invention showed the best whitening effect, and these results show that dentifrice compositions containing β-TCP and calcium hydroxide are more effective, The particle size of β-TCP did not significantly affect the whitening effect. In addition, even though the same amount was included, the dentifrice composition containing β-TCP of Comparative Preparation Example 1 produced according to the conventional method showed relatively low tooth whitening effect.

Experimental Example  5: Analgesic effect of bad breath

To measure the effect of the dentifrice composition of the present invention on halitosis, the degree of halitosis inhibition was measured using a halimeter. A diluted solution obtained by diluting methylmercaptan solution (1 / / 占 벤 benzene solvent) in 0.2 M potassium phosphate buffer solution (pH 7.5) so as to have a halimeter measurement value of 500 to 600 ppb was used as a source of bad breath.

A dentifrice composition of dentifrice composition: water = 1: 4 was prepared using the dentifrice composition prepared according to Examples 1 to 6 and Comparative Examples 1 to 3, and centrifuged to obtain 10 ml of each supernatant. 500 占 퐇 of the above-described odor causing agent was added to the wells, and the mixture was allowed to stand in a water bath at 37 占 폚 for 10 minutes. Then, the amount of sulfur compound was measured using a halimeter to calculate the degree of halitosis inhibition (%). .

division Preparation of TPC-Containing Particles TPC-containing particles (% by weight) Ca (OH) ₂ (% by weight) Fluoride (Na ₂ SiF ₆₎ (% by weight) Bad breath inhibition (%) Example 1 Production Example 3 20 0 0 94 Example 2 Production Example 3 10 0 0 87 Example 3 Production Example 3 5 0 0 82 Example 4 Production Example 3 15 5 0 92 Example 5 Production Example 3 15 5 0.5 97 Example 6 Production Example 4 20 0 0 95 Comparative Example 1 Production Example 3 0 15 0 77 Comparative Example 2 Production Example 3 0 8 0 75 Comparative Example 3 Production Example 3 0 4 0 69 Comparative Example 4 Comparative Preparation Example 1 20 0 0 69 Comparative Example 5 Comparative Preparation Example 1 15 5 0 71

According to Table 3, the dentifrice composition of Example 5 showed the highest inhibitory effect against bad breath, and the higher the content of β-TCP, the higher the effect of suppressing bad breath. In addition, even if the same amount was included, the dentifrice composition containing β-TCP of Comparative Preparation Example 1 prepared according to the conventional method showed relatively low odor suppressing effect.

Claims (21)

Reacting an aqueous calcium solution and an aqueous phosphoric acid solution at pH 4.8 to 5.5 to prepare? -Tricalcium phosphate; And
And milling the β-tricalcium phosphate prepared in the above step with an organic material to form a coating film on the surface of β-tricalcium phosphate particles. The method according to claim 1,
Wherein the reaction is carried out in an atmosphere free of carbon dioxide. 3. The method of claim 2,
Wherein the reaction is carried out in a nitrogen atmosphere or in a vacuum. The method according to claim 1,
Wherein the reaction is carried out at a temperature of from 20 to < RTI ID = 0.0 > 125 C. < / RTI > The method according to claim 1,
Wherein the calcium aqueous solution is supersaturated with calcium ions (Ca ^< ^{2 + &} gt ^; ). The method according to claim 1,
Wherein the concentration of calcium ions (Ca ^< ^{2 + &} gt ^; ) in the aqueous calcium solution is 7 to 10 mM. The method according to claim 1,
The calcium aqueous solution,
comprising the steps of: (a) preparing a calcined calcium oxide (CaO) by the oxidation of calcium carbonate (CaCO _3);
(b) hydrating a calcium oxide (CaO) to produce calcium hydroxide (Ca (OH) ₂ ); And
(c) adding water to the calcium hydroxide (Ca (OH) ₂ ) and stirring the mixture to generate calcium ions (Ca ^< ^{2 +} >). The method according to claim 1,
Wherein the step of allowing the? -Tricalcium phosphate slurry obtained according to the reaction to stand at 60 to 90 占 폚 for 0.5 to 3 days is further carried out. 9. The method of claim 8,
Wherein the step of drying the? -Tricalcium phosphate slurry after the standing is further carried out. 10. The method of claim 9,
Wherein the drying is performed in a carbon dioxide-free atmosphere and at a temperature of 20 to 125 DEG C for 2 to 48 hours. 11. The method of claim 10,
Wherein the product obtained by the drying is further subjected to heat treatment at a temperature of 700 to 900 DEG C for 0.5 to 12 hours. delete The method according to claim 1,
Wherein the organic material is at least one selected from a copolymer of polyoxyethylene polyoxypropylene, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, and gelatin. 13. A dentifrice composition comprising? -Tricalcium phosphate, which is produced according to any one of claims 1 to 11, and which has a coating film of an organic material formed on its surface. 15. The method of claim 14,
The? -Tricalcium phosphate is a? -Tricalcium phosphate particle having a particle diameter of 1 to 50 nm; Or 20 to 50 nm wide and 20 to 200 nm long rectangular beta -triccium phosphate particles. 15. The method of claim 14,
Wherein the? -Triccium phosphate is water-soluble. 15. The method of claim 14,
Wherein the dentifrice composition further comprises at least one selected from calcium hydroxide (CaOH) and dicalcium phosphate dihydrate (CaHPO ₄ .2H ₂ O, DCPD). 18. The method of claim 17,
Wherein the dentifrice composition has a pH of from 7.5 to 8.0. delete 15. The method of claim 14,
Wherein the organic material is at least one selected from a copolymer of polyoxyethylene polyoxypropylene, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, and gelatin. 15. The method of claim 14,
Wherein the dentifrice composition further comprises fluorine.

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