KR20240015412A - Oral composition - Google Patents

Abstract

Oral compositions according to embodiments of the present invention include porous glass nanoparticles having a specific surface area of 250 m ² /g or more, a potassium salt, and a fluorine compound. The remineralization and dentinal tubule sealing ability of demineralized dentin can be improved by porous glass nanoparticles, potassium salts, and fluorine compounds with a high specific surface area, and symptoms of tooth hyperesthesia can be alleviated.

Description

Oral composition {ORAL COMPOSITION}

The present invention relates to compositions for oral use. More specifically, it relates to an oral composition containing bioactive porous glass nanoparticles and a hypersensitivity treatment using the same.

Dentin contains a mineral called hydroxyapatite, collagen, and water, and between the hydroxyapatite and collagen bundles is composed of organic substances such as phosphophorine. In addition, it contains dentinal tubule structures with different inner diameters at the top and bottom.

If dentin or dentinal tubules are exposed, the nerve of the tooth sealed inside the tooth may be exposed, and symptoms such as cold ear or hyperesthesia may occur even with mild stimulation. Additionally, if dentin or dentinal tubules continue to degenerate, inflammation may occur and pain may worsen.

Hypersensitivity of teeth may occur when the dentin of the teeth is exposed due to physical abrasion such as brushing or chemical abrasion due to acid. For example, when the enamel layer and cementum covering dentin are destroyed due to strong physical or chemical stimulation, or when the gum tissue that protects dentin is lost, dentinal tubules may be exposed. When the dentinal tubules are exposed, external stimuli can irritate the nerves within the dentinal tubules, and for example, pain due to highly acidic foods, cold drinks, cold air, or physical contact becomes more likely to occur.

To improve tooth hypersensitivity, pain caused by stimulation can be alleviated by dulling the sensory nerves. Alternatively, by blocking the dentinal tubules using powder such as aluminum salt particles, external stimuli can be prevented from reaching the nerve. However, the above-described powder, etc. are easily dissolved/diluted in water, so most of them do not remain on the teeth and can be washed away, and the dentinal tubules may not be sufficiently sealed and the dentinal tubules may be exposed again.

Therefore, in addition to treating hypersensitivity, there is a need to develop a dental composition that can improve both the remineralization of dentin, the application of the enamel layer, and the penetration effect into the dentin layer.

For example, Korean Patent Publication No. 10-2014-0072055 discloses an example of an oral composition.

Korean Patent Publication No. 10-2014-0072055

One object of the present invention is to provide an oral composition having excellent remineralization properties and dentinal tubule blocking ability.

Oral compositions according to exemplary embodiments include porous glass nanoparticles having a specific surface area of 250 m ² /g or more; potassium salt; and fluorine compounds.

According to exemplary embodiments, the specific surface area of the porous glass nanoparticles may be 250 m ² /g to 800 m ² /g.

According to exemplary embodiments, the volume average particle diameter (D50) of the porous glass nanoparticles may be 30 nm to 100 nm.

According to exemplary embodiments, the pore volume of the porous glass nanoparticles may be 0.1 cm ³ /g to 1 cm ³ /g.

According to exemplary embodiments, the porous glass nanoparticles may include at least one selected from the group consisting of Si, Ca, Cu, Mg, Na, K, P, Al, B, and F.

In some embodiments, the porous glass nanoparticles are SiO ₂ , CaO, CuO, MgO, Na ₂ O, K ₂ O, P ₂ O ₅ , Al ₂ O ₃ , B ₂ O ₃ , NaF and CaF ₂ It may include at least one selected from the configured group.

In some embodiments, the porous glass nanoparticles include 0.5 mol% to 40 mol% of calcium (Ca), 0.1 mol% to 10 mol% of phosphorus (P), and 4 mol% to 90 mol% of silicon (Si). can do.

In some embodiments, the porous glass nanoparticles may be surface modified with a silane group or an amine group (-NH ₂ ).

According to exemplary embodiments, the potassium salt may include at least one of potassium carbonate, potassium bicarbonate, potassium citrate, potassium chloride, potassium sulfate, potassium phosphate, and potassium nitrate.

In some embodiments, the potassium salt may include potassium nitrate.

According to exemplary embodiments, the fluorine compound may include at least one of sodium fluoride, potassium fluoride, ammonium fluoride, tin fluoride, sodium monofluorophosphate, potassium monofluorophosphate, sodium silicon fluoride, and calcium silicon fluoride. there is.

In some embodiments, the fluorine compound may include sodium fluoride.

According to exemplary embodiments, of the total weight of the oral composition, the content of the porous glass nanoparticles is 0.01% by weight to 10% by weight, the content of the potassium salt is 0.5% by weight to 10% by weight, and the fluorine compound The content may be 0.1% by weight to 7.5% by weight.

According to exemplary embodiments, the oral composition may further include polyacrylic acid.

In some embodiments, the content of polyacrylic acid may be 0.5% by weight to 5% by weight of the total weight of the oral composition.

In some embodiments, the oral composition may further include at least one of a surfactant, a humectant, a pH adjuster, an antioxidant, and a solvent.

In some embodiments, the pH of the oral composition may be 2 to 7.5.

Oral compositions according to exemplary embodiments may have any one formulation selected from the group consisting of liquid, powder, syrup, gel, paste, and cream. .

Oral compositions according to exemplary embodiments may include porous glass nanoparticles having a high specific surface area, potassium salts, and fluorine compounds. As porous glass nanoparticles have a high specific surface area and pore volume, the remineralization characteristics of dentin and the dentinal tubule blocking ability can be improved. Therefore, transmission of stimulation to the sensory nerve within the dentinal tubule can be prevented.

Additionally, as the oral composition contains potassium salts, the sensory nerves of the teeth may become dulled. For example, potassium ions can desensitize dental nerves and relieve pain caused by stimulation of sensory nerves.

In addition, by containing a fluorine compound, the increase in oral cavity bacteria can be suppressed, and the loss of oral tissue can be minimized by preventing the accumulation of plaque on the surface of teeth. Additionally, a protective film can be formed on the surface of the teeth by fluorine ions derived from fluorine compounds, and the teeth can be protected from external stimuli.

1A, 1B, 1C and 1D are SEM photographs of the dentin surface observed at 500x magnification after sequentially applying and leaving the oral compositions according to Example 1, Example 2, Example 3 and Example 4. am.
Figures 2a, 2b, 2c and 2d are SEM photographs of the dentin surface observed at 2,000x magnification after sequentially applying and leaving the oral compositions according to Example 1, Example 2, Example 3 and Example 4. am.
Figures 3a, 3b, 3c and 3d are SEM photographs of the dentin surface observed at 500x magnification after sequentially applying and leaving the oral compositions according to Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4. am.
Figures 4a, 4b, 4c and 4d are SEM photographs of the dentin surface observed at 2,000 times magnification after sequentially applying and leaving the oral compositions according to Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4. am.
Figures 5a and 5b are SEM photographs observed at 1,000x magnification of the dentin surface after applying and leaving the oral composition according to Example 3 and Comparative Example 1, respectively.
Figures 6a and 6b are SEM photographs observed at 2,000x magnification of the dentin surface after applying and leaving the oral composition according to Example 3 and Comparative Example 1, respectively.

Oral compositions according to embodiments of the present invention include porous glass nanoparticles, potassium salts, and fluorine compounds. In addition, the oral composition may further include a wetting agent, a surfactant, a pH adjuster, an antioxidant, etc.

The oral composition can be applied to toothpaste, oral cleaner, gum, candy, tooth whitener, oral cleaner, spray, oral patch, oral ointment, etc., and can be applied in liquid, powder, syrup, gel, etc. It can be manufactured in a formulation such as paste or cream.

As used herein, the term “hyperesthesia symptom” may mean a case where thermal, physical, or chemical stimulation stimulates the nerve of the tooth, causing a toothache symptom or when the symptom persists and develops into pain.

The term “alleviation” used herein means reducing or alleviating any symptom, and can be understood as a concept including prevention, treatment, improvement, suppression, or alleviation.

The term “improvement” used herein can be understood as a concept meaning to treat a certain symptom, etc., and restore the symptom to close to its original state.

Hereinafter, oral compositions according to embodiments of the present invention will be described in detail.

Oral compositions according to exemplary embodiments may include porous glass nanoparticles.

Porous glass nanoparticles may refer to ion-releasing glass particles that can induce specific biological actions within living tissue, and may be composed of inorganic materials. For example, porous glass nanoparticles can play a role in providing mineral components necessary for remineralization of dentin.

For example, cement and enamel may be removed by physical stimulation such as strong brushing or strong chemical stimulation, and dentin may be exposed to the outside and demineralized. When dentin and dentinal tubules are demineralized or exposed, external stimuli may be transmitted into the dentinal tubules to stimulate nerves present within the dentinal tubules. In this case, symptoms of irritability or hypersensitivity may appear due to external stimuli.

According to exemplary embodiments, porous glass nanoparticles can promote dentin regeneration by providing minerals such as calcium, silicate, phosphorus, and copper necessary for remineralization of demineralized dentin. For example, by remineralizing dentin, the damaged dentin surface can be restored, and dentinal tubules can be filled with minerals.

As the entrance to the dentinal tubule is blocked by remineralization of dentin, irritant transmitting substances may not be delivered into the dentinal tubule. Therefore, it is possible to suppress external stimuli from being transmitted to the dental pulp through nerves and dentinal fluid, and to suppress or improve symptoms of irritability or hyperesthesia.

The specific surface area of the porous glass nanoparticles may be 250 m ² /g or more. For example, the specific surface area of the porous glass nanoparticles may be 250 m ² /g to 800 m ² /g, preferably 450 m ² /g to 800 m ² /g, more preferably 550 m ² /g to 550 m 2 /g. It may be 750 m ² /g. The specific surface area of porous glass nanoparticles can be measured by the BET (Brunaucr-Emmett-Teller) method.

As the porous glass nanoparticles have a high specific surface area in the above range, the transport/release efficiency of ions per unit weight can be high. In this case, the amount of mineral components supplied to dentin may increase, and hydroxyapatite (hydroxyapatite, the main component of dentin) may increase. The formation of HAp) can be promoted. Accordingly, a hydroxyapatite layer can be formed on the dentin surface, and the entrance of the dentinal tubule can be filled with the supplied mineral component.

For example, when the specific surface area of the porous glass nanoparticles is less than 250 m ² /g, the ion release ability of the porous glass nanoparticles may be reduced, and the remineralization characteristics and dentinal tubule blocking ability may be reduced. For example, if the specific surface area of the porous glass nanoparticles exceeds 800 m ² /g, the mechanical and chemical properties of the porous glass nanoparticles may decrease, and the uniformity of the hydroxyapatite layer formed on the dentin surface may decrease. It can be.

In addition, since the porous glass nanoparticles include a plurality of pores, they can additionally provide a space to support ions that help in dimension regeneration. Therefore, the regeneration of dentin by porous glass nanoparticles can be promoted, and the number of unoccluded dentinal tubules can be relatively reduced.

According to exemplary embodiments, the porous glass nanoparticles may have a pore volume of 0.1 cm ³ /g or more. For example, porous glass nanoparticles may have a pore volume ranging from 0.1 cm ³ /g to 1 cm ³ /g, and preferably may have a pore volume ranging from 0.3 cm ³ /g to 0.7 cm ³ /g. . Pore volume can be measured together with the BET specific surface area measurement described above.

As the porous glass nanoparticles have a high pore volume of 0.1 cm ³ /g or more, the amount of inorganic components released from the porous glass nanoparticles per unit time can be increased. For example, even if porous glass nanoparticles have a small particle size, the area where inorganic ions are released through internal pores may increase. Therefore, regeneration of dentin or tooth surface layer by porous glass nanoparticles can be promoted, and the remineralization rate can be increased.

If the pore volume of the porous glass nanoparticles exceeds 1 cm ³ /g, the overall release amount and supply capacity of inorganic components may decrease as the density of the porous glass nanoparticles decreases, and the mechanical stability of the porous glass nanoparticles may decrease. there is.

According to exemplary embodiments, the average diameter of the pores of the porous glass nanoparticles may be about 2 nm to 50 nm, preferably 2 nm to 25 nm, and more preferably 2.5 nm to 10 nm. The average diameter of pores refers to the arithmetic average of the diameters of pores on the surface of porous glass nanoparticles. The pore diameter can be measured by scanning electron microscopy (SEM) or transmission electron microscopy (TEM), or can be measured together with the BET specific surface area measurement described above.

Within the above range, a decrease in the mechanical strength of the porous glass nanoparticles can be prevented and the dentinal tubules can be quickly filled with the porous glass nanoparticles.

In some embodiments, the porous glass nanoparticles may contain 50% or more of the total pores with a diameter of 5 nm to 20 nm, and preferably 80% or more of the total pores of the porous glass nanoparticles. By containing more than 50% of pores with a surface pore size of 5 nm or more, the adsorption/release characteristics of inorganic ions can be improved, and tooth defects can be quickly improved.

According to exemplary embodiments, the volume average particle diameter (D50) of the porous glass nanoparticles may be 30 nm to 100 nm, and preferably 50 nm to 100 nm. The volume average particle diameter (50) refers to the particle diameter at 50% of the volume fraction in the cumulative particle size distribution.

If the volume average particle diameter of the porous glass nanoparticles is less than 30 nm, the viscosity of the oral composition may locally increase, and the amount of porous glass nanoparticles penetrating into dentin may be reduced. If the average particle diameter of the porous glass nanoparticles is greater than 100 nm, the porous glass nanoparticles may precipitate within the composition, and the remineralization characteristics of dentin may deteriorate.

According to exemplary embodiments, the porous glass nanoparticles include silicon (Si), calcium (Ca), copper (Cu), magnesium (Mg), sodium (Na), potassium (K), phosphorus (P), and aluminum ( It may contain inorganic components such as Al), boron (B), and fluorine (F). For example, the porous glass nanoparticles may include SiO ₂ , CaO, CuO, MgO, Na ₂ O, K ₂ O, P ₂ O ₅ , Al ₂ O ₃ or B ₂ O ₃ . These may be used alone or in combination of two or more.

As the inorganic components are continuously released/eluted from the porous glass nanoparticles, ions such as calcium or silicon can be supplied to the teeth. Accordingly, the formation of hydroxyapatite (HAp) may be induced by deposition of inorganic components on the dentin surface.

Preferably, the porous glass nanoparticles may include CaO, P ₂ O ₅ and SiO ₂ . For example, the porous glass nanoparticles may include 0.5 to 40 mol% of calcium (Ca), 0.1 to 10 mol% of phosphorus (P), and 4 to 90 mol% of silicon (Si). In this case, the mechanical strength and stability of the porous glass nanoparticles can be improved, and dentin regeneration on the damaged tooth surface can be promoted.

In some embodiments, the porous glass nanoparticles may be surface modified with a silane group or an amine group (-NH ₂ ). For example, a silane group or an amine group may be disposed on the surface of the above-mentioned inorganic particle. In this case, the dispersibility of porous glass nanoparticles can be improved by silane groups or amine groups.

For example, as porous glass nanoparticles are composed of inorganic components, their dispersibility in water or solvent may be low. When the surface of the porous glass nanoparticle is modified with a silane group or amine group, which is a hydrophilic functional group, it can have high dispersibility in water or polar solvents, thereby improving the usability of the oral composition.

In some embodiments, the content of the porous glass nanoparticles may be 0.01% by weight to 10% by weight of the total weight of the oral composition. If the content of porous glass nanoparticles is less than 0.01% by weight, hydroxyapatite (HAp) may not be sufficiently formed due to a lack of inorganic components delivered to dentin. If the content of porous glass nanoparticles exceeds 10% by weight, the porous glass nanoparticles may aggregate with each other in the oral composition, and dentin regeneration and dentinal tubule sealing ability may be reduced.

Preferably, the porous glass nanoparticles may be included in 0.1% by weight to 5% by weight of the total weight of the dentin adhesive composition, and more preferably, they may be included in 0.5% by weight to 3% by weight. Within the above range, tooth defects can be quickly filled, and hyperesthesia can be alleviated or improved by blocking exposed sensory nerves.

Fluorine compounds can act as a source of fluoride ions in the oral cavity. Therefore, teeth can be remineralized and a thin protective film can be formed on the outer surface of the teeth. Therefore, teeth, dentin, and dental pulp can be protected from external stimuli or bacteria.

In addition, fluorine ions supplied from a fluorine compound can suppress the increase of oral bacteria, for example, caries bacteria, and prevent plaque from forming on the oral surface. Therefore, symptoms of damage to cementum and enamel or destruction of gum tissue can be alleviated, and symptoms of dental caries and hyperesthesia can be improved.

In addition, fluorine compounds can further alleviate symptoms of hypersensitivity through interaction with the above-mentioned porous glass nanoparticles. For example, fluorine ions can improve the stability and preservation of dentinal tubules sealed by porous glass nanoparticles, and the dentinal tubule sealing ability can be further improved by fluorine compounds.

In one embodiment, the fluorine compound may include sodium fluoride, potassium fluoride, ammonium fluoride, tin fluoride, sodium monofluorophosphate, potassium monofluorophosphate, sodium silicon fluoride, or calcium silicon fluoride. These may be used alone or in combination of two or more.

Preferably, the fluorine compound may include sodium fluoride. Sodium fluoride has high compatibility with other ingredients and high ionization degree, so it can further improve the protection of the dentin surface and the prevention of hypersensitivity.

According to exemplary embodiments, the content of the fluorine compound may be 0.1% by weight to 7.5% by weight of the total weight of the oral composition, preferably 1% by weight to 6% by weight, more preferably 2% by weight. It may be 5% by weight. If the content of the fluorine compound is less than 0.1% by weight, the supply of fluoride ions is low, which may increase the number of caries bacteria in the oral cavity, and symptoms of dental caries and hyperesthesia may worsen. If the content of the fluorine compound exceeds 7.5% by weight, fluorine ions may precipitate from the dentin surface, reducing stability, and excessive fluorine ions may cause yellowing of the teeth.

Potassium salts can dull the sensory nerves of teeth. For example, potassium ions generated from potassium salts can desensitize dental nerves and relieve pain by preventing stimulation from being transmitted to the periodontium through sensory nerves.

In one embodiment, the potassium salt may include potassium nitrate, potassium chloride, potassium sulfate, potassium carbonate, potassium bicarbonate, potassium phosphate, or potassium citrate. Preferably, the potassium salt may include potassium nitrate. Potassium nitrate has a high degree of dissociation into potassium ions, so it can further alleviate pain caused by hyperesthesia.

In some embodiments, the content of the potassium salt may be 0.5% to 10% by weight of the total weight of the oral composition, preferably 1% to 5% by weight, more preferably 2% to 5% by weight. It may be %. If the potassium salt content is less than 0.5% by weight, the concentration of potassium ions is small and the perceptual nerve may not slow down. If the potassium salt content exceeds 5% by weight, the concentration of potassium ions may become excessively high and may precipitate, which may inhibit or interfere with the actions of other ingredients.

According to exemplary embodiments, the oral composition may further include polyacrylic acid. Polyacrylic acid may serve as a thickener or emulsion stabilizer in the oral composition, and the oral composition may be formed by polyacrylic acid. Viscosity can be adjusted.

For example, polyacrylic acid can stabilize an unstable emulsion state caused by immiscible components in an oral composition. Therefore, the miscibility and dispersibility between each of the above-mentioned components can be improved, and the oral composition can have a uniform and stable form. Accordingly, blockage of dentinal tubules and remineralization of dentin by the oral composition can be promoted, and symptoms of hypersensitivity to the joints and ear sensations can be further alleviated.

In addition, polyacrylic acid has high viscosity, so even if only a small amount is added to the oral composition, a high viscosity composition can be formed. Therefore, a small amount of polyacrylic acid can provide an oral composition having the formulation of, for example, a gel or cream.

In some embodiments, the content of polyacrylic acid may be 0.5% by weight to 5% by weight, preferably 1% by weight to 3% by weight, based on the total weight of the oral composition. Within the above range, the oral composition can be stabilized and precipitation and layer separation of each component can be prevented. Additionally, it is possible to prevent the pH of the oral composition from being excessively low due to excessive polyacrylic acid.

In some embodiments, the oral composition may further include a wetting agent, a surfactant, a pH adjuster, an antioxidant, a solvent, etc., as needed, in addition to the ingredients described above.

Wetting agents can function as thickening agents to control the viscosity of oral compositions. For example, the humectant may include sorbitol, propylene glycol, butylene glycol, glycerin, or polyethylene glycol. These may be used alone or in combination of two or more.

The content of the humectant can be determined considering the viscosity and formulation of the oral composition. In one embodiment, the content of the humectant may be 1% by weight to 85% by weight of the total weight of the oral composition, preferably 20% by weight to 80% by weight, more preferably 50% by weight to 75% by weight. It can be.

Surfactants may include anionic surfactants and/or nonionic surfactants.

For example, anionic surfactants include N-acylamino acid salt, α-olefin sulfonate salt, N-acyl sulfonate salt, alkyl sulfate, glycerin fatty acid ester sulfate, POE alkyl sulphosuccinate, POE alkyl ether sulfate, and POE alkyl ether. Phosphate, sodium benzoate, or sodium laureth sulfate may be included. These may be used alone or in combination of two or more.

For example, nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene hydrogenated castor oil, polyoxyethylene ether of glycerin ester, sucrose fatty acid ester, alkylolamide or glycerin. Fatty acid esters, etc. can be mentioned. These may be used alone or in combination of two or more.

In some embodiments, the content of the surfactant may be 0.01% to 5% by weight, preferably 0.1% to 1% by weight, based on the total weight of the oral composition.

The pH regulator may control the pH of the adhesive composition or may serve to buffer pH changes caused by the oral environment.

Examples of the pH adjusting agent include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, citric acid, phosphoric acid, malic acid, gluconic acid, maleic acid, succinic acid, glutamic acid, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium citrate, sodium hydrogen citrate, Examples include sodium phosphate and sodium dihydrogen phosphate. These may be used alone or in combination of two or more.

In one embodiment, the content of the pH adjuster may be 0.01% to 5% by weight of the total weight of the oral composition, for example, 0.1% to 3% by weight. Within the above range, the pH of the oral composition can be appropriately adjusted, and the composition can have excellent stability and activity over time.

In some embodiments, the pH of the oral composition may be about 2 to 7.5, preferably about 3 to 6.5. As the stability of the oral composition is improved within the above range, the remineralization properties by porous glass nanoparticles and the alleviating effect of hyperesthesia symptoms by fluorine compounds and potassium salts can be improved.

Solvents may be contained depending on the formulation and viscosity of the oral composition. For example, the solvent may include water or a lower alcohol such as ethanol or propanol. The solvent may be included in the remaining amount of the oral composition.

In some embodiments, the content of the solvent may be 1% to 90% by weight of the total weight of the oral composition, and in one embodiment, the content of the solvent may be 1% to 20% by weight of the total weight of the oral composition. there is.

In one embodiment, the oral composition may further include additives such as sweeteners, flavors, acidulants, or colorants to increase palatability or refreshing sensation. For example, additives include sugars such as monosaccharides, disaccharides, oligosaccharides, and sugar alcohols; High-intensity sweeteners such as saccharin and stevia extract; Essential oils such as honey, fruit juice, fruit juice concentrate, orange oil, lemon oil, lime oil, and peach-flavored oil; Pigments such as caramel pigment, gardenia pigment, and anthocyanin pigment can be mentioned.

In one embodiment, the content of the additive may be 0.01% by weight to 1% by weight of the total weight of the oral composition.

The oral composition described above can be applied to relieve or improve tooth sensitivity or tooth hypersensitivity symptoms. For example, the oral composition can slow or stabilize the nerve response transmitted to the dental pulp, and remove the original cause of hyperesthesia symptoms through remineralization of teeth and blockage of dentinal tubules.

Hereinafter, experimental examples including specific examples and comparative examples are presented to aid understanding of the present invention, but these are only illustrative of the present invention and do not limit the scope of the appended claims, and do not limit the scope and technical idea of the present invention. It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope, and it is natural that such changes and modifications fall within the scope of the appended patent claims.

Synthesis example: porous glass nanoparticles

Synthesis Example 1: A-1

A solution was prepared by mixing 300 ml of water, 4 ml of ammonium hydroxide, 20 ml of ethylene glycol monoethyl ether, and 40 ml of ethanol. 2 g of hexadecyltrimethylammonium bromide (CTAB) was added to the solution, dissolved, and stirred at a speed of 250 rpm for 30 minutes at room temperature to prepare a mixed solution.

38.38 g of triethoxysilane (TEOS) was added to the mixed solution and stirred at room temperature at a speed of 250 rpm for 5 minutes. Afterwards, 1.76 g of triethylphosphate (TEP) was added and stirred at room temperature at a speed of 250 rpm for 5 minutes. Afterwards, 4 g of calcium nitrate tetrahydrate was added, stirred at room temperature at a speed of 250 rpm for 3 hours, and then filtered under reduced pressure to obtain a solid precipitate.

The obtained precipitate was sequentially washed and filtered with distilled water, ethanol, and distilled water, respectively. Afterwards, the filtered precipitate was dried in an oven at 60°C for 24 hours, heated to 700°C at a temperature increase of 2°C/min, and calcined at 700°C for 3 hours. Afterwards, the calcined precipitate was cooled to prepare 9.74 g of porous glass nanoparticles (A-1).

The prepared porous glass nanoparticles were put into a BET measurement device (ASAP 2020, AutoChem II, Micromeritics Instrument Corp), and the specific surface area, pore volume, and average pore size were measured by the nitrogen gas adsorption flow method.

The specific surface area, pore volume, and average pore size of the prepared porous glass nanoparticles are as follows.

- Specific surface area: 665.09 m ² /g, pore volume: 0.31 cm ³ /g, pore size: 5.78 nm.

Synthesis Example 2: A-2

In the same manner as Synthesis Example 1, except that 40.14 g of triethoxysilane (TEOS), 1.76 g of triethyl phosphate (TEP), and 2 g of calcium nitrate tetrahydrate were added to the mixed solution of Synthesis Example 1. Porous glass nanoparticles (A-2) were prepared.

The specific surface area, pore volume, and average pore size of the prepared porous glass nanoparticles are as follows.

- Specific surface area: 453.18 m ² /g, pore volume: 0.64 cm ³ /g, pore size: 8.94 nm.

Synthesis Example 3: A-3

In the same manner as Synthesis Example 1, except that 17.42 g of triethoxysilane (TEOS), 0.88 g of triethyl phosphate (TEP), and 4 g of calcium nitrate tetrahydrate were added to the mixed solution of Synthesis Example 1. Porous glass nanoparticles (A-3) were prepared.

The specific surface area, pore volume, and average pore size of the prepared porous glass nanoparticles are as follows.

- Specific surface area: 552.10m ² /g, pore volume: 0.30cm ³ /g, pore size: 2.78nm.

Examples and Comparative Examples

Example

An oral composition was prepared by mixing the ingredients listed in Table 1 below in the corresponding amounts (% by weight).

Specifically, a fluorine compound and water were mixed in beaker A, and sodium benzoate, potassium salt, and porous glass nanoparticles were added while stirring at a speed of 210 rpm for 15 to 50 minutes using a magnetic stirrer.

Glycerin and polyacrylic acid were added/mixed in beaker B and stirred at a speed of 200 rpm for 15 minutes. Afterwards, the mixture from beaker A was added to beaker B and stirred at a speed of 200 rpm for 2 hours.

After confirming that the mixture was in the form of a transparent gel without clumps, surfactant and peach scented oil were added to beaker B and stirred at a speed of 200 rpm for 10 minutes. The preparation of the oral composition was carried out at room temperature (25°C).

division
(weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 glass nanoparticles
(A) 0.1
(A-1) 0.5
(A-1) 1.0
(A-1) 1.5
(A-1) One
(A-2) One
(A-3) fluorine compounds
(B) 5 5 5 5 5 5 Potassium salt (C) 3 3 3 3 3 3 Surfactant (D) 0.1 0.1 0.1 0.1 0.1 0.1 polyacrylic acid 2.46 2.3 1.7 1.5 2.3 2.3 sodium benzoate 0.48 0.48 0.48 0.48 0.48 0.48 Peach scented oil 0.1 0.1 0.1 0.1 0.1 0.1 water 18 19 20 20 19 19 glycerin 70.36 69.02 68.12 67.82 69.02 69.02

Comparative example

A dentin adhesive composition was prepared in the same manner as in the Example by mixing the components listed in Table 2 below in the corresponding amounts (% by weight).

division
(weight%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 glass nanoparticles
(A) - One
(A-4) One
(A-5) One
(A-6) fluorine compounds
(B) 5 5 5 5 Potassium salt (C) 3 3 3 3 Surfactant (D) 0.1 0.1 0.1 0.1 polyacrylic acid 2.46 2.3 1.7 1.5 sodium benzoate 0.48 0.48 0.48 0.48 Peach scented oil 0.1 0.1 0.1 0.1 water 18 19 20 20 glycerin 70.36 69.02 68.12 67.82

The specific ingredient names listed in Table 1 and Table 2 are as follows.

Glass nanoparticles (A)

1) A-1: Porous glass nanoparticles prepared in Synthesis Example 1

2) A-2: Porous glass nanoparticles prepared in Synthesis Example 2

3) A-3: Porous glass nanoparticles prepared in Synthesis Example 3

4) A-4: Bioglass 45S5 (specific surface area: 1.011m ² /g, pore volume: 0.0042cm ³ /g, pore size: 16.546nm)

5) A-5: BAG (specific surface area: 164.703m ² /g, pore volume: 0.429cm ³ /g, pore size: 10.427nm)

6) A-6: Silica R7200 (specific surface area: 175 m ² /g, manufactured by Evonik)

Fluorine Compound (B)

Sodium fluoride

Potassium salt (C)

Potassium nitrate

Surfactant (D)

AEO-9: alcohol ethoxylate, 9 moles of added ethylene oxide

Experiment example

Experimental Example 1. pH measurement

The oral compositions according to the Examples and Comparative Examples were measured three times at room temperature (25°C) using a pH meter (TOA HM -7E, TOA Electrocin Ltd), and the average was calculated. The measurement results are shown in Table 3 below.

Experimental Example 2. Evaluation of dentinal tubule blocking ability

Dental caries within 3 months after tooth extraction were prepared. The enamel and pulp were removed using a dental laboratory handpiece and a diamond bur so that only the dentin of the right tooth remained, and moisture was removed using air.

Afterwards, the surface of the caries was etched for 20 seconds using a 37% phosphoric acid etchant (Dentto-Etch, Mediclus), and then the caries were washed with water to remove the smear layer. The surface of the etched uchi was treated with air for 20 seconds.

Afterwards, the tooth was divided into two areas and the prepared oral composition was applied to one area using a microbrush for 1 minute. The beef was left for 2 hours under conditions of a temperature of 37 ± 1°C and a relative humidity of 100%.

Afterwards, the water from the cow teeth was removed with a tissue (Kimtech Science Wipers) to prepare a specimen. The manufactured specimen was dried at room temperature for 24 hours and then precipitated in a platinum solution to coat the specimen with platinum.

The surface of the specimen was observed using SEM equipment to confirm whether the dentinal tubules of the specimen were blocked. Specifically, the dentinal tubule blocking ability was evaluated by comparing the number of dentinal tubules in the area where the oral composition was applied and the area where the oral composition was not applied. The evaluation criteria are as follows.

<Evaluation criteria>

ⓞ: Covers more than 90% of dentinal tubules

○: Covers more than 50% of dentinal tubules

△: Covers less than 50% of dentinal tubules

×: Does not block dentinal tubules

Figures 1a, 1b, 1c and 1d show the dentin surface using a scanning electron microscope (SEM) after sequentially applying and leaving the oral composition according to Example 1, Example 2, Example 3 and Example 4. This is an SEM photo observed at 500x magnification.

Figures 2a, 2b, 2c and 2d show the dentin surface after sequentially applying and leaving the oral compositions according to Example 1, Example 2, Example 3 and Example 4 at 2,000 times magnification using SEM. This is the observed SEM photo.

Figures 3a, 3b, 3c and 3d sequentially show the dentin surface using a scanning electron microscope (SEM) after applying and leaving the oral compositions according to Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4. This is an SEM photo observed at 500x magnification.

Figures 4a, 4b, 4c and 4d show the dentin surface after sequentially applying and leaving the oral compositions according to Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 at 2,000 times magnification using SEM. This is the SEM photo observed.

Referring to FIGS. 1A to 1D and 2A to 2D, it can be seen that the dentinal tubules on the dentin surface are blocked in the specimen to which the oral composition according to the examples was applied. However, referring to FIGS. 3A to 3D and FIGS. 4A to 4D, it can be seen that in the case of specimens coated with oral compositions according to comparative examples, there are a large number of unblocked dentinal tubules on the dentin surface.

Experimental Example 3. Evaluation of remineralization ability

Dental caries within 3 months after tooth extraction were prepared. The pulp was removed using a dental laboratory handpiece and a diamond bur so that only the dentin part of the right tooth remained, and moisture was removed using air.

Afterwards, the surface of the caries was etched for 20 seconds using a 37% phosphoric acid etchant (Dentto-Etch, Mediclus), and then the caries were washed with water to remove the smear layer. The surface of the etched uchi was treated with air for 20 seconds.

Afterwards, the tooth was divided into two areas and the prepared oral composition was applied to one area for 30 seconds using a microbrush. The beef was left for 3 days under conditions of a temperature of 37 ± 1°C and a relative humidity of 100%.

Afterwards, the moisture from the cow teeth was removed with a tissue (Kimtech Science Wipers) to prepare a specimen. The manufactured specimen was dried at room temperature for 24 hours and then precipitated in a platinum solution to coat the specimen with platinum.

The surface of the specimen was observed using SEM equipment to determine whether a hydroxyapatite (HAp) layer was formed. The evaluation criteria for comparing the dentin surface of the area to which the oral composition was applied and the area to which the oral composition was not applied are as follows.

<Evaluation criteria>

ⓞ: Formed on the entire dentin surface

○: More than 50% of dentin surface formed

△: More than 20% and less than 50% of dentin surface formed

×: Less than 20% of dentin surface formed

Figures 5a and 5b are SEM photographs of the dentin surface after applying and leaving the oral composition according to Example 3 and Comparative Example 1, respectively, observed at 1,000x magnification using a scanning electron microscope (SEM).

Figures 6a and 6b are SEM photographs of the dentin surface observed at 2,000x magnification using an SEM after applying and leaving the oral composition according to Example 3 and Comparative Example 1, respectively.

Referring to Figures 5a and 6a, it can be seen that in the case of a specimen using the oral composition according to Example 1 of the present invention, an amorphous hydroxyapatite layer was formed entirely on the surface. However, referring to Figures 5b and 6b, in the case of the specimen using the oral composition according to Comparative Example 1, the hydroxyapatite layer was not observed or was partially observed.

division
(weight%) pH dentinal tubules
containment ability Remineralization capability evaluation Example 1 5.19 ○ ○ Example 2 5.72 ⓞ ○ Example 3 6.23 ⓞ ⓞ Example 4 6.51 ⓞ ⓞ Example 5 6.20 ⓞ ○ Example 6 6.22 ⓞ ○ Comparative Example 1 4.74 × × Comparative Example 2 5.96 × × Comparative Example 3 6.36 × △ Comparative Example 4 6.53 ○ △

Referring to Table 3, it can be seen that the oral compositions according to the examples have excellent dentin remineralization characteristics and dentinal tubule blocking ability as the active particles have a high specific surface area and pore volume. In addition, it can be confirmed that the formation of hydroxyapatite (HAp) is promoted by including porous glass nanoparticles with a high pore volume.

Therefore, as the nerve or periodontal of the tooth is not exposed to the outside, the symptoms of sensitive teeth and hyperesthesia can be improved or alleviated.

On the other hand, in the case of comparative examples that do not contain glass nanoparticles or contain glass nanoparticles with a low specific surface area, it is confirmed that the remineralization characteristics and dentinal tubule sealing ability are deteriorated as the supply/release of inorganic components is not easy. You can.

Therefore, in the case of the oral composition according to the comparative examples, the regeneration rate of damaged dentin is deteriorated, and as the dentinal tubules are not filled with mineral components, the nerve and periodontal of the tooth may be exposed to external stimuli. In this case, external stimulation may be transmitted to the periodontium, causing symptoms of tingling or hypersensitivity.

Claims (18)

Porous glass nanoparticles with a specific surface area of 250 m ² /g or more;
potassium salt; and
An oral composition containing a fluorine compound.
The method according to claim 1, wherein the specific surface area of the porous glass nanoparticles is 250 m ² /g to 800 m ² /g. Oral composition.
The oral composition according to claim 1, wherein the porous glass nanoparticles have a volume average particle diameter (D50) of 30 nm to 100 nm.
The method according to claim 1, wherein the pore volume of the porous glass nanoparticles is 0.1 cm ³ /g to 1 cm ³ /g, the oral composition.
The oral composition according to claim 1, wherein the porous glass nanoparticles include at least one selected from the group consisting of Si, Ca, Cu, Mg, Na, K, P, Al, B, and F.
The method of claim 5, wherein the porous glass nanoparticles are a group consisting of SiO ₂ , CaO, CuO, MgO, Na ₂ O, K ₂ O, P ₂ O ₅ , Al ₂ O ₃ , B ₂ O ₃ , NaF and CaF ₂ An oral composition comprising at least one selected from.
The method of claim 5, wherein the porous glass nanoparticles include 0.5 mol% to 40 mol% of calcium (Ca), 0.1 mol% to 10 mol% of phosphorus (P), and 4 mol% to 90 mol% of silicon (Si). Oral composition.
The oral composition according to claim 1, wherein the porous glass nanoparticles are surface modified with a silane group or an amine group (-NH ₂ ).
The oral composition of claim 1, wherein the potassium salt includes at least one of potassium carbonate, potassium bicarbonate, potassium citrate, potassium chloride, potassium sulfate, potassium phosphate, and potassium nitrate.
The oral composition of claim 9, wherein the potassium salt comprises potassium nitrate.
The oral composition of claim 1, wherein the fluorine compound includes at least one of sodium fluoride, potassium fluoride, ammonium fluoride, tin fluoride, sodium monofluorophosphate, potassium monofluorophosphate, sodium silicon fluoride, and calcium silicon fluoride. .
The oral composition of claim 11, wherein the fluorine compound contains sodium fluoride.
The method of claim 1, wherein, of the total weight of the oral composition,
0.01% to 10% by weight of the porous glass nanoparticles;
0.5% to 10% by weight of the potassium salt; and
An oral composition comprising 0.1% to 7.5% by weight of the fluorine compound.
The oral composition of claim 1, further comprising polyacrylic acid.
The method according to claim 14, wherein the content of polyacrylic acid is 0.5% by weight to 5% by weight of the total weight of the oral composition.
The oral composition according to claim 1, further comprising at least one of a surfactant, a humectant, a pH adjuster, an antioxidant, and a solvent.
The composition for oral use according to claim 1, wherein the pH is 2 to 7.5.
The oral composition according to claim 1, having any one formulation selected from the group consisting of liquid, powder, syrup, gel, paste, and cream.