Oral composition

Abstract

Provided is an oral composition which exhibits excellent fluorine ion release stability, fragrance emission, and amino acid stability during high-temperature storage. An oral composition containing component (A): sodium fluoride; component (B): a water-soluble calcium salt; component (C): at least one selected from the group consisting of pyrophosphoric acid and alkali metal salts thereof; component (D): a sulfur-free amino acid having a primary amino group.

Description

Technical Field

[0001] The present invention relates to an oral composition. Background Art

[0002] Since fluorides such as sodium fluoride have the effect of preventing dental caries, they are widely used as medicinal ingredients in oral compositions such as dentifrices. To make the fluorine compound work effectively, it is effective to retain fluoride ions on the mucosa and tooth surface in the oral cavity for a long time, and it is expected that even after rinsing the oral cavity with water after use, there will be more fluoride ions remaining in the oral cavity.

[0003] In Patent Document 1, as a method for improving the deposition of fluoride in the oral environment, a method of mixing a first component containing a soluble calcium source and a second component containing a soluble fluoride and directly applying the mixture to dental tissue was proposed. In Patent Document 2, as an oral composition having high fluoride ion retention in the oral cavity, a composition containing a complex formed in an aqueous solution containing polyphosphate, a calcium salt, and a fluoride salt was disclosed.

[0004] On the other hand, it is known to make an oral composition contain an amino acid. For example, the anti-inflammatory effects of tranexamic acid and ε-aminocaproic acid on the gums have been confirmed. In Patent Document 3, an oral composition containing isopropylmethylphenol, a water-soluble tin salt, and an amino acid was proposed. The amino acid is considered to play the following role: preventing the aversion to the odor from isopropylmethylphenol caused by the combined use of isopropylmethylphenol and a water-soluble tin salt, improving the odor, and ensuring a good taste feeling during use.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Problems to be Solved by the Invention

[0006] The method of Patent Document 1 has the following problems: Since fluoride ions directly enter the oral cavity, the fluoride ions are immediately washed away by saliva and do not exhibit a sufficient retention effect, or since calcium fluoride precipitates within a short time after mixing the two components, the fluoride ions are not released in the oral cavity and do not exhibit the expected effect. In the composition of Patent Document 2, the retention and release properties of fluoride ions are excellent, but there is room for improvement in the stability of fluoride ion release over time and the stability of fragrance release (fragrance dispersion) during storage at high temperatures. Further, when the composition of Patent Document 2 contains an amino acid, there is room for improvement in the stability of the amino acid depending on the type of amino acid.

[0007] An object of the present invention is to provide an oral composition having excellent stability of fluoride ion release, fragrance dispersion, and stability of amino acids during storage at high temperatures.

Means for Solving the Problem

[0008] As a result of intensive studies by the present inventors, it was found that by combining sodium fluoride, a water-soluble calcium salt, pyrophosphoric acid or an alkali metal salt thereof, and a specific amino acid, it is possible to suppress the deterioration of fluoride ion release, fragrance dispersion, or amino acids during storage at high temperatures. The present invention is an invention based on the above findings and has the following aspects.

[0009] <1> An oral composition containing (A) component: sodium fluoride; (B) component: a water-soluble calcium salt; (C) component: at least one selected from pyrophosphoric acid and alkali metal salts thereof; (D) component: a sulfur-free amino acid having a primary amino group. <2> The oral composition according to <1>, wherein the (B) component is at least one selected from calcium chloride, calcium glycerophosphate, calcium gluconate, calcium lactate, and calcium pantothenate. <3> The oral composition according to <1> or <2>, wherein the (C) component is at least one selected from pyrophosphoric acid, sodium pyrophosphate, and potassium pyrophosphate. <4> The oral composition according to any one of <1> to <3>, wherein the (D) component is at least one selected from alanine, glycine, arginine, glutamic acid, tranexamic acid, and ε-aminocaproic acid. <5> The oral composition according to any one of <1> to <4>, wherein the molar ratio of the (B) component to the (D) component is 0.05 to 145. <6> The oral composition according to any one of <1> to <5>, wherein the oral composition is toothpaste.

Effects of the Invention

[0010] According to the present invention, an oral composition can be provided, which has excellent stability of fluoride ion release, fragrance emission, and stability of amino acids during storage at high temperature. Detailed Description

[0011] In this specification, the "oral composition" refers to a composition intended mainly for use in the oral cavity. "Water-soluble" means a solubility of 1 g / 100 g or more in water at 20°C. The "~" indicating a numerical range means that the values described before and after it are included as the lower limit value and the upper limit value.

[0012] 〔Oral Composition〕 The oral composition of the present invention contains component (A), component (B), component (C), and component (D).

[0013] <Component (A)> Component (A) is sodium fluoride (NaF). Commercially available products can be used as component (A).

[0014] <Component (B)> Component (B) is a water-soluble calcium salt. Since the oral composition contains component (B), the stability of fluoride ion release and the stability of amino acids are excellent.

[0015] Examples of component (B) include calcium chloride, calcium nitrate, calcium acetate, calcium citrate, calcium glycerophosphate, calcium gluconate, calcium benzoate, calcium formate, calcium fumarate, calcium lactate, calcium butyrate, calcium isobutyrate, calcium malate, calcium maleate, calcium propionate, calcium valerate, calcium pantothenate, etc. As component (B), at least 1 kind selected from calcium chloride, calcium glycerophosphate, and calcium lactate is preferred. Component (B) can be a single kind or a combination of 2 or more kinds. Commercially available products can be used as component (B).

[0016] <Component (C)> Component (C) is at least 1 kind selected from pyrophosphoric acid and its alkali metal salts. Since the oral composition contains component (C), the stability of fluoride ion release and the stability of amino acids are excellent.

[0017] Examples of the alkali metal salts include sodium salts, potassium salts, etc. As component (C), from the viewpoint of fluoride ion retention, at least 1 kind selected from pyrophosphoric acid, sodium pyrophosphate, and potassium pyrophosphate is preferred, and at least 1 kind selected from potassium pyrophosphate and sodium pyrophosphate is particularly preferred. Component (C) can be a single kind or a combination of 2 or more kinds. (C) component can use commercially available products.

[0018] <(D) component> (D) component is a sulfur-free amino acid having a primary amino group. "Primary amino group" refers to a monovalent group represented by "-NH 2 ". "Sulfur-free amino acid" refers to an amino acid that does not contain a sulfur atom in the molecule. Since the oral composition contains (D) component, the stability of fluoride ion release and the fragrance emission are excellent.

[0019] As (D) component, for example, natural amino acids and artificial amino acids can be cited. As natural amino acids, for example, acidic amino acids such as aspartic acid and glutamic acid; basic amino acids such as lysine, arginine, and histidine; neutral polar amino acids such as asparagine, glutamine, serine, threonine, and tyrosine; hydrophobic aliphatic amino acids such as alanine, glycine, valine, proline, isoleucine, and leucine; hydrophobic aromatic amino acids such as phenylalanine and tryptophan can be cited. As artificial amino acids, for example, tranexamic acid, ε-aminocaproic acid, D-amino acids, N-methylated amino acids, 2-aminoadipic acid, 3-aminoadipic acid, β-alanine, β-aminopropionic acid, 2-aminobutyric acid, 4-aminobutyric acid, 2-aminoheptanoic acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminoheptanedioic acid, 2,4-diaminobutyric acid, 2,2”-diaminoheptanedioic acid, 2,3-diaminopropionic acid, N-ethylglycine, N-ethylasparagine, hydroxylysine, allo-hydroxylysine, 3-hydroxyproline, 4-hydroxyproline, isodesmosine, alloisoleucine, N-methylglycine, sarcosine, N-methylisoleucine, N-methylvaline, norvaline, norleucine, ornithine can be cited.

[0020] Among the above, from the viewpoints of the stability of amino acids and the persistence of fluoride ion release, at least one selected from hydrophobic aliphatic amino acids, hydrophobic aromatic amino acids, tranexamic acid, and ε-aminocaproic acid is preferred. From the viewpoint of the stability of amino acids, at least one selected from alanine, glycine, arginine, glutamic acid, tranexamic acid, and ε-aminocaproic acid is particularly preferred. Among them, from the viewpoint of fluoride ion release, at least one selected from tranexamic acid and ε-aminocaproic acid is particularly preferred. (D) component can be a single kind or a combination of two or more kinds. (D) component can use commercially available products.

[0021] <Content of each component> The content of component (A) is preferably 0.09 to 1.3% by mass, more preferably 0.10 to 1.1% by mass, based on the total mass of the oral composition. When the content of component (A) is at least the above lower limit value, the stability of fluoride ion release is more excellent. When the content of component (A) is at most the above upper limit value, the stability of fragrance emission and amino acids is more excellent.

[0022] The content of component (B) is preferably 0.02 to 5.0% by mass, more preferably 0.03 to 3.0% by mass, based on the total mass of the oral composition. When the content of component (B) is at least the above lower limit value, the stability of amino acids is more excellent. When the content of component (B) is at most the above upper limit value, the stability of fluoride ion release and fragrance emission are more excellent.

[0023] The content of component (C) is preferably 0.02 to 3.0% by mass, more preferably 0.03 to 1.3% by mass, based on the total mass of the oral composition. When the content of component (C) is at least the above lower limit value, the stability of fluoride ion release and amino acids are more excellent. When the content of component (C) is at most the above upper limit value, the fragrance emission is more excellent.

[0024] The content of component (D) is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.5% by mass, based on the total mass of the oral composition. When the content of component (D) is at least the above lower limit value, the stability of fluoride ion release and fragrance emission are more excellent. When the content of component (D) is at most the above upper limit value, the stability of amino acids (component (D)) is more excellent. The content of component (D) is preferably an amount such that the following (B) / (D) is within the following preferred range.

[0025] The molar ratio of component (B) to component (D) (hereinafter, also referred to as "(B) / (D)") is preferably 0.05 to 145, more preferably 0.1 to 110. When (B) / (D) is at least the above lower limit value, the stability of amino acids is more excellent. When (B) / (D) is at most the above upper limit value, the stability of fluoride ion release and fragrance emission are more excellent.

[0026] <Other components> Within the range that does not hinder the effects of the present invention, the oral composition of the present invention may further contain other components other than component (A), component (B), component (C), and component (D) as needed. The other components can be appropriately selected from known components in consideration of the dosage form of the oral composition, the method of use, etc. Examples of the other components include water, abrasive, binder, thickener, surfactant, colorant, sweetener, preservative, fragrance, active ingredient, pH adjuster.

[0027] Examples of the abrasive include silica-based abrasives such as anhydrous silicic acid, precipitated silica, silica gel, aluminosilicate, and zirconium silicate; calcium hydrogen phosphate dihydrate or anhydrate, calcium dihydrogen phosphate, calcium phosphate, quaternary calcium phosphate, calcium carbonate, calcium hydroxide, aluminum hydroxide, insoluble sodium metaphosphate, trimagnesium phosphate, and magnesium carbonate. From the perspective of the effects of the present invention, silica-based abrasives are particularly preferred. The content of the abrasive is preferably 0 to 60% by mass, more preferably 0 to 30% by mass, and may also be 25% by mass or less, based on the total mass of the oral composition. A content of 0% by mass of the abrasive means that no abrasive is contained.

[0028] Examples of the binder include organic binders such as water-soluble polymer substances selected from cellulose derivatives such as sodium carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, and carboxyethyl cellulose; gums such as xanthan gum, tragacanth gum, karaya gum, and gum arabic; and polyacrylates such as sodium polyacrylate; and inorganic binders such as thickening silica, thickening aluminum silicate, magnesium aluminum silicate (veegum), and laponite. The content of the binder is preferably 0.05 to 13.0% by mass, based on the total mass of the oral composition. When the binder contains an organic binder, the mixing amount of the organic binder is more preferably 0.1 to 3% by mass, and further preferably 0.5 to 2.5% by mass, based on the total mass of the oral composition. When the binder contains an inorganic binder, from the perspective of the adsorption of fluoride ions to the tooth surface, the content of the inorganic binder is more preferably 0 to 10.0% by mass, and further preferably 0 to 8.0% by mass, based on the total mass of the oral composition.

[0029] Examples of the thickener include sugar alcohols such as sorbitol, xylitol, erythritol, and maltitol; and polyhydric alcohols such as glycerin, propylene glycol, and polyethylene glycol having an average molecular weight of 160 to 400 (average molecular weight described in the Standards for Quasi-Drugs Raw Materials 2006). The content of the thickener is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, based on the total mass of the oral composition.

[0030] Examples of the surfactant include nonionic surfactants, anionic surfactants, and amphoteric surfactants. As nonionic surfactants, examples include glycerol fatty acid esters such as decaglycerol laurate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate (average addition mole number of ethylene oxide (hereinafter, simply referred to as "E.O.") 20), alkyl glycosides with 12 to 16 carbon atoms in the alkyl group, sorbitan fatty acid esters such as sorbitan tristearate, sucrose fatty acid esters such as sucrose laurate, and polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether (E.O. 6). As anionic surfactants, examples include alkyl sulfates such as sodium dodecyl sulfate and sodium tetradecyl sulfate, acyl sarcosinates such as sodium lauroyl sarcosinate, acyl amino acid salts such as sodium acyl glutamate, sodium acyl taurine, sodium dodecylbenzenesulfonate, sodium lauryl sulfoacetate, and sodium α-olefin sulfonate. As amphoteric surfactants, examples include coconut fatty acid amide propyl betaine, lauryl dimethylaminoacetic acid betaine, and N-coconut fatty acid acyl-N-carboxymethyl-N-hydroxyethyl ethylenediamine. The content of the surfactant is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 8.0% by mass, based on the total mass of the oral composition.

[0031] As colorants, examples include Red No. 2, Red No. 3, Red No. 225, Red No. 226, Yellow No. 4, Yellow No. 5, Yellow No. 205, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 204, Green No. 3, mica titanium, and titanium oxide. As sweeteners, examples include sodium saccharin, aspartame, stevioside, stevia extract, p-methoxycinnamaldehyde, neohesperidin dihydrochalcone, and perillartine. As preservatives, examples include p-hydroxybenzoic acid esters such as methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, and butyl p-hydroxybenzoate, and benzoic acid or its salts such as sodium benzoate.

[0032] As spices, for example, there may be mentioned natural spices such as peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cinnamon oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, tangerine oil, lime oil, lavender oil, rosemary oil, bay oil, chamomile oil, caraway oil, marjoram oil, bay leaf oil, lemongrass oil, oregano oil, pine needle oil, neroli oil, rose oil, jasmine oil, grapefruit oil, sweetie oil, pomelo oil, iris concrete, peppermint absolute, rose absolute, neroli absolute, etc., or spices after processing of these natural spices (removal of front fractions, removal of back fractions, fractional distillation, liquid-liquid extraction, rectification, powdering of spices, etc.), single-component spices such as menthol, carvone, anethole, cineole, methyl salicylate, cinnamaldehyde, eugenol, 3-methoxy-1,2-propanediol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-p-formamide-3-carboxamide, pinene, octanal, citral, piperitone, diethylene glycol monoethyl ether acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexanepropionate, methyl anthranilate, ethyl methylphenylglycidate, vanillin, undecanolide, hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, methylcyclopentenolone, furfural, trimethylpyrazine, ethyl lactate, ethyl thioacetate, etc., and blended spices such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, mixed fruit flavor, tropical fruit flavor, etc. Known spice raw materials can be used in combination as the oral composition. The content of the spice is not particularly limited. For example, it is 0.000001 to 2% by mass relative to the total mass of the oral composition. The content of the above-mentioned spice raw materials is preferably 0.000001 to 1% by mass relative to the total mass of the oral composition. The content of the flavoring spice using the above-mentioned spice raw materials is preferably 0.05 to 2% by mass relative to the total mass of the oral composition.

[0033] As active ingredients, for example, there may be mentioned bactericides such as isopropylmethylphenol, cetylpyridinium chloride, etc., water-soluble phosphoric acid compounds such as potassium salts and sodium salts of orthophosphoric acid (except for component (C)), enzymes such as dextranase, mutanase, amylase, protease, etc., tranexamic acid, ε-aminocaproic acid, triclosan, lysozyme chloride, allantoin aluminum chloride hydroxide, hinokitiol, ascorbic acid, tocopheryl acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene or water-soluble copper compounds such as sodium copper chlorophyllin, chlorophyll, copper gluconate, etc., aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid or its derivatives, glycyrrhizic acid or its salts, glycyrrhetinic acid or its derivatives, and tartar-preventing agents. An effective amount of the above-mentioned active ingredients can be mixed within the range that does not hinder the effects of the present invention. The oral composition may contain amino acids other than the component (D). From the viewpoint of the stability of fragrance emission, the oral composition does not contain sulfur-containing amino acids such as L-cysteine.

[0034] Examples of the pH adjuster include citric acid, tartaric acid, malic acid, or their salts such as potassium salts and sodium salts, and sodium hydroxide.

[0035] <Form, dosage form> The oral composition can be prepared into various forms such as liquid, paste, and solid, for example. The dosage form of the oral composition is not particularly limited. The dosage form of the oral composition is typically an oral preparation that is discharged from the oral cavity after use. Examples of the oral preparation include dentifrices (liquid dentifrices, liquid dentifrices, toothpastes, wet powder dentifrices, powder dentifrices, etc.), oral cleansers, mouthwashes, coating agents, mouth sprays, patches, tablets, sustained-release agents in the oral cavity, chewing agents, soluble agents in the oral cavity, disintegrating agents in the oral cavity, tongue care agents, oral cooling agents, denture care agents, etc. Among the above, the oral composition of the present invention is preferably used as a dentifrice, and particularly preferably as a toothpaste.

[0036] The oral composition of the present invention can be prepared by a known method. For example, it can be prepared by mixing the component (A), the component (B), the component (C), and the component (D) and other components as needed by a conventional method.

[0037] In the oral composition, it is preferable that fluoride ions, calcium ions, and phosphate ions form a complex. When the above complex is formed, the retention of fluoride ions in the oral cavity is improved, and thus, the adsorption of fluoride ions to the tooth surface is further improved.

[0038] The formation of the above complex can be confirmed by observing the crystal size based on X-ray crystal structure analysis and the exothermic peak at around 450 °C when crystal water dissociates near the phosphate group based on calorimetry (TG-DTA measurement). That is, when the complex is formed, the crystal size obtained from the diffraction peak attributed to CaF 2 becomes less than 10 nm due to the complexation of the phosphate group. In addition, the peak of crystal water generation indicates that CaF 2 seen by X-ray crystal structure analysis is not a crystal composed only of calcium and fluoride ions, but a complex in which phosphate groups interact. Specifically, the formation of the complex can be confirmed by confirming that the crystal size is less than 10 nm by the following method (1) and confirming the presence of an exothermic peak at 450 °C by the following method (2). (1) Crystal size The sample was measured using an X-ray diffractometer (light source Cu: Kα, 40 kV, 20 mA, divergence slit 1 / 2 deg, scattering slit 1 / 2 deg, receiving slit 0.15 mm, scanning speed 4.000° / min, 2θ = 2.000 - 80.000°). The crystallite size was calculated according to the following equation (Scherrer's equation) to evaluate the formation of the complex. L = Kλ / (βcosθ) L: crystallite size, K: coefficient 0.9, β: full width at half maximum, λ: θ: diffraction angle (2) TG-DTA measurement (exothermic peak) Heating rate: 5 °C / min, measurement range: 25 °C to 600 °C

[0039] There is no particular limitation on the method for forming the above complex. When preparing the oral composition, for example, it is preferably any one of the steps of mixing component (B) after mixing components (A) and (C), or mixing component (A) after mixing components (B) and (C). In addition, when components (A) and (B) are mixed simultaneously, a part of calcium fluoride is generated, and the formation efficiency of the complex may deteriorate.

[0040] The oral composition described above contains components (A), (B), (C), and (D), and thus has excellent fluoride ion release property, fragrance emission, and amino acid stability during high-temperature storage. It is considered that through the primary amino group of component (D), the charge of the complex of fluoride ion, calcium ion, and phosphate ion becomes stabilized, and the amorphous structure of the complex can be maintained. Therefore, the fluoride ion release property during high-temperature storage can be maintained. Conversely, it is considered that through the stabilization of component (D) by the complex, the deterioration of component (D) during high-temperature storage is suppressed.

Examples

[0041] The following examples are shown to specifically illustrate the present invention, but the present invention is not limited to the following description. In addition, in the following examples, unless otherwise specified, "%" means "mass %".

[0042] <Raw materials used> Sodium fluoride: manufactured by Stella Chemical Co., Ltd. Also denoted as "NaF" hereinafter. Calcium chloride: manufactured by Tomita Pharmaceutical Co., Ltd. Also denoted as "CaCl" hereinafter. Calcium gluconate: manufactured by Fuso Chemical Industry Co., Ltd. Also denoted as "Ca gluconate" hereinafter. Calcium lactate hydrate: manufactured by Taihei Chemical Industry Co., Ltd., trade name "Calcium lactate". Also denoted as "Ca lactate" hereinafter. Calcium glycerophosphate: manufactured by Iwaki Pharmaceutical Co., Ltd. Hereinafter also referred to as "Ca glycerophosphate". Calcium pantothenate: manufactured by BASF. Hereinafter also referred to as "Ca pantothenate". Potassium pyrophosphate: manufactured by Taihei Chemical Industry Co., Ltd. Hereinafter also referred to as "K pyrophosphate". Sodium pyrophosphate: manufactured by Taihei Chemical Industry Co., Ltd., trade name "Sodium pyrophosphate (anhydrous)". Hereinafter also referred to as "Na pyrophosphate". Sodium tripolyphosphate: manufactured by Taihei Chemical Industry Co., Ltd. Hereinafter also referred to as "Na tripolyphosphate". Tranexamic acid: manufactured by Kyowa Pharmaceutical Chemical Co., Ltd. ε-Aminocaproic acid: manufactured by Daiichi Sankyo Co., Ltd. L-Cysteine: manufactured by Nippon Rikagaku Yakuhin Co., Ltd. Sodium pyrrolidonecarboxylate: manufactured by Ajinomoto Co., Inc. Hereinafter also referred to as "Na pyrrolidonecarboxylate". Alanine: DL-alanine, manufactured by AJINOMOTO HEALTHY SUPPLY CO.,INC. Arginine: manufactured by Kanto Chemical Co., Inc. Glycine: manufactured by Kobe Chemical Industry Co., Ltd. Glutamic acid: manufactured by Kanto Chemical Co., Inc.

[0043] <Examples 1 to 29, Comparative Examples 1 to 7> Dental care compositions (toothpastes) having the compositions shown in Tables 1 to 4 were prepared by conventional methods. The blank columns in the tables indicate that the component was not mixed. The "balance" of purified water represents the amount that makes the total amount of the dental care composition 100%. The obtained dental care compositions were evaluated as follows. The results are also shown in Tables 1 to 4.

[0044] (Stability of fluoride ion release) 50 g of each oral composition was filled into 3 tubular containers (the innermost layer is a laminated tube with a diameter of 26 mm made of linear low-density polyethylene, manufactured by Dainippon Printing Co., Ltd.) and stored at 50 °C for 3 months. For the dental care compositions before and after storage, the release rate (release amount) of fluoride ions into saliva was measured by mucin in the following order to evaluate the stability of fluoride ion release. (1) Add 0.2 g of mucin (manufactured by Sigma-Aldrich) to a 10 mL centrifuge tube, and further add 5 mL of the dentifrice composition (40-fold dilution based on purified water), and let it act for 3 minutes. After washing the mucin with distilled water, treat it with 0.1 N hydrochloric acid for 2 minutes, and measure the fluoride ion concentration contained in the hydrochloric acid using a fluoride ion meter (Orion 11150004-Star: manufactured by Thermo Fisher Scientific Co., Ltd.). Set this value as the retained fluoride ion concentration. (2) After allowing the dentifrice composition to act on the mucin and washing it in the same manner as above, add 5 mL of artificial saliva (CaCl 2 = 1.5 mmol / L, KH 2 PO 4 = 5.0 mmol / L, acetic acid = 100 mmol / L, NaCl = 100 mmol / L, balance = water; pH = 7.0), stir for 1 minute, and allow the fluoride ions adsorbed and retained on the mucin to elute by standing for 3 minutes, 60 minutes, or 180 minutes. Then, centrifuge at 3,000 rpm for 10 minutes respectively, recover the supernatant, and measure the fluoride ion concentration contained in the solution using a fluoride ion meter (Orion 11150004-Star: manufactured by Thermo Fisher Scientific Co., Ltd.). Set this value as the released fluoride ion concentration. (3) Calculate the fluoride ion release rate from the retained fluoride ion concentration and the released fluoride ion concentration according to the following formula. Fluoride ion release rate (%) = {Released fluoride ion concentration (ppm) / Retained fluoride ion concentration (ppm)} × 100 (4) Calculate the retention rate from the fluoride ion release rates before and after storage according to the following formula, and evaluate the stability of the fluoride ion release property according to the following evaluation criteria. Retention rate (%) = {Fluoride ion release rate (%) after storage / Fluoride ion release rate (%) before storage} × 100 [Evaluation criteria] ◎: The retention rate is 97% or more. 〇: The retention rate is 95% or more and less than 97%. △: The retention rate is 93% or more and less than 95%. ×: The retention rate is less than 93%.

[0045] (Stability of amino acids) Fill 50 g of each oral composition into 3 tubular containers (material: the innermost layer is a laminated tube with a diameter of 26 mm made of linear low-density polyethylene, manufactured by Dai Nippon Printing Co., Ltd.) respectively, and repeat the cycle test of storing at -5°C for 6 hours and storing at 40°C for 6 hours for 6 months. Quantify the amino acids in each dentifrice composition before and after the cycling test, calculate the stability of the amino acids from the quantified values according to the following formula, and evaluate using the following criteria. In addition, the quantification of amino acids is performed by liquid-liquid chromatography. Amino acid stability (%) = {Quantified value of amino acids after cycling test (%) / (Quantified value of amino acids before cycling test (%))} × 100 [Evaluation criteria] ◎: Stability is 98% or more. 〇: Stability is 96% or more and less than 98%. △: Stability is 94% or more and less than 96%. ×: Stability is less than 94%.

[0046] (Fragrance emission) Respectively fill 50 g of the oral composition into 3 tubular containers (material: the innermost layer is a laminated tube with a diameter of 26 mm made of linear low-density polyethylene, manufactured by Dainippon Printing Co., Ltd.), and store at 50 °C for 3 months. 10 subjects use the stored dentifrice composition by a conventional method, and evaluate the degree of fragrance emission using the following 5-level scoring criteria. Calculate the average score of 10 people, and make a judgment using ◎, 〇, △, × according to the following evaluation criteria. [Scoring criteria] 5 points: The fragrance emission is very good. 4 points: The fragrance emission is good. 3 points: The fragrance emission is felt. 2 points: The fragrance emission is not very good. 1 point: The fragrance emission is bad. [Evaluation criteria] ◎: The average score is 4.5 points or more. 〇: The average score is 4.0 points or more and less than 4.5 points. △: The average score is 3.0 points or more and less than 4.0 points. ×: The average score is 1.0 points or more and less than 3.0 points.

[0047]

Table 1A

[0048]

Table 1B

[0049]

Table 2A

[0050]

Table 2B

[0051]

Table 3A

[0052]

Table 3B

[0053]

Table 4A

[0054]

Table 4B

[0055] As shown in the above results, the stability of fluoride ion release, the stability of amino acids, and the fragrance emission of the dentifrice compositions of Examples 1 to 29 are excellent. On the other hand, the stability of fluoride ion release of Comparative Example 1 without component (A) is poor. The stability of fluoride ion release and the stability of amino acids of Comparative Example 2 without component (B) are poor. The stability of fluoride ion release and the stability of amino acids of Comparative Example 3 without component (C) are poor. The stability of fluoride ion release and the fragrance emission of Comparative Example 4 without component (D) are poor. The stability of fluoride ion release of Comparative Example 5 containing sodium tripolyphosphate instead of component (C) is poor. The fragrance emission of Comparative Example 6 containing sulfur-containing amino acid instead of L-cysteine as component (D) is poor. The stability of amino acids of Comparative Example 7 containing an amino acid without a primary amino group instead of component (D), i.e., sodium pyrrolidone carboxylate, is poor.

[0056] Then, formulation examples are presented. An oral composition having the following composition is prepared by a conventional method. After evaluation by the same method as above, in any of the formulation examples, the stability of fluoride ion release, the stability of amino acids, and the fragrance emission are excellent.

[0057] <Formulation Example 1 Dentifrice>

[0058] <Formulation Example 2 Dentifrice>

[0059] <Formulation Example 3 Dentifrice>

[0060] <Dental Care Agent of Formulation Example 4>

[0061] <Dental Care Agent of Formulation Example 5>

[0062] <Dental Care Agent of Formulation Example 6>

Claims

1. An oral composition comprising (A) Ingredients: sodium fluoride; (B) ingredient: water-soluble calcium salt; (C) component: at least one selected from pyrophosphoric acid and alkali metal salts thereof; Component (D): a sulfur-free amino acid having a primary amino group.

2. The oral composition according to claim 1, wherein The component (B) is at least one selected from the group consisting of calcium chloride, calcium glycerophosphate, calcium gluconate, calcium lactate, and calcium pantothenate.

3. The oral composition according to claim 1, wherein The component (C) is at least one selected from the group consisting of pyrophosphoric acid, sodium pyrophosphate and potassium pyrophosphate.

4. The oral composition according to claim 1, wherein The component (D) is at least one selected from the group consisting of alanine, glycine, arginine, glutamic acid, tranexamic acid and ε-aminocaproic acid.

5. The oral composition according to claim 1, wherein The molar ratio of the component (B) to the component (D) is 0.05 to 145.

6. The oral composition according to claim 1, wherein The content of the component (A) is 0.09 to 1.3% by mass, the content of the component (B) is 0.02 to 5.0% by mass, the content of the component (C) is 0.02 to 3.0% by mass, and the content of the component (D) is 0.01 to 1% by mass, based on the total mass of the oral composition.

7. The oral composition according to any one of claims 1 to 6, wherein The oral composition is a toothpaste.

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