Liquid oral components

A liquid oral composition with water-soluble copper salts and aluminum salts controls discoloration by adjusting pH and component ratios, addressing the issue of oral staining caused by copper salts in liquid oral compositions.

JP7888385B2Active Publication Date: 2026-07-13DAIICHI SANKYO HEALTHCARE
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Patent Information

Application Number
JP2022115018
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Filing Date
2022-07-19
Publication Date
2026-07-13
Estimated Expiration
2042-07-19

AI Technical Summary

Technical Problem

Liquid oral compositions containing water-soluble copper salts can cause discoloration in the oral cavity, such as on the tongue, oral mucosa, or teeth, due to reactions with components like polyphenols present in the mouth.

Method used

A liquid oral composition comprising water-soluble copper salts and color inhibitors, specifically water-soluble aluminum salts, is formulated to suppress discoloration by controlling the color difference ΔE through specific pH and component ratios, using a method that measures colorimetric values before and after exposure to tannic acid.

Benefits of technology

The composition effectively inhibits discoloration in the oral cavity by maintaining the color difference ΔE within a specific range, thereby preventing staining on the tongue, oral mucosa, or teeth.

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Abstract

To provide technique enabling suppression of intraoral discoloration occurring when liquid composition for oral cavity, including a water-soluble copper salt is applied.SOLUTION: Liquid composition for oral cavity including (a) a water-soluble copper salt and (b) a coloring inhibitor is provided, the liquid composition for oral cavity has a color difference ΔE* measured by the following method of 10 or more. The method comprises: 1. adding an aqueous tannic acid solution to a liquid composition for oral cavity to prepare a measurement solution with a final tannic acid concentration of 0.2 mass%; 2. leaving the measurement solution at 37°C for 1 week; 3. after standing still, centrifuging the measurement solution, collecting the precipitate and measuring the color of the precipitate using a spectrocolorimeter to obtain colorimetric values (L2*, a2*, b2*); 4. obtaining colorimetric values (L1*, a1*, b1*) using a 0.1 mass% copper gluconate aqueous solution as an object using the above steps 1. to 3.; and 5 calculating the color difference ΔE* by the following formula (I): ΔE*=((L2*-L1*)2+(a2*-a1*)2+(b2*-b1*)2)1 / 2 (I).SELECTED DRAWING: None
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Description

[Technical Field]

[0001] This invention relates to a liquid oral composition. [Background technology]

[0002] As a technique for incorporating copper compounds into oral preparations, there are the examples described in Patent Document 1 (Japanese Patent Publication No. 11-269073) and Patent Document 2 (Japanese Patent Publication No. 2021-91654).

[0003] Patent Document 1 describes a formulation containing a copper chlorophyllin salt and an acid (Claim 1), and a method for preventing tongue discoloration by the copper chlorophyllin salt by adding an acid (Claim 7). The same document also describes observations of the degree of tongue discoloration for a granular preparation containing copper chlorophyllin potassium and citric acid (Example 1), and a chewable tablet containing copper chlorophyllin potassium and citric acid (Table 1, etc.).

[0004] Patent Document 2 describes a toothpaste composition containing a water-soluble polyvalent metal salt, which is easy to apply to a toothbrush, has excellent moldability, and has excellent discharge properties from the storage container even after storage (paragraph 0001), and describes a toothpaste composition containing one or more water-soluble polyvalent metal salts selected from water-soluble aluminum salts, water-soluble copper salts, and water-soluble zinc salts, xanthan gum, and a cationic polymer compound (claim 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-269073 [Patent Document 2] Japanese Patent Publication No. 2021-91654 [Overview of the project] [Problems that the invention aims to solve]

[0006] On the other hand, the present inventors have found that when a water-soluble copper salt such as copper gluconate is incorporated into a liquid oral composition, discoloration may occur in the oral cavity, for example, on the tongue, oral mucosa, or teeth.

[0007] Therefore, the present invention provides a technique for suppressing oral discoloration when applying a liquid oral composition containing a water-soluble copper salt. [Means for solving the problem]

[0008] The inventors diligently investigated the cause of discoloration when using a liquid oral composition containing a water-soluble copper salt. As a result, they found that one of the causes is the reaction between the water-soluble copper salt in the liquid oral composition and components present in the oral cavity. For example, it was found that when a water-soluble copper salt is present with polyphenols (such as tannic acid) contained in tea, a brown precipitate may form.

[0009] Therefore, the inventors further investigated how to suppress discoloration caused by water-soluble copper salts in the liquid oral composition and components present in the oral cavity, and discovered that controlling the color characteristics of the liquid oral composition is effective, thus completing the present invention.

[0010] According to the present invention, the following liquid oral composition and method for inhibiting tooth discoloration are provided. [1] (a) water-soluble copper salts, and (b) Color inhibitors A liquid oral composition comprising, The color difference ΔE is measured by the following method * A liquid oral composition in which the ratio is 10 or higher. (method) To 1.30 mL of the liquid oral composition, 10 mL of a 0.8% by mass aqueous solution of tannic acid is added to prepare a measurement solution with a final concentration of 0.2% by mass of tannic acid. 2. Allow the measurement solution to stand at 37°C for one week. 3. After standing, centrifuge at room temperature at 3000 rpm for 10 minutes, remove the supernatant, and collect the precipitate. Measure the color of the precipitate with a spectrophotometer and identify the CIE1976L * a* b * The colorimetric values (L2 * , a2 * , b2 * ) defined in the color system are obtained. 4. Using an aqueous solution of 4.0.1 mass% copper gluconate as a control, the CIE1976L * a * b * The colorimetric values (L1 * , a1 * , b1 * ) defined in the color system are obtained. 5. Calculate the color difference ΔE from the following formula (I): * ΔE * = ((L2 * - L1 * ) 2 + (a2 * - a1 * ) 2 + (b2 * - b1 * ) 2 ) 1 / 2 [[ID=5l]](I) [2] The liquid oral composition according to [1], wherein the pH at 25°C is 3.5 or more and 8 or less. [3] The liquid oral composition according to [1] or [2], wherein the component (b) is a water-soluble aluminum salt. [4] The liquid oral composition according to [3], wherein the water-soluble aluminum salt is an aluminum salt of an organic acid. [5] The liquid oral composition according to [3], wherein the water-soluble aluminum salt is one or more selected from the group consisting of aluminum lactate, potassium aluminum sulfate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum benzoate, and allantoin chloro-hydroxyaluminum. [6] The liquid oral composition according to any one of [1] to [5], wherein the component (a) is one or more selected from the group consisting of copper gluconate, copper sulfate, copper citrate, copper chlorophyll, and sodium copper chlorophyllin. ​[7] The liquid oral composition according to any one of [1] to [6], wherein the content of component (b) relative to the content of component (a) in the liquid oral composition is 0.25 or more and 300 or less by mass ratio. [8] A liquid oral composition according to any one of [1] to [7], which is a tongue discoloration inhibitor. [9] A liquid oral composition according to any one of [1] to [8], which is an oral mucosal discoloration inhibitor.

[10] A mouthwash, a liquid oral composition according to any one of [1] to [9].

[11] (a) water-soluble copper salts, and (b) Color inhibitors Includes, The color difference ΔE is measured by the following method * A method for inhibiting tooth discoloration, comprising applying a composition having a ratio of 10 or more to the oral cavity. (method) To 1.30 mL of the composition, 10 mL of a 0.8% by mass aqueous solution of tannic acid is added to prepare a measurement solution with a final concentration of 0.2% by mass of tannic acid. 2. Allow the measurement solution to stand at 37°C for one week. 3. After standing, centrifuge at room temperature at 3000 rpm for 10 minutes, remove the supernatant, and collect the precipitate. Measure the color of the precipitate with a spectrophotometer and identify the CIE1976L * a * b * Colorimetric values ​​defined in the color system (L2 * a2 * ,b2 * ) obtain. 4.0.1% by mass of copper gluconate aqueous solution is used as a control, and the above procedure 1-3 is followed to prepare CIE1976L * a * b * Colorimetric values ​​defined in the color system (L1 * a1 * ,b1 * ) obtain. 5. The color difference ΔE is obtained from the following equation (I). * Calculate. ΔE * =((L2 * -L1 * ) 2 +(a2* -a1 * ) 2 +(b2 * -b1 * ) 2 ) 1 / 2 (I)

[0011] Furthermore, any combination of these configurations, as well as conversions of the expressions of the present invention between methods, apparatus, etc., are also valid embodiments of the present invention. [Effects of the Invention]

[0012] According to the present invention, it is possible to suppress discoloration in the oral cavity when applying a liquid oral composition containing a water-soluble copper salt. [Modes for carrying out the invention]

[0013] Embodiments of the present invention will be described below. In this embodiment, the composition may contain each component individually or in combination of two or more components. In this specification, the "~" symbol indicating a numerical range represents "greater than or equal to" and "less than or equal to," and includes both of the numbers at either end.

[0014] (Liquid oral composition) In this embodiment, the liquid oral composition comprises the following components (a) and (b). (a) Water-soluble copper salt (b) Color inhibitors The color difference ΔE of the liquid oral composition is measured by the following method. * The value is 10 or more. (method) To 1.30 mL of liquid oral composition, 10 mL of a 0.8% by mass aqueous solution of tannic acid is added to prepare a measurement solution with a final concentration of 0.2% by mass of tannic acid. 2. Allow the measurement solution to stand at 37°C for one week. 3. After standing, centrifuge at room temperature at 3000 rpm for 10 minutes, remove the supernatant, and collect the precipitate. Measure the color of the precipitate using a spectrocolorimeter (specifically, SE7700, manufactured by Nippon Denshoku Industries Co., Ltd.) and apply CIE1976L * a * b* Colorimetric values ​​defined in the color system (L2 * a2 * ,b2 * ) obtain. 4.0.1% by mass of copper gluconate aqueous solution is used as a control, and the above procedure 1-3 is followed to prepare CIE1976L * a * b * Colorimetric values ​​defined in the color system (L1 * a1 * ,b1 * ) obtain. 5. The color difference ΔE is obtained from the following equation (I). * Calculate. ΔE * =((L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ) 1 / 2 (I) Here, the colorimetric values ​​in steps 3 and 4 above are specifically measured under a D65 light source.

[0015] The inventors have determined that the liquid oral composition comprises components (a) and (b), and that the color characteristics of the liquid oral composition, specifically the color difference ΔE calculated by the above formula (I), are * We have newly discovered that by controlling ΔE, discoloration caused by water-soluble copper salts and components present in the oral cavity can be effectively suppressed. Specifically, through the inventors' research, we found that ΔE obtained from the colorimetric values ​​after accelerated testing of liquid oral compositions and specific reference solutions can be effectively suppressed. * It is suitable as an indicator of discoloration in the oral cavity, and ΔE relative to the reference solution * It has become clear that by setting the range to a specific range, a liquid oral composition with excellent stain-inhibiting effects in the oral cavity can be obtained.

[0016] The colorimetric value ΔE of the liquid oral composition calculated by the above formula (I) *is 10 or more, preferably 12 or more, more preferably 15 or more, still more preferably 20 or more, from the viewpoint of improving the coloring suppression effect when applying the liquid oral composition into the oral cavity. Also, ΔE * If it is too large, since it will have a different hue and the cause of coloring becomes unclear, the colorimetric value ΔE of the liquid oral composition calculated by the above formula (I) * is, for example, 100 or less, preferably 90 or less, more preferably 80 or less, still more preferably 70 or less.

[0017] Also, from the colorimetric values obtained in the above-mentioned procedures 3. and 4., ΔL of the liquid oral composition is calculated by the following formula * , Δa * and Δb * are determined. ΔL * =(L2 * -L1 * ) 2 Δa<000,0089>=(a2 * -a1 * ) 2 Δb * =(b2 * -b1 * ) 2

[0018] <0,000303>ΔL of the liquid oral composition * is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, from the viewpoint of improving the coloring suppression effect. Also, from the same viewpoint, ΔL of the liquid oral composition * is preferably 80 or less, more preferably 70 or less, still more preferably 60 or less.

[0019] Δa of the liquid oral composition * ​​​​It is preferably 10 or less, more preferably 7 or less, and even more preferably 4 or less.

[0020] Δb of liquid oral composition * From the viewpoint of improving the color suppression effect, the value is preferably -20 or higher, more preferably -15 or higher, and even more preferably -10 or higher. Furthermore, from the viewpoint of improving the discoloration suppression effect, the Δb of the liquid oral composition * The value is preferably 10 or less, more preferably 4 or less, and even more preferably 3 or less.

[0021] The pH of the liquid oral composition at room temperature (25°C, the same applies hereinafter) is preferably 3.5 or higher, more preferably 4.0 or higher, and also preferably 4.5 or higher, or 5 or higher, or 5.5 or higher, from the viewpoint of suppressing tooth demineralization. Furthermore, from the viewpoint of improving the discoloration suppression effect, the pH of the liquid oral composition at room temperature is preferably 8 or less, more preferably 7.5 or less, and even more preferably 7 or less.

[0022] Next, we will describe the components contained in the liquid oral composition.

[0023] (Component (a)) Component (a) is a water-soluble copper salt, specifically a water-soluble inorganic or organic copper salt. The water-soluble copper salt may be either anhydrous or hydrated. Component (a) can be any ingredient used in pharmaceuticals, food products, or cosmetics. Furthermore, component (a) is one or more selected from the group consisting of, for example, copper gluconate, copper sulfate, copper citrate, copper chlorophyll, and sodium copper chlorophyllin. From the viewpoint of further improving the effects of the water-soluble copper salt, such as the effect of suppressing bad breath, the water-soluble copper salt preferably includes copper gluconate and copper sulfate, and more preferably copper gluconate. For example, a commercially available product can be used as ingredient (a).

[0024] From the viewpoint of further improving the effects of the water-soluble copper salt, such as the effect of suppressing bad breath, the content of component (a) in the liquid oral composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.03% by mass or more, and even more preferably 0.08% by mass or more, relative to the total liquid oral composition. Furthermore, from the viewpoint of improving the effect of suppressing discoloration in the oral cavity, the content of component (a) in the liquid oral composition is preferably 10% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less, and even more preferably 0.2% by mass or less, relative to the total liquid oral composition.

[0025] Furthermore, from the viewpoint of further improving the effects of water-soluble copper salts, such as the bad breath suppression effect, the content of component (a) in the liquid oral composition is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and may also be, for example, 0.01% by mass or more. Furthermore, from the viewpoint of improving the effect of suppressing discoloration in the oral cavity, the content of component (a) in the liquid oral composition is preferably 0.08% by mass or less, more preferably 0.06% by mass or less, and may also be, for example, 0.03% by mass or less, as a copper content.

[0026] (ingredient (b)) Component (b) is a color inhibitor. A specific example of component (b) is a water-soluble aluminum salt.

[0027] From the viewpoint of obtaining a more stable effect in suppressing oral discoloration, component (b) is preferably a water-soluble aluminum salt. Water-soluble aluminum salts specifically refer to inorganic or organic acid salts of aluminum that are water-soluble. Water-soluble aluminum salts can be those used as ingredients in pharmaceuticals, food products, or cosmetics, for example.

[0028] From the viewpoint of more stably suppressing oral discoloration, the water-soluble aluminum salt is preferably one or more selected from the group consisting of aluminum lactate, potassium aluminum sulfate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum benzoate, and allantoin chlorohydroxyaluminum.

[0029] From the viewpoint of more stably suppressing oral discoloration, the water-soluble aluminum salt is preferably an aluminum salt of an organic acid. The aluminum salt of the organic acid is, for example, one or more selected from the group consisting of aluminum lactate, aluminum citrate, and aluminum benzoate, and is preferably aluminum lactate.

[0030] From the viewpoint of improving the effect of suppressing discoloration in the oral cavity, the content of water-soluble aluminum salt in the liquid oral composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.06% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more, relative to the total liquid oral composition. Furthermore, from the viewpoint of improving the discoloration suppression effect and suppressing metallic taste, the content of water-soluble aluminum salt in the liquid oral composition is preferably 5% by mass or less, more preferably 3.5% by mass or less, even more preferably 3% by mass or less, even more preferably 1.5% by mass or less, and even more preferably 1% by mass or less, relative to the total liquid oral composition.

[0031] Furthermore, from the viewpoint of improving the effect of suppressing discoloration in the oral cavity, the content of water-soluble aluminum salt in the liquid oral composition is preferably 0.002% by mass or more, and more preferably 0.005% by mass or more. Furthermore, from the viewpoint of improving the color suppression effect and suppressing metallic taste, the content of water-soluble aluminum salt in the liquid oral composition may be, for example, 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.2% by mass or less, as the amount of aluminum blended.

[0032] The total content of component (b) in the liquid oral composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.06% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more, relative to the entire liquid oral composition, from the viewpoint of improving the effect of suppressing discoloration in the oral cavity. Furthermore, from the viewpoint of improving the color-inhibiting effect, the total content of component (b) in the liquid oral composition is preferably 5% by mass or less, more preferably 3.5% by mass or less, even more preferably 3% by mass or less, even more preferably 1.5% by mass or less, and even more preferably 1% by mass or less, relative to the entire liquid oral composition.

[0033] Furthermore, the ratio of the content of component (a) to the content of component (a) in the liquid oral composition (water-soluble (b) / (a)) is preferably 0.25 or more, and more preferably 0.5 or more, in terms of mass ratio, from the viewpoint of improving the effect of suppressing discoloration in the oral cavity. Furthermore, from the viewpoint of suppressing metallic taste, the above mass ratio (water-soluble aluminum salt / water-soluble copper salt) is preferably 300 or less, more preferably 100 or less, even more preferably 50 or less, even more preferably 20 or less, and even more preferably 5 or less.

[0034] In this embodiment, component (a) is preferably copper gluconate and component (b) is aluminum lactate. In this case, the copper gluconate content is preferably 0.01% by mass or more and 0.2% by mass or less relative to the entire liquid oral composition, and the aluminum lactate content is preferably 0.01% by mass or more and 3% by mass or less relative to the entire liquid oral composition.

[0035] (water) Liquid oral compositions specifically include water. The water content in the liquid oral composition can be, for example, the remainder after removing components other than water from the liquid oral composition.

[0036] Furthermore, the water content in the liquid oral composition is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and preferably 99.99% by mass or less, and more preferably 99.90% by mass or less, relative to the total liquid oral composition.

[0037] (Other ingredients) The liquid oral composition may contain components other than those described above, as long as they do not impair the effects of the present invention. Examples of such components include medicinal ingredients, abrasives, binders, viscosity modifiers, surfactants, flavoring agents, preservatives, fragrances, colorants, pH adjusters, solvents, solubilizers, bases, detergents, adsorbents, etc., which can be appropriately selected depending on the dosage form. Specific examples of additive components are shown below, but the components that can be incorporated in the present invention are not limited to these.

[0038] Examples of medicinal ingredients include one or more selected from the group consisting of antiseptics, anti-inflammatory agents, blood circulation promoters, tartar buildup inhibitors, stain removers, desensitizing agents, vitamins, and plaque-degrading enzymes. These medicinal ingredients are not limited to those that can be used in pharmaceuticals, etc.

[0039] Examples of medicinal ingredients that can be used as antiseptics include one or more selected from the group consisting of isopropylmethylphenol, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, hinokitiol, chlorhexidine hydrochloride, alkyldiaminoethylglycine hydrochloride, sodium lauroyl sarcosinate, and triclosan.

[0040] Examples of anti-inflammatory agents include one or more selected from the group consisting of β-glycyrrhetinic acid, glycyrrhetinic acid, glycyrrhizic acid, diammonium glycyrrhizinate, disodium glycyrrhizinate, trisodium glycyrrhizinate, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, tranexamic acid, ε-aminocaproic acid, sodium azulene sulfonate hydrate, allantoin, allantoin dihydroxyaluminum, epidihydrocholesterol, dihydrocholesterol, and lysozyme hydrochloride.

[0041] Examples of blood circulation-promoting agents include sodium chloride.

[0042] Examples of tartar buildup inhibitors include one or more selected from the group consisting of zeolite, disodium hydrogen phosphate, disodium dihydrogen pyrophosphate, sodium pyrophosphate, anhydrous sodium pyrophosphate, tetrasodium pyrophosphate (anhydrous), disodium monohydrogen phosphate, sodium hydrogen phosphate hydrate, disodium hydrogen phosphate (crystalline), trisodium phosphate, and sodium polyphosphate.

[0043] Examples of stain removers include one or more selected from the group consisting of macrogol (such as macrogol 200, macrogol 300, macrogol 400, macrogol 600, macrogol 1000, macrogol 1500, macrogol 1540, macrogol 4000, macrogol 6000, macrogol 20000), sodium polyphosphate, and polyvinylpyrrolidone.

[0044] Examples of hypersensitivity inhibitors include at least one selected from the group consisting of potassium nitrate and aluminum salts other than water-soluble aluminum salts.

[0045] Examples of vitamin supplements include one or more selected from the group consisting of ascorbic acid, L-ascorbic acid, sodium ascorbate, sodium L-ascorbate, pyridoxine hydrochloride, DL-α-tocopherol acetate, tocopherol acetate, dl-α-tocopherol nicotinate, and tocopherol nicotinate.

[0046] Examples of plaque-degrading enzymes include dextranase.

[0047] Examples of abrasives include silica-based abrasives such as anhydrous silicic acid, silica (crystalline silica or amorphous silica), silica gel, and aluminosilicate; and one or more selected from the group consisting of zeolite, anhydrous calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, alumina, magnesium carbonate, trimagnesium phosphate, zirconium silicate, tricalcium phosphate, hydroxyapatite, tetracalcium phosphate, and synthetic resin-based abrasives.

[0048] Examples of binders include one or more selected from the group consisting of organic binders such as pullulan, gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, carrageenan, sodium alginate, xanthan gum, sodium polyacrylate, gum arabic, guar gum, locust bean gum, polyvinyl alcohol, polyvinylpyrrolidone, and carboxyvinyl polymer, as well as thickening anhydrous silicic acid and bentonite.

[0049] The viscosity agent can be any substance commercially available as a raw material for pharmaceuticals, food, or cosmetics. Examples include polyhydric alcohols, and more specifically, one or more selected from the group consisting of sorbitol, glycerin, concentrated glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, propanediol (1,3-propanediol), polyethylene glycol, polypropylene glycol, xylitol, maltitol, lactitol, trehalose, sodium hyaluronate, and hydrolyzed collagen.

[0050] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and preferably one or more selected from the group consisting of anionic surfactants, nonionic surfactants, and amphoteric surfactants.

[0051] Examples of anionic surfactants include one or more selected from the group consisting of N-acyl amino acid salts, α-olefin sulfonates, N-acyl sulfonates, alkyl sulfates (e.g., sodium lauryl sulfate), and sulfates of glycerol fatty acid esters. Examples of nonionic surfactants include one or more selected from the group consisting of polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene hydrogenated castor oil, polyoxyethylene ethers of glycerin esters, sucrose fatty acid esters, alkylolamides, and glycerin fatty acid esters. Examples of amphoteric surfactants include one or more selected from the group consisting of alkyl betaine surfactants, amine oxide surfactants, and imidazolinium betaine surfactants. Specific examples include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and coconut oil fatty acid amide alkyl betaine.

[0052] Examples of flavoring agents include one or more selected from the group consisting of L-sodium glutamate, saccharin, sodium saccharin, disodium glycyrrhizinate, trisodium glycyrrhizinate, sucrose, glucose, fructose, lactose, honey, aspartame, stevia, sucralose, xylitol, inositol, D-sorbitol, D-mannitol, arabitol, raffinose, lactulose, lactitol, erythritol, reduced palatinose, palatinose, palatinose, acesulfame K, maltose, maltosyltrehalose or maltitol, neohesperidin dihydrochalcone, perillartin, p-methoxycinnamicaldehyde, and thaumatin.

[0053] Examples of preservatives include one or more selected from the group consisting of: sodium benzoate, para-hydroxybenzoic acid esters such as methylparaben, ethylparaben, butylparaben, isopropylparaben, propylparaben, isobutylparaben, and benzylparaben; alcohols such as phenoxyethanol and ethanol; sorbic acid, benzoic acid, dehydroacetic acid, propionic acid and their salts; ethylenediaminetetraacetate salts; and alkyldiaminoethylglycine hydrochloride.

[0054] Examples of fragrances include one or more selected from the group consisting of L-menthol, peppermint, spearmint, fruit flavors, and peppermint oil.

[0055] Examples of colorants include natural pigments such as safflower red pigment, gardenia yellow pigment, gardenia blue pigment, perilla pigment, red yeast rice pigment, red cabbage pigment, carrot pigment, hibiscus pigment, cocoa pigment, spirulina blue pigment, and coumarind pigment; legally approved pigments such as Red No. 3, Red No. 104, Red No. 105, Red No. 106, Yellow No. 4, Yellow No. 5, Green No. 3, and Blue No. 1; and one or more selected from the group consisting of riboflavin and titanium dioxide.

[0056] Examples of pH adjusters include one or more selected from the group consisting of acids and alkalis such as acetic acid, hydrochloric acid, sulfuric acid, nitric acid, citric acid, phosphoric acid, malic acid, gluconic acid, maleic acid, succinic acid, glutamic acid, pyrophosphate, tartaric acid, sodium hydroxide acetate, potassium hydroxide, sodium acetate, sodium carbonate, sodium citrate, sodium hydrogen citrate, phosphoric acid, sodium phosphate, monohydrogen phosphate, dihydrogen dihydrogen phosphate, potassium dihydrogen phosphate, and buffering agents.

[0057] In addition to water, mentioned above, other solvents include lower alcohols such as ethanol and propanol.

[0058] Solubilizers may be added to promote the dissolution of the above-mentioned additives and active ingredients in water. Examples of such solubilizers include polyhydric alcohols such as propylene glycol, dipropylene glycol, butylene glycol, and polyethylene glycol.

[0059] Examples of base materials include sodium bicarbonate.

[0060] Examples of cleaning agents include sodium polyphosphate.

[0061] Examples of adsorbents include β-cyclodextrin.

[0062] Furthermore, in addition to the above-mentioned components, other components suitable for use in oral compositions, such as liquid oral compositions, may be appropriately blended, as long as they do not impair the content of the present invention.

[0063] (Liquid formulation) Furthermore, liquid oral compositions are specifically liquid formulations. Liquid formulations are specifically oral administration formulations. Specific embodiments of the liquid oral composition include one selected from the group consisting of mouthwash, liquid toothpaste, and oral freshener. The liquid oral composition is preferably a mouthwash.

[0064] (Manufacturing method) In this embodiment, the liquid oral composition includes, for example, the steps of blending components (a), (b), water, and other components as appropriate.

[0065] Here, the difference ΔE in the above formula * This can be controlled, for example, by appropriately adjusting the types and proportions of each component that make up the liquid oral composition. More specifically, in this embodiment, it is important to appropriately select and combine the types and amounts of components (a) and (b) to design the formulation.

[0066] The liquid oral composition obtained in this embodiment includes components (a) and (b), and the above ΔE * Because it is within a specific range, it can effectively suppress discoloration when applied to the oral cavity, such as staining of the tongue, oral mucosa, or teeth.

[0067] The liquid oral composition obtained in this embodiment is suitably used, for example, as a tongue stain inhibitor, an oral mucosa stain inhibitor, or a tooth stain inhibitor.

[0068] In this embodiment, the tongue staining inhibition method, the oral mucosa staining inhibition method, and the tooth staining inhibition method all include components (a) and (b), and the above is ΔE * This includes applying a composition in which is 10 or more to the oral cavity.

[0069] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Examples of reference formats are provided below. 1. (a) Water-soluble copper salts, and (b) Color inhibitors A liquid oral composition comprising, The color difference ΔE is measured by the following method * A liquid oral composition in which the ratio is 10 or higher. (method) To 1.30 mL of the liquid oral composition, 10 mL of a 0.8% by mass aqueous solution of tannic acid is added to prepare a measurement solution with a final concentration of 0.2% by mass of tannic acid. 2. Allow the measurement solution to stand at 37°C for one week. 3. After standing, centrifuge at room temperature at 3000 rpm for 10 minutes, remove the supernatant, and collect the precipitate. Measure the color of the precipitate with a spectrophotometer and identify the CIE1976L * a * b * Colorimetric values ​​defined in the color system (L2 * ,a2 * ,b2 * ) obtain. 4.0.1% by mass of copper gluconate aqueous solution is used as a control, and the above procedure 1-3 is followed to prepare CIE1976L * a * b * Colorimetric values ​​defined in the color system (L1 * ,a1 * ,b1 * ) obtain. 5. The color difference ΔE is obtained from the following equation (I). * Calculate. ΔE * =((L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ) 1 / 2 (I) 2. The liquid oral composition described in 1., wherein the pH at 25°C is 3.5 or higher and 8 or lower. 3. The liquid oral composition according to 1. or 2., wherein component (b) is a water-soluble aluminum salt. 4. The liquid oral composition according to 3, wherein the water-soluble aluminum salt is an aluminum salt of an organic acid. 5. The liquid oral composition according to 3, wherein the water-soluble aluminum salt is one or more selected from the group consisting of aluminum lactate, potassium aluminum sulfate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum benzoate, and allantoin chlorohydroxyaluminum. 6. The liquid oral composition according to 1. or 2., wherein component (a) is one or more selected from the group consisting of copper gluconate, copper sulfate, copper citrate, copper chlorophyll, and sodium copper chlorophyllin. 7. The liquid oral composition according to 1. or 2., wherein the content of component (b) relative to the content of component (a) in the liquid oral composition is 0.25 or more and 300 or less by mass ratio. 8. A liquid oral composition according to 1. or 2., which is a tongue discoloration inhibitor. 9. A liquid oral composition according to 1. or 2., which is an oral mucosal discoloration inhibitor. 10. A liquid oral composition as described in 1. or 2., which is a mouthwash. 11. (a) Water-soluble copper salts, and (b) Color inhibitors Includes, The color difference ΔE is measured by the following method * A method for inhibiting tooth discoloration, comprising applying a composition having a ratio of 10 or more to the oral cavity. (method) To 1.30 mL of the composition, 10 mL of a 0.8% by mass aqueous solution of tannic acid is added to prepare a measurement solution with a final concentration of 0.2% by mass of tannic acid. 2. Allow the measurement solution to stand at 37°C for one week. 3. After standing, centrifuge at room temperature at 3000 rpm for 10 minutes, remove the supernatant, and collect the precipitate. Measure the color of the precipitate with a spectrophotometer and identify the CIE1976L * a * b * Colorimetric values ​​defined in the color system (L2 * ,a2 * ,b2 * ) obtain. 4.0.1% by mass of copper gluconate aqueous solution is used as a control, and the above procedure 1-3 is followed to prepare CIE1976L * a * b * Colorimetric values ​​defined in the color system (L1 * ,a1 * ,b1 * ) obtain. 5. The color difference ΔE is obtained from the following equation (I). * Calculate. ΔE * =((L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ) 1 / 2 (I) [Examples]

[0070] The embodiment will be described in detail below with reference to examples and comparative examples, but this embodiment is not limited to these examples.

[0071] (Example test) (Examples 1-4, Comparative Examples 1-7) The mouthwashes for each example were prepared by mixing the ingredients listed in Table 1 and evaluated using the method described below. Details of the ingredients listed in each table are shown below. Copper gluconate: Manufactured by Fuso Chemical Industries Co., Ltd. Aluminum lactate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Tannic acid: Manufactured by Nacalai Tesque.

[0072] (Color measurement) To 30 mL of the mouthwash for each example, 10 mL of a 0.8% by mass aqueous solution of tannic acid was added to prepare a measurement solution in which the final concentration of tannic acid was 0.2% by mass and the final concentrations of components (a) and (b) were as shown in Table 1. The obtained measurement solution was left to stand at 37°C for one week. After standing, the mixture was centrifuged at room temperature at 3000 rpm for 10 minutes, and the supernatant was removed to collect the precipitate. The color of the precipitate was measured using a spectrocolorimeter (SE7700, manufactured by Nippon Denshoku Industries Co., Ltd.) under a D65 light source, and the color was determined using CIE1976L. * a * b * Colorimetric values ​​defined in the color system (L2 * a2 * ,b2 * ) was obtained. On the other hand, using a 0.1% by mass copper gluconate aqueous solution as control example 1, CIE1976L was prepared using the procedure described in steps 1-3 above. * a * b * Colorimetric values ​​defined in the color system (L1 * a1 * ,b1 * ) was obtained. The color difference ΔE is obtained from the following equation (I). * The result was calculated. ΔE * =((L2 * -L1 * ) 2 +(a2 * -a1 * )2 +(b2 * -b1 * ) 2 ) 1 / 2 (I) The measurement results are shown in Table 1.

[0073] (pH measurement) The pH of each mouthwash solution at 25°C was measured using a pH meter (LAQUAtwin, manufactured by AS ONE Corporation). The measurement results are shown in Table 1.

[0074] (Evaluation method) To 30 mL of the mouthwash solution from each example, 10 mL of a 0.8% by mass aqueous solution of tannic acid was added to prepare evaluation samples. The color of the precipitate in the obtained samples was visually confirmed and evaluated according to the following criteria by comparison with control example 1. The results are shown in Table 1. -: Worsening ±: No change +:Improvement

[0075] [Table 1]

[0076] Table 1 shows that in each example, the ΔE of the mouthwash * Because it is within a specific range, discoloration when present with tannic acid could be effectively suppressed.

Claims

1. (a) Water-soluble copper salts, and (b) Color inhibitors A liquid oral composition comprising, The above component (b) is a water-soluble aluminum salt, The product does not contain a disinfectant, or if it does, the disinfectant is one or more selected from the group consisting of isopropylmethylphenol, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, chlorhexidine hydrochloride, alkyldiaminoethylglycine hydrochloride, sodium lauroyl sarcosinate, and triclosan. The color difference ΔE is measured by the following method. * A liquid oral composition in which the ratio is 10 or more. (method) 1. Add 10 mL of a 0.8% by mass aqueous solution of tannic acid to 1.30 mL of the liquid oral composition to prepare a measurement solution with a final concentration of 0.2% by mass of tannic acid.

2. Allow the measurement solution to stand at 37°C for one week.

3. After standing, centrifuge at room temperature at 3000 rpm for 10 minutes, remove the supernatant, and collect the precipitate. Measure the color of the precipitate with a spectrocolorimeter and use CIE1976L. * a * b * Colorimetric values ​​(L2) defined in the color system * a2 * , b2 * ) obtain. Using an aqueous copper gluconate solution of 4.01% by mass as a control, the CIELAB colorimetric values (L1 * a * b * ), defined in the color system, are obtained according to the procedures of 1. to 3. above * , a1 * , b1 * ).

5. The color difference ΔE is obtained from the following equation (I). * Calculate. ΔE * =((L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ) 1 / 2 (I)

2. The liquid oral composition according to claim 1, wherein the pH at 25°C is 3.5 or higher and 8 or lower.

3. The liquid oral composition according to claim 1 or 2, wherein the ΔL* of the liquid oral composition calculated from the colorimetric value by the following formula is 10 or more and 80 or less. ΔL * = (L2 * - L1 *) 2

4. The liquid oral composition according to claim 1 or 2, wherein the water-soluble aluminum salt is an aluminum salt of an organic acid.

5. The liquid oral composition according to claim 1 or 2, wherein the water-soluble aluminum salt is one or more selected from the group consisting of aluminum lactate, potassium aluminum sulfate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum benzoate, and allantoin chlorohydroxyaluminum.

6. The liquid oral composition according to claim 1 or 2, wherein component (a) is one or more selected from the group consisting of copper gluconate, copper sulfate, copper citrate, copper chlorophyll, and sodium copper chlorophyllin.

7. The liquid oral composition according to claim 1 or 2, wherein the content of component (b) relative to the content of component (a) in the liquid oral composition is 0.25 or more and 300 or less by mass ratio.

8. A liquid oral composition according to claim 1 or 2, which is a tongue discoloration inhibitor.

9. A liquid oral composition according to claim 1 or 2, which is an oral mucosal discoloration inhibitor.

10. A liquid oral composition according to claim 1 or 2, which is a mouthwash.

11. A method for inhibiting tooth discoloration, comprising applying the liquid oral composition according to claim 1 or 2 to the oral cavity.

12. The liquid oral composition according to claim 1 or 2, wherein the Δa* of the liquid oral composition calculated from the colorimetric value by the following formula is 0.05 or more and 10 or less. Δa * = (a2 * - a1 *) 2

13. The liquid oral composition according to claim 1 or 2, wherein the Δb* of the liquid oral composition, calculated from the colorimetric value by the following formula, is -20 or more and 10 or less. Δb * = (b2 * - b1 *) 2

14. The liquid oral composition according to claim 1 or 2, wherein the content of component (a) in the liquid oral composition is 0.001% by mass or more and 10% by mass or less with respect to the entire liquid oral composition.

15. The liquid oral composition according to claim 1 or 2, wherein the content of the water-soluble aluminum salt in the liquid oral composition is 0.01% by mass or more and 5% by mass or less with respect to the entire liquid oral composition.

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