Toothpaste composition

Abstract

To provide a dentifrice composition that achieves excellent fluorine ion retention in the mouth, in particular at the oral mucosa, as well as excellent fluorine ion releasability, and has liquid separation stability and hardening stability as well as storage stability.SOLUTION: A dentifrice composition contains (A) a water-soluble polyphosphate, (B) calcium glycerophosphate, (C) a water-soluble fluorine-containing compound, and (D) cationized cellulose.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a dentifrice composition containing a water-soluble fluorine-containing compound that is excellent in the retention of fluoride ions in the oral cavity, particularly on the oral mucosa, and also excellent in its release property.

Background Art

[0002] Fluorine-containing compounds such as sodium fluoride are widely used as medicinal ingredients having functions such as promoting remineralization and suppressing demineralization in oral compositions such as dentifrice compositions for the purpose of preventing dental caries and the like. In order to effectively actuate the fluorine-containing compound, it is effective to retain fluoride ions on the tooth surface in the oral cavity for a long time, and it is also important to leave a large amount of fluoride ions in the oral cavity even after rinsing the oral cavity with water or gargling after use. However, especially since the dentifrice composition is washed away by rinsing after brushing, the fluoride ions remaining in the oral cavity are only trace amounts.

[0003] In order to improve the retention of fluoride ions incorporated in the dentifrice composition in the oral cavity, there is a method of coexisting calcium ions, which are remineralization components, and fluoride ions. However, calcium ions and fluoride ions are highly reactive and, when coexisted, become calcium fluoride, which is an insoluble substance, before acting on the teeth, and thus sufficient effects could not be exerted. Further, in Patent Document 1 (Japanese Patent Publication No. 10-511956), an oral preparation in a form in which calcium fluoride is generated in the oral cavity by mixing the two compositions in the oral cavity or immediately before application to the oral cavity has been proposed. However, in this method, since it enters the oral cavity as fluoride ions, it is immediately washed away by saliva and a sufficient retention effect is not exhibited. Further, since calcium fluoride precipitates in a short time after the two components are mixed, fluoride ions are not sufficiently released and the remineralization prevention effect is not satisfactorily exhibited. Patent Document 2 (Japanese Patent Application Laid-Open No. 2009-137863) proposes a composition in which a complex of polyphosphate, calcium salt, and fluoride salt is prepared in advance. However, this method has problems such as complexity in preparation and liquefaction or solidification after long-term storage as a dentifrice. In addition, Patent Documents 3 to 5 (Japanese Patent Application Laid-Open Nos. 2015-117215, 2013-67567, and 2007-320894) have proposed a method of adsorbing and retaining fluoride ions on the tooth surface by using a specific cationic polymer substance in a dentifrice composition. However, there is still room for improvement in the retention and the remaining amount after brushing, and further improvement in retention is desired.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a dentifrice composition that is excellent in the retention of fluoride ions in the oral cavity, particularly on the oral mucosa, and also excellent in the release property.

Means for Solving the Problems

[0006] As a result of intensive studies to achieve the above object, the present inventors have found that when a water-soluble fluorine-containing compound is combined with a water-soluble polyphosphate and calcium glycerophosphate and further combined with cationized cellulose and formulated into a dentifrice composition, it has excellent retention of fluoride ions in the oral cavity, particularly on the oral mucosa. The fluoride ions remain in the oral cavity at a high rate, and moreover, it has excellent release properties (release amount, sustained release) of fluoride ions. The retained fluoride ions are slowly released, and fluoride ions can be supplied to the oral cavity for a long time. Also, liquid separation and solidification are suppressed even after long-term storage, and good storage stability is obtained. That is, in the present invention, a dentifrice composition containing (A) a water-soluble polyphosphate, (B) calcium glycerophosphate, (C) a water-soluble fluorine-containing compound, and (D) cationized cellulose has excellent retention of fluoride ions in the oral cavity, particularly on the oral mucosa, excellent release properties thereof, and also has liquid separation stability and solidification stability and good storage stability, leading to the completion of the present invention.

[0007] It was expected that the retention of fluoride in the oral cavity would be further enhanced if the fluoride of the water-soluble fluorine-containing compound formulated in the dentifrice composition could sufficiently remain not only on the tooth surface but also on the oral mucosa. However, since the oral mucosa is covered with salivary proteins such as mucin, it is difficult for fluoride to be adsorbed, and in the conventional technology, it was not possible to sufficiently retain fluoride on the oral mucosa. However, in the present invention, by using the components (A) and (B) in combination with the component (C) and combining the component (D), the retention of fluoride ions derived from the component (C) on the oral mucosa is improved by the component (D), and not only the retention of fluoride ions but also its release properties can be made excellent. In this case, the component (D) enhances the adsorptivity of fluoride ions to mucin covering the oral mucosa, thereby improving its retention. Fluoride ions remain in the oral mucosa at a high rate, and moreover, the retained fluoride ions are gradually released into the saliva and supplied to the tooth surface in contact with the saliva for a long time. Therefore, according to the dentifrice composition of the present invention, liquid separation stability and solidification stability can be ensured, and the retention of fluoride ions in the oral cavity can be improved.

[0008] As shown in the comparative examples described later, when components (A), (B) and (C) are formulated and component (D) is not formulated, the fluorine (fluoride ion) retention and fluorine release properties are poor, and the liquid separation stability of the preparation is poor (Comparative Example 3). Even when component (D) is formulated, if component (A) or (B) is not formulated, the fluorine (fluoride ion) retention and fluorine release properties are poor, and the liquid separation stability or solidification stability of the preparation is poor (Comparative Examples 1 and 2). In contrast, the dentifrice composition (Example described later) formulated with components (A), (B), (C) and (D) of the present invention has excellent fluorine retention and fluorine release properties, and good liquid separation stability (absence of liquid separation after storage) and solidification stability (absence of solidification after storage) of the preparation.

[0009] Therefore, the present invention provides the following dentifrice compositions. 〔1〕 (A) Water-soluble polyphosphate, (B) Calcium glycerophosphate, (C) Water-soluble fluorine-containing compound and (D) Cationized cellulose A dentifrice composition characterized by containing the same. 〔2〕 The dentifrice composition according to [1], wherein component (A) is potassium pyrophosphate. 〔3〕 The dentifrice composition according to [1] or [2], wherein (A) / (C) is 0.05 to 1 as a molar ratio. 〔4〕 The dentifrice composition according to any one of [1] to [3], wherein (B) / (C) is 0.05 to 1.5 as a molar ratio. 〔5〕 The dentifrice composition according to any one of [1] to [4], wherein the content of component (A) is 0.1 to 1.5% by mass, the content of component (B) is 0.1 to 2% by mass, the content of component (C) is 500 to 5,000 ppm as fluoride ions, and the content of component (D) is 0.01 to 0.5% by mass. 〔6〕 The dentifrice composition according to any one of [1] to [5], which is a toothpaste or a gel dentifrice.

Effects of the Invention

[0010] According to the present invention, there is provided a dentifrice composition having excellent retention of fluoride ions in the oral cavity, particularly on the oral mucosa, excellent release properties thereof, and having liquid separation stability and solidification stability, and good storage stability. The dentifrice composition of the present invention can leave a relatively large amount of fluoride ions in the oral cavity even after rinsing with water after brushing the oral cavity, and can sufficiently exhibit the effects of promoting remineralization and suppressing demineralization of the water-soluble fluoride-containing compound, and is suitable for preventing dental caries.

Mode for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention contains (A) a water-soluble polyphosphate, (B) calcium glycerophosphate, (C) a water-soluble fluoride-containing compound, and (D) cationized cellulose.

[0012] (A) The water-soluble polyphosphate has an effect of improving the retention of fluoride ions and also has an effect of suppressing liquid separation. As the component (A), examples of the water-soluble polyphosphate include linear polyphosphates such as pyrophosphoric acid, tripolyphosphoric acid, and tetrapolyphosphoric acid, and cyclic polyphosphates such as trimetaphosphoric acid, tetrametaphosphoric acid, and hexametaphosphoric acid. Examples of the salts thereof include alkali metal salts such as sodium salts and potassium salts. Among them, pyrophosphates and tripolyphosphates are preferable, more preferably pyrophosphates, and particularly preferably potassium pyrophosphate. These may be used alone or in combination of two or more.

[0013] The blending amount of the component (A) is preferably 0.1 to 1.5% (mass%, the same hereinafter) of the whole composition, more preferably 0.15 to 1.4%, and still more preferably 0.3 to 1.0%. When the blending amount is 0.1% or more, sufficient retention and release properties of fluoride ions can be obtained, and liquid separation is suppressed over time, and sufficient liquid separation stability can be obtained. When it is 1.5% or less, sufficient retention and release properties of fluoride ions are maintained, and solidification over time is prevented, and sufficient solidification stability is obtained.

[0014] (B) Calcium glycerophosphate has an effect of improving the retention of fluoride ions and also has a solidification inhibition effect. Calcium glycerophosphate can be used whether it is derived from natural products or synthetic products. For example, commercially available products such as the product named "Calcium Glycerophosphate" manufactured by Iwaki Pharmaceutical Co., Ltd. can also be used.

[0015] (B) The blending amount of calcium glycerophosphate is preferably 0.1 to 2% of the whole composition, more preferably 0.15 to 1.8%, and particularly preferably 0.25 to 1.5%. When the blending amount is 0.1% or more, sufficient retention and release properties of fluoride ions can be obtained, and solidification over time is prevented, resulting in sufficient solidification stability. When it is 2% or less, sufficient retention and release properties of fluoride ions are maintained, and liquid separation over time is suppressed, resulting in sufficient liquid separation stability.

[0016] (C) Examples of the water-soluble fluoride-containing compound include sodium fluoride, sodium monofluorophosphate, stannous fluoride, etc. (C) The blending amount of the water-soluble fluoride-containing compound is preferably 500 to 5,000 ppm of the whole composition as fluoride ions, more preferably 1,100 to 3,000 ppm. When the blending amount is 500 ppm or more as fluoride ions, a sufficient effect of improving the retention of fluoride ions can be obtained, and when it is 5,000 ppm or less, the occurrence of harmful effects such as mottled teeth due to excessive intake can be prevented. The blending amount of the water-soluble fluoride-containing compound varies depending on the amount of fluoride ions to be supplied. For example, in the case of sodium fluoride, when the fluoride ions to be supplied are 500 ppm, the blending amount is 0.11% of the whole composition. Specifically, the blending amount of sodium fluoride is preferably 0.1% or more of the whole composition, more preferably 0.25 to 0.7%.

[0017] In the present invention, (A) / (C) representing the quantitative ratio of component (A) and component (C) is preferably 0.05 to 1, more preferably 0.1 to 0.5, particularly 0.10 to 0.50 in terms of molar ratio. Also, (B) / (C) representing the quantitative ratio of component (B) and component (C) is preferably 0.05 to 1.5, more preferably 0.10 to 1 in terms of molar ratio. It is more preferable that the molar ratio of (A) / (C) and the molar ratio of (B) / (C) are respectively within the above ranges. When component (C) is blended within these ranges of molar ratios, the retention property and release property of fluoride ions are more excellent, and the liquid separation stability and solidification stability are also more excellent.

[0018] (D) Cationized cellulose, when combined with components (A) and (B), has the effect of improving the retention property of fluoride ions derived from component (C) and improving its release property, and also has the effect of improving the liquid separation stability.

[0019] Cationized cellulose is cellulose having a cation or a cellulose derivative having a cation. Cationized cellulose may have a counter ion (for example, a halogen ion (chloride ion), a methosulfate ion, etc.). The molecular weight of cationized cellulose is not particularly limited. As component (D), cationized cellulose may be used alone or in combination of two or more. Examples of cationized cellulose include hydroxyethyl cellulose dimethyldiallylammonium salt and O-[2-hydroxy-3-(trimethylammonio)propyl] hydroxyethyl cellulose chloride, and hydroxyethyl cellulose dimethyldiallylammonium salt is preferred. Examples of the counter ion of hydroxyethyl cellulose dimethyldiallylammonium salt include chloride ion, and hydroxyethyl cellulose dimethyldiallylammonium chloride is suitable. The cationized cellulose used in the present invention preferably has a viscosity of 30 to 3,000 mPa·s in its 2% aqueous solution (BH type Brookfield viscometer, rotor No. 2, 20 revolutions, 20 °C, measurement time 1 minute). The average molecular weight of the cationized cellulose is not particularly limited, but is preferably a weight average molecular weight by gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance, and is preferably 100,000 to 1,500,000. The nitrogen content is preferably 0.1 to 3%, more preferably 0.5 to 2.5%. Examples of such cationized cellulose include CELQUAT L-200 (aqueous solution viscosity of 2%: 35 to 350 mPa·s, BH type Brookfield viscometer, rotor No. 2, 20 rotations, 20°C, measurement time 1 minute) commercially available from Akzo Nobel Co., Ltd., and a weight average molecular weight by gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance: 250,000 to 350,000), and it can be used.

[0020] The blending amount of the component (D) is preferably 0.01 to 0.5% of the whole composition, more preferably 0.05 to 0.2%. When blended in an amount of 0.01% or more, sufficient retention and release properties of fluoride ions can be obtained, and liquid separation is suppressed even over time, and sufficient liquid separation stability can be obtained. When it is 0.5% or less, the discomfort to the oral mucosa is sufficiently suppressed.

[0021] In addition, (A) / (D) indicating the amount ratio of the component (A) and the component (D) is preferably 1 to 50 as a mass ratio, more preferably 3 to 25. (B) / (D) indicating the amount ratio of the component (B) and the component (D) is preferably 1 to 50 as a mass ratio, more preferably 2 to 30. (C) / (D) indicating the amount ratio of the component (C) and the component (D) is preferably 1 to 20 as a mass ratio, more preferably 1 to 10. When the component (D) is blended within the range of these mass ratios, the effect of the component (D) is sufficiently exerted, the retention and release properties of fluoride ions are more excellent, and the liquid separation stability is more excellent.

[0022] The dentifrice composition of the present invention is particularly suitable as a paste dentifrice or a gel dentifrice (without abrasive), especially as a paste dentifrice. In addition to the above components, other known components can be blended as necessary within a range that does not interfere with the effects of the present invention. For example, abrasives, binders, thickeners, surfactants, and further, if necessary, colorants, sweeteners, preservatives, fragrances, active ingredients, etc. can be blended. The method for preparing the dentifrice composition is not particularly limited and may be a known method according to the dosage form. For example, components (A) to (D), and further optional components and water can be blended by a usual method for preparation.

[0023] Examples of the abrasive include silica-based abrasives such as anhydrous silicic acid, precipitated silica, silica gel, aluminosilicate, and zirconosilicate; calcium phosphate-based compounds such as dicalcium phosphate dihydrate or anhydrate, monocalcium phosphate, tricalcium phosphate, tetracalcium phosphate, and calcium pyrophosphate; calcium carbonate, calcium hydroxide, aluminum hydroxide, insoluble sodium metaphosphate, magnesium phosphate tribasic, magnesium carbonate, calcium sulfate, bentonite, titanium-bonded silicate, and synthetic resin-based abrasives. Among them, silica-based abrasives are preferred. The blending amount of the abrasive is preferably 5 to 60%, particularly 5 to 30% of the whole composition.

[0024] As the binder, an organic or inorganic binder can be blended. Specifically, cellulose derivatives such as sodium carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxymethyl ethyl cellulose; alginic acid derivatives such as sodium alginate; gums such as xanthan gum, tragacanth gum, karaya gum, and gum arabic; organic binders such as polyacrylate, carrageenan, polyvinyl alcohol, and carboxyvinyl polymer; and inorganic binders such as thickening silica, thickening aluminum silicate, veegum, and laponite can be mentioned. The blending amount of the binder is preferably 0.1 to 5%, particularly preferably 0.2 to 3%, based on the total composition. In the present invention, an organic binder is particularly preferred, and the blending amount of the organic binder is preferably 0.1 to 5%, particularly preferably 0.5 to 3%, based on the total composition. Inorganic binders, particularly thickening silica, are preferably 5% or less, particularly preferably 2% or less, especially preferably 1% or less, based on the total composition when blended, and may be 0% without blending, in terms of the retention of fluoride ions.

[0025] Examples of the thickener include sugar alcohols such as sorbitol, xylitol, erythritol, maltitol, lactitol, 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 Raw Material Standards for Quasi-Drugs 2006). The blending amount of the thickener is usually preferably 5 to 60% based on the total composition.

[0026] As the surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant can be blended. Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, acyl sarcosinates such as sodium lauroyl sarcosinate and sodium myristoyl sarcosinate, sodium dodecylbenzenesulfonate, sodium hydrogenated coconut fatty acid monoglyceride monosulfate, sodium laurylsulfacetate, acyl glutamates such as sodium N-palmitoylglutamate, sodium N-methyl-N-acyltaurine, sodium N-methyl-N-acylalanine, and sodium α-olefin sulfonate. Examples of the nonionic surfactant include polyoxyethylene alkyl ether (for example, those having 16 to 18 carbon atoms in the alkyl group), polyoxyethylene hydrogenated castor oil (for example, those having an average addition mole number of ethylene oxide of 40 to 80), alkyl glucoside, polyoxyethylene polyoxypropylene block copolymer, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkylol amide, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, and the like. Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, N-cocoyl-N-carboxymethyl-N-hydroxyethyl ethylenediamine, coconut fatty acid amide propyldimethylaminoacetic acid betaine, coconut fatty acid amide propyl, etc. The blending amount of the surfactant is usually preferably 0.1 to 10% of the whole composition. The blending amount can be adjusted according to the form of the dentifrice composition, the purpose of use, etc. For example, it can be blended in an amount of 0.1 to 10% in a paste dentifrice.

[0027] Examples of the coloring agent 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, titanium oxide, etc. Examples of the sweetener include sodium saccharin, aspartame, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidin dihydrochalcone, perillartine, etc. Examples of the preservative include paraoxybenzoic acid esters such as methyl paraben, ethyl paraben, butyl paraben, etc., and benzoic acid or its salts such as sodium benzoate.

[0028] Flavors include natural flavors such as peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, perilla oil, cardamom oil, coriander oil, mandarin oil, lime oil, lavender oil, rosemary oil, laurel oil, chamomile oil, caraway oil, marjoram oil, bay oil, lemongrass oil, oregano oil, pine needle oil, neroli oil, rose oil, jasmine oil, grapefruit oil, sweetie oil, pomelo oil, iris concrete, absolute peppermint, absolute rose, orange flower, etc., flavors obtained by processing these natural flavors (such as cut of the fore-run, cut of the tail-run, fractional distillation, liquid-liquid extraction, essence formation, powder flavoring, etc.), and single-component flavors such as menthol, carvone, anethole, cineole, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-p-menthane-3-carboxamide, pinene, octyl aldehyde, citral, pregeone, carvyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexanepropionate, methyl anthranilate, ethyl methylphenylglycidate, vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cyclotene, furfural, trimethylpyrazine, ethyl lactate, ethyl thioacetate, etc. Further, known flavor materials used in dentifrice compositions, such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc., can be used in combination. Also, the blending amount is not particularly limited, but it is preferable to use the above flavor materials in an amount of 0.000001 to 1% in the formulation composition. Further, as the flavoring flavor using the above flavor materials, it is preferable to use it in an amount of 0.05 to 2% in the formulation composition.

[0029] Examples of the active ingredients include bactericides such as isopropylmethylphenol and cetylpyridinium chloride, water-soluble phosphate compounds such as potassium salts and sodium salts of orthophosphoric acid, enzymes such as dextranase, mutanase, amylase, and protease, tranexamic acid, epsilon-aminocaproic acid, triclosan, lysozyme chloride, aluminum chlorohydroxyallantoin, hinokitiol, ascorbic acid, tocopherol acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, water-soluble copper compounds such as copper chlorophyllin sodium, chlorophyll, and copper gluconate, aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid or its derivatives, glycyrrhizic acid or its salts, glycyrrhetinic acid or its derivatives, and tartar inhibitors. Note that the above active ingredients can be blended in an effective amount as long as the effects of the present invention are not impaired.

Examples

[0030] Hereinafter, examples, comparative examples, and formulation examples will be shown to specifically describe the present invention, but the present invention is not limited to the following examples. In the following examples, % indicates mass% unless otherwise specified.

[0031] [Examples, Comparative Examples] Toothpaste compositions (gel toothpastes) having the compositions shown in Tables 1 to 3 were prepared by a conventional method and evaluated by the following method. The results are also shown in the table.

[0032] (1) Evaluation method for fluoride (fluoride ion) retention The retention of fluoride ions was evaluated by an adsorption test of fluoride (fluoride ions) to mucin, which is an oral mucosal component. 0.2 g of mucin (manufactured by Sigma-Aldrich) was added to a 10 mL centrifuge tube, and further 5 mL of the dentifrice composition (40-fold diluted solution with purified water) was added and allowed to act for 3 minutes. Then, centrifugation was performed at 3,000 rpm for 10 minutes, and the supernatant was removed. To the obtained mucin, 5 mL of potassium citrate buffer was added and stirred for 1 minute to forcibly elute the fluoride ions adsorbed and retained in the mucin. Centrifugation was performed at 3,000 rpm for 10 minutes to recover the supernatant, and the fluoride (fluoride ion) concentration contained in the solution was measured with a fluoride ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific K.K.) to obtain the retained fluoride ion concentration (ppm). The fluoride ion retention rate was calculated by the following formula. Fluoride ion retention rate (%) = {(retained fluoride ion concentration (ppm)) / (fluoride ion concentration (ppm) formulated in the preparation / 40)} × 100 Based on the fluoride ion retention rate, the fluoride ion retention property was evaluated according to the following evaluation criteria. Evaluation criteria ◎: Fluoride ion retention rate is 50% or more 〇: Fluoride ion retention rate is 30% or more and less than 50% △: Fluoride ion retention rate is 20% or more and less than 30% ×: Fluoride ion retention rate is less than 20%

[0033] (2) Evaluation method for fluoride (fluoride ion) release property For the compositions (Examples 1 to 14) with an evaluation of △ or higher in (1), the amount of fluoride ion released (release rate) from mucin to saliva and the sustained release property were evaluated. 0.2 g of mucin (manufactured by Sigma-Aldrich) was added to a 10 mL centrifuge tube, and further 5 mL of the dentifrice composition (40-fold diluted solution with purified water) was added and allowed to act for 3 minutes. Then, centrifugation was performed at 3,000 rpm for 10 minutes, and the supernatant was removed. To the obtained mucin, 5 mL of artificial saliva (CaCl2 = 1.5 mmol / L, KH2PO4 = 5.0 mmol / L, acetic acid = 100 mmol / L, NaCl = 100 mmol / L, the balance = water; pH = 7.0) was added and stirred for 1 minute, then allowed to stand for 3 minutes, 60 minutes, or 180 minutes. After eluting the fluoride ions adsorbed and retained in the mucin, centrifugation was performed at 3,000 rpm for 10 minutes each to collect the supernatant, and the fluoride ion concentration contained in the solution was measured with a fluoride ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific K.K.), and the released fluoride ion concentration for each was obtained. From the released fluoride ion concentration, the fluoride ion release rate was calculated by the following formula. Fluoride ion release rate (%) = {(Released fluoride ion concentration (ppm)) / (Retained fluoride ion concentration (ppm))} × 100 Based on the calculated fluoride ion release rate, the fluoride release property (release amount) was evaluated. The fluoride ion release rate after standing for 3 minutes for all the evaluation compositions (Examples 1 to 14) was less than 20%, and the fluoride ion release rate after standing for 60 minutes was in the range of 20 to 60% for all, confirming that there was no immediate release and it had sustained release properties. Based on the fluoride ion release rate after standing for 180 minutes, the fluoride release property was evaluated according to the following evaluation criteria. Those with 〇 or ◎ were judged that the fluoride ions adsorbed and retained in the mucin were gradually released by saliva and the fluoride release property passed. Evaluation criteria ◎: Fluoride ion release rate after standing for 180 minutes is 70% or more 〇: Fluoride ion release rate after standing for 180 minutes is 50% or more and less than 70% △: Fluoride ion release rate after standing for 180 minutes is 20% or more and less than 50% ×: Fluoride ion release rate after standing for 180 minutes is less than 20%

[0034] (3) Evaluation method for storage stability (3-1) Evaluation method for the liquid separation stability of the preparation (absence of liquid separation after storage) 50 g of each dentifrice composition was filled into three tube containers (material: laminated tube with a diameter of 26 mm made of linear low-density polyethylene on the innermost layer, manufactured by Dai Nippon Printing Co., Ltd.), and stored at 40 °C for one month. After storage, the dentifrice composition was extruded from each tube container onto paper, and the state of liquid separation was judged according to the following scoring criteria. The average score of the three was obtained, and the liquid separation stability of the preparation was evaluated according to the following evaluation criteria. Scoring Criteria 4 points: No liquid separation was observed. 3 points: Slight liquid separation was observed at the mouthpiece, but it was at a level that was not a problem. 2 points: Liquid separation was observed at the mouthpiece and the kneaded surface. 1 point: When the dentifrice was extruded from the tube, separation liquid was observed to drip. Evaluation Criteria ◎: Average score is 4.0 points. 〇: Average score is 3.0 points or more and less than 4.0 points. △: Average score is 2.0 points or more and less than 3.0 points. ×: Average score is less than 2.0 points.

[0035] (3-2) Evaluation method for the solidification stability of the preparation (lack of solidification after storage) 50 g of each dentifrice composition was filled into three tube containers (material: laminated tube with a diameter of 26 mm made of linear low-density polyethylene on the innermost layer, manufactured by Dai Nippon Printing Co., Ltd.), and stored at 40 °C for one month. After storage, the dentifrice composition was extruded from each tube container, and the state of solidification was judged according to the following scoring criteria. The average score of the three was obtained, and the solidification stability of the preparation was evaluated according to the following evaluation criteria. Scoring Criteria 4 points: No solidification was observed. 3 points: Slight solidification was observed at the mouthpiece, but it was at a level that was not a problem. 2 points: Solidification was observed at the mouthpiece and the kneaded surface. 1 point: Solidification was observed to the extent that the dentifrice could not be extruded from the tube. Evaluation Criteria ◎: Average score is 4.0 points. 〇: Average score is 3.0 points or more and less than 4.0 points. △: Average score is 2.0 points or more and less than 3.0 points. ×: Average score is less than 2.0

[0036] The details of the raw materials used are shown below. (A) Potassium pyrophosphate; manufactured by Taihei Chemical Industry Co., Ltd. (A) Sodium tripolyphosphate; manufactured by Taihei Chemical Industry Co., Ltd. (B) Calcium glycerophosphate; manufactured by Iwaki Pharmaceutical Co., Ltd. (C) Sodium fluoride; manufactured by Stella Chemifa Corporation (D) Hydroxyethyl cellulose dimethyldiallylammonium chloride; CELQUAT L-200, manufactured by Akzo Nobel N.V., 2% aqueous solution viscosity: 35 - 350 mPa·s (BH type Brookfield viscometer, rotor No. 2, 20 revolutions, 20°C, measurement time 1 minute), gel permeation chromatography weight average molecular weight by the method using polyethylene glycol as the standard substance: 250,000 - 350,000)

[0037]

Table 1

[0038]

Table 2

[0039]

Table 3

[0040] Formulation examples are shown. The raw materials used are the same as above. [Formulation example] Gel toothpaste (A) Potassium pyrophosphate 0.7 (B) Calcium glycerophosphate 0.8 (C) Sodium fluoride 0.32 (D) Hydroxyethyl cellulose dimethyldiallylammonium chloride 0.05 Sorbitol solution (70% aqueous solution) 55 Propylene glycol 3 Sodium polyacrylate 0.7 Carrageenan 0.3 Xanthan gum 0.3 Xylitol 5 Coconut oil fatty acid amide propyl betaine 0.3 Citric acid 0.02 Sodium citrate 0.3 Fragrance 0.5 Purified water Remainder Total 100.0% (A) / (C) (molar ratio): 0.28 (B) / (C) (molar ratio): 0.50 (A) / (D) mass ratio: 14 (B) / (D) mass ratio: 16 (C) / (D) mass ratio: 6.4

Claims

1. (A) a water-soluble polyphosphate, (B) calcium glycerophosphate, (C) a water-soluble fluorine-containing compound and (D) cationized cellulose and having a content of component (A) of 0.1 to 1.5% by mass, a content of component (B) of 0.1 to 2% by mass, a content of component (C) of 500 to 5,000 ppm as fluoride ions, and a content of component (D) of 0.01 to 0.5% by mass. A dentifrice composition.

2. The dentifrice composition according to claim 1, wherein component (A) is potassium pyrophosphate.

3. The dentifrice composition according to claim 1 or 2, wherein (A) / (C) is 0.05 to 1 as a molar ratio.

4. The dentifrice composition according to any one of claims 1 to 3, wherein (B) / (C) is 0.05 to 1.5 as a molar ratio.

5. The dentifrice composition according to any one of claims 1 to 4, which is a chewing dentifrice or a gel dentifrice. ​

Images