Tooth cleaning agent components

Abstract

DEPCT67 What is provided is a toothpaste component that is successful in being retained. Excellent fluorine ion absorption in the oral cavity, especially on the oral mucosa and its release. Excellent fluorine properties, resistance to liquid separation and resistance to freezing. and also has good storage stability, tooth cleaning agent composition (A) Water-soluble polyphosphate,(B)Calcium glycerophosphate,(C)Water-soluble fluorine-containing compounds and (D) cationized cellulose;

Description

Dentifrice composition

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

[0002] Fluorine-containing compounds such as sodium fluoride are widely used in oral compositions such as dentifrice compositions as medicinal ingredients with functions such as promoting remineralization and inhibiting demineralization, for the purpose of preventing dental caries, etc. For fluorine-containing compounds to act effectively, it is effective to allow fluoride ions to remain on the tooth surface in the oral cavity for a long period of time, and it is also important to leave many fluoride ions in the oral cavity even after gargling and rinsing with water after use.However, since dentifrice compositions are washed away by rinsing after brushing, only a trace amount of fluoride ions remain in the oral cavity.

[0003] In order to improve the retention of fluoride ions in the oral cavity, a method of coexisting calcium ions and fluoride ions, which are remineralization components, in a dentifrice composition has been proposed. However, calcium ions and fluoride ions are highly reactive, and when coexistent, they become an insoluble substance called calcium fluoride before acting on teeth, failing to exert a sufficient effect. Patent Document 1 (JP-A-10-511956) proposes an oral preparation in which calcium ions and fluoride ions are mixed in the oral cavity or immediately before application to the oral cavity to generate calcium fluoride in the oral cavity. However, with this method, calcium ions enter the oral cavity as fluoride ions, which are immediately washed away by saliva, resulting in insufficient retention. Furthermore, calcium fluoride precipitates shortly after mixing the two components, resulting in insufficient release of fluoride ions and insufficient remineralization prevention. Patent Document 2 (JP 2009-137863 A) proposes a composition in which a complex of polyphosphate, calcium salt, and fluoride salt is prepared in advance, but this method has problems such as complicated preparation and the dentifrice preparation becoming liquid or solidifying after long-term storage. Furthermore, Patent Documents 3 to 5 (JP 2015-117215 A, JP 2013-67567 A, JP 2007-320894 A) propose methods for adsorbing and retaining fluoride ions on the tooth surface using specific cationic polymeric substances in dentifrice compositions, but there is still room for improvement in retention and the amount remaining after brushing, and further improvement in retention is desired.

[0004] Japanese Patent Publication No. 10-511956 Japanese Patent Publication No. 2009-137863 Japanese Patent Publication No. 2015-117215 Japanese Patent Publication No. 2013-67567 Japanese Patent Publication No. 2007-320894

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

[0006]

[0006] As a result of intensive research to achieve the above object, the present inventors have found that when a dentifrice composition is formulated by combining a water-soluble fluorine-containing compound with a water-soluble polyphosphate and calcium glycerophosphate, and further combining this with cationic cellulose, the composition exhibits excellent retention of fluoride ions in the oral cavity, particularly in the oral mucosa, and retains fluoride ions in the oral cavity at a high rate. Furthermore, the composition exhibits excellent fluoride ion release (amount of release, sustained release), sustained release of the retained fluoride ions, and supplying fluoride ions to the oral cavity over a long period of time. Furthermore, the composition is inhibited from liquid separation and solidification even after long-term storage, resulting in good storage stability.

[0007] That is, the present inventors have found that a dentifrice composition formulated with (A) a water-soluble polyphosphate, (B) calcium glycerophosphate, (C) a water-soluble fluoride-containing compound, and (D) cationic cellulose exhibits excellent retention and release of fluoride ions in the oral cavity, particularly in the oral mucosa, and exhibits excellent liquid separation stability, solidification stability, and good storage stability, thereby achieving the present invention.

[0007] It was expected that the retention of fluorine in the oral cavity would be enhanced if the fluorine in the water-soluble fluorine-containing compound incorporated into the dentifrice composition were sufficiently retained not only on the tooth surface but also on the oral mucosa. However, because the oral mucosa is covered with salivary proteins such as mucin, fluorine is difficult to adsorb, and conventional techniques have not been able to sufficiently retain fluorine in the oral mucosa. However, in the present invention, by combining component (C) with components (A) and (B) and with component (D), component (D) improves the retention of fluoride ions derived from component (C) on the oral mucosa, thereby achieving excellent fluoride ion retention and release. In this case, component (D) enhances the adsorption of fluoride ions to the mucin covering the oral mucosa, improving retention, resulting in a high retention of fluoride ions on the oral mucosa. Furthermore, the retained fluoride ions are gradually released into saliva and supplied to the tooth surface in contact with saliva for a long period of time. Therefore, the dentifrice composition of the present invention ensures liquid separation stability and solidification stability, thereby improving the retention of fluoride ions in the oral cavity.

[0008] As shown in the comparative examples described below, when components (A), (B), and (C) were blended but component (D) was not blended, fluoride (fluoride ion) retention and fluoride (fluoride ion) release properties were poor, and the liquid separation stability of the formulation was poor (Comparative Example 3), and when component (D) was blended but component (A) or (B) was not blended, fluoride retention and fluoride release properties were poor, and the liquid separation stability or solidification stability of the formulation was poor (Comparative Examples 1 and 2). In contrast, the dentifrice composition of the present invention blended with components (A), (B), (C), and (D) (Examples described below) had excellent fluoride retention and fluoride release properties, and the liquid separation stability and solidification stability of the formulation were good.

[0009] Accordingly, the present invention provides the following dentifrice compositions. [1] A dentifrice composition containing (A) a water-soluble polyphosphate, (B) calcium glycerophosphate, (C) a water-soluble fluorine-containing compound, and (D) cationized cellulose. [2] The dentifrice composition of [1], wherein component (A) is potassium pyrophosphate. [3] The dentifrice composition of [1] or [2], wherein the molar ratio of (A) / (C) is 0.05 to 1. [4] The dentifrice composition of any of [1] to [3], wherein the molar ratio of (B) / (C) is 0.05 to 1.5. [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-type dentifrice.

[0010] According to the present invention, there is provided a dentifrice composition which has excellent retention and release properties of fluoride ions in the oral cavity, particularly in the oral mucosa, and which also has excellent liquid separation stability, solidification stability, and good storage stability. The dentifrice composition of the present invention can retain a relatively large amount of fluoride ions in the oral cavity even after brushing, gargling, and rinsing with water, and can fully exert the effects of the water-soluble fluoride-containing compound, such as promoting remineralization and inhibiting demineralization, making it suitable for preventing dental caries.

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

[0012] The water-soluble polyphosphate (A) improves the retention of fluoride ions and also inhibits liquid separation. Examples of the water-soluble polyphosphate (A) include linear polyphosphates such as pyrophosphate, tripolyphosphate, and tetrapolyphosphate, and cyclic polyphosphates such as trimetaphosphate, tetrametaphosphate, and hexametaphosphate, and examples of their salts include alkali metal salts such as sodium salts and potassium salts. Among these, pyrophosphate and tripolyphosphate are preferred, more preferably pyrophosphate, and potassium pyrophosphate is particularly preferred. These may be used alone or in combination of two or more.

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

[0014] (B) Calcium glycerophosphate improves the retention of fluoride ions and inhibits solidification. Calcium glycerophosphate can be derived from natural or synthetic sources. For example, commercially available products such as "Calcium Glycerophosphate" manufactured by Iwaki Pharmaceutical Co., Ltd. can also be used.

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

[0016] Examples of (C) water-soluble fluorine-containing compounds include sodium fluoride, sodium monofluorophosphate, and stannous fluoride. The amount of (C) water-soluble fluorine-containing compound is preferably 500 to 5,000 ppm, more preferably 1,100 to 3,000 ppm, of the total composition in terms of fluoride ions. A content of 500 ppm or more of fluoride ions sufficiently improves the retention of fluoride ions, while a content of 5,000 ppm or less prevents harmful effects such as mottled teeth due to excessive intake. The amount of water-soluble fluorine-containing compound varies depending on the amount of fluoride ions to be supplied. For example, in the case of sodium fluoride, if 500 ppm of fluoride ions are to be supplied, the amount is 0.11% of the total composition. Specifically, the amount of sodium fluoride is preferably 0.1% or more of the total composition, more preferably 0.25 to 0.7%.

[0017] In the present invention, (A) / (C), which represents the ratio of the amount of component (A) to the amount of component (C), is preferably a molar ratio of 0.05 to 1, more preferably 0.1 to 0.5, and particularly preferably 0.10 to 0.50. Furthermore, (B) / (C), which represents the ratio of the amount of component (B) to the amount of component (C), is preferably a molar ratio of 0.05 to 1.5, more preferably 0.10 to 1. It is even more preferable that the molar ratios of (A) / (C) and (B) / (C) are each within the above-mentioned ranges. Blending component (C) within these molar ratio ranges results in superior fluoride ion retention and release, as well as superior liquid separation stability and solidification stability.

[0018] The cationized cellulose (D), when combined with the components (A) and (B), improves the retention of fluoride ions derived from the component (C) and improves their release, and also improves liquid separation stability.

[0019] Cationized cellulose is cellulose having a cation or a cellulose derivative having a cation. The cationized cellulose may have a counter ion (e.g., a halogen ion (chloride ion), a methosulfate ion, etc.). The molecular weight of the cationized cellulose is not particularly limited. As component (D), one type of cationized cellulose may be used alone, or two or more types may be used in combination. Examples of cationized cellulose include hydroxyethyl cellulose dimethyl diallyl ammonium salt and O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride, with hydroxyethyl cellulose dimethyl diallyl ammonium salt being preferred. The hydroxyethyl cellulose dimethyl diallyl ammonium salt may have a chloride ion as a counter ion, with hydroxyethyl cellulose dimethyl diallyl ammonium chloride being preferred. The cationized cellulose used in the present invention preferably has a viscosity of 30 to 3,000 mPa·s in a 2% aqueous solution (BH Brookfield viscometer, rotor No. 2, 20 rpm, 20°C, measurement time 1 minute). The average molecular weight of the cationized cellulose is not particularly limited, but is preferably 100,000 to 1,500,000 as measured by gel permeation chromatography (GPC) using polyethylene glycol as the standard. 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 (viscosity of 2% aqueous solution: 35 to 350 mPa s, BH Brookfield viscometer, rotor No. 2, 20 rpm, 20°C, measurement time 1 minute) commercially available from Akzo Nobel Co., Ltd., and weight average molecular weight measured by gel permeation chromatography (GPC) using polyethylene glycol as the standard: 250,000 to 350,000.

[0020] The amount of component (D) in the composition is preferably 0.01 to 0.5%, more preferably 0.05 to 0.2%, based on the total composition. A content of 0.01% or more ensures sufficient retention and release of fluoride ions, and also inhibits liquid separation over time, ensuring sufficient liquid separation stability. A content of 0.5% or less adequately inhibits discomfort to the oral mucosa.

[0021] Furthermore, (A) / (D), which represents the ratio of the quantity of the component (A) to the component (D), is preferably a mass ratio of 1 to 50, more preferably 3 to 25. (B) / (D), which represents the ratio of the quantity of the component (B) to the component (D), is preferably a mass ratio of 1 to 50, more preferably 2 to 30. (C) / (D), which represents the ratio of the quantity of the component (C) to the component (D), is preferably a mass ratio of 1 to 20, more preferably 1 to 10. When the component (D) is blended within these mass ratio ranges, the effects of the component (D) are fully exhibited, and the retention and release properties of fluoride ions are superior, and the liquid separation stability is also superior.

[0022] The dentifrice composition of the present invention is particularly suitable as a toothpaste or gel-type toothpaste (abrasive-free), and is particularly suitable as a toothpaste. In addition to the above-mentioned components, other known components can be blended as needed within limits that do not impair the effects of the present invention. For example, abrasives, binders, thickeners, surfactants, and, if necessary, colorants, sweeteners, preservatives, flavorings, active ingredients, etc. may be blended. The method for preparing the dentifrice composition is not particularly limited, and may be a known method appropriate for the dosage form. For example, the dentifrice composition can be prepared by blending the components (A) to (D), any optional ingredients, and water in a conventional manner.

[0023] Examples of abrasives include silica-based abrasives such as silicic acid anhydride, precipitated silica, silica gel, aluminosilicate, and zirconosilicate; calcium phosphate-based compounds such as dibasic calcium phosphate dihydrate or anhydrate, monobasic calcium phosphate, tribasic calcium phosphate, tetrabasic calcium phosphate, and calcium pyrophosphate; calcium carbonate, calcium hydroxide, aluminum hydroxide, insoluble sodium metaphosphate, tribasic magnesium phosphate, magnesium carbonate, calcium sulfate, bentonite, titanium-bonded silicate, and synthetic resin-based abrasives. Among these, silica-based abrasives are preferred. The amount of abrasive to be added is preferably 5 to 60%, and more preferably 5 to 30%, of the total composition.

[0024] The binder may be organic or inorganic. Specific examples include cellulose derivatives such as sodium carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and hydroxymethylethylcellulose; alginic acid derivatives such as sodium alginate; gums such as xanthan gum, tragacanth gum, karaya gum, and gum arabic; organic binders such as polyacrylates, carrageenan, polyvinyl alcohol, and carboxyvinyl polymers; and inorganic binders such as thickening silica, thickening aluminum silica, Veegum, and Laponite. The amount of binder is preferably 0.1 to 5%, and more preferably 0.2 to 3%, of the total composition. In the present invention, organic binders are particularly preferred, and the amount of organic binder is preferably 0.1 to 5%, and more preferably 0.5 to 3%, of the total composition. In terms of retention of fluoride ions, inorganic binders, particularly thickening silica, when used, are preferably used in an amount of 5% or less, particularly 2% or less, and especially 1% or less of the total composition, and may be 0% or less.

[0025] Examples of thickeners include sugar alcohols such as sorbitol, xylitol, erythritol, maltitol, and lactite, and polyhydric alcohols such as glycerin, propylene glycol, and polyethylene glycol having an average molecular weight of 160 to 400 (average molecular weight according to the Quasi-drug Raw Materials Standards 2006). The amount of thickener to be blended is usually 5 to 60% of the total composition.

[0026] The surfactant may be an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant. 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, hydrogenated coconut fatty acid monoglyceride sodium monosulfate, sodium lauryl sulfoacetate, acyl glutamates such as sodium N-palmitoyl glutamate, sodium N-methyl-N-acyltaurate, sodium N-methyl-N-acylalanine, and sodium α-olefin sulfonate. Examples of nonionic surfactants include polyoxyethylene alkyl ethers (e.g., those having an alkyl group with 16 to 18 carbon atoms), polyoxyethylene hydrogenated castor oil (e.g., those having an average ethylene oxide addition mole number of 40 to 80), alkyl glucosides, polyoxyethylene polyoxypropylene block copolymers, polyglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkylolamides, polyoxyethylene sorbitan monostearate, and polyoxyethylene polyoxypropylene glycol. Examples of amphoteric surfactants include lauryl dimethylaminoacetate betaine, N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethyl ethylenediamine, coconut oil fatty acid amidopropyl dimethylaminoacetate betaine, and coconut oil fatty acid amidopropyl. The amount of surfactant blended is usually 0.1 to 10% of the total composition. The amount can be adjusted depending on the form and intended use of the dentifrice composition; for example, 0.1 to 10% can be blended in a toothpaste.

[0027] Examples of colorants 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, titanium mica, and titanium oxide. Examples of sweeteners include sodium saccharin, aspartame, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidin dihydrochalcone, and perillartine. Examples of preservatives include parahydroxybenzoic acid esters such as methylparaben, ethylparaben, and butylparaben, and benzoic acid or a salt thereof such as sodium benzoate.

[0028] Fragrances include peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, mint 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, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, grapefruit oil, sweet Natural fragrances such as citron oil, iris concrete, peppermint absolute, rose absolute, orange flower, etc., and fragrances that have been processed (front end cut, back end cut, fractional distillation, liquid-liquid extraction, essence, powdered fragrance, etc.) from these natural fragrances, as well as menthol, carvone, anethole, cineole, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate and the like. The flavoring materials may be used in combination with known flavoring materials used in dentifrice compositions, such as single flavorings such as methyl acrylate, limonene, menthone, menthyl acetate, N-substituted-paramenthan-3-carboxamide, pinene, octyl aldehyde, citral, pulegone, carbelic acid acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methylphenylglycidate, vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cyclotene, furfural, trimethylpyrazine, ethyl lactate, and ethyl thioacetate, as well as blended flavorings such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, and tropical fruit flavor. Although there are no particular limitations on the blending amount, the above-mentioned flavoring materials are preferably used in an amount of 0.000001 to 1% in the formulation, and fragrances using the above-mentioned flavoring materials are preferably used in an amount of 0.05 to 2% in the formulation.

[0029] Examples of active ingredients include disinfectants such as isopropylmethylphenol and cetylpyridinium chloride, water-soluble phosphate compounds such as potassium and sodium orthophosphate, 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 a derivative thereof, glycyrrhizic acid or a salt thereof, glycyrrhetinic acid or a derivative thereof, and anti-tartar agents. The active ingredients may be incorporated in effective amounts within a range that does not interfere with the effects of the present invention.

[0030] The present invention will be specifically described below with reference to examples, comparative examples, and formulation examples, but the present invention is not limited to the following examples. In the following examples, % indicates % by mass unless otherwise specified.

[0031] [Examples and Comparative Examples] Dentifrice compositions (toothpastes) having the compositions shown in Tables 1 to 3 were prepared by conventional methods and evaluated by the following methods. The results are also shown in the tables.

[0032] (1) Method for Evaluating Fluoride (Fluoride Ion) Retention The retention of fluoride ions was evaluated by a test for the adsorption of fluoride (fluoride ions) to mucin, a component of the oral mucosa. 0.2 g of mucin (Sigma-Aldrich) was added to a 10 mL centrifuge tube, followed by 5 mL of a dentifrice composition (40-fold diluted with purified water), and the mixture was allowed to act for 3 minutes. The mixture was then centrifuged at 3,000 rpm for 10 minutes, and the supernatant was removed. 5 mL of potassium citrate buffer was added to the resulting mucin and stirred for 1 minute to forcibly elute the fluoride ions adsorbed and retained on the mucin. The mixture was centrifuged at 3,000 rpm for 10 minutes, and the supernatant was collected. The fluoride (fluoride ion) concentration in the solution was measured using a fluoride ion meter (Orion 1115000 4-Star, Thermo Fisher Scientific) to obtain the retained fluoride ion concentration (ppm). The fluoride ion retention rate was calculated using the following formula: Fluoride ion retention rate (%) = {(retained fluoride ion concentration (ppm)) / (fluoride ion concentration (ppm) blended in the preparation / 40)} x 100 From the fluoride ion retention rate, the fluoride ion retention was evaluated using the following evaluation criteria. Evaluation criteria ◎: Fluoride ion retention rate is 50% or more ○: 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) Method for evaluating fluoride (fluoride ion) release The compositions (Examples 1 to 14) that received a rating of Fair or better in (1) were evaluated for the amount (release rate) of fluoride ions released from mucin into saliva and their sustained release. 0.2 g of mucin (Sigma-Aldrich) was added to a 10 mL centrifuge tube, followed by 5 mL of a dentifrice composition (diluted 40 times with purified water), and the mixture was allowed to act for 3 minutes. The mixture was then centrifuged at 3,000 rpm for 10 minutes, and the supernatant was removed. Five mL of artificial saliva (CaCl = 1.5 mmol / L, KH2PO4 = 5.0 mmol / L, acetic acid = 100 mmol / L, NaCl = 100 mmol / L, remainder = water; pH = 7.0) was added to the resulting mucin, and the mixture was stirred for 1 minute and allowed to stand for 3, 60, or 180 minutes to elute the fluoride ions adsorbed and retained on the mucin. The mixture was then centrifuged at 3,000 rpm for 10 minutes to recover the supernatant, and the fluoride ion concentration in the solution was measured using a fluoride ion meter (Orion 1115000 4-Star, manufactured by Thermo Fisher Scientific Co., Ltd.) to obtain the released fluoride ion concentration for each sample. The fluoride ion release rate was calculated from the released fluoride ion concentration using the following formula: Fluoride ion release rate (%) = {(released fluoride ion concentration (ppm)) / (retained fluoride ion concentration (ppm))} × 100 Fluoride release properties (amount released) were evaluated from the calculated fluoride ion release rates. For the compositions evaluated (Examples 1 to 14), the fluoride ion release rates after standing for 3 minutes were all less than 20%, and the fluoride ion release rates after standing for 60 minutes were all in the range of 20 to 60%, confirming that the compositions did not release fluoride immediately but had a sustained release property. Fluoride release properties were evaluated from the fluoride ion release rates after standing for 180 minutes according to the following evaluation criteria. Qualities marked with ◯ or ⊚ indicated that the fluoride ions adsorbed and retained in mucin were gradually released by saliva, and the fluoride release properties were deemed acceptable. Evaluation criteria: ◎: Fluorine ion release rate after standing for 180 minutes is 70% or more; ○: Fluorine ion release rate after standing for 180 minutes is 50% or more and less than 70%; △: Fluorine ion release rate after standing for 180 minutes is 20% or more and less than 50%; ×: Fluorine ion release rate after standing for 180 minutes is less than 20%

[0034] (3) Evaluation method for storage stability (3-1) Evaluation method for liquid separation stability of preparation (absence of liquid separation after storage) 50 g of the dentifrice composition was filled into three tube containers (material: laminated tubes with a diameter of 26 mm, the innermost layer of which was made of linear low-density polyethylene (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 rating scale. The average score of the three tubes was calculated, and the liquid separation stability of the preparation was evaluated according to the following rating scale. Scoring criteria 4 points: No liquid separation at all 3 points: A slight amount of liquid separation was observed around the opening, but it was not a problematic level 2 points: Liquid separation was observed around the opening and on the surface of the paste 1 point: When the toothpaste was squeezed out of the tube, separated liquid was observed to the extent that it started to drip Evaluation criteria ◎: Average score was 4.0 points 〇: Average score was 3.0 points or more but less than 4.0 points △: Average score was 2.0 points or more but less than 3.0 points ×: Average score was less than 2.0 points

[0035] (3-2) Method for evaluating the solidification stability of the preparation (absence of solidification after storage) 50 g of the dentifrice composition was filled into three tube containers (material: 26 mm diameter laminate tube with the innermost layer made of linear low-density polyethylene (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 rating scale. The average score of the three tubes was calculated, and the solidification stability of the preparation was evaluated according to the following rating scale. Rating scale 4 points: no solidification at all 3 points: slight solidification was observed at the opening, but at an acceptable level 2 points: solidification was observed at the opening and on the surface of the paste 1 point: solidification was observed to the extent that the dentifrice could not be extruded from the tube Rating scale ◎: average score was 4.0 points ◯: average score was 3.0 points or more but less than 4.0 points △: average score was 2.0 points or more but less than 3.0 points ×: average score less than 2.0 points

[0036] Details of the raw materials used are as follows: (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 Co., Ltd. (D) Hydroxyethylcellulose dimethyl diallyl ammonium chloride; CELQUAT L-200, manufactured by Akzo Nobel Co., Ltd. Viscosity of 2% aqueous solution: 35 to 350 mPa s (BH-type Brookfield viscometer, rotor No. 2, 20 rpm, 20°C, measurement time 1 minute), weight average molecular weight by gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance: 250,000 to 350,000).

[0037]

[0038]

[0039]

[0040] Details of the fragrance compositions used are as shown in Tables 4 to 12. In the above examples, the evaluation results were the same even when fragrance compositions B to P were used instead of fragrance composition A, and the same was true for the formulation examples described below.

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] An example of the formulation is shown below. The ingredients used are the same as above. [Formulation Example] Gel-type dentifrice (A) Potassium pyrophosphate 0.7 (B) Calcium glycerophosphate 0.8 (C) Sodium fluoride 0.32 (D) Hydroxyethylcellulose dimethyl diallyl ammonium chloride 0.05 Liquid sorbitol (70% aqueous solution) 55 Propylene glycol 3 Sodium polyacrylate 0.7 Carrageenan 0.3 Xanthan gum 0.3 Xylitol 5 Coconut oil fatty acid amidopropyl betaine 0.3 Citric acid 0.02 Sodium citrate 0.3 Flavoring composition A 0.5 Purified water Balance 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

DEPCT671. A dental cleaning agent composition consisting of: (A) aqueous salts of polyphosphoric acid, (B) calcium glycerophosphate, (C) aqueous fluoride-containing compound, and (D) cationized cellulose.

2. A dental cleaning agent composition of claim 1 in which component (A) is potassium pyrophosphate.

3. A dental cleaning agent composition of claim 1 or 2 in which the molar ratio (A) / (C) is between 0.05 and 1.

4. Any one of the dental cleaning agent compositions of claims 1 through 3 in which the molar ratio (B) / (C) is between 0.05 and 1.

5. Any of the toothpaste or toothpaste cleaning agent components of claims 1 through 4 in which component (A) is present in an amount of 0.1 to 1.5% by weight, component (B) is present in an amount of 0.1 to 2% by weight, component (C) is present in an amount expressed in terms of fluoride ions of 500 to 5,000 parts per million, and component (D) is present in an amount of 0.01 to 0.5% by weight.

6. Any of the toothpaste or toothpaste cleaning agent components of claims 1 through 5 in which toothpaste or toothpaste cleaning agent of the gel type;