JP2022190354A - dentifrice composition - Google Patents

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 The present invention relates to a dentifrice composition containing a water-soluble fluorine-containing compound that exhibits excellent retention of fluoride ions in the oral cavity, particularly in the oral mucosa, and excellent releasability.

Fluorine-containing compounds such as sodium fluoride are widely used in oral compositions such as dentifrice compositions for the purpose of preventing dental caries as medicinal ingredients having functions such as promoting remineralization and inhibiting demineralization. . In order for the fluorine-containing compound to act effectively, it is effective to allow the fluorine ions to remain on the tooth surface in the oral cavity for a long period of time. Although it is important to retain a large amount of fluoride ions in the oral cavity even afterward, only a very small amount of fluoride ions remained in the oral cavity because the dentifrice composition was washed away by rinsing after brushing.

In order to improve the intraoral retention of fluoride ions blended in the dentifrice composition, there is a method of coexisting calcium ions and fluoride ions, which are remineralizing components, but calcium ions and fluoride ions are highly reactive, When it coexists, it turns into an insoluble substance, calcium fluoride, before it acts on teeth, and a sufficient effect could not be exhibited. Further, in Patent Document 1 (Japanese Patent Publication No. 10-511956), by mixing calcium ions and fluoride ions in the oral cavity or immediately before application to the oral cavity, calcium fluoride is added in the oral cavity. However, in this method, since it enters the oral cavity as fluoride ions, it is immediately washed away with saliva and does not exhibit a sufficient retention effect, and after mixing the two components Since calcium fluoride precipitates in a short period of time, the fluoride ions are not sufficiently released, and the anti-remineralization effect cannot be satisfactorily exhibited. Patent Document 2 (Japanese Patent Application Laid-Open No. 2009-137863) proposes a composition in which a complex of a polyphosphate, a calcium salt, and a fluoride salt is prepared in advance. There were problems such as liquefaction and solidification after long-term storage as a dentifrice preparation.
In addition, Patent Documents 3 to 5 (JP-A-2015-117215, JP-A-2013-67567, JP-A-2007-320894) disclose that a specific cationic polymeric substance is used in a dentifrice composition. However, there is still room for improvement in retention and the amount remaining after brushing, and further improvement in retention has been desired.

Japanese Patent Publication No. 10-511956 JP 2009-137863 A JP 2015-117215 A JP 2013-67567 A JP 2007-320894 A

The present invention has been made in view of the above circumstances, and an object thereof is to provide a dentifrice composition which is excellent in retention of fluoride ions in the oral cavity, particularly in the oral mucosa, and which is also excellent in its releasability.

As a result of intensive studies to achieve the above object, the present inventors have found a dentifrice composition comprising a water-soluble fluorine-containing compound, a water-soluble polyphosphate and calcium glycerophosphate, and a cationized cellulose. When blended in, the retention of fluoride ions in the oral cavity, especially in the oral mucosa, is excellent, the fluoride ions are retained in the oral cavity at a high rate, and the release of fluoride ions (release amount, sustained release) is excellent. It was found that the retained fluoride ions are gradually released, the fluoride ions can be supplied to the oral cavity for a long time, and the liquid separation and solidification are suppressed even after long-term storage, resulting in good storage stability. 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) a cationized cellulose is used in the oral cavity, particularly The inventors have found that the fluorine ion retains well in the oral mucosa, is excellent in its releasability, has good liquid separation stability, solidification stability, and good storage stability, and has completed the present invention.

It was expected that if the fluorine contained in the water-soluble fluorine-containing compound contained in the dentifrice composition sufficiently retained not only on the tooth surface but also on the oral mucosa, the retention in the oral cavity would be further enhanced. Since it is covered with salivary proteins, it is difficult for fluorine to be adsorbed. However, in the present invention, the components (A) and (B) are used in combination with the component (C), and the component (D) is combined. As a result, not only the retention of fluorine ions but also the releasability of fluorine ions was improved. In this case, the component (D) enhances the adsorption of fluoride ions to the mucin covering the oral mucosa, thereby improving its retention, and the fluoride ions stay in the oral mucosa at a high rate and stay. Fluoride ions are gradually released into saliva and supplied to the tooth surface in contact with saliva for a long time. Therefore, according to the dentifrice composition of the present invention, the liquid separation stability and the solidification stability can be ensured, and the retention of fluoride ions in the oral cavity can be improved.

As shown in comparative examples below, when components (A), (B) and (C) are blended but component (D) is not blended, fluorine (fluoride ion) retention and fluorine release properties are poor. The liquid separation stability of the formulation was poor (Comparative Example 3). In addition, the liquid separation stability of the formulation or the solidification stability of the formulation was poor (Comparative Examples 1 and 2). On the other hand, the dentifrice compositions containing the components (A), (B), (C) and (D) of the present invention (Examples described later) are excellent in fluorine retention and fluorine release. The liquid separation stability (no liquid separation after storage) and solidification stability (no solidification after storage) of the formulation were good.

Accordingly, the present invention provides the following dentifrice composition.
[1]
(A) a water-soluble polyphosphate;
(B) calcium glycerophosphate;
A dentifrice composition comprising (C) a water-soluble fluorine-containing compound and (D) a cationized cellulose.
[2]
(A) The dentifrice composition according to [1], wherein the component is potassium pyrophosphate.
[3]
The dentifrice composition according to [1] or [2], wherein (A)/(C) has a molar ratio of 0.05 to 1.
[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 content of component (A) is 0.1 to 1.5% by mass, the content of component (B) is 0.1 to 2% by mass, and the content of component (C) is 500 to 5,000 ppm as fluorine ions. , The dentifrice composition according to any one of [1] to [4], wherein 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-like dentifrice.

ADVANTAGE OF THE INVENTION According to the present invention, a dentifrice composition is excellent in retention of fluorine ions in the oral cavity, particularly in the oral mucosa, is also excellent in its releasability, and has good liquid separation stability, solidification stability, and storage stability. can provide things. The dentifrice composition of the present invention can retain a relatively large amount of fluoride ions in the oral cavity even after gargling and rinsing the oral cavity after brushing, and remineralization of the water-soluble fluorine-containing compound. It is also suitable for caries prevention because it can sufficiently exhibit effects such as acceleration of caries and inhibition of demineralization.

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.

(A) The water-soluble polyphosphate has an effect of improving retention of fluorine ions and an effect of suppressing liquid separation.
As the component (A), the water-soluble polyphosphate includes linear polyphosphoric acids such as pyrophosphoric acid, tripolyphosphoric acid and tetrapolyphosphoric acid, and cyclic polyphosphoric acids such as trimetaphosphoric acid, tetrametaphosphoric acid and hexametaphosphoric acid. The salts thereof include alkali metal salts such as sodium salts and potassium salts. Among them, pyrophosphate and tripolyphosphate are preferred, pyrophosphate is more preferred, and potassium pyrophosphate is particularly preferred. These may be used singly or in combination of two or more.

The amount of component (A) is preferably 0.1 to 1.5% (mass%, hereinafter the same) of the entire 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 of fluorine ions can be obtained, and liquid separation can be suppressed over time to obtain sufficient liquid separation stability. When the content is 1.5% or less, retention and release properties of fluoride ions are sufficiently maintained, and solidification over time is prevented to obtain sufficient solidification stability.

(B) Calcium glycerophosphate has an effect of improving retention of fluorine ions and an effect of suppressing solidification.
Calcium glycerophosphate may be derived from natural products or synthetic products. For example, a commercially available product such as “calcium glycerophosphate” manufactured by Iwaki Seiyaku Co., Ltd. can also be used.

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

(C) Water-soluble fluorine-containing compounds include sodium fluoride, sodium monofluorophosphate, tin fluoride and the like.
(C) The content of the water-soluble fluorine-containing compound is preferably 500 to 5,000 ppm, more preferably 1,100 to 3,000 ppm, in terms of fluorine ions, based on the total composition. When the content is 500 ppm or more in terms of fluoride ions, the retention effect of fluoride ions is sufficiently improved, and when it is 5,000 ppm or less, adverse effects such as mottled teeth due to excessive intake can be prevented.
The blending amount of the water-soluble fluorine-containing compound varies depending on the amount of fluoride ions to be supplied. For example, in the case of sodium fluoride, when the amount of fluoride ions to be supplied is 500 ppm, the amount to be blended is 0.11% of the total composition. Specifically, the content of sodium fluoride is preferably 0.1% or more, more preferably 0.25 to 0.7%, based on the total composition.

In the present invention, (A)/(C), which indicates the quantitative ratio of component (A) and component (C), is preferably 0.05 to 1, more preferably 0.1 to 0.5, as a molar ratio. In particular, it is 0.10 to 0.50. Also, (B)/(C), which indicates the quantitative ratio of component (B) to component (C), is preferably 0.05 to 1.5, more preferably 0.10 to 1 as a molar ratio. More preferably, the molar ratio of (A)/(C) and the molar ratio of (B)/(C) are within the above ranges. When the component (C) is blended within these molar ratio ranges, the retention and release properties of fluorine ions are more excellent, and the liquid separation stability and solidification stability are more excellent.

(D) Cationized cellulose, in combination with components (A) and (B), has the effect of improving retention of fluorine ions derived from component (C) and improving their release. It has the effect of improving the separation stability.

Cationized cellulose is cellulose with cations or cellulose derivatives with cations. The cationized cellulose may have counterions (eg, halogen ions (chloride ions), methosulfate ions, etc.). The molecular weight of cationized cellulose is not particularly limited. As the 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 hydroxyethylcellulose dimethyldiallylammonium salt, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, preferably hydroxyethylcellulose dimethyldiallylammonium salt.
Hydroxyethylcellulose dimethyldiallylammonium salt includes chloride ion as a counter ion, and hydroxyethylcellulose dimethyldiallylammonium chloride is preferred.
The cationized cellulose used in the present invention has a 2% aqueous solution viscosity (BH type Brookfield viscometer, rotor No. 2, 20 rotations, 20°C, measurement time 1 minute) of 30 to 3,000 mPa s. preferable.
Although the average molecular weight of the cationized cellulose is not particularly limited, it is preferably 100,000 to 1,500,000 as a weight-average molecular weight determined by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance. The nitrogen content is preferably 0.1-3%, more preferably 0.5-2.5%.
Examples of such cationized cellulose include CELQUAT L-200 (2% aqueous solution viscosity: 35 to 350 mPa s, BH type Brookfield viscometer, rotor No. 2, 20 rotation, 20° C., measurement time of 1 minute), weight average molecular weight by gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance: 250,000 to 350,000).

The blending amount of component (D) is preferably 0.01 to 0.5%, more preferably 0.05 to 0.2% of the total composition. When the content is 0.01% or more, sufficient retention and release of fluorine ions can be obtained, and liquid separation can be suppressed over time to obtain sufficient liquid separation stability. If it is 0.5% or less, discomfort to the oral mucosa is sufficiently suppressed.

In addition, (A)/(D), which indicates the quantitative ratio of component (A) and component (D), is preferably 1-50, more preferably 3-25 as a mass ratio.
(B)/(D), which indicates the quantitative ratio of component (B) to component (D), is preferably 1-50, more preferably 2-30 as a mass ratio.
(C)/(D), which indicates the quantitative ratio between component (C) and component (D), is preferably 1-20, more preferably 1-10 as a mass ratio.
When the component (D) is blended within these mass ratio ranges, the effect of the component (D) is sufficiently exhibited, and the retention and release properties of fluorine ions are more excellent, and the liquid separation stability is more excellent.

The dentifrice composition of the present invention is particularly suitable as a toothpaste or gel-like dentifrice (abrasive-free), especially as a toothpaste, and in addition to the above ingredients, other known ingredients of the present invention It can be blended according to need within a range that does not interfere with the effect. For example, abrasives, binders, thickeners, surfactants, and if necessary, colorants, sweeteners, preservatives, fragrances, active ingredients, etc. can be added. The method for preparing the dentifrice composition is not particularly limited, and may be a known method according to the dosage form. and can be prepared.

Examples of abrasives include silica-based abrasives such as anhydrous silicic acid, precipitated silica, silica gel, aluminosilicate, and zirconosilicate; Calcium phosphate compounds such as tetracalcium phosphate and calcium pyrophosphate, calcium carbonate, calcium hydroxide, aluminum hydroxide, insoluble sodium metaphosphate, trimagnesium phosphate, magnesium carbonate, calcium sulfate, bentonite, titanium-bound silicate, synthetic resin Abrasives can be mentioned. Among them, silica-based abrasives are preferred.
The compounding amount of the abrasive is preferably 5 to 60%, particularly 5 to 30% of the total composition.

The binder can be an organic or inorganic binder. Specifically, cellulose derivatives such as sodium carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxymethylethylcellulose, alginic acid derivatives such as sodium alginate, xanthan gum, tragacanth gum, karaya gum, gum arabic, etc. Examples include organic binders such as gums, polyacrylates, carrageenan, polyvinyl alcohol and carboxyvinyl polymer, and inorganic binders such as thickening silica, thickening aluminum silica, veegum and laponite.
The content of the binder is preferably 0.1 to 5%, particularly 0.2 to 3%, of the total composition. In the present invention, an organic binder is particularly preferred, and the amount of the organic binder to be blended is preferably 0.1 to 5%, particularly 0.5 to 3%, of the total composition. The inorganic binder, especially the thickening silica, is preferably 5% or less, particularly 2% or less, particularly preferably 1% or less of the total composition in terms of retention of fluorine ions, and even if it is not blended, it is 0%. good.

Viscosity agents include sugar alcohols such as sorbit, xylit, erythritol, maltit and lactit, polyhydric alcohols such as glycerin, propylene glycol, and polyethylene glycol with an average molecular weight of 160 to 400 (average molecular weight according to the Standards for Quasi-drug Ingredients 2006). is mentioned. The blending amount of the thickening agent is usually 5 to 60% of the total composition.

Surfactants can be blended with anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Anionic surfactants include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, acyl sarcosinates such as sodium lauroyl sarcosinate and sodium myristoyl sarcosinate, sodium dodecylbenzene sulfonate, hydrogenated coconut fatty acid monoglyceride monosodium sulfate, lauryl Examples include sodium sulfoacetate, acylglutamates such as sodium N-palmitoyl glutamate, sodium N-methyl-N-acyl taurine, sodium N-methyl-N-acylalanine, and sodium α-olefin sulfonate.
Nonionic surfactants include polyoxyethylene alkyl ethers (for example, alkyl groups having 16 to 18 carbon atoms), polyoxyethylene hydrogenated castor oils (for example, those having an average added mole number of ethylene oxide of 40 to 80), Alkyl glucoside, polyoxyethylene polyoxypropylene block copolymer, polyglycerol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkylolamide, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, etc. be done.
Amphoteric surfactants include betaine lauryldimethylaminoacetate, N-coconut fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine, betaine coconut amidopropyldimethylaminoacetate, and amidopropyl coconut oil.
The amount of the surfactant to be blended is usually 0.1 to 10% of the total composition. The blending amount can be adjusted depending on the form of the dentifrice composition, the purpose of use, etc. For example, 0.1 to 10% can be blended in a toothpaste.

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 3. No. 2, mica titanium, titanium oxide, and the like.
Sweeteners include sodium saccharin, aspartame, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidin dihydrochalcone, perillartine and the like.
Examples of the antiseptic include paraoxybenzoic acid esters such as methylparaben, ethylparaben and butylparaben, and benzoic acid such as sodium benzoate and salts thereof.

Peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint 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, Sweetie Oil , Yuzu Oil, Iris Concrete, Absolute Peppermint, Absolute Rose, Orange Flower, etc., and processing of these natural flavors (pre-reservoir cut, post-reservoir cut, fractional distillation, liquid-liquid extraction, essence formation, powder perfume ), and menthol, carvone, anethole, cineol, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone , menthyl acetate, N-substituted-paramenthane-3-carboxamide, pinene, octylaldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl Phenyl glycidate, vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cyclotene, furfural, trimethylpyrazine, ethyl lactate, ethyl thioacetate, etc., strawberry flavor, apple flavor, banana flavor , pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, mixed fruit flavor, tropical fruit flavor, and other known flavor materials used in dentifrice compositions can be used in combination.
In addition, although the blending amount is not particularly limited, it is preferable to use 0.000001 to 1% of the above perfume material in the formulation composition. In addition, it is preferable to use 0.05 to 2% in the formulation composition as a perfume for perfume using the above perfume material.

Active ingredients include bactericides such as isopropylmethylphenol and cetylpyridinium chloride, water-soluble phosphoric acid compounds such as orthophosphate potassium salts and sodium salts, enzymes such as dextranase, mutanase, amylase and protease, tranexamic acid, Epsilon aminocaproic acid, triclosan, lysozyme chloride, aluminum chlorohydroxyallantoin, hinokitiol, ascorbic acid, tocopheryl acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, water-soluble copper compounds such as sodium copper chlorophyllin, chlorophyll, and copper gluconate , aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid or its derivatives, glycyrrhizic acid or its salts, glycyrrhizic acid or its derivatives, and anticalculus agents. In addition, the above active ingredient can be blended in an effective amount within a range that does not impair the effects of the present invention.

EXAMPLES The present invention will be specifically described below by showing 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.

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

(1) Evaluation Method for Fluorine (Fluoride Ion) Retention Fluoride ion retention was evaluated by an adsorption test of fluorine (fluoride ion) to mucin, which is a component of the oral mucosa.
0.2 g of mucin (manufactured by Sigma-Aldrich) was added to a 10 mL centrifuge tube, and 5 mL of a dentifrice composition (40-fold dilution with purified water) was added and allowed to act for 3 minutes. After that, it was centrifuged at 3,000 rpm for 10 minutes and the supernatant was removed. 5 mL of potassium citrate buffer was added to the obtained mucin and stirred for 1 minute to forcibly elute the fluorine ions adsorbed and retained in the mucin. After centrifugation at 3,000 rpm for 10 minutes, the supernatant was collected, and the fluorine (fluoride ion) concentration contained in the solution was measured with a fluorine ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific Co., Ltd.). , to obtain the retained fluoride ion concentration (ppm).
The fluorine ion retention rate was calculated by the following formula.
Fluoride ion retention rate (%) =
{(retained fluoride ion concentration (ppm)) / (fluoride ion concentration (ppm) / 40)} × 100
From the fluorine ion retention rate, the fluorine ion retention was evaluated according to 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%

(2) Fluorine (fluoride ion) release property evaluation method For compositions evaluated as △ or higher in (1) (Examples 1 to 14), the amount (release rate) and sustained release of fluoride ions from mucin to saliva were evaluated. Release was evaluated.
0.2 g of mucin (manufactured by Sigma-Aldrich) was added to a 10 mL centrifuge tube, and 5 mL of a dentifrice composition (40-fold dilution with purified water) was added and allowed to act for 3 minutes. After that, it was centrifuged at 3,000 rpm for 10 minutes and the supernatant was removed.
Artificial saliva ₍ CaCl2 = 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 obtained mucin. ) was added and stirred for 1 minute, left to stand for 3 minutes, 60 minutes or 180 minutes to elute the fluorine ions adsorbed and retained in the mucin, and then centrifuged at 3,000 rpm for 10 minutes to remove the supernatant. After recovery, the fluoride ion concentration contained in the solution was measured with a fluoride ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific Co., Ltd.) to obtain the respective released fluoride ion concentrations.
From the released fluoride ion concentration, the fluoride ion release rate was calculated by the following formula.
Fluoride ion release rate (%) =
{(released fluorine ion concentration (ppm))/(retained fluorine ion concentration (ppm))}×
100
From the calculated fluoride ion release rate, the fluorine release property (release amount) was evaluated.
The fluorine ion release rates of the evaluation compositions (Examples 1 to 14) after standing for 3 minutes are all less than 20%, and the fluoride ion release rates after standing for 60 minutes are all in the range of 20 to 60%. It was confirmed that there was sustained release without immediate release.
From the fluoride ion release rate after standing for 180 minutes, the fluorine releasing property was evaluated according to the following evaluation criteria. Samples rated ◯ or ⊚ were judged to pass the fluoride release property because the fluoride ions adsorbed and retained in the mucin were gradually released by saliva.
Evaluation criteria ◎: Fluoride ion release rate after standing for 180 minutes is 70% or more ○: 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%

(3) Method for evaluating storage stability (3-1) Method for evaluating liquid separation stability of formulation (no liquid separation after storage) 50 g of dentifrice composition in tube container (material: innermost layer is linear Three low-density polyethylene laminate tubes having a diameter of 26 mm (manufactured by Dai Nippon Printing Co., Ltd.) were filled and stored at 40° C. for 1 month. After storage, the dentifrice composition was extruded from each tube container onto paper, and the state of liquid separation was evaluated according to the following rating criteria. The average score of the three samples was obtained, and the liquid separation stability of the formulation was evaluated according to the following evaluation criteria.
Scoring criteria 4 points: no liquid separation at all 3 points: slight liquid separation was observed at the mouth, but the level was not problematic 2 points: liquid separation was observed at the mouth and kneading surface 1 point: tube When the toothpaste was extruded from the toothpaste, it was observed that the separated liquid dripped. 0 points or more and less than 3.0 points ×: Average score is less than 2.0 points

(3-2) Evaluation method for solidification stability of formulation (no solidification after storage) Tube container containing 50 g of dentifrice composition (Material: Laminated tube with a diameter of 26 mm whose innermost layer is made of linear low-density polyethylene ( (manufactured by Dai Nippon Printing Co., Ltd.) and stored at 40° C. for 1 month. After storage, the dentifrice composition was extruded from each tube container, and the state of solidification was determined according to the following rating criteria. The solidification stability of the formulation was evaluated according to the following evaluation criteria by calculating the average score of the three.
Scoring criteria 4 points: no solidification 3 points: slight solidification was observed in the mouth area, but the level was not problematic 2 points: solidification was observed in the mouth area and the kneading surface 1 point: Toothpaste was removed from the tube. Evaluation criteria where solidification was observed to the extent that it could not be extruded ◎: Average score of 4.0 points ○: Average score of 3.0 points or more and less than 4.0 points △: Average score of 2.0 points or more and 3.0 points Less than ×: average score is less than 2.0 points

Details of 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; Co., Ltd. (D) hydroxyethyl cellulose dimethyl diallyl ammonium chloride;
CELQUAT L-200, manufactured by Akzo Nobel Co., Ltd.,
2% aqueous solution viscosity: 35 to 350 mPa s (BH type Brookfield viscometer,
Rotor no. 2, 20 rotations, 20°C, measurement time 1 minute),
Weight-average molecular weight by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance: 250,000 to 350,000)

A prescription example is shown. The raw materials used are the same as above.
[Prescription example] Gel toothpaste (A) Potassium pyrophosphate 0.7
(B) calcium glycerophosphate 0.8
(C) sodium fluoride 0.32
(D) hydroxyethylcellulose dimethyldiallylammonium chloride
0.05
Sorbit solution (70% aqueous solution) 55
Propylene glycol 3
Sodium polyacrylate 0.7
Carrageenan 0.3
Xanthan gum 0.3
Xylit 5
Coconut fatty acid amidopropyl betaine 0.3
Citric acid 0.02
Sodium citrate 0.3
Perfume 0.5
Remainder of purified water
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 (6)

(A) a water-soluble polyphosphate;
(B) calcium glycerophosphate;
A dentifrice composition comprising (C) a water-soluble fluorine-containing compound and (D) a cationized cellulose. 2. The dentifrice composition according to claim 1, wherein component (A) is potassium pyrophosphate. The dentifrice composition according to claim 1 or 2, wherein (A)/(C) is 0.05 to 1 as a molar ratio. 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. 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, and the content of component (C) is 500 to 5,000 ppm as fluorine ions. 5. The dentifrice composition according to any one of claims 1 to 4, wherein the content of component (D) is 0.01 to 0.5% by mass. The dentifrice composition according to any one of claims 1 to 5, which is a toothpaste or a gel-like dentifrice.