JP7447470B2 - dentifrice composition - Google Patents

Description

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

Fluorine-containing compounds such as sodium fluoride are widely used in oral compositions such as dentifrice compositions for purposes such as caries prevention as medicinal ingredients that have functions such as promoting remineralization and inhibiting demineralization. . In order for fluorine-containing compounds to work effectively, it is effective to allow fluoride ions to remain on the tooth surfaces in the oral cavity for a long period of time, and it is also effective to gargle and rinse the oral cavity with water after use. It is also important to keep a large amount of fluoride ions in the oral cavity even after brushing, but since dentifrice compositions are washed away by rinsing after brushing, only a small amount of fluoride ions remain in the oral cavity.

In order to improve the retention of fluoride ions in a dentifrice composition in the oral cavity, there is a method of coexisting calcium ions and fluoride ions, which are remineralizing components, but calcium ions and fluoride ions are highly reactive; If they coexist, calcium fluoride becomes an insoluble substance before acting on the teeth, and the sufficient effect cannot be achieved. Moreover, in Patent Document 1 (Japanese Patent Application Publication No. 10-511956), calcium fluoride ions and fluoride ions are mixed in the oral cavity or immediately before application to the oral cavity, and calcium fluoride is added to the oral cavity. Oral preparations have been proposed that generate Since calcium fluoride was precipitated in a short period of time, fluoride ions were not sufficiently released and the remineralization prevention effect was not satisfactorily exhibited. Patent Document 2 (Japanese Unexamined Patent Publication No. 2009-137863) proposes a composition in which a complex of a polyphosphate, a calcium salt, and a fluoride salt is prepared in advance, but this method is complicated and difficult to prepare. There were problems such as liquefaction and solidification after long-term storage as a toothpaste preparation.
Furthermore, Patent Documents 3 to 5 (Japanese Unexamined Patent Application Publications No. 2015-117215, 2013-67567, and 2007-320894) disclose that specific cationic polymer substances are used in dentifrice compositions. A method of adsorbing and retaining fluoride ions on tooth surfaces has been proposed, but there is still room for improvement in the retention properties and the amount remaining after brushing, and further improvement in retention properties has been desired.

Special Publication No. 10-511956 Japanese Patent Application Publication No. 2009-137863 JP2015-117215A JP2013-67567A Japanese Patent Application Publication No. 2007-320894

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

As a result of intensive studies to achieve the above object, the present inventors have found that sodium fluoride, a specific polyphosphate and a water-soluble calcium salt are used together in specific amounts, and cationized cellulose is also used in toothpaste. When incorporated into a drug composition, it has excellent retention of fluoride ions in the oral cavity, especially in the oral mucosa, and retains a high percentage of fluoride ions in the oral cavity. It has been found that the fluoride ions have excellent storage stability, allowing sustained release of fluoride ions and supplying fluoride ions into the oral cavity for a long period of time.Also, liquid separation and solidification are suppressed even after long-term storage, resulting in good storage stability. That is, in the present invention, (A) 0.1 to 1.5% by mass of one or more selected from tripolyphosphate and pyrophosphate, and (B) 0.1 to 1.5% by mass of water-soluble calcium salt. , (C) sodium fluoride, and (D) cationized cellulose. It was discovered that it has separation stability and solidification stability, and also good storage stability, and the present invention was completed based on this finding.

It was expected that if the fluoride contained in the fluorine-containing compound contained in the dentifrice composition was sufficiently retained not only on the tooth surface but also in the oral mucosa, the retention in the oral cavity would be further improved. This makes it difficult for fluoride to adsorb, and conventional techniques have not been able to sufficiently retain fluoride in the oral mucosa. However, in the present invention, by using the (A) and (B) components together with the (C) component and also combining the (D) component, the amount of the component (A) and the amount of the component (B) are within a specific range. Component (D) improved the retention of fluoride ions derived from component (C) in the oral mucosa, making it possible to improve not only the retention of fluoride ions but also their release. In this case, component (D) improves the retention of fluoride ions by increasing their adsorption to the mucin covering the oral mucosa, resulting in a high rate of fluoride ions staying in the oral mucosa, and Fluoride ions are gradually released into saliva and are supplied to tooth surfaces in contact with saliva for a long time. Therefore, according to the dentifrice composition of the present invention, it is possible to ensure liquid separation stability and solidification stability and improve the retention of fluorine ions in the oral cavity.

As shown in the comparative example below, when components (A), (B), and (C) are blended, but component (D) is not blended, the fluorine (fluoride ion) retention and fluorine release properties of the preparation are Liquid separation stability is poor (Comparative Example 5), and even if component (D) is blended, if the amount of component (A) or component (B) is inappropriate, fluorine retention and fluorine release properties may be impaired. were poor (Comparative Examples 1 to 4). On the other hand, the dentifrice composition of the present invention containing specific amounts of components (A) and (B), components (C), and components (D) (examples described below) has excellent fluoride retention and fluorine The release property was excellent, and the liquid separation stability (no liquid separation after storage) and solidification stability (no solidification after storage) of the formulation were good.

Therefore, the present invention provides the following dentifrice composition.
[1]
(A) 0.1 to 1.5% by mass of one or more selected from tripolyphosphate and pyrophosphate;
(B) 0.1 to 1.5% by mass of water-soluble calcium salt;
A dentifrice composition comprising (C) sodium fluoride and (D) cationized cellulose.
[2]
The dentifrice composition according to [1], wherein the component (A) is potassium pyrophosphate.
[3]
(B) The dentifrice composition according to [1] or [2], wherein the water-soluble calcium salt is calcium chloride.
[4]
The dentifrice composition according to any one of [1] to [3], wherein (A)/(C) is a molar ratio of 0.05 to 1.
[5]
The dentifrice composition according to any one of [1] to [4], wherein (B)/(C) is a molar ratio of 0.1 to 2.
[6]
The dentifrice composition according to any one of [1] to [5], wherein the content of component (C) is 0.11 to 1.1% by mass.
[7]
The dentifrice composition according to any one of [1] to [6], wherein the content of component (D) is 0.01 to 0.5% by mass.
[8]
The dentifrice composition according to any one of [1] to [7], which is a dentifrice composition.

According to the present invention, a dentifrice composition has excellent retention of fluoride ions in the oral cavity, especially the oral mucosa, and excellent release properties, and also has liquid separation stability, solidification stability, and storage stability. I 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 with water, promoting remineralization of fluorine-containing compounds. It is also possible to fully exhibit effects such as suppressing demineralization, and is suitable for caries prevention.

The present invention will be explained in more detail below. The dentifrice composition of the present invention contains (A) one or more selected from tripolyphosphates and pyrophosphates, (B) a water-soluble calcium salt, (C) sodium fluoride, and (D) cationized cellulose. do.

Component (A) is a polyphosphate tripolyphosphate or pyrophosphate. Component (A) has the effect of improving the retention of fluorine ions and also has the effect of suppressing liquid separation.
As component (A), alkali metal salts such as potassium salts and sodium salts of tripolyphosphoric acid and pyrophosphoric acid can be used, and potassium pyrophosphate is particularly preferred. These may be used alone or in combination of two or more.

The blending amount of component (A) is 0.1 to 1.5% (mass%, the same applies hereinafter) of the entire composition, preferably 0.15 to 1.4%, more preferably 0.3 to 1. .0%. If the blending amount is less than 0.1%, fluorine ion retention and release properties will be poor, and liquid separation will occur over time, resulting in poor liquid separation stability. If it exceeds 1.5%, the retention and release properties of fluorine ions will decrease, and solidification will occur over time, resulting in poor solidification stability.

(B) The water-soluble calcium salt has the effect of improving the retention of fluorine ions and also has the effect of inhibiting solidification.
Water-soluble calcium salts include, for example, calcium chloride, calcium nitrate, calcium acetate, calcium citrate, calcium gluconate, calcium benzoate, calcium formate, calcium fumarate, calcium lactate, calcium butyrate and calcium isobutyrate, calcium malate, calcium malate, calcium Examples include calcium acid, calcium propylonate, calcium valerate, and calcium chloride is particularly preferred.

(B) The amount of water-soluble calcium salt blended is 0.1 to 1.5% of the total composition, preferably 0.1 to 0.7%, more preferably 0.3 to 0.7%. be. If the blending amount is less than 0.1%, fluorine ion retention and release properties are poor, and solidification tends to occur over time, resulting in poor solidification stability. If it exceeds 1.5%, fluorine ion retention and release properties will be poor, and liquid separation will occur over time, resulting in poor liquid separation stability.

The amount of sodium fluoride (C) blended is preferably 0.11 to 1.1%, more preferably 0.32 to 0.66% of the total composition. When the blending amount is 0.11% or more, the effect of improving the retention of fluorine ions can be sufficiently obtained. When the content is 1.1% or less, harmful effects such as mottled teeth due to excessive intake can be sufficiently prevented.

In the present invention, (A)/(C) indicating the quantitative ratio of component (A) and component (C) is preferably 0.05 to 1 as a molar ratio, more preferably 0.1 to 0.5, In particular, it is 0.10 to 0.50. Furthermore, the molar ratio (B)/(C) indicating the quantitative ratio of component (B) to component (C) is preferably 0.1 to 2, more preferably 0.3 to 1. It is more preferable that the molar ratio of (A)/(C) and the molar ratio of (B)/(C) are each within the above ranges. When component (C) is blended within these molar ratio ranges, fluorine ion retention and release properties are better, and liquid separation stability and solidification stability are also better.

(D) Cationized cellulose, when combined with components (B) and (C), has the effect of improving the retention of fluorine ions derived from component (C) and improving its release properties, and also It has the effect of improving separation stability.

Cationized cellulose is cellulose with cations or cellulose derivatives with cations. The cationized cellulose may have counter ions (for example, halogen ions (chloride ions), methosulfate ions, etc.). The molecular weight of 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 hydroxyethylcellulose dimethyldiallylammonium salt, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, and hydroxyethylcellulose dimethyldiallylammonium salt is preferred.
Hydroxyethylcellulose dimethyldiallylammonium salt includes a 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 Brookfield viscometer, rotor No. 2, 20 rotations, 20°C, measurement time 1 minute) of 30 to 3,000 mPa・s. preferable.
The average molecular weight of the cationized cellulose is not particularly limited, but is preferably 100,000 to 1,500,000 as determined by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance. The nitrogen content is preferably 0.1 to 3%, more preferably 0.5 to 2.5%.
As such cationized cellulose, for example, CELQUAT L-200 (2% viscosity: 35 to 350 mPa・s, BH type Brookfield viscometer, rotor No. 2, 20 rotations) commercially available from Akzo Nobel Co., Ltd. , 20°C, measurement time: 1 minute), weight average molecular weight measured by gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance: 250,000 to 350,000), and can be used.

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 0.01% or more is added, sufficient retention and release properties of fluorine ions can be obtained, liquid separation is suppressed over time, and sufficient liquid separation stability can be obtained. When it is 0.5% or less, discomfort to the oral mucosa is sufficiently suppressed.

Furthermore, (A)/(D), which indicates the quantitative ratio of component (A) to component (D), is preferably 1 to 50 as a mass ratio, and more preferably 3 to 25. In addition, (B)/(D), which indicates the quantitative ratio of component (B) to component (D), is preferably 1 to 50 as a mass ratio, more preferably 2 to 20, and the mass ratio of component (C) and ( (C)/(D), which indicates the quantitative ratio with component D), is preferably 1 to 20 as a mass ratio, more preferably 1 to 10. When component (D) is blended within these mass ratio ranges, the effects of component (D) are fully exhibited, the retention and release of fluorine ions are better, and the liquid separation stability is better.

The dentifrice composition of the present invention is particularly suitable as a dentifrice composition, and in addition to the above-mentioned components, other known components may be added as necessary within a range that does not impede the effects of the present invention. 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 any known method depending on the dosage form. and can be prepared.

Examples of the abrasive include silica-based abrasives such as anhydrous silicic acid, precipitated silica, silica gel, aluminosilicate, and zirconosilicate, dibasic calcium phosphate dihydrate or anhydrate, monobasic calcium phosphate, tertiary calcium phosphate, Calcium phosphate compounds such as calcium tetraphosphate and calcium pyrophosphate, calcium carbonate, calcium hydroxide, aluminum hydroxide, insoluble sodium metaphosphate, tertiary magnesium phosphate, magnesium carbonate, calcium sulfate, bentonite, titanium-bonded silicate, synthetic resin type Examples include abrasives. Among these, silica-based abrasives are preferred.
The amount of abrasive compounded 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, and hydroxymethylethylcellulose, alginic acid derivatives such as sodium alginate, xanthan gum, gum tragacanth, gum karaya, gum arabic, etc. Examples include organic binders such as gums, carrageenan, polyvinyl alcohol, and carboxyvinyl polymer, and inorganic binders such as thickening silica, thickening aluminum silica, vegum, and laponite.
The blending amount of the binder is preferably 0.2 to 3% of the total composition. In the present invention, organic binders are particularly preferred, and the amount of organic binders to be blended is preferably 0.1 to 5%, particularly 0.5 to 3%, based on the total composition. Inorganic binders, especially thickening silica, are preferably used in an amount of 5% or less, particularly 2% or less, especially 1% or less of the total composition, from the viewpoint of retention of fluoride ions, and even if not added, it may be 0%. good.

Thickeners include sugar alcohols such as sorbitol, xylitol, 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). can be mentioned. The amount of the thickener added is usually 5 to 60% of the total composition.

As the surfactant, anionic surfactants, nonionic surfactants, and amphoteric surfactants can be blended.
Anionic surfactants include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, acyl sarcosinates such as sodium lauroyl sarcosine and sodium myristoyl sarcosine, sodium dodecylbenzenesulfonate, sodium hydrogenated coconut fatty acid monoglyceride monosulfate, and lauryl sulfate. Examples include sodium sulfoacetate, acylglutamates such as sodium N-palmitoylglutamate, sodium N-methyl-N-acyl taurate, sodium N-methyl-N-acylalanine, and sodium α-olefin sulfonate.
Nonionic surfactants include polyoxyethylene alkyl ether (for example, those in which the alkyl group has 16 to 18 carbon atoms), polyoxyethylene hydrogenated castor oil (for example, in which the average number of added moles of ethylene oxide is 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, polyoxyethylene polyoxypropylene glycol, etc. It will be done.
Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, and coconut oil fatty acid amidopropyl fatty acid.
The amount of 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., and for example, it can be blended in a toothpaste in an amount of 0.1 to 10%.

The colorants are 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. Examples include titanium mica, titanium oxide, etc.
Examples of sweeteners include saccharin sodium, aspartame, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidin dihydrochalcone, perillartine, and the like.
Examples of the preservative include paraoxybenzoic acid esters such as methylparaben, ethylparaben, and butylparaben, and benzoic acids or salts thereof such as sodium benzoate.

Fragrances include 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 Natural fragrances such as , yuzu oil, iris concrete, absolute peppermint, absolute rose, orange flower, etc., and processing of these natural fragrances (front distillation cut, rear distillation cut, fractional distillation, liquid-liquid extraction, essence formation, powder fragrance) menthol, carvone, anethole, cineole, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linaryl acetate, limonene, menthone , menthyl acetate, N-substituted-paramenthane-3-carboxamide, pinene, octylaldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexanepropionate, methyl anthranilate, ethyl methyl Individual flavors such as phenylglycidate, vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cyclotene, furfural, trimethylpyrazine, ethyl lactate, ethylthioacetate, as well as strawberry flavor, apple flavor, and 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.
Further, the amount of the above fragrance material is preferably used in the formulation composition in an amount of 0.000001 to 1%, although there are no particular limitations on the amount. Furthermore, it is preferable to use 0.05 to 2% of the above-mentioned fragrance materials in the formulation composition.

Active ingredients include disinfectants such as isopropylmethylphenol and cetylpyridinium chloride, water-soluble phosphoric acid compounds such as potassium salts and sodium salts of orthophosphoric acid, enzymes such as dextranase, mutanase, amylase, and protease, tranexamic acid, Water-soluble copper compounds such as epsilon aminocaproic acid, triclosan, lysozyme chloride, aluminum chlorohydroxyallantoin, hinokitiol, ascorbic acid, tocopherol acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, sodium copper chlorophyllin, chlorophyll, copper gluconate, etc. , aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid or its derivatives, glutyrrhizic acid or its salts, glycyrrhetinic acid or its derivatives, and anti-tartar agents. In addition, the above-mentioned active ingredients can be blended in an effective amount within a range that does not impede the effects of the present invention.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below. In addition, in the following examples, % indicates mass % unless otherwise specified.

[Examples, comparative examples]
Dentifrice compositions (toothpaste) 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 listed in the table.

(1) Evaluation method of fluorine (fluoride ion) retention The retention of fluoride ions 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 times diluted with purified water) was added and allowed to act for 3 minutes. Thereafter, the mixture 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. The supernatant was collected by centrifugation at 3,000 rpm for 10 minutes, and the concentration of fluorine (fluoride ions) contained in the solution was measured using a fluorine ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific Co., Ltd.). , the retained fluorine ion concentration (ppm) was obtained.
The fluorine ion retention rate was calculated using the following formula.
Fluorine ion retention rate (%) =
{(Residual fluoride ion concentration (ppm))/(Fluoride ion concentration (ppm) blended into the preparation/40)}×100
Fluorine ion retention was evaluated based on the fluorine ion retention rate using the following evaluation criteria.
Evaluation criteria ◎: Fluorine ion retention rate is 50% or more ○: Fluorine ion retention rate is 30% or more and less than 50% △: Fluorine ion retention rate is 20% or more and less than 30% ×: Fluorine ion retention rate is less than 20%

(2) Method for evaluating fluorine (fluoride ion) release properties For compositions that were evaluated as △ or higher in (1) (Examples 1 to 13, Comparative Example 2), the amount of fluoride ions released from mucin to saliva (released rate) and sustained release properties were 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 times diluted with purified water) was added and allowed to act for 3 minutes. Thereafter, the mixture was centrifuged at 3,000 rpm for 10 minutes, and the supernatant was removed.
To the obtained mucin, artificial saliva (CaCl ₂ = 1.5 mmol/L, KH ₂ PO ₄ = 5.0 mmol/L, acetic acid = 100 mmol/L, NaCl = 100 mmol/L, remainder = water; pH = 7.0 ) was added, stirred for 1 minute, left to stand for 3 minutes, 60 minutes, or 180 minutes to elute the fluorine ions adsorbed and retained in mucin, and then centrifuged at 3,000 rpm for 10 minutes to remove the supernatant. The fluorine ion concentration contained in the solution was measured using a fluorine ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific Co., Ltd.) to obtain the released fluorine ion concentration of each solution.
The fluoride ion release rate was calculated from the released fluoride ion concentration using the following formula.
Fluorine ion release rate (%) =
{(released fluorine ion concentration (ppm))/(retained fluorine ion concentration (ppm))}×
100
The fluorine release property (release amount) was evaluated from the calculated fluorine ion release rate.
The fluoride ion release rates of the compositions of Examples 1 to 13 and Comparative Example 2 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%. It was confirmed that there was no immediate release but sustained release.
The fluorine release property was evaluated based on the fluoride ion release rate after standing for 180 minutes using the following evaluation criteria. If ○ or ◎, the fluoride ions adsorbed and retained in mucin were gradually released by saliva, and the fluoride release property was judged to be acceptable.
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% ×: Fluorine 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 (no liquid separation after storage) of the preparation 50 g of the dentifrice composition was placed in a tube container (material: innermost layer is linear) The mixture was filled into three laminate tubes (manufactured by Dainippon Printing Co., Ltd.) made of low-density polyethylene and having a diameter of 26 mm, 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 evaluated using the following scoring criteria. The average score of the three samples was calculated, and the liquid separation stability of the formulation was evaluated using the following evaluation criteria.
Scoring criteria 4 points: No liquid separation at all 3 points: Slight liquid separation was observed at the mouth area, but it was at a level that was not a problem 2 points: Liquid separation was observed at the mouth area and the kneading surface 1 point: Tube When the toothpaste was pushed out, the separated liquid was observed to drip out.Evaluation criteria: ◎: Average score is 4.0 points. ○: Average score is 3.0 points or more and less than 4.0 points. △: Average score is 2.0 points. 0 points or more and less than 3.0 points ×: Average score is less than 2.0 points

(3-2) Method for evaluating the solidification stability (no solidification after storage) of the formulation Place 50 g of the dentifrice composition in a tube container (material: a 26 mm diameter laminate tube whose innermost layer is 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 evaluated using the following scoring criteria. The average score of the three samples was determined, and the solidification stability of the preparation was evaluated using the following evaluation criteria.
Scoring criteria: 4 points: There was no solidification at all. 3 points: There was a slight amount of solidification at the mouth area, but it was at a level that was not a problem. 2 points: There was some solidification at the mouth area and the surface of the toothpaste. 1 point: Toothpaste was removed from the tube. Solidification was observed to the extent that it could not be extruded Evaluation criteria ◎: Average score was 4.0 points ○: Average score was 3.0 points or more and less than 4.0 points △: Average score was 2.0 points or more and less than 3.0 points Less than ×: Average score is less than 2.0 points

Details of the raw materials used are shown below.
(A) Potassium pyrophosphate; manufactured by Taihei Kagaku Sangyo Co., Ltd. (A) Sodium tripolyphosphate; manufactured by Taihei Kagaku Sangyo Co., Ltd. (B) Calcium chloride; manufactured by Kanto Kagaku Co., Ltd. (C) Sodium fluoride; Stella Chemifa ( Co., Ltd. (D) hydroxyethyl cellulose dimethyl diallylammonium chloride;
CELQUAT L-200, manufactured by Akzo Nobel Co., Ltd.
2% 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 determined by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance: 250,000 to 350,000)

Claims (9)

(A) 0.1 to 1.5% by mass of one or more selected from tripolyphosphate and pyrophosphate;
(B) 0.1 to 1.5% by mass of water-soluble calcium salt;
Contains (C) sodium fluoride and (D) cationized cellulose, the mass ratio of (A)/(D) is 1 to 50, and the mass ratio of (B)/(D) is 1 to 50. A dentifrice composition characterized by: The dentifrice composition according to claim 1, wherein component (A) is potassium pyrophosphate. The dentifrice composition according to claim 1 or 2, wherein the water-soluble calcium salt (B) is calcium chloride. The dentifrice composition according to any one of claims 1 to 3, wherein (A)/(C) is a molar ratio of 0.05 to 1. The dentifrice composition according to any one of claims 1 to 4, wherein (B)/(C) is a molar ratio of 0.1 to 2. The dentifrice composition according to any one of claims 1 to 5, wherein the content of component (C) is 0.11 to 1.1% by mass. The dentifrice composition according to any one of claims 1 to 6, 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 7, wherein (A)/(D) has a mass ratio of 3 to 28, and (B)/(D) has a mass ratio of 2 to 26. The dentifrice composition according to any one of claims 1 to 8 , which is a toothpaste composition.