JP2021095380A - Dentifrice composition - Google Patents

Abstract

To provide a dentifrice composition that is excellent in intraoral retentivity of fluorine ions, is also excellent in releasability of the fluorine ions, has liquid separation stability and solidification stability and also has excellent storage stability.SOLUTION: A dentifrice composition contains (A) at least one selected from tripolyphosphate and pyrophosphate of 0.1-1.5 mass%, (B) water-soluble calcium salt of 0.1-1.5 mass%, (C) sodium fluoride, and (D) cationized cellulose.SELECTED DRAWING: None

Description

The present invention relates to a dentifrice composition containing a fluorine compound, which is excellent in the retention of fluorine ions in the oral cavity, particularly in the oral mucosa, and also in the release property thereof.

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 components having functions such as promoting remineralization and suppressing decalcification. .. In order for the fluoride-containing compound to act effectively, it is effective to allow fluoride ions to stay on the tooth surface in the oral cavity for a long period of time, and after use, the oral cavity is gargled and rinsed with water. It is important to leave a large amount of fluoride ions in the oral cavity even afterwards, but in particular, since the dentifrice composition is washed away by rinsing after brushing, the amount of fluoride ions remaining in the oral cavity is only a small amount.

In order to improve the retention of fluoride ions in the dentifrice composition in the oral cavity, there is a method in which calcium ions and fluoride ions, which are remineralizing components, coexist, but calcium ions and fluoride ions are highly reactive and are highly reactive. When coexisted, it became calcium fluoride, which is an insoluble substance before it acted on the teeth, and it was not possible to exert a sufficient effect. Further, in Patent Document 1 (Japanese Patent Laid-Open No. 10-511956), calcium fluoride is calcium fluoride in the oral cavity by mixing the two compositions in the oral cavity or immediately before application to the oral cavity. However, in this method, since it enters the oral cavity as fluoride ions, it is immediately washed away by saliva, and a sufficient retention effect is not exhibited, and after mixing the two components, Since calcium fluoride was precipitated in a short time, fluorine ions were not sufficiently released and the effect of preventing remineralization 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 in terms of preparation. There were problems such as liquefaction and solidification after long-term storage as a dentifrice preparation.
Further, in Patent Documents 3 to 5 (Japanese Patent Laid-Open Nos. 2015-117215, 2013-67567, 2007-320894), a specific cationic polymer substance is used in the dentifrice composition. However, a method of adsorbing and retaining fluorine ions on the tooth surface has been proposed, but there is still room for improvement in the retention property and the residual amount after brushing, and further improvement in the retention property is desired.

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

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 having excellent retention of fluoride ions in the oral cavity, particularly in the oral mucosa, and excellent release property thereof.

As a result of diligent studies to achieve the above object, the present inventors have combined sodium fluoride with a specific polyphosphate and a water-soluble calcium salt in specific amounts, and further combined with cationized cellulose for toothpaste. When blended in the agent composition, it has excellent retention of fluoride ions in the oral cavity, especially in the oral mucosa, fluoride ions stay in the oral cavity at a high rate, and release of fluoride ions (release amount, sustained release). It was found that the retained fluoride ions were slowly released, the fluoride ions could be supplied to the oral cavity for a long period of time, and liquid separation and solidification were suppressed even after long-term storage, resulting in good storage stability. That is, in the present invention, one or more selected from (A) tripolyphosphate and pyrophosphate is 0.1 to 1.5% by mass, and (B) water-soluble calcium salt is 0.1 to 1.5% by mass. The dentifrice composition containing (C) sodium fluoride and (D) cationized cellulose has excellent retention of fluoride ions in the oral cavity, especially in the oral mucosa, and has excellent release property, and is also a liquid. It has been found that it has separation stability and solidification stability and has good storage stability, and has led to the present invention.

It was expected that the retention in the oral cavity would be further enhanced if the fluorine of the fluorine-containing compound contained in the dentin composition sufficiently retained not only on the tooth surface but also on the oral mucosa, but the oral mucosa is a salivary protein such as mucin. Since it is covered with mucin, it is difficult for fluorine to be adsorbed, and it was not possible to sufficiently retain fluorine in the oral mucosa by the conventional technique. However, in the present invention, by using the components (A) and (B) in combination with the component (C) and combining the components (D), the amount of the component (A) and the amount of the component (B) are within a specific range. Therefore, the retention of fluoride ions derived from the component (C) in the oral mucosa was improved by the component (D), and it was possible to improve not only the retention of fluoride ions but also the release property thereof. In this case, the component (D) enhances the adsorptivity of fluoride ions to the mucin covering the oral mucosa, thereby improving the retention of fluoride ions, and the fluoride ions stay in the oral mucosa at a high rate. 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, it is possible to secure liquid separation stability and solidification stability and improve the retention of fluoride ions in the oral cavity.

As shown in the comparative example described later, if the components (A), (B) and (C) are blended and the component (D) is not blended, fluorine (fluorine ion) retention and fluorine release property, and the pharmaceutical product Liquid separation stability is poor (Comparative Example 5), and even if the component (D) is blended, if the amount of the component (A) or the amount of the component (B) is inappropriate, the fluorine retention and the fluorine release property Was bad (Comparative Examples 1 to 4). On the other hand, the dentifrice composition (Examples described later) containing a specific amount of the components (A) and (B), (C) and (D) of the present invention has fluorine 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 preparation were good.

Therefore, the present invention provides the following dentifrice compositions.
[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) has a molar ratio of 0.05 to 1.
[5]
The dentifrice composition according to any one of [1] to [4], wherein (B) / (C) has a molar ratio of 0.1 to 2.
[6]
The dentifrice composition according to any one of [1] to [5], wherein the content of the 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 the 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 having excellent retention of fluoride ions in the oral cavity, particularly in the oral mucosa, excellent release property thereof, liquid separation stability and solidification stability, and good 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 gargle and rinse with water after brushing the oral cavity, and promote remineralization of the fluoride-containing compound. , It is also possible to fully exert effects such as decalcification suppression, and it is suitable for caries prevention.

Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention contains (A) one or more selected from tripolyphosphate and pyrophosphate, (B) water-soluble calcium salt, (C) sodium fluoride, and (D) cationized cellulose. To do.

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

The blending amount of the component (A) is 0.1 to 1.5% (mass%, the same applies hereinafter) of the entire composition, preferably 0.15 to 1.4%, and more preferably 0.3 to 1. It is 0.0%. If the blending amount is less than 0.1%, the retention and release of fluorine ions are inferior, and liquid separation occurs over time, resulting in inferior liquid separation stability. If it exceeds 1.5%, the retention and release of fluorine ions are lowered, and solidification occurs over time, resulting in poor solidification stability.

(B) The water-soluble calcium salt has an effect of improving the retention of fluoride ions and an effect of suppressing 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, malein. Calcium acid, calcium propyronate, calcium valerate and the like can be mentioned, and calcium chloride is particularly preferable.

The amount of the water-soluble calcium salt (B) blended is 0.1 to 1.5% of the entire composition, preferably 0.1 to 0.7%, and more preferably 0.3 to 0.7%. is there. If the blending amount is less than 0.1%, the retention of fluorine ions and their release property are inferior, and they are easily solidified with time, and the solidification stability is inferior. If it exceeds 1.5%, the retention and release of fluorine ions are inferior, and liquid separation occurs over time, resulting in inferior liquid separation stability.

The blending amount of sodium fluoride (C) 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 it is 1.1% or less, it is possible to sufficiently prevent the occurrence of harmful effects such as mottled teeth due to excessive intake.

In the present invention, (A) / (C), which indicates the amount ratio of the component (A) to the 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. Further, (B) / (C), which indicates the quantitative ratio of the component (B) to the component (C), is preferably 0.1 to 2, more preferably 0.3 to 1, as a molar ratio. It is more preferable that the molar ratio of (A) / (C) and the molar ratio of (B) / (C) are within the above ranges, respectively. When the component (C) is blended within these molar ratios, the retention and release of fluorine ions are more excellent, and the liquid separation stability and solidification stability are more excellent.

When the cationized cellulose (D) is combined with the components (B) and (C), it has an effect of improving the retention of fluorine ions derived from the component (C) and improving the release property thereof, and also a liquid. It has the effect of improving separation stability.

The cationized cellulose is a cellulose having a cation or a cellulose derivative having a cation. The cationized cellulose may have a counter ion (for example, a halogen ion (chlorine ion), a metosulfate ion, etc.). The molecular weight of the 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 the cationized cellulose include hydroxyethyl cellulose dimethyldiallylammonium salt and O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose chloride, and hydroxyethyl cellulose dimethyldiallylammonium salt is preferable.
As the hydroxyethyl cellulose dimethyl diallyl ammonium salt, chloride ion is mentioned as a counter ion, and hydroxyethyl cellulose dimethyl diallyl ammonium chloride is preferable.
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.
The average molecular weight of the cationized cellulose is not particularly limited, but is a weight average molecular weight by the gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance, and is preferably 100,000 to 1,500,000. The nitrogen content is preferably 0.1 to 3%, more preferably 0.5 to 2.5%.
Examples of such cationized cellulose include CELQUAT L-200 (2% viscosity: 35 to 350 mPa · s, BH type Brookfield viscometer, rotor No. 2, 20 rotations) commercially available from Axonobel Co., Ltd. , 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), and can be used.

The blending amount of the component (D) is preferably 0.01 to 0.5%, more preferably 0.05 to 0.2% of the entire composition. When 0.01% or more is blended, the retention of fluorine ions and the release property thereof can be sufficiently obtained, and the liquid separation is suppressed even with time, and sufficient liquid separation stability can be obtained. When it is 0.5% or less, the discomfort to the oral mucosa is sufficiently suppressed.

Further, (A) / (D) indicating the quantitative ratio of the component (A) to the component (D) is preferably 1 to 50, more preferably 3 to 25, as a mass ratio. Further, (B) / (D) indicating the quantitative ratio of the component (B) and the component (D) is preferably 1 to 50, more preferably 2 to 20 as a mass ratio, and the component (C) and (C). As for (C) / (D) indicating the amount ratio with the component D), the mass ratio is preferably 1 to 20, more preferably 1 to 10. When the component (D) is blended within the range of these mass ratios, the effect of the component (D) is sufficiently exhibited, the retention and release 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 dentifrice composition, and in addition to the above components, other known components can be blended as necessary within a range that does not interfere with the effects of the present invention. For example, an abrasive, a binder, a thickener, a surfactant, and if necessary, a colorant, a sweetener, a preservative, a flavor, an active ingredient, and the like can be blended. The method for preparing the dentifrice composition is not particularly limited, and a known method depending on the dosage form may be used. For example, the components (A) to (D), further, any component, and water are blended by a usual method. And can be prepared.

The polishing agent is, for example, a silica-based polishing agent such as silicic anhydride, precipitated silica, silica gel, aluminosilicate, zirconosilicate, calcium dibasic phosphate / dihydrate or anhydride, calcium phosphate 1st, calcium phosphate 3rd, and the like. 4 Calcium phosphate compounds such as calcium phosphate 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 Polishing agents can be mentioned. Of these, silica-based abrasives are preferable.
The blending amount of the abrasive is preferably 5 to 60%, particularly 5 to 30% of the total composition.

As the binder, an organic or inorganic binder can be blended. Specifically, cellulose derivatives such as sodium carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxymethyl ethyl cellulose, alginate derivatives such as sodium alginate, xanthan gum, tragacant gum, carrageenan gum, Arabic gum and the like. Examples include organic binders such as gums, carrageenan, polyvinyl alcohol and carboxyvinyl polymers, and inorganic binders such as thickening silica, thickening aluminum silica, bee gum and laponite.
The blending amount of the binder is preferably 0.2 to 3% of the total composition. In the present invention, an organic binder is particularly preferable, and the blending amount of the organic binder is preferably 0.1 to 5%, particularly 0.5 to 3% of the entire composition. Inorganic binders, especially thickening silica, are preferably 5% or less, particularly 2% or less, particularly 1% or less of the entire composition when blended in terms of the retention of fluorine ions, and even 0% without blending. Good.

The viscous agent includes sugar alcohols such as sorbitol, xylit, erythritol, martit, and lacchit, and polyhydric alcohols such as glycerin, propylene glycol, and polyethylene glycol having an average molecular weight of 160 to 400 (average molecular weight described in the raw material standard for non-pharmaceutical products 2006). Can be mentioned. The blending amount of the thickener is usually 5 to 60% of the total composition.

As the surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant can be blended.
Anionic surfactants include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, acyl sarcosates such as sodium lauroyl sarcosin and sodium myristyl sarcosin, sodium dodecylbenzene sulfonate, hydrogenated coconut fatty acid monoglyceride monoglyceride sodium monosulfate, and lauryl. Examples thereof include sodium sulfoacetate, acyl glutamate 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, those having an alkyl group having 16 to 18 carbon atoms), polyoxyethylene hydrogenated castor oil (for example, those having an average number of moles of ethylene oxide added of 40 to 80), and the like. Alkyl glucoside, polyoxyethylene polyoxypropylene block copolymer, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkylol amide, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, etc. Be done.
Examples of the amphoteric surfactant include betaine lauryldimethylaminoacetate, acyl-N-carboxymethyl-N-hydroxyethylethylenediamine of N-palm oil fatty acid, betaine amide propyl dimethylaminoacetic acid of coconut oil, and amide propyl of coconut oil fatty acid.
The blending amount of the surfactant is usually preferably 0.1 to 10% of the total composition. The blending amount can be adjusted according to the form of the dentifrice composition, the purpose of use, etc. For example, 0.1 to 10% can be blended in dentifrice.

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

Fragrances are peppermint oil, sparemint oil, anis oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamon oil, coriander oil, mandarin oil, lime. Oil, lavender oil, rosemary oil, laurel oil, camomill oil, caraway oil, majorum 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 and other natural fragrances, and processing of these natural fragrances (pre-reservoir cut, rear-reservoir cut, distilling, liquid extraction, essence, powder fragrance Perfume, menthol, carboxylic, anator, cineole, methyl salicylate, synamic aldehyde, eugenol, 3-l-mentoxypropane-1,2-diol, timole, linalol, linaryl acetate, limonene, menton , Menthylacetate, N-substituted-paramentan-3-carboxamide, pinen, octylaldehyde, citral, pregon, calvier acetate, anisaldehyde, ethylacetate, ethylbutyrate, allylcyclohexanepropionate, methylanthranilate, ethylmethyl Single flavors such as phenylglycidate, vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethylsulfide, cycloten, furfural, trimethylpyrazine, ethyllactate, ethylthioacetate, strawberry flavor, apple flavor, banana flavor , Peppermint flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor and other blended flavors, and other known flavoring materials used in toothpaste compositions can be used in combination.
Further, the blending amount is not particularly limited, but it is preferable to use 0.000001 to 1% of the above-mentioned fragrance material in the formulation composition. Further, as a fragrance for fragrance using the above fragrance material, it is preferable to use 0.05 to 2% in the composition of the preparation.

As active ingredients, bactericides such as isopropylmethylphenol and cetylpyridinium chloride, water-soluble phosphoric acid compounds such as potassium salt of orthophosphate and sodium salt, enzymes such as dextranase, mutanase, amylases and protease, tranexamic acid, etc. Water-soluble copper compounds such as epsilon aminocaproic acid, triclosan, lysozyme chloride, aluminum chlorohydroxyalantin, hinokithiol, ascorbic acid, tocopherol acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, sodium copper chlorophyllin, chlorophyll, copper gluconate, etc. , Aluminum lactate, strontium chloride, potassium nitrate, velverin, hydroxamic acid or a derivative thereof, glutyllithic acid or a salt thereof, glycyrrhetinic acid or a derivative thereof, and an anti-dental stone agent. The active ingredient can be blended in an effective amount within a range that does not interfere with the effects of the present invention.

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

[Examples, comparative examples]
Toothpaste compositions (dentifrices) having the 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 of fluorine (fluoride ion) retention The retention of fluorine ions was evaluated by an adsorption test of fluorine (fluoride ion) to mucin, which is an oral mucosal component.
0.2 g of mucin (manufactured by Sigma-Aldrich) was added to a 10 mL centrifuge tube, and 5 mL of a dentifrice composition (40-fold diluted solution with purified water) was further added and allowed to act for 3 minutes. Then, the mixture was centrifuged at 3,000 rpm for 10 minutes to remove the supernatant. To the obtained mucin, 5 mL of potassium citrate buffer was added and stirred for 1 minute to forcibly elute the fluoride ions adsorbed and retained on the mucin. Centrifuge at 3,000 rpm for 10 minutes to collect the supernatant, and measure the concentration of fluorine (fluoride ion) contained in the solution with a fluorine ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific Co., Ltd.). , The retained fluoride ion concentration (ppm) was obtained.
The fluoride ion retention rate was calculated by the following formula.
Fluoride ion retention rate (%) =
{(Standing Fluoride Ion Concentration (ppm)) / (Fluoride Ion Concentration in Formulation (ppm) / 40)} x 100
From the fluoride ion retention rate, the fluoride ion retention was evaluated according to the following evaluation criteria.
Evaluation Criteria ◎: Fluoride ion retention rate is 50% or more 〇: Fluoride ion retention rate is 30% or more and less than 50% Δ: Fluoride ion retention rate is 20% or more and less than 30% ×: Fluoride ion retention rate is less than 20%

(2) Evaluation Method of Fluoride (Fluoride Ion) Release Amount (Release) of Fluoride Ion from Mucin to Saliva with respect to the composition (Examples 1 to 13, Comparative Example 2) evaluated above Δ in (1). Rate) and sustained release 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-fold diluted solution with purified water) was further added and allowed to act for 3 minutes. Then, the mixture was centrifuged at 3,000 rpm for 10 minutes to remove the supernatant.
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, balance = water; pH = 7.0 ) Is added and stirred for 1 minute, allowed to stand for 3 minutes, 60 minutes or 180 minutes to elute the fluoride ions adsorbed and retained in mutin, and then centrifuged at 3,000 rpm for 10 minutes to prepare the supernatant. The fluoride was collected and the concentration of fluoride ions 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 concentration of each released fluoride ion.
From the released fluoride ion concentration, the fluoride ion release rate was calculated by the following formula.
Fluoride ion release rate (%) =
{(Released fluoride ion concentration (ppm)) / (Standing fluoride ion concentration (ppm))} ×
100
From the calculated fluorine ion release rate, the fluorine release property (release amount) was evaluated.
The fluoride ion release rates of the compositions of Examples 1 to 13 and Comparative Example 2 after standing for 3 minutes were both 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 sustained release without immediate release.
From the fluorine ion release rate after standing for 180 minutes, the fluorine release property was evaluated according to the following evaluation criteria. Fluoride ions adsorbed and retained in mucin were gradually released by saliva, and it was judged that the fluorine-releasing property was acceptable.
Evaluation criteria ⊚: Fluoride ion release rate after 180 minutes standing is 70% or more 〇: Fluoride ion release rate after 180 minutes standing is 50% or more and less than 70% Δ: Fluoride ion release rate after 180 minutes standing 20% or more and less than 50% ×: Fluoride ion release rate after standing for 180 minutes is less than 20%

(3) Evaluation method of storage stability (3-1) Evaluation method of liquid separation stability (no liquid separation after storage) of the preparation 50 g of dentifrice composition in a tube container (material: innermost layer is linear) It was filled in 3 laminated tubes (manufactured by Dainippon Printing Co., Ltd.) having a diameter of 26 mm made of low-density polyethylene and stored at 40 ° C. for 1 month. After storage, the dentifrice composition was extruded onto paper from each tube container, and the state of liquid separation was judged according to the following scoring criteria. The average score of 3 bottles was calculated, and the liquid separation stability of the pharmaceutical product was evaluated according to the following evaluation criteria.
Rating criteria 4 points: No liquid separation at all 3 points: Liquid separation was slightly observed in the mouth but at a level that was not a problem 2 points: Liquid separation was observed in the mouth and kneading surface 1 point: Tube Evaluation criteria recognized to the extent that the separation liquid drips when the toothbrush is extruded from ◎: Average score is 4.0 points 〇: Average score is 3.0 points or more and less than 4.0 points △: Average score is 2. 0 points or more and less than 3.0 points ×: Average score is less than 2.0 points

(3-2) Evaluation method of solidification stability (non-solidification after storage) of the pharmaceutical product 50 g of dentifrice composition in a tube container (Material: Laminated tube with a diameter of 26 mm made of linear low-density polyethylene in the innermost layer) It was filled in 3 tubes (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 solidified state was judged according to the following scoring criteria. The average score of 3 bottles was calculated, and the solidification stability of the preparation was evaluated according to the following evaluation criteria.
Rating criteria 4 points: No solidification 3 points: Slight solidification was observed in the mouth but at a level that was not a problem 2 points: Solidification of the mouth and kneaded surface was observed 1 point: Toothbrush from the tube Evaluation criteria for solidification to the extent that it cannot be extruded ◎: Average score is 4.0 points 〇: Average score is 3.0 points or more and less than 4.0 points △: Average score is 2.0 points or more and 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; Taihei Kagaku Sangyo Co., Ltd. (A) Sodium tripolyphosphate; Taihei Kagaku Sangyo Co., Ltd. (B) Calcium chloride; Kanto Kagaku Co., Ltd. (C) Sodium fluoride; Stella Chemifa ( (D) Hydroxyethyl Cellulose Dimethyldiallyl Ammonium Chloride
CELQUAT L-200, manufactured by AkzoNobel 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 by gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance: 250,000 to 350,000)

Claims (8)

(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. The dentifrice composition according to claim 1, wherein the component (A) is potassium pyrophosphate. (B) The dentifrice composition according to claim 1 or 2, wherein the water-soluble calcium salt is calcium chloride. The dentifrice composition according to any one of claims 1 to 3, wherein (A) / (C) has a molar ratio of 0.05 to 1. The dentifrice composition according to any one of claims 1 to 4, wherein (B) / (C) is 0.1 to 2 in terms of molar ratio. The dentifrice composition according to any one of claims 1 to 5, wherein the content of the 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 the component (D) is 0.01 to 0.5% by mass. The dentifrice composition according to any one of claims 1 to 7, which is a dentifrice composition.