JP2009155217A - Dentifrice composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dentifrice composition that has excellent retention of fluoride in the oral cavity, especially on tooth surfaces, excellent shaping on a toothbrush and improved storage stability of preparation with time regardless of preservation temperature and sufficiently foams and contains a fluoride. <P>SOLUTION: The dentifrice composition is prepared by mixing a sodium fluoride-containing dentifrice composition with (A) 0.4-3 mass% of fatty acid amide propyl betaine, (B) 0.4-1.6 mass% of carrageenan and (C) 0.4-2.2 mass% of at least one kind of a cellulose derivative selected from hydroxyethyl cellulose, hydroxypropylmethyl cellulose and methyl cellulose in the mass ratio of the component (B)/the component (C) of 0.7-3.5. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is excellent in retention of fluoride in the oral cavity, fluoride effectively acts on the tooth surface, has good moldability and storage stability over time, has excellent foaming properties, and has a feeling of use. It relates to a good dentifrice composition.

  In the dentifrice composition, a surfactant (foaming agent) is blended in order to improve the feeling of use during brushing as well as to quickly reach the toothpaste ingredients in the oral cavity, and lauryl has excellent foaming properties. Anionic surfactants such as sodium sulfate are used in many products.

  On the other hand, since toothpaste preparations are collected and used on a toothbrush, they are easily formulated into toothbrushes by giving them a certain formability. In order to create this moldability, many dentifrice formulations contain an anionic water-soluble polymer such as sodium carboxymethylcellulose and sodium alginate as a binder.

  In addition, many of the dentifrice preparations contain various active ingredients in addition to these bases. Among them, fluorides such as sodium fluoride and sodium monofluorophosphate are used as ingredients having an effect of preventing dental caries. It is blended into many products and marketed.

  Fluoride is highly reactive with polyvalent metal ions, and sodium fluoride is known to be less effective due to the formation of calcium fluoride when calcium ions are present in the formulation. Depending on the formulation, fluorides such as sodium monofluorophosphate are used, and the types are used properly. In addition, fluoride is known to cause acute poisoning due to large intakes, dental fluorosis and osteofluorosis due to chronic overdose. In many countries, there is an upper limit of blending, and exceptionally around 5,000 ppm is allowed, but in general, 1,000 to 1,500 ppm is set as the upper limit of blending as fluorine. Yes.

  Based on these facts, there is a need for a technology that allows fluoride to act on the tooth surface more efficiently at a certain concentration, thereby providing a high caries prevention effect. Studies are underway to improve efficiency.

  Examples of such a technique include a liquid composition for oral cavity that improves the retention by using gellan gum and a nonionic surfactant in combination (Patent Document 1), and an oral composition that uses colloidal calcium carbonate together (patent) Document 2), a dentifrice composition using a wax together (Patent Document 3), a liquid oral composition using a specific alginate, xanthan gum and phosphate together (Patent Document 4) have been proposed.

  However, these technologies do not necessarily sufficiently improve the working efficiency of fluoride, and when formulated, the moldability on a toothbrush, liquid separation over time, deterioration of appearance at low temperature, etc. There was not necessarily what fully satisfied the feeling of use due to ensuring sufficient preparation stability to be suppressed and foaming properties. Therefore, a technique for increasing the working efficiency of new fluorides has been desired.

JP-A-8-3074 JP-A-11-130463 Japanese Patent Laid-Open No. 2002-3351 JP 2006-206581 A JP-A-2-1402 JP-A-8-333226 Japanese Patent Laid-Open No. 3-5417 JP 2001-163743 A

  The present invention has been made in view of the above circumstances, and is excellent in retention of fluoride in the oral cavity, particularly on the tooth surface, excellent in moldability on a toothbrush, and stable storage of the formulation over time regardless of the storage temperature. An object of the present invention is to provide a dentifrice composition containing a fluoride having good properties and sufficient foaming.

  In order to achieve the above object, the present inventors have intensively studied the influence on the interaction between fluorine and the tooth surface in a dentifrice composition containing fluoride. As a result, the dentifrice composition containing sodium fluoride. By blending the product with (A) fatty acid amidopropyl betaine, (B) carrageenan, and (C) a cellulose derivative selected from hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose at a specific ratio, the above problems are solved, Fluoride retention in the oral cavity is enhanced, the action efficiency of fluoride on the tooth surface is improved, excellent caries prevention effect is exhibited, and it is excellent in moldability when placed on a toothbrush, and more than room temperature When stored at medium to high temperature (40-50 ° C) (the storage temperature may actually exceed 40 ° C, but generally 4 The condition of storage at 6 ° C for 6 months is said to correspond to storage at room temperature for 3 years, which is an index for early determination of stability at room temperature.) In addition, it was found that a dentifrice composition having better foaming and good usability was obtained, and the present invention was made.

  Fatty acid amidopropyl betaine, carrageenan, and cellulose derivatives are all known substances as ingredients of dentifrice compositions, fatty acid amidopropyl betaine is a carboxybetaine type amphoteric surfactant, and carrageenan is an anion derived from seaweed. Cellulose binder (polymer substance) and cellulose derivative are nonionic water-soluble polymer substances obtained by adding hydroxyalkyl or the like to cellulose. In general, the mechanism by which sodium fluoride stays on the tooth surface is thought to be due to the electrostatic interaction between the fluorine ion dissociated into anions and the tooth surface. Therefore, other ionic compounds are present in the aqueous solution. It has been found that the presence of fluorine in the oral cavity tends to decrease. However, in the present invention, surprisingly, the retention of high fluoride is obtained by blending fatty acid amidopropyl betaine and carrageenan having ionic properties, and also has the above-mentioned excellent characteristics, and the object of the present invention is It is a new finding that can be achieved. Although fatty acid amidopropyl betaine shows good ionic bubbling, the neutralization is carried out within the molecule due to the presence of cationic and anionic sites in the vicinity of three methylene groups. It is considered that it does not affect the retention of fluoride by becoming a state. On the other hand, the reason why carrageenan enhances the retention of fluoride is not clear, but carrageenan is specific to the 4-position carbon (secondary carbon) of the sugar structure where the anionic sulfate group is bonded, and anionic The site is in close contact with the sugar chain skeleton. Thereby, compared with other anionic binders, such as sodium polyacrylate, the flexibility of an anionic site | part becomes small, and it is guessed that this has some influence.

  In addition, the dentifrice composition (patent document 5) which prevented the daily deterioration of bactericidal power by mix | blending binder and amphoteric surfactant, such as a hydroxyethylcellulose, carrageenan, or carboxymethylcellulose, with a triclosan compound (Patent document 5), anion Brushing a non-aerosol type non-gas normal pressure vessel filled with a liquid composition of a specific viscosity containing an amphoteric surfactant such as a surfactant, a nonionic surfactant and an alkylbetaine, and a thickener or binder. A foamy oral composition (Patent Document 6) having a good lubricating feeling due to foam lubrication is known at times, and these techniques are applied to the sodium fluoride-containing dentifrice composition described above (A) to ( By blending the component C), the retention of fluoride on the tooth surface can be improved, and it has excellent moldability, storage stability with time, foaming properties, and the like. Not Sosonokasuru thing.

  Furthermore, since fluoride ions dissociated in an aqueous solution have an anionic property, a technique is known in which a fluoride is retained in the oral cavity by electrostatic action by using a cationic compound (Patent Document 7). , 8). However, from the above-mentioned Patent Documents 7 and 8, it is not predictable that an anionic carrageenan having a sulfate group in the present invention can improve the retention in the oral cavity of an anionic fluoride as well.

Accordingly, the present invention provides a dentifrice composition containing sodium fluoride.
(A) 0.4-3 mass% fatty acid amidopropyl betaine,
(B) 0.4 to 1.6% by mass of carrageenan,
(C) 0.4 to 2.2% by mass of at least one cellulose derivative selected from hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose
A dentifrice composition characterized by comprising (B) component / (C) component in a mass ratio of 0.7 to 3.5.

  The dentifrice composition of the present invention is excellent in retention of fluoride in the oral cavity, particularly on the tooth surface, and is excellent in moldability when collected on a toothbrush, and is at a medium to high temperature (40 to 50 ° C.) above room temperature. No liquid separation when stored at a low temperature, the appearance of the preparation does not deteriorate during low-temperature storage, the storage stability over time at low or medium temperatures is good, and sufficient foaming is obtained during brushing Therefore, it is useful as a dentifrice composition for preventing dental caries.

  Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention contains sodium fluoride and contains at least one selected from (A) fatty acid amidopropyl betaine, (B) carrageenan, (C) hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose. It will be.

  In the composition of the present invention, any sodium fluoride may be used as long as it is usually used in a dentifrice composition. For example, a commercially available product available from Stella Chemifa Co., Ltd. may be used. it can. The blending amount of sodium fluoride is preferably 0.05 to 0.5% (mass%, the same applies hereinafter) of the entire composition. In addition, as content of a fluorine, it is 226-2,263 ppm, and using within the designated mixing | blending upper limit is preferable.

As the fatty acid amide propyl betaine of the component (A), amide propyl betaine laurate, coconut oil fatty acid amide propyl betaine and the like can be suitably used, and one kind may be used alone, or two or more kinds may be used in combination.
Lauric acid amidopropyl betaine consists mainly of lauric acid amidopropyl dimethylaminoacetic acid, and coconut oil fatty acid amidopropyl betaine consists mainly of coconut oil fatty acid amidopropyldimethylaminoacetic acid.

  As these fatty acid amidopropyl betaines, commercially available products can be used. Examples of amide propyl betaines of lauric acid include Amphithol 20AB (Kao Co., Ltd.), Softazoline LPB (Kawaken Fine Chemical Co., Ltd.), and palm oil fatty acid amidopropyl betaine. For example, commercially available products such as TEGO BETAIN CK (Goldschmidt), Anhitoal 55AB (Kao Corporation), NIKKOL AM-3130N (Nikko Chemicals Corporation) can be used.

  The compounding quantity of fatty-acid amide propyl betaine is 0.4 to 3% of the whole composition, Preferably it is 0.6 to 2.0%. If it is less than 0.4%, sufficient foaming will not be obtained at the time of toothbrushing, the appearance of the paste preparation will deteriorate after storage at low temperature, and if it exceeds 3%, the retention of fluoride will decrease, and the liquid separation stability Becomes worse.

The component (B) carrageenan is a natural polymer substance that is generally extracted and purified from red algae seaweed, and is a polysaccharide mainly composed of D-galactose or 3,6-anhydro-D-galactose. Is an anionic polymer compound containing a sulfate group. Carrageenan has a difference in sugar structure due to the difference in the type of seaweed used as a raw material, and includes κ (kappa) -carrageenan, ι (iota) -carrageenan, and λ (lambda) -carrageenan. In the present invention, κ (kappa) ) -Carrageenan, iota-carrageenan can be suitably used, and these may be used alone or in combination.
As such a carrageenan, for example, GENUVISCO type PJ-JPE, GENUGEL type CJ manufactured by CP Kelco, and GENUGEL type WR-78-J, GENUGEL type WG-115, etc. are used as κ-type. be able to.

  The compounding amount of carrageenan is 0.4 to 1.6%, preferably 0.6 to 1.2% of the whole composition. If it is less than 0.4%, sufficient moldability may not be obtained or the liquid separation stability may be lowered. If it exceeds 1.6%, the retention of fluoride is inferior, and 0.4 to 1. If it is out of the range of 6%, the appearance stability during low-temperature storage may be inferior.

  Component (C) is a cellulose derivative selected from hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose, and one of these can be used alone or in combination of two or more. The cellulose derivative, which is a nonionic binder, is considered to have little influence on the retention because it has little influence on the electrostatic interaction between fluorine ions and the tooth surface. It is considered that foaming is enhanced due to the function as a polymer surfactant composed of the cellulose skeleton and the hydrophobic part of the cellulose skeleton, and that the water retention function further improves the liquid separation stability.

As hydroxyethyl cellulose, those having a weight average molecular weight of 100,000 to 3,000,000 are preferable in terms of imparting moldability. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polyethylene oxide calibration curve.
As such hydroxyethyl cellulose, for example, HEC Daicel SE600, SE850, SE900 (Daicel Chemical Industries, Ltd.) are commercially available and can be used.

  As hydroxypropyl methylcellulose, for example, METOLOSE 65SH400, 65SH1500, 65SH4000, 60SH4000 and the like, which are commercially available from Shin-Etsu Chemical Co., Ltd. under the trade name of Metrows, can be used. METOLOSE SM400, SM1500, SM4000, etc., commercially available from Co., Ltd. can be used. Among these cellulose derivatives, those having a viscosity (mPa · s) in a 2% aqueous solution of 50 to 4000 mP · s are preferable in terms of imparting moldability. The viscosity was measured with a single cylindrical rotational viscometer Brookfield viscometer LV type (rotor # 2, temperature 20 ° C., 12 rpm, 1 minute).

  (C) The compounding quantity of the cellulose derivative of a component is 0.4-2.2% with respect to the whole composition, Preferably it is 0.6-1.8%. If it is less than 0.4%, sufficient moldability of the preparation cannot be obtained, or liquid separation stability is deteriorated. If it exceeds 2.2%, the viscosity of the preparation increases, and sufficient foaming cannot be obtained during brushing. Or the appearance after low-temperature storage deteriorates.

  The blending ratio (mass ratio) of component (B) / component (C) is 0.7 to 3.5, preferably 1.0 to 3.0. If it is less than 0.7, the moldability on the toothbrush and the liquid separation stability are lowered, and if it exceeds 3.5, the retention of fluoride is lowered, and the appearance after low-temperature storage is deteriorated.

  In addition to the above-described components, the dentifrice composition of the present invention includes other components that are usually added to the dentifrice composition as optional components, such as abrasives, thickeners, binders, surfactants, and sweeteners. Appropriate components such as coloring agents, preservatives, pH adjusters, fragrances, and medicinal components can be blended within a range not impairing the effects of the present invention.

  As abrasives, dicalcium phosphate dihydrate, anhydrous dibasic calcium phosphate, calcium pyrophosphate, aluminum hydroxide, alumina, titanium dioxide, crystalline zirconium silicate, polymethyl methacrylate, insoluble calcium metaphosphate, light calcium carbonate , Heavy calcium carbonate, magnesium carbonate, tribasic magnesium phosphate, zeolite, zirconium silicate, tricalcium phosphate, hydroxyapatite, fluoroapatite, calcium deficient apatite, tricalcium phosphate, tetracalcium phosphate, eighth calcium phosphate, synthetic resin system Examples thereof include silica-based abrasives such as abrasives, precipitated silica, silica gel, aluminosilicate, and zirconosilicate. In consideration of reactivity with fluoride ions in the preparation, abrasives that do not release calcium ions are preferable, and silica-based abrasives are particularly preferable. For example, precipitated silica, silica gel, aluminosilicate, zirconosilicate, etc. Is mentioned. The blending amount of the abrasive is usually 2 to 50%, particularly 10 to 40% of the whole composition.

  As thickeners, glycerin, sorbit, xylitol, erythritol, maltitol, ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol having a molecular weight of 200 to 6000, polyhydric alcohol such as reduced starch saccharified product, sugar alcohol 1 type, or 2 or more types can be used, and a normal compounding quantity is 5 to 50%.

  In addition to carrageenan, hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose, examples of the binder include other binders, specifically, sodium carboxymethylcellulose, sodium alginate, xanthan gum, sodium polyacrylate, and the like. The amount of other binder is 0 to 1.0%.

  In the present invention, the effect of improving the retention of fluoride may be reduced by the addition of other anionic compounds. Therefore, in order to ensure sufficient retention of fluoride on the teeth, other than carrageenan It is preferable not to mix other anionic binders, for example, anionic polymers such as sodium polyacrylate, sodium carboxymethylcellulose, and sodium alginate. Specifically, when other anionic binder is blended, the blending amount is 0.4% or less, particularly preferably 0 to 0.2% in the composition, and the lower limit is 0%. Most preferably, it is substantially free (0%). If the content exceeds 0.4%, the effect of improving the retention of fluoride on teeth, which is an effect of the present invention, may be reduced.

  As the surfactant, in addition to the fatty acid amidopropyl betaine of the component (A), other surfactants usually used in dentifrice compositions can be blended, and amphoteric surfactants other than the above fatty acid amidopropyl betaine Nonionic surfactants, anionic surfactants, and the like can be blended, but it is preferable not to blend anionic surfactants.

  As described above, in the present invention, the effect of improving the retention of fluoride may be reduced by the addition of an anionic surfactant, so in order to satisfactorily demonstrate the retention of fluoride on teeth, It is desirable not to add an anionic surfactant such as sodium lauryl sulfate or sodium lauroyl sarcosine, which is added to a general dentifrice composition. When an anionic surfactant is blended, the content thereof is preferably 0.05% or less in the composition, and the lower limit is 0%. Most preferably, it is substantially free (0%). When content exceeds 0.05%, the retention improvement effect to the tooth of the fluoride which is the effect of this invention may reduce.

  Therefore, when blending other surfactants, it is preferable to blend nonionic surfactants, for example, polyoxyethylene alkyl ethers having 16 to 18 carbon atoms in the alkyl group, addition moles of ethylene oxide. Examples include polyoxyethylene hydrogenated castor oil having a number of 40 to 80 mol, alkylglycoside, polyoxyethylene polyoxypropylene block copolymer, polyglycerin fatty acid ester, sorbitan fatty acid ester, and the like.

  When these other surfactants are blended, the blending amount is preferably 0 to 6% in the composition, and the range in which the total blending amount combined with the component (A) is usually about 0.4 to 9% is preferable. It is.

  Medicinal ingredients include sodium fluoride and other medicinal ingredients such as chlorhexidine, triclosan, isopropylmethylphenol, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, potassium sorbate, hinokitiol, and dextranase. And plaque formation inhibitors such as mutanase and protease, anti-inflammatory agents such as tranexamic acid, epsilon aminocaproic acid and allantoin, and various vitamins such as tocopherol acetate. A compounding quantity is an effective quantity in the range which does not prevent the effect of this invention.

  As a sweetener, saccharin sodium, stevioside, neohesperidyl dihydrochalcone, glycyrrhizin, perilartin, p-methoxycinnamic aldehyde, aspartame, and the like can be blended.

As coloring agents, Red No. 2, Red No. 3, Red No. 225, Red No. 226, Yellow No. 4, Yellow No. 5, Yellow No. 205, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 204, Green No. 3, mica titanium, titanium oxide and the like.
Examples of the preservative include paraoxybenzoic acid esters such as methyl paraben, propyl paraben, and butyl paraben, and sodium benzoate.

  Examples of the pH adjuster include citric acid, malic acid, lactic acid, tartaric acid, acetic acid, phosphoric acid, pyrophosphoric acid, glycerophosphoric acid, various salts thereof, sodium hydroxide, and the like. The pH of the dentifrice composition of the present invention is preferably adjusted to be in the range of 6 to 10, preferably 7 to 9.

  Perfumes are 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, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, iris concrete, absolute peppermint Natural flavors such as absolute rose and orange flower, and flavors that have been processed (total reservoir cut, rear reservoir cut, fractional distillation, liquid extraction, essence, powdered flavor, etc.), and Menthol, Carvone, Anethole, Cineol, Methyl salicylate , Synamic aldehyde, eugenol, 3-1-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramentane-3-carboxamide, pinene, octylacetate Dehydr, citral, pregon, calbeetoacetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, hexanal, ethyl alcohol, propyl alcohol , Butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, methyl lactate Single-flavored ingredients such as ethyl thioacetate, as well as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc. The well-known fragrance | flavor raw material used for a thing can be used, It is not limited to the fragrance | flavor of an Example.

The material in particular of the container which accommodates the dentifrice composition of this invention is not restrict | limited, Usually, the container used for a dentifrice composition can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used. Furthermore, for example, a laminated tube tube having a diameter of 26 mm and a mouth inner diameter of 5 mm (LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30 from the outermost layer) can be preferably used. The above abbreviations are as follows, and the number at the end indicates the thickness (μm).
LDPE: Low density polyethylene White LDPE: White low density polyethylene LLDPE: Linear low density polyethylene AL: Aluminum PET: Polyethylene terephthalate EMAA: Copolymer resin of ethylene / methacrylic acid

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples,% is mass% unless otherwise specified, and the blending amounts shown in Tables 1 and 2 indicate blending amounts in terms of pure content.

Examples and comparative examples
Prepare a dentifrice composition having the composition shown in Tables 1 and 2, and evaluate the retention of fluoride, the moldability on the toothbrush, the liquid separation stability of the preparation, the appearance of the paste preparation after low-temperature storage, Evaluation of foaming at the time of toothbrushing brushing was evaluated by the following method. The results are shown in Tables 1 and 2.

Preparation of test dentifrice composition:
Preparation of the dentifrice composition was made by dissolving saccharin sodium and sodium fluoride in purified water, then adding sorbite solution and glycerin, and separately adding at least one selected from carrageenan, hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose in ethylene glycol The liquid in which was dispersed was added and stirred. Then, a fragrance | flavor, an abrasive | polishing agent, and fatty-acid amide propyl betaine were added, and also it stirred under reduced pressure (5.3 kPa), and obtained the dentifrice composition. A unimixer (FM-SR-25, POWEX CORPORATION, volume 25 L) was used for the production, and 20 kg was prepared.

As each component used for the preparation of these dentifrice compositions, coconut oil fatty acid amidopropyl betaine (Amphithol 55AB, Kao Corporation, 30% aqueous solution), lauric acid amidopropyl betaine (Amphitol 20AB, Kao Corporation), 30 % Aqueous solution), κ-carrageenan (GENUGEL type WR-78-J, CP-Kelco), ι-carrageenan (GENUVISCO type PJ-JPE, CP-Kelco), hydroxyethyl cellulose (Daicel Chemical Industries, SE850) , Hydroxypropyl methylcellulose (Shin-Etsu Chemical Co., Ltd., 65SH400), methylcellulose (Shin-Etsu Chemical Co., Ltd., SM400), abrasive silica (Rhodia Nikka Co., Ltd., TIXOSIL 73), 70% sorbite liquid (Towa Kasei Kogyo) (stock) 85% glycerin aqueous solution (Lion Chemical Co., Ltd.), POE (polyoxyethylene) (20) Cetyl ether (Japan Emulsion Co., Ltd.), POE (60) hydrogenated castor oil (Nikko Chemicals Co., Ltd.), sodium fluoride (Stella Chemifa Co., Ltd.), sodium lauryl sulfate, sodium lauroyl sarcosine, sodium alginate, thickening silica (Tokusil UR, Tokuyama Co., Ltd.), ethylene glycol, saccharin sodium, water Those conforming to 2006 were used. In addition, the compounding quantity about sorbit, glycerin, coconut oil fatty acid amide propyl betaine, and lauric acid amide propyl betaine in the table | surface showed the value of pure part conversion.
About the fragrance | flavor, the fragrance | flavor A-the fragrance | flavor I shown in Table 3 were created using the flavor composition shown in Tables 4-9, and were mix | blended.

In the following evaluation, a laminate tube tube (Dai Nippon Printing Co., Ltd.) filled with about 50 g was used. As the laminate tube, a layered structure of LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30 from the outermost layer having a thickness of 257 μm, a diameter of 26 mm, and a mouth inner diameter of 5 mm was used.
The above abbreviations are as follows, and the number at the end indicates the thickness (μm).

LDPE: Low density polyethylene White LDPE: White low density polyethylene LLDPE: Linear low density polyethylene AL: Aluminum PET: Polyethylene terephthalate EMAA: Copolymer resin of ethylene / methacrylic acid

(1) Evaluation of retention of fluoride After adding 24 g of purified water to 8 g of a dentifrice composition (sample dentifrice composition) having the composition shown in Tables 1 and 2, well dispersed, and then centrifuged (10,000 rpm × 10 min) ) To obtain a supernatant. 8 mL of the supernatant was added to 200 mg of hydroxyapatite beads (PENTAX Co., Ltd., average particle size 10 μm), stirred at 37 ° C. for 3 minutes, suction filtered, and the hydroxyapatite beads collected on the filter paper were purified with water ( 16 mL) and suction filtered again to collect hydroxyapatite beads on the filter paper. To this, 1N hydrochloric acid (4 mL) was added and dissolved, followed by heat treatment at 100 ° C. for 10 minutes. 1 mL of this solution was sampled, 3 mL of acetate buffer (pH 5.2) was added, and the fluoride ion concentration was measured with a fluoride ion meter. Further, a 0.21% sodium fluoride aqueous solution was prepared, and hydroxyapatite was similarly applied to a solution obtained by adding 24 g of purified water to 8 g of the aqueous solution, and the fluorine ion concentration was measured. From these results, the fluoride retention (%) was determined from the following (Formula 1) with 100% when the sodium fluoride aqueous solution was allowed to act. The acetic acid buffer (pH 5.2) was prepared by dissolving 160 g of ammonium chloride and 230 g of ammonium acetate in 800 mL of purified water with heating, adjusting the pH to 5.2 by adding acetic acid (100), and then adding purified water. What was measured up to 1,000 mL was used.

The fluorine retention was evaluated by the following index. In the case of ○ and ◎, it was judged that the fluoride retention was good.
Evaluation criteria;
◎: Fluoride retention is 80% or more ○: Fluoride retention is 60% to less than 80% △: Fluoride retention is 40% to less than 60% X: Fluoride retention is less than 40%

(2) Evaluation of moldability on toothbrush The sample dentifrice composition was filled with 50 g of the above-mentioned laminate tube having a diameter of 26 mm and a mouth inner diameter of 5 mm, and the shape change when 0.5 g was placed on the toothbrush was based on the following criteria. It was evaluated with.
Evaluation criteria;
4 points: Displacement on the toothbrush is observed.
3 points: Slight deformation on the toothbrush is observed.
2 points: Gradually lose shape on the toothbrush.
1 point: immediately deforms on the toothbrush

The evaluation results of 5 times were averaged and judged according to the following criteria, and those with ○ and ○ were judged to be dentifrice compositions with foaming ensured and satisfactory usability.
◎: Moldability on toothbrush is 3.5 points or more and 4.0 points or less ○: Moldability on toothbrush is 3.0 points or more and less than 3.5 points Δ: Moldability on toothbrush is 2 0 point or more and less than 3.0 point ×: Formability on toothbrush is less than 2.0 point

(3) Evaluation of liquid separation stability of the preparation 50 g of the dentifrice composition of the sample was filled in the above-mentioned laminate tube having a diameter of 26 mm and a mouth inner diameter of 5 mm, and each of the three compositions was stored at 50 ° C. for 1 month. A 10 cm dentifrice composition was extruded on top, the length of the liquid that exuded on the straw half paper was measured, and the degree of liquid separation was evaluated in the following four stages. In addition, the liquid separation stability of the preparation in medium and high temperature storage at 40 ° C. or higher tends to promote liquid separation depending on the temperature, and the storage temperature that can be evaluated in a storage period of one month is 50 ° C. Selected.
Evaluation criteria;
4 points: No liquid separation is observed.
3 points: When extruded, a slight liquid separation is observed at the mouth.
2 points: When extruded, 1 to 3 cm of liquid separation is observed at the mouth.
1 point: When extruded, liquid separation is recognized at the mouth over 3 cm.

The average value of the three evaluation points was determined and judged according to the following criteria, and those with ◎ and ○ were judged to be dentifrice compositions having excellent liquid separation stability during storage at medium and high temperatures.
A: The degree of liquid separation is 3.5 points or more and 4.0 points or less. ○: The degree of liquid separation is 3.0 points or more and less than 3.5 points. Δ: The degree of liquid separation is 2.0 points or more and 3 or more. Less than 0 point x: Degree of liquid separation is less than 2.0 point

(4) Evaluation of appearance of paste preparation after low-temperature storage The sample dentifrice composition was filled in 50 g in the above-mentioned laminate tube having a diameter of 26 mm and a mouth inner diameter of 5 mm, and each of the three compositions was stored at -5 ° C for 1 month. After returning to room temperature (25 ° C) for 1 day and immediately extruding 15cm of toothpaste onto a straw half paper, the following criteria for gloss, crushing, wrinkle and uniformity are evaluated as the surface condition of toothpaste. It was evaluated with.
Evaluation criteria;
4 points: The surface is glossy, has no crushing or wrinkling, and has a uniform and smooth surface.
3 points: The surface is crushed and slightly wrinkled, but the surface is almost uniform and smooth.
Two points: crushing or wrinkling is recognized in the surface state, and there is no uniformity of the kneaded surface.
1 point: Crushing or wrinkling is remarkably observed in the surface state, the surface of the kneaded surface is non-uniform and not continuous.

The average value of the three evaluation points was determined and judged according to the following criteria, and those of ◎ and ○ were judged to be excellent dentifrice compositions that do not cause deterioration of the appearance of the paste formulation due to low-temperature storage (surface roughness). .
A: Surface state is 3.5 points or more and 4.0 points or less. ○: Surface state is 3.0 points or more and less than 3.5 points. Δ: Surface state is 2.0 points or more and less than 3.0 points. Surface condition is less than 2.0 points

(5) Evaluation of foaming at the time of toothbrushing brushing It evaluated by the sensory test using ten expert panelists. About 0.7 g of the dentifrice composition was placed on the toothbrush and used in a normal brushing method. The foaming of the dentifrice composition in the oral cavity during use was evaluated according to the following criteria.

Evaluation criteria;
4 points: The amount of foaming is sufficiently large.
3 points: A little foaming amount.
2 points: Slightly less foaming.
1 point: Less foaming.

The evaluation results of 10 people were averaged and judged according to the following criteria, and those with ◎ and ○ were judged to be dentifrice compositions with foaming ensured and satisfactory usability.
◎: Bubbling in the oral cavity is 3.5 points to 4.0 points or less ○: Bubbling in the oral cavity is 3.0 points to less than 3.5 points △: Bubbling in the oral cavity is 2.0 points Or more to less than 3.0 points x: foaming in the oral cavity is less than 2.0 points

※フッ化ナトリウム：０．２１％配合はフッ素含有量として９５０ｐｐｍに相当。

* Sodium fluoride: 0.21% content corresponds to 950ppm fluorine content.

  From the results of Tables 1 and 2, the dentifrice composition (Example) of the present invention is excellent in retention of fluoride on the tooth surface, excellent in moldability when collected in a toothbrush, and from the formulation over time. There was little liquid separation, the appearance of the preparation was not deteriorated when placed at a low temperature, and sufficient foaming was obtained during brushing.

なお、上記表中、部はいずれも質量部である（以下、同様。）。

In the above table, all parts are parts by mass (the same applies hereinafter).

Claims (1)

To dentifrice composition containing sodium fluoride,
(A) 0.4-3 mass% fatty acid amidopropyl betaine,
(B) 0.4 to 1.6% by mass of carrageenan,
(C) 0.4 to 2.2% by mass of at least one cellulose derivative selected from hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose
A dentifrice composition comprising (B) component / (C) component in a mass ratio of 0.7 to 3.5.