JP4892966B2 - Dentifrice composition - Google Patents

Description

  The present invention is a dentifrice composition containing an ascorbic acid phosphate salt and a silica-based abrasive, and has the stability of an ascorbic acid phosphate salt and an excellent gingivitis-preventing effect. It is related with the dentifrice composition which improved irritation, bitterness, and astringency.

  Ascorbic acid phosphate ester salt has recently attracted attention as an antioxidant vitamin that eliminates excess active oxygen produced in the body and protects living tissues from oxygen injury. Furthermore, ascorbic acid phosphate ester salts have a variety of physiological activities and are known to be effective in the prevention and treatment of gingivitis and periodontitis in the oral cavity field. Oral compositions such as toothpaste and troches Attempts have been made to blend them into products (Patent Document 1; JP-A-2-292221, Patent Document 2; JP-A-3-294227, etc.).

Moreover, the composition for oral cavity containing ascorbic acid phosphate ester salt had a problem that the residual rate of ascorbic acid phosphate ester salt decreased after long-term storage, and its effectiveness was not fully exhibited, Stability is maintained by maintaining the pH of the composition on the alkali side, such as setting the pH of the composition after storage at 25 ° C. for 1 month to 8.0 or more (Patent Document 3; No. 20292, Patent Document 4; JP 2003-212741 A).
However, when the pH of the oral composition is set to the alkali side, there is a problem that irritation to the oral mucosa becomes strong.

Moreover, patent document 4 is the proposal of the present applicant, and ascorbic acid phosphoric acid is used by using the silica type abrasive | polishing agent whose pH of ascorbic acid phosphate ester or its salt and 5 mass% water slurry is 9 or more. It has been proposed that an ester or a salt thereof is stably blended to ensure the stability of the alkali-labile fragrance component.
That is, when the conventional abrasive silica is used, the pH after storage is lowered, and the residual rate of the ascorbic acid phosphate compound after the lapse of time occurs, so that the initial pH setting on the alkali side and the ascorbic acid phosphoric acid are reduced. In order to adjust the ester compound to a stable pH range, a large amount of pH adjuster is required, which affects the feeling of use such as flavor. In addition, abrasive | polishing agents other than a silica react with ascorbic acid phosphate ester and its salts, and a residual rate falls.
For this reason, a 5 mass% water slurry is used as a dentifrice composition in which the pH is not lowered and the pH can be controlled with a less pH adjuster, the ascorbic acid phosphate and its salts are stably blended, and have a good flavor. By blending 5% by mass or more of abrasive silica having a pH of 9 or more measured in step 1, ascorbic acid phosphate and its salts are stably blended, and a large amount of pH adjuster is unnecessary, which is good. A toothpaste composition with a savory flavor can be obtained.

  However, such a dentifrice composition still has room for improvement in terms of the bitterness derived from ascorbic acid phosphate ester salt and the lack of astringency derived from silica-based abrasives, and the amount of flavor added to mask this There is also a problem that the stimulation may further increase when the value is increased.

  Therefore, in a dentifrice composition containing an ascorbic acid phosphate salt and a silica-based abrasive, a technology that can further improve the stability of the ascorbic acid phosphate salt, the bitterness and astringency during use, etc. Development is desired.

JP-A-2-292211 JP-A-3-294227 JP 2002-20292 A JP 2003-212741 A Japanese Patent Laid-Open No. 9-25221 JP-T-2001-508423 JP 2004-217614 A

  The present invention has been made in view of the above circumstances. In a dentifrice composition containing an ascorbic acid phosphate salt and a silica-based abrasive, the stability of the ascorbic acid phosphate salt is high, and excellent gingivitis prevention. An object of the present invention is to provide a dentifrice composition that has an effect, improves irritation during biting and after dentifrice, bitterness and astringency, and has a good feeling of use.

As a result of intensive studies to achieve the above object, the present inventor has obtained a dentifrice composition containing an ascorbic acid phosphate ester salt , and (C) a 5 mass% water slurry having a pH at 25 ° C. of 7.5. ˜11.0 silica-based abrasive is blended in an amount of 5 to 40% by mass , trimethylglycine is blended at a specific ratio with respect to the silica-based abrasive, and an alkali agent is blended. After initial pH and storage for 1 month By making the pH of the specific range, there is almost no decrease in pH during storage, the stability of ascorbic acid phosphate ester salt is improved, and it has an excellent gingivitis prevention effect, as well as a high pH during and after dentifrice That improves the bitterness of ascorbic acid phosphate ester salt and the astringent taste of silica-based abrasives, and provides a dentifrice composition with an excellent feeling of use. Furthermore, acidic mucopolysaccharides It was found that the above-mentioned bitterness and astringency improving effect was further enhanced by blending in the composition, and a dentifrice composition having a superior gingivitis prevention effect and a feeling of use was obtained. It came to make.

  Trimethylglycine is a known substance that is widely used as an amino acid humectant in skin cosmetics and hair cosmetics. Examples of applications of trimethylglycine to the oral cavity include tongues that are used in combination with various enzymes. An effect of removing plaque has been reported (Patent Document 5; JP-A-9-25221). Moreover, the moisturizing effect of the oral mucosa has been reported as well as on the skin (Patent Document 6; JP-T-2001-508423). Furthermore, it has been reported that the smoothness and refreshing feeling of teeth after oral cleaning with a mouthwash can be obtained in combination with an anionic surfactant (Patent Document 7; JP 2004-217614 A). ). As described above, the development of application of trimethylglycine to oral compositions has been studied, but trimethylglycine was added to a dentifrice composition containing ascorbic acid phosphate and silica-based abrasive. In addition, by satisfying the above essential requirements, ascorbic acid phosphate salt can be stably blended, and stimulation derived from high pH during and after dentifrice, bitterness derived from ascorbic acid phosphate salt and silica-based It is a new finding of the present inventor that the astringency derived from the abrasive can be improved.

Accordingly, the present invention provides (A) a dentifrice composition containing an ascorbic acid phosphate salt , and (C) a silica-based polishing in which a 5 mass% water slurry has a pH at 25 ° C. of 7.5 to 11.0. 5 to 40% by mass of the agent and 0.1 to 15% by mass of (B) trimethylglycine , and the blending ratio of (B) component / (C) component is 0.02 to 3.0 as a mass ratio. blended in the range, and (D) were blended an alkali agent, is characterized in that a 8.0 to 9.5 a pH of 1 month saved 25 ° C. after at initial pH and 25 ° C. of the composition A dentifrice composition, further comprising (E) at least one acidic mucopolysaccharide is provided.

  The dentifrice composition of the present invention has a high stability of ascorbic acid phosphate ester salt, has an excellent gingivitis-preventing effect, is stimulated by high pH during and after dentifrice, and ascorbic acid phosphate ester The bitterness derived from salt and the astringency derived from silica-based abrasives are improved, and the use feeling is good.

Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention can be prepared as a dentifrice such as a toothpaste, a liquid dentifrice, a liquid dentifrice, etc. (A) ascorbic acid phosphate , (B) trimethylglycine, (C) a silica-based abrasive , (D) were blended an alkali agent, a dentifrice composition of pH at 25 ° C. after storage for one month at an initial pH and 25 ° C. of the composition is 8.0 to 9.5.

  As (A) ascorbic acid phosphate ester salt used here, one or two or more hydroxyl groups at 2, 3, 5, and 6 positions of ascorbic acid are esters of compounds such as phosphoric acid and polyphosphoric acid. For example, ascorbic acid-2-phosphate ester, ascorbic acid-3-phosphate ester, ascorbic acid-6-phosphate ester, ascorbic acid-2-polyphosphate ester, etc. Examples of the salts include alkali metal salts such as sodium salt, potassium salt, calcium salt, and magnesium salt, and alkaline earth metal salts. In particular, it is used for the oral cavity, and a magnesium salt or sodium salt of ascorbic acid phosphate is suitably used from the viewpoint of preventing gingivitis.

  The compounding amount of the ascorbic acid phosphate ester salt is preferably 0.01 to 10% (mass%, the same applies hereinafter), particularly 0.01 to 5%, based on the total amount of the composition. When the blending amount is less than 0.01%, the gingivitis preventing effect may not be sufficiently exerted, and when it exceeds 10%, the feeling of use may be lowered due to the bitterness.

  (B) In addition to trimethylglycine, trimethylglycine is called by the names of glycine betaine and betaine, and is a known substance that is widely used as an amino acid humectant in skin cosmetics and hair cosmetics. Trimethylglycine is sold under the trade name of AQUADU from Ajinomoto Co., Inc. and Amino Coat from Asahi Kasei Chemicals Co., Ltd., and these commercially available products can be used in the present invention.

In the present invention, the amount of trimethylglycine is 0.1 to 15% of the total dentifrice composition, more preferably from 0.5% to 10%. Blending amount in the case of less than 0.1% not exhibited sufficient effect of improving the stimulation and bitterness and astringency, more than 15% arising bitter.

(C) Silica-based abrasives include silicic anhydrides such as silica gel, precipitated silica and ignitable silica, compounds mainly composed of silicates such as aluminosilicate, zirconosilicate and titanium-bonded silica. It can be used without limitation to its production method, the kind of trace components, and the like . Specifically, as precipitated silica, TIXOSIL 73, 63 (manufactured by Rhodia), Zedent 113 (manufactured by Huber), Sident 3,20 (manufactured by Degussa), zirconosilicate, manufactured by Taki Chemical Co., Ltd., silica gel, SYLOPURE 25, 30, 35 (manufactured by Fuji Silysia), and the like . In the present invention, the silica-based polishing described above is used. Among the agents, a silica-based abrasive having a pH of 7.5 to 11.0 at 25 ° C. of a 5 mass% water slurry, That is, a slurry suspended in water at a ratio of 5% by mass and having a pH of 7.5 to 11.0 at 25 ° C. can be used. Since it can stabilize more, it can be used more suitably.

For example, as a silica-based abrasive having a pH of 7.6 to 8.4 at 25 ° C. in a 5% by mass water slurry, TIXOSIL 73 manufactured by Rhodia Corporation may be used. Moreover, the zirconosilicate whose pH in 25 degreeC of 5 mass% water slurry is 8.8-10.5 is still more preferable from the point which reduces the quantity of an alkaline agent and eases irritation | stimulation. In such zirconosilicate, as disclosed in Japanese Patent No. 3626202, zirconium obtained by reacting water-soluble alkali metal silicate, water-soluble zirconium salt, and mineral acid as essential raw materials is ZrO _2. X-ray diffraction angle 2θ = 21 to 23 ° (d = 4.07 to 4.09) when bonded to SiO _{2 in} the range of 1.5 to 3.5% by mass and fired at 900 ° C. for 1 hour. ) And 2θ = 35 to 37 ° (d = 2.48 to 2.50), and a synthetic amorphous silicate having a product 5% by mass slurry having a pH of 8.8 to 10.5 Can be obtained from Taki Chemical Co., Ltd.

The amount of the silica-based polishing agent is usually 5-40% by total amount of the composition is preferred. Amount is when less than 5% is not effective enough exerted to maintain the initial pH, the you decrease feeling like astringency occurs in excess of 40%.

  In the present invention, the mass ratio [(B) component / (C) component] of the blending ratio of (B) trimethylglycine and (C) silica-based abrasive is derived from stimulation derived from high pH and ascorbic acid phosphate ester salt. From the point which improves the bitter taste of this, and the astringency derived from a silica type abrasive | polishing agent, it is 0.02-3.0, Preferably it is 0.05-3.0, More preferably, it is 0.1-2.5. When the ratio is less than 0.02, the effect of improving irritation, bitterness and astringency is not sufficiently exhibited. When the ratio exceeds 3.0, the dentifrice composition after initial storage at 25 ° C. for 1 month The blending amount of the alkaline agent for maintaining the pH at 25 ° C. at 8.0 to 9.5 is increased, resulting in irritation and bitterness.

  (D) As the alkali agent, commonly used alkali agents can be used, but sodium hydroxide, potassium hydroxide and the like can be suitably used, and sodium bicarbonate, triethanolamine and the like can also be preferably used. .

  The blending amount of the alkali agent is usually 0.01 to 1.0%, particularly 0.05 to 0.5%, based on the total amount of the composition. When the blending amount is less than 0.01%, the initial pH may not be 8.0 or more, and when it exceeds 1.0%, irritation may occur.

In order to maintain the stability and effectiveness of the ascorbic acid phosphate ester salt, the dentifrice composition of the present invention has an initial pH and a pH at 25 ° C. of 1 month at 25 ° C. It is necessary to be 9.5, preferably 8.5 to 9.0, and it is particularly preferable that the pH at 25 ° C. after storage for 1 month at 25 ° C. is 8.5 to 9.0. When the silica type abrasive | polishing agent concerning this invention is selected as an abrasive | polishing agent seed | species, there is almost no fall of pH after a preservation | save, pH in 25 degreeC after 1 month preservation | save at 25 degreeC is thus 8.0-9. However, when an abrasive species other than a silica-based abrasive is selected, the abrasive is decomposed by an alkaline agent, and the pH decreases after storage. In the present invention, the dentifrice composition is stored at 25 ° C. for 1 month, and the pH at 25 ° C. is 8.0 to 9.5, preferably 8.5 to 9.0. The initial pH at 25 ° C. is 8.0 to 9.5, preferably 8.5 to 9.0.
When the initial dentifrice composition containing a silica-based abrasive has a pH of less than 8.0 at 25 ° C., the pH at 25 ° C. after storage at 25 ° C. for 1 month becomes less than 8.0, and ascorbine. The stability of the acid phosphate ester salt is not maintained and the effectiveness is not sufficiently exhibited. In addition, when the initial pH and the pH at 25 ° C after storage exceeds 9.5, the stability of the ascorbic acid phosphate ester salt is not maintained, and the effectiveness is not sufficiently exhibited, or during or after dentifrice The stimulation is strong and the effects of the present invention are not fully exhibited.

  In the present invention, the (A) acidic mucopolysaccharide is further added to the dentifrice composition containing the above components (A) to (D), thereby stimulating irritation and bitterness and astringency during and after dentifrice. Further improvement can be made to have a better feeling of use.

  Examples of acidic mucopolysaccharides include chondroitin sulfate, chondroitin polysulfate, hyaluronic acid, heparin, heparan sulfate, keratosulfuric acid, keratopolysulfuric acid, or salts thereof. Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium Examples thereof include alkali metal salts such as salts, and alkaline earth metal salts. Preferred acidic mucopolysaccharides are sodium chondroitin sulfate and sodium hyaluronate.

  The blending amount of the acidic mucopolysaccharide is preferably 0.01 to 5%, particularly 0.05 to 1%, based on the total amount of the composition. If the blending amount is less than 0.01%, the effect of improving irritation, bitterness and astringency may not be sufficiently exerted, and if it exceeds 5%, the dentifrice composition has a bitter taste or a high viscosity. Usability may be significantly reduced.

  The dentifrice composition of the present invention can contain other additives as optional components in addition to the essential components as long as the effects of the present invention are not impaired. That is, unless the effect of the present invention is significantly impaired, abrasives, binders, thickeners, moisturizers, surfactants, sweeteners, preservatives, fragrances, coloring agents, Appropriate ingredients such as storage stabilizers and medicinal ingredients can be blended.

  As an abrasive, in addition to the above-mentioned silica-based abrasive, other commonly used abrasives can be blended within a range that does not impair the effects of the present invention. For example, calcium phosphate hydrogen phosphate for dental use that is commonly used (With an average particle size of about 1 to 30 μm), calcium pyrophosphate, calcium carbonate, aluminum hydroxide, alumina, magnesium carbonate, tertiary magnesium phosphate, insoluble sodium metaphosphate, insoluble potassium metaphosphate, titanium oxide And synthetic resin abrasives.

  The blending amount of other abrasives is preferably in the range of 0 to 5% of the total composition in addition to the blending amount of the above-mentioned (C) silica-based abrasive.

  As the binder, cellulose derivatives such as carboxymethylcellulose, gums such as xanthan gum, tragacanth gum, karaya gum, arabic gum, polyvinyl alcohol, carboxyvinyl polymer such as cross-linked sodium polyacrylate, non-cross-linked sodium polyacrylate, carrageenan, Examples thereof include organic binders such as sodium alginate and polyvinyl pyrrolidone, and inorganic binders such as silica gel, aluminum silica gel, bee gum and laponite. The compounding quantity of a binder is 0.2 to 10% of the whole composition normally.

  As thickeners and humectants, polyvalents such as sorbit, glycerin, polyethylene glycol having a weight average molecular weight of 200 to 6000, ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, polypropylene glycol, xylitol, maltitol, etc. One kind or two or more kinds of alcohol, sugar alcohol, hydrogenated partially hydrolyzed polysaccharide and the like can be blended. The usual compounding quantity of a thickener and a moisturizer is 5 to 50% with respect to the composition whole quantity.

  As the surfactant, an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be blended. Examples of anionic surfactants include sodium alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, sodium N-acyl sarcosinate such as sodium N-lauroyl sarcosinate, sodium N-myristoyl sarcosinate, sodium dodecylbenzenesulfonate, hydrogen Added coconut fatty acid monoglyceride sodium monosulfate, sodium lauryl sulfoacetate, N-acyl glutamate such as sodium N-palmitoyl glutamate, N-methyl-N-acyl taurine sodium, N-methyl-N-acylalanine sodium, α-olefin sulfone Examples include sodium acid. Nonionic surfactants include sugar alcohol fatty acid esters such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid Ether type activator such as polyhydric alcohol fatty acid ester such as ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene copolymer, polyoxyethylene alkylphenyl ether, polyoxyethylene hydrogenated castor oil, lauric acid diethanolamide And fatty acid alkanolamides. Examples of the cationic surfactant include alkylammonium and alkylbenzylammonium salts. Examples of amphoteric surfactants include betaine acetate, imidazolinium betaine, and lecithin. The compounding quantity of surfactant is 0.2 to 15% of the whole composition normally, Preferably it is 0.5 to 10%.

  Examples of the sweetener include saccharin sodium, stevioside, stevia extract, neohesperidyl dihydrochalcone, glycyrrhizin, perilartin, p-methoxycinnamic aldehyde, aspartame, xylitol and the like.

  Examples of the preservative include parabens such as butylparaben, propylparaben and ethylparaben, paraoxybenzoic acid ester, sodium benzoate, cetylpyridinium chloride, isopropylmethylphenol, potassium sorbate and the like.

  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 fragrances such as absolute rose and orange flower, and fragrances that have been processed (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder fragrance, etc.), and Menthol, Carvone, Anethole, Cineol, Methyl salicylate , Synamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramentane-3-carboxamide, pinene, octylaldehyde , Citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, hexanal, propyl alcohol, butanol, isoamyl Alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, methyl lactate, ethylthioacete Toothpaste composition such 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 known fragrance | flavor raw material used can be used, It is not limited to the fragrance | flavor of an Example.

  Moreover, although a compounding quantity is not specifically limited, It is preferable to use said fragrance | flavor raw material 0.000001 to 1% in a formulation composition. Moreover, as a fragrance | flavor for fragrance | flavor which uses the said fragrance | flavor raw material, it is preferable to use 0.1 to 2.0% in a formulation composition.

  Examples of the colorant include Blue No. 1, Blue No. 4, Green No. 3, and the like. In addition, the compounding quantity of these components can be made into a normal quantity in the range which does not prevent the effect of this invention.

  Examples of the storage stabilizer include vitamin C, vitamin E, sodium sulfite, sodium pyrosulfite, sodium hydrogen sulfite, butylhydroxytoluene, propyl gallate, and butylhydroxyaryl.

  As various active ingredients, in addition to ascorbic acid phosphate ester salts, for example, fluorine compounds such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, sodium monofluorophosphate, potassium salt of orthophosphoric acid Water-soluble phosphate compounds such as sodium salt, tranexamic acid, epsilon-aminocaproic acid, allantoin, allantochlorohydroxyaluminum, hinokitiol, ascorbic acid, sodium chloride, dl-tocopherol acetate, coenzyme Q10, dihydrocholesterol, α-bisabolol , Chlorhexidine salts, triclosan, hinokitiol, isopropylmethylphenol, sanguinarine extract azulene, glycyrrhetin, glycyrrhetinic acid, copper chlorophyllin sodium, chlorophyll, g Chelating phosphate compounds such as cellophosphate, copper compounds such as copper gluconate, aluminum lactate, strontium chloride, potassium nitrate, aluminum lactate, berberine, hydroxamic acid and its derivatives, pyrophosphate, tripolyphosphate, zeolite, methoxyethylene, Maleic anhydride copolymer, polyvinylpyrrolidone, epidihydrocholesterin, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, sodium chloride, dihydrocholesterol, trichlorocarbanilide, zinc citrate, dextranase, mutanase, protease In addition, extracts such as soft extract of sugar beet, extract of buckwheat, chamomile, clove, rosemary, hornon, safflower and the like can be blended within a range not impeding the effect of the present invention.

  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 composition for oral cavity can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used.

  EXAMPLES Hereinafter, although an experiment example and an Example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the blending amount is mass%.

[Experimental Example 1]
Dentifrice compositions having the compositions shown in Tables 1 to 3 were prepared by the following production method.
Manufacturing method of dentifrice composition:
(1) A phase was prepared by mixing and dissolving water-soluble components (excluding binder and propylene glycol) in purified water at room temperature.
(2) A phase B in which a binder was dispersed at room temperature in propylene glycol was prepared.
(3) B phase was added and mixed in A phase under stirring, and C phase was prepared.
(4) In phase C, ingredients other than water-soluble ingredients such as fragrances and abrasives are mixed at room temperature using a 1.5 L kneader (manufactured by Ishiyama Kogakusho), defoamed under reduced pressure, and a dentifrice composition 1.2 kg was obtained.
In addition, 20% aqueous solution was prepared for sodium hydroxide as an alkali agent, and the initial pH at 25 ° C. of the dentifrice composition was added to 8.0 to 9.5. The amount of sodium hydroxide in the table is shown in terms of pure content.

  The dentifrice composition produced as described above was prepared by laminating a 26 mm diameter laminated tube (LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30, thickness 257 μm) whose innermost layer is made of linear low density polyethylene. (Dai Nippon Printing Co., Ltd.) was filled with 60 g, and the pH after 3 minutes at the initial 25 ° C. and the pH after 3 minutes at 25 ° C. after storage for 1 month at 25 ° C. It dispensed and measured in the container (measuring instrument: METTLER TOLEDO MP220, electrode: METTLER TOLEDO InLab 410).

The abbreviations and names in the layer structure of the laminated tube used are as follows, and the numbers following the abbreviations indicate the thickness (μm) of each layer.
LDPE: Low density polyethylene white LDPE: White low density polyethylene LLDPE: Linear low density polyethylene AL: Aluminum PET: Polyethylene terephthalate EMAA: Ethylene / methacrylic acid copolymer resin

  About the obtained dentifrice composition, the storage stability of ascorbic acid-2-phosphate magnesium (hereinafter abbreviated as APM) or sodium ascorbate after storage at 40 ° C. for 6 months is measured by liquid chromatography. The evaluation was as follows.

Storage stability of APM or sodium ascorbate:
About the dentifrice composition shown to Tables 1-3, it preserve | saved for 6 months in a -5 degreeC and a 40 degreeC thermostat. After leaving this to reach room temperature, the content of APM or sodium ascorbate was quantified by the following method to evaluate the storage stability.

<Quantitative APM>
Weighed 0.1 g of each dentifrice composition, added 10 mM phosphate buffer (pH 7), stirred vigorously for 20 minutes, and made up to 10 mL. A part of this solution was taken and filtered with a pretreatment filter, and then high performance liquid chromatography (pump: JASCO PU1580, autosampler: Shimadzu Corporation SIL-10A, UV detector: Shimadzu Corporation SPD-6A, Using a recording apparatus: Shimadzu Corporation C-R4A), the quantitative determination was performed by the absolute calibration curve method. The mobile phase is a mixture of 25 mM potassium dihydrogen phosphate + 5 mM tetrabutylammonium / acetonitrile = 91/9. The stationary phase is a stainless tube with a diameter of about 4.6 mm and a length of about 150 mm filled with 5 μm of octadecylsilylated silica gel for liquid chromatography. Column (example: TSK-gel ODS-80Ts (manufactured by Tosoh Corporation)), column temperature of about 40 ° C., detection wavelength of 240 nm, flow rate of 0.8 mL / min, and APM retention time of about 7 minutes. APM in a 40 degreeC preservation | save goods was computed, and the residual rate when content of APM in a -5 degreeC preservation | save goods was made into 100% was calculated | required.

<Quantitative determination of sodium ascorbate>
10 g of the dentifrice composition shown in Comparative Example 1 of Table 2 was weighed, 10 mM phosphate buffer (pH 7) was added, and the mixture was vigorously stirred for 20 minutes, and then made up to 50 mL. When 10 mL of this solution is used to measure the sodium ascorbate content in the dentifrice composition according to the cosmetic raw material standard sodium ascorbate determination method, and the content of sodium ascorbate in the -5 ° C stored product is 100% The residual rate of was determined.

<Score of storage stability of APM and sodium ascorbate>
○: Residual rate of APM or sodium ascorbate in dentifrice composition stored at 40 ° C for 6 months is 90% or more ×: APM or sodium ascorbate in dentifrice composition stored at 40 ° C for 6 months Remaining rate is less than 90%

[Experiment 2]
Gingivitis prevention effect:
The dentifrice compositions shown in Tables 1 to 3 were prepared by the above method and stored for 1 week at 40 ° C., followed by a one-week use test using the dentifrice composition to prevent gingivitis. Was observed. That is, 45 healthy people are divided into 9 groups of 5 people, and each group takes one of the following dentifrices of the sample groups (i) to (ix) for one week. After that, the oral cavity cleaning was stopped for 3 days, and the state of the gingival marginal part of the upper and lower jaws of the anterior teeth was observed and evaluated as follows. In addition, the interval between each dentifrice was used for 1 week or more.

Samples used by each group (Each sample is used in sequence, and each sample is evaluated.)
(I) Example 1, Example 10, Comparative Example 1
(Ii) Example 2, Example 11, Comparative Example 2
(Iii) Example 3, Example 12, Comparative Example 3
(Iv) Example 4, Example 13, Comparative Example 4
(V) Example 5, Example 14, Comparative Example 5
(Vi) Example 6, Example 15, Comparative Example 6
(Vii) Example 7, Example 16, Comparative Example 7
(Viii) Example 8, Example 17, Comparative Example 8
(Ix) Example 9, Example 18, Comparative Example 9

<Evaluation criteria for preventing gingivitis>
Gingivitis was observed: Inflammation symptoms such as redness and swelling of the gingival margin were observed. Gingivitis was not observed: No inflammation symptoms were observed in the gingival margin. Means that gingivitis was not recognized, and the score of gingivitis prevention effect was evaluated by the ratio of the number of people who did not recognize gingivitis, that is, the number of people who recognized gingivitis prevention effect.
<Score>
○: Number of people with gingivitis prevention effect 4-5 people ×: Number of people with gingivitis prevention effect 0-3

[Experiment 3]
No irritation in the oral cavity:
Regarding the dentifrice compositions shown in Tables 1 to 3, an appropriate amount was taken on a toothbrush and brushed for about 3 minutes by 10 subjects with sensitive oral mucosa. After completion of dentifrice, each subject was asked to perform sensory evaluation on the following criteria for the degree of stimulation in the oral cavity during and after dentifrice, and the average value was obtained. In addition, the sample of the comparative example 2 was used as a control sample, and it evaluated on the basis of this.

<Evaluation criteria for lack of oral irritation>
4 points: No stimulation at all 3 points: Stimulation is weak compared to the control sample 2 points: Stimulation is slightly weaker than the control sample 1 point: Stimulation is equivalent or strong compared to the control sample <Score>
A: Average point of non-stimulation in the oral cavity 3.5 points to 4.0 points or less ○: Average point of non-stimulation in the oral cavity 3.0 points to less than 3.5 points Δ: Stimulation in the oral cavity Average score of 2.0 or more and less than 3.0 points ×: average score of no irritation in the oral cavity less than 2.0 points

[Experimental Example 4]
Evaluation of bitterness and astringency in the oral cavity:
With respect to the dentifrice compositions shown in Tables 1 to 3, an appropriate amount was taken on a toothbrush by 10 subjects and brushed for about 3 minutes. After completion of dentifrice, each subject was asked to perform sensory evaluation on the following criteria for the degree of bitterness and astringency during and after dentifrice, and the average value was obtained. In addition, the sample of the comparative example 2 was used as a control sample, and it evaluated on the basis of this.

<Evaluation criteria for bitterness and astringency in the oral cavity>
4 points: no bitterness or astringency 3 points: bitterness or astringency is weak compared to the control sample 2 points: bitterness or astringency is slightly weaker than the control sample 1 point: compared to the control sample Bitterness and astringency are the same, or bitterness and astringency are strong.
◎: Average score of bitterness and astringency in the oral cavity 3.5 points to 4.0 points or less ○: Average score of bitterness and astringency in the oral cavity 3.0 points to less than 3.5 points Δ: Average score of bitterness and astringency in the oral cavity 2.0 points to less than 3.0 point ×: Average score of bitterness and astringency in the oral cavity Less than 2.0 points

  The results are shown below. In addition, the numerical value showing the compounding quantity in Tables 1-3 is all the mass%.

(1) APM: Wako Pure Chemical Industries, Ltd. For biochemistry (2) Trimethylglycine: Ajinomoto Co., Inc. Aqua Duou AN-100
(3) Precipitating silica: Examples 1 to 5 TIXOSIL 73 manufactured by Rhodia
(5 mass% water slurry pH: 8.0)
(4) Zirconosilicate: Examples 6 to 9 Taki Chemical Co., Ltd.
(5 mass% water slurry pH: 9.5)
(5) Sodium hydroxide: Kominato Pharmaceutical Co., Ltd.

＊；アスコルビン酸ナトリウムの保存安定性

*: Storage stability of sodium ascorbate

(1) APM: Wako Pure Chemical Industries, Ltd. For biochemistry (2) Sodium ascorbate: Wako Pure Chemical Industries, Ltd.
(3) Trimethylglycine: Ajinomoto Co., Inc. Aqua Duo AN-100
(4) Precipitating silica: Comparative Examples 1, 2, 5 TIXOSIL 73 manufactured by Rhodia
(5 mass% water slurry pH: 8.0)
(5) Zirconosilicate: Comparative Examples 6-9 Taki Chemical Co., Ltd.
(5 mass% water slurry pH: 9.5)
(6) Aluminum hydroxide: Comparative Example 3 Showa Denko K.K.
(7) Calcium hydrogen phosphate: Comparative Example 4 Tosoh Corporation
(8) Sodium hydroxide: Kominato Pharmaceutical Co., Ltd.

  From Tables 1 and 2, the dentifrice composition lacking any of the essential requirements of the present invention (Comparative Examples 1 to 9) is inferior in APM stability and gingivitis-preventing effect, irritation and bitterness during and after dentifrice. The dentifrice composition of the present invention (Examples 1 to 9) is excellent in APM stability and gingivitis-preventing effect, and irritation during and after dentifrice. It was confirmed that the bitterness and astringency were improved.

(1) APM: Wako Pure Chemical Industries, Ltd. For biochemistry (2) Trimethylglycine: Ajinomoto Co., Inc. Aqua Duou AN-100
(3) Precipitating silica: Examples 10 to 14 TIXOSIL 73 manufactured by Rhodia
(5 mass% water slurry pH: 8.0)
(4) Zirconosilicate: Examples 15 to 18 Taki Chemical Co., Ltd.
(5 mass% water slurry pH: 9.5)
(5) Sodium hydroxide: Kominato Pharmaceutical Co., Ltd.
(6) Sodium hyaluronate: Wako Pure Chemical Industries, Ltd.
(7) Sodium chondroitin sulfate: Wako Pure Chemical Industries, Ltd.

  From Table 3, it was found that by adding the acidic mucopolysaccharide, it was possible to further improve the irritation and the bitterness and astringency of the dentifrice composition during and after dentifrice.

Claims (3)

(A) To dentifrice composition in which ascorbic acid phosphate ester salt is blended, (C) 5 to 40 mass of silica abrasive with pH of 7.5 to 11.0 at 25 ° C. of 5 mass% water slurry. % while blended, blended to an extent the (B) .02 to 3.0 trimethylglycine 0.1 to 15 wt%, as the component (B) / (C) proportion of component mass ratio, and (D) blending alkali agent, dentifrice composition characterized in that a 8.0 to 9.5 a pH in the initial pH and 25 ° C. after storage for one month at 25 ° C. of the composition.   The dentifrice composition according to claim 1, further comprising (E) at least one acidic mucopolysaccharide. And (E) chondroitin sulfate, chondroitin polysulfate, heparin, heparan sulfate, keratosulfuric acid, keratopolysulfuric acid, and at least one acidic mucopolysaccharide selected from alkali metal salts and alkaline earth metal salts thereof. The dentifrice composition according to claim 1.