JP5526619B2 - Toothpaste composition - Google Patents

Description

The present invention has excellent gingivitis has a preventive effect and halitosis preventive effect, to smoothness and toothpaste composition excellent in taste during use of the composition surface.

  Periodontal disease is an infection caused by bacteria, mainly obligate anaerobic gram-negative bacilli such as P. gingivalis, and the cause of bad breath is such as Fusobacterium nucleatum. Oral bacteria are involved. Therefore, as an effective means for preventing and improving periodontal disease and bad breath, it is considered useful to maintain plaque control, that is, keep the number of pathogenic bacteria in the oral cavity at a low level.

  As a means for reducing the number of pathogenic bacteria in the oral cavity, it is an effective means to add a poorly water-soluble bactericidal agent or a cationic bactericidal agent to an oral care product. Since a poorly water-soluble disinfectant has a characteristic that the antibacterial spectrum tends to be wide, it has been proposed to be blended into a dentifrice composition (see Patent Documents 1 to 4).

  However, various factors are involved in the development of periodontal disease, and it may not be possible to actually exhibit an excellent preventive effect simply by adding such a poorly water-soluble fungicide having bactericidal activity.

  On the other hand, in recent years, ascorbic acid phosphate ester salt has attracted attention as an antioxidant vitamin that eliminates excessive active oxygen produced in the living body and protects living tissue from oxygen injury. Furthermore, ascorbic acid phosphate ester salt has various physiological activities and is known to be effective in the prevention and treatment of gingivitis and periodontitis in the oral cavity field. Attempts have been made to blend into compositions (see Patent Documents 5 and 6).

As a means for improving the periodontal disease prevention effect, the applicant applied a composition in which ascorbic acid or a derivative thereof and an antiplasmin agent were used in combination, a vitamin E or a derivative-containing composition, a nonionic surfactant and an ascorbic acid derivative or a salt thereof. The composition (patent documents 7 and 8) with which the effect of vitamin E or its derivative lasts was proposed. Japanese Patent Application Laid-Open No. 2009-149565 proposed a composition in which ascorbic acid phosphate ester or a salt thereof was combined with ε-aminocaproic acid and / or tranexamic acid.

  However, as the applicant further researched, when ascorbic acid phosphate or a salt thereof was combined with vitamin E or a derivative thereof, or ε-aminocaproic acid and / or tranexamic acid, a certain periodontal disease prevention effect was recognized. However, the effect of reducing the number of pathogenic bacteria, which is the main cause, is not satisfactorily recognized, and a new technology capable of obtaining a composition that exhibits a higher periodontal disease prevention effect and halitosis prevention effect is strongly desired. .

  Under these circumstances, it is known that the prevention and improvement effect of gingivitis is improved by using an ascorbic acid phosphate ester salt, an antiplasmin agent and an antibacterial agent together (see Patent Document 7).

  In addition, many researches have been made on techniques for fully exhibiting the effects of poorly water-soluble antibacterial agents such as isopropylmethylphenol, and the knowledge that the bactericidal effect is improved by adding a nonionic surfactant is described. (See Patent Documents 1, 3, and 9).

  However, when the present inventors examined, when the ascorbic acid phosphate salt, isopropylmethylphenol and the nonionic surfactant were blended at the same time, the stability of the ascorbic acid phosphate salt decreased with time. It has been found that there is a problem that satisfactory effects of preventing periodontal disease and bad breath are not sufficiently observed, and further, particles are formed on the surface of the composition, resulting in a problem of smoothness.

JP 2003-292426 A Japanese Patent Laid-Open No. 2004-250381 JP 2005-179266 A JP 2008-115115 A JP-A-2-292211 JP-A-3-294227 JP-A-11-011422 JP 2004-323488 A JP 59-101417 A

  Therefore, as described above, there is still room for improvement in the prevention or improvement effect of periodontal disease and bad breath in the conventional technology, and in view of the above circumstances, the present invention is ascorbic acid phosphate ester and salt thereof, isopropylmethylphenol and When blending nonionic surfactants, maintaining the stability of ascorbic acid phosphate or its salt after long-term storage, it is derived from ascorbic acid phosphate or its salt and isopropylmethylphenol even after long-term storage. An object of the present invention is to provide a dentifrice composition that can effectively develop the effect, can effectively prevent or improve gingivitis and bad breath, and is excellent in the smoothness and feel of use of the composition surface.

As a result of intensive studies to achieve the above object, the inventors of the present invention have (A) ascorbic acid phosphate ester or salt thereof, (B) isopropylmethylphenol, and (C) an alkyl group having 14 to 14 carbon atoms. 18 and at least one nonion selected from polyoxyethylene alkyl ether having an average addition mole number of ethylene oxide of 2 to 20 moles and polyoxyethylene hydrogenated castor oil having an average addition mole number of ethylene oxide of 5 to 30 moles Active surfactant, (D) chelating agent, (E) alkaline agent, (D) / (A) mass ratio is 0.2 to 3.5 , and initial pH at 25 ° C. is 8. By being 0-9.3, the stability of ascorbic acid phosphate ester or a salt thereof after storage over a long period can be satisfactorily maintained, and pathogenicity in the oral cavity High bactericidal power against bacteria can also be maintained, and as a result, synergistic gingivitis and bad breath can be prevented or improved by ascorbic acid phosphate or a salt thereof and isopropylmethylphenol, and the composition surface is smooth ( excellent smoothness) of the kneading surface and found that toothpaste composition having good usability without off-taste from the chelating agent is obtained, leading to completion of the present invention.

  That is, according to the present invention, the chelating agent captures the metal in the composition even if the ascorbic acid phosphate ester or a salt thereof, isopropylmethylphenol and a nonionic surfactant are blended at the same time in the above configuration. In addition, ascorbic acid phosphate ester or a salt thereof can be stably retained after long-term storage, and furthermore, high bactericidal power against oral pathogenic bacteria that cause bad breath such as Fusobacterium nucleatum can also be retained. In such a dentifrice composition of the present invention, the effect of preventing gingivitis and bad breath derived from ascorbic acid phosphate ester or a salt thereof and isopropylmethylphenol is synergistically produced, and further particles are formed on the surface of the dentifrice composition. Can solve the problem of poor smoothness. Such an effect of the present invention is exhibited by combining the above-mentioned components and blending them in an appropriate blending amount and ratio, as will be understood from the examples described later, and is indispensable for any of the present invention. It is a special case that cannot be achieved if the ingredients are missing or the amount and ratio of each ingredient is inappropriate.

  In addition, as for the applicant, in Japanese Patent Application No. 2009-136994, ascorbic acid phosphate ester or a salt thereof, vitamin E or a derivative thereof, a suitable polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether or alkyl glucoside, By blending a nonionic or cationic fungicide at an appropriate blending amount and blending ratio, ascorbic acid phosphate or a salt thereof, vitamin E or a derivative thereof and a fungicide are blended stably at the same time. We have proposed a composition for oral cavity that has a high effect of improving the bad breath and gingival crevice exudate from diseases and a bactericidal effect against periodontal disease-causing bacteria, and also has good appearance (separation) stability. Ascorbic acid phosphate or a salt thereof, vitamin E or a derivative thereof, and a bactericidal agent are stably blended at the same time, and the above-described excellent Effects are those which expressed, the present invention differs from the art. In the present invention, (A) ascorbic acid phosphate or a salt thereof, (B) isopropylmethylphenol, (C) a specific nonionic surfactant, (D) a chelating agent, and (E) an alkali agent It is important to add vitamin E or a derivative thereof, and it is possible to maintain the stability of the ascorbic acid phosphate ester or a salt thereof even if it is not added, and the surface of the dentifrice is excellent in smoothness. The above-mentioned special effects are achieved.

Accordingly, the present invention provides a toothpaste composition below.
Claim 1;
(A) Ascorbic acid phosphate or a salt thereof,
(B) isopropylmethylphenol,
(C) Polyoxyethylene alkyl ether having an alkyl group with 14 to 18 carbon atoms and an average addition mole number of ethylene oxide of 2 to 20 moles, and polyoxyethylene curing with an average addition mole number of ethylene oxide of 5 to 30 moles At least one nonionic surfactant selected from castor oil,
(D) a chelating agent,
(E) An alkaline agent is blended, the component (A) is 0.1 to 2% by mass, the component (B) is 0.01 to 0.5% by mass, and the component (D) is 0.05 to 2% by mass. % containing, (D) / weight ratio of (a) is 0.2 to 3.5 toothpaste composition characterized by an initial pH of 8.0 to 9.3 at 25 ° C..
Claim 2;
Chelating agent, citric acid, pyrophosphoric acid, tripolyphosphate, and toothpaste composition of claim 1, wherein those selected from alkali metal salts thereof.
Claim 3;
The nonionic surfactant of component (C) is an average added mole number of polyoxyethylene alkyl ether and ethylene oxide in which the carbon number of the alkyl group is 14 to 18 and the average added mole number of ethylene oxide is 2 to 20 moles. The dentifrice composition according to claim 1 or 2, which is 5 to 30 mol of polyoxyethylene hydrogenated castor oil.
Claim 4 ;
Component (C) 0.3 to 5 wt%, according to claim 1, 2 or 3 toothpaste composition according to 0.01 to 1.0% by weight of component (E).

  The dentifrice composition of the present invention exhibits excellent gingivitis prevention effect and bad breath prevention effect after long-term storage, has high stability of ascorbic acid phosphate ester or salt thereof, and also has bactericidal power against oral pathogenic bacteria It is high, excellent in the smoothness of the surface of the composition, has almost no off-taste, and has a good feeling of use, and is effective in preventing or improving periodontal diseases.

Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention comprises (A) ascorbic acid phosphate or salt thereof, (B) isopropylmethylphenol, (C) an alkyl group having 14 to 18 carbon atoms, and an average added mole number of ethylene oxide. At least one nonionic surfactant selected from polyoxyethylene alkyl ethers having 2 to 20 moles and polyoxyethylene hydrogenated castor oil having an average addition mole number of ethylene oxide of 5 to 30 moles, (D) chelate agent, (E) containing an alkali agent, (D) / in (a) of 0.2 to 3.5 toothpaste, wherein the initial pH is 8.0 to 9.3 at 25 ° C. Agent composition.

  As (A) ascorbic acid phosphate used here, one or two or more hydroxyl groups at any of the 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, ascorbic acid-3-phosphate, ascorbic acid-6-phosphate, ascorbic acid-2-polyphosphate, etc., and salts thereof Examples thereof 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 amount of ascorbic acid phosphate or a salt thereof is 0.1 to 2% (mass%, the same applies hereinafter), particularly 0.2 to 1%, based on the total amount of the composition. When the amount is less than 0.1%, the effect of preventing gingivitis is not sufficiently exhibited . If it exceeds 2%, not only will the effect not be improved, but the feeling of use will be reduced, such as the occurrence of off-flavors .

  (B) Isopropylmethylphenol is 1-hydroxy-4-isopropyl-3-methylphenol, and commercially available products such as those sold by Osaka Kasei Co., Ltd. under the trade name Biosol can be used.

The blending amount of isopropylmethylphenol is preferably 0.01 to 0.5%, particularly 0.03 to 0.2%, based on the total amount of the composition. When the amount is less than 0.01%, a sufficient bactericidal effect is not exhibited . When the content exceeds 0.5%, a feeling of use is lowered, for example, a nasty taste occurs, and a problem arises in terms of storage stability .

  In the present invention, (C) a polyoxyethylene (hereinafter abbreviated as POE) alkyl ether having 14 to 18 carbon atoms and an average added mole number of ethylene oxide of 2 to 20 moles, and ethylene oxide. At least one nonionic surfactant selected from POE hydrogenated castor oil having an average addition mole number of 5 to 30 moles is blended.

  Carbon number of the alkyl group of POE alkyl ether is 14-18, More preferably, it is 16-18. When the number of carbon atoms of the alkyl group is less than 14 or greater than 18, the sufficient bactericidal effect is not exhibited. Specific examples of such POE alkyl ethers include POE cetyl ether, POE myristyl ether, and POE stearyl ether, with POE stearyl ether being particularly preferred. Further, the average addition mole number of EO of the POE alkyl ether is in the range of 2 to 20 moles, preferably 3 to 10 moles, more preferably 5 to 10 moles, and when the average addition mole number is less than 2 moles, When it is larger than 20 mol, a sufficient bactericidal effect may not be exhibited. Such POE alkyl ethers are commercially available products such as EMALEX 102, 103, 105, 107, 110, 112, 115, 117, 120, 602, 603, 605, 608, 611, 615, 620, etc., from Nippon Emulsion Co., Ltd. Can be used.

  The average added mole number of EO of POE hydrogenated castor oil is 5 to 30 mol, preferably 10 to 30 mol, more preferably 20 to 30 mol. When the average added mole number of EO is smaller than 5 moles or larger than 30 moles, a sufficient bactericidal effect may not be exhibited. As such POE hydrogenated castor oil, commercially available products such as NIKKOL HCO-5, HCO-10, HCO-20, and HCO-30 from Nikko Chemicals Co., Ltd. can be used.

  As the component (C), the aforementioned POE alkyl ether or POE hydrogenated castor oil may be blended, or two or more selected from POE alkyl ether and POE hydrogenated castor oil may be blended. It is particularly preferable to use together POE stearyl ether having an average added mole number of 5 to 10 moles and POE hydrogenated castor oil having an average added mole number of EO of 20 to 30 moles.

  The total amount of these POE alkyl ethers and / or POE hydrogenated castor oil is preferably 0.3 to 5%, more preferably 0.5 to 2%, based on the total amount of the composition. If the blending amount is less than 0.3%, there may be a problem with the stability of isopropylmethylphenol after long-term storage, and the sufficient bactericidal effect may not be exhibited. May cause problems.

  The chelating agent (D) used in the present invention captures metal ions in the composition, thereby preventing the ascorbic acid phosphate ester or salt thereof from becoming an insoluble precipitate, and stably exhibiting the effect of the composition. I think that As chelating agents, specifically those having a carboxyl group, citric acid, tartaric acid, malic acid, succinic acid, gluconic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc., and alkali metal salts such as sodium salts and potassium salts thereof Examples of those having a phosphate group include condensed phosphoric acid such as pyrophosphoric acid and tripolyphosphoric acid, phytic acid, and alkali metal salts such as sodium salt and potassium salt thereof. Acid, tripolyphosphoric acid and sodium and potassium salts thereof are preferably used.

The amount of the chelating agent is preferably 0.05 to 2%, particularly 0.1 to 0.8%, based on the total amount of the composition. When the amount is less than 0.05%, the effect of improving the smoothness of the dentifrice surface is not sufficiently exhibited, also, it can not be maintained stable ascorbic acid phosphoric acid ester or its salt. If it exceeds 2%, a nasty taste occurs .

The blending ratio of the component (D) to the component (A) is such that the mass ratio of (D) / (A) is 0.2 to 3.5 in order to maintain the effectiveness, stability and usability of the composition. In particular, 0.3 to 3.5 is preferable. When (D) / (A) in the dentifrice composition is less than 0.10, the stability of the ascorbic acid phosphate ester or its salt after long-term storage cannot be maintained, and when it exceeds 4.0 , occurs off-taste from the chelating agent, the present invention effects not have such a sufficiently exhibited.

  (E) Although the alkali agent generally used can be used for (E) alkali agent, sodium hydroxide and potassium hydroxide can be used conveniently and sodium bicarbonate, a triethanolamine, etc. can also be used preferably.

  The blending amount of the alkaline agent is preferably 0.01 to 1.0% with respect to the total amount of the composition. When the blending amount is less than 0.01%, there may be no effect of raising the initial pH above 8.0. When the blending amount exceeds 1.0%, there is a problem with the smoothness of the surface of the dentifrice and the taste during use. There is.

  In order to maintain the stability and effectiveness of ascorbic acid phosphate ester or a salt thereof, the pH of the dentifrice composition has an initial pH at 25 ° C. of 8.0 to 9.3, preferably 8.0 to 9 .0. If the initial pH at 25 ° C. in the dentifrice composition is less than 8.0, the stability of the ascorbic acid phosphate ester or a salt thereof may not be maintained, and the gingivitis prevention effect and the bad breath prevention effect may not be sufficiently exhibited. In addition, when the initial pH and the pH at 25 ° C. after storage exceeds 9.3, the stability of ascorbic acid phosphate ester or a salt thereof cannot be maintained, and gingivitis prevention effect and bad breath prevention effect are not sufficiently exhibited. Or the user may experience a nasty taste during or after dentifrice.

Dentifrice composition of the present invention are prepared as tooth paste, within a range not to impair the effects of the present invention can be blended with other known additives as optional components in addition to the above essential components. That is, the abrasives, binders, thickeners, moisturizers, surfactants, sweeteners, preservatives, fragrances, coloring agents, storage stabilizers, medicinal ingredients, etc. Ingredients may be blended.

  As an abrasive, a commonly used abrasive can be blended within a range that does not impair the effects of the present invention. For example, generally used anhydrous silicic acid can be blended, and specifically, hydrogen phosphate for dentifrice. Examples include calcium, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, alumina, magnesium carbonate, tribasic magnesium phosphate, insoluble sodium metaphosphate, insoluble potassium metaphosphate, titanium oxide, and synthetic resin-based abrasives. Is preferred. The blending amount of the abrasive is usually preferably 2 to 40%, particularly 10 to 25% with respect to the total amount of the composition.

  As the binder, cellulose derivatives such as carboxymethyl cellulose, gums such as xanthan gum, tragacanth gum, karaya gum, arabic gum, polyvinyl alcohol, carboxyvinyl polymer such as cross-linked sodium polyacrylate and 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 amount of the binder is usually 0.2 to 10% of the composition.

  Examples of the thickener include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, sorbit, xylit, malt, lactit, polyethylene glycol having an average molecular weight of 200 to 6,000, ethylene glycol, and reduced starch sugar compound. These compounding amounts are usually 5 to 50%, particularly 20 to 45% of the whole composition.

  As the surfactant, in addition to the component (C), other nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants 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 Examples thereof include polyhydric alcohol fatty acid esters such as fatty acid esters, ether type surfactants such as polyoxyethylene polyoxypropylene copolymers and polyoxyethylene alkylphenyl ethers, and fatty acid alkanolamides such as lauric acid diethanolamide. Examples of the cationic surfactant include alkyl ammonium and alkyl benzyl ammonium salts. Examples of amphoteric surfactants include betaine acetate, imidazolinium betaine, and lecithin. The blending amount of these surfactants is usually 0.2 to 15%, preferably 0.5 to 10% of the composition, and the total blending amount with the (C) component is 0.3 to 15%. Is preferred.

  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, 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 Fragrances, natural roses such as absolute rose, orange flower, etc., and fragrances processed by these natural fragrances (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-mentoxypropane-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, allylcyclohexane 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, ethylthioacetate Used in dentifrice compositions 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 perfume material can be used. 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, sodium sulfite, sodium pyrosulfite, sodium hydrogen sulfite, butylhydroxytoluene, propyl gallate, and butylhydroxyaryl.

  Various active ingredients include: fluorides such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, sodium monofluorophosphate, and water-soluble phosphate compounds such as orthophosphoric acid potassium salt and sodium salt. Allantoin, allantoin chlorohydroxyaluminum, hinokitiol, ascorbic acid, sodium chloride, coenzyme Q10, dihydrocholesterol, α-bisabolol, chlorhexidine salts, triclosan, hinokitiol, sanguinarine extract, azulene, glycyrrhetin, glycyrrhetinic acid, copper chlorophyllin sodium, chlorophyll, Chelating phosphate compounds such as glycerophosphate, copper compounds such as copper gluconate, aluminum lactate, strontium chloride, potassium nitrate, aluminum lactate, bell Phosphorus, hydroxamic acid and its derivatives, zeolite, methoxyethylene, maleic anhydride copolymer, polyvinylpyrrolidone, epidihydrocholesterine, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, sodium chloride, dihydrocholesterol, trichlorocarbanilide Extracts from plants such as zinc citrate, dextranase, mutanase, protease, etc., soft extract of sugar beet, duckweed extract, chamomile, clove, rosemary, hornon, safflower, etc. Can be added in an effective amount.

  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 experimental example, an Example, a comparative example, and a formulation 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.

In addition, the dentifrice composition of the composition shown to Tables 1-4 was prepared with the following manufacturing 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 to prepare C phase.
(4) Ingredients other than water-soluble ingredients such as fragrances and abrasives in phase C are mixed at room temperature using a 6 L kneader (manufactured by Ishiyama Kogakusho), defoamed under reduced pressure (4 kPa), and dentifrice composition 5 kg Got.
Sodium hydroxide as an alkaline agent was added in a 20% aqueous solution so that the initial pH of the dentifrice composition at 25 ° C. was 8.0 to 9.3. The amount of sodium hydroxide in the table is shown in terms of pure content.

  The dentifrice composition produced as described above was laminated tube (LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30) whose innermost layer is made of linear low-density polyethylene and has a diameter of 26 mm and an aperture of 8 mm. , With a thickness of 257 μm (Dai Nippon Printing Co., Ltd.) was filled, and the initial pH after 3 minutes at 25 ° C. was dispensed into a 20 mL plastic container and measured (measuring instrument: METTLER TOLEDO) ) MP220, electrode: METTLER TOLEDO Co., Ltd. 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

[Experimental Example 1] Evaluation of bactericidal power after storage at 40 ° C for 6 months After preparing the dentifrice composition (toothpaste) shown in Tables 1 to 4, it was stored in a constant temperature bath at 40 ° C for 6 months. did. After storage, this was allowed to stand at room temperature, 10 g of each dentifrice composition was weighed, artificial saliva (30 mL) was added and stirred, then centrifuged (10,000 rpm, 20 min), and the resulting supernatant was collected. The sample stock solution was used. After 2 mL of the sample stock solution was allowed to act on 2 mL of the oral bacterial dispersion (Fusobacterium nucleatum ) previously cultured in artificial saliva and adjusted to turbidity (OD ₆₆₀ ) = 1 at a wavelength of 660 nm for 30 seconds 50 microliters was fractionated and used as a bactericidal power evaluation sample, and the bactericidal power was evaluated by the following method.

Bactericidal evaluation;
Each bactericidal activity evaluation sample solution (50 μL) was added to THB liquid medium (4 mL), cultured (8 hours at 37 ° C.), and then the amount of proliferated bacteria was measured using turbidity (OD ₆₆₀ ) as an index. Smaller ones were evaluated as having higher sterilizing power.
As artificial saliva, 3.73 g of potassium chloride, 0.14 g of potassium dihydrogen phosphate, 0.15 g of calcium chloride dihydrate, and 0.02 g of magnesium chloride hexahydrate were purified. Dissolved in water and adjusted to pH 7 with potassium hydroxide to a volume of 1,000 mL was used.
Grades;
◎: Turbidity (OD ₆₆₀ ) less than 1.0 ○: Turbidity (OD ₆₆₀ ) 1.0 or more and less than 2.0 ×: Turbidity (OD ₆₆₀ ) 2.0 or more

Experimental Example 2 Ascorbic acid-2-phosphate magnesium (hereinafter abbreviated as APM) or sodium ascorbyl-2-phosphate (hereinafter abbreviated as APS) after storage at 40 ° C. for 6 months. ) Or storage stability of sodium ascorbate After preparing the dentifrice compositions shown in Tables 1 to 4, they were stored in a thermostatic bath at −5 ° C. and 40 ° C. for 6 months. The stored product at −5 ° C. was used as a control product without decomposition. This was allowed to stand at room temperature, and then used for evaluating the storage stability of APM or APS or sodium ascorbate, and evaluated by the following method. All reagents were manufactured by Kanto Chemical.

Quantification of APM or APS;
Weigh 0.1 g of each dentifrice composition and add 10 mmol / L phosphate buffer (1.5 mmol / L potassium dihydrogen phosphate, 23.5 mmol / L dipotassium hydrogen phosphate, pH 8.0), After vigorously stirring for 20 minutes with a shaker, the volume was adjusted to 10 mL. After taking 1 mL of this liquid and filtering with a pretreatment filter, high performance liquid chromatography (pump: JASCO PU1580, autosampler: Shimadzu SIL-10A, UV detector: Shimadzu SPD-6A, recording device: Shimadzu C-R4A ) And was quantified by the absolute calibration curve method. The mobile phase is a 25 mmol / L potassium dihydrogen phosphate + 5 mmol / L tetrabutylammonium / acetonitrile = 91/9 mixture (volume ratio), the column is a stainless steel tube having a diameter of about 4.6 mm and a length of about 150 mm, and a 5 μm liquid chromatograph. A product filled with octadecylsilylated silica gel (for 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 retention of APM or APS The time was about 7 minutes. APM or APS in a 40 degreeC preservation | save goods was computed, and the residual rate when the content of APM in a -5 degreeC preservation | save goods was made into 100% was calculated | required.

Determination of sodium ascorbate;
10 g of the dentifrice composition shown in Table 4 was weighed, 10 mmol / L phosphate buffer (pH 7.2) 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)
○: APM or APS after storage for 6 months at 40 ° C or sodium ascorbate is 90% or more ×: APM or APS after storage for 6 months at 40 ° C or sodium ascorbate Remaining rate is less than 90%

[Experimental Example 3] Gingitis prevention effect after storage at 40 ° C. for 6 months After preparing the dentifrice compositions shown in Tables 1 to 4, the dentifrice composition after storage at 40 ° C. for 6 months A 10-day use test using the product was carried out, and the prevention effect of gingivitis was observed.
That is, 50 healthy people are divided into five groups of 10 people, and each group has about 1 g of the dentifrice composition in one sample group of <1> to <5> below. The condition of the gingival margins of the upper and lower jaws of the anterior teeth when the oral cleaning was stopped for 3 days thereafter was observed and evaluated as follows. In addition, the interval between each dentifrice composition use was opened for one week so that gingivitis disappeared, and the dentifrice composition of the comparative example 20 which does not contain the component which has a gingivitis prevention effect in the meantime was used. Thereafter, the remaining samples were similarly tested. The order of using the dentifrice composition in each group was adjusted to be random.
<1> Examples: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10
Comparative example: 1, 2, 3, 4
<2> Examples: 11, 12, 13, 14, 15 , 16 , 17 , 18
Comparative examples: 5, 6, 7, 8
<3> Examples: 19, 20, 21, 22, 23, 24, 25, 26 , 27
Comparative examples: 9, 10, 11, 12
<4> Examples: 28 , 29, 30, 31, 32, 33, 34, 35, 36 , 37
Comparative examples: 13, 14, 15, 16
<5> Examples: 38, 39, 40, 41, 42, 43, 44, 45 , 46, 47 , 48
Comparative examples: 17, 18, 19

Evaluation criteria for prevention of gingivitis;
Gingivitis was observed: Inflammatory symptoms such as redness and swelling of the gingival margin were observed. Gingivitis was not observed: Rating that no inflammatory symptoms were observed in the gingival margin;
◎: 0 to 1 subjects with gingivitis ○: 2 to 3 subjects with gingivitis △: 4 to 5 subjects with gingivitis Person ×: Number of subjects with gingivitis observed 6-10

[Experimental Example 4] Bad breath prevention effect after storage at 40 ° C for 6 months After preparing the dentifrice composition shown in Tables 1 to 4, the dentifrice composition after storage at 40 ° C for 6 months The bad breath evaluation test using was carried out.
For the evaluation of bad breath, the UBC sensory evaluation method by one expert (odor judge) of odor identification and determination was adopted. Subjects who had an exhalation of 1 hour after only rinsing without brushing their teeth were subject to a score of 2 or less according to the following evaluation criteria, and the average value of bad breath was equal. Were divided into five groups of five. Each group uses about 1 g of the dentifrice composition of one sample group among <1> to <5> sample groups of [Experimental Example 3] to brush the teeth, and then cleans the mouth, eats and drinks The bad breath of each subject was determined when the test was stopped for 2 hours. Thereafter, the remaining samples were similarly tested. The order of using the dentifrice composition in each group was adjusted to be random.
The breath collection method is as follows. First, mouth breathing is performed three times, then the mouth is closed for 1 minute, and only the breath stayed in the mouth is blown to the odor judge through a predetermined plastic pipe. It was evaluated as follows.

Evaluation criteria for bad breath;
4 points: no odor at all 3 points: no odor at all 2 points: some odor is felt
◎: Average point of bad breath 3.5 points or more ○: Average point of bad breath 3.0 points to less than 3.5 points △: Average point of bad breath 2.0 points to less than 3.0 points ×: Average bad breath Point Less than 2.0

[Experimental Example 5] Smoothness evaluation of dentifrice composition surface after storage at 40 ° C for 6 months The dentifrice composition shown in Tables 1 to 4 was extruded 15 cm onto paper and visually dentifrice. It was evaluated whether wrinkles and grains were observed on the kneaded surface of the composition.
Grades;
◎: No wrinkles / grains are observed on the surface of the dentifrice composition ○: Almost no wrinkles / grains are observed on the surface of the dentifrice composition ×: Wrinkles / grains are observed on the surface of the dentifrice composition

[Experimental Example 6] Evaluation of dentifrice of dentifrice For the dentifrice composition shown in Tables 1 to 4, 25 subjects were divided into five groups of five, and each group described above [Experimental Example 3]. ] [1] to <5> of the sample group, the dentifrice composition of one sample group was used at about 1 g per time to brush the teeth. After the completion of brushing, each subject had a sensory evaluation on the following criteria regarding the degree of taste during and after brushing. Thereafter, the remaining samples were similarly tested. The order of use of the dentifrice composition in each group was adjusted to be random.

Evaluation criteria for tastelessness;
4 points: I do not feel any nasty taste 3 points: I do not feel so tasty 2 points: I feel some nasty taste 1 point: A score that feels quite strange taste;
◎: Average point of tastelessness 3.5 points or more ○: Average point of tastelessness 3.0 points to less than 3.5 points △: Average point of tastelessness 2.0 points to 3.0 points Less than x: Average point of tastelessness Less than 2.0 points The results are shown below.

＊：アスコルビン酸ナトリウム（比較品）の保存安定性

*: Storage stability of sodium ascorbate (comparative product)

＊＊：歯肉炎予防効果にかかわる成分を含まない歯磨剤組成物

**: Dentifrice composition that does not contain ingredients related to the prevention of gingivitis

In addition, the component used by said each example is as follows.
1) Ascorbic acid-2-phosphate magnesium: manufactured by Showa Denko KK (ascorbic acid PM)
2) Sodium ascorbate-2-phosphate: DMS Nutrition Japan (Stay C50)
3) Isopropylmethylphenol: Osaka Kasei Co., Ltd. (Biosol)
4) Polyoxyethylene (5) stearyl ether: manufactured by Nippon Emulsion Co. (EMAL
EX605)
5) Polyoxyethylene (10) cetyl ether: manufactured by Nippon Emulsion (EMALE
X110)
6) Polyoxyethylene (20) hydrogenated castor oil: manufactured by Nippon Chemicals Co., Ltd. (NIKKOL)
HCO-20)
7) Polyoxyethylene (30) hydrogenated castor oil: manufactured by Nippon Chemicals Co., Ltd. (NIKKOL)
HCO-30)
8) Citric acid: manufactured by Fuso Chemical Industries, Ltd. 9) Tartaric acid: manufactured by Fuso Chemical Industries, Ltd. 10) Succinic acid: manufactured by Fuso Chemical Industries, Ltd. 11) Malic acid: manufactured by Fuso Chemical Industries, Ltd. 12) Sodium gluconate: manufactured by Fuso Chemical Industries, Ltd. 13) Sodium pyrophosphate: manufactured by Taihei Chemical Industrial Co., Ltd. 14) Sodium tripolyphosphate: manufactured by Taihei Chemical Industrial Co., Ltd. 15) Sodium hydroxide: manufactured by Kominato Pharmaceutical Co., Ltd.

As is clear from the results of Tables 1 to 3, the components (A) to (E) according to the present invention are blended, (D) / (A) is 0.2 to 3.5 , and the initial pH is 8 The dentifrice compositions (Examples 1 to 48 ) of 0.0 to 9.3 have an excellent bactericidal effect and gingivitis preventive effect, and use an ascorbic acid phosphate salt and isopropylmethylphenol in combination. It has a synergistic effect on the prevention of bad breath. In addition, the dentifrice composition of the present invention had no off-taste during use and after use, was excellent in surface smoothness, and was excellent in use feeling and appearance.
On the other hand, as can be seen from the results in Table 4, the dentifrice composition lacking any of the essential requirements of the present invention (Comparative Examples 1 to 19) has a bactericidal effect, a gingivitis preventive effect, a bad breath preventive effect, and further a dentifrice use None of the samples were satisfactory in terms of no taste during and after use and smoothness of the surface of the dentifrice composition. In this case, sodium ascorbate is not stably blended even if sodium ascorbate is blended in place of ascorbic acid phosphate ester salt (comparative examples 1 and 2), and is inferior in preventing gingivitis and bad breath, instead of isopropylmethylphenol Even when cetylpyridinium chloride was added, the bactericidal activity and bad breath prevention effect were inferior (Comparative Examples 4 and 5), and even when the surfactant was inappropriate, the bactericidal power and bad breath preventing effect were inferior (Comparative Examples 9 to 12). . In addition, when the D / A ratio is inappropriate, the storage stability of the ascorbic acid phosphate ester salt cannot be improved, the satisfactory gingivitis and bad breath prevention effects cannot be obtained, and the satisfactory gingivitis even if the initial pH is inappropriate In addition, the object of the present invention could not be achieved in any case.

  Next, the dentifrice composition of the following prescription examples 1-10 was produced by the method similar to an Example, it filled with the accommodation container, and evaluated similarly. In all of the following examples, the initial pH was in the range of 8.0 to 9.3. The dentifrice composition of the following prescription example has the bactericidal power after long-term storage, the storage stability of ascorbic acid phosphate ester salt, the gingivitis prevention effect and the bad breath prevention effect, as well as the oral irritation during and after use. In addition, it was excellent in both the smoothness of the dentifrice surface.

[Prescription Example 1] Toothpaste Ascorbic acid-2-phosphate magnesium 0.4%
Isopropyl methylphenol 0.1%
Polyoxyethylene (10) cetyl ether 1.0%
Sodium citrate 0.1%
70% sorbit solution 45%
Propylene glycol 3%
Sodium carboxymethylcellulose 1.4%
Saccharin sodium 0.18%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.2%
Sodium hydroxide 0.4%
Silicic anhydride 18%
Fragrance 1.3%
Purified water balance
Total 100%

[Prescription Example 2] Toothpaste Ascorbic acid-2-phosphate magnesium 0.3%
Isopropyl methylphenol 0.1%
Polyoxyethylene (5) stearyl ether 1.0%
Potassium citrate 0.2%
70% sorbit solution 45%
Propylene glycol 3%
Sodium carboxymethylcellulose 1.0%
Sodium polyacrylate 0.4%
Saccharin sodium 0.18%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.2%
Sodium hydroxide 0.4%
Silica anhydride 20%
Fragrance 1.3%
Purified water balance
Total 100%

[Prescription Example 3] Toothpaste Ascorbic acid-2-phosphate magnesium 0.2%
Isopropyl methylphenol 0.1%
Polyoxyethylene (15) myristyl ether 1.0%
Sodium succinate 0.15%
70% sorbit solution 45%
Propylene glycol 3%
Sodium carboxymethylcellulose 1.0%
Carrageenan 0.4%
Saccharin sodium 0.18%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.2%
Sodium hydroxide 0.4%
Silicic anhydride 18%
Fragrance 1.3%
Purified water balance
Total 100%

[Prescription Example 4] Toothpaste Ascorbic acid-2-phosphate magnesium magnesium 0.5%
Isopropyl methylphenol 0.05%
Triclosan 0.05%
Polyoxyethylene (6) stearyl ether 0.5%
Polyoxyethylene (10) hydrogenated castor oil 1.0%
Sodium tartrate 0.4%
Sodium polyphosphate 0.05%
70% sorbit solution 45%
Propylene glycol 3%
Xanthan gum 0.9%
Sodium polyacrylate 0.5%
Saccharin sodium 0.18%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.2%
Sodium hydroxide 0.4%
Silica anhydride 20%
Fragrance 1.3%
Purified water balance
Total 100%

[Prescription Example 5] Toothpaste Ascorbic acid-2-phosphate magnesium 0.5%
Isopropyl methylphenol 0.05%
Cetylpyridinium chloride 0.05%
Polyoxyethylene (30) hydrogenated castor oil 1.0%
Potassium tartrate 0.25%
Potassium polyphosphate 0.05%
70% sorbite solution 40%
Propylene glycol 3%
Sodium carboxymethylcellulose 1.2%
Sodium polyacrylate 0.2%
Saccharin sodium 0.18%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.0%
Sodium hydroxide 0.4%
Silicic anhydride 21%
Fragrance 1.3%
Purified water balance
Total 100%

[Formulation Example 6] Toothpaste Ascorbic acid-2-phosphate magnesium 0.4%
Isopropyl methylphenol 0.05%
Triclosan 0.05%
Cetylpyridinium chloride 0.05%
Polyoxyethylene (10) cetyl ether 0.6%
Polyoxyethylene (20) hydrogenated castor oil 0.8%
Malic acid 0.1%
70% sorbite solution 43%
Propylene glycol 3%
Sodium carboxymethylcellulose 0.9%
Carrageenan 0.5%
Saccharin sodium 0.17%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.0%
Sodium hydroxide 0.4%
Silicic anhydride 22%
Fragrance 1.3%
Purified water balance
Total 100%

[Prescription Example 7] Toothpaste sodium ascorbate-2-phosphate 0.4%
Isopropyl methylphenol 0.05%
Polyoxyethylene (5) stearyl ether 0.5%
Polyoxyethylene (20) hydrogenated castor oil 0.5%
Sodium gluconate 0.3%
Sodium pyrophosphate 0.1%
70% sorbite solution 50%
Propylene glycol 3%
Xanthan gum 0.8%
Sodium polyacrylate 0.4%
Carrageenan 0.2%
Saccharin sodium 0.19%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.0%
Sodium hydroxide 0.4%
Silica anhydride 20%
Fragrance 1.3%
Purified water balance
Total 100%

[Prescription Example 8] Toothpaste Ascorbic acid-2-phosphate sodium salt 0.5%
Isopropyl methylphenol 0.1%
Polyoxyethylene (15) myristyl ether 0.6%
Polyoxyethylene (30) hydrogenated castor oil 0.6%
Sodium citrate 0.05%
Sodium ethylenediaminetetraacetate 0.1%
70% sorbite solution 40%
Propylene glycol 4%
Sodium carboxymethylcellulose 1.0%
Sodium polyacrylate 0.2%
Carrageenan 0.2%
Saccharin sodium 0.18%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.1%
Sodium hydroxide 0.4%
Silica anhydride 20%
Fragrance 1.2%
Purified water balance
Total 100%

[Prescription Example 9] Toothpaste sodium ascorbate-2-phosphate 0.3%
Isopropylmethylphenol 0.075%
Triclosan 0.05%
Polyoxyethylene (10) cetyl ether 0.6%
Polyoxyethylene (10) hydrogenated castor oil 0.6%
Sodium polyphosphate 0.1%
70% sorbite solution 42%
Propylene glycol 3%
Sodium carboxymethylcellulose 0.8%
Sodium polyacrylate 0.2%
Carrageenan 0.4%
Saccharin sodium 0.18%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.2%
Sodium hydroxide 0.4%
Silicic anhydride 18%
Fragrance 1.2%
Purified water balance
Total 100%

[Prescription Example 10] Toothpaste Ascorbic acid-2-phosphate magnesium magnesium 0.2%
Ascorbic acid-2-phosphate sodium salt 0.2%
Isopropyl methylphenol 0.08%
Polyoxyethylene (6) stearyl ether 0.7%
Polyoxyethylene (20) hydrogenated castor oil 0.7%
Citric acid 0.1%
Sodium polyphosphate 0.05%
70% sorbite solution 42%
Propylene glycol 4%
Sodium carboxymethylcellulose 1.0%
Sodium polyacrylate 0.4%
Saccharin sodium 0.17%
Sodium monofluorophosphate 0.73%
Sodium lauryl sulfate 1.2%
Sodium hydroxide 0.4%
Silicic anhydride 18%
Fragrance 1.2%
Purified water balance
Total 100%

Claims (4)

(A) Ascorbic acid phosphate or a salt thereof,
(B) isopropylmethylphenol,
(C) Polyoxyethylene alkyl ether having an alkyl group with 14 to 18 carbon atoms and an average addition mole number of ethylene oxide of 2 to 20 moles, and polyoxyethylene curing with an average addition mole number of ethylene oxide of 5 to 30 moles At least one nonionic surfactant selected from castor oil,
(D) a chelating agent,
(E) An alkaline agent is blended, the component (A) is 0.1 to 2% by mass, the component (B) is 0.01 to 0.5% by mass, and the component (D) is 0.05 to 2% by mass. % containing, (D) / weight ratio of (a) is 0.2 to 3.5 toothpaste composition characterized by an initial pH of 8.0 to 9.3 at 25 ° C.. Chelating agent, citric acid, pyrophosphoric acid, tripolyphosphate, and toothpaste composition of claim 1, wherein those selected from alkali metal salts thereof. The nonionic surfactant of component (C) is an average added mole number of polyoxyethylene alkyl ether and ethylene oxide in which the carbon number of the alkyl group is 14 to 18 and the average added mole number of ethylene oxide is 2 to 20 moles. The dentifrice composition according to claim 1 or 2, which is 5 to 30 mol of polyoxyethylene hydrogenated castor oil. Component (C) 0.3 to 5 wt%, according to claim 1, 2 or 3 toothpaste composition according to 0.01 to 1.0% by weight of component (E).