JPH11310522A - Composition for application to oral cavity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition effective for removal of dental plaque, prevention of halitosis or the like without spoiling the stability with the passage of days of the germicide, and germicidal effect by making the composition include a porous calcium carbonate and a water-insoluble non-cationic germicide. SOLUTION: This composition is obtained by including (A) a porous calcium carbonate and (B) a water-insoluble non-cationic germicide. The ingredient A is preferably having 0.05-0.5 μm mean primary particle size, 0.05-0.8 g/ml bulk density and 15-100 m<2> /g BET specific surface area. The ingredient B is preferably a halogenated diphenyl ether, a halogenated salicylanilide or the like, e.g. 2',4,4'-trichloro-2-hydroxy-diphenyl ether (triclosan). The composition preferably contains 0.1-40 wt.% ingredient A and 0.001-3 wt.% ingredient B. Therefore, the composition may keep good performances even if kept in a container having the resin innermost layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an oral composition and a dental plaque having improved stability of the bactericidal activity of a water-insoluble non-cationic bactericide when the innermost layer is filled in a container made of synthetic resin. The present invention relates to an oral composition which exhibits excellent effects on removal, prevention of bad breath, and removal of tooth colorant.

[0002]

2. Description of the Related Art It has been shown that plaque adsorbed on teeth is an important factor for the onset of gingivitis. Means for removing such plaque include physical cleaning of the mouth by brushing or the like, but it takes a long time and it is very difficult to remove it sufficiently.

Therefore, various oral compositions such as dentifrices containing a disinfectant have been studied in order to supplement the effect of removing plaque, and in particular, cationic disinfectants are effective in suppressing plaque formation. It has been known. However, cationic fungicides have poor compatibility with the components in the composition and are difficult to formulate.
In recent years, it has been proposed to incorporate a water-insoluble non-cationic bactericide, such as triclosan, having excellent compatibility with the components in the composition into the oral composition in order to solve such a drawback.

However, when a composition containing a water-insoluble non-cationic bactericide is filled in a container made of a synthetic resin, the bactericidal agent deteriorates over time due to adsorption of the bactericide to the inner surface of the container. However, there is a problem that the sterilizing power is weakened.

As means for solving this problem, for example, JP-A-2-288820, JP-A-6-92
830 and JP-A-6-279248 propose that a special polymer is used for the inner layer portion of the container, and that the adsorption of the nonionic germicide to the container is improved by devising the container. Also, Japanese Patent Application Laid-Open No. 8-19862
No. 3 discloses that porous calcium carbonate having excellent oil absorbency and water absorbency can be developed and used for food additives. However, it has not yet been proposed to apply the porous calcium carbonate to an oral composition for the purpose of stabilizing a bactericide, removing plaque or preventing bad breath.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-insoluble non-cationic bactericide, which is deteriorated in chronological stability and bactericidal activity even when a general synthetic resin material such as polyethylene is used. An object of the present invention is to provide a composition for the oral cavity free from plaque, to prevent bad breath, and to remove a coloring substance on the tooth surface.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that an oral composition containing porous calcium carbonate and a water-insoluble non-cationic bactericide has It has been found that the effect of porous calcium carbonate to improve the day-to-day stability of water-insoluble non-cationic bactericides, to remove plaque, to prevent bad breath, and to remove tooth-coloring substances, has led to the completion of the present invention. Was.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The porous calcium carbonate used in the present invention is different from heavy calcium carbonate which does not form secondary particles, ultrafine calcium carbonate, or ordinary light calcium carbonate which forms secondary particles by spontaneous aggregation. Differently, it is a high-purity high-purity light calcium carbonate having a high porosity, in which secondary particles are formed by performing multi-step carbonation of chain-like particles in which a series of fine particles are formed. For example, as Poacar-N (manufactured by Shiraishi Calcium Co., Ltd.) Available. Although the porous calcium carbonate used in the present invention is not limited, the average primary particle diameter is particularly 0.05 to 0.5 μm, preferably 0.1 to 0.5 μm.
0.5 μm, bulk density 0.05-0.8 g / ml, B
Porous calcium carbonate having an ET specific surface area in the range of 15 to 100 m ² / g is preferably used.

In the present invention, the amount of the porous calcium carbonate is 0.1 to 40% by weight, preferably 0.5 to 10% by weight. If the amount is less than 0.1% by weight, the stability improvement of the water-insoluble non-cationic bactericide is not sufficient,
Further, if the content exceeds 40% by weight, no further effect can be expected.

The water-insoluble, non-cationic bactericide used in the present invention includes halogenated diphenyl ether, halogenated salicylanilide, halogenated carbanilide, p-
It is selected from any of hydroxybenzoic acid esters and phenolic compounds.

As the halogenated diphenyl ether,
2 ', 4,4'-trichloro-2-hydroxy-diphenyl ether (triclosan), 2,2'-dihydroxy-5,5'-dibromo-diphenyl ether, and 4', 5-dibromosalicylanilide as a salicylanilide halide , 3,4 ', 5-trichlorosalicylanilide, 2,3,3', 5-tetrachlorosalicylanilide, 3,5-dibromo-3'-trifluoromethylsalicylanilide, and the like; Examples of p-hydroxybenzoic acid esters such as 4,4′-trichlorocarbanilide and 3-trifluoromethyl-4,4′-dichlorocarbanilide include p-hydroxybenzoic acid esters.
Methyl hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, and the like, and examples of the phenolic compound include isopropylmethylphenol.

Among these water-insoluble non-cationic germicides, halogenated diphenyl ethers are preferred, and triclosan (2 ', 4,4'-trichloro-2-hydroxydiphenyl ether) is particularly preferred. In the present invention, the compounding amount of the non-cationic bactericide is 0.00% based on the total amount of the composition.
It is 1 to 3% by weight, preferably 0.01 to 1% by weight. If the amount is less than 0.001% by weight, sufficient bactericidal activity will not be exhibited, and if it is more than 3% by weight, it will be irritating to the oral mucosa and pose a practical problem.

The oral composition of the present invention can be produced in the form of toothpaste, toothpaste, water toothpaste, ointment, pasta, chewing gum and the like by conventional methods, and toothpaste is a practically preferred form. These compositions can be made of commonly used resinous materials such as polyolefin resins such as polyethylene resins and polypropylene resins, polyester resins, polyethylene terephthalate resins, polycarbonate resins, polystyrene resins, polyamide resins, and polyvinyl chloride resins. Containers, such as single-layer tubes, laminating tubes, bottles, jars
And the like.

The oral composition of the present invention may contain, in addition to the above essential components, known components as long as the effects of the present invention are not impaired. For example, in the case of toothpaste, as an abrasive, calcium carbonate, calcium phosphate, dibasic calcium phosphate, calcium pyrophosphate, insoluble sodium metaphosphate, titanium oxide, amorphous silica, crystalline silica,
Aluminosilicate, aluminum oxide, aluminum hydroxide, resin, hydroxyapatite, etc. can be used alone or in combination of two or more, and the amount is usually 10 to 60% by weight based on the total amount of the composition.
It is.

Anionic surfactants as foaming agents and detergents include sodium alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, and N-type surfactants such as sodium N-lauroyl sarcosinate and sodium N-myristoyl sarcosinate. N-acyl glutamates such as sodium acyl sarcosinate and sodium N-palmitoyl glutamate; and sulfosuccinic acid type surfactants such as disodium polyoxyethylene alkyl sulfosuccinate and sodium dialkyl sulfosuccinate.

Examples of the nonionic surfactant include sugar fatty acid esters such as sucrose fatty acid ester, maltose fatty acid ester and lactose fatty acid ester, polyoxyethylene alkyl ethers, fatty acid alkanolamides, and polyoxyethylene sorbitan monolau. And polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate; polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil; sorbitan fatty acid esters; fatty acid monoglycerides; and polyoxyethylene polyoxypropylene block copolymers. Can be

Examples of the amphoteric surfactant include N-alkyldiaminoethylglycine such as N-lauryldiaminoethylglycine and N-myristyldiethylglycine;
N-alkyl-N-carboxymethylammonium betaine, 2-alkyl-1-hydroxyethylimidazoline betaine sodium, lauryl dimethylaminoacetate betaine, and the like. These surfactants can be used alone or in combination of two or more, and the amount is preferably 0.1 to 10% by weight based on the total amount of the composition.

Examples of the binder include cellulose derivatives such as hydroxyethyl cellulose and sodium carboxymethyl cellulose; alkali metal alginate such as sodium alginate; gums such as carrageenan, xanthan gum, tragacanth gum and gum arabic; polyvinyl alcohol; polyacrylic acid Synthetic binders such as sodium and inorganic binders such as silica gel, aluminum silica gel and veegum can be used alone or in combination of two or more. These amounts are usually
It is 0.1 to 10% by weight based on the total amount of the composition.

The humectants include sorbitol, glycerin, ethylene glycol, propylene glycol, 1,
3-butylene glycol, polyethylene glycol, polypropylene glycol, xylit, maltitol, lactit and the like can be blended alone or in combination of two or more. The compounding amount is usually 5 to 70% by weight based on the total amount of the composition.

Examples of the pH adjuster include citric acid,
Phosphoric acid, malic acid, pyrophosphoric acid, lactic acid, tartaric acid, glycerophosphoric acid, acetic acid, nitric acid, silicic acid, or a chemically possible salt thereof, sodium hydroxide, and the like, which have a pH of 5 They may be used alone or in combination of two or more so as to be in the range of 9 to 9. The compounding amount is usually 0.01 to 2% by weight based on the total amount of the composition.

Further, as a flavoring agent, menthol, carvone, eugenol, methyl eugenol, methyl salicylate, methyl eugenol, thymol, anethole,
Limonene, ocimene, n-decyl alcohol, citronell, α-terpineol, methyl acetate, citronenyl acetate, cineol, linalool, ethyl linalool, crocodile, thyme, nutmeg, spearmint oil, peppermint oil, lemon oil, orange oil, Sage oil, rosemary oil, cinnamon oil, perilla oil, winter green oil, clove oil, eucalyptus oil, Pimento oil, or the like, alone or in combination of two or more, is 0.1 to 5 wt. %, Preferably about 0.5 to 2% by weight.

As sweeteners, saccharin sodium, acesulfame potassium, stevioside, neohesperidyl dihydrochalcone, glycyrrhizin, perillartin, thaumatin, asparatyl phenylalanyl methyl ester, xylit, etc. are added in an amount of 0.1% to the total amount of the composition. It can be blended at a ratio of 01 to 1% by weight, preferably 0.05 to 0.5% by weight.

Further, the oral composition of the present invention contains acetic acid d as a medicinal ingredient other than the water-insoluble non-cationic bactericide.
Vitamin E such as l-α-tocopherol, tocopherol succinate, or tocopherol nicotinate, chlorhexidine hydrochloride, cetylpyridinium chloride, benzethonium chloride and the like, amphoteric fungicides such as dodecyldiaminoethylglycine, dextranase, Enzymes such as amylase, protease, mutanase, lysozyme, and lytic enzyme (Litec enzyme); alkali metal monofluorophosphates such as sodium monofluorophosphate and potassium monofluorophosphate; and hydrofluoric acid such as sodium fluoride and stannous fluoride. Chloride, tranexamic acid, epsilon aminocaproic acid, aluminum chlorohydroxyl allantoin, dihydrocholesterol, glycyrrhizin salts, glycyrrhetinic acid, glycerophosphate, Chlorophyll, sodium chloride, Karopeputaido, a water-soluble inorganic phosphoric acid compounds may be blended singly or in combination of two or more.

[0024]

EXAMPLES The present invention will be described in more detail with reference to Test Examples and Examples below, but the present invention is not limited to these Examples. The amounts in the examples are all by weight.

[Test Example] Stability evaluation of non-cationic bactericide (1) Sample preparation The following toothpaste was prepared according to a conventional method, filled in a laminated tube having polyethylene as the innermost layer, and stored at 40 ° C for one month. The rate and the bactericidal effect were determined by the following methods. Ingredient Content (%) Porous calcium carbonate (shown in Table 1) Calcium carbonate (shown in Table 1) Anhydrous silica 3.0 Sorbit (shown in Table 1) Sodium carboxymethylcellulose 2.0 Sodium lauryl sulfate (shown in Table 1) Shown) Nonionic surfactant (shown in Table 1) Saccharin sodium 0.1 Fragrance 1.0 Water-insoluble non-cationic bactericide 0.3 Purified water Remainder Total 100.0

(2) Method for Measuring Residual Rate of Water-Insoluble Non-Cationic Disinfectant The method for measuring residual rate of water-insoluble non-cationic disinfectant will be described by taking the following triclosan as an example. (Method for measuring residual ratio of triclosan) 2.5 g of prepared dentifrice
After adding 20 ml of methanol to the mixture and stirring for 20 minutes to sufficiently disperse, centrifugation (17000 rpm, 10 minutes)
And the same operation was repeated twice on the residue, and the supernatant was combined. Add methanol to this and add 10
It was used as a test solution, and the amount of triclosan was quantified by liquid chromatography. The residual ratio of triclosan was determined by the following equation (1) and evaluated according to the following evaluation criteria.

[0027]

(Equation 1)

Evaluation criteria ○: Triclosan residual ratio is 90% or more ×: Triclosan residual ratio is less than 90%

(Bactericidal test) 5 ml of 4 times slurry of toothpaste
Streptococcus mutans (10 ⁸ -10 ⁹ CFU / ml)
s) Add 0.1 ml of the bacterial suspension and in a hot water bath at 37 ° C for 3 hours.
After performing a bactericidal reaction for one minute, one loopful of the sample solution was collected, and trypticase soy agar (TSS) containing 0.5% of polyoxyethylene monooleate and 0.7% of lecithin was used.
A) Coating on a flat plate, under anaerobic conditions (N ₂ / H ₂ / CO ₂ =
(85/10/5) at 37 ° C for 2 days, and the minimum bactericidal concentration (%) (hereinafter referred to as MBC) was measured. In addition,
As a standard, a 0.05% aqueous solution of triclosan (solubilized with a small amount of SLS) was used. The evaluation criteria are as follows. Evaluation criteria ○ ・ ・ ・ MBC of test sample is equivalent to standard MBC,
Or less ×: MBC of test sample is larger than standard MBC Table 1 also shows the results of the residual ratio of triclosan and the bactericidal activity test.

As is evident from the results in Table 1, it was recognized that, in comparison with the comparative example, in the examples in which the porous calcium carbonate was added, the bactericide was improved in chronological stability and the bactericidal activity could be maintained.

[0031]

[Table 1]

2. Plaque removal model test (1) Sample preparation The following toothpaste was prepared according to a conventional method and used for evaluation. Ingredient Compounding amount (%) Powder component (shown in Table 2) Sorbit 40.0 Sodium carboxymethylcellulose 2.0 Sodium lauryl sulfate 1.5 Pluronic surfactant (POE200 POP40) 5.0 Saccharin sodium 0.1 Fragrance 1 0.0 Purified water Remainder Total 100.0

(2) Evaluation S. mutans ATCC25175 which is a plaque component as a plaque model
A strain-produced insoluble glucan solution (1 mg / ml-pH7 veronal buffer solution) was used. 0.5 g of each of the toothpastes of Examples and Comparative Examples shown in Table 2 and 3 ml of the above insoluble glucan solution were mixed, shaken for 30 minutes, and then centrifuged to remove the supernatant. The residue was colored with sugar by the phenol sulfate method, and the absorbance at 490 nm was measured. A calibration curve was similarly prepared by coloring the sugar with the insoluble glucan solution, and the amount of glucan adsorbed on the powder was determined from the calibration curve. The adsorption rate was calculated with the amount of glucan initially added as 100. As shown in Table 2, the oral composition containing porous calcium carbonate of Example 8 is different from the ordinary light calcium carbonate of Comparative Example 4 or the oral composition containing normal heavy calcium carbonate of Comparative Example 5. In comparison, the composition for oral cavity of the present invention can be suitably used for removing plaque because of its excellent glucan adsorption power.

3. Bad Breath Prevention Model Test 4 g of the 4-fold slurry of Example 8 and Comparative Example 4 in Table 2 were placed in a glass vial and sealed. 0.5 ml of a methyl mercaptan solution (2 μg / ml-ethanol solution) is poured into a vial, shaken gently at 37 ° C. for 10 minutes, and 5 ml of a head space gas is collected. The amount of methyl mercaptan is determined by gas chromatography. The concentration was determined using a methyl mercaptan calibration curve. Deodorization rate (%) with the amount of methyl mercaptan added initially as 100
Was calculated. As shown in Table 2, the examples are superior to the comparative examples in terms of their deodorizing effect, and the porous calcium carbonate adsorbs and removes (deodorizes) the bad breath component. It was found to be useful for prevention.

4. Tooth surface coloring substance removal model test Tea polyphenol 0.5 was used as a model of tooth surface coloring substance.
% And 0.5% ammonium iron (III) citrate. 0.5 g of the toothpastes of the examples and comparative examples shown in Table 2 and 5 ml of the tooth surface coloring substance model solution were mixed, shaken for 30 minutes, centrifuged, and the absorbance of the supernatant was measured.
00 nm was measured. The adsorption rate was calculated by the following equation. Absorbance of tooth surface coloring substance model solution stock solution: A

[0036]

(Equation 2)

As shown in Table 2, the Example is superior to the Comparative Example in the effect of removing and adsorbing the tooth-coloring substance. It was found to be suitable as an oral composition for removing surface coloring substances.

[0038]

[Table 2]

Example 9 A toothpaste was prepared from the following components according to a conventional method, and filled in the same laminated tube as described above. Ingredient Content (%) Porous calcium carbonate 30.0 (Average primary particle diameter 0.2 μm, bulk density 0.5 g / ml, BET specific surface area 23 m ² ) Aluminum hydroxide 5.0 Sorbit 20.0 Xylit 5 2.0 Sodium carboxymethylcellulose 1.5 Sodium lauryl sulfate 1.5 Saccharin sodium 0.1 Fragrance 0.9 Triclosan 0.1 Purified water Remainder Total 100.0

Example 10 A toothpaste was prepared from the following components according to a conventional method, and filled in the same laminated tube as described above. Ingredient Content (%) Porous calcium carbonate 6.0 (average primary particle diameter 0.08 μm, bulk density 0.4 g / ml, BET ratio table area 35 m ² ) Calcium phosphate 25.0 Sorbit 30.0 Propylene glycol 5. 0 Sodium carboxymethylcellulose 1.2 Sodium N-lauroylsarcosinate 1.5 Sodium monofluorophosphate 0.5 Stevioside 0.1 Fragrance 0.9 Isopropylmethylphenol 0.5 Polyoxyethylene (200) Polyoxypropylene (70) Block copolymer 1.0 Purified water Remainder Total 100.0

Example 11 A toothpaste was prepared from the following components according to a conventional method, and filled in the same laminate tube as described above. Ingredient Compounding amount (%) Porous calcium carbonate 20.0 (average primary particle diameter 0.1 μm, bulk density 0.2 g / ml, BET specific surface area 60 m ² ) sorbitol 25.0 sodium carboxymethylcellulose 1.5 lauryl sulfate Sodium 1.5 Saccharin sodium 0.1 Fragrance 0.9 Ethyl p-hydroxybenzoate 0.1 Triclosan 0.2 Sodium fluoride 0.2 Polyoxyethylene (200) Polyoxypropylene (70) block copolymer 2.0 Purified water Remainder Total 100.0

Example 12 A liquid dentifrice was prepared from the following components according to a conventional method and filled in a PET resin container. Ingredient Content (%) Anhydrous silica 20.0 Porous calcium carbonate 0.5 (Average primary particle diameter 0.05 μm, bulk density 0.1 g / ml, BET ratio table area 90 m ² ) Sorbit 25.0 glycerin 12. 0 Carrageenan 1.0 Sodium lauryl sulfate 1.5 Sodium benzoate 0.2 Sodium saccharin 0.1 Fragrance 0.5 Triclosan 0.3 dl-α-tocopherol acetate 0.5 Polyoxyethylene (150) Polyoxypropylene (35) block Copolymer 1.5 Sodium silicate 0.5 Purified water Remainder Total 100.0

Example 13 A toothpaste was prepared from the following components according to a conventional method, and filled in a laminate tube similar to the above. Ingredient Content (%) Porous calcium carbonate 6.0 (average primary particle diameter 0.3 μm, bulk density 0.4 g / ml, BET specific surface area 25 m ² ) Calcium phosphate 25.0 Sorbit 30.0 Propylene glycol 5. 0 Sodium carboxymethyl cellulose 1.2 Sodium N-lauroyl sarcosinate 1.5 Sodium monofluorophosphate 0.5 Stevioside 0.1 Fragrance 0.9 Polyoxyethylene (200) Polyoxypropylene (70) block copolymer 1.0 Purification Water balance total 100.0

Example 14 A toothpaste was prepared from the following components according to a conventional method, and filled in the same laminated tube as described above. Ingredient Content (%) Porous calcium carbonate 5.0 (average primary particle size 0.2 μm, bulk density 0.5 g / ml, BET specific surface area 23 m ² ) Light calcium carbonate 30.0 Sorbit 35.0 carboxymethyl Cellulose Sodium 0.5 Sodium Lauryl Sulfate 1.5 Sodium Monofluorophosphate 0.5 Sodium Saccharin 0.1 Polyoxyethylene (200) Polyoxypropylene (40) Block Copolymer 1.0 Perfume 0.9 Purified Water Remainder Total 100.0

Example 15 Chewing gum was prepared from the following components according to a conventional method. Ingredient Content (%) Gum base 28.0 Porous calcium carbonate 0.5 (Average primary particle diameter 0.3 μm, bulk density 0.4 g / ml, BET specific surface area 25 m ² ) Xylitol 40.0 Reduced maltose starch syrup 26.5 Flavor 5.0 Total 100.0 Even in the oral compositions prepared according to Examples 9 to 12 above, the daily stability and sterilization of excellent water-insoluble non-cationic bactericides such as triclosan and the like. Activity stability was observed. Moreover, the plaque removing effect, the bad breath preventing effect, and the tooth surface coloring substance removing effect were recognized in the oral compositions of Examples 9 to 15.

[0046]

According to the present invention, the stability of the water-insoluble non-cationic bactericide in the container whose innermost layer is made of a synthetic resin is improved over time and the bactericidal activity is stabilized. It is possible to provide a composition for the oral cavity which exhibits excellent effects of removing debris, preventing bad breath, and removing colored substances.

Claims (8)

[Claims] 1. An oral composition comprising porous calcium carbonate. 2. An oral composition comprising porous calcium carbonate and a water-insoluble non-cationic bactericide. 3. The water-insoluble non-cationic bactericide is halogenated diphenyl ether, halogenated salicylanilide,
The oral composition according to claim 2, wherein the composition is at least one selected from a halogenated carbanilide, a p-hydroxybenzoic acid ester, and a phenolic compound. 4. The method according to claim 1, wherein the water-insoluble non-cationic bactericide is 2 ′,
3. The oral composition according to claim 2, wherein the composition is 4,4'-trichloro-2-hydroxy-diphenyl ether (triclosan). 5. An average primary particle diameter of 0.05 to 0.5 μm.
With a bulk density of 0.05 to 0.8 g / ml, BET
4. A porous calcium carbonate having a specific surface area of 15 to 100 m ² / g.
And the oral composition according to any one of claims 4 to 5. 6. The oral composition according to claim 1, which is a dental composition for removing plaque. 7. The oral composition according to any one of claims 1 to 5, which is an oral composition for preventing bad breath. 8. The oral composition according to any one of claims 1 to 5, which is an oral composition for removing a tooth surface coloring substance.