JP3004468B2 - Oral composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oral composition, and more particularly, to an oral composition which exhibits an excellent plaque control effect by killing and removing microorganisms in the oral cavity.

2. Description of the Related Art It is known that a water-insoluble solid (hereinafter referred to as an organosilicon-type immobilized bactericide) having immobilized organosilicon quaternary ammonium exhibits antibacterial activity.
For example, Japanese Patent Application Laid-Open No. Sho 62-177284 discloses that antibacterial treatment of synthetic fibers with such organosilicon quaternary ammonium is disclosed. However, application of the organosilicon-type immobilized bactericide in the field of oral hygiene has not yet been proposed.

[0002]

SUMMARY OF THE INVENTION The present inventors have made intensive studies to apply organosilicon-type immobilized germicides to oral compositions. That is, since this organosilicon-type immobilized bactericide is cationic, it usually reacts with an anionic component such as a foaming agent or a binder used in an oral composition, and its antibacterial activity is significantly reduced. There is a problem. Therefore, in order to incorporate the organosilicon-type immobilized bactericide into the oral composition, it is necessary to take measures to stabilize it.

Accordingly, the present inventors have conducted intensive studies with the aim of stably blending a water-insoluble solid having organosilicon quaternary ammonium immobilized into an oral composition. As a result, they have found that a polyoxyethylene / polyoxypropylene block copolymer surfactant specifically stabilizes the organosilicon-type immobilized bactericide, thereby completing the present invention.

[0004]

According to the present invention, a water-insoluble solid having organosilicon quaternary ammonium immobilized thereon is used as an active ingredient, and polyoxyethylene / polyoxygen is used as a stabilizer for the organosilicon-type immobilized germicide. An object of the present invention is to provide an oral composition comprising a propylene block copolymer surfactant.

The oral composition of the present invention exhibits an excellent plaque control effect by efficiently disinfecting and removing oral microorganisms and preventing accumulation and calcification of the products. Hereinafter, the present invention will be described specifically.

In the present invention, an organosilicon quaternary ammonium salt is immobilized and used as a bactericide. The organosilicon quaternary ammonium salt has the _{^{formula: R 1 3 N + R 2}} SiR 3 nX 3-n · Y - in known compound represented by the usually commercially available as an alcohol solution. In the above formula, X is a hydrolyzable group such as a halogen atom, an alkoxy group and an acyl group, and Y is chlorine or bromine. R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, in particular, two of the three R ¹ are methyl groups and the other one is an alkyl group having 8 to 22 carbon atoms. Preferably, there is. R ² is a divalent hydrocarbon group, particularly preferably an alkylene group having 2 to 4 carbon atoms or —CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ —. R ³ is a lower alkyl group such as a methyl group, a phenyl group or a CF ₃ CH ₂ CH ₂ group. n represents 0, 1 or 2, and is preferably 0.

Among the above organosilicon quaternary ammonium salts, those represented by the following formula are particularly preferred.

Embedded image (In the formula, R ¹ represents an alkyl group having 8 to 22 carbon atoms.)

[0008] The water-insoluble solid that immobilizes the organosilicon quaternary ammonium may be any type of water-insoluble solid, including inorganic and organic substances. The solids can be synthetic or natural and include, for example, metal oxides and carbonates, siliceous materials, cellulosic materials, resins and plastics. Examples of particularly preferred solids are metals and metal oxides such as iron, aluminum, copper, nickel, titanium dioxide, alumina, zinc oxide, magnesium oxide, iron oxide, calcium carbonate, calcium hydrogen phosphate and magnesium carbonate; silicate Materials, such as glass, silica, diatomaceous earth, ground quartz, mica, zeolites, aluminum silicate, aluminum calcium silicate, magnesium silicate and zirconium silicate; resins and plastics, such as polyester,
Polyamide, cellulose acetate, rayon, polystyrene, polyethylene, polypropylene, epoxy resin, phenolic resin, silicone resin and polycarbonate resin; cellulosic materials such as wood, cotton and hemp and other natural organic materials such as silk and wool Can be.

The organosilicon quaternary ammonium can be immobilized on a water-insoluble solid by a method known per se. For example,
Applying a solvent solution of an organosilicon quaternary aluminum salt to the water-insoluble solid by dipping or spraying;
The coating material can be fixed by air drying or heating after the coating step. Preferably, the water-insoluble solid is coated with an aqueous or organic solvent solution of an organosilicon quaternary ammonium salt. Such solutions are readily prepared by adding the corresponding hydrolyzable silane to water or a solvent such as methanol, ethanol or hexane. Satisfactory results are obtained with a concentration of organosilicon quaternary ammonium salt of 0.25 to 10% by weight in the processing solution. When the treated surface is dried (or heated), the organosilicon quaternary ammonium coating is immobilized on the solid surface. When the treated solid is heated at 65-100 ° C. for several minutes, the organosilicon quaternary ammonium coating is more firmly immobilized on the surface. If desired, conventional silanol condensation catalysts can be added to the processing solution to enhance silanol condensation and form an improved bond of the compound.

The oral composition of the present invention comprises the organosilicon-type immobilized bactericide thus obtained in an amount of about 0.001 to 50% by weight, preferably 0.1% by weight, based on the total weight of the composition.
It is prepared by blending at a ratio of 1 to 10% by weight. When the amount is less than 0.001% by weight, a sufficient effect of adsorbing microorganisms is not exhibited. On the other hand, when the amount is more than 50% by weight, the properties of the composition become unstable.

In the oral composition of the present invention, the polyoxyethylene / polyoxypropylene block copolymer surfactant forms an aqueous gel, and acts as a stabilizer for the organosilicon-type immobilized bactericide. This surfactant is a known surfactant composed of polyoxyethylene / polyoxypropylene glycol, and is commercially available, for example, from BASF Corporation in the United States under the trade name of “PLURONIC”.
The surfactant is generally chemically defined by the weight% of the polyoxypropylene hydrophobic portion and the polyoxyethylene hydrophilic portion in the total molecular weight, and is preferably a hydrophobic group (polyoxypropylene). Has a molecular weight of 1,400 to 4,000, and the ratio of the hydrophilic group (polyoxyethylene) to the total molecular weight is in the range of 30 to 80% by weight.

The polyoxyethylene / polyoxypropylene block copolymer surfactant is used in an amount of about 15 to 80% by weight, preferably 20 to 50% by weight, based on the total amount of the composition.
In a proportion of If the amount is less than 15% by weight,
Since the gelation does not proceed sufficiently, solid-liquid separation occurs and the properties of the composition become unstable. On the other hand, if the amount is more than 80% by weight, the gelation proceeds excessively. And an appropriate viscosity cannot be obtained.

[0013] The oral composition of the present invention can be made into toothpaste, ointment, pasta, liniment, cream and the like by a method known per se, for example, dentifrice and gingival massage preparations Abrasives, flavors, thickeners, sweeteners, other medicinal ingredients and the like can be blended depending on the desired use of the present invention as long as the effects of the present invention are not impaired.

For example, in the case of dentifrices, dibasic calcium phosphate dihydrate and anhydride, monobasic calcium phosphate, tribasic calcium phosphate, calcium carbonate, calcium pyrophosphate, aluminum hydroxide, alumina, silicic anhydride, silica gel, Aluminum silicate, insoluble sodium metaphosphate, tribasic magnesium phosphate, magnesium carbonate, calcium sulfate, polymethyl methacrylate, bentonite, zirconium silicate, synthetic resin, etc. can be used alone or in combination of two or more. . The compounding amount is usually 5.0 to 90 with respect to the total amount of the composition.
%, Especially 5 to 60% by weight for toothpaste.

As the thickener, sorbitol, glycerin, ethylene glycol, propylene glycol,
1,3-butylene glycol, polyethylene glycol, polypropylene glycol, xylit, maltitol, lactit and the like can be used 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.

Further, as a flavoring agent, menthol carboxylic acid, anethole, eugenol, methyl salicylate,
Limonene, ocimene, n-decyl alcohol, citronell, α-terbineol, methyl acetate, citronellyl acetate, methyl eugenol, cineole,
Linalool, ethyl linalool, crocodile, thymol,
Spearmint oil, peppermint oil, lemon oil, orange oil, sage oil, rosemary oil, cinnamon oil, pimento oil,
Diatom oil, perilla oil, winter green oil, clove oil, eucalyptus oil, etc.
They may be used alone or in combination of two or more kinds in a proportion of about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight, based on the total amount of the composition. Also, as a sweetener,
Saccharin sodium, stevioside, neoheshelidyl dihydrochalcone, glycyrrhizin, perillartin, thaumatin, asparatyl phenylalanyl methyl ester, p-methoxycinnamic aldehyde, etc., in an amount of 0.01 to 1% by weight based on the total amount of the composition, preferably It can be blended at a ratio of 0.05 to 0.5% by weight.

Further, the oral composition of the present invention contains as a medicinal ingredient a bactericide such as cetylpyridinium chloride, chlorhexidine salt, triclosan, dextranase, amylase, protease, mutanase, lysozyme, lytic enzyme (Litec enzyme). Enzymes such as sodium monofluorophosphate and potassium monofluorophosphate, fluorides such as sodium fluoride and stannous fluoride, tranexamic acid and epsilon aminocaproic acid, aluminum chlorohydroxyl allantoin, dihydro Cholesterol, glycyrrhizin salts, glycyrrhetinic acid, glycerophosphate, chlorophyll, sodium chloride, caropeptide, water-soluble inorganic phosphate compounds, etc., alone or in combination of two or more It can be formulated.

The compounding amounts of these medicinal components are almost the same as in the case of the conventional oral composition, and those skilled in the art can appropriately determine them according to the use of the composition. The polyoxyethylene / polyoxypropylene block copolymer surfactant used as a stabilizer in the present invention also has a function as a binder and a surfactant. There is no need to mix agents and surfactants.

[0019]

The present invention will now be described in more detail with reference to examples and comparative examples of the present invention. However, the present invention is not limited to these examples. Unless otherwise specified, "%" represents% by weight. Example 1 The sterilizing and removing effects of the organosilicon-type immobilized germicides of the carriers shown in Table 1 were evaluated by the experiments described below. Table 1 shows the results.

Evaluation method of microbial removal effect (1) Preparation of contact bacterial solution Streptococcus sob.
(rinus ) OMZ176 was cultured in a brain heart infusion liquid medium under anaerobic conditions at 37 ° C for 20 hours, and then centrifuged (7,000 rpm, 10 minutes) to collect the cells. The obtained cells were washed with sterile physiological saline, and suspended in sterile physiological saline so that the bacterial concentration was about 10 ⁷ cells / ml (OD ₅₆₀ = 0.02). And (2) Evaluation of Microorganism Removal Effect (Shake Flask Method) A predetermined amount of a sample was placed in a 100 ml Erlenmeyer flask, and 36 ml of sterilized water was added to sufficiently disperse the sample. The Erlenmeyer flask was placed in a thermostat at 37 ° C.
ml was added and shaken at 120 strokes / min for 3 minutes.
Thereafter, the Erlenmeyer flask was taken out of the thermostat and allowed to stand for a while, after which 1 ml of the supernatant was taken and diluted with sterile physiological saline. Then, 0.1 ml of the diluted product was spread on a brain heart infusion agar plate and cultured under anaerobic conditions at 37 ° C. for 48 hours, and the number of colonies formed was counted.
Thereby, the viable cell count after contact with the sample for 3 minutes can be calculated.

The microbial removal rate (%) of the sample was evaluated by the following equation, and it was determined that an excellent microbial removal effect was obtained for a sample having 90% or more.

(Equation 1)

[0022]

[Table 1]

As is clear from the results shown in Table 1, Samples 1 to 5 on which organosilicon quaternary ammonium was immobilized
7, especially 1-4 and 6 show a clearly higher microbial removal rate as compared to samples 8-17 with only the immobilized carrier. Further, it can be seen that the microorganism removing effect of Samples 4 to 6 depends on the concentration of the immobilized bactericide and shows an extremely high removal rate at 0.001 to 50%. Further, the alkyl chain length of the organosilicon quaternary ammonium salt is higher at C ₁₈ than at C ₆ , indicating a higher microorganism removing effect.

Examples 2 to 5 and Comparative Examples 1 to 3 Using the organosilicon-type immobilized bactericide shown in Table 1, mixed and stirred with other components shown in Table 2 according to a conventional method. To 5, and the dentifrice compositions of Comparative Examples 1 to 3 were prepared. The microorganism removing effect of the obtained composition was evaluated by the above evaluation method. Table 2 shows the results.

[0025]

[Table 2]

As is clear from Table 2, since the dentifrice compositions of Examples 2 to 5 were blended together with polyoxyethylene / polyoxypropylene glycol, the removal rate was 90%.
% Or more, and the properties of the composition were stable without solid-liquid separation. On the other hand, the dentifrice composition of Comparative Example 3 used the same surfactant as in Examples 2 to 5, but did not exhibit the microorganism removing effect because it did not contain the organosilicon-type immobilized bactericide. Was. Also,
The dentifrice compositions of Comparative Examples 1 and 2 were formulated with an organosilicon-type immobilized bactericide, but used a nonionic surfactant other than the polyoxyethylene / polyoxypropylene block copolymer system. The agent was not stabilized and did not show good microbial removal effects. From the above, in the dentifrice compositions of Examples 2 to 5, since the organosilicon-type immobilized bactericide is blended with a surfactant that specifically stabilizes the same, its antibacterial activity is not impaired, and It can be seen that the microorganisms are efficiently removed.

Example 6 In this example, a toothpaste was prepared according to a conventional method according to the following formulation. Component amount (% by weight) Sample 4 (Table 1) 0.5 Cetylpyridinium chloride 0.1 Sodium monofluorophosphate 0.7 Pluronic F-88 30.0 (Average degree of polymerization: Ethylene oxide 194, Propylene oxide 39) When a microorganism adsorption rate of calcium hydrogen phosphate 20.0 glycerin 20.0 perfume 1.0 Sodium saccharin 0.2 purified water balance 100.0 resultant toothpastes was evaluated by the above method showed good microbial removal effect Was.

Example 7 In this example, a gingival massage cream was prepared according to the following formulation according to a conventional method. Component amount (% by weight) Sample 1 (Table 1) 5.0 Tocopherol nicotinate 0.5 Pluronic F-127 40.0 (Average degree of polymerization: ethylene oxide 196, propylene oxide 67) Glycerin 20.0 Fragrance 0.6 Dipotassium glycyrrhizinate 0.1 Purified water residue 100.0 The microorganism removal rate of the obtained gingival massage cream was evaluated by the above-mentioned method. As a result, a favorable microorganism removal effect was exhibited.

[0029]

According to the present invention, a novel oral composition having an excellent bactericidal action and containing stably immobilized organosilicon quaternary ammonium can be obtained.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-223512 (JP, A) JP-A-62-177284 (JP, A) JP-A-5-124944 (JP, A) JP-A-5-124 124942 (JP, A) JP-A-5-70314 (JP, A) JP-A-2-45412 (JP, A) JP-A-61-76411 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 7/22

Claims (1)

(57) [Claims] 1. A _{^{formula: R 1 3 N + R 2}} SiR 3 nX 3-n · Y - [ wherein, X is a group selected from the group consisting of a halogen atom, an alkoxy group and an acyl group, Y R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, R ² is a divalent hydrocarbon group, R ³ is a lower alkyl group, a phenyl group or CF ₃ CH ₂ C
And are H ₂ group, and n is a water insoluble solid with immobilized organosilicon quaternary ammonium salt represented by 'represents 0, 1 or 2, and polyoxyethylene-polyoxypropylene block copolymer surfactant An oral composition characterized by comprising: