JP2016141661A - Oral composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oral composition that has the excellent persistence of oral malodor inhibitory effect, inhibits a metallic taste, and gives a good feeling in use with a favorable taste, the oral composition containing a water-soluble copper compound.SOLUTION: An oral composition comprises (A) water-soluble copper compound of 0.001-0.3 mass%, and (B) propylene glycol alginate of 0.01-3 mass%, where a compounding ratio between (A) component and (B) component, represented by (A)/(B), is 0.01-5 as a mass ratio.SELECTED DRAWING: None

Description

  The present invention relates to a composition for oral cavity containing a water-soluble copper compound that is excellent in sustainability of bad breath suppression effect, has a metallic taste suppressed, and gives a good feeling of good taste.

  Copper compounds such as copper gluconate, copper sulfate and copper citrate have the effect of suppressing and improving bad breath, but bad breath cannot be completely suppressed in terms of the production mechanism of its main causative substances, A long lasting effect was desired. Moreover, the copper compound has astringency and bitterness peculiar to metals, and there is a big problem in palatability when used as a composition for oral cavity.

  So far, Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-189358) has excellent bad breath suppression effect by blending copper gluconate and copper sulfate with allantoin and a nonionic surfactant in combination. It has been proposed that the bitterness derived from copper is suppressed and the usability is improved. Patent Document 2 (International Publication No. 2010/113688) discloses that a combination of a gluconic acid copper and copper sulfate with a betaine-type amphoteric surfactant and a specific sugar alcohol provides an excellent astringent feeling-imparting effect, and copper. It has been proposed to improve the unpleasant bitterness characteristic of the compound. However, these do not mention the persistence of the halitosis suppression effect and do not mention the metal taste, but the improvement effect of the copper compound-derived taste is not sufficient and there is room for improvement.

  On the other hand, propylene glycol alginate is known as a thickener, stabilizer, gelling agent and the like, and Patent Document 3 (International Publication No. 2012/0703602) shows that propylene glycol alginate is a cause of periodontal disease. It has the effect of suppressing the adhesion of tooth surfaces to bacteria, and when combined with isopropylmethylphenol and a nonionic surfactant in a dentifrice composition, it can effectively suppress the generation of periodontopathic biofilms. Proposed.

JP 2010-189358 A International Publication No. 2010/113688 International Publication No. 2012/0773602

  Therefore, in the composition for oral cavity which mix | blended the copper compound, persistence of the bad breath suppression effect and reduction of the taste peculiar to a copper compound became a subject.

  The present invention has been made in view of the above circumstances, and provides a composition for oral cavity containing a water-soluble copper compound that is excellent in sustainability of bad breath suppression effect, has a metallic taste suppressed, and has a good taste when used. The purpose is to do.

  As a result of intensive investigations to achieve the above object, the present inventor has found that when (A) a water-soluble copper compound and (B) propylene glycol alginate are used in combination, the components (A) and (B) When the mass ratio of (A) / (B) indicating the blending ratio is within a specific range, the sustainability of the bad breath suppression effect is improved, and the metal taste peculiar to the copper compound is suppressed, thereby improving the taste. By blending the component (B) with the mass ratio of (A) / (B) to the oral composition containing the component (A) within a specific range, the effect of suppressing bad breath is excellent and the metallic taste is excellent. It has been found that a preparation that is suppressed and gives an excellent feeling of use with good taste and is suitable for prevention or suppression of bad breath can be obtained, and the present invention has been made.

  That is, from the point of the production mechanism of the main causative substances, bad breath that is difficult to suppress persistently and effectively is suppressed over a long period of time, and at this time, the metal taste peculiar to water-soluble copper compounds is suppressed. Although it has not been possible so far, in the present invention, when (B) a propylene glycol alginate is properly used in combination with (A) a water-soluble copper compound, surprisingly, the persistence of the effect of suppressing bad breath derived from component (A) Improved and has a long-term bad breath suppression effect that effectively suppresses bad breath even after 4 hours of use in the oral cavity, and the metal taste peculiar to water-soluble copper compounds has been reduced to significantly improve the taste. In addition, the feeling of stickiness derived from propylene glycol alginate is reduced and a preparation suitable for use can be provided. In this case, although the bad breath suppressing effect is not recognized in the propylene glycol alginate, the above-mentioned special effects can be given specifically by the combined system of the components (A) and (B).

  In addition, improvement of halitosis suppression effect and bitterness suppression by combined use of allantoin and nonionic surfactant in Patent Document 1, and convergence by combined use of betaine-type amphoteric surfactant and specific sugar alcohol in Patent Document 2 From the improvement of the feeling imparting effect and the suppression of the bitterness, it is impossible to predict that the propellant glycol ester of alginic acid improves the sustainability of the bad breath suppression effect derived from the water-soluble copper compound, and the metal taste is also suppressed.

Accordingly, the present invention provides the following oral composition.
[1]
(A) 0.001 to 0.3% by mass of a water-soluble copper compound,
(B) 0.01 to 3% by mass of propylene glycol alginate, and (A) / (B) indicating the blending ratio of component (A) and component (B) is 0.01 to The composition for oral cavity characterized by being 5.
[2]
(A) The oral composition according to claim 1, wherein the water-soluble copper compound is copper gluconate and / or copper sulfate.

  ADVANTAGE OF THE INVENTION According to this invention, the oral cavity composition containing the water-soluble copper compound which is excellent in the persistence of the bad breath suppression effect, suppresses a metal taste, and provides the outstanding feeling of good taste can be provided.

  The present invention will be described in detail below. The composition for oral cavity of this invention contains (A) water-soluble copper compound and (B) alginate propylene glycol ester.

Examples of the water-soluble copper compound of component (A) include copper gluconate, copper citrate, copper sulfate and the like, and one kind may be used alone or two kinds may be used in combination. Particularly preferred is copper gluconate. As the water-soluble copper compound, not only an anhydride but also a hydrate containing crystal water such as copper sulfate pentahydrate can be used.
A commercially available product can be used as the water-soluble copper compound. For example, as copper gluconate, Hellcious Cu manufactured by Fuso Chemical Industry Co., Ltd., and as copper sulfate, copper sulfate manufactured by Kanto Chemical Co., Inc. Pentahydrate etc. can be used.

(A) The compounding quantity of the water-soluble copper compound of a component is 0.001-0.3% (mass%, the following is the same) of the whole composition, Preferably it is 0.01-0.2%. . When the content is less than 0.001%, a bad breath suppression effect cannot be expected for a long time. Moreover, when it exceeds 0.3%, the metallic taste peculiar to a water-soluble copper compound will become strong, and even if it uses alginate propylene glycol ester together, a metallic taste cannot be reduced.
In addition, within the range of the above blending amount, the blending amount of the water-soluble copper salt of the component (A) is preferably 0.0001 to 0.05%, particularly preferably 0.001 to 0.03% of the whole composition as copper. .

(B) Propylene glycol ester of alginic acid is obtained by esterifying the carboxyl group of alginic acid with propylene oxide, and various degrees of polymerization, that is, various molecular weights, various intramolecular β-D-mannuronic acid / α-L, depending on the application. -Gluuronic acid quantitative ratio (M / G ratio (molar ratio), the same shall apply hereinafter) and various esterification degrees can be used. In the present invention, particularly preferred propylene glycol alginate has an M / G ratio exceeding 1.0 and the upper limit is 2 or less.
Further, the esterification degree of the carboxyl group is preferably 40% or more, more preferably 70 to 95%.

  Furthermore, it is preferable that the viscosity at 20 ° C. (hereinafter the same) of a 1% aqueous solution by a measuring method using a B-type viscometer described later is in the range of 10 to 1,300 mPa · s, particularly 10 to 200 mPa · s.

As such alginate propylene glycol ester, those commercialized under a trade name such as Kimiloid manufactured by Kimika Co., Ltd., for example, Kimika Kimiloid BF, LLV, NLSK, LV, MV, HV, kelp Commercially available products such as acids 501, 503, and 542, and Duckroid LF and PF of Food Chemifa Co., Ltd. can be used.
The propylene glycol alginate can be used alone or in combination of two or more depending on the type of product.
Specifically, the following commercially available products can be used.
Alginic acid propylene glycol ester: manufactured by Kimika Co., Ltd., trade name: Kimiloid BF, M / G ratio: 1.3, degree of esterification: 80%, viscosity of 1% aqueous solution (20 ° C.): 20 mPa · s (rotor no. 1, 60 rpm)
Propylene glycol ester alginate: manufactured by Kimika Co., Ltd., trade name: Kimiloid LV, M / G ratio: 1.3, degree of esterification: 80%, viscosity of 1% aqueous solution (20 ° C.): 90 mPa · s (rotor no. 1, 30 rpm)
Propylene glycol alginate: manufactured by Kimika Co., Ltd., trade name: Kimiloid HV, M / G ratio: 1.3, degree of esterification: 80%, viscosity of 1% aqueous solution (20 ° C.): 200 mPa · s (rotor No. 2, 60 rpm)
Propylene glycol ester alginate: manufactured by Kimika Co., Ltd., trade name: kelp acid 503, M / G ratio: 1.3, degree of esterification: 80%, viscosity of 1% aqueous solution (20 ° C.): 18 mPa · s (rotor No. .1, 60 rpm)

The viscosity is a value measured by a BL type viscometer, and specifically, a measured value by the following method.
Viscosity measurement method (Duck Lloyd, Food Chemifa Corporation)
4 g of propylene glycol alginate is collected and placed in a 600 mL beaker, and 396 g of purified water is added little by little while stirring with a stir bar. First, dissolve well with a small amount of water. Thereafter, the mixture is allowed to swell for 1 hour, and after 1 hour, the mixture is stirred for 1 minute at 12,000 rpm with a high-speed stirrer (homomixer). This solution is put into a 300 mL tall beaker and allowed to stand in a 20 ° C. water bath. When the foam rises and the beaker solution is clear, remove the foam with a spoon. A thermometer is put in a beaker to confirm that the test solution has reached 20 ° C., and the viscosity is measured.
Viscometer: Tokyo Keiki BL type viscometer rotor: No. 1
Rotation speed: 60rpm
Measurement time: 1 minute

Viscosity measurement method (Kimiloid, Kimlicum, Kimika Co., Ltd.)
In a 300 mL tall beaker, 297 g of purified water is taken and 3.0 g of alginic acid propylene glycol ester is added and completely dissolved while stirring with a stirrer or three-one motor. Next, after leaving still in a 20 degreeC thermostat for 1 hour, the viscosity after 1 minute is measured correctly using BL type | mold viscometer.
Viscometer: Tokyo Keiki BL type viscometer measurement conditions ・ When 1% aqueous solution viscosity is 10-80 mPa · s: Rotor No. 1. Rotation speed 60rpm
When the 1% aqueous solution viscosity exceeds 80 mPa · s and is 160 mPa · s or less: Rotor No. 1, rotation speed 30rpm
When the 1% aqueous solution viscosity exceeds 160 mPa · s and is 400 mPa · s or less: Rotor No. 2, rotation speed 60rpm
When the 1% aqueous solution viscosity exceeds 400 mPa · s and is 800 mPa · s or less: Rotor No. 2, rotation speed 30rpm
When the 1% aqueous solution viscosity exceeds 800 mPa · s and is 1600 mPa · s or less: Rotor No. 3, rotation speed 60rpm
Measurement time: 1 minute

  In the present invention, the blending amount of the propylene glycol alginate as the component (B) is 0.01 to 3% of the whole composition from the viewpoint of long-term bad breath suppressing effect and metallic taste reducing effect, and preferably is 0.00. It is 05 to 3%. If the blending amount is less than 0.01%, the effect of suppressing bad breath for a long time and the effect of reducing the metallic taste derived from copper cannot be expected. If it exceeds 3%, the alginic acid propylene glycol ester becomes sticky and the usability is poor.

In this invention, by mix | blending (A) component and (B) component by a suitable ratio, the bad breath suppression effect is excellent, the reduction effect of a metallic taste is improved, and a sticky feeling can also be suppressed. In this case, (A) / (B) which shows the ratio of the blending amount of the component (A) and the component (B) is 0.01 to 5, preferably 0.03 to 2, more preferably Is 0.1-2. If (A) / (B) is less than 0.01, a bad breath suppression effect cannot be expected for a long time. If it exceeds 5, the metallic taste derived from copper cannot be reduced.
In addition, in the mass ratio of (A) / (B), the ratio of the blending amount of the water-soluble copper compound of the component (A) as copper and the blending amount of the component (B) is shown (A-1 ) / (B) is preferably 0.001 to 1.0, and particularly preferably 0.01 to 0.3 as a mass ratio.

  The oral composition of the present invention can be prepared as a dentifrice such as a toothpaste and a liquid dentifrice, a mouthwash, and the like, but is particularly suitable as a dentifrice, especially a toothpaste. Moreover, the well-known component normally used besides the said component can be mix | blended as needed according to the dosage form. For example, in a dentifrice such as a toothpaste, an abrasive, a thickener, a binder, a surfactant, a sweetener, an antiseptic, a colorant, a fragrance, an active ingredient other than the above, and the like, the effects of the present invention are achieved. It can be used in a normal amount as long as it does not interfere.

Examples of the abrasive include silica-based abrasives such as silica gel, precipitated silica, aluminosilicate, zirconosilicate, calcium phosphate-based abrasives such as dicalcium phosphate, aluminum hydroxide, alumina, calcium carbonate, synthetic resin-based abrasives, etc. It is done.
The blending amount of the abrasive is usually 5 to 50%.

  Examples of the thickener include polyhydric alcohols such as polyethylene glycol, propylene glycol, and glycerin having an average molecular weight (average molecular weight described in Quasi-drug Raw Material Standard 2006) 190 to 3800, sorbit, and the like. The amount of these thickeners is usually 5 to 50%. In addition, sorbit etc. are suitable for a viscous agent.

  Examples of the binder include gums such as xanthan gum, polyacrylic acid such as sodium polyacrylate or derivatives thereof, and cellulose derivatives such as sodium carboxymethylcellulose. The amount of the binder is usually 0 to 5%, particularly 0.1 to 5%.

As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a betaine surfactant can be blended.
Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate. Examples of nonionic surfactants include polyhydric acids such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sugar alcohol fatty acid esters such as sucrose fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, and polyoxyethylene glycerin fatty acid esters. Examples include alcohol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, and fatty acid alkanolamides. Examples of the cationic surfactant include alkyl ammonium type. As the surfactant, an alkyl sulfate such as sodium lauryl sulfate can be suitably used.
The blending amount of the surfactant is preferably 0.5 to 5% of the entire composition.

  Examples of the sweetening agent include saccharin sodium. Examples of the preservative include paraoxybenzoic acid esters such as methylparaben, benzoic acid or a salt thereof. Examples of the colorant include blue No. 1, yellow No. 4, titanium oxide and the like.

  Perfumes include peppermint oil, spearmint oil, anise oil, eucalyptus oil, winter green 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, grapefruit oil, sweetie Natural fragrances such as oil, coconut oil, Iris concrete, absolute peppermint, absolute rose, orange flower, and processing of these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder Perfumes, etc.) and menthol, Rubon, Anethole, Cineol, Methyl salicylate, Synamic aldehyde, Eugenol, 3-1-Mentoxypropane-1,2-diol, Thymol, Linalol, Linarel acetate, Limonene, Menthone, Menthyl acetate, N-Substituted paramenthane 3-carboxamide, pinene, octyl aldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, Hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, ethyl Oral compositions such as single flavors such as o-acetate, and other flavors 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. It can be used in combination with known perfume materials used in the above. The blending amount is usually 0.00001 to 3%.

  As the active ingredient, known ingredients that are usually blended in oral compositions can be used, for example, fluorides, bactericides, anti-inflammatory agents, enzymes, plant extracts, tartar inhibitors, plaque inhibitors, etc. . Specifically, fluorides such as sodium fluoride and sodium monofluorophosphate, nonionic fungicides such as isopropylmethylphenol, cationic fungicides, enzymes such as dextranase, tranexamic acid, epsilon aminocaproic acid and the like Examples include anti-inflammatory agents. In addition, the said active ingredient can be mix | blended in an effective amount in the range which does not prevent the effect of this invention.

  EXAMPLES Hereinafter, although an Example, a comparative example, a formulation example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “%” means “% by mass” unless otherwise specified.

[Examples and Comparative Examples]
Oral compositions (toothpastes) having the compositions shown in Tables 1 and 2 were prepared by a conventional method and evaluated by the following methods. The results are shown in Tables 1 and 2.

(1) Evaluation method of halitosis suppression effect (long-term halitosis suppression effect) Using 4 healthy subjects with no disease and not taking antibiotics, oral cleaning was stopped from the day before the test, and excessive amounts of alcohol and odor Ingestion of tight food was prohibited. The next morning, 0.5 ml of the breath of the subject who finished eating and drinking by 2 hours before the test was collected, and the concentration (initial concentration) of methyl mercaptan was measured using oral chroma manufactured by FIS Co., Ltd. Thereafter, the tooth was brushed with 1 g of the sample for 3 minutes, and the breath after 4 hours was collected again, and the concentration of methyl mercaptan was similarly measured. When the initial value was set to 100, the initial value (vs. initial decrease rate) was calculated from the following formula, and the bad breath suppression effect was evaluated according to the following criteria.
Formula for calculating initial value:
Vs. initial value (%) = (concentration after 4 hours) / (initial concentration) × 100
Evaluation criteria for long-term bad breath suppression effect:
A: Initial reduction rate after 4 hours is less than 60% B: Initial reduction rate after 4 hours is 60% or more and less than 80% Δ: Initial reduction rate after 4 hours is 80% or more and less than 100% ×: 100% reduction in initial rate after 4 hours

(2) Evaluation method of metallic taste reduction effect Using 10 subjects, about 1 g of the oral composition was put on a toothbrush and the tooth taste was brushed for 3 minutes. Evaluation was made with 3 points for feeling metallic taste, 2 points for feeling metallic taste, and 1 point for feeling very metallic taste.
The metal taste reduction effect was evaluated from the average score of 10 people according to the following criteria.
Evaluation criteria for metallic taste reduction effect:
◎: Average point 3.5 or more and less than 4.0 point ○: Average point 3.0 or more and less than 3.5 point △: Average point 2.0 or more and less than 3.0 point ×: Average point 1.0 point More than 2.0 points

(3) Evaluation method of the reduction effect of stickiness Using 10 subjects, about 1 g of the composition for oral cavity is put on a toothbrush, and when sticking for 3 minutes, the stickiness is felt at all 4 points, feels slightly sticky 3 points, 2 points for feeling sticky, and 1 point for feeling very sticky.
The reduction effect of stickiness was evaluated from the average score of 10 people according to the following criteria.
Evaluation criteria for reduction of stickiness:
◎: Average point 3.5 or more and less than 4.0 point ○: Average point 3.0 or more and less than 3.5 point △: Average point 2.0 or more and less than 3.0 point ×: Average point 1.0 point More than 2.0 points

Details of the raw materials used are shown below.
(A) Copper gluconate; manufactured by Fuso Chemical Industry Co., Ltd.
(A) Copper sulfate; manufactured by Kanto Chemical Co., Inc., copper sulfate pentahydrate (B) alginate propylene glycol ester;
Product name: Kimiloid BF, M / G ratio: 1.3, degree of esterification: 80%, viscosity of 1% aqueous solution (20 ° C.): 20 mPa · s (BL viscometer, rotor No. 1, 60 rpm)

  Hereinafter, Table 3 shows formulation examples. The raw materials used are the same as in the examples.

Claims (2)

(A) 0.001 to 0.3% by mass of a water-soluble copper compound,
(B) 0.01 to 3% by mass of propylene glycol alginate, and (A) / (B) indicating the blending ratio of component (A) and component (B) is 0.01 to The composition for oral cavity characterized by being 5.   (A) The oral composition according to claim 1, wherein the water-soluble copper compound is copper gluconate and / or copper sulfate.