JP6981243B2 - Toothpaste composition - Google Patents

Description

The present invention relates to a dentifrice composition containing a water-soluble copper compound, which provides an excellent halitosis suppressing effect and a tight feeling, reduces a metallic taste, and has a good taste.

Conventionally, it has been known that a water-soluble copper compound such as copper gluconate has an effect of suppressing halitosis caused by periodontal disease, particularly methyl mercaptan, which is a halitosis component.
On the other hand, since the water-soluble copper compound has a metallic taste and an unpleasant taste, in order to improve the usability of the oral composition, a chelating agent is used in combination with the water-soluble copper compound to form a complex ion to form a metallic taste. Etc. are masked.
However, as the metallic taste is masked, there is a trade-off relationship that the water-soluble copper salt forming the complex cannot fully exert its effectiveness in the oral cavity, and the effect of the water-soluble copper compound should be maximized. I couldn't.

Patent Document 1 (Japanese Patent No. 2580657) proposes a kneaded toothpaste having an excellent effect of suppressing mouth odor, which is obtained by blending a copper compound such as copper gluconate with a polybasic acid such as citric acid or a salt thereof. In Patent Document 2 (Japanese Patent Laid-Open No. 4-159211), the residual amount of the soluble copper compound is improved by blending amino acids, and in Patent Document 3 (Japanese Patent Laid-Open No. 3922329), water-soluble transition of copper gluconate or the like is made. It is proposed that the astringency and metallic taste can be improved by adding a specific amino acid to a toothpaste composition containing a metal compound and condensed phosphoric acid.

Japanese Patent No. 2580657 Japanese Unexamined Patent Publication No. 4-159211 Japanese Patent No. 3922329 Japanese Unexamined Patent Publication No. 2014-125440 Special Table 2012-508741 Japanese Unexamined Patent Publication No. 2003-137755

The present invention has been made in view of the above circumstances, and is a dentifrice composition containing a water-soluble copper compound, which gives an excellent halitosis suppressing effect and a tight feeling, suppresses a metallic taste, and has a good feeling of use. The purpose is to provide.

As a result of diligent studies to achieve the above object, the present inventors have added (1R, 2S, 5R) -N to a dentifrice composition containing a water-soluble copper compound and a substance having a specific chelating action. -When (4- (cyanomethyl) phenyl) menthylcarboxamide is blended in a specific amount ratio, the metallic taste of the water-soluble copper compound is masked and reduced, and the effect of the water-soluble copper compound is fully utilized to suppress mouth odor and the effect of suppressing mouth odor. It was found that the feeling of tightness can be improved. That is, according to the present invention, one selected from (A) a water-soluble copper compound and (C) an organic acid having 10 or less carbon atoms, polyphosphoric acid, α-amino acid and salts thereof as a substance having a chelating action. (B) (1R, 2S, 5R) -N- (4- (cyanomethyl) phenyl) menthylcarboxamide is blended in the dentifrice composition containing the above, and (B) / (A) is 0 as a mass ratio. When it is 0.0005 or more and (C) / (A) is 0.005 to 30 in mass ratio, it gives an excellent mouth odor suppressing effect and a tight feeling, and also suppresses a metallic taste, resulting in a good usability. It has been found that the dentin composition having can be provided, and the present invention has been made.

In the present invention, when the component (B) is combined with the components (A) and (C), the mass ratio of (B) / (A) and (C) / (A) is within a specific range, respectively, and the component (B) The metallic taste of the component (A) is specifically masked and reduced, and at the same time, the action and effect of the component (A) are sufficiently and sufficiently exhibited even when the component (C), which is a chelating agent, is used in combination. As a result, it was possible to achieve both the effect of suppressing bad breath, the improvement of the tightness, and the suppression of metallic taste.
As shown in the comparative example described later, even if the components (A), (B) and (C) are blended, the mass ratio of (B) / (A) or the mass ratio of (C) / (A) If is inappropriate, the lack of metallic taste is inferior (×, Comparative Examples 8 and 9), and if the component (B) is not blended, the components (A) and (C) are blended, and N of mentholcarboxamides is blended. Even if -ethyl-p-menthane-3-carboxamide is blended, or even if menthol, which is a common fragrance for dentin, is blended, the lack of metallic taste is inferior (x, Comparative Examples 3 to 5). In these cases, the action and effect of the present invention were inferior. On the other hand, as shown in Examples, the dentifrice composition containing the components (A), (B) and (C) of the present invention in a specific amount ratio is excellent in halitosis suppressing effect and tightness, and is a metal. The taste was also low.
According to the present invention, it is possible to suppress the blending amount of the chelating agent, and it is also possible to prevent an adverse effect on the effect of the water-soluble copper compound.
It is known that mentancarboxamides, which are cooling sensitizers, are applied to improve the feeling of use in oral compositions (Patent Documents 4 to 6; JP-A-2014-125440, JP-A-2012-508741). Japanese Patent Application Laid-Open No. 2003-137755), and Patent Document 6 uses N-ethyl-p-menthane-3-carboxamide and menthol to improve the metallic taste of a dentifrice containing copper gluconate. However, in the present invention, the component (B) improves the halitosis suppressing effect, the tightness and the metallic taste, and a special effect that cannot be achieved when N-ethyl-p-menthane-3-carboxamide or menthol is used. It is effective. In Patent Document 6, the blending amount of N-ethyl-p-menthane-3-carboxamide is relatively large, and the flavor may be limited to a very strong cooling sensation. However, in the present invention, the component (B) is used. Since the action and effect can be obtained even if the blending amount is small, the above-mentioned problems are unlikely to occur.

Therefore, the present invention provides the following dentifrice composition.
[1]
(A) Water-soluble copper compound,
(B) (1R, 2S, 5R) -N- (4- (cyanomethyl) phenyl) menthylcarboxamide, and (C) organic acids having 10 or less carbon atoms, polyphosphates, α-amino acids and salts thereof. A dentin composition containing at least one kind, (B) / (A) having a mass ratio of 0.00005 or more, and (C) / (A) having a mass ratio of 0.005 to 30. thing.
[2]
(A) The dentin composition according to [1], wherein the water-soluble copper compound is at least one selected from copper gluconate, copper citrate and copper sulfate.
[3]
The dentin composition according to [1] or [2], wherein the organic acid is at least one selected from citric acid, lactic acid, succinic acid, tartaric acid, malic acid and edetic acid.
[4]
The dentifrice composition according to any one of [1] to [3], wherein (B) / (A) is 0.0001 or more and 0.5 or less as a mass ratio.
[5]
The dentifrice composition according to any one of [1] to [4], wherein (C) / (A) is 0.1 or more and 5 or less as a mass ratio.
[6]
[1] to [5] containing 0.01 to 5% by mass of the component (A), 0.00001 to 0.02% by mass of the component (B), and 0.01 to 10% by mass of the component (C). The dentifrice composition according to any one.
[7]
The dentifrice composition according to any one of [1] to [6], which is a dentifrice.

According to the present invention, it is possible to provide a dentifrice composition containing a water-soluble copper compound, which gives an excellent halitosis suppressing effect and a tightness feeling, reduces a metallic taste, and has a good taste in use. This dentifrice composition can be suitably used for suppressing bad breath.

Hereinafter, the present invention will be described in more detail. The dentin composition of the present invention comprises (A) a water-soluble copper compound, (B) (1R, 2S, 5R) -N- (4- (cyanomethyl) phenyl) menthylcarboxamide, and (C) a specific organic acid. It contains one or more selected from polyphosphoric acid, α-amino acid and salts thereof, and is characterized in that the amount ratio of each component is a specific ratio.

(A) The water-soluble copper compound has an effect of suppressing bad breath and an effect of imparting a feeling of tightening.
Specific examples of the water-soluble copper compound include water-soluble copper salts such as copper gluconate, copper citrate, copper sulfate, copper chloride, sodium copper chlorophyllin, and copper acetate. These may be used alone or in combination of two or more. Of these, copper gluconate, copper citrate, and copper sulfate are preferable.
The blending amount of the (A) water-soluble copper compound is preferably 0.01 to 5% (mass%, the same applies hereinafter) of the entire composition, and more preferably 0.1 to 1%. When it is 0.01% or more, a sufficient halitosis suppressing effect and a tight feeling can be obtained. When it is 5% or less, the metallic taste due to the component (A) can be sufficiently suppressed.

(B) (1R, 2S, 5R) -N- (4- (cyanomethyl) phenyl) menthylcarboxamide is a masking agent having a metallic taste, and has an effect of suppressing the metallic taste due to the component (A). As the component (B), a commercially available product can be used.
The blending amount of the component (B) is preferably 0.00001 to 0.02%, more preferably 0.00003 to 0.01% of the entire composition. When it is 0.00001% or more, a sufficient masking effect can be obtained. When it is 0.02% or less, it is possible to sufficiently prevent the irritation of the component (B) itself and the development of taste and maintain a good usability.

The component (C) is one or more selected from organic acids, polyphosphoric acids, α-amino acids and salts thereof having 10 or less carbon atoms. These are substances having a chelating action.
Specific examples of the organic acid having 10 or less carbon atoms include citric acid, lactic acid, succinic acid, tartaric acid, malic acid, phthalic acid, salicylic acid, edetic acid, benzoic acid and the like. The salt is an alkali metal salt such as a sodium salt or a potassium salt. Among these, citric acid, lactic acid, succinic acid, tartrate acid, malic acid, edetic acid or salts thereof are particularly preferable, and citric acid, lactic acid, edetic acid or alkali metal salts thereof, particularly alkali metal of citric acid. It is salt.
Examples of polyphosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, trimetaphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid and the like, and the salt is an alkali metal salt such as a sodium salt and a potassium salt. Of these, sodium tripolyphosphate is particularly preferable.
Examples of the α-amino acid or a salt thereof include glycine, alanine, histidine and the like and salts thereof, and among these, glycine or a salt thereof (preferably hydrochloride) is particularly preferable.
As the component (C), an organic acid having 10 or less carbon atoms, particularly an alkali metal salt of citric acid, is particularly preferable in terms of a mouth odor suppressing effect, a tightness feeling, and a lack of metallic taste.
As the component (C), a commercially available product can be used.

The blending amount of the component (C) is preferably 0.01 to 10%, more preferably 0.05 to 1% of the entire composition. When it is 0.01% or more, a sufficient metallic taste masking effect can be obtained. When it is 10% or less, the effect of suppressing bad breath and the effect of imparting a tightness can be sufficiently ensured.

In the present invention, (B) / (A) indicating the quantitative ratio of the component (A) to the component (B) has a mass ratio of 0.00005 or more, preferably 0.0001 or more, particularly 0.0005 or more. Is. The upper limit is not particularly limited, but is preferably 0.5 or less, more preferably 0.1 or less, from the viewpoint of flavor balance. When the mass ratio of (B) / (A) is less than 0.00005, the metallic taste due to the component (A) is strong and the usability is inferior.

Further, (C) / (A) indicating the quantitative ratio of the component (A) to the component (C) is 0.005 to 30 as a mass ratio, preferably 0.05 to 5, and more preferably 0. 1 to 5 When the mass ratio of (C) / (A) is less than 0.005, the metallic taste due to the component (A) is strong and the usability is inferior. If it exceeds 30, the effect of suppressing bad breath and the effect of imparting a feeling of tightness are weakened.

The dentifrice composition of the present invention can be prepared as dentifrice, liquid dentifrice, dentifrice, etc., and dentifrice is particularly suitable. Further, in addition to the above-mentioned components, if necessary, other known components usually used in the dentifrice composition are blended within a range that does not impair the effects of the present invention, and water is blended in the usual method. Can be prepared with. Examples of the optional ingredients that can be blended include abrasives, thickeners, binders, surfactants, sweeteners, fragrances, pH adjusters, preservatives, medicinal ingredients and the like.

The polishing agent is a calcium phosphate-based polishing agent such as calcium dibasic phosphate / dihydrate salt or anhydrous salt, calcium primary phosphate, calcium tertiary phosphate, calcium pyrophosphate, etc .; sedimentation silica, aluminosilicate, zirconosilicate, titanium-binding silica, etc. Calcium-based abrasives; calcium carbonate-based abrasives such as calcium carbonate; calcium hydroxide, aluminum hydroxide, tertiary magnesium phosphate, magnesium carbonate, calcium sulfate, bentonite, hydroxyapatite, and one or two of these. Can contain more than seeds. Among these, silica-based abrasives and calcium carbonate-based abrasives containing silicates as main components such as sedimentation silica, aluminosilicate, zirconosilicate, and titanium-binding silica, and silica-based such as sedimentation silica in particular. A polishing agent is preferable in terms of suppressing mouth odor and imparting a tightness feeling. The precipitating silica is preferably, for example, having a particle size of 1 to 40 μm and a BET specific surface area of 80 to 250 square meters per gram.
The blending amount of these abrasives is preferably 8 to 70% of the total composition.

Further, the abrasive may be granules, and granules can be blended as a component having abrasiveness. The granules are granulated particles obtained by forming water-insoluble powder into granules, and a binder may be used for granulation. In particular, silica granules and zeolite granules are suitable.
Water-insoluble powders include dibasic calcium phosphate, tertiary calcium phosphate, water-insoluble calcium metaphosphate, silica, aluminum hydroxide, magnesium phosphate, red iron oxide, calcium carbonate, calcium pyrophosphate, zeolite, aluminosilicate, magnesium carbonate, and zirconosilicate. , Inorganic powder such as calcium sulfate and mixtures thereof.
The volume average particle size (median diameter d50) of the granules is preferably 50 to 500 μm. The volume average particle size is a value measured by a particle size distribution measuring device (Microtrak particle size distribution meter manufactured by Nikkiso Co., Ltd., dispersion medium; water).
The average disintegration strength of the granules is preferably 10 to 200 g / piece. The average disintegration strength is the automatic breaking strength measurement value of 30 granules by a reometer (Sun Reometer CR-200D, manufactured by Sun Kagaku Co., Ltd.) (this granule disintegrates when one granule is compressed at a rate of 10 mm / min. It is the average value of the measured value of the load at the time of.
As the silica granules, wet gel method silica and precipitation method silica are preferably used, and the primary particle size is preferably about 3 to 15 nm, preferably 4 to 10 nm. For example, a method of classifying silica gel granules having an average particle size of 50 to 500 μm by washing and drying a mass of silica gel whose primary particle size has been grown to about 4 to 10 nm by a gel method and then pulverizing the silica gel hydrosol. Granules can be prepared by spraying them in the air and gelling them, or by a precipitation method to agglomerate the granules while suppressing the growth of the primary particles and then to grow the primary particle size to about 4 to 10 nm. Known and these methods can be used to prepare silica gel granules.
In addition, colored granules can also be used.
The blending amount of these granules is preferably 0.1 to 20% of the total composition.

Examples of the viscous agent include polyhydric alcohols such as glycerin, propylene glycol and polyethylene glycol, and sugar alcohols such as sorbitol and xylit. The blending amount of the thickener is preferably 5 to 50%, particularly 20 to 45% of the whole composition.

Binders include xanthan gum, sodium carboxymethyl cellulose, sodium polyacrylate, sodium alginate, polyvinylpyrrolidone, carrageenan, methyl cellulose, hydroxyethyl cellulose sodium, tragant gum, karaya gum, arabiya gum, locust bean gum, polyvinyl alcohol, carboxyvinyl polymer, carbopol, Organic binders such as bee gum and propylene glycol alginate, and inorganic binders such as thickening silica and aluminum silicate can be blended. These can be used in one type or two or more types. The blending amount of these binders is preferably 1.4 to 10%, particularly 1.4 to 8% of the total composition.

Examples of the surfactant include an anionic surfactant, a nonionic surfactant, and an amphoteric active agent, and an anionic surfactant is particularly preferable.
Examples of the anionic surfactant include N-acyl taurates such as alkyl sulfate, α-olefin sulfonate, hydrogenated coconut fatty acid monoglyceride monosulfate, lauryl sulfoacetate, and N-methyl-N-acyl taurine salt. Examples thereof include acyl amino acid salts such as acyl sulfosin salt and N-acyl-L-glutamate. Among them, an anionic surfactant containing a sulfonic acid group, which has good foaming and foaming quality, is preferable, and an alkyl sulfate and an α-olefin sulfonate are more preferable. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like, and sodium salt is particularly preferable.
The alkyl sulfate preferably has 12 to 14 carbon atoms in the alkyl group, and specific examples thereof include sodium lauryl sulfate and sodium myristyl sulfate.
The α-olefin sulfonate is preferably an alkali metal salt such as sodium or potassium of an α-olefin sulfonic acid having 14 to 16 carbon atoms, and particularly an α-olefin sulfonate having 14 carbon atoms, particularly a sodium salt (generic name). ; Sodium tetradecene sulfonate) is preferred.
These surfactants may be used alone or in combination of two or more.
The blending amount of the surfactant, particularly the anionic surfactant, is preferably 0.6 to 2.5%, particularly preferably 1 to 2.5% of the entire composition.

Examples of the sweetener include sodium saccharin, glycerin, stebioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidyldihydrochalcone, perillartine, glycyrrhizin, thaumatin, aspalathylphenylalanine methyl ester and the like.

The fragrances are known fragrances such as menthol, anator, carboxylic, eugenol, limonene, n-decyl alcohol, citronellol, α-terepineol, citronellyl acetate, cineole, linalol, ethyllinalol, varnish, timole, sparemint oil, peppermint oil, Lemon oil, orange oil, sage oil, rosemary oil, katsura oil, pimento oil, katsura leaf oil, perilla oil, winter green oil, choji oil, eucalyptus oil can be mentioned.

Examples of the pH adjuster include inorganic compounds such as hydrochloric acid, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, and sodium dihydrogen phosphate.
Examples of the preservative include paraoxybenzoic acid ester and sodium benzoate.

Optional medicinal ingredients include enzymes such as dextranase, amylase, protease, mutanase; anti-inflammatory agents such as tranexamic acid, epsilon aminocaproic acid, aluminum chlorhydroxyalantin, azulene, glycyrrhizinate, glycyrrhetinate; sodium chloride, vitamins. Cell activators such as isopropylmethylphenol, cetylpyridinium chloride, benzalkonium chloride, hinokithiol, lysodium chloride and the like; antiseptic agents such as zeolite; blood circulation promoters such as vitamin E can be blended. The blending amount of the medicinal ingredient can be an effective amount within a range that does not interfere with the effect of the present invention.

Further, as optional components, inorganic compounds such as mica titanium, titanium oxide and bentonite; cellulose-based organic powders such as crystalline cellulose; natural polymer compounds such as agar, gelatin, starch and glucomannan; polyvinyl acetate, acrylic, Synthetic polymer compounds such as polyurethane, polyester, polyvinyl chloride, nylon powder, polyethylene powder or their copolymers; waxes such as carnauba wax, rosin, rice wax, microcrystallin wax, honey wax, paraffin wax; cetanol, stearyl Higher alcohols such as alcohols; polyisobutylene, polybutadiene, polyurethane, silicone, natural rubber and the like can be blended within a range that does not interfere with the effects of the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples,% indicates mass% unless otherwise specified.

[Examples, comparative examples]
The dentifrice composition (dentifrice) having the composition shown in Tables 1 to 4 was prepared by a usual method and evaluated by the following method. The results are also shown in the table.

<Evaluation method>
The usability was evaluated by 5 subjects. 1 g of a sample dentifrice composition was placed on a toothbrush (Clinica Advantage Habrush, 4-row compact normal type, manufactured by Lion Corporation), and the teeth were brushed for 3 minutes. The effect of suppressing bad breath after rinsing and the metallic taste (no metallic taste) and the tightness as a feeling of use were evaluated using the following scoring criteria. From the average value of the scores of 5 people, the evaluation was made according to the following evaluation criteria.
The halitosis-suppressing effect was evaluated by a specialized panelist according to the following criteria, and the metallic taste (no metallic taste) and the tightness were evaluated by the subjects.

Rating criteria for halitosis suppression effect 1. I feel bad breath 2. I feel bad breath 3. I feel a little bad breath, but there is no problem. I hardly feel bad breath 5. Evaluation criteria for halitosis suppression effect ◎: Average score of 5 people is 4 points or more ○: Average score of 5 people is 3 points or more and less than 4 points ×: Average score of 5 people is less than 3 points

Rating criteria for metallic taste (no metallic taste) 1. Feel the metallic taste 2. I feel a lot of metallic taste. I feel a little metallic taste, but it is a level that is acceptable and there is no problem. Almost no metallic taste 5. Evaluation criteria for metallic taste (no metallic taste) ◎: Average score of 5 people is 4.5 points or more ○: Average score of 5 people is 4 points or more and less than 4.5 points △: 5 people Average score is 3 points or more and less than 4 points ×: Average score of 5 people is less than 3 points

Criteria for squeezing feeling 1. I didn't feel the tightness 2. I felt almost no tightness. I felt a little tightness 4. I felt a tight feeling 5. Evaluation criteria for a feeling of tightness ◎: Average score of 5 people is 4.5 points or more ○: Average score of 5 people is 4 points or more and less than 4.5 points △: Average score of 5 people is 3 points Points or more and less than 4 points ×: Average score of 5 people is less than 3 points

Claims (7)

(A) Water-soluble copper compound,
(B) (1R, 2S, 5R) -N- (4- (cyanomethyl) phenyl) menthylcarboxamide, and (C) organic acids having 10 or less carbon atoms, polyphosphates, α-amino acids and salts thereof. A dentin composition containing at least one kind, (B) / (A) having a mass ratio of 0.00005 or more, and (C) / (A) having a mass ratio of 0.005 to 30. thing. (A) The dentin composition according to claim 1, wherein the water-soluble copper compound is at least one selected from copper gluconate, copper citrate and copper sulfate. The dentin composition according to claim 1 or 2, wherein the organic acid is at least one selected from citric acid, lactic acid, succinic acid, tartaric acid, malic acid and edetic acid. The dentifrice composition according to any one of claims 1 to 3, wherein (B) / (A) is 0.0001 or more and 0.5 or less as a mass ratio. The dentifrice composition according to any one of claims 1 to 4, wherein (C) / (A) is 0.1 or more and 5 or less as a mass ratio. Any of claims 1 to 5 containing 0.01 to 5% by mass of the component (A), 0.00001 to 0.02% by mass of the component (B), and 0.01 to 10% by mass of the component (C). The dentifrice composition according to item 1. The dentifrice composition according to any one of claims 1 to 6, which is a dentifrice.