JP7275850B2 - Toothpaste composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a toothpaste composition that contains a water-soluble copper compound and vitamin E, has a high halitosis suppressing effect, and has excellent vitamin E stability, and is effective for suppressing halitosis.

Water-soluble copper compounds such as copper gluconate have deodorant and antibacterial effects, and are excellent in suppressing halitosis components such as methyl mercaptan caused by periodontal disease. However, due to its high reactivity and the influence of other ingredients, the effect of suppressing bad breath is not sufficiently exhibited, and discoloration may occur. Techniques for improving these and imparting bad breath suppressing effects are Patent Documents 1 to 6 (Patent No. 2580656, Patent No. 2738021, Japanese Patent Publication No. 4-159211, Japanese Patent No. 2827500, Japanese Patent Publication No. 8-310928). No. 2882017).

Halitosis is often caused by periodontal diseases such as gingivitis and periodontitis, and prevention or control of these periodontal diseases is also important for controlling halitosis. As ingredients effective against gingivitis, periodontitis, etc., vitamin E such as tocopherol, which promotes blood flow and has tissue repair effects, is known. It is difficult to solubilize and stabilize it in , and it is difficult to satisfactorily express its efficacy. and stabilization using an inorganic acid, an organic acid, or an alkali metal salt thereof, or stabilization using a specific amino acid. Further, Patent Document 9 (Japanese Patent No. 2561829) proposes stabilization by blending a salt such as sodium carbonate into a vitamin E-containing toothpaste packed in a container.

Japanese Patent No. 2580656 Japanese Patent No. 2738021 JP-A-4-159211 Japanese Patent No. 2827500 JP-A-8-310928 Japanese Patent No. 2882017 JP 2017-214297 A Japanese Patent Publication No. 7-88292 Japanese Patent No. 2561829

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a toothpaste composition that contains a water-soluble copper compound and vitamin E, has a high bad breath suppressing effect, and has excellent vitamin E stability. do.

As a result of intensive studies to achieve the above objects, the present inventors have found that a water-soluble copper compound and tocopherol and/or its derivatives as vitamin E are used in combination, and sodium sulfate and/or sodium hydrogen carbonate are water-soluble. It was found that a toothpaste composition excellent in both halitosis suppressing effect and vitamin E stability can be obtained by blending a copper compound at a specific ratio and further blending with a specific water-soluble polymer substance. bottom.
That is, in the present invention, (A) a water-soluble copper compound, vitamin E as (B) one or more selected from tocopherol, esters thereof with organic acids, and salts thereof, and (C) sodium sulfate and sodium hydrogen carbonate. and (D) one or more water-soluble polymer substances selected from xanthan gum, carboxyvinyl polymer and sodium carboxymethylcellulose, and the content of component (A) is 0.001 to 0 as copper ions. A toothpaste composition in which (A) (copper ion concentration)/(C) is 0.0003 to 2 as a mass ratio (A) (copper ion concentration)/(C) provides a high bad breath suppressing effect and (B) is stable. The inventors have found that the stability of vitamin E is excellent due to the combination of the above ingredients, and that the occurrence of liquid separation can be suppressed even after storage, so that the appearance stability can be maintained, and the present invention has been completed.

In the present invention, when the components (A), (B), (C) and (D) are combined, the mass ratio of (A) / (C) is within a specific range, and an excellent bad breath suppressing effect is provided and (B ) component can be stabilized. In this case, if a water-soluble copper compound and vitamin E are used together, the stability of vitamin E is poor, and if an inorganic sodium salt such as sodium sulfate is added to improve the stability of vitamin E, a caking agent is added. Even if it is stored, liquid separation may occur after storage, which may cause problems in ensuring long-term stability of the formulation, and may lead to a decrease in the effect of suppressing bad breath. Both the bad breath suppressing effect and the stabilization of vitamin E could not be satisfied. Therefore, as a result of further intensive studies to solve the above problem, the (A) and (B) components are combined with the (C) component at a specific mass ratio of (A) / (C), and further (D ) components in combination, even after storage at high temperature (60 ° C), the occurrence of liquid separation is suppressed and the appearance of the formulation is maintained stably, giving an excellent bad breath suppressing effect, and even after storage at high temperature (60 ° C) ( It was possible to stabilize and blend the B) component.
The effects of the present invention were inferior when any one of the components (A), (B), (C) and (D) was lacking, as shown in Comparative Examples below. In this case, if the component (C) is not blended, the component (B) is not stabilized and the stability of vitamin E (VE) is poor (Comparative Example 3), and if the component (D) is not blended, Furthermore, even when sodium polyacrylate as a binder was blended, the lack of liquid separation was inferior (Comparative Example 4). In addition, even if the components (A), (B), (C) and (D) were blended, the stability of VE was inferior when the mass ratio of (A)/(C) was inappropriate (comparison Examples 5, 6). On the other hand, a toothpaste composition ( Example) was excellent in bad breath suppressing effect and VE stability, and was also excellent in no liquid separation.

Accordingly, the present invention provides the following toothpaste composition.
(A) a water-soluble copper compound,
(B) one or more selected from tocopherol, esters thereof with organic acids, and salts thereof;
(C) one or more selected from sodium sulfate and sodium bicarbonate and (D) one or more water-soluble polymeric substances selected from xanthan gum, carboxyvinyl polymer and sodium carboxymethylcellulose, and (A) component A toothpaste composition, wherein the amount is 0.001 to 0.2% by mass as copper ions, and (A) (copper ion concentration)/(C) is 0.0003 to 2 as a mass ratio.

According to the present invention, it is possible to provide a toothpaste composition that contains a water-soluble copper compound and vitamin E, has a high bad breath suppressing effect, has excellent vitamin E stability, and has good appearance stability.

The present invention will be described in further detail below. The toothpaste composition of the present invention comprises (A) a water-soluble copper compound, (B) one or more selected from tocopherol, esters thereof with organic acids, and salts thereof, and (C) sodium sulfate and sodium hydrogen carbonate. and (D) one or more water-soluble polymeric substances selected from xanthan gum, carboxyvinyl polymer and sodium carboxymethylcellulose.

(A) The water-soluble copper compound has deodorant power and acts as a bad breath suppressant.
The water-soluble copper compound is preferably a water-soluble copper salt such as copper gluconate, copper sulfate or copper chloride, more preferably copper gluconate or copper chloride. These may be used singly or in combination of two or more.

The content of the water-soluble copper compound is 0.001 to 0.2% (mass %, the same shall apply hereinafter) of the total composition as copper ions, preferably 0.01 to 0.2%. If it is less than 0.001%, a sufficient bad breath suppressing effect cannot be obtained. If it exceeds 0.2%, the metallic taste increases to the extent that masking is difficult, and discoloration occurs during storage to the extent that suppression is difficult.

Component (B) is tocopherol or a derivative thereof, and is one or more selected from tocopherol, esters thereof with organic acids, and salts thereof. These are medicinal ingredients that promote blood flow and tissue repair, and are effective in preventing or suppressing periodontal diseases such as gingivitis and periodontitis.
Examples of component (B) include tocopherols such as d-α-tocopherol, dl-α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol, and acetic acid, nicotinic acid, succinic acid, linolenic acid, and the like. and esters thereof with organic acids, salts thereof, and the like. Examples of such tocopherol derivatives include tocopherol acetate esters such as d-α-tocopherol acetate and dl-α-tocopherol acetate; tocopherol nicotinate esters such as d-α-tocopherol nicotinate and dl-α-tocopherol nicotinate; Acid d-α-tocopherol, tocopherol succinate such as dl-α-tocopherol succinate, tocopherol linolenic acid ester such as d-α-tocopherol linolenate, dl-α-tocopherol linolenate, tocopherol calcium succinate. . One or more of these may be used, but tocopherol acetate, tocopherol nicotinate, and particularly tocopherol acetate are preferred in terms of color tone and appearance of the formulation.
These tocopherols or derivatives thereof can be used in conformity with the former Cosmetic Ingredient Standards (Cosmetic Base) or Quasi-drug Ingredients Standards 2006, manufactured by DSM Nutrition Japan Co., Ltd., manufactured by Eisai Food Chemical Co., Ltd., manufactured by BASF Japan Co., Ltd. etc. can be used.

The blending amount of component (B) is preferably 0.01 to 2%, more preferably 0.05 to 1%, based on the total composition. When it is 0.01% or more, sufficient efficacy is exhibited, and when it is 2% or less, it is possible to sufficiently maintain the solubility in the formulation and prevent the occurrence of liquid separation (oil separation).

Component (C) is selected from sodium sulfate and sodium hydrogencarbonate, and may be either sodium sulfate or sodium hydrogencarbonate, or sodium sulfate and sodium hydrogencarbonate may be used in combination. Component (C) acts as a stabilizer for component (B).

The content of component (C) is preferably 0.05 to 40%, more preferably 0.1 to 10%, of the total composition. When it is 0.05% or more, the component (B) is sufficiently stabilized. The upper limit is not particularly limited, but if it is 40% or less, the usability of the formulation can be sufficiently maintained.

Component (D) is one or more water-soluble polymeric substances selected from xanthan gum, carboxyvinyl polymer and sodium carboxymethylcellulose. Component (D) has the effect of stabilizing the appearance of the formulation and suppressing liquid separation. It also acts as a binder.
As the component (D), xanthan gum and carboxyvinyl polymer are preferred from the viewpoint of suppressing liquid separation, and xanthan gum is more preferred from the viewpoint of moldability and appearance of the formulation.
Component (D) includes commercially available products such as xanthan gum under the trade name of Monat Gum DA (manufactured by DSP Gokei Food & Chemical Co., Ltd.) and carboxyvinyl polymer under the trade name of Carbopol 980 (manufactured by Lubrizol Co., Ltd.). Available.

The content of component (D) is preferably 0.5 to 3%, more preferably 1 to 2%, of the total composition. When it is 0.5% or more, the appearance of the formulation is stabilized and liquid separation can be sufficiently prevented. When it is 3% or less, it is possible to satisfactorily maintain the easiness of extruding the formulation from the storage container.

In the present invention, (A) (copper ion concentration)/(C), which indicates the ratio between the content of component (A) as copper ions (copper ion concentration) and the content of component (C), is a mass ratio. It is 0.0003 to 2, preferably 0.001 to 0.2, more preferably 0.01 to 0.15. Within this range, the bad breath suppressing effect and the stability of the component (B) are more excellent. If the (A)/(C) mass ratio is less than 0.0003, the effect of suppressing bad breath is reduced, and if it exceeds 2, the stability of the component (B) is reduced.

In the present invention, since component (D) also acts as a binder, organic binders other than component (D), such as hydroxymethyl cellulose, hydroxyethyl cellulose, sodium polyacrylate, etc., may not be blended. When blended, it is preferably 5% or less, particularly 0.15 to 3% of the total composition including component (D). In addition, inorganic binders such as gelling silica, gelling aluminum silica, and other thickening silicas are preferably added, particularly from the viewpoint of stabilizing the appearance of the formulation, and the amount to be added is 10% of the total composition. Below, 1 to 6% is particularly preferable.

In addition to the above components, the toothpaste composition of the present invention may optionally contain other known components as long as the effects of the present invention are not impaired. Specific examples include abrasives, wetting agents, surfactants, and, if necessary, sweetening agents, coloring agents, preservatives, fragrances, and active ingredients.

Abrasives that are commonly used for the oral cavity can be used. For example, silicic anhydride such as precipitated silica and igneous silica, silica-based abrasives such as aluminosilicate, zirconosilicate, and titanium-bonded silica, dicalcium phosphate dihydrate or anhydrate, monocalcium phosphate , calcium phosphate-based abrasives such as tribasic calcium phosphate, calcium carbonate, calcium hydroxide, aluminum hydroxide, insoluble sodium metaphosphate, synthetic resin-based abrasives, and silica-based abrasives generally used for dentifrices are suitable. be. The blending amount of these abrasives is usually 2 to 40%, particularly 10 to 30%.

Wetting agents include sugar alcohols such as sorbitol and xylite, and polyhydric alcohols such as glycerin and propylene glycol. The amount of wetting agent is usually 5-50%, especially 10-40%.

As surfactants, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be blended.
Examples of anionic surfactants include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, N-acylsarcosinates such as sodium N-lauroylsarcosinate and sodium N-myristoylsarcosinate, sodium dodecylbenzenesulfonate, hydrogen Added coconut fatty acid monoglyceride monosulfate, sodium lauryl sulfoacetate, sodium α-olefin sulfonate, N-acyl glutamate such as sodium N-palmitoyl glutamate, N-acyl taurate such as sodium N-methyl-N-acyl taurate. be done. Examples of cationic surfactants include alkylammonium and alkylbenzylammonium salts.

Examples of nonionic surfactants include sugar fatty acid esters such as sucrose fatty acid esters and maltose fatty acid esters, sugar alcohol fatty acid esters such as maltitol fatty acid esters and lactol fatty acid esters, alkylolamides, polyoxyethylene sorbitan monostearate, and the like. polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters such as hydrogenated castor oil, fatty acid diethanolamides such as lauric acid mono- or diethanolamide, sorbitan fatty acid esters, polyoxyethylene higher alcohol ethers, polyoxyethylene polyoxy Propylene copolymers, polyoxyethylene polyoxypropylene fatty acid esters, polyglycerin fatty acid esters, and pluronics are included.
Zwitterionic surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, N-alkyldiaminoethylglycine such as N-lauryldiaminoethylglycine, N-myristyldiaminoethylglycine, N-alkyl -1-Hydroxyethylimidazoline betaine sodium.

These surfactants may be used alone or in combination of two or more, and the blending amount is preferably 0 to 10%, particularly 0.01 to 5% of the total composition.

Sweetening agents include saccharin sodium and the like. Colorants include Blue No. 1, Yellow No. 4, titanium dioxide, and the like. Examples of preservatives include paraoxybenzoic acid esters, benzoic acid, salts thereof, and the like.

Peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, lime. Oil, Lavender Oil, Rosemary Oil, Laurel Oil, Chamomile Oil, Caraway Oil, Marjoram Oil, Bay Oil, Lemongrass Oil, Origanum Oil, Pine Needle Oil, Neroli Oil, Rose Oil, Jasmine Oil, Grapefruit Oil, Sweetie Oil , Yuzu Oil, Iris Concrete, Absolute Peppermint, Absolute Rose, Orange Flower, etc., and processing of these natural flavors (pre-reservoir cut, post-reservoir cut, fractional distillation, liquid-liquid extraction, essence formation, powder perfume ), and menthol, carvone, anethole, cineol, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone , menthyl acetate, N-substituted-paramenthane-3-carboxamide, pinene, octylaldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl Phenyl glycidate, vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cyclotene, furfural, trimethylpyrazine, ethyl lactate, ethyl thioacetate, etc., strawberry flavor, apple flavor, banana flavor , pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, mixed fruit flavor, tropical fruit flavor, and the like. can be done.
The blending amount of the above perfume material is preferably 0.000001 to 1%, and the blending amount of the perfume for perfuming using the above perfume material is preferably 0.1 to 2%.

Active ingredients other than components (A) and (B), for example, cationic fungicides such as cetylpyridinium chloride and benzalkonium chloride, anti-inflammatory agents such as tranexamic acid, epsilonaminocaproic acid, allantoin, dextranase, etc. enzymes, fluorine-containing compounds such as sodium fluoride and sodium monofluorophosphate, ascorbic acid or derivatives thereof, dipotassium glycyrrhizinate, potassium nitrate, aluminum lactate, sodium chloride, plant extracts such as thyme. These active ingredients can be blended in an effective amount within a range that does not impair the effects of the present invention.

EXAMPLES The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, % indicates % by mass unless otherwise specified.

[Examples, Comparative Examples]
Toothpaste compositions having the compositions shown in Tables 1 to 3 were prepared by conventional methods and evaluated by the following methods. The results are also shown in the table.
Tocopherol acetate (manufactured by DSM Nutrition Japan) was used as the component (B).

(1) Evaluation method of halitosis suppressing effect Five expert panelists as subjects evaluated usability. 1 g of the toothpaste composition was placed on a toothbrush (clinica advantage toothbrush, 4-row compact regular type, manufactured by Lion Corporation) and brushed for 3 minutes. Immediately after rinsing, the feeling of bad breath suppression was evaluated according to the following rating criteria. Eating and drinking was prohibited during the halitosis suppression evaluation.
Rating criteria 5: I do not feel bad breath 4: I hardly feel bad breath 3: I feel bad breath a little, but there is no problem level 2: I feel bad breath considerably 1: I feel bad breath very much The halitosis control effect was evaluated according to the evaluation criteria.
Evaluation criteria ◎: 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

(2) Appearance stability evaluation method The toothpaste composition was filled in a laminate tube with a diameter of 8 mm, stored at 60°C for 1 month, and then extruded from the tube. was visually observed and evaluated according to the following evaluation criteria.
Evaluation Criteria ◎: Liquid separation is not observed ○: Liquid separation is hardly observed ×: Liquid separation is observed The tube was filled and stored at 60°C or -5°C for 1 month. After allowing them to stand until they reach room temperature, 10 g of the sample was extruded from the tube, extracted with methanol, and then VE was quantified by HPLC (high performance liquid chromatography) using an absolute calibration curve method. The ratio (%) of the residual amount of tocopherol acetate in the product stored at -5°C to that in the product stored at 60°C was determined, and the stability of VE was evaluated according to the following evaluation criteria.
Evaluation criteria ◎: The VE content of the product stored at 60°C is 95% or more of the product stored at -5°C ○: The VE content of the product stored at 60°C is 90% or more and less than 95% of the product stored at -5°C VE content is less than 90% of the product stored at -5°C

Claims (7)

(A) a water-soluble copper compound,
(B) one or more selected from tocopherol, esters thereof with organic acids, and salts thereof;
(C) sodium sulfate
and (D) contains one or more water-soluble polymeric substances selected from xanthan gum, carboxyvinyl polymer and sodium carboxymethylcellulose, and the content of component (A) is 0.007 to 0.2% by mass as copper ions, The content of component (B) is 0.01 to 2% by mass, the content of component (C) is 0.05 to 10% by mass, the content of component (D) is 0.5 to 3% by mass, and ( A) A toothpaste composition characterized in that (copper ion concentration)/(C) is 0.007 to 1.4 as a mass ratio. (A) The toothpaste composition according to claim 1, wherein the water-soluble copper compound is one or more selected from copper gluconate and copper chloride. 3. The toothpaste composition according to claim 1, wherein component (B) is selected from tocopherol acetate and tocopherol nicotinate. The toothpaste composition according to any one of claims 1 to 3, wherein the water-soluble polymeric substance of component (D) is selected from xanthan gum and carboxyvinyl polymer. The toothpaste composition according to any one of claims 1 to 4, wherein the content of component (C) is 0.1 to 1% by mass. The toothpaste composition according to any one of claims 1 to 5, wherein (A) (copper ion concentration)/(C) is 0.01 to 0.2 as a mass ratio. The toothpaste composition according to any one of claims 1 to 6, which is a toothpaste composition containing a silica-based abrasive.