WO2019111723A1

WO2019111723A1 - Toothpaste composition

Info

Publication number: WO2019111723A1
Application number: PCT/JP2018/043143
Authority: WO
Inventors: 三四郎成松; 高橋　雅人; 麻里今崎; 晶子曽我
Original assignee: ライオン株式会社
Priority date: 2017-12-07
Filing date: 2018-11-22
Publication date: 2019-06-13
Also published as: CN111031999A; JP7000823B2; JP2019099532A; CN111031999B

Abstract

The present invention provides a toothpaste composition that contains a water-soluble copper compound and silicic anhydride, that has an excellent deodorizing effect and is capable of retaining said effect even after being stored, that exhibits superior appearance stability, and that is suitable for suppressing bad breath. This toothpaste composition comprises (A) 0.05-1 mass% of a water-soluble copper compound, (B) 5-20 mass% of silicic anhydride, (C) 0.5-2 mass% of one or more types of anionic surfactants selected from among acyl taurine, acylamino acid, and salts of those compounds, (D) 24-55 mass% of one or more types of moistening agents selected from among glycerin, propylene glycol, and polyethylene glycols having an average molecular weight of at most 630, and (E) one or more selected from among dicarboxylic acid, tricarboxylic acid, and alkali metal salts of those acids, wherein the mass ratio (E)/(A) is 0.4-10, and the composition contains at most 10 mass% of sorbitol or does not contain sorbitol.

Description

Toothpaste composition

The present invention relates to a toothpaste composition which contains a water-soluble copper compound and anhydrous silicic acid, is excellent in deodorizing effect and is maintained even after storage, and is excellent in appearance stability and suitable for breath malodor control.

Conventionally, it has been known that water soluble copper compounds such as copper gluconate have a deodorizing action and an antibacterial action, and the oral cavity containing a water soluble copper compound that prevents periodontal disease such as bad breath with the water soluble copper compound Compositions have been proposed (Patent Documents 1 to 3; Patent No. 2569639, Patent No. 2540892, and Japanese Patent No. 2540895).

Furthermore, in the oral composition containing a water-soluble copper compound, problems such as the decrease in stability of the water-soluble copper compound and the occurrence of metal taste and discoloration due to copper may occur. Technology for suppressing metal taste with derivatives (patent document 4; JP-A-2003-137755), stabilization of copper compound by using polybasic acid in combination, and technology for improving halitosis removal effect thereby (patent document 5; patent No. 2580657), a technology for suppressing discoloration by using a dye and a parahydroxybenzoic acid alkyl ester in combination (Patent Document 6: JP-A-8-310928) and the like have been proposed.

On the other hand, in the composition for oral cavity, especially dentifrices such as toothpaste, anhydrous silica such as abrasive silica and thickening silica is generally used for the purpose of imparting cleaning power and giving appropriate viscosity. If the condition inside is weak, such as teeth or gums, it may cause unpleasant irritation. In recent years, considering the increasing oral environment of the elderly, it is possible to reduce the influence on aging weakened teeth and gum tissue, that is, to suppress the compounding amount of anhydrous silicic acid which may have an influence relatively small. Also, it has been desired that the deodorizing action and the like by the water-soluble copper compound be effectively developed to prevent bad breath and the like.

Patent No. 2569639 Patent No. 2540892 Patent 2540895 gazette JP 2003-137755 Patent No. 2580657 JP-A-8-310928 Patent No. 2580656 Japanese Patent Application Laid-Open No. 4-159211 Patent No. 3922329 gazette

The present invention has been made in view of the above circumstances, and provides a toothpaste composition which contains a water-soluble copper compound and anhydrous silicic acid, is excellent in deodorizing effect, is maintained even after storage, and is excellent in appearance stability. The purpose is

The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, a toothpaste composition containing (A) a water-soluble copper compound in a specific amount and (B) anhydrous silica in a specific amount or less (C) a specific anionic surfactant and (D) a wetting agent selected from a specific polyhydric alcohol in a specific amount, and (E) a specific carboxylic acid or a salt thereof, E) (A) is blended so that the mass ratio is within a specific range, and when the content of Sorbit in the composition is less than a specific amount, the deodorizing effect particularly against bad breath is excellent and maintained after storage The present invention provides a toothpaste composition having excellent appearance stability and good taste, whereby it is possible to effectively suppress or prevent bad breath even with a relatively small amount of anhydrous silicic acid. It came to eggplant.

In the present invention, by combining the components (A), (B), (C), (D) and (E), the deodorizing effect is improved when the mass ratio of (E) / (A) is within a specific range. And the stabilization of the appearance of the preparation are compatible with each other, giving a remarkable effect.
More specifically, when the present inventors examined the combined use of a water-soluble copper compound and anhydrous silicic acid in a toothpaste composition, the deodorizing effect was reduced particularly during storage, liquid separation, discoloration, and further. Not only does it have various problems such as the appearance of a metallic taste unique to copper, but when the amount of silicic anhydride is reduced, a new problem arises that a brown precipitate is generated upon storage, and particularly with regard to the brown precipitate, It was found that (A) is a phenomenon uniquely generated by the water-soluble copper compound when the blending amount of silicic anhydride is below a certain value. On the other hand, in the present invention, components (C) and (D) are blended in specific amounts together with components (A) and (B), and component (E) is blended in an appropriate ratio to component (A). And the mass ratio of (E) / (A) is within the specific range, and the occurrence of the brown precipitates during storage described above is suppressed as the amount of sorbite is below the specific value, and even after storage immediately after preparation A high deodorizing effect can be provided, whereby the combination of the above-mentioned five components can solve all the above-mentioned problems and give a remarkable effect. Accordingly, the toothpaste composition of the present invention has a deodorizing ability (immediately after preparation), a deodorizing ability maintaining effect during storage, and a precipitate suppressing effect (no precipitates) as shown in the examples described later. The absence of liquid separation and the absence of discoloration are excellent, and the absence of metallic taste is also excellent.
Patent Documents 4 to 6 do not mention at all the occurrence of brown precipitates in a system in which the blending amount of anhydrous silicic acid is equal to or less than a specific value. Patent documents 7 to 9 (Japanese Patent No. 2580656, JP-A-4-15211, Japanese Patent No. 3922329) disclose a toothpaste composition containing a water-soluble copper compound and an anhydrous silicic acid, There is no mention of brown precipitates. From Patent Documents 1 to 9, it is not possible to predict the suppression of brown precipitates and the remarkable effect of the present invention by the combination of the components (A), (B), (C), (D) and (E).

Accordingly, the present invention provides the following toothpaste composition.
[1]
(A) 0.05 to 1% by mass of a water-soluble copper compound,
(B) 5 to 20% by mass of anhydrous silicic acid,
(C) 0.5 to 2% by mass of one or more anionic surfactants selected from acyl taurine, acyl amino acids and salts thereof
(D) 24 to 55% by mass of one or more wetting agents selected from glycerin, propylene glycol and polyethylene glycol having an average molecular weight of 630 or less
And (E) a dicarboxylic acid, a tricarboxylic acid and one or more selected from alkali metal salts thereof, wherein (E) / (A) has a mass ratio of 0.4 to 10, and a composition A toothpaste composition containing no more than 10% by mass of sorbite or no sorbite therein.
[2]
(A) The toothpaste composition according to [1], wherein the water-soluble copper compound is one or more selected from copper gluconate, copper citrate and copper sulfate.
[3]
(B) The toothpaste composition according to [1] or [2], wherein the silicic anhydride is one or more selected from abrasive silica and thickening silica.
[4]
(B) When the abrasive silica is contained as anhydrous silicic acid, its content is 5 to 19.9 mass%, and when it contains thickening silica, its content is 0.1 to 15 mass% The toothpaste composition according to [3].
[5]
The component (C) is one or more anionic surfactants selected from acyl taurine salts, acyl glutamate salts and acyl alanine salts in which the acyl group has 8 to 18 carbon atoms [1] to [1] The dentifrice composition in any one of 4].
[6]
The toothpaste composition according to any one of [1] to [5], wherein the component (E) is one or more selected from citric acid, succinic acid, malic acid, tartaric acid and sodium salts thereof. .
[7]
A toothpaste composition as described in any one of [1] to [6], wherein the content of the component (E) is 0.02 to 3% by mass.

According to the present invention, it is possible to provide a toothpaste composition containing a water-soluble copper compound and an anhydrous silicic acid, which is excellent in the deodorizing effect and maintained even after storage, and is excellent in the appearance stability. This toothpaste composition can effectively suppress or prevent bad breath without adversely affecting the weakened tooth and gum tissue by suppressing the amount of anhydrous silica relatively, and it can be used for suppressing bad breath It is effective as

Hereinafter, the present invention will be described in more detail. The toothpaste composition of the present invention comprises (A) a water-soluble copper compound, (B) anhydrous silica, (C) a specific anionic surfactant, and (D) a specific anionic surfactant. And (E) a specific carboxylic acid or a salt thereof.

The water soluble copper compound (A) is a deodorizing agent and is preferably a water soluble copper salt such as copper gluconate, copper citrate and copper sulfate. These may be used alone or in combination of two or more.
The compounding amount of the water-soluble copper compound (A) is 0.05 to 1% (% by mass, hereinafter the same) of the whole composition, and preferably 0.1 to 0.5%. If it is less than 0.05%, the deodorizing ability is inferior. If it exceeds 1%, the metallic taste may be enhanced to the extent that masking is difficult, and there may be separation of the solution during storage and discoloration of the preparation to the extent that inhibition is difficult.

As the (B) anhydrous silicic acid, abrasive silica and / or thickening silica blended for the purpose of imparting cleaning power and holding properties of the preparation can be used, and abrasive silica or thickening silica may be used.

Examples of the abrasive silica include anhydrous silicic acid such as precipitated silica and pyrogenic silica, and compounds having as a main component silicate such as aluminosilicate, zirconosilicate, and titanium-binding silica. These may be used alone or in combination of two or more.
As the abrasive silica, one having a median diameter (d50) of preferably 5 to 40 μm, particularly 10 to 30 μm using volume average may be used.
The median diameter of the above-mentioned silica is a value measured using a particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., Microtrac particle size distribution analyzer, dispersion medium; water) (the same applies hereinafter).

As the thickening silica, it is preferable to use one or two or more silicas obtained by a known method such as precipitated silica and pyrogenic silica having a liquid absorption volume in the range of 2 to 3 ml / g. it can. Thickening silica has a liquid absorption as described above, while the liquid absorption of abrasive silica is usually less than 2 ml / g.
The method of measuring the above-mentioned liquid absorption amount is as follows (same below).
Weigh 1.0 g of the sample on a clean glass plate, and mix it with a stainless steel spatula using a microburette while adding 42.5% glycerin little by little. The amount of liquid (ml) required for the sample to become one lump and to be peeled off from the glass plate with a spatula is defined as the amount of liquid absorbed.

The blending amount of (B) anhydrous silicic acid is 5 to 20%, preferably 7 to 18%, more preferably 10 to 15% of the whole composition. If it is less than 5%, sufficient cleaning power and shape retention can not be obtained. If it exceeds 20%, the deodorizing power decreases. In addition, generation | occurrence | production of a brown precipitate is not recognized when it exceeds 20%.
When the abrasive silica is contained within the range of the amount of the component (B), the content thereof is preferably 5 to 19.9%, particularly 5 to 15%, especially 5 to 12% of the whole composition. %, And when it contains a thickening silica, its content is preferably 0.1 to 15%, in particular 0.1 to 10%, especially 1 to 8%, of the total composition.

Component (C) is one or more anionic surfactants selected from acyl taurine, acyl amino acids and salts thereof.
The component (C) is preferably selected from an acyl taurine salt, an acyl glutamate salt and an acyl alanine salt each having an acyl group having 8 to 18 carbon atoms, particularly 12 to 16 carbon atoms, among them an acyl taurine Salts, acyl glutamates, especially acyl taurine salts are preferred. Also, these salts are alkali metal salts such as sodium and potassium, alkaline earth metal salts, organic amine salts and the like, and particularly preferably sodium salts.

Examples of the acyl taurine salt include sodium lauroyl methyl taurine, myristoyl methyl taurine sodium, coconut oil fatty acid methyl taurine sodium and the like.
Examples of the acyl glutamate salt include sodium lauroyl glutamate, sodium myristoyl glutamate, coconut oil fatty acid acyl potassium glutamate and the like.
As the acyl alanine salt, sodium lauroyl methyl alanine and the like can be mentioned.
Commercially available products can be used. Specifically, NIKKOL LMT (sodium lauroyl methyl taurine, Nikko Chemicals Co., Ltd.), NIKKOL MMT (myristoyl methyl taurine sodium, Nikko Chemicals Co., Ltd.), aminosurfact ALMS-P1 ( N-Lauroyl-L-glutamate sodium, Asahi Kasei Chemicals Co., Ltd., Amisoft LS-11 (N-lauroyl-L-glutamate sodium, Ajinomoto Healthy Supply Co., Ltd.), Aminosurfact AMMS-P1 (N-Myristoyl-L Sodium glutamate, Asahi Kasei Chemicals Co., Ltd., Amisoft MS-11 (N-myristoyl-L-glutamate sodium, Ajinomoto Healthy Supply Co., Ltd.), NIKKOL alaninate LN-30 (lauroylmethyl-β) Sodium alanine, and Nikko Chemicals Co.) can be used.

The blending amount of the component (C) is 0.5 to 2%, preferably 0.6 to 1.5%, more preferably 0.8 to 1.5% of the whole composition. If the amount is less than 0.5%, the effect of suppressing precipitates during storage and the effect of reducing metallic taste are inferior. Moreover, it may be inferior to foamability. If it exceeds 2%, the bitterness of the component (C) may be so strong that masking is difficult, and the feeling of use may be reduced.

In the present invention, anionic surfactants other than the above component (C) may be blended as long as the effects of the present invention are not impaired, but in particular, no alkyl sulfate such as sodium lauryl sulfate is blended. The blending amount is preferably 0.5% or less, particularly 0.2% or less, especially 0.1% or less of the whole composition.

Component (D) is one or more wetting agents selected from glycerin, propylene glycol and polyethylene glycol having an average molecular weight of 630 or less, and glycerin is particularly preferable. When using 2 or more types, it is preferable to combine glycerol and propylene glycol or the said polyethylene glycol.

The polyethylene glycol has an average molecular weight (average molecular weight described in the quasi-drug raw material standard 2006, the same applies hereinafter) is 630 or less, preferably 600 or less, more preferably 200 to 600, still more preferably 300 to 600.
Examples of the polyethylene glycol include polyethylene glycol 200 (average molecular weight 190 to 210), polyethylene glycol 300 (average molecular weight 280 to 320), polyethylene glycol 400 (average molecular weight 380 to 420), and polyethylene glycol 600 (average molecular weight 570 to 630). Commercially available products can be used.

The compounding amount of the component (D) is 24 to 55%, preferably 28 to 50%, more preferably 32 to 45% of the whole composition, from the viewpoint of liquid separation suppression. If the blending amount is less than 24%, the liquid separation suppressing effect is inferior. If it exceeds 55%, discoloration of the preparation upon storage is aggravated. In addition, the dispersibility of the preparation in the oral cavity may be deteriorated to lower the usability.
When glycerin is blended within the range of the blending amount of the component (D), the blending amount is preferably 21% or more, particularly 25% or more of the whole composition as a pure part.

In the present invention, as a wetting agent other than the component (D), sugar alcohols such as sorbite and xylit can be further blended. The blending amount of the sugar alcohol is preferably such that the total amount with the (D) component is within the range of the blending amount of the (D) component.
In the toothpaste composition of the present invention, the content of sorbite in the sugar alcohol is 10% or less, preferably 8% or less, particularly 4% or less of the whole composition, and no blending is carried out. % Is particularly preferred. If it is added in excess of 10%, the effect of maintaining the deodorizing ability upon storage will decrease, and the color change of the preparation upon storage will also deteriorate.

The component (E) is one or more carboxylic acids or salts thereof selected from dicarboxylic acids, tricarboxylic acids and alkali metal salts thereof. These are known as chelating agents, but in the present invention, they contribute to the maintenance effect of the deodorizing ability during storage and the precipitation suppression effect during storage.
As the component (E), citric acid, succinic acid, malic acid, tartaric acid and alkali metal salts thereof are preferable, and citric acid or an alkali metal salt thereof is more preferable.

The compounding amount of the component (E) is mainly determined by the mass ratio of (E) / (A) shown below and can be set to satisfy the mass ratio of (E) / (A), but preferably the composition It is 0.02 to 3% of the whole, in particular 0.05 to 2%. The maintenance effect of the deodorizing power at the time of storage, and the precipitation inhibitory effect at the time of storage are fully acquired as it is 0.02% or more. The fall of the deodorizing ability especially immediately after preparation can be fully prevented as it is 3% or less, and the expression of the offensive taste derived from (E) component can fully be prevented especially.

In the present invention, (E) / (A), which indicates the blending ratio of the component (E) to the component (A), is a mass ratio of 0.4 to 10, preferably 0.5 to 6, and more preferably 0. 6 to 5, more preferably 0.7 to 5. Within this range, the deodorizing power and the maintenance effect of the deodorizing power are excellent, and the precipitate suppressing effect during storage is excellent. When the mass ratio of (E) / (A) is less than 0.4, the effect of maintaining the deodorizing ability during storage and the effect of suppressing precipitates are inferior. If it exceeds 10, the deodorizing ability immediately after preparation is reduced.

In addition to the above components, other known components can be added to the toothpaste composition of the present invention as needed, as long as the effects of the present invention are not impaired. Specifically, abrasives other than anhydrous silicic acid, caking agents other than anhydrous silicic acid, surfactants other than anionic surfactants, and if necessary, sweeteners, colorants, preservatives, perfumes, water-soluble copper Active ingredients other than compounds can be blended.

As the polishing agent, calcium phosphate based compounds such as dibasic calcium phosphate dihydrate or anhydrous, monobasic calcium phosphate, tribasic calcium phosphate, calcium carbonate, calcium hydroxide, aluminum hydroxide, insoluble sodium metaphosphate, synthetic resin system An abrasive is mentioned. When these abrasives are blended, the blending amount thereof is preferably 1 to 15%, and may be 0% without blending.

Examples of the caking agent include cellulose derivatives such as sodium carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose and hydroxyethyl cellulose, alginic acid derivatives such as sodium alginate, gums such as xanthan gum, carrageenan, polyvinyl alcohol and organic caking such as sodium polyacrylate Agents. The blending amount of the caking agent is usually 0.1 to 5%.

As surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be blended. Specifically, nonionic surfactants include sugar fatty acid esters such as sucrose fatty acid esters, sugar alcohol fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene cured castor oil and the like Examples thereof include polyoxyethylene fatty alcohol esters such as oxyethylene fatty acid ester and polyoxyethylene stearyl ether, and fatty acid alkanolamides such as lauric acid diethanolamide. Examples of cationic surfactants include alkyl ammonium types such as distearylmethyl ammonium chloride, and alkyl benzyl ammonium salts. Amphoteric surfactants include alkyl betaines, betaine acetates such as alkyldimethylaminoacetic acid betaines and fatty acid amidopropyl betaines, betaines such as alkylimidazolinium betaines, and imidazolines. The blending amount of these surfactants is usually from 0 to 10%, particularly from 0.01 to 5%.

As a sweetening agent, saccharin sodium etc. are mentioned, As a coloring agent, blue No. 1, yellow No. 4, titanium dioxide etc. are mentioned. Examples of preservatives include p-oxybenzoic acid esters such as methyl p-hydroxybenzoate, benzoic acid or salts thereof.

As flavoring agents, peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, mint oil, cardamom oil, coriander oil, mandarin oil, Lime oil, lavender oil, rosemary oil, laurel oil, camomile oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, grapefruit oil, sweetie Processing of natural flavors such as oil, soy sauce, iris concrete, absolute peppermint, absolute rose, orange flower, and processing of these natural flavors (pre-cut, pre-cut, fractional distillation, liquid-liquid extraction, essence, powder Perfumes, etc.), and menthol, Bonnet, anethole, cineole, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-mentoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted paramentan 3-carboxamide, pinene, octylaldehyde, citral, plegon, 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 thiocyanate For oral compositions such as single flavors such as acetate, and also blended 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 combining the well-known fragrance | flavor raw material used.
It is preferable to use 0.00001 to 1% of the above-mentioned spice material to the whole composition, and 0.1 to 2% of fragrant material using the above-mentioned spice material is used to the whole composition Is preferred.

The active ingredients include nonionic bactericidal agents such as isopropylmethylphenol, cationic bactericidal agents such as cetyl pyridinium chloride and benzalkonium chloride, tranexamic acid, anti-inflammatory agents such as epsilon aminocaproic acid and allantoin, dextranase etc. Enzymes, fluorine-containing compounds such as sodium fluoride and sodium monofluorophosphate, vitamins such as ascorbic acid and tocopherol acetate, dipotassium glycyrrhizinate, potassium nitrate, aluminum lactate, sodium chloride and plant extracts such as thyme . 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 The present invention will be specifically described below by showing Examples, Comparative Examples, and Formulation Examples, but the present invention is not limited to the following Examples. In the following examples,% indicates% by mass unless otherwise specified.

Example, Comparative Example
The dentifrice composition (toothpaste) having the composition shown in Tables 1 to 3 was prepared by a conventional method and evaluated by the following method. The results are shown in the table.

(1) Evaluation method of deodorizing power (immediately after preparation) <experimental method>
In a 20-mL test tube, 1 mL of a 3,000-fold diluted solution of dentifrice composition and 1.5 mL of artificial saliva are mixed and incubated at 37 ° C, and 0.5 mL of 100 ng / mL aqueous solution of methyl mercaptan is added. After sealing with a silicone plug, the reaction was stirred and reacted for 6 minutes with shaking in a 37 ° C. water bath. After that, 5 mL of air was injected into the test tube with a syringe for gas chromatography injected into a gas chromatograph (GC). After vigorously stirring for 30 seconds, 5 mL of the gas was also withdrawn from the head space with the same syringe for gas chromatography and injected immediately into the GC to measure the peak area of methyl mercaptan. From the obtained peak area value, the deodorizing rate (%) was determined based on the following equation.

The gas chromatography conditions are as follows.
Equipment: GC-2014 (manufactured by Shimadzu Corporation)
Detector: FPD
Separation column: Teflon (registered trademark), packing material Chromosorb W
60/80 AW-DM, CS processing (made by Shinwa Kako Co., Ltd.)
Inlet temperature: 130 ° C
Column temperature: 80 ° C
Detector temperature: 150 ° C
Carrier gas: N ₂
Carrier gas flow rate: 50 mL / min

The deodorizing power (immediately after preparation) was evaluated based on the following judgment criteria from the deodorizing rate determined.
Judgment criteria ◎: 90% or more and 100% or less ○: 70% or more and less than 90% Δ: 50% or more and less than 70% ×: less than 50%

(2) Evaluation method of maintenance effect of deodorizing power at the time of storage 50g of dentifrice composition is filled in a laminated tube of 8mm in diameter, stored for 3 months at 50 ° C or -5 ° C, 50 ° C stored goods and -5 The methyl mercaptan deodorizing power of each of the stored products was measured using GC under the same test conditions in the same manner as the evaluation method of deodorizing power. The deodorizing power of -5 ° C stored products is 100%, the ratio (%) of the deodorizing power of 50 ° C stored products compared with this is calculated, and the deodorizing power maintenance effect is evaluated based on the following judgment criteria did.
Judgment criteria ◎: 90% or more and 100% or less of the product stored at -5 ° C :: 70% or more and less than 90% of the product stored at -5 ° C :: 50% or more and less than 70% of the product stored at -5 ° C X: less than 50% for -5 ° C stored products

(3) Evaluation method of precipitate suppressing effect at the time of storage 50g of dentifrice composition in an 8mm caliber laminate tube and stored for 1 month at 60 ° C, the dentifrice composition is about 3cm on the paper from the laminate tube The precipitate (brown precipitate) observed in the appearance when extruded and pressed out on the paper surface was visually observed. The precipitate suppressing effect (the absence of precipitate) was evaluated based on the following judgment criteria.
Judgment criteria ○: No precipitation of brown particles is observed ×: Precipitation of brown particles is observed

(4) Evaluation Method of Lack of Metallic Taste 1 g of the dentifrice composition was put on a toothbrush by 10 expert panelists, and the metallic taste felt when brushing teeth by a usual method was evaluated according to the following scoring criteria. The average value of the evaluation points of 10 persons was determined, and based on the following judgment criteria, the metal taste was evaluated.
Rating criteria 4 points: no metallic taste in the oral cavity 3 points: a slight metallic taste in the oral cavity but no problem 2 points: metallic taste in the oral cavity and unpleasant 1 point: metallic taste in the oral cavity Strong and feel very unpleasant Judgment criteria :: Average point 3.5 points or more and 4.0 points or less ○: Average point 3.0 or more and less than 3.5 points Δ: Average point 2.0 or more 3.0 points Less than ×: Less than 2.0 points on average

(5) Evaluation Method of Improper Separation of Liquid When 50 g of a dentifrice composition is filled in a laminated tube of 8 mm in diameter and stored at 40 ° C. for 6 months, separation of the liquid when extruded from the laminated tube The state was visually observed. Based on the following judgment criteria, it evaluated about the nonexistence of liquid separation.
Judgment criteria :: No liquid separation observed ○: Only slight liquid separation (surface gloss on the surface is observed) is a level at which there is no problem with quality △: Liquid separation is observed × : Very large liquid separation is observed

(6) Evaluation method of no discoloration during storage 50g of dentifrice composition in an 8mm caliber laminated tube, stored at 60 ° C or -5 ° C for 1 month, -5 ° C stored goods and 60 ° C stored goods For each of the above, the color change (when not the local color but the color of the entire dentifrice changed) was visually observed when extruded from the laminate tube. From the degree of discoloration of the 60 ° C. stored article as compared to the −5 ° C. stored article, no discoloration was evaluated based on the following judgment criteria.
Judgment criteria :: No discoloration is observed in comparison to the -5 ° C stored product ○: A slight change in color is observed but no problem compared to the -5 ° C stored product △: -5 ° C stored product and Discoloration is observed by comparison. X: Discoloration is highly observed compared to the -5 ° C preservation product.

Details of the raw materials used are shown below.
(A) Copper gluconate; Wako Pure Chemical Industries, Ltd. (A) Copper citrate; Kanto Chemical Co., Ltd. (A) Copper sulfate; Kanto Chemical Co., Ltd. (B) abrasive silica; Co., Ltd., abrasive silica median diameter (d50) in the range of 5 to 40 μm (B) Thickening silica; trade name "Carplex" made by DSL Japan Co., Ltd.
Absorbent volume: 2.0 to 3.0 ml / g (C) lauroyl methyl taurine sodium; Nikko Chemicals Co., Ltd. product (C) myristoyl sodium glutamate; Asahi Kasei Chemicals Co., Ltd. product (C) lauroyl glutamate sodium; Asahi Kasei Chemicals (D) glycerin (85% product); Lion Chemical (D) propylene glycol; ADEKA (D) polyethylene glycol 300; Sanyo Chemical Industries, Ltd., average molecular weight 300
(D) polyethylene glycol 400; manufactured by Sanyo Chemical Industries, Ltd., average molecular weight 400
(D) polyethylene glycol 600; manufactured by Sanyo Chemical Industries, Ltd., average molecular weight 600
Sorbit solution (70%); sodium citrate (E) manufactured by Rocket Co .; (E) citric acid manufactured by Komatsuya Co., Ltd .; citric acid manufactured by Sakai Chemical Industry Co., Ltd .; sodium tartrate (E) manufactured by Sakai Chemical Industry Co., Ltd .; Wako Pure Chemical Industries, Ltd. (E) Sodium succinate; Kanto Chemical Co., Ltd. (E) sodium malate; Junsei Chemical Co., Ltd. (E) malic acid; Wako Pure Chemical Industries, Ltd. sodium lauryl sulfate; BASF

* Net total amount (same below).

An example of prescription is shown below. The details of the raw materials used are the same as above.
The toothpaste of the formulation example has good deodorizing ability (immediately after preparation), deodorizing effect during storage, precipitate suppressing effect, absence of liquid separation and no discoloration, and no metallic taste. The

[Formulation Example 1] Toothpaste (A) Copper Gluconate 0.3%
(B) Abrasive silica 15
(B) Thickening silica 5
(B) Component total amount 20
(C) lauroyl methyl taurine sodium 1
(D) Glycerin (85%) 40
(D) Propylene glycol 3
(D) Total amount of ingredients ^* 37
(E) Sodium citrate 0.3
(E) citric acid 0.15
Mass ratio of (E) / (A) 1.5
Monofluorophosphate sodium 0.7
Isopropyl methyl phenol 0.1
ε-Aminocaproic acid 0.1
Lauroyl sarcosine sodium 0.5
Hydroxyethyl cellulose 1
Sodium alginate 0.3
Polyoxyethylene (20) hydrogenated castor oil 1.5
Saccharin sodium 0.1
Titanium oxide 0.5
Fragrance 1
Purified water
100% in total

[Formulation Example 2] Toothpaste (A) Copper Gluconate 0.3%
(B) Abrasive silica 12
(B) Thickening silica 3
(B) Component total amount 15
(C) lauroyl methyl taurine sodium 1.5
(D) Glycerin (85%) 40
(D) Propylene glycol 3
(D) Total amount of ingredients ^* 37
(E) Sodium citrate 0.3
(E) / (A) mass ratio 1
Sodium monofluorophosphate 1.1
Isopropyl methyl phenol 0.1
Tocopheryl acetate 0.2
Tranexamic acid 0.1
Lauroyl sarcosine sodium 0.1
Carboxymethylcellulose sodium 0.5
Xanthan gum 0.8
Sodium alginate 0.3
Polyoxyethylene (5) stearyl ether 1
Polyoxyethylene (20) hydrogenated castor oil 1
Saccharin sodium 0.1
Titanium oxide 0.5
Fragrance 1
Purified water
100% in total

[Formulation Example 3] Toothpaste (A) Copper Gluconate 0.5%
(B) Abrasive silica 10
(B) Thickening silica 5
(B) Component total amount 15
(C) lauroyl glutamate sodium 1
Sodium lauryl sulfate 0.5
(D) Glycerin (85%) 45
(D) Polyethylene glycol 400 3
(D) Total amount of ingredients ^* 41.3
(E) Sodium malate 0.5
(E) Malic acid 0.2
Weight ratio of (E) / (A) 1.4
Sodium monofluorophosphate 1.1
Tocopheryl acetate 0.1
β-Glycyrrhetinic acid 0.1
Cetyl pyridinium chloride 0.05
Carrageenan 0.6
Sodium alginate 1
Polyoxyethylene (5) stearyl ether 1.5
Coconut oil fatty acid amide propyl betaine 0.5
Saccharin sodium 0.1
Titanium oxide 0.5
Fragrance 1
Green No. 3 0.0005
Purified water
100% in total

[Formulation Example 4] Toothpaste (A) Copper Gluconate 0.1%
(B) Abrasive silica 18
(B) Thickening silica 2
(B) Component total amount 20
(C) Myristoyl glutamate sodium 1
(D) Glycerin (85%) 35
(D) Propylene glycol 3
(D) Total amount of ingredients ^* 32.8
Sorbit liquid (70%) 5
(E) Sodium citrate 0.2
Weight ratio of (E) / (A) 2.0
Sodium fluoride 0.3
Isopropyl methyl phenol 0.1
Dipotassium glycyrrhizinate 0.1
Cetyl pyridinium chloride 0.05
Sodium chloride 5
Carboxymethylcellulose sodium 0.5
Xanthan gum 0.5
Glycerin fatty acid ester 1.5
Saccharin sodium 0.1
Zeolite 5
Fragrance 1
Purified water
100% in total

Claims

(A) 0.05 to 1% by mass of a water-soluble copper compound,
(B) 5 to 20% by mass of anhydrous silicic acid,
(C) 0.5 to 2% by mass of one or more anionic surfactants selected from acyl taurine, acyl amino acids and salts thereof
(D) 24 to 55% by mass of one or more wetting agents selected from glycerin, propylene glycol and polyethylene glycol having an average molecular weight of 630 or less
And (E) a dicarboxylic acid, a tricarboxylic acid and one or more selected from alkali metal salts thereof, wherein (E) / (A) has a mass ratio of 0.4 to 10, and a composition A toothpaste composition containing no more than 10% by mass of sorbite or no sorbite therein.
The toothpaste composition according to claim 1, wherein the water soluble copper compound (A) is one or more selected from copper gluconate, copper citrate and copper sulfate.
The toothpaste composition according to claim 1 or 2, wherein (B) anhydrous silicic acid is one or more selected from abrasive silica and thickening silica.
(B) When the abrasive silica is contained as anhydrous silicic acid, its content is 5 to 19.9 mass%, and when it contains thickening silica, its content is 0.1 to 15 mass% The toothpaste composition according to claim 3.
The component (C) is one or more anionic surfactants selected from acyl taurine salts, acyl glutamate salts and acyl alanine salts in which the acyl group has 8 to 18 carbon atoms. Toothpaste composition according to any one of the preceding claims.
The toothpaste composition according to any one of claims 1 to 5, wherein the component (E) is one or more selected from citric acid, succinic acid, malic acid, tartaric acid and sodium salts thereof.
The toothpaste composition according to any one of claims 1 to 6, wherein the content of the component (E) is 0.02 to 3% by mass.