JP2003212741A - Dentifrice composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dentifrice composition capable of being stably mixed with an ascorbic phosphoric ester or its salt and therefore capable of being furnished with good flavors even after stored for a long period. <P>SOLUTION: This dentifrice composition containing an alkali-unstable perfume contains the ascorbic phosphoric ester or its salt and an abrasive silica in an amount of ≥5 mass%, wherein the abrasive silica has a pH of ≥9 when measured in an aqueous slurry having a concentration of 5 mass%. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dentifrice composition containing an alkali-labile perfume containing ascorbic acid phosphoric acid ester or a salt thereof.

[0002]

BACKGROUND OF THE INVENTION Ascorbic acid phosphoric acid esters and salts thereof are whitening cosmetics (JP-A-63-243014, JP-A-1-30500).
No. 9, No. 3-133914), an oral drug (JP-A-62-96408), and a bath agent (JP-A-62-9).
No. 6410), a composition for oral cavity (JP-A-2-2922).
No. 10, No. 2-292211), and a skin external preparation (JP-A-7-206632 and No. 8-133951).
Etc., and is known to be very useful.

In particular, in recent years, it has been attracting attention as an antioxidant vitamin that eliminates excess active oxygen produced in the living body and protects biological tissues from oxygen damage, and is known to have various physiological activities. . Therefore, it is useful for the prevention and treatment of gingivitis and periodontitis, and ascorbic acid or an ascorbic acid derivative (hereinafter referred to as ascorbic acid) has been conventionally used.
It is known to mix the composition with an oral composition such as toothpaste. For example, ascorbic acid phosphoric acid esters (JP-A-62-96408 and JP-A-62-273910) and ascorbic acid sulfuric acid esters (JP-A-3-29422).
No. 7), and higher ascorbic acid fatty acid esters (JP-A No. 7-157417) are described in the composition for oral cavity.

However, in particular, a dentifrice composition containing ascorbic acid phosphoric acid ester or its salt has a problem that the residual amount of ascorbic acid phosphoric acid ester or its salt decreases after long-term storage, resulting in poor stability. The solution of the point was desired.

[0005]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to meet the above-mentioned demands, the present inventor has found that ascorbic acid phosphoric acid ester or a salt thereof is contained and an alkali-labile fragrance is contained. It has been found that it is effective to add abrasive silica having a pH of a 5% (mass percentage, the same applies hereinafter) water slurry of 9 or more to a dentifrice composition containing the above.

That is, the present applicant has previously proposed that the pH of the composition is important for formulating ascorbic acid phosphoric acid ester and its salt in a dentifrice composition in a stable and active state. (Japanese Patent Application No. 2000-199213).

However, using conventional abrasive silica,
Since the pH after storage decreases, and the residual rate of the ascorbic acid phosphoric acid ester compound decreases after a lapse of time, to set the initial pH on the more alkaline side and to adjust the stable pH range of the ascorbic acid phosphoric acid ester compound. It has been found that a large amount of pH adjuster is required, which affects flavor. In particular, it has been found that the ester-based fragrance contained in the fragrance component is significantly deteriorated when the pH is initially set to be more alkaline. In this case, there is no pH buffering agent that can be administered in the oral cavity within this setting range, or even if it is present, the taste is deteriorated,
It is not a fundamental solution.

It should be noted that abrasives other than silica react with ascorbic acid phosphoric acid ester and its salts to reduce the residual rate.

Therefore, there has been a demand for technical development of a dentifrice composition which does not cause a pH decrease and can control the pH with a smaller pH adjusting agent.

From this point of view, as a result of intensive research on a dentifrice composition containing ascorbic acid phosphoric acid ester and its salts stably and having a good flavor, 5
% By mixing 5% or more of abrasive silica having a pH of 9 or more measured with a water slurry, ascorbic acid phosphate and its salts are stably mixed, and a large amount of pH adjusting agent is unnecessary. It was found that a dentifrice composition having a good flavor can be obtained, and the present invention has been completed.

Conventionally, in JP-A-4-173727, in order to improve coloring and the like, the pH of the composition is set to 7 to 7.
Although the range of 9 has been already disclosed, the compounding effect of the above specific silica is not shown. Also, the pH
It is known that a dentifrice composition containing hydrous silica gel of 6 to 10 enables quick drying and less absorption of moisturizers and the like into water-containing pores. However, ascorbic acid phosphate and its salts There is no description of stabilizing blending in toothpaste (Japanese Patent Laid-Open No. 55-13265).

The present invention will be described in more detail below.
The dentifrice composition of the present invention contains ascorbic acid phosphoric acid ester or a salt thereof, abrasive silica having a pH of 5% water slurry of 9 or more, and an alkali-labile fragrance.

Here, ascorbic acid phosphoric acid ester and salts thereof include one or more of hydroxyl groups at 2, 3, 5 and 6 positions of ascorbic acid, which are compounds such as phosphoric acid and polyphosphoric acid. It is an ester, and for example, ascorbic acid-2-phosphate ester, ascorbic acid-3-phosphate ester, ascorbic acid-6-phosphate ester, ascorbic acid-2-polyphosphate ester and the like can be used. Examples of the salts include alkali metal salts such as sodium salts, potassium salts, calcium salts, magnesium salts, alkaline earth metal salts, and the like. Among them, ascorbic acid phosphoric acid ester magnesium salt and sodium salt are preferably used from the viewpoint of preventing and improving periodontal diseases.

From the viewpoint of effectiveness and feeling of use, the compounding amount is preferably 0.001 to 10%, particularly 0.01 to 5% of the total composition.

Examples of the abrading silica include silica gel, precipitating silica, igneous silica, aluminosilicate, zirconosilicate, titanium-bonding silica, and other compounds containing silicate as a main component. There is no limitation on the manufacturing method and the type of trace ingredients, but
%, The pH of the slurry suspended is preferably 9 or more, preferably 9 to 11, and more preferably 9 to 10. The blending amount of silica imparts abrasiveness as toothpaste, and is preferably 5% or more, particularly 5 to 40% of the total composition.

Alkali-labile fragrances are those that decompose at pH 8 or higher, and ester-based fragrances such as ethyl butyrate, ethyl acetate, isoamyl butyrate, isoamyl acetate, menthyl acetate, methyl salicylate, citronellyl acetate, linalyl acetate, Benzyl acetate, tervinyl acetate, bornyl acetate, ethyl acetoacetate, phenylethyl acetate, geranyl butyrate, linalyl butyrate, citronellyl butyrate, benzyl butyrate,
Benzyl isobutyrate, isoeugenyl acetate,
Milcenyl acetate, linalyl propionate, citronellyl propionate, geranyl propionate, allyl cyclohexane propionate, propyl isovalerate, methyl cinnamate, ethyl anisate, menthyl anthranilate, ethyl methylphenylglycidate Etc. The compounding amount is 0.
It is preferably 000001 to 2%, particularly preferably 0.0001 to 1%. In the dentifrice composition of the present invention, fragrances other than the above alkali-labile fragrances, such as peppermint oil, menthol, spearmint oil, carvone, anethole, citral, isomentone, limonene, mensofuran, octanol, menthone, linalool, pinene, cineol. , Eugenol, etc. can be added.

The dentifrice composition of the present invention can be made into a dentifrice formulation such as toothpaste, liquid dentifrice, powder dentifrice and the like. In this case, in the dentifrice composition of the present invention, in addition to the above-mentioned components, various base components used in a usual dentifrice composition, for example, an abrasive, a thickener, a sweetener, a fragrance, etc. are added in a usual dose. It may be blended.

As the polishing agent, in addition to the above silica, calcium hydrogen phosphate dihydrate, tertiary calcium phosphate, calcium carbonate, calcium pyrophosphate, aluminum hydroxide, aluminum silicate, insoluble sodium metaphosphate can be used. , Tribasic magnesium phosphate,
One or more of magnesium carbonate, calcium sulfate, bentonite, zirconium silicate, polymethylmethacrylate, and other synthetic resins may be blended within a range that does not impair the effects of the present invention.

As the binder, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, alginic acid derivatives such as carrageenan, alginate and propylene glycol alginate, gums such as xanthan gum, gellan gum, tragacanth gum, karaya gum and polyvinyl alcohol. One or more of synthetic binders such as carboxyvinyl polymer and inorganic binders such as veegum and laponite may be blended.

Moisturizers include glycerin, sorbit, propylene glycol, polyethylene glycol,
One or more polyhydric alcohols such as xylitol, maltitol and lactitol may be blended.

Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate and sodium lauroyl sarcosine, nonionic surfactants such as decaglyceryl laurate and diethanolamide myristic acid, and amphoteric surfactants such as betaine. Can be blended.

Further, sweeteners such as sodium saccharin, perillartin, thaumatin and the like may be added.

Further, according to the present invention, cationic bactericides such as chlorhexidine, benzethonium chloride, benzalkonium chloride, cetylpyridinium chloride and decalinium chloride, phenolic compounds such as triclosan, hinokitiol and biozole, dextranase and mutanase. , Lysozyme, amylase, protease, lytic enzyme, SO
Enzymes such as D, sodium monofluorophosphate, alkali metal monofluorophosphates such as potassium monofluorophosphate, sodium fluoride, fluorides such as stannous fluoride, tranexamic acid, epsilon aminocaproic acid, allantoin, dihydrocholate Stanol, glycyrrhizinic acid, glycyrrhetinic acid, glycerophosphate, chlorophyll, sodium chloride, xylitol, zinc chloride, water-soluble inorganic phosphate compounds, vitamins such as vitamin A, vitamin B group, vitamin E and their derivatives, etc. The active ingredient may be used alone or in combination of two or more.

In the present invention, the initial p of the entire composition is
It is preferable to set H to 8.5 or more, more preferably 8.5 to 9.5, and further preferably 8.5 to 9.0, whereby the silica of 5% water slurry having a pH of 9 or more is blended. As a result, the pH of the composition is stable, and the pH of the composition does not significantly decrease with the passage of time, or conversely, the pH does not significantly increase, so that the ascorbic acid phosphoric acid ester or salt thereof is stably retained, Alkali-unstable fragrances such as ester-based fragrances are also stably retained, and a good feeling of use is exhibited even after long-term storage.

The dentifrice composition of the present invention is manufactured by a conventional method. That is, in a mixing tank capable of vacuum suction operation, various base components used in ordinary toothpaste compositions, for example, abrasives, binders, thickeners, moisturizers, surfactants, sweeteners, and fragrances. , The active ingredient is prescribed and the vacuum degree is 200T.
orr (about 26.7 kPa) or less, especially 20 to 40 To
It can be manufactured by mixing while maintaining it in the range of rr (about 2.7 to 5.3 kPa).

The oral composition of the present invention can be used as a container such as an aluminum laminate tube, an EVAL tube, an aluminum tube, a glass vapor-deposited plastic tube and the like, as well as a mechanical or differential pressure dispenser container, a squeeze container, and a laminated film container. It can also be filled into bottles and the like. The laminated film is
Usually has two or more layers, the material is polyethylene,
Synthetic resins such as polyethylene terephthalate, polyester, biaxially oriented polypropylene, non-oriented polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer,
It is composed of a metal foil such as aluminum, gold or silver, or paper. Considering strength, flexibility, weather resistance, etc., generally 2
~ 5 layers are used. The material of the bottle is not particularly limited, but synthetic resins such as polyethylene, polyethylene terephthalate, polyester, polypropylene, and glass can be preferably used. Bottle manufacturing method, injection, hollow, press, molding by vacuum, etc., also molding the container and filling the formulation at the same time, so-called in-line filling method,
The method does not matter.

[0027]

EFFECTS OF THE INVENTION The dentifrice composition of the present invention achieves stable incorporation of ascorbic acid phosphoric acid ester and its salt, and gives a good flavor even after long-term storage.

[0028]

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 addition, in the following examples,% indicates a mass percentage.

[Examples 1 to 3 and Comparative Examples 1 to 6] The following dentifrices using silica having a pH value of 5% water slurry shown in Table 1 were prepared and housed in a polyethylene tube laminated with aluminum. . For each dentifrice, pH change data was then acquired and the storage stability of ascorbic acid phosphate (APM) was evaluated. In addition, the dentifrice after storage was used and the flavor was evaluated.
The results are shown in Table 1.

Dentifrice Ascorbic acid-2-phosphate 0.3% Magnesium salt (APM) Silica (Table 1) 20 Sodium lauryl sulphate 1.5 70% Sorbitt solution 50 Propylene glycol 5 Carboxymethylcellulose 1.5 Paraben 0. 1 Saccharin sodium 0.1 Fragrance (composition A) 1 Titanium dioxide 0.5 Sodium hydroxide Appropriate amount (Table 1) Purified water balance 100% Fragrance composition A 1-Menthol 20% Peppermint oil 50 Anethole 10 Menthyl acetate 2 d-Limonene 1 Zabinene hydrate 0.5 Methyl salicylate 0.1 Cardamom oil 0.3 Clove oil 0.1 Orange oil 0.1 Ethyl acetate 0.2 Isoamyl butyrate 0.2 Cineol 1 Eugenol 0.5 Apple flavor 0.1 Melon Flavor 0.1 Ethanol Residual 100%

[0031]

[Table 1] APM (ascorbic acid-2-phosphate magnesi
Stability ○: APM residual rate after storage at 40 ° C for 6 months: 90% or more ×: APM residual rate after storage at 40 ° C for 6 months: less than 90% Flavor evaluation (after storage at 40 ° C for 6 months) Evaluation of toothpaste) ○: Slightly deteriorated, but can be used in the mouth without any problem. Δ: It is clearly deteriorated and feels strange, but it can be used. X: Not significantly usable, having a base odor.

From the results shown in Table 1, by using silica having a pH of 9 or more in a 5% water slurry as an abrasive,
It is observed that PM is held stable.

The dentifrice compositions of the following examples also have good AP.
It has M stability. In the following examples, silica A
~ C are the same as those in Table 1, and the fragrance A is the same as the above. The fragrance B has the following composition.

Fragrance composition B 1-menthol 10% 1-carvone 10 peppermint oil 20 spearmint oil 40 anethole 8 cineol 1 eugenol 0.5 menthyl salicylate 0.3 citral 0.2 cardamom oil 0.5 ethyl acetate 0.1 isoamyl buty Rate 0.1 Mentone 3 Anise Oil 1 Lemon Oil 0.1 Banana Flavor 0.1 Peach Flavor 0.1 Ethanol Residual 100%

[Example 4] Liquid toothpaste Propylene glycol 5% 70% Solbit solution 50 Glycerin 10 Carrageenan 1.2 Saccharin sodium 0.2 Sodium lauryl sulfate 1.2 Ethyl paraoxybenzoate 0.1 Ascorbic acid-2-phosphate Magnesium salt 0.2 Silica A 10 Fragrance A 0.9 Potassium hydroxide Appropriate amount of water Residual 100% Initial pH: 8.80

Example 5 Toothpaste Polyethylene glycol 400 5% Glycerin 20 Xanthan gum 1.1 Xylit 10 Sodium lauryl sulfate 0.9 Myristic acid diethanolamide 0.6 Dipotassium phosphate 0.6 Palmitic acid 0.5 Ascorbic acid -2-Phosphoric acid ester sodium salt 1 Ethyl paraoxybenzoate 0.1 Silica B 20 Perfume B 1.2 Sodium hydroxide qs water balance 100% Initial pH: 8.70

[Example 6] Toothpaste Propylene glycol 4% 70% Sorbit solution 40 Carboxymethyl cellulose 2 Sodium saccharin 0.15 Sodium lauryl sulfate 1 Lauroyl sarcosine sodium 0.2 Sodium benzoate 0.8 Tranexamic acid 0.1 Ascorbic acid- 2-Phosphate sodium salt 0.05 Sodium myristate 0.2 Silica C 25 Perfume B 1 Trisodium phosphate, appropriate amount Water balance 100% Initial pH: 8.75

Example 7 Toothpaste Stearic Acid 0.3% Sodium Lauryl Sulfate 1.2 Pluronic F127 0.4 Propylene Glycol 5 70% Solbit Solution 50 Carrageenan 1.2 Saccharin Sodium 0.2 Paraoxy Ethyl Benzoate 0.1 Ascorbic acid-2-phosphate magnesium salt 0.2 Citric acid monohydrate 0.2 Silica A 15 Silicic anhydride (manufactured by Tokuyama Corporation) 3 Perfume B 0.9 Sodium hydroxide suitable amount Purified water Residual 100% initial pH: 8.68

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C083 AA122 AB032 AB171 AB172                       AB242 AB282 AC122 AC132                       AC242 AC302 AC331 AC342                       AC472 AC482 AC642 AC662                       AC782 AC842 AC862 AD042                       AD272 AD352 AD532 AD641                       AD642 BB41 CC41 DD22                       DD23 EE01

Claims (2)

[Claims] 1. An alkali-labile perfume-containing dentifrice composition comprising ascorbic acid phosphoric acid ester or a salt thereof and 5% by mass or more of abrasive silica having a pH of a 5% by mass aqueous slurry of 9 or more. . 2. The dentifrice composition according to claim 1, wherein the fragrance contains an ester fragrance.