JPS6115820A - Composition for oral cavity - Google Patents

Abstract

PURPOSE:A composition for oral cavity suppressing effectively astringency and bitterness of silica, having a good feeling in use, obtained by blending a specific modified aluminum hydroxide with silica. CONSTITUTION:Aluminum hydroxide (preferably 1-30mu average particle size) is treated with an acid or its salt to give modified aluminum hydroxide, preferably aluminum hydroxide is treated with an acid or its salt to give aluminum hydroxide having an aluminum phosphate-containing layer (preferably 10-1,000Angstrom thickness) on the surface of particle. A brushing agent consisting of the aluminum is blended with gelatinizing silica and a silica brushing agent. Preferably an amount of the modified aluminum hydroxide is 5-95wt%, especially 5-50wt% in the case of toothpaste, an amount of the silica brushing agent is 5-30wt%, and an amount of the gelatinizing silica is 1-10wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to the use of toothpastes and the like that contain silica and modified aluminum hydroxide obtained by treating aluminum hydroxide with an acid or its salt as an abrasive. More specifically, the present invention relates to an oral composition that is comfortable to use and has suppressed the bitterness and astringency of silica.

BACKGROUND OF THE INVENTION Conventionally, gelling silica, precipitated silica, silica xerodal, silica aerodal, and other abrasive silicas have been incorporated into oral compositions such as toothpastes. However, silica generally has a unique bitterness and astringency, so when silica is added to an oral composition, this bitterness and astringency can cause the composition to have a poor feel when used. This becomes noticeable when it is added in an amount of 3% (by weight, the same applies hereinafter) or more of the composition. In particular, this tendency becomes remarkable when silica having a particle size of 1 μm or less is used, and in this case, even a compounding amount of about 2 μm causes a feeling of discomfort during use.

In addition, as a silica-based abrasive, the particle size of the primary particles is 500m.
Even when using particles with a secondary particle size of 1 to 30 μm or more, this product has a relatively weak bitterness and astringency, but if it is added in a proportion of 5% or more, a strange feeling will occur. .

To this end, conventionally, silica-containing toothpastes and other oral compositions have been blended with flavoring materials such as silica and cloves containing additives such as gelatin and soalkynolamide. Although attempts have been made to mask bitterness and astringency, the masking effect is not sufficient, and it has been reported that the use of oral compositions that contain too much gelatin or sialkinolamide may result in poor usability or browning during storage. Therefore, there has been a desire for an oral composition that effectively suppresses the bitterness and astringency of silica rice and has a good feeling of use.

Features of the Invention In view of the above circumstances, the present inventors conducted intensive research on suppressing the bitterness and astringency of silica blended into oral compositions such as toothpaste, and as a result, they discovered that aluminum hydroxide was used as an abrasive. When silica is added to an oral composition using modified aluminum hydroxide obtained by treatment with an acid or its salt, the bitterness and astringency are surprisingly effective even when a considerable amount of silica is added. The inventors have discovered that it is possible to obtain an oral composition that suppresses the effects of oxidation and has a good feeling of use, and has led to the present invention.

The present invention will be explained in more detail below.

Structure of the Invention The oral composition according to the present invention contains silica and modified aluminum hydroxide obtained by treating aluminum hydroxide with an acid or a salt thereof.

The modified aluminum hydroxide used in the present invention is obtained by treating aluminum hydroxide with an acid or its salt. In this case, there are no particular restrictions on the aluminum hydroxide used for modification, and it is usually A commercially available product obtained by the method described above can be used. In addition, the average particle size of the aluminum hydroxide used is 1 to 30μ, especially 3 to 30μ, from the viewpoint of processability.
It is preferable to set it to 20μ. In this case, it is preferable to use aluminum hydroxide that has been pulverized into the desired shape and particle size using a mail mill, jet mill, or rotary impact pulverizer, and the resulting modified aluminum hydroxide The polishing force can be adjusted in various ways.

Moreover, as the acid or salt used for modifying the aluminum hydroxide, inorganic acids, organic acids, and salts thereof can be used. Examples of inorganic acids and their salts include phosphoric acid, sulfuric acid, hydrochloric acid, and their salts, and examples of organic acids and their salts include acetic acid, oxalic acid, tartaric acid, succinic acid, and their salts. Phosphoric acid and its salts are preferably used for this purpose, and for such modified aluminum hydroxide, its 10% water slurry usually has a concentration of about 5 to 8, and 10% of unmodified aluminum hydroxide. Since the water slurry has a low value compared to the normal value of around 9, the composition is not prepared at a high temperature, and therefore the decomposition and deterioration of fragrance ingredients, especially ester fragrance ingredients, can be suppressed. Therefore, it is possible to freely create fragrances using various fragrance ingredients.

Here, as the phosphoric acid and its salt, orthophosphoric acid (I
(lPO4), -rophosphoric acid (H4P2O7), metaphosphoric acid (HPO,), triphosphoric acid (HsPsOt.), tetraphosphoric acid (le p4o□,), polymetaphosphoric acid ((HPO,)n
) and their alkali metal salts, and these can be used alone or in combination of two or more. The alkali metal salts include hydrogen phosphate-alkali metal salt (MH, PO4), di-alkali metal hydrogen phosphate (HPO,), tri-alkali metal IJ phosphate (MsPO4), and the like.

The method of treating aluminum hydroxide with an acid or its salt is not particularly limited, but for example, a method in which aluminum hydroxide is suspended in an aqueous solution of an acid or its salt and modified by neutralization treatment is preferably adopted. It is possible. In this case, aluminum hydroxide is an aqueous solution of an acid or its salt.
A slurry of 90% by weight, particularly 30 to 70% by weight is preferable, and the acid concentration varies depending on the concentration of aluminum hydroxide added, but is 0.05 mol/l.
It is preferable to set it to 5 mol/l. Also, the reaction is 10
It is preferable to carry out the reaction at -50°C, especially 20-30°C, for 2-50 hours, especially 2-30 hours, and it is preferable to stir during the reaction.

After the above operation is completed, the aluminum hydroxide removed from the slurry by filtration is washed with water or the like and dried to obtain modified aluminum hydroxide.

In addition, in the above-mentioned modification operation, the modification operation can be carried out once or repeatedly using one or more of the above-mentioned acids or salts at the same time. It is also possible to repeat each modification operation using salt. For example, aluminum hydroxide can be first treated with sulfuric acid, hydrochloric acid, etc., and then treated with phosphoric acid.

Among the above-mentioned modified aluminum hydroxides, those obtained by treatment with phosphoric acid or its salts, especially orthophosphoric acid or its alkali metal salts are particularly preferred. Products modified with this phosphoric acid or its salt have an aluminum phosphate-containing layer formed on the particle surface, but when using this type of modified aluminum hydroxide, the aluminum phosphate-containing layer on the surface A layer in which the entire layer is made of aluminum phosphate may be used, or a layer in which aluminum hydroxide and aluminum phosphate coexist may be used, but ESCA (ElectronSpe
ctrosaopy for Chemical An
It is preferable to use a layer that shows the presence of 0.1 to 10% of phosphorus atoms in the aluminum phosphate-containing layer when surface analysis is performed using the aluminum phosphate-containing layer. The above-mentioned modified aluminum hydroxide preferably has an aluminum phosphate-containing layer having a thickness of 10 to 1000 Å, and the modified aluminum hydroxide has a P2O6 content of 0.01 to 0.
Preferably it is 5%.

In the present invention, the above-mentioned modified aluminum hydroxide is blended into oral compositions such as toothpaste. In this case, as the modified aluminum hydroxide, add 10% by weight of this to water.
It is preferable to use a slurry suspended at a ratio of 4 to 8 and a copper plate polishing value of 1 to 10.

In addition, the copper plate polishing value is 50q of modified aluminum hydroxide.
6. Create a regular toothpaste containing 501
This is the abrasiveness when the powder is dispersed in 40 f of 60 tiglycerin and 20,000 strokes are applied using a tilted abrasive tester ('pepsodent type) [``Recent Cosmetic Science'' (Yakuji Nippo Publishing Co., Ltd.: 1972). April 10th)
See page 184].

In addition, when using modified aluminum hydroxide as an abrasive, the average particle size is 1 to 30 μm, particularly 7 to 25 μm.
It is preferable that the average particle size is larger than 30 μm, which may give a rough feeling, and if it is smaller than 1 μm, the polishing properties may be poor.

However, when used as a polishing agent, particles with a finer particle size can also be used.

Furthermore, in the present invention, silica is blended into the oral composition. In this case, in the present invention, the properties such as the type of silica and the average particle size may vary depending on the type of composition, and are not particularly limited.8 For example, as silica, Cab-
0-811■, 'l'okus, a glugable, large-forming ultrafine powdered silica sold under the trademark AeroaLl■
Igneous fine powder gelatinous silica with secondary particles of several micrometers or less, or abrasive silica sold under the trademarks 11■, 1taail■, and N1psil■ are selected as appropriate depending on the type of composition, etc. , compounded and used. Here, as the silica-based abrasive, for example, Japanese Patent Application Laid-Open No. 49-9199
Publication No. 4, JP-A-49-94712, JP-A-50
-64198 publication, JP-A-50-65497 publication,
JP-A-51-928695, JP-A-51-136
Those described in Japanese Patent Publication No. 841, Japanese Patent Publication No. 54-4919, etc. can be used. To give a more specific example, Zeodent■e Ze(XE)s 5id
The primary particles sold under the trademark ent@ are 500 mμ.
Below, precipitated silica, silica xerogel, silica aerogel, etc. having secondary particles of 1 to 30 microns can be used. In this case, precipitated silica is particularly preferably used, Sin.

Content: 70% or more, preferably 90% or more, alkaline/alkaline earth metal oxide content: 0~5%, binding fθ~10% of metal oxides such as aluminum, magnesium, calcium, etc. per 5 inl, preferably 0~5q6 , adhering moisture content (loss on drying) of 1 to 10 cm, average particle size of 0
．． 5-30μ, preferably 1-15μ, specific surface area per 1f (CBET method) 500m' or less, more preferably 300- or less, refractive index 1.44-1.47, liquid absorption 110
．． Those having a property of 6 to 1.3 cc/f O are preferably used. Specifically, ZeO49 from Huber, USA;
Zeodent 113, 5yloid AU, -1,63,74 from W, R. Grace, USA.

404, UK J, Croasfield & 5ons
NeosylET from Deguasa, Germany, 5i from Deguasa
Examples include dent3, 20, etc.

The amounts of modified aluminum hydroxide and silica are not particularly limited and are appropriately selected depending on the type of oral composition, etc., but usually the modified aluminum hydroxide accounts for 5 to 95% of the total composition. In the case of toothpaste, it is 5 to 50%, and when using a silica-based abrasive as the silica, it is 1 to 50% of the entire composition.
In particular, it is preferably 5 to 30%, and when using silica, it is preferably 1 to 10% of the total composition. in this case,
Since the oral composition of the present invention contains modified aluminum hydroxide, it is possible to incorporate 3% or more of silica without developing bitterness or astringency. In addition, when using silica with a particle size of 1μ or less, it is necessary to add modified aluminum hydroxide in an amount of 5 times or more by weight, and when using silica with a particle size of more than 1μ, It is preferable to blend modified aluminum hydroxide in an amount of .5 times or more by weight in order to effectively suppress the bitterness and astringency of silica.

In the present invention, the abrasive may be composed of only modified aluminum hydroxide or only modified aluminum hydroxide and a silica-based abrasive, but it may be used in combination with other abrasives. Here, other abrasives include, for example, calcium hydrogen phosphate dihydrate, calcium hydrogen phosphate anhydrate, calcium carbonate, calcium birophosphate, insoluble methaline, sodium acid, aluminum oxide, microcrystalline cellulose, resin , tertiary magnesium phosphate, magnesium carbonate, and the like. Further, conventional aluminum hydroxide can also be blended within a range that does not significantly impair the properties of the modified aluminum hydroxide. In addition, when using modified aluminum hydroxide and silica-based abrasives together with other abrasives, the ratio is not limited, and modified aluminum hydroxide may be used as the main abrasive, or other abrasives may be used as the main abrasive. The modified aluminum hydroxide of the present invention may be used as an abrasive, and is determined depending on the purpose of use of the oral composition. It is preferable to do so.

Furthermore, the oral composition of the present invention contains lysozyme chloride, dextranase, lytic enzyme, mutanase, chlorhexidine or its salt, turic acid, alexidine, hinokitiol, cetylpyrizonium chloride, alkylglycine, alkylzoamino Ethylglycine salt, plantin, 6-aminocadenoic acid, tranexamic acid, azulene, vitamin E1 sodium monofluorophosphate, sodium fluoride, stannous fluoride, water-soluble mono- or di-phosphate, Active ingredients such as quaternary ammonium compounds and sodium chloride can be blended, and the oral composition of the present invention contains these active ingredients, particularly fluorine-containing compounds, chlorhexinones,
Dextranase, tranexamic acid, epsilon aminocaproic acid, allantoin chlorhydroxyaluminum, sodium chloride, etc. can be stably blended.

The oral composition of the present invention may further contain other components depending on its type. For example, binders such as caloxymethylcellulose, hydroxyethylcellulose, alginate, caradanan, arabic gum, polyvinyl alcohol, thickeners such as polyethylene glycol, sorbitol, glycerin, propylene glycol, sodium lauryl sulfate, dodecylbenzenesulfonic acid, etc. Sodium, Hydrogenated Coconut Fatty Acid Monoglyceride Sodium Monosulfate, Sodium Lauryl Sulfoacetate, N-
Foaming agents such as sodium lauroylsarcosinate, N-acylglutamate, lauroylgetanolamide, sucrose fatty acid ester, sodium saccharin, stevioside, neohesberidyl dihydrochalcone, glycyrrhizin, perillartin, p-methoxinnamic aldehyde, thaumatin, etc. Sweeteners, preservatives, flavoring ingredients, etc. may be added. In this case, the oral composition of the present invention can have a low level of - by incorporating the above-mentioned modified aluminum hydroxide, so that decomposition and deterioration of the fragrance during storage can be effectively suppressed.

Therefore, the oral composition of the present invention contains menthol, cargane, ino-4-mint oil, spearsant oil, anethole,
Ester fragrance accent, lactone fragrance accent, aldehyde fragrance accent, phenol fragrance accent, and other MONTCLAIR, N, J,
5TEFFEN A issued by (U.S.A.)
'Perfume and Fl by RCTANIR
Avor Chemicals' fragrance ingredients, as well as orange oil, lemon oil, clove oil, cassia oil,
Various fragrance ingredients such as essential oils such as fennel oil, cardamom oil, cinnamon oil, coriander oil, eucalyptus oil, caraway oil, sage oil, and thyme oil can be effectively blended.

The oral composition of the present invention can be produced by a conventional method using the above-mentioned components, but when producing a toothpaste, it is preferable that the number of components is 5 to 8. In this case, since the modified aluminum hydroxide of the present invention has a low pH, the pH of the composition can be easily adjusted to a range of 5 to 8, and the P)I
It remains stable within the range for a long period of time.

Furthermore, the oral composition of the present invention can be filled into a plastic container, a laminate container made of aluminum laminated on one or both sides with plastic, or a metal container made of aluminum or the like. Since this can be suppressed, aluminum tubes and the like can be used without any problems. In addition, in the composition of the present invention, the addition of an alkali metal monofluorophosphate or magnesium chloride can further significantly suppress corrosion of aluminum.

As described in detail of the invention, the oral composition according to the present invention contains silica and modified aluminum hydroxide obtained by treating aluminum hydroxide with an acid or a salt thereof. The bitterness and astringency of silica are well suppressed, and therefore the product has an excellent feeling of use without causing any discomfort during use.

Next, a production example of modified aluminum hydroxide used in the present invention will be shown.

[Production Example 1] Water (pure water or industrial water, the same applies hereinafter) is added to high-white aluminum hydroxide that has been pulverized using a rotary impact type pulverizer (average particle size: 6μ, light transmission method), and the mixture is stirred. , 50 Ti slurry is prepared. Next, add orthophosphoric acid aqueous solution (concentrated [
2 mot/l) and stirred at room temperature for 2 to 4 hours to neutralize the slurry, and then filter the slurry. Thereafter, water was added to the residue to prepare a 50% slurry, which was stirred and then filtered. Washing operation f was repeated twice, and finally the residue was dried to obtain modified aluminum hydroxide.

The surface of this aluminum hydroxide was coated with aluminum phosphate.

Next, the particle surface gold ESCA and FT-IR-(Four
ier Transformatlon 1nfrar
ed).

■ The results of analysis by ESCA are shown in Tables 1 and 2. Table 1 shows the results of quantitative analysis of constituent ions, and Table 2 shows the results of state analysis of phosphorus.For comparison, commercially available (unmodified) aluminum hydroxide was mixed with aluminum phosphate. The analysis results for aluminum phosphate and aluminum phosphate are also listed.

According to the results in Table 1, it is recognized that phosphorus ions are present in the modified aluminum hydroxide.

Furthermore, since P and Na are reduced by etching, it is concluded that phosphorus is chemically bonded to the surface.

Furthermore, according to the results in Table 2, the factors of the peak energy value of phosphorus are in good agreement between the modified aluminum hydroxide and aluminum phosphate, and it is recognized that the surface forming substance is aluminum phosphate.

(2) Results of analysis by FT-IR When the modified aluminum hydroxide was analyzed by FT-IR, the presence of aluminum phosphate was confirmed.

[Production example 2] Modified aluminum hydroxide was obtained in the same manner as in Production Example 1.

However, when stirring for 2 to 4 hours during the neutralization treatment, a phosphoric acid aqueous solution was added in the latter half of the neutralization treatment.This modified aluminum hydroxide has aluminum hydroxide and aluminum phosphate coexisting on the surface. Ta.

Next, an experimental example will be shown.

[Experiment example]

Toothpastes with a base composition were prepared using the modified aluminum hydroxide obtained in Production Example 1.2 as an abrasive, and the properties of these toothpastes were measured immediately after preparation and after storage for a predetermined period of time.

For comparison, a similar experiment was conducted using unmodified aluminum hydroxide (commercially available aluminum hydroxide).

The results are shown in Table 3.

Toothpaste Composition Abrasive 46 Chiro0 Thisolbit 26
Ticalpoxymethylcellulose sodium
0.8% carrageenan
0.3 Sodium thilauryl sulfate
1.8% gelling silica
3.0% Propylene Glycol 2.5% Saccharin Sodium 0.181 Butylno Mother Pen 0.00
2 Chiecilno and Laben
0.005% Chloryxison hydrochloride
O,OO1% fragrance
1.0% purified water
Total remaining 100. o
96 Table 3 From the results in Table 3, the toothpaste using modified aluminum hydroxide as an abrasive has a lower pH than the toothpaste using unmodified aluminum hydroxide, and has a long-lasting effect. It was observed that the condition was maintained at a low level.

EXAMPLES Hereinafter, the present invention will be specifically explained by showing Examples and Comparative Examples.

[Examples 1 to 5, Comparative Examples 1 to 7] Silica, modified aluminum hydroxide,
Preserved products made by preparing toothpastes with the following compositions containing commercially available aluminum hydroxide and calcium hydrogen phosphate dihydrate by a conventional method, filling tubes, and storing these toothpastes at a specified temperature for a specified period of time. The feeling of use was sensory evaluated. The results are also listed in Table 4. The evaluation criteria for the feeling of use are as follows.

Composition Powder Quantity Cal shown in Table 4: Sodium oxymethylcellulose 1.0
%Propylene glycol
2.0 Sodium lauryl sulfate
1.2 Sorbit (70%) 25 Flavor 1.
0 Saccharin Sodium 0.
15 total 100.0
Evaluation Criteria for Usability: No bitterness or astringency, good usability △ Somewhat bitterness or astringency × Or oak Bitterness or astringency, leaving a strange feeling after use.

[Examples 6 to '9, Comparative Examples 8 to 11] The toothpastes of Examples 6 to 9 and Comparative Examples 8 to 11 having the compositions shown in Table 5 were each prepared by a conventional method and filled into tubes,
These toothpastes were stored at a predetermined temperature for a predetermined period of time, and the feeling of use was sensory evaluated.

The results are also listed in Table 5. Note that the evaluation criteria for the usability are the same as described above.

In general, stored toothpaste containing silica exhibits more bitterness and astringency than those immediately after manufacture, but the results in Table 4.5 show that modified aluminum hydroxide and silica It was found that the toothpaste of the present invention containing silica had a good feeling of use even after long-term storage because the bitterness and astringency of silica were suppressed. In this case, for silica (Aeroall) with a particle size of 1μ or less, by blending modified aluminum hydroxide in an amount of 5 times or more by weight, the particle size can be reduced to 1μ or less.
0 for silica (zeodent) exceeding μ
．． It has been found that by blending 5 times or more by weight of modified aluminum hydroxide, the bitterness and astringency of silica can be effectively suppressed. On the other hand, toothpastes that contain silica and are made from commercially available aluminum hydroxide or calcium hydrogen phosphate dihydrate that have not been modified as abrasives have a bitter and astringent taste. Ta.

Claims (1)

[Scope of Claims] 1. An oral composition comprising silica and modified aluminum hydroxide obtained by treating aluminum hydroxide with an acid or a salt thereof. 2. The modified aluminum hydroxide is obtained by treating aluminum hydroxide with phosphoric acid or its salt, and an aluminum phosphate-containing layer is formed on the surface of the particles.Claim 1 Oral composition as described. 3. P_2O_5 min in modified aluminum hydroxide is 0.
The oral composition according to claim 2, wherein the amount is 01 to 0.5% by weight. 4. Oral composition according to claim 2 or 3, in which the modified aluminum hydroxide contains 0.1 to 10% by weight of phosphorus atoms in the aluminum phosphate-containing layer. thing. 5. The oral cavity composition according to any one of claims 2 to 4, wherein the modified aluminum hydroxide has an aluminum phosphate-containing layer having a thickness of 10 to 1000 Å. 6. The average particle size of modified aluminum hydroxide is 1 to 30μ
An oral composition according to any one of claims 1 to 5. 7. Add silica-based abrasive as silica to 1 to 4 of the entire composition.
The oral composition according to any one of claims 1 to 6, containing 0% by weight. 8. The oral cavity composition according to any one of claims 1 to 6, which contains gelling silica as the silica. 9. The oral composition according to any one of claims 1 to 8, wherein the composition has a pH of 5 to 8. 10. The oral composition according to any one of claims 1 to 9, which contains an ester fragrance.