JPH0419964B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oral composition containing modified aluminum hydroxide obtained by treating aluminum hydroxide with sulfuric acid or its salt as an abrasive. This invention relates to an oral composition in which fragrance components are less likely to decompose or deteriorate. BACKGROUND ART It has been known to incorporate aluminum hydroxide as an abrasive into oral compositions such as toothpaste. However, as shown in the experimental example below, aluminum hydroxide has a high pH, so
When this is added to toothpaste as an abrasive, the PH of the toothpaste becomes high, and this PH tends to gradually increase during storage. There is a problem in that ester-based flavor components such as methyl decompose and deteriorate during storage, resulting in changes in the flavor of toothpaste. For this reason, oral compositions such as toothpastes containing aluminum hydroxide have traditionally had to be scented using flavoring ingredients that do not deteriorate easily even at high pH, and the number of flavoring ingredients that can be used is very limited. Because of these limitations, it has been difficult to select fragrance ingredients, making it difficult to create fragrances that are popular with consumers. In view of the above circumstances, the present inventors conducted various studies and found that modified aluminum hydroxide obtained by treating aluminum hydroxide with sulfuric acid or its salts was used as an abrasive for use in oral cavity products such as toothpaste. When incorporated into a composition, this modified aluminum hydroxide
Since the PH is low, the composition will not be prepared to a high PH, and therefore, the decomposition and deterioration of fragrance ingredients, especially ester-based fragrance ingredients, can be suppressed. Therefore, fragrances can be freely mixed using various fragrance ingredients. I found out that I can get it. That is, the present inventors found that the modified aluminum hydroxide has a 10% (wt%) water slurry having a pH of usually about 5 to 8, and that the 10% water slurry of unmodified aluminum hydroxide has a pH of about 5 to 8. Slurry pH is usually 9
It has been found that by incorporating this modified aluminum hydroxide into an oral composition as an abrasive, an oral composition having the above-mentioned excellent properties can be obtained. , which led to the present invention. The present invention will be explained in more detail below. The oral composition according to the present invention is prepared by treating aluminum hydroxide with sulfuric acid or a salt thereof in an oral composition used as a toothpaste, a dentifrice such as a dentifrice, a profilaxis paste, etc. It is made by blending the modified aluminum hydroxide obtained in this way. The modified aluminum hydroxide used in the present invention is obtained by treating aluminum hydroxide with sulfuric acid or its salt. In this case, there is no particular restriction on the aluminum hydroxide used for modification, and a normal method can be used. A commercially available product can be used. Note that the average particle size of the aluminum hydroxide used is preferably 1 to 30 microns, particularly 3 to 20 microns, from the viewpoint of processability. In this case, it is preferable to use aluminum hydroxide that has been pulverized into the desired shape and particle size using a ball mill, jet mill, rotary impact pulverizer, etc., and the abrasive power of the resulting modified aluminum hydroxide can be varied in various ways. can be adjusted to As the sulfuric acid and its salts, commercially available dilute solutions of sulfuric acid, sodium sulfate, potassium sulfate, ammonium sulfate, and the like can be used. Here, the method of treating aluminum hydroxide with sulfuric acid or its salt is not particularly limited, but for example, aluminum hydroxide is suspended in an aqueous solution of sulfuric acid or its salt, and the modification is carried out by performing a neutralization treatment. method can be suitably employed. In this case, aluminum hydroxide is added in an aqueous solution of sulfuric acid or its salts.
A 90% by weight slurry, particularly a 30 to 70% by weight slurry, is preferable, and the concentration of sulfuric acid varies depending on the concentration of aluminum hydroxide added.
It is preferable to set it as 0.05 mol/-5 mol/. Further, the reaction is preferably carried out at 10 to 50°C, particularly 20 to 30°C, for 2 to 50 hours, particularly 2 to 30 hours, and stirring is preferably performed during the reaction. After the above operations are completed, modified aluminum hydroxide is obtained by filtering, washing the aluminum hydroxide with water, etc., and drying. In addition, in the above-mentioned reforming operation, it is possible to perform the reforming operation once or repeatedly using one or more of the above-mentioned sulfuric acid or salts at the same time, but it is also possible to carry out the reforming operation once or repeatedly using different sulfuric acid or salts. You can also repeat the operation. For example, aluminum hydroxide can be treated with sulfuric acid and then with sulfate. In the present invention, the above-mentioned modified aluminum hydroxide is blended into oral compositions such as toothpaste. In this case, the amount of modified aluminum hydroxide blended is not particularly limited and is appropriately selected depending on the type of oral composition, but usually 5 to 95% of the total composition.
%, especially in the case of toothpaste, preferably 5 to 50%. In addition, in the present invention, as modified aluminum hydroxide, the pH of the 10% water slurry is 6 to 7.5.
It is preferable to use one in which liquid separation is less likely to occur. In addition, when using modified aluminum hydroxide as an abrasive, it is preferable that the average particle size is 1 to 30μ, particularly 3 to 15μ;
If it is larger than 30μ, a rough feeling may occur, and if it is smaller than 1μ, the polishing properties may be poor. In this case, in the present invention, modified aluminum hydroxide can be used alone as the abrasive, but it may also be used in combination with other abrasives. Here, other abrasives include, for example, calcium hydrogen phosphate dihydrate, calcium hydrogen phosphate anhydrate, calcium carbonate, calcium pyrophosphate,
Examples include insoluble sodium metaphosphate, precipitated silica, aluminosilicate, aluminum oxide, microcrystalline cellulose, resin, tertiary magnesium phosphate, and magnesium carbonate. 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 modified aluminum hydroxide is used in combination 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. Although these are determined depending on the purpose of use of the oral composition, the modified aluminum hydroxide of the present invention is mixed in an abrasive with a concentration of 20 to 100%.
%, particularly preferably 40 to 100%. Since the oral composition of the present invention contains the above-mentioned modified aluminum hydroxide, the pH can be lowered, so that decomposition and deterioration of the fragrance during storage can be effectively suppressed. Therefore, the oral composition of the present invention may generally contain 0.1 to 5% (by weight, the same hereinafter), preferably 0.5 to 2%, of fragrance. In this case, the composition of the fragrance is not particularly limited, but for example, menthol 10-70% (in fragrance) carvone 0-30 peppermint oil spearmint oil 0-90 anethole 0-30 ethanol 0-40 accent 0.1- 90〃 composition can be used. here,
Examples of the accent components are listed below, and these are essential components for characterizing the flavor (characterizing the oral composition), but the oral composition of the present invention contains these accent components, especially esters. Without decomposing or cooling the accents of the system,
Furthermore, it is possible to suppress the decomposition and deterioration of easily deteriorated components in natural essential oils such as peppermint oil and spearmint oil, and the flavor hardly changes even after long-term storage. Therefore, in the present invention, ester fragrances and the like can be effectively incorporated. Accent content: Ester-based methyl salicylate: 0.1-60% in fragrance formulation
(preferably 1-30%) Menthyl acetate: 0.001-10% (0.01-1
%) Ethyl acetate Isoamyl acetate: 〃 Citronellyl acetate Linalyl acetate: 〃 Pornyl acetate Terpinyl acetate: 〃 Benzyl acetate Phenylethyl acetate: 0.0001-0.1%
(0.001~0.01%) Isoeugenyl acetate: 0.001~10%
(0.01-1%) Myrcenyl acetate Ethyl propionate: 〃 Isoamyl propionate Citronellyl propionate: 〃 Linalyl propionate Geranyl propionate: 〃 Allyl cyclohexane propionate Ethyl butyrate: 〃 Isoamyl butyrate Ethyl-2-methylbutyrate: 〃 Geranyl butyrate: 〃 Linanyl butyrate: Citronellyl butyrate Citronellyl isobutyrate: 〃 Benzyl butyrate Benzyl isobutyrate: 〃 Propyl isovalerate: 〃 Isoamyl isovalerate Geranyl Isovalerate: 〃 Benzyl isovalerate Methylheptine carbonate: 0.001-0.1%
(0.001~0.01%) Ethyl acetoacetate: 0.001~10% (0.01
~1%) Methyl cinnamate: 0.001~10% (0.01~1
%) Ethyl anisate Methyl anthranilate: 〃 Methyl methyl anthranilate Ethyl methyl phenyl glycidate:
〃 Ethyl p-methyl-β-phenylglyside:
〃 Allyl caproate: 0.0001~0.1% (0.001~
0.01%) Allyl caprylate: 〃 etc. Lactone γ-undecalactone: 0.0001-1% (0.001
~0.1%) γ-nonyl lactone: 〃 Ethylene brachylate: 〃 etc. Aldehyde type n-heptylaldehyde: 0.0001~0.1%
(0.001-0.01%) n-octylaldehyde: 〃 n-nonylaldehyde: 〃 nonadienal: 〃 citral: 0.001-20% (0.01-10%) citronellal: 0.001-1% (0.001-0.5%) hydroxycitronellal: 0.001~1%
(0.001-0.5%) Perilaldehyde: 0.001-10% (0.01-1%) Benzaldehyde: Phenylacetaldehyde: 0.0001-1%
(0.001~0.5%) Cinnamic aldehyde: 0.001~30% (0.01
~10%) Vanillin: 0.001~10% (0.001~5%) Ethyl vanillin: Trans-2-hexenal: 0.0001~1%
(0.001-0.5%) Myrtenal: 0.001-2% (0.01-1%) etc. Phenols Eugenol: 0.0001-10% (0.001-1%) Isoeugenol: Thymol: 0.0001-1% (0.001-0.1%) Carba Kroll: 〃 etc.Furthermore, fragrance ingredients described in "Perfume and Flavor Chemicals" by STEFFEN ARCTANDER published by MONTCLAIR, NJ (USA) are also preferably used, and orange oil, lemon oil, clove oil, cassia oil , fennel oil, cardamom oil, cinnamon oil, coriander oil, eucalyptus oil, caraway oil, sage oil,
Essential oils such as thyme oil can also be used effectively. Furthermore, the oral composition of the present invention contains lysozyme chloride, dextranase, lytic enzyme, mutanase, chlorhexidine or a salt thereof, sorbic acid,
Alexidine, hinokitiol, cetylpyridinium chloride, alkylglycine, alkyldiaminoethylglycine salt, allantoin, ε-aminocaproic acid, tranexamic acid, azulene, vitamin E, sodium monofluorophosphate, sodium fluoride, stannous fluoride, water-soluble The oral composition of the present invention can contain active ingredients such as primary or secondary phosphates, quaternary ammonium compounds, sodium chloride, etc., and the oral composition of the present invention contains these active ingredients, especially fluorine-containing compounds, chlorhexidine, dextranase,
tranexamic acid, epsilon aminocaproic acid,
Allantoin chlorohydroxyaluminum, 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, sodium carboxymethyl cellulose, hydroxyethyl cellulose, alginate, carrageenan, gum arabic, binders such as polyvinyl alcohol, polyethylene glycol, sorbitol,
Thickening agents such as glycerin and propylene glycol,
Foaming agents such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid monoglyceride monosulfate, sodium lauryl sulfoacetate, sodium N-lauroyl sarcosinate, N-acyl glutamate, lauroyl diethanolamide, sucrose fatty acid ester, etc. , saccharin sodium, stevioside, neohesperidyl dihydrochalcone, glycyrrhizin, perillartin, p-methoxinamicaldehyde, thaumatin, and other sweeteners, preservatives, and the like may be 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 to have a pH of 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 can be stably maintained in this PH 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 without internal coating can be used without any problems. Next, an example of manufacturing modified aluminum hydroxide used in the present invention will be shown. [Production Example] Water (pure water or industrial water, hereinafter the same) is added to high-white aluminum hydroxide that has been pulverized using a rotary impact pulverizer (average particle size 4μ <light transmission method>), and the mixture is stirred. Prepare a 50% slurry. Next, an aqueous sulfuric acid solution (concentration 2 mol/l) is added to the mixture, and the mixture is stirred at room temperature for 2 to 4 hours for neutralization, and then the slurry is filtered. Thereafter, water was added to the residue to prepare a 50% slurry, which was stirred and then filtered, a washing operation repeated twice, and finally the residue was dried to obtain modified aluminum hydroxide. Next, experimental examples will be shown to specifically explain the effects of the present invention. [Experimental Example 1] Toothpastes having the following composition were prepared using the modified aluminum hydroxide obtained in the above production example as an abrasive, and the pH of these toothpastes was measured immediately after preparation and after storage for a predetermined period of time. For comparison, similar experiments were conducted using unmodified aluminum hydroxide (commercially available aluminum hydroxide) and calcium hydrogen phosphate dihydrate. The results are shown in the drawing. Toothpaste composition: Abrasive 46% Modified aluminum hydroxide (a) Commercially available aluminum hydroxide (b) Calcium hydrogen phosphate dihydrate (c) 60% Sorbit 26% Sodium carboxymethylcellulose 0.8% Carrageenan 0.3% Sodium lauryl sulfate 1.8% Gellable silica 3.0% Propylene glycol 2.5% Satucalin sodium 0.18% Butylparaben 0.002% Ethylparaben 0.005% Chlorhexidine hydrochloride 0.001% Fragrance 1.0% Purified water Remaining total 100.0% Based on the results of the drawing, modified water It has been found that toothpaste that uses aluminum oxide as an abrasive has a lower pH than toothpaste that uses unmodified aluminum hydroxide, and that it maintains a low pH for a long period of time. It was done. [Experimental Example 2] Stability of Methyl Salicylate A toothpaste with the following composition was prepared using the abrasive shown in Table 1, and after storing the toothpaste at -5°C for 3 months and at 40°C for 3 months. The strength of the gradient of the toothpaste after storage was sensory evaluated using a 5-point method.
Methyl Salicylate (Methyl Sa) in each toothpaste
-licylate) was investigated. Results first
Shown in the table. Toothpaste composition Abrasives shown in Table 1 46% 60% Sorbit 26% Sodium carboxymethylcellulose 0.8% Carrageenan 0.3% Sodium lauryl sulfate 1.8% Gellable silica 3.0% Propylene glycol 2.5% Sodium saccharin 0.18% Butyl paraben 0.002% Ethyl Paraben 0.005% Chlorhexidine hydrochloride 0.001% Fragrance (methyl salicylate) 1.0% Purified water Remaining total 100.0%

[Experiment example 3]

Using modified aluminum hydroxide treated with sulfuric acid (2 types of 10% slurry, PH5.7 and PH6.5), toothpastes with the following formulations were prepared. After storing this at 40℃ for 1 month and 3 months, the liquid separation was observed with the naked eye.
Sensory evaluation was performed using the point method to investigate the effect of slurry pH on liquid separation. The results are shown in Table 2. Modified aluminum hydroxide 45% Gellable silica 2% Sodium carboxymethyl cellulose 0.5% Carrageenan 0.5% Propylene glycol 2% Sorbit (60%) 25% Sodium lauryl sulfate 1.5% Sodium saccharin 0.07% Fragrance 0.6% Paraben 0.2% Mono Sodium fluorophosphate 0.76% Chlorhexidine hydrochloride 0.001% Water Remaining total 100.0%

[Table] From the results in Table 2, the slurry with a pH of 6.5 has a
It is recognized that liquid separation is less likely to occur than a slurry of 5.7, and it is preferable to use modified aluminum hydroxide in which the PH of the 10% slurry is 6 or more in the oral composition of the present invention because liquid separation is less likely to occur. Ta. Examples are shown below. Note that the following examples are all examples of toothpaste. In addition, the disposal of fragrances is as follows.

[Example 1]

Modified aluminum hydroxide 35% Dibasic calcium phosphate anhydrous 10 Gellable silica 2.5 Sodium carboxymethyl cellulose 0.7 Carrageenan 0.3 Propylene glycol 3 Sorbit (60%) 25 Sodium lauryl sulfate 1.5 Sodium saccharin 0.2 Fragrance 1 Paraben 0.2 Chlorhexidine hydrochloride 0.001 water remaining 100.0% [Example 2] Modified aluminum hydroxide 30% dicalcium phosphate dihydrate 10 Gellable silica 3 Carrageenan 0.5 Sodium alginate 0.5 Gelatin 0.5 Propylene glycol 2 Sorbit (60%) 35 Sodium lauryl sulfate 1 Lauric acid diethanolamide 1.5 Satucharin sodium 0.15 Fragrance 1 Paraben 0.1 Sodium monofluorophosphate 0.76 Dextranase (1 million units/g) 0.2 Water remaining 100.0% [Example 3] Modified aluminum hydroxide 50% Gellability Silica 2 Carboxymethyl cellulose 1 Propylene glycol 3 Sorbit (60%) 12 Glycerin (85%) 10 Sodium lauryl sulfate 1.5 Sodium saccharin 0.15 Fragrance 1 Paraben 0.2 Tranexamic acid 0.1 Water Remaining 100.0% [Example 4] Modified aluminum hydroxide 5% Precipitated silica 20 Gellable silica 3 Sodium carboxymethyl cellulose 0.9 Propylene glycol 2.5 Sorbit (60%) 55 Sodium lauryl sulfate 1.5 Sodium saccharin 0.1 Fragrance 1 Paraben 0.1 Chlorhexidine hydrochloride 0.001 Water Remaining 100.0% [Example 5] Modified aluminum hydroxide 35% Calcium carbonate (light) 5 Gellable silica 3 Sodium carboxymethylcellulose 1 Proprene glycol 2 Sorbit (60%) 25 Sodium lauryl sulfate 2 Sodium saccharin 0.1 Fragrance 0.7 Paraben 0.2 Allantoin chlorhydroxy aluminum
0.05 Sodium chloride 10 Epsilon aminocaproic acid 0.05 Water Balance 100.0%

[Brief explanation of drawings]

The figure is a graph showing changes in pH over time during storage of toothpastes using various abrasives.

Claims (1)

[Scope of Claims] 1. An oral composition comprising modified aluminum hydroxide obtained by treating aluminum hydroxide with sulfuric acid or a salt thereof. 2. The oral composition according to claim 1, wherein the modified aluminum hydroxide has a pH of 6 to 7.5 in a 10% by weight water slurry. 3 The average particle size of modified aluminum hydroxide is 1 to
The oral composition according to claim 1 or 2, which has a particle size of 30μ. 4. The oral composition according to any one of claims 1 to 3, wherein the composition has a pH of 5 to 8. 5. The oral cavity composition according to any one of claims 1 to 4, which contains an ester fragrance.