JPS6043326B2 - toothpaste composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dentifrice composition that can improve the acid resistance of tooth substance and is suitable for preventing dental caries.

Conventionally, soluble stannous compounds such as stannous fluoride have been used to treat tooth enamel and dentin with a solution containing them.
It is known that the action of tin ions imparts tooth structure with high acid resistance, and it has also been proposed to incorporate soluble stannous compounds into dentifrice compositions. However, even when using soluble stannous compounds, especially fluorine-containing stannous compounds such as stannous fluoride, which is recognized to have a higher tooth acid resistance effect by containing fluorine, However, the effect may not be sufficient, and even if some degree of tooth acid resistance is achieved after treatment, the effect is relatively easily lost due to the self-cleaning effect of saliva, brushing, chewing of food, etc. There's a problem.

In view of these points, the present applicant first added a phytic acid compound to stannous fluoride in a specific ratio, that is, the molar ratio of the phytic acid compound to the stannous fluoride was 0.01 to 4, preferably 0. .02-3, total content of phytic acid compound is 0
．． We have proposed an oral composition that can significantly increase the acid resistance of tooth enamel by blending it in an amount of 1% by weight or more, preferably 0.3 to 20% by weight (Japanese Patent Application Laid-Open No.
No. 6-22720).

In addition, in particular, a phytic acid compound is added to stannous fluoride.
At the same time, water-soluble fluoride such as sodium fluoride is added in an amount of 3.5 mol or less, especially 2 mol or less per mole of fluorine per mole of stannous tin. By adding so that it becomes .2 to 3.2 mol,
We proposed an oral composition that provides extremely high tooth acid resistance even at pH levels of 4 to 7, and provides excellent effects even under low fluorine concentration conditions with a total fluorine content of around 1000 ppm or less (Japanese Patent Laid-Open No. 56-22721). issue).

Furthermore, the present applicant has developed a method for producing tooth enamel by blending a phytic acid compound with sparingly soluble stannous tin of stannous pyrophosphate and further with soluble stannous tin such as stannous fluoride. proposed a composition for oral cavity that can form a film with high acid resistance and improve the acid resistance of enamel (Japanese Patent Application Laid-open Nos. 56-13900 & 45047-8).

As a result of further intensive studies based on the above proposal, the present inventors found that phytic acid was added to soluble stannous compounds such as the above-mentioned stannous fluoride and/or sparingly soluble stannous compounds such as stannous pyrophosphate. In a dentifrice composition consisting of a system containing a compound,
Insoluble as an abrasive. Metaphosphate alkali metal salt and/or
Alternatively, if silicic anhydride is used, there is very little deactivation of stannous ions and even fluorine ions even after long-term storage under harsh high-temperature conditions of 40°C, and the interaction between stannous ions and phytic acid compounds is extremely low. Outstanding tooth acid resistance based on synergistic effects.

If the effect is maintained over a long period of time, and in this case, it is particularly effective to use a nonionic water-soluble polymer compound such as hydroxyethyl cellulose, alginate propylene glycol ester, xanthan gum, guar gum, etc. as a binder. This discovery led to the present invention. That is, the present invention provides a dentifrice composition in which a phytic acid compound is blended with a soluble stannous compound and/or a poorly soluble stannous compound, and in which an insoluble alkali metal metaphosphate salt and/or anhydrous silicic acid is blended as an abrasive. In addition, the present invention provides a dentifrice composition preferably containing a nonionic water-soluble polymer compound as a binder. The present invention will be explained in detail below.

In the present invention, examples of soluble stannous compounds include stannous fluoride, stannous chloride, stannous fluoride chloride, sodium stannous fluoride, potassium stannous fluoride, stannous acetate, and hexafluoride. Stannous fluorozirconate, stannous sulfate, stannous tartrate, stannous gluconate, etc. can be used, and stannous fluoride is particularly preferred.

The amount of these soluble tin compounds is not particularly limited,
It may be blended in excess of the saturated solubility amount. There is no problem even if a part of it exists as a precipitate, but preferably 0.02% (weight%, the same applies hereinafter) to 7% tin in the toothpaste composition.
．． 5%, more preferably 0.06-3%.

For example, in the case of L-tin fluoride, its optimum blending amount is 0.08
~4%. Further, as the sparingly soluble stannous compound, stannous pyrophosphate, stannous oxide, stannous metaphosphate, stannous oxalate, stannous phosphate, etc. can be used.

The blending amount of these poorly soluble stannous compounds is also not particularly limited, but it is usually 0.2 to 10%, preferably 0.5 to 10% as tin.
It is 3%. In this case, it is preferable to blend the sparingly soluble stannous compound so that one end is precipitated and in a non-dissociated state, and the precipitated stannous compound is a 4′Rese of the stannous ion.
It acts as rv'0ir'2 and maintains the amount of dissolved active L-tin ions at a substantially constant amount over a long period of time. Examples of phytic acid compounds include phytic acid, and those in which some or all of the hydrogen atoms of the phosphoric acid groups at positions 1 to 6 of phytic acid are replaced with desired metal groups, such as sodium phytic acid, potassium phytic acid, and phytic acid. Alkali metal salts of phytic acid such as lithium, ammonium phytate, or valent metal salts of phytic acid such as magnesium phytate, zinc phytate, calcium phytate, aluminum phytate, phytate, and complex salts thereof. One species or two or more species can be used, and water-soluble ones are particularly preferred.

By blending these phytic acid compounds, they act synergistically with stannous ions to provide a remarkable tooth acid resistance effect,
In addition, when a poorly soluble stannous compound is blended, the elution of the stannous ion from the poorly soluble stannous compound is promoted, and the storage stability of the stannous ion is increased. is maintained in an active state to fully exhibit the effects of stannous ions. The amount of these phytic acid compounds to be blended is not necessarily limited, but is preferably 0.1 to 20%, more preferably 0.4 to 15%, and even more preferably 0.5 to 3%.

In this case, when only L-tin fluoride is used as the tin source, the molar ratio of the phytic acid compound to the stannous fluoride is preferably 0.01 to 4, more preferably 0.02. -3, most preferably 0.025-2.
It is desirable to mix it so that it becomes 5. In the present invention, either the above-mentioned soluble stannous compound or poorly soluble stannous compound is blended alone or in combination together with the phytic acid compound in a dentifrice composition. It is preferable to use a system in which a monotin compound and a poorly soluble stannous compound are used in combination, and a part of the sparingly soluble stannous compound is used in a precipitated state, and a phytic acid compound is blended therein.

That is, systems that use a soluble stannous compound and a sparingly soluble stannous compound in combination have been known, but this system has a tendency to reduce the initial amount of dissolved L tin ions and the amount of dissolved ions after long-term storage in an oxidizing atmosphere. The amount is low, and even if tooth enamel is treated with this system, the effect of improving the acid resistance of enamel is not necessarily high. By adding a phytic acid compound to the tooth, the effective supply of dissolved stannous ions and the effect of maintaining the activity of the stannous ions are increased, and the effect of improving the acid resistance of tooth enamel is exhibited even after long-term storage. Accordingly, the present invention provides a dentifrice composition comprising a phytic acid compound blended with the above-mentioned soluble stannous compound and/or sparingly soluble stannous compound, which contains an insoluble alkali metal metaphosphate salt and/or as an abrasive. Alternatively, silicic anhydride is used, whereby the synergistic effect between the stannous compound and the phytic acid compound is maintained even after long-term storage.

In this case, sodium salt, potassium salt, etc. are used as the insoluble alkali metal salt of metaphosphate. In addition, examples of silicic anhydride include silica xerogel, silica aerogel,
Hydrated precipitated silica etc. can be used, preferably SlO297
% or more and 3% or less of Al2O3, especially Al. The one containing 032% or less is used. Note that the amount of the abrasive is usually 15 to 60%. Further, in the present invention, it is preferable to use a nonionic water-soluble polymer compound as the binder, thereby making it possible to maintain the effects of the stannous compound and the phytic acid compound more reliably.

As the nonionic water-soluble polymer compound, one or two of hydroxyethyl cellulose, alginate propylene glycol ester, xanthan gum, guar gum, etc.
More than one species can be used, and the blending amount is usually 0.5 to 4%. As the other components of the present invention, known components depending on the type of dentifrice composition may be used.

For example, in the case of toothpaste, moisturizers such as glycerin, sorbitol, propylene glycol, ethylene glycol, and xylitol (10 to 30%), sodium lauryl sulfate, sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid monoglyceride monosulfate, etc. Foaming agents (a) such as sodium, sodium lauryl sulfoacetate, sodium N-lauroyl sarcosinate, N-acyl glutamate, sucrose fatty acid ester, etc. 5-3%
), sweeteners such as saccharin, stevioside, glycyrrhizin, chalcone, and dihydrochalcone, preservatives such as ethyl roseoxybenzoate and butyl roseoxybenzoate, fragrances, and lysozyme chloride, dextranase, lytic enzyme, mutanase, chlorhexidine, and sorpic acid. , alexidine, hinokitiol, cetylpyridinium, alkylglycine, alkyldiaminoethylglycine salt, water-soluble primary or secondary phosphate, quaternary ammonium compound, sodium chloride, etc., and mix the above ingredients with water. Manufactured by combining.

In addition, in the present invention, in addition to the above-mentioned stannous compounds, sodium fluoride, potassium fluoride, lithium fluoride, ammonium fluoride, sodium monofluorophosphate, potassium monofluorophosphate, and sodium monofluorohydrogenphosphate are used. , ammonium monozofluorophosphate, potassium hexafluorozirconate, potassium hexafluorotitanate, and other water-soluble fluorine compounds may also be blended.

In addition, cesium fluoride, aluminum fluoride, copper fluoride, lead fluoride, nickel fluoride, zirconium fluoride, silver fluoride, hexylamine hydrofluoride, laurylamine hydrofluoride, cetylamine hydrofluoride, glycine hydrofluoride Fluoride, lysine hydrofluoride, alanine hydrofluoride, etc. may also be used. These fluorine compounds have a total fluorine concentration of 100
It is preferable to set the blending amount to 0 ppm or less. Moreover, it is preferable that the pH of the dentifrice composition of this invention shall be 3-7. In this case, to adjust the pH, use organic acids such as citric acid, tartaric acid, lactic acid, malonic acid, malic acid, L-ascorbic acid, acetic acid, and succinic acid, or their alkali metal salts, or inorganic acids such as hydrochloric acid and phosphoric acid, or hydroxide. An alkali such as sodium may be used. As explained above, the dentifrice composition of the present invention uses an insoluble alkali metal metaphosphate salt or anhydrous silicic acid as an abrasive, and preferably uses a nonionic water-soluble polymer compound as a binder. As a result, the deactivation of L-tin ions and even fluoride ions is small, and even after long-term storage, the synergistic effect of the stannous compound and the phytic acid compound is exerted, and the effect of improving tooth acid resistance is maintained.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

In addition, in the following examples, all percentages are percentages by weight. Example 1 A toothpaste composition having the following formulation was prepared.

Abrasives (compounds shown in Table 1) Amounts shown in Table 1 Next,
For each linear dentifrice composition, the enamel acid resistance effect immediately after preparation and after storage at 400C for 1, 2, and 3 months was measured by the following method, and the results shown in Table 1 were obtained.

Measurement of enamel acid resistance effect After adding an equal weight of water to each sample (toothpaste composition) and stirring well, bovine tooth enamel was immersed in the solution at 30° C. for 3 minutes.

Next, brush the bovine tooth enamel with a toothbrush twice in each direction.
It was brushed 0 times and then washed with water for 10 to 20 minutes (temperature 20°C). After washing with water, wash the treated tooth with demineralizing solution (
stomach). Immerse in 1M acetate buffer, pH 4.5) at 20°C.
The hardness of the enamel surface after demineralization was measured using a Vickers hardness meter, and the acid resistance effect of the enamel of the sample was evaluated based on the measured value. That is, the higher the Vickers hardness value, the higher the enamel acid resistance effect. Note: VHN of undecalcified teeth is 350, VHN of untreated demineralized teeth
liN is 60 or less.

As is clear from the results in Table 1, when stored at 40°C for 3 months, only the toothpaste containing insoluble sodium metaphosphate and silicic anhydride as abrasives showed an acid-resistant effect on the tooth substance, and stannous ions and fluoride Although the synergistic effect of the ions and the phytic acid compound was exhibited over a long period of time, it was found that the effect was completely lost when other abrasives were added.

In particular, those containing insoluble sodium metaphosphate are
Even after long-term storage, when tooth enamel is treated with this product, it maintains a sufficiently high Vickers hardness and has been found to be extremely superior in that the enamel acid resistance effect is not lost. In addition, in a system in which 0.4% of stannous fluoride, 1.0% of stannous pyrophosphate, and 1.0% of pentasodium phytate were added to water, the amount of dissolved Sn2+ immediately after its preparation was 0.4.
After treating bovine tooth enamel with this system, the Vickers hardness of enamel was demineralized in the same manner as above and the Vickers hardness of the enamel was measured at 22.
After storage for several days, the amount of dissolved Sn2+ was 0.33%, and the Vickers hardness value was 160.
In the case of a system containing 0.4% tin and 1.0% stannous pyrophosphate, the amount of dissolved Sn2+ immediately after its preparation was 0.20%, and the Vickers hardness value was 103. Oxygen desiccation; 20℃ in the evening,
After storage for 10 days, the amount of dissolved Sn2+ was 0.14% and the Vickers hardness value was 93.

Therefore, the system according to the present invention in which a phytic acid compound is added to a poorly soluble stannous compound has a very high enamel acid resistance effect. Example 2 Using the abrasives shown in Table 1, samples with the following formulation were prepared.

Next, each sample was stored at 20°C for 2 months, and the changes over time in the dissolved amounts of Sn2+ ions and F- ions were examined to calculate the residual rates of Srl2+ and F- ions.

FIG. 1 shows the relationship between the number of days of storage and the residual rate of Sn2+, and FIG. 2 shows the relationship between the number of days of storage and the residual rate of F1. In addition, A in the figure
B uses insoluble sodium metaphosphate as the polishing agent (Example), B uses silicic anhydride (Example)
, C uses calcium pyrophosphate (comparative example),
D, E, F, G, and H are those using aluminum hydroxide, aluminosilicate, calcium carbonate, dibasic calcium phosphate, and dibasic magnesium phosphate, respectively (comparative examples)
It is. After adding twice the weight of water to the measurement sample for the amount of dissolved stannous ions and stirring for 2 hours, the precipitate was removed by centrifugation (10,000 to 12,000 rpm), and the amount of dissolved stannous ions in the supernatant was removed. Tin ions were titrated with 0.05N iodine solution.

Measurement of Dissolved F-Ion Amount To measure the dissolved stannous ion amount, fluorine ions in the centrifuged supernatant were quantified using a fluorine electrode.

From the results shown in Figures 1 and 2, the one containing insoluble sodium metaphosphate showed the highest Sn2+ residual rate, and the F
There was almost no decrease in quantity.

In addition, those containing silicic anhydride also have a Srl2+ residual rate,
The F-residual rate showed a high value. This has a good correlation with the results of Example 1, and from the above, insoluble sodium metaphosphate and anhydrous silicic acid can be used as a polishing agent for a system containing a soluble stannous compound, a sparingly soluble L-tin compound, and a phytic acid compound. It was found to be suitable. Example 3 A toothpaste composition having the following formulation was prepared using the binder shown in Table 2.

As is clear from the results in Table 2, products using nonionic water-soluble polymer compounds such as hydroxyethyl cellulose, alginate propylene glycol ether, xanthan gum, and guar gum as binders retain enamel even after long-term storage. When treated, it showed a sufficiently high Vickers hardness value and was recognized to be very excellent in maintaining the enamel acid resistance effect.

Example 4 A toothpaste composition having the following formulation was prepared.

Example 5 A toothpaste composition having the following formulation was prepared.

*Next, using each composition, the Vickers hardness after enamel demineralization was measured when bovine tooth enamel was treated immediately after preparation and after storage at 40°C for 1, 2, and 3 months in the same manner as in Example 1. The enamel acid resistance effect of each composition was evaluated.

The results are shown in Table 2.

[Brief explanation of the drawing]

Figure 1 is a graph showing the relationship between the number of storage days and the Srl2+ residual rate when toothpaste compositions with different types of abrasives are stored, and Figure 2 is the relationship between the number of storage days and the F1 residual rate of the same composition. This is a graph showing.

Claims (1)

[Scope of Claims] 1. A dentifrice composition containing a soluble stannous compound and/or a sparingly soluble stannous compound and a phytic acid compound, which contains an insoluble alkali metal metaphosphate salt and/or anhydrous silicic acid as an abrasive. A dentifrice composition characterized by: 2. The dentifrice composition according to claim 1, which contains a nonionic water-soluble polymer compound as a binder. 3. The dentifrice composition according to claim 2, wherein the nonionic water-soluble polymer compound is selected from hydroxyethyl cellulose, propylene glycol alginate, xanthan gum, and guar gum. 4. Any one of claims 1 to 3, in which a soluble stannous compound and a sparsely soluble stannous compound are used together, and the sparingly soluble stannous compound is blended in a partially precipitated state. The dentifrice composition described. 5 Soluble stannous compound is stannous fluoride, stannous chloride,
From stannous fluoride chloride, sodium stannous fluoride, potassium stannous fluoride, stannous acetate, stannous hexafluorozirconate, stannous sulfate, stannous tartrate, stannous gluconate and the sparingly soluble stannous compound is selected from stannous pyrophosphate, stannous metaphosphate, stannous oxide, stannous oxalate, and stannous phosphate. A dentifrice composition according to any one of the ranges 1 to 4. 6 Claims 1 to 5 in which a water-soluble fluorine compound is blended so that the total fluorine amount is 1000 ppm or less
The dentifrice composition according to any one of paragraphs.