JPH07223930A - Dentifrice composition - Google Patents

Abstract

PURPOSE:To obtain a dentifrice composition having pH of nearly neutrality and capable of efficiently removing dental plaque an promoting remineralization of the tooth surface and making the tooth surface glossy by blending calcium salt powder having ability capable of converting to hydroxyapatite in the presence of saliva in oral cavity. CONSTITUTION:This dentifrice composition contains calcium salt powder (especially octacalcium phosphate) capable of converting to hydroxyapatite by contacting with water (especially saliva in oral cavity) and it has pH 5-8. As the calcium salt powder, tricalcium phosphate, a mixture (molar ratio of Ca/P: 1.30-1.67 of tetracalcium phosphate with calcium primary phosphate (anhydride or monohydrate), a mixture (molar ratio of Ca/P: 1.30-1.67) of tetracalcium phosphate with secondary calcium phosphate (anhydride or monohydrate), a mixture (molar ratio of Ca/P: 1.30-1.50) of tricalcium phosphate with calcium primary phosphate, etc., is preferably used. This composition can not only remove a contaminant such as dental plaque, but repair also damage by promotion of remineralization of the toot surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dentifrice composition capable of efficiently removing plaque attached to the surface of a tooth and promoting remineralization of the scratched tooth surface to lubricate it.

[0002]

2. Description of the Related Art Toothpastes have conventionally been compounded with abrasives such as calcium carbonate, dicalcium phosphate, aluminum hydroxide and calcium pyrophosphate. Originally, these abrasives are blended for the purpose of removing contaminants such as dental plaque from the tooth surface by the abrasive action. However, these abrasives not only polish contaminants such as dental plaque, but actually also polish and scrape the healthy tooth surface itself. This polishing action reduces the smoothness of the tooth surface, making it easier for plaque to adhere,
It may cause new caries or cause hypersensitivity due to so-called over-polishing.

Generally, it is said that brushing with a toothbrush is sufficient to remove plaque on the tooth surface, and recently, a liquid dentifrice containing no abrasive has been developed. However, the plaque accumulated up to now in the fine scratches on the tooth surface caused by the abrasive cannot be removed only by brushing and causes dental caries. In order to efficiently remove the plaque accumulated in such fine scratches, an abrasive is still required as in the past. Therefore, a vicious cycle in which a new scratch is further generated on the tooth surface due to this polishing agent is repeated. That is, once a flaw is generated on the tooth surface, the damage on the tooth surface will progress forever unless the flaw is restored by some method to restore the same condition as the original healthy tooth.

A dentifrice which attempts to remineralize the tooth surface by incorporating fine particles of hydroxyapatite having a crystal structure similar to the inorganic component of the tooth has also been developed.
However, hydroxyapatite is a chemically stable compound and has poor reactivity. Further, the hydroxyapatite used for such a dentifrice is industrially produced, and strictly speaking, its crystalline structure is different from that of hydroxyapatite which constitutes teeth in a living body, so that the effect of remineralization is sufficient. Not.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a dentifrice composition which not only removes pollutants such as dental plaque but also efficiently repairs scratches on the tooth surface by promoting remineralization of the tooth surface. The main purpose is to do.

[0006]

Means for Solving the Problems The present inventor has found that, without impairing the performance of removing contaminants such as dental plaque as a dentifrice,
As a result of intensive research on a dentifrice having excellent properties for remineralizing the tooth surface, a dentifrice composition containing a calcium salt powder capable of converting into hydroxyapatite in the presence of water (saliva) in the oral cavity. It has been found that the problems of the prior art are substantially eliminated or alleviated when using a.

That is, the present invention provides the following dentifrice compositions.

1. A dentifrice composition comprising a calcium salt powder which is converted into hydroxyapatite when contacted with water and has a pH of 5-8.

2. The dentifrice composition according to the above 1, wherein the calcium salt powder that is converted into hydroxyapatite when contacted with water is octacalcium phosphate.

3. The dentifrice composition according to the above 1, wherein the calcium salt powder which is converted into hydroxyapatite by contact with water is tricalcium phosphate.

4. The calcium salt powder that is converted to hydroxyapatite in contact with water is a mixture of tetracalcium phosphate and monocalcium phosphate (anhydrous or monohydrate) (Ca / P molar ratio 1.30 to 1.67). The dentifrice composition as described in 1 above, which is characteristic.

5. The calcium salt powder that is converted into hydroxyapatite in contact with water is a mixture of tetracalcium phosphate and dicalcium phosphate (anhydrous or dihydrate) (Ca / P molar ratio 1.30 to 1.67). The dentifrice composition as described in 1 above, which is characteristic.

6. The calcium salt powder that is converted into hydroxyapatite in contact with water is a mixture of tricalcium phosphate and primary calcium phosphate (anhydrous or monohydrate) (Ca / P molar ratio 1.30 to 1.50). The dentifrice composition as described in 1 above, which is characteristic.

7. The calcium salt powder which is converted into hydroxyapatite in contact with water is a mixture of tricalcium phosphate and dicalcium phosphate (anhydrous or dihydrate) (Ca / P molar ratio 1.30 to 1.50). The dentifrice composition as described in 1 above, which is characteristic.

8. The calcium salt powder that is converted into hydroxyapatite by contact with water is a mixture of tetracalcium phosphate and tricalcium phosphate (Ca / P molar ratio 1.50 to 50).
1.67), The dentifrice composition as described in 1 above.

9. The calcium salt powder that is converted into hydroxyapatite by contact with water is a mixture of tetracalcium phosphate and octacalcium phosphate (Ca / P molar ratio of 1.33 to
1.67), The dentifrice composition as described in 1 above.

10. The calcium salt powder that is converted into hydroxyapatite by contact with water is a mixture of tricalcium phosphate and octacalcium phosphate (Ca / P molar ratio 1.33).
~ 1.50), The dentifrice composition as described in 1 above.

11. The calcium salt powder that is converted to hydroxyapatite when contacted with water is a mixture of tricalcium phosphate and calcium carbonate (Ca / P molar ratio of 1.50 to 50).
1.67), The dentifrice composition as described in 1 above.

12. The calcium salt powder which is converted into hydroxyapatite by contact with water is a mixture of monobasic calcium phosphate (anhydrous or monohydrate) and calcium carbonate (C
The dentifrice composition according to the above 1, wherein the a / P molar ratio is 1.30 to 1.67).

The dentifrice composition of the present invention contains, as an essential component, calcium phosphate which is converted into hydroxyapatite by contact with water (saliva) in the oral cavity, and if necessary, various known additives are added. Good.

[0021] Examples of the calcium salt powder which has the ability to be converted into hydroxyapatite in contact with water include tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, monobasic calcium phosphate, dibasic calcium phosphate and calcium carbonate. .

Of these calcium salt powders, tricalcium phosphate and octacalcium phosphate can be used alone. Also, tetracalcium phosphate,
Monobasic calcium phosphate, dibasic calcium phosphate, calcium carbonate and the like have the ability to be converted into hydroxyapatite only when used as a mixture with at least one other calcium salt. Tricalcium phosphate and octacalcium phosphate may also be used as a mixture with at least one other calcium salt.

A particularly preferred specific example of use is as follows.

1. Octacalcium phosphate is used alone.

2. Tricalcium phosphate is used alone.

3. A mixture of tetracalcium phosphate and monocalcium phosphate (anhydrous or monohydrate) is used.
The Ca / P molar ratio in the mixture is 1.30 to 1.67. When the Ca / P molar ratio is less than 1.30, a large amount of dicalcium phosphate may be generated, and unreacted monocalcium phosphate may remain. The Ca / P molar ratio is 1.
Above 67, a large amount of unreacted tetracalcium phosphate remains.

4. A mixture of tetracalcium phosphate and dicalcium phosphate (anhydrous or dihydrate) is used.
The Ca / P molar ratio in the mixture is 1.30 to 1.67. When the Ca / P molar ratio is less than 1.30, a large amount of unreacted dicalcium phosphate remains. When the Ca / P molar ratio exceeds 1.67, a large amount of unreacted tetracalcium phosphate remains.

5. A mixture of tricalcium phosphate and monocalcium phosphate (anhydrous or monohydrate) is used.
The Ca / P molar ratio in the mixture is 1.30 to 1.50. When the Ca / P molar ratio is less than 1.30, a large amount of dicalcium phosphate may be generated, and unreacted monocalcium phosphate may remain. The Ca / P molar ratio does not exceed 1.50 regardless of the mixing ratio of the calcium salt.

6. A mixture of tricalcium phosphate and dicalcium phosphate (anhydrous or dihydrate) is used.
The Ca / P molar ratio in the mixture is 1.30 to 1.50. When the Ca / P molar ratio is less than 1.30, a large amount of unreacted dicalcium phosphate remains. Regardless of the mixing ratio of the calcium salt, the Ca / P molar ratio is 1.5
It cannot exceed 0.

7. A mixture of tetracalcium phosphate and tricalcium phosphate is used. The Ca / P molar ratio in the mixture is 1.50 to 1.67. The Ca / P molar ratio is 1.
Above 67, a large amount of unreacted tetracalcium phosphate and tricalcium phosphate remains. Regardless of the mixing ratio of the calcium salt, the Ca / P molar ratio is 1.5
It will never be less than zero.

8. A mixture of tetracalcium phosphate and octacalcium phosphate is used. The Ca / P molar ratio in the mixture is 1.33 to 1.67. The Ca / P molar ratio is 1.
Above 67, a large amount of tetracalcium phosphate remains. Ca regardless of the mixing ratio of the calcium salt
The / P molar ratio never goes below 1.33.

9. A mixture of tricalcium phosphate and octacalcium phosphate is used. The Ca / P molar ratio in the mixture is 1.33 to 1.50. The Ca / P molar ratio does not become less than 1.33 or exceed 1.50 regardless of the mixing ratio of the calcium salt.

10. A mixture of tricalcium phosphate and calcium carbonate is used. The Ca / P molar ratio in the mixture is 1.50 to 1.67. The Ca / P molar ratio is 1.
Above 67, a large amount of unreacted calcium carbonate remains. Regardless of the mixing ratio of the calcium salt,
The Ca / P molar ratio never goes below 1.50.

11. A mixture of monocalcium phosphate (anhydrous or monohydrate) and calcium carbonate is used. The Ca / P molar ratio in the mixture is 1.30 to 1.67. When the Ca / P molar ratio is less than 1.30, a large amount of dicalcium phosphate may be generated, and unreacted monocalcium phosphate may remain. The Ca / P molar ratio is 1.
Above 67, a large amount of unreacted calcium carbonate remains.

Various calcium salts used in the present invention are converted into hydroxyapatite in the presence of water (saliva) as shown in the following reaction formulas 1 to 11.

[0036] Scheme _{1: 5Ca 8 H 2 (PO} 4) 6 · 5H 2 O → 4
Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ + 6H ₃ PO ₄ Reaction formula 2: 10Ca ₃ (PO ₄ ) ₂ → 3Ca ₁₀ (PO
₄ ) ₆ (OH) ₂ + 2H ₃ PO ₄ Reaction formula 3: 7Ca ₄ (PO ₄ ) ₂ O + 2Ca (H ₂ P
O ₄ ) ₂ → 3Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ Reaction formula 4: 2Ca ₄ (PO ₄ ) ₂ O + 2CaHPO ₄
→ 3Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ Reaction formula 5: 5Ca ₃ (PO ₄ ) ₂ + 5Ca (H ₂ PO
₄ ) ₂ → 2Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ + 8H ₃ PO ₄ Reaction formula 6: 5Ca ₃ (PO ₄ ) ₂ + 5CaHPO ₄ →
2Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ + 3H ₃ PO ₄ Reaction formula 7: Ca ₄ (PO ₄ ) ₂ O + 2Ca ₃ (P
O ₄ ) ₂ → Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ Reaction formula 8: 3Ca ₄ (PO ₄ ) ₂ O + Ca ₈ H
_{2 (PO 4) 6 · 5H} 2 O → 2Ca 10 (PO 4) 6 (O
H) ₂ reaction formula 9: 10Ca ₃ (PO ₄ ) ₂ + 5Ca ₈ H
_{2 (PO 4) 6 · 5H} 2 O → 7Ca 10 (PO 4) 6 (O
H) ₂ + 8H ₃ PO ₄ Reaction formula 10: 3Ca ₃ (PO ₄ ) ₂ + CaCO ₃ → Ca
₁₀ (PO ₄ ) ₆ (OH) ₂ + xH ₂ CO ₃ + (1-x)
CO ₂ reaction formula 11: 3Ca (H ₂ PO ₄ ) ₂ + 7CaCO ₃ →
_{Ca 10 (PO 4) 6 (} OH) 2 + 7xH 2 CO 3 +7
The average particle size of the (1-x) CO ₂ calcium salt powder is usually about 1 to 5 μm, and more preferably 2 to 3 μm. In addition, the maximum particle size is usually about 5 to 15 μm, and more preferably 7 to 10 μm. If the particle size is too large, that is, if the average particle size exceeds 5 μm and the maximum particle size is 15 μm
If it exceeds m, the polishing action becomes excessive and the adsorptivity of the particles to the tooth surface decreases. If the particle size is too small, that is, if the average particle size is less than 1 μm and the maximum particle size is less than 5 μm, the properties as an abrasive are not exhibited. When the use of the dentifrice of the present invention is limited only to the promotion of remineralization of the tooth surface and the polishing action is not required, the average particle size is 0.1 to 1 μm and the maximum particle size is 1 to 5 μm. Good.

The calcium salt particles adsorbed on the teeth by the usual tooth brushing operation are converted into hydroxyapatite in a short time. At this time, since the hydroxyapatite is hardened by setting and hardening, the adsorption of the hydroxyapatite on the tooth surface becomes stronger. The produced hydroxyapatite has a crystal structure equivalent to that of the adjacent tooth composition in the crystal growth process, and furthermore, this hydroxyapatite has a high chemical reaction activity. Therefore, as compared with the case where industrially produced hydroxyapatite is used as it is, it acts extremely effectively in remineralization on the tooth surface.

The dentifrice composition of the present invention is assumed to be weakly acidic to weakly alkaline, that is, pH 5 to 8, and pH 5.5.
It is more preferable to set it to ˜7.5.

In the dentifrice composition of the present invention, known additives such as wetting agents, foaming agents, sweeteners, fragrances, thickeners, pH adjusters, solubilizers, preservatives and other effects are also included. If necessary, agents and enzymes (hereinafter may be simply referred to as "medicinal ingredients") that show the following, agents that accelerate the conversion reaction of calcium salt to hydroxyapatite (hereinafter sometimes referred to as "calcification accelerator"), etc. It can be blended.

Examples of the wetting agent include glycerin, sorbit, propylene glycol and the like.

Examples of the foaming agent include sodium lauryl sulfate and lauromacrogol.

As the sweetener, saccharin sodium,
Examples include saccharin, aspartame, xylose, sorbit, disodium glycyrrhizinate, trisodium glycyrrhizinate, and the like.

As the fragrance, acacia oil, fennel oil, kuchen oil, columbus oil, camphor oil, cinnamon oil, cinnamon oil, cauliflower oil, peppermint oil, rose oil, sandalwood oil, clove oil, orange oil, eucalyptus oil. , Herb oil, banana oil, apple oil, lemon oil and the like.

Examples of the thickener include carrageenan and hydroxyethyl cellulose.

Examples of the pH adjusting agent include sodium hydrogen phosphate and sodium hydrogen citrate.

Examples of the solubilizer include polyoxyethylene hydrogenated castor oil, polyoxyethyleneoxypropylene glycol and the like.

Examples of preservatives include sodium benzoate and paraben.

Examples of the medicinal component include sodium fluoride, sodium monofluorophosphate, chlorhexidine gluconate, cetylpyridinium chloride, dextranase and the like.

Examples of the calcification accelerator include magnesium chloride, sodium chloride, sodium lactate, sodium succinate, sodium citrate, sodium phosphate, sodium silicate and the like.

When the additives are used, the total amount of the additives to be added is usually 100 with respect to 100 parts by weight of the calcium salt powder.
To 600 parts by weight, and more preferably 150 to 400 parts by weight.

Incidentally, in order to promote crystal growth due to the conversion reaction of the calcium salt powder into hydroxyapatite, hydroxyapatite may be added in advance as a seed crystal. The amount of hydroxyapatite added is usually 1 to 100 parts by weight of calcium salt powder.
50 parts by weight, more preferably 5 to 20 parts by weight.

[0052]

According to the present invention, the following remarkable effects can be obtained.

(1) Not only the plaque on the tooth surface is efficiently removed only by a normal tooth brushing operation, but also remineralization of the tooth surface is promoted, and the tooth can be returned to its original healthy state. .

(2) The abrasive component adsorbed on the tooth surface is
Converts to hydroxyapatite, which has a crystalline structure similar to teeth.

(3) When the polishing component adsorbed on the tooth surface is converted into hydroxyapatite, it is hardened by condensation, so that the dropout of these particles is suppressed as much as possible, which effectively and efficiently acts on remineralization.

(4) In the conventional dentifrice, a component having only a polishing action can be used as a calcification accelerator.

[0057]

EXAMPLES Examples will be shown below. The present invention is not limited to the following examples.

Example 1 An adult permanent tooth was cut into an enamel trabecula and a slice having a thickness of about 200 μm was prepared. This toothpaste was brushed for 5 minutes using a toothpaste prepared in the mixing ratio shown in Table 1 and a commercially available toothbrush, and then washed under running water, and then saliva (diluted 50 times with distilled water) at 37 ° C. And allowed to stand for 24 hours. After repeating this operation 30 times, a section was taken out and the tooth surface was observed with a polarizing microscope.

A coating layer of hydroxyapatite having a thickness of 1 to 5 μm was observed on the entire surface of the tooth structure.

The blending ratio of the composition used in this example is shown in Table 1 below. All units in the table are% by weight.
Is.

[0061]

[Table 1]

Examples 2 to 11 The same operations as in Example 1 were carried out except that the toothpaste prepared in the proportions shown in Table 1 was used.

A coating layer of hydroxyapatite having a thickness of 1 to 5 μm was observed on the entire surface of the tooth structure in all the examples.

Comparative Example 1 The same operation as in Example 1 was carried out except that a commercially available dentifrice containing dicalcium phosphate was used.

No hydroxyapatite coating layer was observed on the entire surface of the tooth structure.

Comparative Example 2 The same operation as in Example 1 was carried out except that a commercially available dentifrice containing calcium carbonate was used.

No hydroxyapatite coating layer was found on the entire surface of the tooth structure.

Comparative Example 3 The same operation as in Example 1 was carried out except that a commercially available liquid dentifrice was used.

No hydroxyapatite coating layer was observed on the entire surface of the tooth structure.

Comparative Example 4 The same operation as in Example 1 was carried out except that a commercially available dentifrice containing hydroxyapatite was used.

No hydroxyapatite coating layer was observed on the entire surface of the tooth structure.

Claims (12)

[Claims] 1. A dentifrice composition comprising a calcium salt powder which is converted into hydroxyapatite in contact with water and has a pH of 5-8. 2. The dentifrice composition according to claim 1, wherein the calcium salt powder which is converted into hydroxyapatite when contacted with water is octacalcium phosphate. 3. The dentifrice composition according to claim 1, wherein the calcium salt powder which is converted into hydroxyapatite by contact with water is tricalcium phosphate. 4. A calcium salt powder which is converted to hydroxyapatite when contacted with water is a mixture of tetracalcium phosphate and monocalcium phosphate (anhydrous or monohydrate) (C
The dentifrice composition according to claim 1, which has an a / P molar ratio of 1.30 to 1.67). 5. A calcium salt powder which is converted to hydroxyapatite in contact with water is a mixture of tetracalcium phosphate and dicalcium phosphate (anhydrous or dihydrate) (C
The dentifrice composition according to claim 1, which has an a / P molar ratio of 1.30 to 1.67). 6. A calcium salt powder which is converted to hydroxyapatite in contact with water is a mixture of tricalcium phosphate and monocalcium phosphate (anhydrous or monohydrate) (C).
The dentifrice composition according to claim 1, having an a / P molar ratio of 1.30 to 1.50). 7. A calcium salt powder which is converted to hydroxyapatite in contact with water is a mixture of tricalcium phosphate and dicalcium phosphate (anhydrous or dihydrate) (C
The dentifrice composition according to claim 1, having an a / P molar ratio of 1.30 to 1.50). 8. A calcium salt powder which is converted into hydroxyapatite in contact with water is a mixture of tetracalcium phosphate and tricalcium phosphate (Ca / P molar ratio of 1.50 to 50).
1.67), The dentifrice composition according to claim 1. 9. A calcium salt powder which is converted into hydroxyapatite in contact with water is a mixture of tetracalcium phosphate and octacalcium phosphate (Ca / P molar ratio 1.33 to
1.67), The dentifrice composition according to claim 1. 10. A calcium salt powder which is converted into hydroxyapatite in contact with water is a mixture of tricalcium phosphate and octacalcium phosphate (Ca / P molar ratio of 1.33 to
1.50), The dentifrice composition according to claim 1. 11. A calcium salt powder which is converted into hydroxyapatite when contacted with water is a mixture of tricalcium phosphate and calcium carbonate (Ca / P molar ratio 1.50 to 1.
67) The dentifrice composition according to claim 1, which is 12. A calcium salt powder which is converted to hydroxyapatite when contacted with water is a mixture of monobasic calcium phosphate (anhydrous or monohydrate) and calcium carbonate (C).
The dentifrice composition according to claim 1, which has an a / P molar ratio of 1.30 to 1.67).