JPH05163125A - Composition for oral cavity - Google Patents

Abstract

PURPOSE:To obtain a composition for oral cavity having remarkable effects on prevention of dental carries and periodontal disease without causing discoloration and deterioration with time and excellent also in use feeling. CONSTITUTION:The objective composition for oral cavity contains an antimicrobial zeolite having 0.1-50mum average particle diameter, obtained by substituting part or all of ion-exchangeable ions in a zeolite by an ammonium ion and an antimicrobial metallic ion and containing the ammonium ion and antimicrobial metallic ion in a ratio of >=0.07:1.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to oral compositions such as toothpaste and oral pasta. More specifically, by containing an antibacterial zeolite that is stable over time, it causes caries
The present invention relates to a stable oral composition which has a remarkable effect on the prevention of periodontal diseases and has no discoloration or deterioration.

[0002]

BACKGROUND OF THE INVENTION It is generally accepted that the primary cause of dental caries and periodontal disease is the accumulation of plaque. Streptococcus mutans, which is a bacterium resident in the oral cavity, produces water-insoluble glucan by the action of glucosyltransferase using sucrose as a substrate, and firmly adheres to the tooth surface to form plaque.
Dental cartilage is a phenomenon in which dentin is decalcified by organic acids such as lactic acid produced by the decomposition of sugar in the above process. In addition, when dental plaque is accumulated and the anaerobic environment is adjusted, and periodontopathic bacteria such as Gram-negative bacteria are established and proliferated, toxins and inflammatory substances produced by the bacteria cause gingivitis, which eventually causes periodontal disease. Develop.

Therefore, as one of the methods for preventing caries and periodontal diseases, antibacterial agents such as chlorhexidine gluconate and cetylpyridinium chloride have been blended in oral compositions such as dentifrices. While these antibacterial agents have an excellent antibacterial action, they have another problem in safety such as irritation and tooth coloring. Further, in recent years, powders having antibacterial properties have been developed, and one of them is an antibacterial zeolite in which an antibacterial component is carried by the zeolite (Japanese Patent Laid-Open No. Sho 60).
-181002). Unlike the above-mentioned water-soluble antibacterial agent, the antibacterial zeolite is in the form of powder, and is not absorbed into the mucous membrane and is highly safe. Further, an oral composition containing such an antibacterial zeolite is also known (JP-A-3-2113).

Further, for the purpose of preventing discoloration of the antibacterial zeolite itself, the antibacterial zeolite carrying ammonium ions together with the antibacterial metal (Japanese Patent Laid-Open No. 63-265).
No. 809), and is applied to a preservative for cosmetics (Japanese Patent Laid-Open No. 1-305013) and an antibacterial spray (Japanese Patent Laid-Open No. 63-250325).

[0005]

The antibacterial zeolite blended in the above oral composition is certainly an antibacterial agent having excellent durability of antibacterial activity when left in water or air. However, the antibacterial zeolite is known to have a catalytic action on organic substances, and there is a problem that the organic substances in the oral composition are deteriorated or gradually discolored with time. Therefore, depending on the type, the product value may be significantly reduced.

The object of the present invention is to prevent the periodontal disease from being seriously affected by incorporating an antibacterial zeolite which does not deteriorate or discolor over time and has an antibacterial effect equivalent to or higher than that of conventional antibacterial zeolite. Excellent and safe,
It is intended to provide an oral composition having good usability.

[0007]

That is, the present invention provides an oral cavity characterized by containing an antibacterial zeolite in which some or all of the ion-exchangeable ions in the zeolite are replaced with ammonium ions and antibacterial metal ions. It is a composition for use.

The present invention will be described below. In the present invention, as the "zeolite", both natural zeolite and synthetic zeolite can be used. Zeolites is generally aluminosilicate having a three dimensional framework structure, are displayed as general formula _{xM 2 / n O · Al 2} O 3 · ySiO 2 · zH 2 O. Here, M is a metal ion that is an ion-exchangeable ion. n is the valence of the (metal) ion. x and y represent the coefficients of metal oxide and silica, respectively, and z represents the number of crystal waters. Specific examples of the zeolite include A-type zeolite, X-type zeolite, and Y-type zeolite.
Type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcime, clinoptilolite, chabazite, eruonite and the like. However, it is not limited to these.

The antibacterial zeolite of the present invention is obtained by substituting a part or all of the ion-exchangeable ions in the above zeolite, such as sodium ion, potassium ion, iron ion, etc., with ammonium ion and antibacterial metal ion. .. Examples of the antibacterial metal ions include silver, copper, zinc, tin and bismuth ions, preferably silver, copper and zinc ions.

From the viewpoint of antibacterial effect, it is appropriate that the above antibacterial metal ion is contained in the zeolite in an amount of 0.5 to 20% by weight.

On the other hand, ammonium ions are decomposed and denatured into ethylene or ether by dehydrogenation or dehydration of organic substances in the oral composition, particularly alcohols such as alcohols, glycols and glycerin due to the inherent catalytic effect of zeolite. Suppress the action. Primarily due to this effect, the oral composition is maintained in a stable state for a long period of time. The ammonium ion content is preferably 0.07 parts by weight or more, and more preferably 0.5 parts by weight or more, relative to 1 part by weight of the antibacterial metal ion in the zeolite, from the viewpoint of preventing discoloration or deterioration.

In the present specification, "% of the supported substance in the antibacterial zeolite" means "% by weight on a dry basis at 110 ° C".

The average particle size of the antibacterial zeolite used in the composition for oral cavity of the present invention is preferably 0.1 to 50 μm, and more preferably 1 to 10 from the viewpoint of feeling in use in the oral cavity and polishing effect.
It is preferably μm. The shape may be any shape such as a granular shape, a spherical shape, and a needle shape. Further, these particles may be used alone or in the form of granules together with other particles. The content of the antibacterial zeolite is 0.01 to 30%, preferably 0.05 to 20% of the total amount of the oral composition. If it is less than 0.01%, the caries and periodontal disease preventing effect when the antibacterial zeolite is mixed cannot be expected, and if it exceeds 30%, it is not economical.

Further, when a calcium compound and / or a magnesium compound such as dicalcium phosphate, tricalcium phosphate, calcium pyrophosphate, calcium carbonate, magnesium carbonate and the like are used in combination in the oral composition, the discoloration with time and the antibacterial property are more stable. Can be kept at The amount of these compounds used is appropriately 1 to 50%, preferably 2 to 10% of the total amount of the oral composition.

In addition to the above-mentioned essential components, the oral composition of the present invention contains an abrasive, a foaming agent, a foaming aid, a wetting agent, a binder, a sweetener, and a thickening agent depending on the type of the oral composition. Ingredients usually used in oral compositions can be blended, such as a sticky agent, a fragrance, a dye, an antiseptic / antifungal agent, an antioxidant and a medicinal ingredient.
Further, the dosage form of the oral composition of the present invention is also arbitrary, and it can be used for toothpaste, powdered toothpaste, moisturizing toothpaste, water toothpaste, oral pasta, mouthwash such as mouthwash, mouthwash, etc. it can.

[0016]

The present invention will be described in detail below with reference to examples.
The present invention is not limited to this. Here, the blending amount is% by weight. Reference example (Preparation of antibacterial zeolite) Y-type zeolite as zeolite (average particle size 0.3μ
m), A-type zeolite (average particle size 1.5 μm), mordenite (average particle size 10 μm), clinoptilolite (150-250 mesh product, crushed by jet mill to average particle size 3.0, 18, 45 μm) 6) were used. As a salt to provide each ion for ion exchange
_{AgNO 3, Cu (NO 3)} 2, were used four types of nitrate Zn (NO _{3) 2} and NH ₄ NO _3.

Table 1 shows the type of zeolite used in the preparation of each sample and the type and concentration of salt contained in the aqueous nitrate solution. Samples of 12 kinds of antibacterial zeolites No. 1 to No. 12 were prepared (Comparative examples in which No. 11 and No. 12 do not contain ammonium ions or have a small amount).

1 kg of each zeolite powder sample dried by heating at 110 ° C. was taken, suspended in 1 liter of water, and a 0.05 N nitric acid aqueous solution was added dropwise at a dropping rate of 100 ml / 30 minutes to a predetermined amount. The pH value (5-7) was adjusted.
Next, for ion exchange, 3 liters of an aqueous solution containing a predetermined concentration of antibacterial metal salt and ammonium salt was added to the slurry. This reaction was stirred at room temperature to 60 ° C. for 10 to 24 hours to reach an equilibrium state.

After the completion of the ion exchange, the zeolite phase was filtered and washed with room temperature water or warm water until the excess exchange cations in the zeolite phase disappeared. Next, the sample was heated and dried at 110 ° C. to obtain 12 kinds of samples.

Example 1 (toothpaste formulation A) A toothpaste having the following formulation containing each antibacterial zeolite obtained in Reference Example was prepared. As a control, one containing no antibacterial zeolite (formulation C-1) one containing an antibacterial zeolite containing no ammonium ion (formulation C-2)
Also prepared. Table 2 shows the details of each composition.

Dicalcium phosphate dihydrate 40.0 (%) Glycerin 10.0 Sorbit 10.0 Sodium carboxymethyl cellulose 1.5 Sodium lauryl sulfate 1.5 Saccharin 0.1 Perfume 1.0 Antibacterial zeolite 0.0 05-20 Purified water Residual

Example 2 (dentifrice formulation B) An oral composition having the following formulation containing the antibacterial zeolite obtained in Reference Example was prepared. (Formulation B-1) Silicic anhydride 41.0 (%) Glycerin 22.0 Sorbitol 10.0 Carboxymethyl cellulose 1.1 Sodium lauryl sulfate 1.8 Saccharin 0.1 Chlorhexidine gluconate 0.05 Perfume 1.0 Antibacterial property Zeolite (No. 8) 0.5 Purified water Residue The silicic acid anhydride was replaced with calcium carbonate (formulation B-2) and magnesium carbonate (formulation B-3).

Example 3 (pasta formulation for oral cavity) An oral composition having the following formulation containing the antibacterial zeolite obtained in Reference Example was prepared. Vaseline 10.0 (%) Propylene glycol 7.0 Stearyl alcohol 10.0 Polyethylene glycol 1500 30.0 Antibacterial zeolite (No. 7) 5.0 Polyethylene glycol 400 Residual

Example 4 (Mouthwash formulation) An oral composition having the following formulation containing the antibacterial zeolite obtained in Reference Example was prepared. Ethanol 40.0 (%) Glycerin 15.0 Polyoxyethylene hydrogenated castor oil 1.0 Saccharin 0.1 Perfume 1.0 Antibacterial zeolite (No. 9) 1.0 Purified water Residual

Example 5 (Chewing gum formulation) An oral composition having the following formulation containing the antibacterial zeolite obtained in Reference Example was prepared. Gum base 25.0 (%) Glycerin 10.0 Calcium carbonate 2.0 Fragrance 1.0 Copper chlorophyll 0.05 Antibacterial zeolite (No. 10) 0.05 Purified water Residual

Test Example 1 (Aging Change Test) Each oral composition of the formulations A-1, C-1 and C-2 prepared in Example 1 was left in the air at room temperature (15 to 25 ° C.). The change over time was evaluated according to the following criteria. (Criteria for alteration)-: No alteration is observed.

±: Slight alteration (odor, condition) is recognized. +: Clearly alteration (odor, condition) is observed. ++: Significant alteration (odor, condition) is observed. Further, the composition was applied onto a glass plate in a thickness of 1 mm, and this was continuously irradiated with an ultraviolet standard light source (364 nm, 50 W) for 500 hours to measure the degree of discoloration before and after irradiation with a color difference meter (Minolta CR
-100 type), each color value of the L-a-b color system was measured, the color difference (ΔE) was calculated, and the discoloration property was evaluated. Generally ΔE
It is said that if the value is 1.5 or less, the discoloration is extremely slight, and if it is 3.0 or more, there is a clear discoloration. The results are shown in Table 2.

The results show that the compositions A-1 to A-9 and B-1 to 1 formulated with the antibacterial zeolite containing ammonium ion.
B-3 shows slight deterioration and discoloration, while composition C-1 containing no antibacterial zeolite and composition C-2 formulated with antibacterial zeolite containing no ammonium ion show remarkable deterioration and discoloration. ing.

Test Example 2 (Caries and periodontal disease preventive effect test) A toothbrush, an oral cleaning method and a dentifrice for 60 volunteer men with periodontal disease who live in a dormitory and have a relatively same living environment. The toothpaste was carried out for 4 weeks. Immediately before the start of the test and every week during the test, objectives (marginal gingivitis, papillary gingivitis) and subjective symptoms (bleeding gums, halitosis, and oral discomfort) were observed. The toothpaste used in the test is three points, Formula A-1, Formula C-1 and C-2. The results are shown in Table 3.

The prescription A-1 and the prescription C-2 containing the antibacterial zeolite are the prescription C- which does not contain the antibacterial zeolite.
It was confirmed that it had an excellent effect on tooth inflammation, bleeding, bad breath, etc. The oral compositions obtained in Examples 3 to 5 also had no discoloration or deterioration over time, and were excellent in preventing tooth decay and periodontal disease.

[0031]

Since the oral composition of the present invention contains an antibacterial zeolite containing ammonium ions, it does not discolor or deteriorate over time, and has a remarkable effect in preventing tooth decay and periodontal disease. It has a good usability.

[0032]

[Table 1] Table-1 ─────────────────────────────────── ZE Nitrate (M _{2 / n} ( NO ₃ ) _n ) Average concentration of aqueous solution in zeolite (M / liter) Yield Content of M (%) Particle No. La ────────────────────── ─── Diameter Y M (μm) To Ag Cu Zn NH ₄ (g) Ag Cu Zn NH ₄ NH ₄ / M ──────────────────────── ──────────── 1 Y 0.04 1.8 ── 1.0 930 1.5 7.8 ── 1.8 0.194 0.3 2 〃 0.12 2.0 ── 1.8 945 4.0 9.2 ── 4.6 0.348 0.3 3 A 0.08 ── 1.8 0.7 950 2.6 ── 6.5 1.4 0.153 1.5 4 〃 0.08 ── 1.8 1.6 945 2.6 ── 6.5 4.7 0.516 1.5 5 〃 0.08 ── 1.8 3.0 945 2.6 ── 6.5 6.9 0.758 1.5 6 〃 0.40 ── ─ 3.5 960 14.0 ─── ─ 10.8 0.771 1.5 7 a 0.01 ── ── 0.2 950 0.5 ──── 0.10 0.200 3.0 8 b 0.06 ── ── 0.3 940 2 .5 ──── 0.30 0.120 10 9 a 0.20 0.6 0.6 1.3 950 7.0 1.5 1.5 2.8 0.280 18 10 a ── 2.2 ── 0.6 950 ── 12.0 ── 0.85 0.071 45 11 A 0.08 ── 1.8 ─ ─ 950 2.6 ─ ─ 6.5 ── ─ 1.5 ─────────────────────────────────── Note a: Clinoptilolite b: Mordenite

[0033]

[Table 2] Table-2 ─────────────────────────────────── Antibacterial Zeolite Alteration Test Discoloration Test No. ───────────────────────── No. Compounding amount (%) 0 months 1 month 3 months 6 months Color difference value ───── ─────────────────────────────── Prescription A-1 11.0 − − − − 1.2 A-22 1.0 − − − − 1.8 A-3 3 1.0 − − − − 2.0 A-4 4 1.0 − − − − 0.9 A-5 5 1.0 − − − − 0 .8 A-6 6 0.05 − − − − 0.8 A-7 5 3.0 − − − − 1.0 A-8 5 5.0 − − − − 1.2 A-9 7 20 − −−− 1.5 B−18 0.5 −−−−− 2.0 B−2−0.8 0.5 −−−− 1.5 B−30.8 0.5 −−−−− 1.5 Prescription C -1 − − − − − − 0.8 -2 11 1.0 - ± + ++ 5.2 ───────────────────────────────────

[0034]

[Table 3] Table-3 ─────────────────────────────────── Item No. Prescription A-1 Prescription C -1 Formulation C-2 (Example) (Comparative Example) (Comparative Example) Reduction rate,% ───────────────────────────── ─────── Marginal periodontitis (objective) 30.0 5.0 30.0 Papillary periodontitis (objective) 45.0 10.0 40.0 Gum bleeding (awareness) 35.0 10.0 35.0 Bad breath (consciousness) 55.0 5.0 50.0 Discomfort in the mouth when waking up (consciousness) 65.0 100.0 60.0 ──────────── ──────────────────────── (Gingivitis) The percentage of people who were judged as A or B below by the diagnosis of a doctor is shown. (Subjective symptom) The ratio of the following A and B by the subject's own declaration is shown.

* Evaluation method A: A remarkable therapeutic effect was observed. B: A little therapeutic effect was observed. C: No change in symptoms was observed. D: The symptoms were slightly deteriorated.

E: The symptom became very bad. * Calculation method Decrease rate (%) = (Number of testees in Evaluation A and Evaluation B) / Total number of testees x 100

Claims (3)

[Claims] 1. An oral composition comprising an antibacterial zeolite in which a part or all of the ion-exchangeable ions in the zeolite are replaced with ammonium ions and antibacterial metal ions. 2. The oral composition according to claim 1, wherein the antibacterial metal ion of the antibacterial zeolite is an ion of at least one metal selected from the group consisting of silver, copper, zinc, tin and bismuth. 3. The oral composition according to claim 1 or 2, which contains a calcium compound and / or a magnesium compound.