JPH0315604B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oral composition containing at least one of chitin and chitosan. Sodium monofluorophosphate, epsilon-aminocaproic acid, chlorhexidine hydrochloride, etc. are used in dentifrices such as toothpaste, moisturized toothpaste, powdered toothpaste, and liquid toothpaste, mouth rinses, mouth fresheners, and even oral compositions such as chewing gum. It has been conventionally practiced to prevent caries, alveolar pyorrhea, and bad breath by incorporating medicinal ingredients. However, all oral compositions are typically spit out after use;
Since it is customary for toothpastes to be rinsed with water after use, the disadvantage is that in order to expect the desired effect from the medicinal ingredients, the amount of the medicinal ingredients must be increased considerably. By the way, chitin exists in the shells of arthropods and bones of molluscs, and also exists in the mycelia and spores of molds.
Although its deacetylated product, chitosan, has a chemical structure similar to cellulose,
Its resistance to chemicals is much greater than that of cellulose, and because it has acetamido and amino groups in its molecule, it has many interesting properties. However, the reality is that chitin and chitosan (hereinafter both are collectively referred to as chitin) are extremely less utilized than cellulose and other polysaccharides. As a result of repeated research aimed at the effective use of chitin, etc., the present inventors found that chitin, etc. has a medicinal effect that is superior to, if not inferior to, medicinal ingredients that have been conventionally incorporated into oral compositions. It has been found that when combined, an oral composition that is effective in preventing dental caries, alveolar pyorrhea, and halitosis can be obtained. Therefore, the oral composition according to the present invention contains at least one of chitin and chitosan, which is a deacetylated product thereof.
It should be understood that the oral compositions of the present invention may also contain a mixture of chitin and chitosan. As mentioned above, chitin exists naturally as an organic skeletal substance in arthropods and molluscs, and in plants in fungal hyphae and spores, so it can be obtained by known means using these as raw materials. For example, when using the shells of crabs, shrimp, krill, etc. as raw materials, the shells are crushed, treated with hydrochloric acid to remove calcium carbonate, and then treated with caustic soda to remove proteins and other impurities, and then washed with water. By drying, white amorphous powdered chitin can be obtained. Chitosan can also be obtained as a white amorphous powder by deacetylating chitin with alkali treatment. However, the chitin raw material used in the present invention is not limited to the above-mentioned shells, and any chitin or chitosan obtained by any method from various chitin sources can be used. There are no restrictions on molecular weight. Commercial products can also be used as the chitin of the present invention, and an example of such a commercial product is "REGITEX" (trade name) manufactured by Nanyo Kasei Co., Ltd. As a reminder, the classification index between chitin and chitosan has not been established even in academic societies, so in the present invention, we defined chitosan as having a deacetylation degree of 60% or more, and chitin as less than that. . In the oral composition of the present invention, in order for the oral composition to exhibit the effect of chitin etc., the amount of chitin etc. needs to be at least 0.01% by weight, but the permissible amount depends on the type of individual oral composition. It varies depending on. By the way, for toothpaste, it is 0.01~
A suitable blending amount is 70% by weight, preferably 0.05 to 50% by weight; if it exceeds 70% by weight, moldability and shape retention during extrusion may be impaired. The amount added in Junsei toothpaste is 0.01 to 80% by weight, preferably 0.05
~75% by weight is suitable, and if it exceeds 80% by weight, it will not be possible to maintain the moist toothpaste-like appearance. The appropriate amount of toothpaste to be added is 0.01 to 97% by weight, preferably 0.05 to 95% by weight, and if it exceeds 97% by weight, foaming agents, sweeteners, fragrances, etc. necessary for dentifrice are added. This is not desirable as there will be no room left. In addition, in solid mouth fresheners, it is appropriate that the amount of chitin etc. is 0.01 to 70% by weight, preferably 0.05 to 60% by weight, and 70% by weight.
If it exceeds the weight percentage, it becomes difficult to form particles using gum arabic liquid or the like. For liquid oral compositions such as liquid toothpaste, liquid mouth fresheners, and mouthwashes,
The amount of chitin etc. is 0.01 to 20% by weight, preferably
A suitable content is 0.05 to 20% by weight. 20% by weight
If the amount exceeds this amount, even if chitin or the like is solubilized, the entire amount cannot be dissolved in the liquid composition, and the viscosity will also increase, making it impossible to obtain a practical liquid oral composition. When chitin or the like is added to chewing gum, the appropriate amount is 0.01 to 60% by weight, preferably 0.05 to 50% by weight. Addition of more than 60% by weight of chitin etc. deteriorates the shape retention of the gum and worsens the texture. In the oral composition of the present invention, any of the ingredients used in conventional oral compositions can be used as composition ingredients other than chitin. There are no restrictions on its use. For example, for toothpaste, thickening agents such as glycerin, sorbitol, propylene glycol, dicalcium phosphate, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, aqueous silica, pyrophoric silica, calcium sulfate, magnesium phosphate, sulfite, etc. calcium, zeolite,
Abrasives such as insoluble sodium metaphosphate, binders such as carboxymethyl cellulose and carrageenan, sodium lauryl sulfate, sodium α-olefin sulfonate, lauric acid monoglyceride sulfate, acyl taurate, lauric acid monoglyceride sulfonate, lauryl sarcoside Anionic active agents such as sucrose esters, stearic acid monoglyceride, lauryl diethanolamide, polyoxyethylene sorbitan monolaurate, amphoteric active agents, flavoring agents such as menthol and anethole, sweeteners, chlorhexidine hydrochloride, glucone Medicinal ingredients such as chlorhexidine acid, epsilon-aminocaproic acid, dihydrocholestanol, tranexamic acid, allantoin, allantoin chlorhydroxyaluminum, sodium monofluorophosphate, dextranase, polyethylene glycol, and sodium chloride, preservatives, and water are used. Ru. Similarly, various ingredients normally used in mouth fresheners, mouth rinses, chewing gum, etc. can be used together with chitin and the like. however,
Chitin and the like are effective in preventing dental caries, alveolar pyorrhea, and halitosis. Therefore, some or all of the medicinal ingredients that have been incorporated into conventional oral compositions in anticipation of these effects have been replaced with chitin and the like in the present invention. Of course, it can be replaced with Next, examples show the caries preventive effect of chitin, etc.
The effect of preventing alveolar pyorrhea and the effect of preventing bad breath will be specifically explained. Experimental Example 1 This example and the following Experimental Example 2 are experimental examples regarding the caries preventive effect of chitin and the like. Chitosan REGITEX manufactured by Nanyo Kasei Co., Ltd.
NA-50 (molecular weight 47,000, degree of deacetylation 77%) and REGITEX-NA-500 (molecular weight 114,000, degree of deacetylation 60%) were each finely ground, and the products that passed through a 200-mesh sieve were used for experiments. . Accurately weigh 60 mg of chitosan, add purified water to make 20 ml, and measure the lactic acid neutralization ability of the obtained sample using a lactic acid aqueous solution (200 ppm) and a desktop PH meter manufactured by Denki Kagaku Keiki Co., Ltd.
Measured with COM-10. The results are shown in the attached drawings.
From the drawing, it is NA-500 like REGITEX-NA-50.
The lactic acid neutralization ability of is 300ppm/mg and
It can be seen that it is 12ppm/mg. Experimental Example 2 1 g of toothpaste having the composition A shown in Example 1 below was extruded onto a toothbrush, the teeth were brushed using a rolling brushing method for 3 minutes, and after rinsing thoroughly with water, a tabletop PH meter (manufactured by Denki Kagaku Keiki Co., Ltd.) was used. Glass flat electrode CE301S−
PH on the tongue was measured using OT). As a control, a toothpaste of composition A in which chitosan was replaced with water was used. In addition, 10 adult males with similar PH values on the tongue were selected as subjects. Table 1 shows the pH values on the tongue of each subject before brushing their teeth. By brushing your teeth, the PH value on your tongue increases compared to before brushing your teeth.
Thereafter, it decreases over time, but Table 2 shows the change over time in [PH value after tooth brushing - PH value before tooth brushing].

【table】

[Table] As is well known, caries is caused by organic acids (mainly lactic acid) produced by the decomposition and fermentation of carbohydrates that erode (demineralize) tooth enamel. It has been reported that this occurs when the oral pH value is below 5.4. Therefore, it can be prevented by maintaining the pH value in the oral cavity at around 7 or higher. Incidentally, according to another experiment conducted by the present inventors, adding just 1 ml of lactic acid at a concentration of 0.2 ppm into the oral cavity lowers the PH value in the oral cavity to 5.4 or less. However, as is clear from Experimental Example 1, the chitin used in the present invention has a moderate ability to neutralize lactic acid, and as is clear from Experimental Example 2, toothpaste containing chitin, etc. The agent has the ability to maintain a higher pH value in the oral cavity for a longer period of time than a control toothpaste that does not contain this agent. These experimental facts prove that chitin etc. are effective in preventing dental caries. Just to be sure, in Experimental Example 2, when using a toothpaste containing chitin, etc., the reason why the oral cavity was able to maintain a relatively high PH value for a long time was due to the high retention of chitin in the oral cavity. This is thought to be because polycations such as chitin are electrically bonded to the anionic oral mucosa at multiple points of action. Experimental Example 3 This example is an experimental example regarding the preventive effect of chitin on alveolar pyorrhea. The dorsal skin of 6-week-old male Slc-Wister rats was removed under Nembutal anesthesia, and after disinfection with alcohol, a linear laceration with a length of 4 cm reaching the subcutaneous fascia was made with a scalpel along the midline. Next, the wound was sutured at 1 cm intervals using a Mitsuhel needle, and the Mitsuhel needle was removed 4 days later. The drug was applied to the entire wound twice a day for 7 consecutive days. Seven days after wound creation, rats were killed with chloroform, the wound tissue was peeled off, and a width of 1 mm perpendicular to the wound line was removed.
Three cm-sized skin pieces were taken from the rat, and the tension required to separate the sutures of the wound skin pieces was measured using an Instron tension measuring machine, and the average value was taken as an index of wound healing. There were 6 rats in each group, and physiological saline was used as a drug control. Table 3 shows the relationship between the contents of the drugs used and their dosing methods and the rat groups, and Table 4 shows the relationship between the rat groups and the wound healing effect (tensile strength). Note that the ratios in Table 4 are expressed as relative values with respect to the tensile strength of rat group A as 100.

【table】

[Table] In the drug treatment of alveolar pyorrhea, drugs that have a cell activating effect (wound healing effect) are said to be effective. Drugs with cell activation effects include:
Allantoin-based compounds are well known, and allantoin, aluminum chlorohydroxyallantoinate, aluminum dihydroallantoinate, etc. have been widely used. As is clear from the results shown in Table 4, chitin, etc. used in the present invention exhibits medicinal efficacy superior to aluminum dihydroxyallantoinate in terms of wound healing effects, and therefore, chitin, etc. is effective in preventing alveolar pyorrhea. It can be understood that Furthermore, allantoin-based drugs are decomposed in alkaline environments, which limits the active agents that can be used when they are added to toothpaste, but chitin and other drugs are chemically stable. Therefore, the above restrictions are not imposed. Experimental Example 4 This example is an experimental example regarding the halitosis preventive effect of chitosan. Bioshell Inc. (635 Water Ave.E., Albany)
Chitosan Lot No. 2200 (molecular weight
88000, deacetylation degree 77%) was finely ground and the product that passed through a 200 mesh sieve was used for the experiment. 1% of chitosan
20 g of suspension water was accurately weighed into a 50 ml wide-mouth reagent bottle, a fixed amount of 1.5 ppm methyl mercaptan aqueous solution was added thereto, the bottle was tightly stoppered, and the bottle was left in a constant temperature bath at 37° C. for 5 minutes. Thereafter, the reagent bottle was opened, and the odor in the head space was sensory evaluated to measure the methyl mercaptan adsorption ability of chitosan. As shown in Table 5, the sensory evaluation scores are based on methyl mercaptan concentration.
The odor at 0.015ppm is given 1 point, the odor at 0.045ppm is given 3 points, and the odor at 0.15ppm is given 5 points.
A 5-step method was adopted in which each intermediate odor was scored as 2 and 4 points. Table 5 also shows the relationship between each rating and human halitosis.

【table】

[Table] More than 90% of the substances that cause bad breath are said to be methyl mercaptan and hydrogen sulfide, but as is clear from Table 6, the chitin used in the present invention completely eliminates odors with methyl mercaptan concentrations up to 6 ppm. adsorbs to. Considering that the human odor threshold for methyl mercaptan odor is 0.001 ppm or higher, it can be seen that chitin is extremely effective in preventing bad breath. Next, the specific composition of the oral composition according to the present invention will be shown in Examples. All compositions in Examples are weight%
It is. Example 1 This example shows an example of the composition of a toothpaste.

【table】 Example 2 This example shows an example of the composition of a dentifrice.

【table】 Example 3 This example shows an example of the composition of toothpaste powder.

[Table] Example 4 This example shows a composition example of a liquid toothpaste. Glycerin 35% Sodium polyacrylate 5 Paraphinsulfonate 1.5 Satucalin 0.1 Fragrance 1 Sodium monofluorophosphate 0.76 Water-soluble chitin *4 0.5 Dipotassium phosphate 0.1 Monosodium phosphate 0.2 Water Balance meter 100% *4 Method of Sannan T et al. [Markromol .,
Chem., 176 1191 (1975)] Water-soluble chitin (degree of deacetylation: 48%) Example 5 This example shows an example of the composition of a mouthwash.

【table】 Example 6 This example shows an example of the composition of chewing gum.

【table】

【table】 Example 7 This example shows a composition example of a liquid mouth freshener.

[Table] Example 8 This example shows a solid mouth freshener composition. Peppermint oil 1% Lemon oil 0.2 Eugenol 0.1 Anethole 0.2 Carvone 0.3 Chitin *2 20 Chitosan *1 25 Licorice powder 30 Xyrite 7 Oris root powder 4 Cinnamon powder 3 Porphyra powder 2 Powder powder 1 Gum arabic liquid Balance meter 100 *1, *2 ...See Example 1 The solid mouth freshener shown in this example was prepared by sufficiently powdering and mixing solid raw materials, adding liquid raw materials thereto, kneading well, and granulating this.

[Brief explanation of drawings]

The attached drawing is a graph showing the experimental results of measuring the lactic acid neutralizing ability of chitosan.

Claims (1)

[Claims] 1. An oral composition characterized by containing at least one of chitin and chitosan.