JPH0521087B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a breath odor removing composition, and more particularly to a breath odor removing composition containing as an active ingredient a synergistic composition of a polar solvent extract of leaves of a plant of the Camellia family and copper gluconate. The present invention relates to a breath odor removal means for deodorizing the entire area of bad breath using a composition and a mouthwash containing the same, chewing gum, candy, tablets, toothpaste, etc. [Prior art] It has been known that polar solvent extracts of plants of the Camellia family have a deodorizing effect (Japanese Patent Publication No. 58-18098).
(see publication). There is a review article on the removal of bad breath using an extract of green tea, which is made from the leaves of the tea tree, which is a representative plant of the Camellia family (Food Industry, Vol. 26, No. 16,
1983: Green tea flavonoids: Volume 27, No. 8,
1984: Regarding green tea flavonoid entrance odor removal gum). Also, US Patent No. 2894876; No. 3044939
No.; and No. 4112066 disclose the use of copper gluconate as a breath odor removing composition. Furthermore, copper gluconate is listed in the Merck Index 10th edition, No. 378.
On page 2629, cupric gluconate is described as a breath odor remover. According to the above conventional technology, the deodorizing effect of green tea flavonoids is great against amine compounds (ammonia, trimethylamine, etc.), while the deodorizing effect of green tea flavonoids is strong against sulfides (hydrogen sulfide, methyl mercaptan, etc.) due to the effect of chlorophyll. It is used in combination with chewing gum, etc. US Pat. No. 4,112,066 discloses the deodorizing effect of copper gluconate on sulfides. On the other hand, bad breath is a general term for odorous substances from the oral cavity, and is thought to include amines, alcohols, sulfur compounds, fatty acids, and tryptophan derivatives. The main components are sulfides and amines that form volatile sulfides through sulfur-containing amino acids and odors that come from food and drink. In particular, methyl mercaptan and trimethylamine have a strong correlation with bad breath. It is believed that. [Problems to be solved by the invention] Therefore, a composition for the purpose of removing bad breath must be effective against both sulfur compounds (especially methyl mercaptan) and amines (especially trimethylamine). As a known technique, the above-mentioned green tea flavonoid and chlorophyll are used in combination, and in this case, in order for chlorophyll to be effective against sulfide odor, the amount added is 0.05~
It is necessary to add 0.5% or more, but this addition amount has the disadvantage that the color tone becomes dark green to blackish green, which significantly reduces the commercial value. In view of the drawbacks of chlorophyll mentioned above, the present inventors conducted repeated experiments on a breath odor removing composition that can be used in a small amount and does not have the disadvantage of coloring. There have been no reports on the fact that it is suitable to use a leaf extract of a Camellia plant in combination with copper gluconate, and surprisingly, a synergistic effect of 3 to 5 times can be obtained by combining the two, and the amount used can be significantly reduced. The present invention was completed by discovering that the initial objective could be achieved. Therefore, an object of the present invention is to provide a halitosis removing composition that can completely remove bad breath consisting of both amine odor and sulfur compound odor by adding very small amounts, and that can freely adjust the color tone without coloring the additives. There is something to do. Another object of the present invention is to provide a method for removing bad breath, in which the entire area of bad breath is deodorized using a mouth-fitting product containing the halitosis removing composition according to the present invention. [Means for Solving the Problems] In order to achieve the above object, the present invention provides a polar solvent extract of leaves of plants of the Camellia family that is required to substantially deodorize 1 ml of a 1000 ppm aqueous solution of trimethylamine. 500ppm aqueous solution is 1
ml is defined as 1.0 deodorizing potency, the ratio of the amount of the prescribed extract to the deodorizing potency n of the prescribed extract x (4.5 to 5.5) parts by weight and 1 part by weight of copper gluconate. It is characterized by a halitosis-removing composition that covers the entire range of bad breath and contains as an active ingredient. There have already been many reports on the deodorizing effect of polar solvent extracts of leaves of Camellia plants, and it is believed that a group of flavonoids, which are the main components, play the leading role in deodorizing substances. The applicant's application states that, for example, a polar solvent extract of black tea, which has been fermented with an autooxidizing enzyme from leaves of Camellia family plants, has a stronger deodorizing effect than a green tea extract. (Refer to Japanese Patent Application Laid-open No. 153778/1983). As described above, the deodorizing effect of polar solvent extracts of leaves of Camellia family plants varies depending on the type of plant, the condition of the leaves (season, fermented, non-fermented), type of solvent, degree of purification, etc. The amount must also be changed. In the present invention, as shown in the experimental examples described below, an extract that is relatively rich in flavonoids and has a large deodorizing effect than green tea is used as a standard and has a deodorizing potency of 1.0. That is, 1 ml of a 500 ppm aqueous extract solution is required to substantially deodorize 1 ml of a 1000 ppm aqueous solution of trimethylamine, and the deodorizing potency is inversely proportional to the flavonoid content and should be proportional to the amount added. Representative plants of the Camellia family used in the present invention include tea plants, camellias, sasanqua flowers, and sakaki trees, and commercially available green teas such as bancha and sencha can be conveniently used. Of course, black tea and oolong tea can also be suitably used. The polar solvents used include water, glycols (glycerin, ethylene glycol, propylene glycol, etc.), lower alcohols (methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), or any of these. Water has the disadvantage of extracting a lot of impurities such as sugars, proteins, and amino acids, while alcohols and ketones often extract substances other than chlorophyll, making it difficult to extract flavonoids with relatively high purity. is preferably extracted with a 20-80% aqueous glycerin solution at 50-100°C. The halitosis-removing composition according to the present invention relates to both a halitosis-removing composition that is applied directly into the mouth and a raw material composition for preparing the halitosis-removing composition. The raw material composition is a mixture of a polar solvent extract of leaves of a Camellia family plant and copper gluconate in a predetermined ratio, and is prepared in a form convenient for blending into a desired breath odor removing composition, and includes liquid, powder, It may be appropriately prepared into granules or emulsions by conventional methods. However, the most important thing is the mixing ratio,
A raw material composition is prepared in which both components are mixed at a mixing ratio that provides the most significant synergistic effect. That is, the deodorizing potency of the polar solvent extract of the leaves of the Camellia family plant to be used is determined by the method described in Examples below, and this deodorizing potency n×(5
±0.5): A polar solvent extract of leaves of a Camellia plant and copper gluconate are blended at a ratio of 1.0 parts by weight. Examples of forms that can be applied directly into the mouth include mouthwash, chewing gum, candy, tablets, and toothpaste.
The proportions of both components blended in these are naturally the proportions mentioned above, but the blended amounts are in the range of 0.005 to 0.5% by weight of the tooth polar solvent extract of Camellia plant and 0.0001 to 0.1% by weight of copper gluconate. Selected by [Examples] Next, the bad breath removing composition according to the present invention will be specifically explained using Examples and Experimental Examples. Experimental example 1 Add 300 g of a 20% glycerin aqueous solution to 100 g of commercially available average sencha green tea pulverized with a grinder and less than 50 mesh.
g and stirred for extraction at 50°C for 3 hours, and the extract was collected using a centrifuge. The same operation was repeated to cool the extract twice at 10°C for 24 hours, and the precipitated chlorophyll, wax, etc. were removed.The extract was concentrated under reduced pressure, further filtered with a small amount of Celite, and then impurities were removed under high vacuum. After distillation, a 3.1% green tea extract containing green tea flavonoids as the main component was obtained. Experimental Example 2 Camellia leaves were steamed using distillation and then dried under hot air at 60°C to obtain dried camellia leaves equivalent to green tea. The same procedure as in Experimental Example 1 was performed except that 100 g of the pulverized material of 50 mesh or less of this dried material was extracted with water to obtain an extract of 31.5%. Experimental Example 3 Green tea extract and camellia leaf extract obtained in Experimental Examples 1 and 2,
The deodorizing effect of copper gluconate on methyl mercaptan and trimethylamine was measured. Take 1 ml of methyl mercaptan 25 ppm aqueous solution and trimethylamine 1000 ppm aqueous solution into 100 ml wide-mouthed bottles, add 1 ml of aqueous solutions of green tea extract, camellia leaf extract, and copper gluconate at specified concentrations, and shake for 5 minutes. Gas chromatographic analysis was performed. Gas chromatographic analysis of trimethylamine: Column: Glass tube with inner diameter of 3 mm and length of 3 m; Stationary phase liquid: 5% Ranpha (Ranpha: Wako Pure Chemical Industries, Ltd.)
(filler developed for amine compounds manufactured by Co., Ltd.);
Stationary phase carrier...Chromosolp W; Column temperature...
75℃; Injection temperature...75℃; Sample amount...300μ;
Carrier gas...Helium; Detector...Hydrogen flame ionization detector Gas chromatographic analysis of methyl mercaptan: Column...Inner diameter 3 mm: Length 5 m; Teflon tube;
Stationary phase liquid...20% DOP; Stationary phase solid...Chromosorp W; Column temperature...75℃; Injection temperature...
120℃; Sample amount...300μ; Carrier gas...
Nitrogen; Detector...Flame photometric detector The analysis value was the relative area of the gas chromatograph peak based on the integrator display of the gas chromatograph, and the deodorization rate was calculated from the control analysis value and the sample analysis value. The results are shown in Table 1.

【table】

[Table] From Table 1, the respective combinations of copper gluconate and green tea extract or copper gluconate and camellia leaf extract are as follows:
It was observed that the deodorizing effect was synergistically increased compared to when each was used alone. In addition, to completely deodorize 1 ml of 25 ppm methyl mercaptan aqueous solution, at least 1 ml of copper gluconate 60 ppm aqueous solution (0.5 ml of copper gluconate 20 ppm aqueous solution + 100 ppm green tea extract)
0.5ml of aqueous solution) or more (copper gluconate
20ppm aqueous solution 0.5ml + camellia leaf extract 10 ³ ppm aqueous solution 0.5
ml), and to completely deodorize 1 ml of trimethylamine 100 ppm aqueous solution, 1 ml or more of the aqueous solution,
1 ml of camellia leaf extract 5×10 ³ ppm aqueous solution, or (0.5 ml of copper gluconate 20 ppm aqueous solution + green tea extract
100ppm0.5ml) or more, or (copper gluconate
20ppm aqueous solution 0.5ml + camellia leaf extract 10 ³ ppm aqueous solution 0.5
ml) and above. By the way, the deodorizing effect of a polar solvent extract of a plant of the Camellia family can be considered to be proportional to its furanoboid content, but there are many types of extracts. Considering the relationship between Experimental Examples 1 and 2, it is recognized that the deodorizing effect of the camellia leaf extract is about 1/10 of that of the green leaf extract. Therefore, in the present invention, it is preferable to uniformly process the green leaf extract of Experimental Example 1, which is relatively rich in furanovoids, as a standard.
That is, when 1 ml of a 1000 ppm aqueous solution of trimethylamine is substantially deodorized by 1 ml of a 500 ppm aqueous extract solution according to the gas chromatographic analysis of trimethylamine in Experimental Example 3, the deodorizing potency is defined as 1.0.
If the deodorizing potency of a given extract is determined to be n, then the breath odor removing composition according to the present invention contains n x (4.5 to 5.5) parts by weight of the extract and 1.0 parts by weight of copper gluconate. It is what it is. Example 1 Powder raw material composition for preparing a bad breath removing composition: 1 part by weight of copper gluconate, 5 parts by weight of the green leaf extract of Experimental Example 1 (deodorizing potency 1), 14 parts by weight of dextrin, and 100 parts by weight of water. The solution heated and dissolved in was spray-dried to obtain 20 parts by weight of a powder raw material composition. Example 2 Granular raw material composition for preparing a bad breath removing composition: 1 part by weight of copper gluconate, 50 parts by weight of the camellia leaf extract (deodorizing potency 10) obtained in Experimental Example 2, and 9 parts by weight of powdered sugar. Mix well and use a granulator to make granular raw material composition 60
Parts by weight were obtained. Example 3 Breath odor removing composition for mouthwash: Mouthwash flavor 0.3 parts by weight Pluronic P-85 (manufactured by Wyandot Chemical Co.) 4.840 Caramel 1% aqueous solution 1.0 Ethyl alcohol (95%) 20.3 Water 72.27 Monofluorophosphoric acid Sodium 0.7 1% hinokitiol alcohol solution 0.5 Composition of Example 1 0.09 The deodorizing effect on methyl mercaptan and trimethylamine was measured using the method described in Experimental Example 3 for 1 ml of the obtained mouthwash. As a result, 100% deodorizing effect was confirmed against both methyl mercaptan and trimethylamine. Furthermore, the head space gas subjected to gas chromatography analysis was determined to be substantially odorless by a sensory test conducted by a dedicated panel. This indicates that this mouthwash is an effective breath odor removing composition for all areas of halitosis. Example 4 Composition for removing bad breath from chewing gum: Chewing gum base 20 parts by weight Sugar 55 Water Candy 20 Flavor 0.73 Composition of Example 2 0.27 Softener 4.0 Chewing gum was obtained by a conventional method using the above formulation. In order to examine the effectiveness of prototype chewing gum in removing bad breath, sensory tests were conducted on tobacco odor, garlic odor, and artificial odor. The evaluation criteria are shown in Table 2, and Table 3 shows the average of the evaluations by the five expert panels. For cigarette odor, smoke 3 Highlights at the same time for 3 minutes to about 2/3 of the original size, take breath 3, which is the bad breath you get right after smoking cigarettes, then chew 10g of prototype chewing gum for 3 minutes, remove the chewing residue, and then take breath 3. This was taken as the bad breath immediately after tasting the sample. Garlic odor was obtained by rinsing the mouth with 100 ml of pressed garlic juice diluted 200 times with water, and taking breath sample 3 to obtain the garlic odor immediately after bad breath occurred.Furthermore, as in the case of tobacco odor, exhalation after chewing gum was taken. 3 was taken as the bad breath immediately after tasting. Artificial bad breath contains hydrogen sulfide 100ppm, methyl mercaptan 5ppm, dimethyl sulfide 10ppm
After rinsing the mouth with 100 ml of an aqueous solution, the breath odor was collected in the same manner as for garlic odor.

【table】

〔Effect of the invention〕

According to the halitosis-removing composition of the present invention, it is possible to provide a halitosis-removing composition that can deodorize the entire area of halitosis substantially odorless by applying a very small amount, and does not stain or stain products.

Claims (1)

[Scope of Claims] 1. In a polar solvent extract of leaves of Camelliaaceae plants, 1 ml of a 500 ppm aqueous solution of trimethylamine is required to substantially deodorize 1 ml of a 1000 ppm aqueous solution of trimethylamine.
ml is defined as 1.0 deodorizing potency, the ratio of the amount of the prescribed extract to the deodorizing potency n of the prescribed extract x (4.5 to 5.5) parts by weight and 1 part by weight of copper gluconate. A halitosis-removing composition that covers all areas of bad breath and contains as an active ingredient. 2. Leaves of plants belonging to the Camellia family are tea plants, camellias, sasanqua flowers, and sakaki trees, and include fresh leaves of these leaves, leaves dried after inactivating autooxidizing enzymes by heating, and fermented leaves on which autooxidizing enzymes have been applied. Claim 1
The bad breath removing composition described in Section 1. 3. The polar solvent extraction according to claim 1 or 2, wherein the polar solvent extraction is thermal extraction with water, glycerin, ethylene glycol, propylene glycol, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, or a mixture thereof. Bad breath removal composition. 4 The extract of the leaves of the Camellia plant makes green tea 11% more hydrated.
%, then pulverized to less than 50 mesh, heated and extracted with a 20-80% glycerin aqueous solution, and separated by centrifugation.
2. The bad breath removing composition according to claim 1, which is an extract mainly containing green tea flavonoids obtained by distilling off the solvent from a filtrate from which chlorophyll and the like are removed by cooling at 24 hours.