JPH0753174B2 - Deodorants - Google Patents

Description

TECHNICAL FIELD The present invention has excellent deodorizing power and high safety, and can be widely used for a bad odor generated in human body, house, environment, etc. Regarding deodorant.

2. Description of the Related Art Conventionally, as a deodorant for removing bad breath and for a bad odor generated in general households and factories, a deodorant containing a plant extract having a deodorant power as an effective deodorant (Japanese Patent Laid-Open No. 57-
No. 204278, No. 61-240960, Japanese Patent Application No. 61-169567, etc.),
Deodorants using chemicals such as sodium perborate and hydrogen peroxide, deodorants containing enzymes such as proteolytic enzymes such as papain (Japanese Patent Laid-Open Nos. 52-38026 and 52-38027,
No. 60-58150), and deodorants focusing on the deodorizing power of quinone (Japanese Patent Publication Nos. 51-33974 and 53-45372) have been proposed.

Problems to be Solved by the Invention However, these deodorants have a weak deodorizing effect and are insufficient in effect, and when a large amount of deodorant active ingredient is blended, coloring and taste deterioration, precipitation, etc. There may be problems. Further, although deodorants using chemicals and enzymes have a relatively strong deodorizing effect, there are some that have a problem in terms of safety to the human body.

Therefore, there is a demand for the development of a deodorant having excellent properties such as a strong deodorant ability and safe use.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a deodorant having a sufficient deodorizing power, high safety in use, and a wide range of applications.

Means and Actions for Solving Problems The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, the deodorant active ingredient selected from red algal plants, brown algae plants, gymnosperms and angiosperms 1 Selected from solvent extracts of one or more kinds of plants, those using CH-OH as a donor, those using diphenol or a related compound as a donor, and those which incorporate a molecular enzyme and act on a pair of donors It was found that the deodorant having a very high deodorizing effect can be obtained by the synergistic action of the both with the redox enzyme.

Hereinafter, the present invention will be described in more detail.

The deodorant of the present invention is a combination of a deodorant active ingredient and an oxidoreductase, and is used for preventing and removing garlic odor, halitosis, tobacco odor, etc. in the mouth, toothpaste, mouthwash, mouth spray and the like. Oral products such as troches and gums, foods and drinks, soaps and sprays for preventing and removing body odors and physiological odors of the human body,
For skin such as shampoo, conditioner, cream, lotion,
Cosmetics for hair, foot sprays, shoe soles, deodorants and deodorizers for indoor house wall odors, indoor cleaning filters, deodorants and deodorants for toilet sewage odors and dung odors, neutralizers, and garbage Deodorant and deodorant for garbage odor and rotten odor, soap for preventing and removing animal odor of pets, body shampoo, deodorant and deodorant for vehicle exhaust gas and vehicle odor, sewage treatment in factories and livestock farms Factory or processing plant,
Deodorant deodorant used in pulp mills, low-odor feed, etc.
Widely used as a deodorizer for bad odors generated in houses and the environment.

The deodorant active ingredient of the present invention includes red algae plants, brown algae plants,
Use solvent extracts of gymnosperms and angiosperms. Specific examples of these plants include Rhodophyta from the phylum Rhodophyta and Rhizophoraceae from the family Lagomorpha, Snomatida from the family Lagomorpha, Henisozo, Kurosozo, Kobosozo, Papilazozo from the family Anodontidae, Mozuku from the family Amaranthaceae from the Phalaenopsis phylum. Laminaria of the kelp family, kurome, Vivamata, Hijiki of the family Hydrangeaceae, Hondawara, Akamoku, Sawmillimo, Umitranoo, Obana anemone, Nejimoku, Narasamo, Meadowara, Yatsumatakumaku, Yakumokaku, Tomomakuta, Astragalus vulgaris, Astragalus vulgaris, Endeavorae Seaweed, Ginkgo biloba, Ginkgo biloba, Ginkgo biloba, Metasequoia, Pseudocephalus, Pepperidae, Pepperidae, Pepperidae, Clover, Beech, Birchaceae, Cercus, Polygonaceae Family die Cormorant, Salix ginkgo, Ranunculaceae magnoliaceae, honoki, button of trash and buttercup family, Coptis chinensis, salmon ginger, butterflies of the buttercup family alveolaceae, nanthene of the barberry family, sassafras of the family camphoraceae, camphoraceae, poppy family Poppies and cruciferous Taisei, Helicoptera moss moss, Moss moss, Rosaceae witch hazel Melis, Rosaceae Yamazakura, Snake strawberry, Hawthorn, Leguminous rattania, Suou, Ougi, Cranaceae citrus salamander, yellowfin, Henrouter and medusae of the family Saccharidae, tea of the Membraneaceae of the lateral membrane, Camellia japonica, Pomegranate of the family Pomegranate, Pomegranate of the family Peachaceae, clove, eucalyptus, allspice, celery, anise, scorpion, azalea of the family Aceraceae. Assemblage of the azalea family, convoluted flowers Of Oleaceae forsythia, tubular flowers eyes mint family of sage, thyme, marjoram, rosemary, Scutellaria, elsholtzia ciliata, Melissa, Netherlands mint, black mint, shiso, basil,
Examples include oregano, savory, wolfberry of the Solanaceae family, Coleoptera of the Pleurotus family, Acenyak of the Rubiaceae family, Chigo, Tarragon, Arnica of the Asteraceae family, Kajutsu and Sanna of the Ginger family.

When obtaining a solvent extract from these plants, whole plants may be used as plants, or leaves, bark, flowers, pericarps, fruits, rhizomes, roots and other parts of the plant may be used. Depending on the plant to be used, a site containing a relatively large amount of the deodorant active ingredient of the plant can be selected and used.

When obtaining deodorant active ingredients from these plants, known methods can be adopted, for example, after drying the plants, cutting them into powders, water, ethyl ether, ethylene chloride, dioxane, acetone, ethanol, One or more polar solvents such as n-butanol, ethyl acetate and propylene glycol, or n-hexane, petroleum ether, ligroin, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, toluene, benzene. It is possible to employ a method of extracting with one or more non-polar solvents such as the above or a mixed solvent of these polar solvents and non-polar solvents. In this case, an ordinary method can be adopted as the extraction operation, for example, a method of digesting the plant in a solvent can be adopted.

The extract obtained by the above extraction operation is usually mixed with the deodorant after distilling off the solvent, but in some cases, especially when the solvent is water, ethanol, etc., the solvent is distilled off. It is also possible to mix it in the deodorant without removing it.

As the plant extract, one kind of the above extracts may be used alone or as a mixture of two or more kinds (a mixture of extracts or one obtained by simultaneously extracting two or more kinds of plants).

Furthermore, the types of oxidoreductases used in the present invention are
One or more of the following are used.

CH-OH as a donor Alcohol dehydrogenase, homoserine dehydrogenase, butanediol dehydrogenase, acetoin dehydrogenase, glucuronate reductase, shikimate dehydrogenase, pyridoxine-4-dehydrogenase, pyridoxal dehydrogenase, alcohol oxidase, 2-oxopantoyl Lactone reductase, cholesterol oxidase, catechol oxidase, sorbose dehydrogenase, malate dehydrogenase, etc.

Using diphenol or related compounds as a donor Trans-acenaphthene-1,2-cyol dehydrogenase, L-ascorbate-cytochrome b ₅ reductase, catechol oxidase, laccase (polyphenol oxidase), ascorbate oxidase, o-
Aminophenol oxidase, etc.

Those that take in molecular oxygen and act on a pair of donors Anthranilate 1,2-dioxygenase, anthranilate 2,3-dioxygenase, benzene 1,2-dioxygenase, salicylate 1-monooxygenase, 4-hydro Benzoate 3-monooxygenase, orcinol 2-monooxygenase, phenol 2-monooxygenase, trans-cinnamate 2-monooxygenase, monophenol monooxygenase, p-coumarate 3-monooxygenase and the like.

It should be noted that, as the oxidoreductase, it is preferable to use the most suitable one depending on the type of the plant extract, but among the above oxidoreductases, ascorbate oxidase, o-aminophenol oxidase, polyphenol oxidase,
Catechol oxidase and p-coumarate 3-monooxygenase are preferably used.

Further, the oxidoreductase may be used as it is, or may be used in a suitable solvent such as water, a buffer solution having a buffer action between pH 4 and 9 (acetic acid, citric acid, phosphoric acid, tartaric acid, lactic acid, phthalic acid, succinic acid, Boric acid, glycine, veronal buffer, etc.), alcohol, etc. may be used after dissolving in the above solvent and the like.

The deodorant of the present invention uses a deodorant active ingredient and an oxidoreductase in combination as described above, whereby a remarkable deodorant effect is achieved by the synergistic action of both components. Is selected in various ways, for example, (1) a deodorant active ingredient to which oxidoreductase has been acted in advance is blended, or (2) a deodorant active ingredient and oxidoreductase are mixed and blended. Is mentioned.

Here, in the case of the above (1), the deodorant active ingredient is activated by previously acting an oxidoreductase,
The obtained enzyme-activated product is blended with a deodorant.
In this case, the method of reacting the oxidoreductase and the reaction conditions can be the same as in the ordinary enzyme reaction. For example, the oxidoreductase is added to the plant extract, the enzyme reaction is allowed to proceed under a constant temperature condition, and the reaction is completed. Alternatively, the solution may be dried using a membrane filter or the like, or the solution may be dried, or the oxidoreductase may be immobilized. The enzyme reaction conditions are
Although it depends on the type of oxidoreductase used, it is preferable to carry out the reaction under a temperature condition of 10 to 50 ° C., more preferably 20 to 40 ° C. for 1 minute to 24 hours, particularly 2 minutes to 8 hours. .

In the case of the above (2), the deodorant active ingredient and the oxidoreductase are mixed and blended in the deodorant. It is also possible to employ a method in which the ingredients are separately or separately isolated and mixed into a product, and mixed and activated at the time of use.

The amount of the deodorant active ingredient of the present invention varies depending on the type of the deodorant, etc., but when a plant extract is used, for example, the amount of the solid component of the plant extract is 0.0001 to 50% by weight with respect to the total amount of the deodorant component. %, Particularly preferably 0.001 to 10% by weight.

The amount of oxidoreductase is not particularly limited, but is preferably 0.01 to 100000 units, and more preferably 0.5 to 5000 units with respect to 1 g of the deodorant active ingredient. Here, 1 unit is the amount of the enzyme that oxidizes or reduces 1 μmol of the standard substrate of the enzyme in 1 minute at 36 ° C.

The deodorant active ingredient of the present invention may be used alone or in combination with other deodorant active ingredients.

The deodorant according to the present invention can be prepared in various dosage forms. For example, a solution in which the deodorant active ingredient of the present invention and oxidoreductase are dissolved in an appropriate solvent, or a paste, powder,
What was prepared in the desired form, such as a block form and a microcapsule form, can be used.

Further, as the other components of the deodorant of the present invention, appropriate components may be blended according to the type and dosage form of the deodorant. For example, when used as an oral deodorant for preventing bad breath and removing bad breath, as a toothpaste component, dibasic calcium phosphate, calcium carbonate, calcium pyrophosphate, insoluble sodium metaphosphate, amorphous silica, crystalline silica,
Abrasives such as aluminosilicate, aluminum oxide, aluminum hydroxide, microwave oven (blending amount usually 20-60% by weight), binding agents such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, alginate, carrageenan, gum arabic, polyvinyl alcohol (usually 0.
3 to 5% by weight), thickening agents such as polyethylene glycol, sorbitol, glycerin and propylene glycol (usually 10 to 70% by weight), sodium lauryl sulfate, sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid monoglyceride sodium monosulfate, Foaming agents such as sodium lauryl sulfoacetate, sodium N-lauroyl sarcosinate, N-acyl glutamate, sodium N-myristoyl sarcosinate, N-acyl alanine, lauric acid diethanolamide, sucrose fatty acid ester (usually
0.1-5% by weight), and essential oils such as peppermint, spearmint, l-menthol, carvone, eugenol,
Fragrances such as anethole, saccharin sodium, steviozide, neohesperidyl dihydrochalcone, glycyrrhizin, perillartine, sweeteners such as p-methoxycinnamic aldevidide, preservatives, and other ingredients are mixed, and these ingredients are mixed with water. And manufactured according to a conventional method. Further, in mouthwashes such as mouthwash and the like, components suitable for the properties of the product are appropriately mixed.
In these oral compositions, lysozyme chloride, dextranase, lytic enzyme, mutanase, chlorhexidine, sorbic acid, alexidine, hinokitiol, cetylpyridinium chloride, alkylglycine, alkyldiaminoethylglycine salt, allantoin, ε-aminocaproic acid. , Active ingredients such as tranexamic acid, azulene, vitamin E, sodium monofluorophosphate, sodium fluoride, stannous fluoride, water-soluble primary or secondary phosphates, quaternary ammonium compounds, sodium chloride You can also do it.

Also, in the case of household and industrial deodorants used for bad odors generated in houses and the environment, the components usually used for deodorants can be blended according to the type, such as sodium perborate, Oxidizing agents such as hypochlorous acid, manganese dioxide, permanganate, benzoquinone and naphthoquinone, aldehydes such as glyoxal and acrolein, ketones, 1,
Epoxy compounds such as 2-propylene oxide, 1,2-n-butylene oxide, α, β-unsaturated compounds such as methacrylic acid esters and maleic acid derivatives, metal salts such as copper sulfate and zinc sulfate, activated carbon, silica gel, alumina It is possible to blend an adsorbent and the like.

Effect of the Invention As described above, the deodorant of the present invention has a deodorant power superior to that of a deodorant using a conventional deodorant active ingredient alone, and is highly safe in use. It can be widely used as a deodorant against bad odors generated in the human body, houses, environment, etc.

Further, according to the present invention, the compounding amount of the deodorant active ingredient can be reduced, and problems such as coloring, deterioration of taste, precipitation and the like are improved, and therefore, formulation is easy, and from this point as well. It can be widely applied.

Hereinafter, experimental examples of the deodorant active ingredient according to the present invention will be shown.

[Experimental Example 1] 0.1 mg of the plant extract shown in Table 1 and 1 unit of oxidoreductase (amount of enzyme capable of oxidizing or reducing 1 μmol of standard substrate of each enzyme at 36 ° C. for 1 minute) were adjusted to pH 0.05. Put the sample (sample) dissolved in 2.5 ml of M phosphate buffer into a 25 ml capacity test tube, and
0.5 ml of 1 ppm methyl mercaptan was added and the mixture was tightly stoppered and reacted at 36 ° C. for 6 minutes.

After completion of the reaction, the amount of methyl mercaptan in the head space of the test tube was measured by gas chromatography.

The methyl mercaptan deodorization rate of these samples was calculated according to the following formula using as a control a test tube containing only a phosphate buffer solution.

S: Amount of methyl mercaptan in the headspace of the sample C: Amount of methyl mercaptan in the control headspace The same applies when the deodorant active ingredients and oxidoreductases in Table 1 are used alone. The amount of methyl mercaptan in the headspace was measured, and the individual deodorizing rate of each was calculated.

The above results are shown in Table 1.

From the results in Table 1, it was confirmed that the deodorizing rate (II) when used in combination was considerably higher than the deodorizing rate (I) used alone, and that the synergistic action of the two exhibited excellent deodorizing power. .

[Experimental Example 2] 100 ml of the plant extract shown in Table 2 (containing about 2 g of the dry solid matter) contained the oxidoreductase 10 shown in Table 2.
00 units was added, and the enzyme reaction was carried out at 30 ° C. for 2 hours. After the reaction was completed, it was passed through a membrane filter (cut off with a molecular weight of 10,000 or more), and the resulting filtered solution was dried to obtain a deodorant consisting of an activated plant extract.

For this activated plant extract deodorant, the methyl mercaptan deodorant rate was determined in the same manner as in Experimental Example 1. The deodorization rate of methyl mercaptan when each of the plant extracts that had not been activated by the enzyme was used alone was measured and calculated in the same manner.

The above results are shown in Table 2.

From the results shown in Table 2, the enzyme-activated plant extract deodorant obtained by previously reacting the plant extract with the redox enzyme had a deodorant effect as compared with the case where the plant extract was used alone. It was confirmed to be excellent.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

In the following examples,% means% by weight.

[Example 1] Toothpaste Aluminum hydroxide 43% Glycerin 20 Sodium carboxymethyl cellulose 2 Sodium lauryl sulfate 2 Fragrance 1 Sodium saccharin 0.1 Ougon 30% Ethanol extract 0.15 Polyphenol oxidase (500 units, manufactured by Tanabe Seiyaku Co., Ltd.) 0.05 N- Lauroyl sarcosine sodium 0.2 Water residual 100.0% [Example 2] Toothpaste dicalcium phosphate 45.0% Silicic anhydride 2.0 Carboxymethyl cellulose sodium 0.3 Carrageenan 0.8 Sorbite 20.0 Propylene glycol 2.0 Sodium lauryl sulfate 1.5 Activated product of eleuthero extract (o-aminophenol) oxidase treated) 0.05 perfume qs water residue total 100.0% example 3 liquid dentifrice sodium polyacrylate 50% glycerol 30 perfume 0.9 sodium saccharin 0.1 Ala Of aqueous extract 0.25 catechol oxidase (100 units) 0.05 Ethanol 3 N-lauroyl sarcosine sodium 0.2 0.04 water remaining total 100.0% linoleic acid Example 4 Mouthwash Ethanol 20% Perfume 1 Saccharin sodium 0.05 plantago 30% ethanol extract 0.2 o -Aminophenol oxidase 0.1 sodium monofluorophosphate 0.1 chlorhexidine hydrochloride 0.01 lauryl diethanolamide 0.3 water residual 100.0% [Example 5] troche gum arabic 6% palatinose 30 maltitol 20 isomaltose 22 gelatin 3 fragrance 0.2 rhubarb 50% ethanol extract 0.5 ascorbic acid oxidase (100 units, Tanabe Seiyaku Co., Ltd.) 0.1 water remaining total 100.0% example 6 chewing gum The gum base 20% sugar 16 isomaltose 20 maltose 20 Konshiro Flop 11.3 Starch syrup 11.5 flavors 0.5 rosemary methanol extract 0.5 Ascorbic acid oxidase (200 units, Tanabe Seiyaku Co., Ltd.) 0.2 Total 100.0% Example 7 toilet soap carboxymethylcellulose 8% superfatting agent 2 soap base 50 lauryl sulfate Triethanolamine 30 7-Hydroxy-6,8-dimethoxycoumarin-D-glucoside 0.01 Time 30% Ethanol extract 0.3 Polyphenol oxidase (100 units) 0.01 Dye, perfume, appropriate amount Water balance 100.0% [Example 8] Handlo Syon Cetyl monostearate 1.0% Isopropyl palmitate 4.0 Polyethylene glycol 100 Distearate 2.0 Glycerin 8.0 Sodium cetyl sulfate 5.0 Birch water extract 1.0 Catechol oxidase (200 units) (7-Hydroxy-6,8-dimethoxycoumarin and its D-glucose Side 0.5% included) 0.1 Dyes, fragrances, preservatives Proper amount of water balance 100.0% [Example 9] lotion citric acid 0.1% zinc paraphenolsulfonate 0.2 sorbit 2.0 glycerin 3.0 polyoxyethylene (20EO) oleyl ether 1.0 ethanol 15.0 Clove water extract 0.2 p-coumarate-3-monooxygenase (50 units) (7-hydroxy-6,8-dimethoxycoumarin and its D-glucoside 8% content) 0.05 Fragrance, preservative proper amount water balance 100.0% [ Example 10] After-shaving lotion Ethanol 40.0% Menthol 0.05 Benzyl alcohol 0.25 Glycyrrhetinic acid 0.05 Polyoxyethylene hydrogenated castor oil monoviroglutamate monoisostearate 0.7 Perfume 0.1 Chinpi 30% ethanol extract 0.2 Ascorbate oxidase (100 units) ( 7-Hydroxy-6,8- Metokishiku marine and D- glucoside 7% contained) 0.1 Water remaining Total 100.0% Example 11 activator (polyphenol oxidase treated liquid shampoo Glycerin 10.0% sodium alkylbenzene sulfonate 20.0 chromate 30% ethanol extract) 0.05 Perfume Appropriate amount Water balance 100.0% [Example 12] Hair rinse Stearyldimethylammonium chloride 3.0% Glycerin monostearate 3.0 Keihi 30% Ethanol extract 0.2 Trans-cinnamate-2-monooxygenase (50 units) 0.05 Colorant 0.05 Perfume 0.05 Water residue 100.0% [Example 13] Deodorant for kitchen garbage Ethanol 70% Itohimehagi ethanol extract 1 Ascorbate oxidase (100 units) 0.1 Perfume 1 water Residual 100.0% [Example 14] Footspray Ethanol 50% Dichlorodifluoromethane 49.9 Umit (Time of extraction, catechol oxy Dark-peptidase processing) activator of n- butanol extract of Noo was dissolved gelatin powder 5g 0.1 Total 100.0% Example 15 Microencapsulation oral dosage hot water 100 ml, oak dry extract 2.0g And 0.5 g (500 units) of ascorbate oxidase were added and well dispersed.

On the other hand, a 3: 4 mixed solution of ethyl acetate: chloroform containing 0.2% polyoxyethylene hydrogenated castor oil as a surfactant was prepared and sufficiently cooled. Next, the above-mentioned dispersion liquid was added dropwise to this mixed solution to disperse it, and then the mixture was filtered to obtain microcapsules.

[Example 16] 2 g of granules of enteric coated microcapsules rosemary dry extract and 0.2 g of porphenol oxidase
(2000 units) After spraying the solution, a sodium bicarbonate aqueous solution of cellulose acetate phthalate containing sodium pyrosulfate was further sprayed to obtain microcapsules in which 0.3 to 2% by weight of cellulose acetate phthalate was attached to the rosemary dried extract.

When this microcapsule was subjected to a disintegration test according to the disintegration test method of the Japanese Pharmacopoeia (10th revision), the second liquid (pH
It was an enteric-coated capsule that disintegrated in about 7.5).

[Example 17] Pet spray ethanol 50% Dichlorodifluoromethane 49.95 Activated product of ethanol extract of marjoram (polyphenol oxidase treatment during extraction) 0.05 Total 100.0% [Example 18] Indoor deodorant ethanol 20% Rhizoma 50% ethanol Activated extract (ascorbic acid oxidase treatment at extraction) 0.05 Perfume, appropriate amount Water balance 100.0%

Claims (4)

[Claims] 1. A red alga plant, a brown alga plant as a deodorant active ingredient,
A solvent extract of one or more plants selected from gymnosperms and angiosperms, those using OH-CH as a donor, those using diphenol or a related compound as a donor, and a pair of molecular enzymes incorporated A deodorant characterized by being used in combination with an oxidoreductase selected from those which act on the donors of. 2. The deodorant according to claim 1, wherein the oxidoreductase is selected from ascorbate oxidase, o-aminophenol oxidase, polyphenol oxidase, catechol oxidase and p-coumarate 3-monooxygenase. . 3. The deodorant according to claim 1 or 2, wherein a deodorant active ingredient to which an oxidoreductase is previously reacted is blended. 4. The deodorant according to claim 1 or 2, wherein the deodorant active ingredient and the oxidoreductase are mixed and blended.