Abstract:
A deodorant composition comprising a phenolic compound and an enzyme oxidizing said phenolic compound is disclosed. The deodorant composition is useful to remove environmental smells such as bad breath, the smell in refrigerator, smells derived from pets and domestic animals, smells in factories, the stench of factory effluent, and other smells that are offensive to people.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a deodorant composition, more particularly, a deodorant composition to remove environmental smells such as bad breath, the smell in refrigerator, smells derived from pets and domestic animals, smells in factories, the stench of factory effluent, and other smells that are offensive to people. 
     2. Description of the Related Arts 
     There are several kinds of smells surrounding us, for example, smells in refrigerators or the like, bad breath, smells of domestic animals, and so forth. Since these smells are offensive to people, various means for deodorization have been developed. One of well-known means is to remove the source substances of the stenches using an adsorbent. Well-known examples of such adsorbents are active carbon and teas containing catechins. 
     However, active carbon can neither adsorb a trace of substance nor be used for foods or other products which should be kept in one&#39;s mouth. Besides, active carbon has a further drawback that discarding the active carbon which have absorbed a great deal causes a deterioration of the earth environment. Meanwhile, natural substances like catechins are friendly to the earth environment and capable of blended with a chewing gum or the like to prevent bad smell. However, such substances are not sufficient in the deodorizing effect. 
     OBJECT OF THE INVENTION 
     Accordingly, an object of the present invention is to provide a deodorant composition which has an excellent deodorizing effect and is friendly to the earth environment. 
     SUMMARY OF THE INVENTION 
     The inventors earnestly investigated in view of the fact that phenolic compounds like catechins have deodorizing effects, and unexpectedly found that surprising deodorizing effects can be obtained when these compounds are used together with polyphenol oxidases, and finally, have achieved the present invention. 
     The deodorizing activities of the phenolic compounds are supposed to be exhibited by the following mechanism: the compounds are oxidized with oxygen or oxidases surrounding them to have highly reactive quinone structure; and the oxidized compounds react with substances causing stenches. In the present invention, polyphenol oxidases are intentionally made to coexist with the compounds. According to the present invention, it is expected the auto-oxidation would be promoted and that the stenches can be removed in a short time and at a high deodorizing rate. 
     In summary, an aspect of the present invention is a deodorant composition comprising at least one phenolic compound and at least oxidase capable of oxidizing said phenolic compounds. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The phenolic compounds, which are one ingredient of the deodorant composition according to the present invention, include compounds having one or more of phenolic hydroxyl groups. The term &#34;phenolic hydroxyl group&#34; used herein stands for a hydroxyl group directly bonded to an aromatic ring like the benzene ring. The aromatic ring may be any of benzene, pyridine, thiophene, naphthalene, biphenyl, and other aromatic rings which have a structure to be converted into ketones by oxidation of hydroxyl groups. Benzene ring is most preferred. 
     The examples of the phenolic compounds may include diphenols such as catechol, 4-methylcatechol, 5-methylcatechol, resorcinol, 2-methylresorcinol, 5-methylresorcinol, and hydroquinone; biphenyldiols such as 4,4&#39;-biphenyldiol and 3,4&#39;-biphenyldiol; catechins such as (+)-catechin, (-)-epicatechin, (-)-epigallocatechin, (-)-epigallocatechin gallate; and catechol derivatives such as dopa, dopamine, chlorogenic acid, caffeic acid, paracoumaric acid, tyrosine. Preferable are catechol, catechins, tyrosine and chlorogenic acid, and particularly preferable are catechins and chlorogenic acid. 
     Two or more of the above-described compounds may also be used together in the present invention. 
     The enzymes capable of oxidizing the phenolic compounds, which are the other ingredient of the deodorant composition according to the present invention, include the following types of enzymes: enzymes which has a function of oxidizing the above-described phenolic compounds into compounds having the quinone structure; and oxidases of the same kind which has a further function of adding phenolic hydroxyl groups and oxidizing the resultants into quinones. The oxidases to be used are not limited as long as they have the above-described function. The examples of such oxidases may include polyphenol oxidases, monophenol oxidases, oxidases forming hydrogen peroxide, and peroxidases. More specifically, preferable are laccases, tyrosinases, glucose oxidases, and peroxidases. The above-described oxidases may also be used in combination thereof. 
     Further, substances or compositions that contain any of the above-described enzymes should fall within the scope of the enzyme according to the present invention which can oxidize the phenolic compounds. The example of such substances or compositions are extracts of plants or microorganisms containing the above-described enzymes, and powders such as acetone powders, prepared from the plants or the microorganisms. Preferred plants containing the above-oxidases are fruits and vegetables such as apples, pears, peaches, plums, apricots, cherries, burdocks, potatoes, eggplants and chicory. Also preferred microorganisms are fungi classified under genus Agricus or the genus Boletus such as A. bisporus, B. pulverulentus and B. subvelutipes. 
     While enzymes commercially available can be used for the present invention, they can also be prepared by any suitable method publicly known before the filing date of the present application. 
     In addition to the above-described two ingredients, carrier materials, stabilizers, bulking agents and other conventional additives may optionally be added or blended. 
     The deodorant composition according to the present invention can quench stinking substances, for example, sulfur-containing compound such as mercaptan, and nitrogen-containing compound such as indole, skatole, and amines. 
     The deodorization using the deodorant composition of the present invention is achieved by subjecting the composition to contact reaction in the presence of the stinking substances. For easy progression of the reaction, it is desirable to mix the composition and the stinking substances. On mixing, presence of water is advantageous since the reaction progresses smoothly. 
     Though the temperature for the deodorization is not limited as long as it is set within a temperature range where the enzymatic reaction progresses, the ambient temperature is suitable to mixing because the reaction quickly progresses. The reaction time from a few minute to some ten hours are usually enough for the deodorization, though it depends on the types of the enzymes and amount of the composition used. 
     Other reaction conditions can be optionally set without any limitation, provided that the oxidation reaction progresses in the conditions. 
     The present invention will be further illustrated with the following examples, which are not directed to limiting the scope of the present invention. 
    
    
     REFERENTIAL EXAMPLE 1 
     The below-described method is a preparation method for producing an enzyme capable of oxidizing phenolic compounds, namely, the preparation method for producing an acetone powder. 
     Four hundreds milliliters of acetone at -20° C. was added to 100 g of a plant or a fungus (such as apples or burdocks as described in below Examples), and the mixture was subjected to homogenization with a mixer followed by aspiration filtration. The residue was sufficiently washed with 500 ml of 80% acetone solution at 5° C. After removal of acetone, the residue was freeze-dried to obtain an acetone powder. 
     Examples 1-7 
     A commercially available enzyme (manufactured by SIGMA Chemical Co.) described in Table 1 was placed into a 30-ml vial at an amount described in Table 1 with 1 ml of water and 2 μl of 15% CH 3  SNa aqueous solution as a stinking substance. Then, 0.5 ml of an aqueous solution containing 2 mg of a commercially available substrate (a phenolic compound) described in Table 1. was added and the mixture was shaken with hands. The color of the reaction mixture changed by the shaking or standing for the time described in Table 1. Ten milliliters of the gas in the vial was then applied to a detector tube (manufactured by Gastec Co., Ltd.) to measure the concentration of the stinking substance which had remained in the gas. The results are shown in Table 1. 
     
                                           TABLE 1__________________________________________________________________________           Amount          Reading           of              of   Rate ofSample          Addition   Reaction                           Detector                                DeodorizationNo.    Enzyme   (mg) Substrate                      Time tube (%)__________________________________________________________________________Example 1  Tyrosinase*.sup.1           1    Catechol                      10 min.                           0    100                      or lessExample 2  Tyrosinase           1    (-)-Epi-                      3 hrs.                           0    100                catechinExample 3  Tyrosinase           1    Chlorogenic                      4.5 hrs.                           0    100                acidExample 4  Tyrosinase           1    Tyrosine                      2 hrs.                           0    100Example 5  Tyrosinase           1    Dopa  1.5 hrs.                           0    100Example 6  Peroxidase*.sup.2           0.4  Catechol                      1.5 hrs.                           0    100Example 7  Glucose oxidase*.sup.3           0.2  Glucose                      10 min.                           0    100  and           and   or less  Peroxidase           0.04 Chlorogenic                acidComparative 1  --       --   Chlorogenic                      4.5 hrs.                           48    0                acid__________________________________________________________________________ Note: Product number of the Enzyme; *.sup.1 : T7755, *.sup.2 : P8125, *.sup.3 : G6125 : Reading of detector tube is the value of the scale of the detector tube at the boundary of the color change. 
    
     Examples 8-14 
     Ten milligrams of the above-prepared acetone powder and 1 ml of water were placed in a 30-ml vial to make a suspension. Then, 2 μl of 15% CH 3  SNa aqueous solution was added to the suspension. Further, 0.5 ml of an aqueous solution containing 2 mg of a commercially available substrate (a phenolic compound) described in Table 2 was added and the mixture was shaken with hands for 10 min. Ten milliliters of the gas in the vial was then applied to a detector tube (manufactured by Gastec Co., Ltd.) to measure the concentration of the stinking substance which had remained in the gas. Further the gas was smelled for a sensory examination. The results are shown in Table 2. 
     
                                           TABLE 2__________________________________________________________________________  Material of Reading  Enzyme      ofSample (Acetone    Detector                   Rate of                          SensoryNo.    Powder)        Substrate              Tube Deodorization                          Examination__________________________________________________________________________Comparative 2  --    --    45   0      StinkingComparative 3  Apple --    50   0      StinkingComparative 4  --    Chlorogenic              47   0      Stinking        acidExample 8  Apple Chlorogenic              0    100    No        acid              stinkingExample 9  Burdock        Chlorogenic              0    100    No        acid              stinkingComparative 5  --    (-)-Epi-              47   0      Stinking        catechinExample 10  Pear  (-)-Epi-              0    100    No        catechin          stinkingExample 11  Burdock        (-)-Epi-              0    100    No        catechin          stinkingComparative 6  --    Instant              53   0      Stinking        CoffeeExample 12  Burdock        Instant              0    100    No        Coffee            stinkingExample 13  Pear  Instant              25   52.8   Slightly        Coffee            stinkingExample 14  Mushroom*.sup.4        Catechol              0    100    No  (A. bisporus)           stinking__________________________________________________________________________ Note: *.sup.4 ; The amount of the acetone powder was 40 mg. 
    
     Example 15 
     Three grams of a chewing gum (A) was prepared so as to contain 2 mg of chlorogenic acid and 10 mg of burdock acetone powder. For comparison, three grams of another chewing gum (B) was also prepared so as to contain 2 mg of chlorogenic acid. 
     Subjects (A) were forced to keep 0.5 g of grated garlic in their mouths for 5 min. to be rendered stinking, and rinsed their mouths with water. After the subjects (A) chewed the above-mentioned chewing gum (A) for 10 min., the halituses were collected individually in polyester bags and examined on the smells. The same procedure was carried out in subjects (B), except that they chewed the chewing gum (B) instead of the chewing gum (A). As a result, the each breath of the subjects (A) stank little while that of the subjects (B) still remains stinking of garlic. 
     Example 16 
     There were prepared 0.5 ml of an aqueous solution containing 2 mg of chlorogenic acid and 40 mg of burdock acetone powder. For comparison, there was prepared another 0.5 ml of the aqueous solution containing 2 mg of chlorogenic acid. 
     Subjects (C) were forced to keep 0.5 g of grated garlic in their mouths for 5 min. to be rendered stinking, and rinsed their mouths with water. The subjects (C) were then made to keep the above-mentioned 0.5 ml of the aqueous solution containing 2 mg of chlorogenic acid and the 40 mg of burdock acetone powder in their mouths for 5 min. After rinsing their mouths, the halituses of the subjects (C) were collected individually in the same manner described in Example 15, and examined on the smells. The same procedure was carried out in subjects (D), except that they were made to keep 0.5 ml of the aqueous solution containing 2 mg of chlorogenic acid alone in their mouths instead of the combination of the solution and the burdock acetone powder. As a result, the each breath of the subjects (C) stank little while that of the subjects (D) still remains stinking of garlic. 
     Example 17 
     Ten milligrams of an apple acetone powder was placed in a 30-ml vial with 1 ml of water and 20 μl of a fluid separated from excrement of domestic animals. Zero point five milliliters of an aqueous solution containing 2 mg of chlorogenic acid was further added to the mixture and shaken with hands for 10 min. The gas in the vial was then smelled for the sensory examination. For comparison, three mixtures were prepared. They had the same composition as the above-prepared mixture, except that one of them lacked 10 mg of the apple acetone powder, another of them lacked 0.5 ml of the aqueous solution containing 2 mg of chlorogenic acid, and the remaining of them lacked both the acetone powder and the solution chlorogenic acid. The mixtures were then treated in the same manner as the above, and gases derived from them were also smelled for the sensory examination. The results are shown in Table 3. 
     
                       TABLE 3______________________________________    Chlorogenic              AcetoneSample No.    acid      Powder   Sensory Examination______________________________________Comparative 7    None      None     Strong stench of amine and                       Stench of excrement                       existed.Comparative 8    Present   None     The stench of amine dis-                       appeared, while strong                       stench of mercaptan still                       remained.Comparative 9    None      Present  The stench of amine dis-                       appeared, while strong                       stench of mercaptan still                       remained.Example 17    Present   Present  Stenches disappeared.______________________________________ 
    
     Advantages of the Invention 
     In the deodorization method using the deodorant composition according to the present invention, a phenolic compound as the deodorant base material is activated by coexisting with an enzyme capable of oxidizing the compound, and by virtue of that, the oxidization reaction progresses in short time and an excellent deodorization effect can be obtained. The deodorant composition according to the present invention would have high safety by use of food materials such as vegetables and fungi as an ingredient, and therefore, can be used for prevention of bad breath. Further, the deodorant composition of the present invention can also be used for removal of environmental stenches without causing problems such as environmental contamination.