JPS642379B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a component obtained by extracting green tea with an organic solvent of alkyl ketones and heating it with an aqueous solution of caustic alkaline to saponify it, or a component obtained by heating green tea with an aqueous alkali solution and saponifying it, and then extracting it with an organic solvent of alkyl ketones. The present invention relates to a deodorizing agent characterized by containing a component obtained by extraction or a component obtained by heating green tea using an aqueous alkaline solution and alkyl ketones to simultaneously perform saponification and extraction. Conventional deodorization methods include masking bad odors with aromatic substances, decomposing odorous substances with oxidizing agents such as potassium permanganate to make them odorless, and methods of eliminating odors. The odor-causing substances are fixed using metal salts such as zinc sulfate, aluminum sulfate, and iron sulfate, such as ammonia and hydrogen sulfide, and neutralizing agents such as salts, nitric acid, caustic soda, soda carbonate, and bicarbonate of soda. There are methods such as making it odorless by making it odorless, and deodorizing it by adsorbing it on activated carbon. However, in these methods, the method of using a masking agent causes discomfort due to its own scent, and also causes oxidation, neutralization,
Methods based on immobilization and adsorption have drawbacks such as selectivity for odorous substances. On the other hand, in Japanese Patent Application Laid-Open No. 53-66434, active ingredients were extracted from plants of the Camellia family or Lauraceae family to deodorize and
It has been disclosed that it can be used as a deodorizing agent, and chlorophyll, a component of chlorophyll, is also widely known to have a deodorizing effect. Deodorizers are desired. As a result of various research, the present inventor focused on green tea,
The present invention was completed based on the knowledge that if the component is heated with caustic alkali to saponify it, it becomes a component with extremely excellent deodorizing properties. In addition to its excellent properties, the deodorizing agent obtained by the present invention has an extremely wide range of uses because it does not cause any harm when it comes into contact with the human body or even if it is eaten. The green tea used in the present invention is made by heating tea leaves with steam or roasting to deactivate the oxidizing enzymes contained in the leaves and retain the chlorophyll in the tea, such as sencha, gyokuro, Tencha etc. are used, but it is preferable to use one that has not been extremely heated. To produce the deodorizing agent of the present invention, green tea is first extracted with an organic solvent of alkyl ketones. The extraction is stirred at the boiling temperature of the solvent for 2 to 7 hours. As the organic solvent for the alkyl ketones, acetone, methyl ethyl ketone, cyclohexanone, isobutylethyl ketone, etc. are used, and among these, cyclohexanone is particularly preferred in view of its boiling point temperature and degree of extraction of active ingredients. Solvents other than alkyl ketones, i.e. aliphatic or aromatic hydrocarbons, such as n-pentane, isopentane, n-hexane,
Benzene, toluene, xylene, etc. are unsuitable because their polarity is low and the extraction effect of the active ingredient is unsatisfactory. Next, an aqueous caustic alkali solution is added to this extract and the mixture is heated and stirred at 50 to 100°C for about 3 to 5 hours.
Caustic soda and caustic potash are used as the caustic alkali, and the concentration thereof is about 2 to 20%, preferably 2.
Adjust to ~10%. After saponification, this is neutralized with an acid such as hydrochloric acid, sulfuric acid, acetic acid, etc., the organic solvent layer is separated, and the organic solvent is removed by distillation to obtain the desired product.
At this time, the product is shaped into powder, paste, or liquid depending on the product form and use. In other words, in addition to being used as a deodorizer without adding other ingredients, for example, it can be made into a powder by mixing dextrin, talc, etc.
Further, the product form can be adjusted depending on the application, such as by adding propylene glycol or the like to form a paste, or by using other solvents, such as ethanol, as a solution. When no other ingredients are added, it is a brown paste-like liquid with a faint green tea aroma and slight sweetness. In the process described above, the same product can be obtained even if the order of saponification and extraction is changed, or even if they are performed simultaneously. Sunahachi, Mazu green tea and 5%
Aqueous caustic potassium solution of about 4 to 70℃ at 60 to 70℃
After heating and stirring for 5 hours, the mixture is neutralized with acid and thoroughly extracted with an organic solvent such as an alkyl ketone to drive off the solvent to obtain the desired product. Furthermore, the desired product can be obtained from the organic solvent layer by mixing green tea, an organic solvent of alkyl ketones, and an aqueous caustic solution, heating the mixture, saponifying it, and neutralizing it with an acid. The deodorizing agent of the present invention obtained in this manner is composed of flavanols, flavones, flavonols, flavanones, and other flavone-based compounds, organic acids such as tannic acid, and other unsaturated aldehyde compounds, which come from the raw material green tea, and which bind off-odor components. It is thought to exhibit deodorizing and deodorizing effects, and in particular, it is thought that components containing sulfur or nitrogen in off-flavor components, especially those with low molecular weight, are combined to form macromolecules and become odorless. Components in green tea are converted into glycosides through a reaction such as saponification by heating with an alkaline aqueous solution, which is a feature of the present invention. It is thought that the deodorizing effect is further improved. This relationship will be explained by way of examples. The deodorizer of the present invention is
It is made from green tea, and in addition to its excellent deodorizing properties, it is harmless even if it comes into direct contact with human skin, and is edible, so it can be used in a wide range of applications. In addition, the dosage form can be easily adjusted to powder, liquid, paste, etc. depending on the intended use. Applications include shampoo to remove bad odors, hair tonic, conditioner, addition to soap, lipstick without oily odor, nail lacquer, cold perm liquid without thioglycolic acid odor, hair dye without ammon odor, bath Salt, rinsing liquid for wet towels, deodorizing spray for rooms and toilets, deodorizing agents for factory exhaust, agents for filter-type air purifiers, garbage bags, etc. To remove odor from the mouth, toothpaste, powdered toothpaste, etc. mouthwash,
Furthermore, it can be added to chewing gum and canned food to eliminate mouth odor, and it can also be added during the production of canned goods to remove can odor, and it can be added during the production of soy milk to obtain products that do not have a grassy odor. It can be used in a wide range of fields, such as processing food products such as cigarettes, removing pungent odors by adding it to cigarettes, and removing chemical odors by adding it to paints. Next, the present invention will be explained with reference to Examples. Example 1 Put 10 kg of green tea into a 300° stainless steel pot, add 200° cyclohexanone, and heat at 150 to 160°C for 50 minutes.
Stir for hours. After cooling to room temperature, take out the liquid from the bottom of the pot, transfer the remaining part in the pot to a centrifuge, centrifuge, mix the separated liquid with the previous bottom liquid, and leave it in a sedimentation tank for 24 hours. I left it still. 170% of the supernatant liquid was separated and charged into a 1000% stainless steel pot, 5 kg of caustic soda and 100% of water were added, and the mixture was stirred at 70°C for 3 hours. After the reaction is completed, cool and add 2% sulfuric acid aqueous solution 320
After neutralization using 100% water and stirring, the solvent layer was separated, 100% water was further added, stirred, separated, and washed with this water three times. After washing with water, remove the solvent layer at 50-100℃/20mmHg.
The solvent was removed by distillation to obtain 1.1 kg of brown paste. Propylene glycol 50% was added to this, stirred to make it homogeneous, and filtered through a 300 mesh stainless steel mesh to obtain a product. Example 2 10kg of 5% sodium hydroxide solution in 10kg of green tea,
Cyclohexanone 150 was placed in a 500 stainless steel pot and stirred at a temperature of 70°C for 5 hours to saponify it. After cooling, the reaction solution was centrifuged to remove tea scum, and the solution was neutralized with 5% sulfuric acid aqueous solution 130%, separated, and diluted with water 70%
Add and wash. After performing the washing operation twice, the oil layer is concentrated and cyclohexanone is recovered at 50-100°C under 20 mmHg to obtain 1.2 kg of brown paste. Example 3 Add 100 g of 5% potassium hydroxide aqueous solution to 10 kg of green tea.
Prepared in a 500 stainless steel pot and heated at a temperature of 60 to 70℃.
Stir for ~5 hours to saponify. After cooling, the reaction solution was centrifuged to remove tea dregs, and the liquid part was mixed with a 5% sulfuric acid aqueous solution.
90, add isobutyl ethyl ketone 100 and decompose and extract. The oil layer is washed twice with 100% saturated saline solution, and the oil layer is concentrated under the conditions of Example 2 to obtain 1.1 kg of brown paste. Example 4 20 ml of water was added to 10 kg of green tea, left to swell for a while, and then processed in a crush mill to obtain 9.2 kg of paste of 100 to 200 mesh passes. Next, put the green tea paste into a 500 stainless steel pot, add 80 kg of 6% sodium hydroxide aqueous solution and 150 kg of cyclohexanone.
Add. Saponify by stirring at a temperature of 70-75°C for 5 hours. After cooling, the reaction solution is neutralized with 130% 10% aqueous hydrochloric acid solution, centrifuged, and the solvent portion is separated. more water
Add 70 and wash. After washing twice, add propylene glycol 10 to the cyclohexanone part.
After adding Kg, collect cyclohexanone at 50-100℃ at 20mmHg and brown propylene glycol liquid.
Gain 11.1Kg. Furthermore, store this in a -20℃ refrigerator.
After storage for a week, a brown precipitate settled in the lower layer obtained.
Gain 0.5Kg. After washing with water and drying under reduced pressure, 0.3 kg of brown powder was obtained.
get. Example 5 An adsorption power test was conducted on the product of the present invention obtained in Example 1 and a product obtained by simply extracting green tea with an organic solvent (referred to as green tea extract). (1) Adsorption power test test method using trimethylamine 0.5 g each of the product of the present invention and green tea extract were placed in a 100 ml vial and sealed. Apply gas containing 0.5 mg of trimethylamine using a gas-tight syringe.
It was injected into a sealed vial. After 1 minute, 3 minutes, 10 minutes and 20 minutes of standing at room temperature, 1 ml of the gas in the vial was injected into the gas chromatograph. Gas chromatograph conditions: Column; Chromosorb W (60/80) Glass; 3mmφ×2.0m Temperature; Oven: 80℃, Injection: 200℃,
Detector: 200℃ Carrier Gas; N ₂ : 2.6Kg/cm ² , H ₂ : 0.5Kg/
cm ² , Air: 1.0Kg/cm ² Chart Speed: 10mm/min Type: Hitachi 063 (FID) Test results The residual rate of trimethylamine was determined with the control at each measurement time as 100. The results were as follows. . Trimethylamine residual rate (unit %)

[Table] (2) Adsorption power test using ethyl mercaptan In the test in (1) above, 5 g of the sample was used instead of 0.5 g, and 0.2 mg of ethyl mercaptan was used instead of 0.5 mg of trimethylamine.
The following results were obtained by slightly changing the gas chromatograph conditions and performing the same procedure. Ethyl mercaptan residual rate (unit: %)

[Table] (3) Adsorption power test using ammonia Put 0.5g of the sample into a 100ml vial,
Sealed. 28% ammonia water in an Erlenmeyer flask 10
ml was taken, the double cap was sealed, and after leaving it at room temperature, 3 ml of ammonia gas was injected into the vial using a gas-tight syringe. Below, the carrier gas of the gas chromatograph is He: 80ml/min
Use Oven temperature: 150℃, Injection: 170℃
℃, Detector: The same operation as in test (1) was performed at 170℃, and the following results were obtained. Ammonia residual rate (unit %)

[Table] (4) Adsorption power test using hydrogen sulfide 5 g of the sample was placed in a 100 ml vial and sealed. Take iron sulfide in an Erlenmeyer flask, add IN sulfuric acid, seal it with a double cap, and leave it at room temperature.
7 ml of hydrogen sulfide gas was injected into the vial using a gas-tight syringe. Below, the carrier gas of the gas chromatograph is He; 60 ml/min, the temperature is
Oven; 110℃, Injection; 170℃, Detector;
The same procedure as in test (1) was carried out at 150°C, and the following results were obtained. Hydrogen sulfide residual rate (unit: %)

[Table] Example 6 (Hair tonic) Formula: (weight ratio) Ethanol (95%) 80 Castor oil 10 Resorcin monoacetate 2 Glycerin 0.5 Inventive product of Example 1 1 Water 6.5 100 Hair tonic made with the above formulation and , and the additive-free product of the present invention, the following tests were conducted on four male models. A comparison test was conducted between a product with the extract paste added and a product with no additives by having four men go about their daily lives for one week after washing their hair without using any hair conditioners. The test method is to test 10 times each for additives and non-additives.
ml of the product was applied to the hair, massaged thoroughly for 2 minutes, and then subjected to a sensory test and evaluated on the following 5 scales. Very strong sweat odor +2 Strong +1 Slight sweat odor 0 None -1 Not at all -2 Result:

[Table] The above results completely deodorized the sweat of men who did not wash their hair for a week. Example 7 (Toothpaste) Prescription: (Weight ratio) Dibasic calcium phosphate 42 Glycerin 17 Carrageenan 1 Sodium lauryl sulfate 1.1 Sucrose fatty acid ester 2 Inventive product obtained in Example 1 1.1 Butyl paraoxybenzoate 0.005 Appropriate amount of water 100 This paste The following panel test was conducted regarding toothpaste. Specifically, 6 men milled 10 g of onion with 100 c.c. of water, each put 1 c.c. into their mouths for 2 minutes, and then rinsed twice with 100 c.c. of water. After this, the three people brushed their teeth with the above prescription, and the other three
A person may use toothpaste without the addition of the present invention in the above prescription.
About these 6 people who brushed their teeth for 2 minutes using
A panel of 10 people examined the lingering scent. The residual fragrance was evaluated according to the following five grades. Very strong +2 Strong +1 Slightly 0 None -1 Not at all -2 Result:

[Table] * indicates a toothpaste using the above formulation containing the product of the present invention.
As a result, when the toothpaste containing the product of the present invention was used, the onion flavor completely disappeared. Example 8 (Chewing gum) Prescription: (weight ratio) Vinyl acetate resin 27 Ester gum 10 Polyisobutylene 27 Wax 20 Monoglyceride 1 Calcium carbonate 14 Invention product 1 of Example 1 100 Chewing gum obtained with the above formulation and the invention product Five men and women each chewed the additive-free product for about 5 minutes, and another five panelists evaluated the sensory evaluation. In other words, 100g of onion was finely chopped, 900ml of water was added, and five men and women each were asked to gargle several times with 100ml of onion-containing water.
The chewing gum obtained from the above formulation was chewed for about 5 minutes, and a sensory evaluation was performed by five panelists. This was evaluated in the following five stages. Very strong slope +2 Strong +1 Slightly 0 None -1 No slope at all -2

[Table] As a result, chewing chewing gum containing 1% of the product of the present invention had a remarkable effect on masking onion odor. Furthermore, when an additive-free product was similarly chewed, no onion odor masking effect was observed. Example 9 (Soy milk) Recipe: 100 ml of soy milk (purchased from a commercial tofu shop) 1 g of extracted paste Add 1 g of extracted paste to 100 ml of soy milk and stir for 30 minutes.
Do this for a minute to make it even. The deodorizing effect on the grassy taste peculiar to soy milk was measured using the following test. A sensory test was conducted by having 10 panelists put about 10 ml of the above formula and the soy milk only into their mouths.

【table】 Items that I felt were completely free of grassy taste -2 Items that I felt had a slightly grassy smell -1 Something with a grassy smell +2 Result The grassy taste of soy milk was almost completely eliminated.

Claims (1)

[Claims] 1. A component obtained by extracting green tea with an organic solvent of alkyl ketones and then heating and saponifying it with an aqueous caustic alkali solution, or a component obtained by heating green tea with an aqueous caustic alkali solution and saponifying it, and then extracting it with an organic solvent of alkyl ketones. A deodorizing agent characterized by containing a component obtained by heating green tea using an aqueous caustic alkali solution and an alkyl ketone, and simultaneously saponifying and extracting it.