JP2005298246A - Oxygen generator and method for using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen generator which less suffers from an enzyme activity lowering even when the constituent catalase is used in combination with a hydrogen peroxide adduct and therefore has excellent storage stability. <P>SOLUTION: The oxygen generator comprises a hydrogen peroxide adduct such as sodium percarbonate, catalase (especially preferably in the form of a hydrogen-peroxide-adduct-resistant catalase formulation prepared by adding a stabilizer such as ethanol or sodium glutamate to catalase, forming the mixture into a powder, and coating and granulating the powder with a coating agent), and a phosphate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an oxygen generator excellent in storage stability, in which a hydrogen peroxide adduct, a catalase preparation and a phosphate are mixed, and a method for using the oxygen generator.

  In recent years, the industrial role played by enzymes has been increasing, and catalase is also widely used as a decomposing agent for hydrogen peroxide used in food, fiber, machinery, electronics industry, and the like.

  On the other hand, hydrogen peroxide adducts are used as safer bleaching and foaming components without the risk of chlorine gas generation instead of chlorine bleach, and are used as contact lens cleaners, bath tub cleaners, and washing tubs. Cleaners, pipe cleaners, automatic foaming soaps, automatic dishwasher detergents, kitchen cleaners such as sinks and drains, bathroom cleaners such as bathtubs and drains, toilet cleaners, drain pits Widely used as sanitary, medical, and industrial materials as cleaning agents for precision parts, cleaning agents for textile processing, bleaching agents, mold removers, pressurizing agents for spraying, oxygen generators for suction, etc. Has been.

  However, the free decomposition of hydrogen peroxide, which occurs when the hydrogen peroxide adduct is dissolved in water, is slow in speed, so that it takes a long time for the treatment, or it is heated if it is effective in a short time. Operations that increase the degradation rate, such as treatment and enzyme treatment, must be taken. Therefore, as a method of increasing the decomposition rate of hydrogen peroxide released from the hydrogen peroxide adduct by coexisting with the hydrogen peroxide adduct, peroxide particles are microencapsulated and the catalase is adhered to the outer surface. In addition, an oxygen generator (see, for example, Patent Document 1), a bath cleaner (see, for example, Patent Document 2) composed of a catalase and a hydrogen peroxide adduct held in liquid form or on a carrier, and the like are proposed.

However, the above-mentioned catalase of oxygen generator and bath tub cleaning agent is affected by oxidation based on the hydrogen peroxide adduct when the hydrogen peroxide adduct and the catalase are mixed and stored. There was a problem in that the enzyme activity of the protein decreased rapidly. Therefore, as a matter of fact, it is necessary to store the powdered catalase or the aqueous solution of catalase separately from the hydrogen peroxide adduct and to mix it immediately before use, and there is a problem that the method of use becomes complicated. For this reason, there has been a demand for an oxygen generator mixed with a stable catalase which is not affected by the hydrogen peroxide adduct and is not affected by the enzyme activity. There was no proposal of an oxygen generator that solved this problem.
JP-A-6-107401 JP-A-8-283788

  An object of the present invention is to provide an oxygen generator and its use, in which the enzyme activity is unlikely to decrease even in the presence of a hydrogen peroxide adduct and catalase.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and have completed the present invention.
That is, the present invention is an oxygen generator containing a hydrogen peroxide adduct, catalase and phosphate.

  If the oxygen generator of the present invention is used, it can be commercialized in the form of an integrated product in which a hydrogen peroxide adduct and catalase are mixed. Therefore, it is possible to solve the problem that the catalase and the hydrogen peroxide adduct had to be separated as in the prior art. In this way, the characteristic that oxygen can be generated simply by adding water without the need for two-component mixing for ergonomics greatly contributes to the industry by promoting the downsizing of oxygen generators and the versatility of applications. is there.

  Catalase can be used regardless of origin such as animals, plants, microorganisms, etc., and commercially available catalase can also be used. Among them, it is particularly preferable to use a hydrogen peroxide-resistant adduct catalase preparation that is powdered by adding a stabilizer to catalase and then coated and granulated with a coating agent.

  Catalase powder for producing a hydrogen peroxide-resistant adduct catalase preparation, for example, after adding ethanol or ethanol and sodium glutamate as a stabilizer to catalase, fine powder, granule, small lump What was processed into the powder can be used. Among them, it is preferable to process into a granule which is low in hygroscopicity and easy to operate because of its small surface area. Examples of the method for treating catalase into granules include using a fluid granulator, a high speed mixer, a spray dryer, an extrusion granulator, etc., and spraying a catalase solution onto a nucleating agent or drying a catalase solution. The obtained powder can be bound to a nucleating agent, or a catalase granule can be obtained directly from a catalase solution. The nucleating agent may be any substance that does not inhibit the expression of catalase activity, and commonly used starch, dextrin, sucrose, salt and the like are used.

  The amount of ethanol added to the catalase to produce a hydrogen peroxide-resistant adduct catalase preparation is preferably 3 v / v% or more with respect to the catalase solution before the pulverization treatment subjected to desalting treatment or the like. / v% or more is more preferable. Further, the amount of sodium glutamate to be added together with ethanol as required is preferably 50 w / w% or more based on the solid content weight of the catalase solution before the powdering treatment, which has also been desalted. Thus, by adding ethanol or ethanol and sodium glutamate to catalase, the storage stability of the catalase preparation can be enhanced to some extent. When powdering a catalase solution, a substance that does not inhibit catalase activity may be added in addition to ethanol or ethanol and sodium glutamate.

  However, in order to maintain good storage stability over a long period of time even if it coexists with a hydrogen peroxide adduct, it is further allowed to coexist with the hydrogen peroxide adduct by coating with a specific coating agent. Even catalase preparations that are enzymatically stable can be obtained. In addition, since the hydrogen peroxide-resistant adduct catalase preparation needs to avoid moisture until it is used, it is preferable that the coating agent to be coated has a low hygroscopic property and a high drying property. Examples of the coating agent include saccharides. As specific examples of the saccharide, trehalose, lactose, maltose and the like are preferable, and among them, trehalose is more preferable. For coating agents other than saccharides, polyethylene glycol, paraffin, sodium sulfate and the like are preferable. The ratio of the coating agent to be coated is preferably 0.5 w / w% or more, more preferably 10 to 20 w / w%, based on the weight of the powdered catalase preparation. The coating agent may be one or more selected from low hygroscopic and high drying sugars, polyethylene glycol, and paraffin, and the low hygroscopic and high drying sugar may be trehalose, lactose, or maltose.

As the hydrogen peroxide adduct, a substance capable of liberating hydrogen peroxide in an aqueous solution, such as a percarbonate such as sodium percarbonate, a perborate such as sodium perborate, urea peroxide or the like can be used.
As the phosphate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate and the like can be used. Sodium is preferably used.

  The mixture of hydrogen peroxide adduct, catalase, and phosphate may be in any form of fine powder, granule, powder, small lump, and tablet. The mixing ratio of the hydrogen peroxide adduct and catalase is not particularly limited, but the catalase is preferably 0.001 w / w% or more of the hydrogen peroxide adduct. The mixing ratio of the hydrogen peroxide adduct and phosphate is preferably 1:10 to 10: 1 by weight.

  A desiccant can be blended in the oxygen generator of the present invention. The type of desiccant is not particularly limited, but it is preferable to use at least one selected from silica gel, activated alumina, and zeolite in consideration of performance and ease of handling. Furthermore, you may mix | blend soap components, such as surfactant, in order to increase detergency.

  The mixing method of hydrogen peroxide adduct, catalase, and phosphate is only required to be mixed without using a solvent such as water, but if necessary, mixing with a mixer such as a rotary type, a vibration type, or a stirring type. May be. When tableting, add hydrogen peroxide adduct, catalase and phosphate with excipients, binders, lubricants, mix with rotary type, vibration type, stirring type etc. Etc. to make a tablet.

  Oxygen generating agent of the present invention, contact lens cleaner, bath tub cleaner, laundry tub cleaner, pipe cleaner, automatic foaming laundry soap, automatic dishwasher detergent, kitchen cleaner such as sink / drain, bathtub・ When using as a cleaning agent for bathrooms such as drains, cleaning agents for toilets, cleaning agents for drain pits, cleaning agents for precision parts, cleaning agents for textile processing, bleaching agents, and mold removal agents At least one of an anionic, cationic, amphoteric and nonionic surfactant, builder, chelating agent, fragrance, acid, alkali and the like can be added to the mixture.

  As an anionic surfactant, alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester thereof, alkyl aether carboxyl Acid salts, alkenyl ether carboxylates, fatty acid salts, alkyl phosphates and the like can be mentioned. Examples of the cationic surfactant include alkyltrimethylammonium salts, and examples of the amphoteric surfactant include carbobetaine type and sulfobetaine type amphoteric surfactants.

As nonionic surfactants, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyalkylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, Examples thereof include alkyl glucoside, alkyl glucose amide, alkyl amine oxide, and pluronic type nonionic surfactant. When these surfactants are added, one kind may be used or a plurality of kinds may be mixed and used. Moreover, it is sufficient to add a mixture of a hydrogen peroxide adduct and a hydrogen peroxide adduct resistant catalase preparation to an existing powder soap.
Moreover, when using as a pressurizing agent for spraying, an oxygen generating agent for suction, etc., solid chelating agents, perfumes, acids, alkalis, and the like can be added.

To use as a cleaning agent, a mixture of a hydrogen peroxide adduct and a hydrogen peroxide-resistant adduct catalase preparation is added to the object to be cleaned, and water or hot water of 70 ° C. or lower, preferably 50 ° C. or lower, is added. Stir accordingly. The mixture may be added after filling with water or hot water.
As a method for using as an oxygen generator, a mixture of a hydrogen peroxide adduct and a hydrogen peroxide-resistant adduct catalase preparation is put into a container, and water or hot water of 70 ° C. or lower, preferably 50 ° C. or lower, is filled. And stir. The mixture may be added after filling with water or hot water. However, when inhaled by humans, it is preferable to reduce the decomposition rate of hydrogen peroxide by using water at room temperature instead of hot water in order to lengthen the oxygen generation time.
When used as a pressurizing agent for spraying, for example, the desired contents are put into a spray can, and then a mixture of a hydrogen peroxide adduct and a hydrogen peroxide resistant catalase preparation is put into the lid of the spray can. Is closed and oxygen is generated in the spray can and pressurized.

  For example, when sodium percarbonate is used as the hydrogen peroxide adduct, the oxygen generator of the present invention can generate 3 moles of oxygen from 4 moles of sodium percarbonate. It is determined according to the amount of oxygen to be performed. Catalase catalyzes the generation of oxygen by decomposition of hydrogen peroxide adducts. When oxygen is generated in a short period of time, the amount of mixing is increased or the reaction temperature is increased, and oxygen is gradually generated over a long period of time. In some cases, the oxygen generation time can be controlled by reducing the mixing amount or lowering the reaction temperature.

  Next, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.

Production Example (Production of Catalase Formulation)
A 6,000 ml catalase solution (Ask Super: manufactured by Mitsubishi Gas Chemical Co., Ltd.) was concentrated 6 times using an ultrafiltration module (Microza UF Lab Module ACP-1010: manufactured by Asahi Kasei Kogyo Co., Ltd.), and then concentrated into a concentrated solution. The operation of adding an equal amount of water and desalting the concentrated solution was repeated three times. About 1,000 ml of the obtained solution, 50 w / w% of ethanol 5.0 v / v% and sodium glutamate were added to the weight of the solid content of the liquid. The solution is sprayed onto 4,000 g of non-parrel 101 (manufactured by Freund Sangyo Co., Ltd.), which has been fluidized, using a flow granulator flow coater FLO-5 (manufactured by Freund Sangyo Co., Ltd.), dried and granulated. A catalase preparation was obtained.
Next, 400 g (10.0 w / w%) of trehalose of 10.0 w / w% is coated and granulated with 4,000 g of the granular catalase preparation to form a granular hydrogen peroxide adduct resistant catalase preparation. Obtained.

Example 1
[Oxygen generation by mixture of hydrogen peroxide adduct and hydrogen peroxide resistant catalase preparation]
A test sample of oxygen generator was prepared by adding 0.10 g of the catalase preparation shown in the production example to 10 g of sodium percarbonate (SPC-G manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 10 g of sodium dihydrogen phosphate and mixing them well.
Add 200 ml of purified water to a 300 ml Erlenmeyer flask and adjust the temperature to 25 ° C. Add the entire amount of the test sample under magnetic stirrer stirring, leave it at 25 ° C for 5 minutes, and measure the amount of oxygen generated during that time with a graduated cylinder. As a result, it was 730 ml.
As a storage stability confirmation test, a test specimen was taken in a polyethylene container, stored at 37 ° C., and after 2 months, the amount of oxygen generated was measured in the same manner as described above.

Example 2
Furthermore, it carried out like Example 1 except mixing 1g of silica gel. The oxygen generation amount of the oxygen generator immediately after mixing was 730 ml, and the oxygen generation amount after 2 months of storage was 710 ml.

Comparative Example 1
It carried out like Example 1 except not using sodium dihydrogen phosphate. The oxygen generation amount of the oxygen generator immediately after mixing was 720 ml, and the oxygen generation amount after 2 months of storage was 470 ml.

Claims (8)

  An oxygen generator containing hydrogen peroxide adduct, catalase and phosphate.   The oxygen generator according to claim 1, wherein the hydrogen peroxide adduct is one or more selected from percarbonates, perborates, and urea peroxide.   2. The oxygen generator according to claim 1, wherein the catalase is a hydrogen peroxide-resistant adduct catalase preparation that has been powdered by adding a stabilizer to the catalase and then coated and granulated with a coating agent.   The oxygen generator according to claim 3, wherein the stabilizer is ethanol, or ethanol and sodium glutamate.   The oxygen generator according to claim 1, wherein the phosphate is sodium dihydrogen phosphate.   Furthermore, the oxygen generator of Claim 1 containing a desiccant.   The oxygen generator according to claim 6, wherein the desiccant is at least one selected from silica gel, activated alumina, and zeolite.   The oxygen generating agent according to any one of claims 1 to 7, comprising a contact lens cleaner, a bath cleaner, a washing tub cleaner, a pipe cleaner, an automatic foaming laundry soap, an automatic dishwasher detergent, and a kitchen cleaner. , Bathroom cleaners, toilet cleaners, drain pit cleaners, precision parts cleaners, textile processing cleaners, bleaching agents, mold removers, spray pressurizers, and oxygen generation for suction Method used as an agent.