JPWO2011040424A1 - Deodorizing agent with sterilizing function, deodorizing material with sterilizing function, dropping supply device for deodorizing function with sterilizing function, spraying method of deodorant with sterilizing function - Google Patents

Abstract

(A) Peroxide, (B) catechins, and (C) a deodorizer with a sterilization function characterized by containing a proteolytic enzyme agent; A deodorizing material, a dropping supply device of a deodorant with a sterilizing function, a dropping supply method of a deodorant with a sterilizing function, and a spraying method of a deodorant with a sterilizing function.

Description

  The present invention provides sterilization functions against harmful bacteria and malodorous components, particularly Salmonella, Escherichia coli, Staphylococcus aureus, fungi, viable bacteria having a protein structure, and a deodorizing function against hydrogen sulfide odor, methyl mercaptan odor, ammonia odor, trimethylamine odor, etc. The present invention relates to a deodorizing agent with a sterilizing function, a deodorizing material with a sterilizing function, a dropping supply device for the deodorizing function with a sterilizing function, and a spraying method of the deodorizing function with a sterilizing function.

Japan is one of the world's leading consumers of deodorizing and decontaminating antibacterial and antibacterial antibacterial agents, with over 28,000 tons per year. In particular, there is a close relationship between odor and generation of harmful bacteria in daily life and production life. Inside various automobiles, hotel rooms, smoking rooms, inside and outside kitchen facilities, inside and outside animal breeding facilities, inside toilets, shoe boxes, closets, waste liquid storage tanks, etc. The use of food and spices, the discharge of excrement and the storage of products that are closely related to daily life make it an environment where odors and harmful bacteria are likely to be generated. Produce. Therefore, the deodorizing and deodorizing agent and the disinfecting antibacterial agent are strongly required to have both a quick and reliable deodorizing and deodorizing ability, a disinfecting ability, and a recurrence preventing function. At present, many deodorizing and deodorizing agents and harmful bacteria removing agents have been proposed against these backgrounds, but few have the functions of quick deodorizing and antibacterial antibacterial effects with one agent when in use. .

  Harmful bacteria that occur in the life of human beings and animals include Salmonella, Escherichia coli, Staphylococcus aureus, fungi including fungi, live bacteria, etc. Also, bad odors include hydrogen sulfide, methyl mercaptan, ammonia, trimethylamine, etc. Odor components are present alone or in combination. The main generation factors include foods and drinks, residue, sludge decay, physiological phenomena such as body odor, dust adhering to the human body and animal bodies, filth adhering to daily commodities, etc. If this occurs, there is a concern that it may adversely affect the human body, such as food poisoning, nerve paralysis, and oxygen deficiency.

  The main cause of bad odor is that the decay of things progresses due to the growth and propagation of harmful bacteria that inhabit the water and air, and it is accompanied by bad odor. Therefore, the deodorizing and deodorizing agent contains many components that disinfect and remove harmful bacteria. For example, antibacterial antibacterial components such as 8-hydroxyquinoline, isothiazoline, formaldehyde, acetic acid, boric acid, chlorophyll, benzalkonium chloride, chlorhexidine, saponin, and organic surface active components are generally well known. Although these components are highly effective, depending on the concentration of the components, there are many concerns about the safety to human bodies and the like because they are often positive for mutagenicity in safety tests and the like.

  In addition, it is generally known that a large amount of aroma deodorants such as inorganic, organic, synthetic, and natural fragrances and alcohol and oil are blended as masking additives in the deodorant and the like. ing. For example, there is a functional article (see Patent Document 1) containing an additive for deodorization and proanthocyanidins. In addition, these aroma deodorizing materials have an effect of relieving mental feelings including calmness in their use, but have a poor ability to act on disinfecting antibacterial properties and deodorizing properties. In addition, there are those that are limited in its use, such as loss of active ingredients due to volatilization and elution and precipitation of residual components, and it is expensive because it is difficult to synthesize industrially and mass production is not possible. Many.

  In the functional aspect of deodorant deodorizers, there are few that have the function of directly removing bad odor sources such as hydrogen sulfide odor, methyl mercaptan odor, ammonia odor and trimethylamine odor only by decomposition action. Many of them attempt to deodorize and deodorize indirectly by using a masking action by a fragrance, an adsorption action by activated carbon, and a suppression action by a stabilizer. For example, there is a defecation deodorant (see Patent Document 2) in which a chelate compound, eggplant vinegar, dietary fiber, gelatin, polyphenol is supported on the surface of activated carbon. In addition, the deodorized and deodorized substances obtained by these functions are re-separated from the support material, etc. due to changes in various physical use conditions such as temperature, pressure, pH value, weather, and other environmental conditions. There is concern about the possibility of acting.

  For deodorizing and deodorizing agents, natural minerals such as zeolite, ammonite and bentonite as well as stimulating compounds such as wasabi and chili are used as active ingredient materials for deodorizing deodorants in order to supplement the deodorizing and deodorizing antibacterial activity. It is known to be used as For example, there are deodorant cleaning agents for crops (see Patent Document 3) comprising a water-soluble composition containing a surfactant, an enzyme, a component having a deodorizing component, and an irritating compound.

  In addition, as a support for the deodorant and deodorizer, a fired solid such as coal ash, an artificial inorganic material using ceramic particles such as hydroballs, and a solid resin or gel resin such as urethane resin, phenol resin, or polyacrylic acid resin In general, a holding material for a deodorant and deodorant having water retention is known. For example, there is a composite deodorizing and deodorizing material (see Patent Document 4) including a green mineral powder having a deodorizing function, natural mineral zeolite powder particles having a large adsorption function such as nitrogen, and bamboo charcoal short pieces having a high deodorizing function.

  In addition, in the above-mentioned artificial inorganic materials and solid resin bodies and gel resin bodies that have water retention properties, those that utilize water retention and transpiration characteristics made of components such as minerals, natural products, and polyacrylic resin as raw materials. Is often used as a holding material, but depending on the chemical nature of the adsorbed and dissipated components and the physical environment such as high temperature and humidity, the adsorption and dissipating properties may vary, promoting decomposition into malodorous components and floating in the air There is a risk that the efficacy of sterilizing harmful bacteria tends to become unstable.

  In a device for spraying or supplying a deodorant / deodorant, a spraying device for generating spray particles, a DDC control device and an analog measuring device through processing functions such as supply pressure, ultrasonic vibration, heating and humidification, 2. Description of the Related Art Supply devices that use a combination of pumps and the like are known. For example, a deodorant supply device (see Patent Document 5) characterized by comprising a measuring device for the concentration of hydrogen sulfide or mercaptans, and a device for controlling the addition of a drug based on the detected concentration of the measuring device. .

  In the above supply apparatus, depending on the non-uniform size of the spray particles resulting from the mechanical functional characteristics and the characteristics from the material forming the particles, it is a source of malodor from the aspect of maintaining retention of the spray particles in the space. There is a possibility that the effect of contact with harmful bacteria will be reduced and the effects including deodorizing and deodorizing and quick eradication effects will be lacking. Furthermore, in a device for supplying a deodorant and deodorizing agent equipped with a control function such as a pump, it is difficult to miniaturize the supply amount or minimize the device, and the price of the device including the installation of excessive functions becomes expensive. There is a possibility that the environmental load such as power consumption required for the apparatus increases.

JP 2006-25943 A JP 2005-247784 A JP 2001-329300 A JP 2004-33717 A JP 2000-246234 A

  The object of the present invention is to solve the problems in the prior art and inhabit widely in cars and passenger cars, animal breeding rooms and hotel rooms, smoking rooms, food and beverage tenant kitchens, toilets, shoe boxes, closets, waste liquid storage tanks, etc. Deodorizing agent with sterilizing function, which is excellent in deodorizing and sterilizing effects against various odorous components caused by harmful bacteria and corrosion of these cells, and can prevent recurrence over a long period of time. It is providing the deodorizing material with a microbe function, the dripping supply apparatus of the deodorizer with a microbe function, and the spraying method of the deodorizer with a microbe function.

  As a result of diligent investigations to solve the above problems, the present inventors have combined the radical reaction force of peroxide, the inclusion force of catechins, and the enzymatic decomposition force of proteolytic enzymes to produce sulfur that becomes a source of malodor. Harmful bacteria such as Salmonella, Escherichia coli, Staphylococcus aureus, and fungi including fungi, which are promoted to decompose malodorous components such as hydrogen odor, methyl mercaptan odor, ammonia odor, trimethylamine odor, etc. The present inventors have found that an excellent sterilizing function can be continuously obtained, and have arrived at the present invention.

That is, the present invention is as follows.
[1] A deodorizer with a sterilizing function, comprising a peroxide (A), a catechin (B), and a proteolytic enzyme agent (C).
[2] The deodorizer with a sterilization function according to [1], further comprising an inorganic salt (D) and / or a chelating agent (E).
[3] The proteolytic enzyme agent (C) is at least one selected from the group consisting of trypsin, protamine, pepsin, papain, bromelain, pancreatin, protease, lipase, aminopeptidase, and carboxypeptidase. The deodorizer with a sterilizing function according to [1] or [2], which is characterized.

[4] A water-absorbing polymer material molded into a circular, elliptical, or polygonal sheet, particle, or foam and having a water retention ratio of 1 to 50 times, and any one of [1] to [3] A deodorizing material with a sterilizing function, which is impregnated with the deodorizing agent with a sterilizing function described in 1.
[5] The water-absorbing polymer material is a hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule and an amine compound having two or more primary or secondary amino groups in one molecule. The deodorizing material with a sterilizing function according to [4], which is obtained by curing and molding a composition containing (b) as an essential component.
[6] A hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule and an amine compound (b) having two or more primary or secondary amino groups in one molecule as essential components Into the composition containing, an aqueous solution containing the deodorant with antibacterial and antibacterial function according to any one of [1] to [3], and cured in a water-containing state, a circular, elliptical, polygonal sheet, A deodorizing material with a sterilizing function, which is obtained by molding into a particulate or foamed form.

[7] A deodorant with a sterilizing function according to any one of [1] to [3] filled in a plastic pack is dropped and supplied in a range of 0.01 ml to 200 ml per minute. A deodorizing agent dropping supply device with a sterilization function.

[8] Deodorization in which a deodorizing agent with a sterilizing function according to any one of [1] to [3] filled in a plastic pack is dropped and supplied in a range of 0.01 ml to 200 ml per minute. A method for dripping and supplying the agent.
[9] The alcohol-containing water containing the deodorizer with the sterilizing function or the deodorizer with the sterilizing function according to any one of [1] to [3] is sprayed with fine particles having a particle diameter of 0.1 μm to 50 μm. A method of spraying a deodorant, characterized by:

  Moreover, it is preferable that the peroxide (A) in this invention is hydrogen peroxide. Furthermore, it is preferable that catechin (B) is an extract obtained by carrying out dry distillation extraction after steaming a plant body without prefermenting.

  According to the present invention, harmful bacteria that inhabit in automobiles and passenger cars, animal breeding rooms and hotel rooms, smoking rooms, food and beverage tenant kitchens, toilets, shoeboxes, closets, waste liquid storage tanks, etc., and corrosion of these cells Deodorant with sterilization function, deodorization material with sterilization function, sterilization, which is excellent in deodorization and sterilization effect against various malodorous components generated from the above, and can prevent recurrence over a long period of time It is possible to provide a dropping device for supplying a deodorant with a function and a spraying method for a deodorant with a sterilization function.

It is a figure which shows the reduction transition of the hydrogen sulfide odor by the deodorizer with a microbe elimination function of an Example and a comparative example. It is a figure which shows the transition transition of the reduction | decrease of the methyl mercaptan odor by the deodorizer with a microbe elimination function of an Example and a comparative example. It is a figure which shows the reduction transition of the ammonia odor by the deodorizer with a microbe elimination function of an Example and a comparative example. It is a figure which shows the reduction transition of the trimethylamine odor by the deodorizer with a microbe elimination function of an Example and a comparative example. It is a figure which shows hydrogen sulfide odor reduction transition by the deodorizing material with a microbe elimination function of an Example and a reference example. It is a figure which shows the score transition of the odor sensory evaluation by the deodorizer with a microbe elimination function of an Example and a reference example. It is a figure which shows a living microbe generation | occurrence | production transition by the deodorizing material with a microbe elimination function of an Example and a reference example. It is a figure which shows the dripping transition of the deodorizing agent dropping supply apparatus with a disinfection function of an Example and a reference example. It is a schematic diagram of the deodorizer dropping supply apparatus with a disinfection function used in Example 15. It is a figure which shows the disinfection rate transition by the deodorizing material with a disinfection function of an Example and a reference example. It is a figure which shows odor intensity transition by the deodorizing material with a microbe elimination function of an Example and a reference example.

  The deodorant with a sterilizing function of the present invention (hereinafter sometimes simply referred to as “deodorant of the present invention”) contains a peroxide (A), a catechin (B), and a proteolytic enzyme agent (C). .

  Examples of the peroxide (A) include a hydrogen peroxide aqueous solution, a peracetic acid aqueous solution, ozone water, and a sodium percarbonate acid adjusting aqueous solution. One or more of these can be used, but a hydrogen peroxide aqueous solution is preferred. It is. The concentration of the peroxide used in the present invention is preferably 0.01% by weight to 6% by weight. If it is higher than 6% by weight, deodorizing and sterilizing effects can be obtained against bad odor sources, but it should be 6% by weight or less considering the safety of handling, restrictions by the Poisonous and Deleterious Substances Control Law, and economic efficiency. Is preferred.

  The aqueous hydrogen peroxide solution used in the present invention is not particularly limited, but is diluted with industrial hydrogen peroxide that is widely used and highly purified ultrapure hydrogen peroxide that is used in the field of semiconductor cleaning. An aqueous solution can be used. Moreover, you may contain soft oxidation water (oxidation reduction water whose effective chlorine concentration is 50-80 ppm).

  Peroxide exhibits a radical oxidative reactivity against malodorous sources and decomposes, while at the same time promoting the oxidative activity of the proteolytic enzyme agent (C) and has a strong sterilizing antibacterial activity against harmful bacteria having a protein structure. It is possible to obtain a deodorizing effect of a malodorous source and a disinfecting antibacterial effect against harmful germs having a protein structure which is an element of the malodorous source.

  Moreover, in terms of the action of decomposing into bad odor sources, it acts on hydrogen sulfide odor, methyl mercaptan odor, ammonia odor, and trimethylamine odor in general, and shows a specific action on hydrogen sulfide odor and methyl mercaptan odor. In addition, it has a strong antibacterial action against bacteria such as Salmonella, Escherichia coli, Staphylococcus aureus, and molds, especially fungi. It acts strongly on live bacteria and fungi containing.

  Catechins (B) is a general term for flavonoid-based compounds having a basic structure of flavonoids. Catechin [C], catechin gallate [catechin gallate, Cg], gallocatechin gallate [gallocatechin gallate, GCg] , Epicatechin [EC], epigallocatechin [EGC], epicatechin gallate [epicatechin gallate, ECg], epigallocatechin gallate [epigallocatechin gallate, EGCg] and the like, or one of these, or A mixture containing two or more species is preferable, and an extract obtained by dry distillation extraction after steaming the plant body without pre-fermentation is more preferable.

  The plant body is not particularly limited as long as it contains catechins in the range of 1% to 100% in the leaves of the plant leaves generated by steaming without pre-fermentation. A group of tea leaves such as leaves, black tea leaves, blue tea leaves, white tea leaves, yellow tea leaves, at least one selected from the group of medicinal plants such as bamboo, bamboo shoots, dokudami, jikitarisu, mishima psycho, ginger, bellflower, aloe, herbs Although it can be used, it is particularly preferably a green tea leaf containing a large amount of epigallocatechin (EGC), epicatechin (EC), epicatechin gallate (ECg) which is a gallic acid ester, and epigallocatechin gallate (EGCg).

  For example, as a method of extracting catechins from tea leaves, the concentration in the extraction solution is 1% by weight by subjecting the tea made by steaming without pre-fermentation to a dry distillation at an extraction temperature of 60 ° C to 100 ° C. An extract containing -100% by weight of catechins can be obtained. For extraction of catechins, a solvent extraction method using a general organic solvent or the like can be used, but dry distillation extraction is preferred because contamination in the extract can be reduced.

  The catechins (B) are easily combined with a peptide body by-produced when the proteolytic enzyme activated by the peroxide (A) decomposes harmful bacteria having a protein structure to form peptide catechins. As a result, the deodorizing and deodorizing action against bad odor sources and the antibacterial action against harmful bacteria are amplified and the deodorizing effect is greatly improved. Peroxide (A) (for example, 100 wt% hydrogen peroxide when the peroxide (A) is an aqueous hydrogen peroxide solution) and catechins (B) (for example, catechins (B) are green tea In the case of the leaf dry distillation extract, the weight ratio of 100% by weight as green tea leaves) is preferably (B) / (A) = 0.01-10, more preferably (B) / (A). = 0.1-5, most preferably (B) / (A) = 0.5-2.

Examples of the proteolytic enzyme agent (C) include pepsin, papain, bromelain, trypsin, protamine, pancreatin, protease, lipase, aminopeptidase, carboxypeptidase and the like. At least one selected from these can be used, preferably pepsin, papain and bromelain, which are activated by peroxide to form many peptide bodies upon digestion and degradation of harmful bacteria having a protein structure. is there.
In addition, when using pepsin, papain, and bromelain, it is preferable that the pH of the deodorizing agent with a sterilizing function of the present invention is acidic (preferably pH: 2.5 to 5.5).

  Since the activity of the proteolytic enzyme agent (C) is increased by peroxide, many peptide bodies can be formed at the time of digestion and degradation action against harmful bacteria having a protein structure, and catechin is added to these enhanced peptide bodies. By binding the species to form peptide catechins, it is possible to enhance the deodorizing and deodorizing action against bad odor sources and the antibacterial action against harmful bacteria. Enzymes such as urease, egg white lysozyme, and catalase, which are not proteolytic enzymes, cannot enhance the formation of peptide catechins even when combined with peroxides, and promote deodorizing and deodorizing action and disinfecting antibacterial action. Can not.

  The proteolytic enzyme agent (C) may be used in the form of powdered solid or liquid, and may be used after diluting with water or the like. Moreover, the proteolytic enzyme agent (C) of the present invention has a weight ratio of {(A) + (B)} (mixed component) to (C) component as (C) / {(A) + (B)}. = 0.001 to 10 is preferable, 0.005 to 1.0 is more preferable, and 0.01 to 0.5 is most preferable. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

Inorganic salts (D) are not particularly limited, but include sodium chlorite, sodium chlorate, halides such as ammonium chloride, and halides, sulfates such as sodium sulfite and ammonium persulfate, sodium phosphate and phosphoric acid. Phosphates such as ammonium, carbonates such as sodium bicarbonate and ammonium carbonate, silicates and borates such as sodium perborate and sodium silicate, metal salts such as aluminate and antimonate, ammonium alum and soda alum Or a combination of two or more selected from the group consisting of nitrates such as sodium nitrate and calcium nitrate, and nitrates such as sodium nitrite and calcium nitrite. Among these, nitrates and / or nitrites are preferable, and sodium nitrate and sodium nitrite are particularly preferable.
By including the inorganic salt (D) in the deodorizer of the present invention, the deodorizing effect of the deodorizer and the duration of the sterilization antibacterial effect can be extended.

  The inorganic salts (D) may be used in the form of powder solid or liquid, and may be used after diluted with water or the like. Here, the weight ratio of {(A) + (B) + (C)} (mixed component) and inorganic salt (D) is (D) / {(A) + (B) + (C)} = The range is preferably 0.001 to 5.0, more preferably 0.005 to 1.0, and most preferably 0.05 to 0.5. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

  The chelating agent (E) of the present invention is preferably an organic aminocarboxylate, and examples thereof include EDTA, NTA, DTPA, PDTP, GLDA, HEDTA, GEDTA, TTHA, HIDA, and DHEG. By including the chelating agent (E) in the deodorizer of the present invention, the deodorizer can be prevented from deteriorating and further stabilized, so that the deodorizing effect and the sterilizing antibacterial effect of the deodorizer can be extended. it can. These chelating agents may be in powder form or in solution form, but may be used as they are, or may be used after being dissolved or diluted with water or the like. Here, the weight ratio of {(A) + (B) + (C)} (mixed component) and chelating agent (E) is (E) / {(A) + (B) + (C)} = It is preferable that it is the range of 0.01-5.0, More preferably, it is 0.01-2.0, Most preferably, it is 0.05-1.0. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

  The form of the deodorizer of the present invention may be any of liquids, granules, powders, tablets, wettable powders, pastes, etc., and can also be used by impregnating a water-absorbing polymer. As a method of use, each component of the deodorizer may be added directly to the aqueous solution, or may be used after mixing in advance. When mixing in advance, it is possible to mix in any form of powder solid, granular, liquid, and it may be used diluted to the concentration to be used, but the concentration of this mixture is increased in advance, In actual use, it is convenient to dilute it with water 2 to 1,000 times. It can be manufactured by a powder crusher for powdered solids, manufactured by a granulator for granules, and manufactured by a tableting machine for tablets.

  In the deodorizer of the present invention, a deodorizing active ingredient can be used together or mixed as necessary. Deodorizing active ingredients include alkylbenzene sulfonate, alkyl sulfate ester, higher alcohol sulfate ester, alkyl aryl sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, sucrose fatty acid ester surfactant Etc. By using the deodorant active ingredient, the activity promoting effect of the deodorant can be expected. The deodorant active ingredient may be used either in the form of powder solid or liquid, and may be used after diluted with water or the like. The weight ratio of {(A) + (B) + (C)} (mixed component) and (deodorant active component) component is (deodorant active component) / {(A) + (B) + ( C)} is preferably in the range of 0.01 to 5.0, more preferably 0.1 to 1.0, and most preferably 0.4 to 0.6. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

  In the deodorizer of the present invention, a pH adjuster can be used together or mixed as necessary. As pH adjusters, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, formic acid, acetic acid, citric acid, malic acid, propionic acid, lactic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, methyl apple Acid, isocitric acid, tartaric acid, gluconic acid, maleic acid, methylmaleic acid, methylfumaric acid, itaconic acid, acetylenic acid, lauric acid, linoleic acid, oleic acid, acrylic acid, polyacrylic acid, hydroxyacetic acid, sorbic acid, alginic acid, One or more selected from the group consisting of aspartic acid, benzoic acid, gallic acid, nicotinic acid, abietic acid, cinnamic acid, phthalic acid, terephthalic acid, trimellitic acid and sodium percarbonate may be used, but preferably gallic acid. Acid, alginic acid, nicotinic acid. By using a pH adjuster, the deodorizing and deodorizing function, the sterilizing antibacterial function and the antioxidant function of the deodorizing agent can be expected. The weight ratio of {(A) + (B) + (C)} (mixed component) and pH adjuster is: (pH adjuster) / {(A) + (B) + (C)} = 0.001 It is preferable that it is the range of -5.0, More preferably, it is 0.005-1.0, Most preferably, it is 0.01-0.5. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

In the deodorizer of the present invention, a stabilized chlorine dioxide agent which is a precursor of chlorine dioxide can be used together or mixed. As the stabilized chlorine dioxide agent, a stabilized chlorine dioxide gas as a free chlorine dioxide ClO ₂ aqueous solution having a safe and effective sterilizing ability is preferable. A chlorine dioxide agent purified from a chlorine aqueous solution, a chlorous acid aqueous solution One or more selected from the group consisting of a chlorine dioxide agent purified from the above, a chlorine dioxide agent produced from sodium chlorite, and a chlorine dioxide agent purified from chlorine gas can be used, but chlorous acid is preferred. A chlorine dioxide agent purified from an aqueous solution and / or a chlorine dioxide agent purified from sodium chlorite.
By using a stabilized chlorine dioxide agent, the deodorizing and deodorizing action and antibacterial action of the deodorizing agent can be expected. The stabilized chlorine dioxide agent may be used in the form of a powder solid or liquid. Further, the stabilized chlorine dioxide agent may be used as it is or after being activated with an activator such as citric acid, or diluted with water or the like. May be used. Here, the weight ratio of {(A) + (B) + (C)} (mixed component) and stabilized chlorine dioxide is (stabilized chlorine dioxide) / {(A) + (B) + (C) } = 0.01-5.0 is preferable, 0.05-1.0 is more preferable, and 0.1-0.3 is most preferable. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

In the deodorizing agent of the present invention, silver particles (nanosilver) are dispersed and nano-sized for the purpose of maintaining a long-term antibacterial and antibacterial action and a deodorizing and deodorizing action on odors generated from the cells. Nano silver dispersants based on those can be used together or mixed.
The nano silver dispersant is a dispersant having a pH of 3.0 to 5.0 and having a silver fine particle diameter of 5 nm to 10 nm and a polyvinyl pyrrolidone (amphiphilic polymer) having ionic characteristics and a pH of 3.0 to 5.0. Any of those that are supported and ground on a support material such as silica or inorganic mineral, those that are processed into a colloidal form, or a liquid form may be used, and those that are colloidal or liquid may be diluted with water. In addition, the silver delta plus ion (Agδ +) action as a sterilization and antibacterial action of nanosilver, the active oxygen action of colloidal silver, and the antibacterial and bactericidal action as a nanoparticle metal are applied. Also good. Here, the weight ratio of {(A) + (B) + (C)} (mixed component) and nanosilver dispersant is (nanosilver) / {(A) + (B) + (C)} = The range is preferably 0.001 to 5.0, more preferably 0.005 to 0.1, and most preferably 0.01 to 0.03. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

  The deodorant of the present invention is used in combination with a natural or synthetic fragrance for the purpose of improving the calmness without inhibiting the deodorant deodorizing action and sterilizing antibacterial action of the deodorant or It can also be mixed. As the fragrance, one or more selected from the group consisting of jasmine oil, butterfly oil, brackish oil, vanilla, rose oil, bergamot oil, lavender oil, potato incense, ryuzen incense, geraniol, vanillin, heliotrobin, etc. are used. However, rose oil and lavender oil are preferable. Here, the weight ratio of {(A) + (B) + (C)} (mixed component) to fragrance is (fragrance) / {(A) + (B) + (C)} = 0.01- The range is preferably 5.0, more preferably 0.1 to 1.0, and most preferably 0.4 to 0.6. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

A photocatalyst can be used together or mixed in the deodorizer of the present invention. By using a photocatalyst, it can be expected to maintain the efficacy obtained from the deodorizing and deodorizing action and the sterilizing antibacterial action of the deodorizer for a long time. These photocatalysts may be used in either a powder solid state or a liquid state. As the photocatalyst, a semiconductor photocatalyst such as titanium dioxide, a metal oxide photocatalyst such as zinc oxide, tungsten oxide, cadmium oxide, and indium oxide, a metal complex photocatalyst such as a ruthenium complex, a polypyridyl complex, and a porphyrin complex, CdS / TiO ₂ , One or more selected from the group consisting of mixed photocatalysts such as CdS / AgI, CdS / ZnO, and CdS / PbS can be used, but a semiconductor photocatalyst is preferred. Here, the weight ratio of {(A) + (B) + (C)} (mixed component) and photocatalyst is (photocatalyst) / {(A) + (B) + (C)} = 0.001 The range is preferably 5.0, more preferably 0.01 to 1.0, and most preferably 0.09 to 0.11. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

  The deodorizer of the present invention preferably has a pH of 2.5 to 5.5, more preferably 3.0 to 4.5, taking into account the activity maintaining activity of the protein digestive enzyme. The pH can be adjusted with a pH adjuster or the like as necessary.

  Examples of the method of using the deodorant with a sterilization function of the present invention include a method of spraying or spraying the deodorant with a sterilization function with a hand spray or a mechanical spray device. At this time, the deodorizing agent with the antibacterial and antibacterial function may be directly sprayed or sprayed in the same concentration, or may be diluted with water or the like and sprayed or sprayed. The spraying or spraying time in the latter case is preferably about 1 to 30 minutes.

  The deodorizer of this invention contains the said (A), (B) and (C) component as an essential component, and contains the (D) component and / or (E) component as needed. The total content of the above components in the deodorizer of the present invention can be appropriately selected depending on the type of malodorous source, the use form of the deodorant, the method of using the deodorant, and the like. For example, when using a deodorizer as aqueous solution, (A), (B) and (C) component can be mix | blended, for example as 0.001 to 100 weight% as the total content.

  Even as a deodorizing material obtained by impregnating the water-absorbing polymer with the deodorizing agent with the sterilizing function of the present invention, the deodorizing and deodorizing function against malodorous sources and the sterilizing antibacterial function against harmful bacteria having a protein structure can be maintained. As a preferable deodorizing material, a water-absorbing polymer material formed into a polygonal sheet shape such as a circle, an ellipse, a triangle or a rectangle, a particle shape or a foam shape and having a water retention ratio of 1 to 50 times is used. A deodorizing material obtained by impregnating the agent.

  The water-absorbing polymer material used for the deodorizing material of the present invention comprises a hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule and two or more primary or secondary amino groups in one molecule. The composition is cured by using an amine compound (b) having an essential component as an essential component. The shape of the cured product of the water-absorbing polymer material is not particularly limited, and can be molded, cured, cured, or molded freely, such as a circle, an ellipse, or a polygonal sheet such as a triangle or a quadrangle, a particle, or a foam. It is possible. The water retention ratio of the absorbent polymer material is about 1 to 50 times.

  The epoxy resin (a) used in the present invention is not particularly limited as long as it is a hydrophilic compound having at least two epoxy groups in one molecule. Specific examples include polyether-type epoxy resins obtained from the reaction of ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene polypropylene glycol and the like with epichlorohydrin, glycerin, polyglycerol, trimethylolpropane. And polyhydric alcohol type epoxy resins obtained from the reaction of sorbitol and the like with epichlorohydrin, and the like, and one or two or more kinds can be used as appropriate. Suitable include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether and mixtures thereof.

  The amine compound (b) used in the present invention is not particularly limited as long as it is a compound having at least two primary or secondary amino groups in one molecule. Specific examples include aliphatic primary amines such as ethylenediamine, polyethylenediamine, polyetherdiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and xylylenediamine; alicyclic groups such as bisaminomethylcyclohexane and isophoronediamine. Primary amines; aromatic primary amines such as metaphenylenediamine and diaminodiphenylmethane; ethylene oxide additions such as ethylenediamine, polyethylenediamine, polyetherdiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and xylylenediamine Secondary amines such as alicyclics; alicyclic secondary amines such as ethylene oxide adducts such as bisaminomethylcyclohexane and isophoronediamine Piperazine, is like dicyandiamide, may be used to Teki且 mixing one or two or more. Suitable examples include polyethylene diamine, polyether diamine, xylylenediamine, bisaminomethylcyclohexane, and isophorone diamine.

  The amount of the amine compound is preferably in the range of 0.3 to 3.0 equivalents of amine equivalent to 1.0 epoxy equivalent of epoxy resin (a), and more preferably in the range of 0.6 to 1.2 equivalents of amine equivalent. It is. The water-absorbing polymer of the present invention comprises a composition containing an epoxy resin (a) and an amine compound (b) as essential components at normal pressure or under pressure at 0 to 150 ° C. for 1 to 48 hours, preferably It is obtained by curing at 40 to 120 ° C. for 2 to 10 hours. The cured shape can be cured into a free shape such as a circle, an ellipse, or a polygonal sheet such as a triangle or a rectangle.

  In the present invention, in addition to the deodorizing material as described above, an aqueous solution containing the deodorizer with a sterilizing function of the present invention is added to the composition containing the epoxy resin (a) and the amine compound (b) as essential components. A deodorizing material in which a water-absorbing polymer is impregnated with a deodorizing agent can also be obtained by blending and curing in a water-containing state. Such a deodorizing material includes a hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule and an amine compound (b) having two or more primary or secondary amino groups in one molecule. Is mixed with an aqueous solution containing the deodorizer with antibacterial and antibacterial function of the present invention, and cured in a water-containing state, in the form of a polygonal sheet such as a circle, an ellipse, a triangle or a rectangle, or a particle Alternatively, it can be obtained by foaming. The amount of the aqueous solution containing the deodorizing agent with a sterilizing function of the present invention is 1 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Moreover, after hardening the composition containing said epoxy resin (a) and an amine compound (b) as an essential component and obtaining a water absorbing polymer, it stirs and mixes with the aqueous solution containing the deodorizer with a microbe elimination function of this invention. By this, it is possible to impregnate the water-absorbing polymer with the deodorizing agent with the sterilizing function of the present invention. There is no particular limitation on the method of including the water-absorbing polymer in the aqueous solution containing the deodorant with the sterilizing function of the present invention, but the resin cured product or the hydrous resin cured product may be adjusted to a desired size as necessary. Examples thereof include a method of mixing with an aqueous solution containing an appropriate amount of a deodorizing agent with antibacterial and antibacterial function after pulverization and washing treatment, and treating at 20 to 250 ° C. at normal pressure or under pressure for 1 to 96 hours.

  The method of using the water-absorbing polymer impregnated with the deodorant with a sterilizing function of the present invention is not particularly limited, but the deodorizing and deodorizing source of bad odor is obtained by spraying the water-absorbing polymer and water into a container such as a hand spray. How to disinfect antibacterial bacteria with a protein structure that is a component of odor sources, and water-absorbing polymers in containers such as glass and plastic containers, vases and bags, and water as needed Deodorizing and decontaminating antibacterial bacteria that have a protein structure that is a component of deodorizing and deodorizing odor sources and odor sources by contacting gas bodies and mist bodies of deodorized and deodorized components and sterilizing antibacterial components that are evaporated and evaporated And a usage method for preventing the recurrence. Moreover, it becomes possible to carry out the sterilization antibacterial of the harmful bacteria which have the protein structure which is one element of the deodorization deodorization of a bad smell source, or a bad smell source by these usage methods.

  As a harmful bacterium which is one element of malodorous source and malodorous source to which the deodorizing agent with a sterilizing function of the present invention and its holding material can be applied, hydrogen sulfide odor, methyl mercaptan odor, ammonia odor, trimethylamine odor, Salmonella bacterium, Escherichia coli, S. aureus, live fungi including fungi, fungi, etc., mainly with radical reactivity by peroxide etc., inclusion power by catechins extracted from plant leaves etc., enzymatic degradation power by proteolytic enzymes, respectively It is preferably applied to odorous components and fungi that are easily affected by single or synergistic decomposition power.

The apparatus for dropping and supplying a deodorant with a sterilization function of the present invention is a drip supply of the deodorant with a sterilization function of the present invention filled in a plastic pack in a range of 0.01 ml to 200 ml per minute. It is a device that can do. In addition, the method of dropping and supplying the deodorant with a sterilizing function of the present invention is a method in which a deodorant with a sterilizing function of the present invention filled in a plastic pack is instilled at a supply rate of 0.01 to 200 ml per minute. It is to be supplied dropwise.
In order to adjust the supply amount to the above range, it is preferable to employ a slide type roller valve that can adjust the flow rate range from a minute flow rate to a large flow rate.

  Here, the shape of the pack body from the input port to the discharge port of the plastic pack is preferably a polygonal shape such as a circle, an ellipse, a triangle or a quadrangle. The order of good shape is polygon (polygon more than pentagon), circle, ellipse, and rectangle. By using the polygonal shape, it is possible to prevent the input / output port from being easily welded to the side, and to reduce the probability of causing liquid leakage due to poor sealing. For example, by adopting a saddle shape as shown in FIG. 9, the strength against bending of the pack is increased, the liquid pool is reduced, and the input / output ports are easily welded.

  In the supply device, the deodorant is sealed in a plastic pack having a gas barrier layer such as polyethylene terephthalate, nylon 6, EVOH, nylon MXD6, etc., so that the performance of the deodorizer in the pack can be maintained and the deodorizer can be maintained. Can be supplied stably and accurately from a very small amount to a large flow rate, does not require power energy for supply, and has many advantages such as fewer operating parts, so it cannot be maintained and inspected It can be applied to reservoirs, piping, air-conditioning drain pans, etc., which are located in narrow places, places where power supply is difficult to take, and places with a feeling of blockage.

  As another spraying method of the deodorizer with a sterilizing function of the present invention, a method of supplying using a hand spray, a mechanical spray device or the like can be mentioned. At this time, the deodorizer with a sterilization function of the present invention is sprayed after mixing alcohol-containing water as an aqueous solution or as a promoter, so that the particle size (laser light scattering type particle size distribution measuring device manufactured by East Japan Computer Application Co., Ltd.) It is possible to spray with fine spray particles having a particle diameter measured in (1) of 0.1 μm to 50 μm. The spraying state is improved by mixing alcohol-containing water as a facilitating agent and then spraying, and the contact efficiency with malodorous sources and harmful bacteria increases, so that the deodorizing antibacterial function of the deodorizing agent with the sterilizing function and The deodorizing and deodorizing function can be improved.

  Examples of alcohols include amyl alcohol, arapitol, allyl alcohol, ethyl alcohol, erythritol, oleyl alcohol, glycol, glycerin, cinnamic alcohol, cetyl alcohol, fusel oil, butanol, benzyl alcohol, methyl alcohol, and lauryl alcohol. In particular, purified water containing alcohols in which glycerin and arabitol are contained in purified water is preferable. The alcohol concentration in the alcohol-containing water is preferably 1 to 10% by weight, more preferably 5 to 8% by weight.

  In the alcohols of the present invention, the weight ratio of {(A) + (B) + (C)} (mixed component) to alcohols is (alcohols) / {(A) + (B) + (C) } = 0.01-5.0 is preferable, more preferably 0.1-1.0, and most preferably 0.4-0.6. Here, as the weight of (A), for example, when the peroxide (A) is an aqueous hydrogen peroxide solution, the weight as 100 wt% hydrogen peroxide is used. The weight of (B) is, for example, 100% by weight as green tea leaves when the catechin (B) is a green tea leaf dry distillation extract.

  The method of the present invention will be described more specifically with reference to examples, reference examples and comparative examples. However, the present invention is not limited to these examples.

Example 1
A deodorization test was conducted on odor components (hydrogen sulfide) prepared using commercially available reagents. The odor component concentration was measured using a detector tube (manufactured by Gastec, No. 4LL, No. 4LT) and an odor bag. (A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4 g), (C) 2 g of a proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) was dissolved in pure water to prepare a deodorizing agent with a sterilizing function with a total amount of 1,000 g. Next, hydrogen sulfide prepared in a 1 L capacity odor bag was added and the concentration in the bag was adjusted to 0.85 ppm, and 50 g of the prepared deodorizer with a sterilizing function was added and stirred for about 5 minutes. The deodorizing effect was evaluated by measuring the odor concentration in the bag at regular intervals under conditions immersed in a constant temperature bath at 35 ° C. The evaluation of the deodorizing effect was carried out by measuring the concentration every hour from the start of the test, and using the transition of the reduction in hydrogen sulfide concentration until the lapse of 4 hours as an effect index. The results are shown in Table 1 and FIG. The deodorizer had a pH of 3.96.

Example 2
Instead of the deodorizing agent with the sterilizing function of Example 1, (A) peroxide (2 wt% hydrogen peroxide aqueous solution) 200 g (4 g as 100 wt% hydrogen peroxide), (B) catechins (green tea leaves 2) 200 g (4 g as 100 wt% green tea leaf), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture), (D) 3 g of inorganic salts (sodium nitrate), (E) chelating agent (EDTA) 6 g, deodorant active ingredient (alkylsulfosuccinate) 5.3 g, pH adjuster (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen manufactured by Biocide Japan), fragrances (Lavender oil) 5 g, semiconductor photocatalyst (Ishihara Sangyo Visible Light Responsive Photocatalyst Dispersion MPT-428) 1 g was dissolved in pure water to make the total amount 1,000 g. Except for using as the agent was performed in the same manner as in Example 1. The results are shown in Table 1 and FIG. The deodorant had a pH of 4.01.

Comparative Example 1
Instead of the deodorizer with the sterilization function of Example 1, the same procedure as in Example 1 was performed except that pure water was used and the total amount was 1,000 g. The results are shown in Table 1 and FIG. The deodorizer had a pH of 5.67.

Comparative Example 2
Instead of the deodorizer with the sterilizing function of Example 1, (A) 200 g of a peroxide (2% by weight aqueous hydrogen peroxide solution) was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. Except for this, the same procedure as in Example 1 was performed. The results are shown in Table 1 and FIG. The deodorizing agent had a pH of 4.3.

Comparative Example 3
Instead of the deodorant with the sterilization function of Example 1, (B) 200 g of catechins (green tea leaf 2% by weight dry distillation extract) dissolved in pure water to a total amount of 1,000 g was used as the deodorant. Except for this, the same procedure as in Example 1 was performed. The results are shown in Table 1 and FIG. The deodorizer had a pH of 4.93.

Comparative Example 4
Instead of the deodorizing agent with the sterilizing function of Example 1, (C) 2 g of proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) dissolved in pure water to a total amount of 1,000 g was used as the deodorizing agent. Except for this, the same procedure as in Example 1 was performed. The results are shown in Table 1 and FIG. The deodorant had a pH of 4.4.

Comparative Example 5
Instead of the deodorant with the sterilization function of Example 1, 200 g of (A) peroxide (2 wt% hydrogen peroxide aqueous solution) and 200 g of (B) catechin (green tea leaf 2 wt% dry distillation extract) were purified. The same procedure as in Example 1 was conducted except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 1 and FIG. The deodorizer had a pH of 4.39.

Comparative Example 6
Instead of the deodorant with the sterilizing function of Example 1, 200 g of (A) peroxide (2% by weight aqueous hydrogen peroxide solution) and 2 g of (C) proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) were purified. This was carried out in the same manner as in Example 1 except that a total amount of 1,000 g dissolved in was used as a deodorizer. The results are shown in Table 1 and FIG. The deodorizer had a pH of 4.37.

Comparative Example 7
Instead of the deodorizing agent with the sterilizing function of Example 1, 200 g of (B) catechins (green tea leaf 2% by weight extract) and 2 g of (C) proteolytic enzyme agent (equivalent mixture of pepsin and papain) are purified water. This was carried out in the same manner as in Example 1 except that a total amount of 1,000 g dissolved in was used as a deodorizer. The results are shown in Table 1 and FIG. The deodorant had a pH of 4.75.

Comparative Example 8
Instead of the deodorant with the sterilizing function of Example 1, (D) 3 g of inorganic salts (sodium nitrate), (E) 6 g of chelating agent (EDTA), 5.3 g of deodorizing active ingredient (alkylsulfosuccinate), pH Conditioner (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen from Bioside Japan) 2 g, fragrances (lavender oil) 5 g, semiconductor photocatalyst (visible light responsive photocatalyst dispersion manufactured by Ishihara Sangyo) MPT-428) The same procedure as in Example 1 was conducted except that 1 g of MPT-428 was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. The results are shown in Table 1 and FIG. The deodorizer had a pH of 5.03.

Example 3
A deodorization test was conducted on an odor component (methyl mercaptan) prepared using a commercially available reagent. The odor component concentration was measured using a detector tube (manufactured by Gastec Corporation, No. 71) and an odor bag.
(A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4 g), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture) was dissolved in pure water to produce a deodorant with a sterilization function with a total amount of 1,000 g, and the odor component prepared was methyl mercaptan The same treatment as in Example 1 was performed except that the concentration was 55 ppm. The results are shown in Table 2 and FIG. The deodorizer had a pH of 3.96.

Example 4
Instead of the deodorizing agent with the sterilizing function of Example 3, (A) peroxide (2 wt% hydrogen peroxide aqueous solution) 200 g (4 g as 100 wt% hydrogen peroxide), (B) catechins (green tea leaves 2) 200 g (4 g as 100 wt% green tea leaf), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture), (D) 3 g of inorganic salts (sodium nitrate), (E) chelating agent (EDTA) 6 g, deodorant active ingredient (alkylsulfosuccinate) 5.3 g, pH adjuster (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen manufactured by Biocide Japan), fragrances (Lavender oil) 5 g and 1 g of a semiconductor photocatalyst (Ishihara Sangyo Visible Light Responsive Photocatalyst Dispersion MPT-428) dissolved in pure water to a total amount of 1,000 g Except for using as a deodorant was carried out in the same manner as in Example 3. The results are shown in Table 2 and FIG. The deodorant had a pH of 4.01.

Comparative Example 9
Instead of the deodorizer with the sterilization function of Example 3, the same procedure as in Example 3 was performed except that pure water was used and the total amount was 1,000 g. The results are shown in Table 2 and FIG.
The pH of the deodorizer was 5.67.

Comparative Example 10
Instead of the deodorizer with the sterilizing function of Example 3, 200 g of (A) peroxide (2% by weight aqueous hydrogen peroxide solution) was dissolved in pure water to make the total amount 1,000 g. Except for this, the same procedure as in Example 3 was performed. The results are shown in Table 2 and FIG. The deodorizer had a pH of 4.3.

Comparative Example 11
Instead of the deodorant with the sterilization function of Example 3, 200 g of (B) catechins (green tea leaf 2% by weight dry distillation extract) dissolved in pure water to a total amount of 1,000 g was used as the deodorant. Except for this, the same procedure as in Example 3 was performed. The results are shown in Table 2 and FIG. The deodorizer had a pH of 4.93.

Comparative Example 12
Instead of the deodorizing agent with the sterilizing function of Example 3, (C) 2 g of proteolytic enzyme agent (equivalent mixture of pepsin and papain) was dissolved in pure water to give a total amount of 1,000 g as the deodorizing agent. Except for this, the same procedure as in Example 3 was performed. The results are shown in Table 2 and FIG. The deodorant had a pH of 4.4.

Comparative Example 13
Instead of the deodorant with the sterilization function of Example 3, 200 g of (A) peroxide (2% by weight aqueous hydrogen peroxide solution) and 200 g of (B) catechin (2% by weight of green tea leaf dry distillation extract) were purified. The same procedure as in Example 3 was conducted except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 2 and FIG. The deodorizer had a pH of 4.39.

Comparative Example 14
Instead of the deodorizing agent with the sterilizing function of Example 3, (A) 200 g of a peroxide (2 wt% hydrogen peroxide aqueous solution) and (C) 2 g of a proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) are purified water. Example 3 was carried out in the same manner as in Example 3 except that a total amount of 1,000 g dissolved was used as a deodorizer. The results are shown in Table 2 and FIG. The deodorizer had a pH of 4.37.

Comparative Example 15
Instead of the deodorant with the sterilization function of Example 3, 200 g of (B) catechins (green tea leaf 2% by weight dry distillation extract) and 2 g of (C) proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) are purified. The same procedure as in Example 3 was conducted except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 2 and FIG. The deodorant had a pH of 4.75.

Comparative Example 16
Instead of the deodorant with the sterilization function of Example 3, (D) 3 g of inorganic salts (sodium nitrate), (E) 6 g of chelating agent (EDTA), 5.3 g of deodorizing active ingredient (alkyl sulfosuccinate), pH Conditioner (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen from Bioside Japan) 2 g, fragrances (lavender oil) 5 g, semiconductor photocatalyst (visible light responsive photocatalyst dispersion manufactured by Ishihara Sangyo) MPT-428) The same procedure as in Example 3 was conducted except that 1 g of MPT-428 was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. The results are shown in Table 2 and FIG. The deodorizer had a pH of 5.03.

Example 5
A deodorizing test was conducted on the odor component (ammonia) prepared using a commercially available reagent. The odor component concentration was measured using a detector tube (manufactured by Gastec, No. 3L) and an odor bag.
(A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4 g), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture) was dissolved in pure water to make a deodorant with a sterilization function with a total amount of 1,000 g, and the odor component prepared was 80 ppm of ammonia. The same processing as in Example 1 was carried out except that. The results are shown in Table 3 and FIG. The deodorizer had a pH of 3.96.

Example 6
In place of the deodorant with the sterilizing function of Example 5, (A) peroxide (2 wt% hydrogen peroxide aqueous solution) 200 g (4 g as 100 wt% hydrogen peroxide), (B) catechins (green tea leaves 2) 200 g (4 g as 100 wt% green tea leaf), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture), (D) 3 g of inorganic salts (sodium nitrate), (E) chelating agent (EDTA) 6 g, deodorant active ingredient (alkylsulfosuccinate) 5.3 g, pH adjuster (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen manufactured by Biocide Japan), fragrances (Lavender oil) 5 g and 1 g of a semiconductor photocatalyst (Ishihara Sangyo Visible Light Responsive Photocatalyst Dispersion MPT-428) dissolved in pure water to a total amount of 1,000 g Except for using as a deodorant was carried out in the same manner as in Example 5. The results are shown in Table 3 and FIG. The deodorant had a pH of 4.01.

Comparative Example 17
The same procedure as in Example 5 was performed except that pure water was used instead of the deodorizer with a sterilization function in Example 5 and the total amount was 1,000 g. The results are shown in Table 3 and FIG.

Comparative Example 18
Instead of the deodorizer with the sterilizing function of Example 5, (A) 200 g of a peroxide (2% by weight aqueous hydrogen peroxide solution) was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. Except for this, the same procedure as in Example 5 was performed. The results are shown in Table 3 and FIG. The deodorizer had a pH of 4.3.

Comparative Example 19
Instead of the deodorizer with the sterilization function of Example 5, (B) 200 g of catechins (green tea leaf 2 wt% dry distillation extract) dissolved in pure water to a total amount of 1,000 g was used as the deodorizer. Except for this, the same procedure as in Example 5 was performed. The results are shown in Table 3 and FIG. The deodorizer had a pH of 4.93.

Comparative Example 20
Instead of the deodorant with the sterilizing function of Example 5, (C) 2 g of proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) dissolved in pure water to a total amount of 1,000 g was used as the deodorant. Except for this, the same procedure as in Example 5 was performed. The results are shown in Table 3 and FIG. The deodorant had a pH of 4.4.

Comparative Example 21
Instead of the deodorant with the sterilization function of Example 5, 200 g of (A) peroxide (2 wt% hydrogen peroxide aqueous solution) and 200 g of (B) catechin (2 wt% green tea leaf dry extract) were purified. The same procedure as in Example 5 was performed except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 3 and FIG. The deodorizer had a pH of 4.39.

Comparative Example 22
Instead of the deodorizing agent with the sterilizing function of Example 5, 200 g of (A) peroxide (2% by weight aqueous hydrogen peroxide solution) and 2 g of (C) proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) were purified water. Example 5 was carried out in the same manner as in Example 5 except that a total amount of 1,000 g dissolved in was used as a deodorizer. The results are shown in Table 3 and FIG. The deodorizer had a pH of 4.37.

Comparative Example 23
Instead of the deodorant with the sterilization function of Example 5, 200 g of (B) catechins (green tea leaf 2% by weight dry distillation extract) and 2 g of (C) proteolytic enzyme agent (equivalent mixture of pepsin and papain) were purified. The same procedure as in Example 5 was performed except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 3 and FIG. The deodorant had a pH of 4.75.

Comparative Example 24
Instead of the deodorizing agent with the sterilizing function of Example 5, (D) 3 g of inorganic salts (sodium nitrate), (E) 6 g of chelating agent (EDTA), 5.3 g of deodorizing active ingredient (alkylsulfosuccinate), pH Conditioner (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen from Bioside Japan) 2 g, fragrances (lavender oil) 5 g, semiconductor photocatalyst (visible light responsive photocatalyst dispersion manufactured by Ishihara Sangyo) MPT-428) The same procedure as in Example 5 was conducted except that 1 g of MPT-428 was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. The results are shown in Table 3 and FIG. The deodorizer had a pH of 5.03.

Example 7
A deodorization test was conducted on an odor component (trimethylamine) prepared using a commercially available reagent. The odor component concentration was measured using a detector tube (manufactured by GASTECH, No. 180, No. 180L) and an odor bag.
(A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4 g), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture) was dissolved in pure water to produce a deodorant with a sterilization function with a total amount of 1,000 g, and the odor component prepared was 80 ppm of trimethylamine The same processing as in Example 1 was carried out except that. The results are shown in Table 4 and FIG. The deodorizer had a pH of 3.96.

Example 8
In place of the deodorant with the sterilizing function of Example 7, (A) peroxide (2 wt% hydrogen peroxide aqueous solution) 200 g (4 g as 100 wt% hydrogen peroxide), (B) catechins (green tea leaves 2) 200 g (4 g as 100 wt% green tea leaf), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture), (D) 3 g of inorganic salts (sodium nitrate), (E) chelating agent (EDTA) 6 g, deodorant active ingredient (alkylsulfosuccinate) 5.3 g, pH adjuster (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen manufactured by Biocide Japan), fragrances (Lavender oil) 5 g and 1 g of a semiconductor photocatalyst (Ishihara Sangyo Visible Light Responsive Photocatalyst Dispersion MPT-428) dissolved in pure water to a total amount of 1,000 g Except for using as a deodorant was carried out in the same manner as in Example 7. The results are shown in Table 4 and FIG. The deodorant had a pH of 4.01.

Comparative Example 25
It carried out similarly to Example 7 except having used what used pure water and made the whole quantity 1,000g instead of the deodorizer with the microbe elimination function of Example 7. FIG. The results are shown in Table 4 and FIG.
The pH of the deodorizer was 5.67.

Comparative Example 26
Instead of the deodorant with the sterilizing function of Example 7, (A) 200 g of a peroxide (2% by weight aqueous hydrogen peroxide solution) was dissolved in pure water to give a total amount of 1,000 g as a deodorant. Except for this, the same procedure as in Example 7 was performed. The results are shown in Table 4 and FIG. The deodorizer had a pH of 4.3.

Comparative Example 27
Instead of the deodorizing agent with the sterilizing function of Example 7, (B) 200 g of catechins (green tea leaf 2% by weight dry distillation extract) dissolved in pure water to a total amount of 1,000 g was used as the deodorizing agent. Except for this, the same procedure as in Example 7 was performed. The results are shown in Table 4 and FIG. The deodorizer had a pH of 4.93.

Comparative Example 28
Instead of the deodorant with the sterilization function of Example 7, (C) 2 g of proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) dissolved in pure water to a total amount of 1,000 g was used as the deodorant. Except for this, the same procedure as in Example 7 was performed. The results are shown in Table 4 and FIG. The deodorant had a pH of 4.4.

Comparative Example 29
Instead of the deodorant with the sterilizing function of Example 7, 200 g of (A) peroxide (2 wt% hydrogen peroxide aqueous solution) and (B) 200 g of catechins (green tea leaf 2 wt% dry distillation extract) were purified. The same procedure as in Example 7 was performed except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 4 and FIG. The deodorizer had a pH of 4.39.

Comparative Example 30
Instead of the deodorant with the sterilization function of Example 7, 200 g of (A) peroxide (2 wt% hydrogen peroxide aqueous solution) and 2 g of (C) proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) were purified. This was carried out in the same manner as in Example 7 except that a total amount of 1,000 g dissolved in was used as a deodorizer. The results are shown in Table 4 and FIG. The deodorizer had a pH of 4.37.

Comparative Example 31
Instead of the deodorant with the sterilizing function of Example 7, 200 g of (B) catechins (green tea leaf 2% by weight dry distillation extract) and 2 g of (C) proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) were purified. The same procedure as in Example 7 was performed except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 4 and FIG. The deodorant had a pH of 4.75.

Comparative Example 32
Instead of the deodorant with the sterilizing function of Example 7, (D) 3 g of inorganic salts (sodium nitrate), (E) 6 g of chelating agent (EDTA), 5.3 g of deodorizing active ingredient (alkylsulfosuccinate), pH Conditioner (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen from Bioside Japan) 2 g, fragrances (lavender oil) 5 g, semiconductor photocatalyst (visible light responsive photocatalyst dispersion manufactured by Ishihara Sangyo) MPT-428) The same procedure as in Example 7 was conducted except that 1 g of MPT-428 was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. The results are shown in Table 4 and FIG. The deodorizer had a pH of 5.03.

  As shown in Examples 1 to 8 in Tables 1 to 4, a deodorizer with a sterilizing function, which contains (A) a peroxide, (B) catechins, and (C) a proteolytic enzyme agent of the present invention. Compared with a deodorant containing the components (A) to (B) alone or a deodorant containing only two components selected from (A) to (B), It was found that one agent has an efficient and sufficient deodorizing action.

Preparation Example 1
95 parts by weight of polyethylene glycol diglycidyl ether (Denacol EX-841, epoxy equivalent: 550 g / eq, manufactured by Nagase Kasei Co., Ltd.) and metaxylylenediamine (MXDA, active hydrogen equivalent: 34 g / eq, Mitsubishi Gas Chemical Company, Inc.) 5 parts by weight are mixed and dissolved in 100 parts by weight of ion-exchanged water, heated in a dryer at 80 ° C. for 30 minutes, and cured water-containing resin (water-absorbing polymer) having a water retention ratio of 10 times per 1 g. Got. Thereafter, the obtained cured resin was pulverized with a mill to obtain a granular water-absorbing polymer.

Example 9
(A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4 g), (C) 2 g of a proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) was dissolved in pure water to prepare a deodorizing agent with a sterilizing function with a total amount of 1,000 g. 100 g of the water-absorbing polymer obtained in Preparation Example 1 is immersed in this deodorizer and left at room temperature for 24 hours to create a deodorizing material with a sterilizing function that completely absorbs the deodorizing function with a sterilizing function. did. The same procedure as in Example 1 was carried out except that 50 g of the deodorizing material with a sterilizing function thus prepared was put in a 1 L capacity odor bag. The results are shown in Table 5 and FIG. The deodorizer had a pH of 3.96.

Reference example 1
Instead of the deodorizing material with the sterilizing function of Example 9, 100 g of the water-absorbing polymer obtained in Preparation Example 1 was immersed in pure water and allowed to stand at room temperature for 24 hours to completely absorb pure water. The same procedure as in Example 9 was conducted except that the odor was used as a deodorizing material with a sterilizing function. The results are shown in Table 5 and FIG.

Reference example 2
In place of the water-absorbing polymer obtained in Preparation Example 1, 100 g of a commercially available urethane resin foam (manufactured by Softbren Kogyo Co., Ltd., soft urethane foam) was immersed in the deodorizer with a sterilization function of Example 9, It was carried out in the same manner as in Example 9 except that a deodorant with a sterilization function was completely absorbed by leaving it to stand at room temperature for 24 hours and used as a deodorization material with a sterilization function. The results are shown in Table 5 and FIG.

Reference example 3
Instead of the water-absorbing polymer obtained in Preparation Example 1, 10 g of a commercially available polyacrylic acid water-absorbing resin (manufactured by Tech Jam Co., Ltd., super water-absorbing resin KN3110985) was used as the deodorizer with a sterilizing function in Example 9. It was carried out in the same manner as in Example 9 except that a deodorizing material with a sterilizing function was used as a deodorizing material with a sterilizing function by completely immersing the deodorant with a sterilizing function by leaving it at room temperature for 24 hours. The results are shown in Table 5 and FIG.

Reference example 4
Instead of the water-absorbing polymer obtained in Preparation Example 1, 100 g of a commercially available hydroball was immersed in the deodorant with a sterilizing function of Example 9 and allowed to stand at room temperature for 24 hours to completely sterilize it. The same procedure as in Example 9 was performed except that a deodorizer with a function of absorbing water was used as a deodorizing material with a sterilization function. The results are shown in Table 5 and FIG.

Example 10
(A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4 g), (C) 2 g of a proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) was dissolved in pure water to prepare a deodorizing agent with a sterilizing function with a total amount of 1,000 g. 100 g of the water-absorbing polymer obtained in Preparation Example 1 is immersed in this deodorizer and left at room temperature for 24 hours to create a deodorizing material with a sterilizing function that completely absorbs the deodorizing function with a sterilizing function. did. Take 60 g of this deodorizing material with sterilizing function and put it in a plastic cup together with a commercially available culture medium for petrol check 25 (SCDL) for environmental microorganism testing (Eiken Chemical Co., Ltd.). The whole tray was wrapped in a plastic bag and sealed, and cultured in an incubator at 37 ° C. for 14 days. At regular times, the state of occurrence of viable bacteria including molds every day was visually confirmed, and the state of occurrence was evaluated. The results are shown in Table 6. The deodorizer had a pH of 3.96.

Reference Example 5
Instead of the deodorizing material with the sterilizing function of Example 10, 100 g of the water-absorbing polymer obtained in Preparation Example 1 was immersed in pure water and allowed to stand at room temperature for 24 hours to completely absorb pure water. This was carried out in the same manner as in Example 10 except that the material was used as a deodorizing material with a sterilizing function. The results are shown in Table 6.

Reference Example 6
In place of the water-absorbing polymer obtained in Preparation Example 1, 100 g of a commercially available urethane resin foam (manufactured by Softbren Kogyo Co., Ltd., soft urethane foam) was immersed in the deodorizer with a sterilization function of Example 10, It was carried out in the same manner as in Example 10 except that a deodorant with a sterilizing function that was completely absorbed by leaving it at room temperature for 24 hours was used as a deodorizing material with a sterilizing function. The results are shown in Table 6.

Reference Example 7
Instead of the water-absorbing polymer obtained in Preparation Example 1, 10 g of a commercially available polyacrylic acid water-absorbing resin (manufactured by Techjam Co., Ltd., super water-absorbing resin KN311985) was immersed in the deodorizer with a sterilizing function in Example 10. This was carried out in the same manner as in Example 10 except that a deodorant with a sterilization function was completely absorbed by being treated and allowed to stand at room temperature for 24 hours. The results are shown in Table 6.

Reference Example 8
Instead of the water-absorbing polymer obtained in Preparation Example 1, 100 g of a commercially available hydroball was immersed in the deodorizer with a sterilizing function of Example 10 and allowed to stand at room temperature for 24 hours to completely sterilize it. The same procedure as in Example 10 was performed except that a deodorizer with a function of absorbing water was used as a deodorization material with a sterilization function. The results are shown in Table 6.

  The deodorizing material with the sterilization function of the present invention shown in Examples 9 and 10 is more depleted of hydrogen sulfide than the deodorizing materials using other water-absorbing polymers (Reference Examples 2 to 4 and Reference Examples 6 to 8). It was found that the removal effect is remarkably high and the fungus body generation suppression effect is excellent.

Example 11
A sterilization test was carried out using a culture sample of manure wastewater cultured in 0.9% physiological saline. The bacterial cells were detected using commercially available Petancheck 25 medium for environmental microorganism testing (Eiken Chemical Co., Ltd.), Salmonella (MLCB), Escherichia coli (DESO), Staphylococcus aureus (MSEY), fungi (SAB), live bacteria ( SCDL). (A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4g), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture) dissolved in pure water to make a deodorant with a sterilizing function with a total amount of 1,000 g, and put 50 ml in a 100 ml hand spray A deodorizer with a disinfection function for spray was obtained. The deodorizer had a pH of 3.96.

  Next, 50 g of a deodorant with a disinfection function for spraying was sprayed from a height of 1 m onto a medium in which a bacterial cell sample cultured and prepared for each medium of Petan Check 25 was applied with a brush, and the culture was carried out with a lid. The culture was performed in an incubator at 37 ° C. for 24 hours. The results are shown in Table 7.

Example 12
Instead of the deodorant with the sterilizing function of Example 11, (A) peroxide (2 wt% hydrogen peroxide aqueous solution) 200 g (4 g as 100 wt% hydrogen peroxide), (B) catechins (green tea leaves 2) 200 g (4 g as 100 wt% green tea leaf), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture), (D) 3 g of inorganic salts (sodium nitrate), (E) chelating agent (EDTA) 6 g, deodorant active ingredient (alkylsulfosuccinate) 5.3 g, pH adjuster (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen manufactured by Biocide Japan), fragrances (Lavender oil) 5 g, semiconductor photocatalyst (Ishihara Sangyo visible light responsive photocatalyst dispersion MPT-428) 1 g dissolved in pure water to a total amount of 1,000 g Used as a deodorant, except for using 50ml purse spray sterilization function deodorant to hand spray this was similar to that of Example 11. The results are shown in Table 7. The deodorant had a pH of 4.01.

Reference Example 9
Instead of the deodorizing agent with the sterilizing function of Example 11, 100 ml of pure water was put in a hand spray and the same procedure as in Example 11 was carried out except that the deodorizing agent with the sterilizing function for spraying was used. The results are shown in Table 7.

Reference Example 10
Instead of the deodorizer with the sterilization function of Example 11, (A) a peroxide (2 wt% aqueous hydrogen peroxide solution) 200 g was dissolved in pure water to make a total amount of 1,000 g as a deodorizer, This was carried out in the same manner as in Example 11 except that 50 ml was put in a hand spray and used as a deodorizer with a disinfection function for spraying. The results are shown in Table 7. The deodorizer had a pH of 4.3.

Reference Example 11
Instead of the deodorant with the sterilization function of Example 11, 200 g of (A) peroxide (2 wt% hydrogen peroxide aqueous solution) and 200 g of (B) catechin (green tea leaf 2 wt% dry distillation extract) were purified. The same procedure as in Example 11 was performed except that a total amount of 1,000 g dissolved in water was used as a deodorizer, and 50 ml of this was added to a hand spray to prepare a deodorizer with a disinfection function for spraying. The results are shown in Table 7. The deodorizer had a pH of 4.39.

Reference Example 12
Instead of the deodorant with the sterilization function of Example 11, (A) 200 g of a peroxide (2 wt% aqueous hydrogen peroxide solution) and (C) 2 g of a proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) were purified water. This was carried out in the same manner as in Example 11 except that a total amount of 1,000 g dissolved in was used as a deodorizer, and 50 ml of this was added to a hand spray to prepare a deodorizer with a disinfection function for spraying. The results are shown in Table 7. The deodorizer had a pH of 4.37.

Reference Example 13
Instead of the deodorant with the sterilization function of Example 11, (D) 3 g of inorganic salts (sodium nitrate), (E) 6 g of chelating agent (EDTA), 5.3 g of deodorizing active ingredient (alkylsulfosuccinate), pH Conditioner (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen from Bioside Japan) 2 g, fragrances (lavender oil) 5 g, semiconductor photocatalyst (visible light responsive photocatalyst dispersion manufactured by Ishihara Sangyo) MPT-428) Same as Example 11 except that 1 g dissolved in pure water and made to a total amount of 1,000 g was used as a deodorizer, and 50 ml was put into a hand spray to make a deodorizer with a disinfection function for spraying. Went to. The results are shown in Table 7. The deodorizer had a pH of 5.03.

  When the deodorizing agent with the sterilizing function of the present invention shown in Examples 11 and 12 is sprayed on various cells, various bacteria are used as compared with the case where other deodorizing agents are used (Reference Examples 9 to 13). It was shown to be excellent in the effect of suppressing the generation of bacterial cells against the body.

Example 13
The generation transition of malodorous and harmful bacteria was confirmed using a cell culture sample containing mold and urine wastewater cultured in 0.9% physiological saline. Odor is confirmed by a sensory test, and fungus generation including fungi is confirmed by detection using live bacteria (SCDL) in a commercially available petacheck 25 medium for environmental microorganism testing (Eiken Chemical Co., Ltd.). went. (A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4g), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture) dissolved in pure water to make a deodorant with a sterilizing function with a total amount of 1,000 g, and put 50 ml in a 100 ml hand spray A deodorizer with a disinfection function for spray was obtained. The deodorizer had a pH of 3.96.

  Next, 50 ml of a cell-producing sample collected and cultured in a 250 mm × 300 mm plastic tray and a petane check 25 viable culture medium (SCDL) are placed in a petri dish, and a deodorant with a disinfection function for spraying. Is sprayed 5 times (25 ml), the whole tray is covered with a transparent bag having a high gas barrier property and sealed, and 2 L of air is put in an inhaler in a 37 ° C. incubator and incubated for 10 days. At regular times every day, count the number of viable bacteria generated in the Petan Check 25 (SCDL) medium, extract 130 ml of air from the bag with an aspirator, and collect in a commercially available odor bag (Tedlar Bag Omi Odo Air Service). The sensory test by five panelists conducted a comprehensive evaluation according to the odor confirmation and evaluation criteria, and the evaluation score was recorded. The results are shown in Table 8, Table 9, FIG. 6 and FIG.

  In a sensory test with five panelists, each panelist evaluated (1) odor intensity score, (2) stimulus score, and (3) pleasant / discomfort score according to the odor sensory evaluation criteria shown in Table 8 below. The average value of five people was calculated and shown in Table 8 as the overall score for each day.

Example 14
Instead of the deodorant with the sterilizing function of Example 13, (A) peroxide (2 wt% hydrogen peroxide aqueous solution) 200 g (4 g as 100 wt% hydrogen peroxide), (B) catechins (green tea leaves 2) 200 g (4 g as 100 wt% green tea leaf), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture), (D) 3 g of inorganic salts (sodium nitrate), (E) chelating agent (EDTA) 6 g, deodorant active ingredient (alkylsulfosuccinate) 5.3 g, pH adjuster (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen manufactured by Biocide Japan), fragrances (Lavender oil) 5 g, semiconductor photocatalyst (Ishihara Sangyo visible light responsive photocatalyst dispersion MPT-428) 1 g dissolved in pure water to a total amount of 1,000 g Except for using as a deodorant was carried out in the same manner as in Example 13. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorant had a pH of 4.01.

Reference Example 14
The same procedure as in Example 13 was performed, except that pure water was used instead of the deodorizer with a sterilization function in Example 13 and the total amount was 1,000 g. The results are shown in Table 8, Table 9, FIG. 6 and FIG.

Reference Example 15
Instead of the deodorizer with the sterilization function of Example 13, (A) 200 g of a peroxide (2 wt% aqueous hydrogen peroxide solution) was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. Except for this, the same procedure as in Example 13 was performed. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorizer had a pH of 4.3.

Reference Example 16
Instead of the deodorizer with the sterilization function of Example 13, (B) 200 g of catechins (green tea leaf 2% by weight dry distillation extract) dissolved in pure water to a total amount of 1,000 g was used as the deodorizer. Except for this, the same procedure as in Example 13 was performed. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorizer had a pH of 4.93.

Reference Example 17
Instead of the deodorizing agent with the sterilizing function of Example 13, (C) 2 g of proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) dissolved in pure water to a total amount of 1,000 g was used as the deodorizing agent. Except for this, the same procedure as in Example 13 was performed. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorant had a pH of 4.4.

Reference Example 18
Instead of the deodorant with the sterilizing function of Example 13, 200 g of (A) peroxide (2 wt% hydrogen peroxide aqueous solution) and 200 g of (B) catechin (2 wt% green tea leaf dry extract) were purified. The same procedure as in Example 13 was performed except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorizer had a pH of 4.39.

Reference Example 19
Instead of the deodorant with the sterilization function of Example 13, (A) 200 g of a peroxide (2 wt% hydrogen peroxide aqueous solution) and (C) 2 g of a proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) were purified water. This was carried out in the same manner as in Example 13 except that a total amount of 1,000 g dissolved in was used as a deodorizer. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorizer had a pH of 4.37.

Reference Example 20
Instead of the deodorizing agent with the sterilization function of Example 13, 200 g of (B) catechins (green tea leaf 2% by weight dry distillation extract) and 2 g of (C) proteolytic enzyme agent (a mixture of equal amounts of pepsin and papain) were purified. The same procedure as in Example 13 was performed except that a total amount of 1,000 g dissolved in water was used as a deodorizer. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorant had a pH of 4.75.

Reference Example 21
Instead of the deodorizing agent with the sterilizing function of Example 13, (D) 3 g of inorganic salts (sodium nitrate), (E) 6 g of chelating agent (EDTA), 5.3 g of deodorizing active ingredient (alkylsulfosuccinate), pH Conditioner (gallic acid) 3 g, alcohols (glycerin) 5 g, stabilized chlorine dioxide (Puorogen from Bioside Japan) 2 g, fragrances (lavender oil) 5 g, semiconductor photocatalyst (visible light responsive photocatalyst dispersion manufactured by Ishihara Sangyo) MPT-428) The same procedure as in Example 13 was conducted except that 1 g of MPT-428 was dissolved in pure water to make a total amount of 1,000 g as a deodorizer. The results are shown in Table 8, Table 9, FIG. 6 and FIG. The deodorant had a pH of 5.03.

  In the above table, the odor sensory test evaluation criteria, “Odor intensity score”, “Stimulus score”, and “Pleasure / discomfort score” are evaluation criteria in the olfactory measurement method, and “odor intensity” refers to human sensation. Is quantified in 6 stages. “Stimulation” is also a numerical expression of human senses in four stages, and “Pleasure / discomfort” is a numerical value of the odor smell judgment scale.

  As shown in Examples 13 and 14 of Tables 8 and 9, a deodorizer with a sterilization function containing (A) a peroxide, (B) catechins, and (C) a proteolytic enzyme agent of the present invention. Compared with a deodorant containing only one component among the components (A) to (C), or a deodorizer containing only two components selected from (A) to (C), It was found that one agent has an effective and sufficient sterilization and deodorization effect. Furthermore, by containing (D) inorganic salts and (E) chelating agent in the components (A) to (C), the living bacteria can be obtained without impairing the sterilization and deodorizing effect of the drugs (A) to (C). It was found that it is possible to extend the duration of the sterilization and deodorizing effect of

Configuration example 1 of drip supply device
FIG. 9 shows a configuration example of the dropping supply device used in this example. The dripping supply device is provided with an input port 2 with a cap on a vertical dripping pack 1, and a discharge port 3, an adjustment valve 4, a dripping pot 5, a tube 6, and a dripping nozzle 7 at the lower part of the vertical dripping pack 1. Are provided in this order.
The vertical dripping pack 1 is a multi-layer plastic sheet with high gas barrier properties (polyethylene // nylon // polyethylene terephthalate = 0.13 mm // 0.015 mm // 0.012 mm, total sheet thickness 0.2 mm) cut into a vertical shape. (Size: Triangular pyramid apex distance 18cm, upper base part distance 9cm, left and right hip part apex distance 23.5cm), the sides other than the upper base part are sealed with a thermocompression sealing machine, so that the capacity of the pack becomes 1 liter It has been made.

In order to facilitate installation, a bracket was attached to each side. A sliding roller valve that can adjust the flow range from minute flow to large is adopted. A catheter needle having a slit groove was adopted as a nozzle so that a liquid bulb at the tip of the nozzle can be easily formed at the time of dropping.
In addition, the pack body and drip tube part can be attached and detached one-touch, and moreover, the attachment and removal can be performed many times. Detachable polyethylene packing was adopted.
In addition, a cap is screwed into the input / output port of the pack, but a screw stopper was added to the port side to prevent cap stress cracking due to excessive screwing.
Also, the cap screw part concave side and the port thread part convex thread edge part are cut into a round shape to increase the clearance between the screw part and the screw part and release the stress generated in this part. Thus, it was made possible to avoid stress cracking that occurs in the cap portion.
Furthermore, a dropping pot was attached in the middle of the tube so that bubbles would not be caused by bubbles remaining in the dropping tube, so that the bubbles could escape and the stability of dropping was not impaired. A tube thermoplastic elastomer (AAL00003 manufactured by Tygon Co., Ltd.) made of a material having a high pressure resistance and a strong restoring force was used for the tube portion on which the roller valve for controlling the flow rate was mounted.

Example 15
(A) 200 g of peroxide (2 wt% hydrogen peroxide aqueous solution) (4 g as 100 wt% hydrogen peroxide), (B) 200 g of catechin (2 wt% green tea leaf dry extract) as 100 wt% green tea leaves 4 g), (C) 2 g of proteolytic enzyme agent (pepsin, papain equivalent mixture) was dissolved in pure water to produce a deodorant with a sterilization function with a total amount of 1,000 g, and obtained in Processing Example 1 800 ml was put into the dropping supply device, and a deodorizing agent supply device with a sterilization function was prepared. Set the dropping flow rate of this deodorant supply device with a sterilization function to 0.01 ml / min with an adjustment valve, drop it into a 300 ml measuring cup for 10 hours in a continuous manner for 24 hours in a 22 ° C environment, and measure it regularly on a precision balance every day. The effectiveness of dripping accuracy was confirmed. The pH of the deodorizer was 3.96. The results are shown in Table 10 and FIG.

Reference Example 22
It replaced with the dripping supply apparatus obtained in the processing example 1, and carried out similarly to Example 15 except having used the commercially available capillary-type dripping supply apparatus (Dia Aqua Solutions Co., Ltd. make, brand name pack L). The results are shown in Table 10 and FIG.

Reference Example 23
It replaced with the dripping supply apparatus obtained in the processing example 1, and carried out similarly to Example 15 except having used the commercially available PET bottle type dripping supply apparatus (Good Life Shop Co., Ltd. automatic watering water supply). The results are shown in Table 10 and FIG.

  As Example 15 and Reference Examples 22 and 23 in Table 10 show, the deodorant dropping supply device with a sterilizing function prepared in Processing Example 1 (Example 15) accurately drops the deodorant with a sterilizing function. It was shown that it can be supplied, and it can be suitably used for removal of malodorous sources and harmful bacteria.

  In the capillary type dropping supply device used in Reference Example 22, a tube applying the principle of capillary tube is connected to the container body at the dropping nozzle part, and the liquid in the container is sucked and dropped by the capillary principle. However, due to factors such as the length of the tube, the length of the capillary tube, and changes in the environmental temperature, it was difficult to control the dropping of a certain amount. In the PET bottle type drip supply device used in Reference Example 23, a dripping nozzle having a hole with a constant diameter is attached to the PET bottle, and the hole of the nozzle is always capped with a force of a spring. When the pressure in the PET bottle (primary pressure) overcomes the pressure on the secondary side of the nozzle, the spring is pushed up to open the lid, and the liquid is supplied dropwise through a hole with a certain diameter. With the supply device, the number of drops drastically fluctuated due to changes in the head pressure such as the height of the PET bottle and the inner solution, and the expansion and contraction of the liquid depending on the ambient temperature, making it difficult to control the dropping.

Preparation Example 2
3 g of sludge separated and collected from the parlor wastewater is suspended in 50 g of 0.9% physiological saline and stirred for 10 minutes with a stirrer, and the resulting slurry solution is filtered through a commercially available filter paper (manufactured by Advantech) 5C125mm. After filtration, 20 g of liquid is obtained. Next, a solution obtained by mixing and dissolving the filtered solution in 980 g of pure water is cultured for 24 hours in a 37 ° C. incubator to prepare a cell culture solution having a viable cell count of 1 × 10 ⁵ . Thereafter, 10 g of the obtained bacterial cell culture solution was sprayed onto a 10 cm × 10 cm square knitted cloth using a hand spray to obtain a bacterial cell-supporting cloth sheet.

Here, parlor wastewater is a cream-colored or brown-colored wastewater in which milking machine washing water and excreta used in cowsheds are turbid, with a minimum of 1 * 10 ⁶ bacteria and a odor. It refers to wastewater that is drained mainly by livestock farmers with level 5 odors that smell stunningly with odor intensity.

Example 16
(A) Peroxide (6 wt% hydrogen peroxide aqueous solution) 330 g (19.8 g as 100 wt% hydrogen peroxide), (B) Catechin (green tea leaf 6 wt% dry distillation extract) 330 g (100 wt% green tea) 19.8 g as leaves), (C) 2 g proteolytic enzyme agent (pepsin, papain equivalent mixture), (D) 3 g inorganic salts (sodium nitrate), (E) 5 g chelating agent (PDTP), pH adjuster (overload) 1 g of sodium carbonate and 1 g of nano silver (PR-WB14R particle size: 10 nm, manufactured by Nippon Ion) were dissolved and dispersed in pure water to prepare a deodorizing agent with a sterilizing function with a total amount of 1,000 g. This deodorizer is sprayed with 10 g of the fungus cloth sheet obtained in Preparation Example 2 by hand spraying, left at room temperature in a plastic bag until after 1 day, and then shaken 5 times in a container containing 100 g of ultrapure water. Wash. The bacterial cells in the solution after shaking washing are cultured and detected in an incubator at 37 ° C. for 24 hours using a simple microorganism measuring device Sun Bio Checker for total bacterial count measurement (manufactured by Sanai Petroleum). The bacterial cell carrying sheet that has been washed by shaking is sprayed again with 10 g of the bacterial cell culture solution obtained in Preparation Example 2, placed in a plastic bag, and left at room temperature. This operation from washing to bacterial cell detection is performed once a time / about every 3 to 7 days, and is continued until the number of shaking washing is 45 times, and sterilized from the total bacterial state including molds present in the washing liquid. The odor intensity was evaluated by obtaining the rate and confirming the sensory odor state generated by the biochecker after 24 hours of culture. The results are shown in Table 11 and FIG. The deodorant had a pH of 4.01.

Reference Example 24
The same procedure as in Example 16 was performed except that pure water was used instead of the deodorizing agent with the sterilizing function in Example 16 and the total amount was 1000 g. The pH of the deodorizer was 5.67. The results are shown in Table 11 and FIG.

Example 17
In place of the deodorizer with the sterilizing function of Example 16, (A) peroxide (6 wt% hydrogen peroxide aqueous solution) 330 g (19.8 g as 100 wt% hydrogen peroxide), (B) catechins (green tea) 330 g (19.8 g as 100 wt% green tea leaf), 2 g of (C) proteolytic enzyme agent (mixed mixture of pepsin and papain), (D) 3 g of inorganic salts (sodium nitrate), E) It carried out like Example 16 except having used 5 g of chelating agents (PDTP), and 1 g of pH adjusters (sodium percarbonate). The results are shown in Table 11 and FIG. The deodorant had a pH of 4.01.

  As shown in Example 16 of Tables 11 and 12, (A) peroxide, (B) catechins, (C) proteolytic enzyme agent, (D) inorganic salts, (E) chelating agent, pH adjustment The deodorizer with a sterilization function containing the agent and the nanosilver agent is a deodorizer (Example 15) containing (A) to (E) or a deodorizer containing no (A) to (E) ( Compared with Reference Example 24), it is possible to suppress the sterilization antibacterial action and the odor generated from the cells for a long time and at the same time extend the duration of the sterilization antibacterial deodorization effect on the total bacteria. It was.

1 ・ ・ 嬰 type dripping pack 2 ・ ・ Input port with cap 3 ・ ・ Discharge port 4 ・ ・ Adjusting valve 5 ・ ・ Drip pot 6 ・ ・ Tube 7 ・ ・ Drip nozzle

Claims (9)

  A deodorizer with a sterilizing function, comprising a peroxide (A), a catechin (B), and a proteolytic enzyme agent (C).   Furthermore, inorganic salt (D) and / or a chelating agent (E) are contained, The deodorizer with the microbe elimination function of Claim 1 characterized by the above-mentioned.   The proteolytic enzyme agent (C) is at least one selected from the group consisting of trypsin, protamine, pepsin, papain, bromelain, pancreatin, protease, lipase, aminopeptidase, and carboxypeptidase. The deodorizer with the disinfection function according to claim 1 or 2.   The water-absorbing polymer material which is molded into a circular, elliptical or polygonal sheet, particle or foam and has a water retention ratio of 1 to 50 times, according to any one of claims 1 to 3. A deodorizing material with a sterilizing function, which is impregnated with a deodorizing agent with a sterilizing function.   The water-absorbing polymer material comprises a hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule and an amine compound (b) having two or more primary or secondary amino groups in one molecule. The deodorizing material with a sterilization function according to claim 4, wherein the deodorizing material is obtained by curing and molding a composition containing as an essential component.   Composition containing, as essential components, a hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule and an amine compound (b) having two or more primary or secondary amino groups in one molecule An aqueous solution containing the deodorizing agent with the antibacterial and antibacterial function according to any one of claims 1 to 3 is blended with a product, cured in a water-containing state, and in a circular, elliptical, polygonal sheet shape, particle shape or A deodorizing material with a sterilizing function, which is obtained by molding into a foam.   The deodorizer with a sterilizing function according to any one of claims 1 to 3 filled in a plastic pack is supplied by instillation in a range of 0.01 ml to 200 ml per minute. A deodorizing and dropping device with a sterilizing function.   The deodorizing agent dripping which supplies the deodorizing agent with the sterilization function according to any one of claims 1 to 3 which is filled in the plastic pack by instillation in a range of 0.01 ml to 200 ml per minute. Supply method.   Spraying the alcohol-containing water containing the deodorizer with the sterilization function according to any one of claims 1 to 3 or the deodorizer with the sterilization function with fine particles having a particle diameter of 0.1 to 50 µm. A method for spraying a deodorizing agent.

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