Deodorant

Abstract

To provide a deodorant which can effectively deodorize malodors of a fatty acid compound type, an amine compound type, a sulfur compound type and a neutral compound type in a well-balanced state, uses anions existing in nature, does not contain sulfate ions and chloride ions, can contribute to environmental preservation, is water-soluble, is safe in spite of repetitive use and makes end consumers feel safe.SOLUTION: The deodorant contains at least one zinc citrate complex selected from zinc monohydrogen citrate and zinc dihydrogen citrate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a deodorizer that can be used for cleaning linens in hospitals and nursing homes, deodorizing furniture, especially living room furniture, and homes, deodorizing during cleaning and dry cleaning in hospitals, nursing homes, and factories, and deodorizing during special cleaning, and that can be sprayed or applied in sol or aqueous solution form, or placed in aqueous solution form, gel or sol form, or impregnated into a carrier, to remove bad odors. [Background technology]

[0002] Furniture, especially living room furniture such as sofas and chairs, carpets, curtains, beds, futons, cushions, mattresses, toilets, rooms, walls, shoe cabinets, pet hygiene products, kitchens and other areas where food waste is generated, patient rooms in hospitals and nursing homes, private rooms in nursing homes, offices, lodgings, and entertainment facilities that require building maintenance, and car, train, and airplane seats are often deodorized by spraying, applying, or wiping. In addition, when cleaning linens in hospitals and nursing homes that are stained with blood or other filth and cannot be deodorized by washing, commercial deodorizers containing enzymes and deodorizing ingredients are sprayed to eliminate odors. Furthermore, in special cleaning areas where odors are too strong for standard house cleaning, such as rooms where people have died alone, properties where accidents have occurred, so-called garbage houses, facilities where multiple animals are kept, and fire sites, commercial specialty deodorizers are also used to remove odors such as excrement, bloodstains, the smell of death, garbage, decay, and animal odors.

[0003] These odors can be broadly divided into different types: fatty acid compound odors such as isovaleric acid, which are derived from body odor, sweat odor, aging, etc. or are produced by bad bacteria such as normal inhabitants of the body and various germs; aromatic amine compound odors such as ammonia and trimethylamine, which are derived from body odor, sweat odor, aging, excrement, putrid urine, biological components, and fishy odors, indole, which is derived from feces, and pyridine, which is derived from smoking; sulfur compound odors such as hydrogen sulfide and methyl mercaptan, which has a mercapto group, which are derived from feces, rotten vegetables, and biological components; and neutral compound odors such as methyl sulfide and nonenal, which are produced by bad bacteria, which are normal inhabitants of the body and various germs.

[0004] There are several mechanisms for eliminating such bad odors: chemical deodorization, which involves reacting the bad odor components with deodorant components to neutralize or oxidize them, thereby turning them into odorless components; physical deodorization, which involves suppressing or wrapping up the bad odor components and preventing them from volatilizing by adsorption or encapsulation; biological deodorization, which involves using antibacterial agents to inhibit the growth of bacteria that causes odors such as garbage garbage, or using microorganisms to prey on the bacteria; and sensory deodorization, which involves masking the bad odor components by disguising them with aromatic components.

[0005] Chemical deodorization methods are fast-acting, have a large deodorizing capacity, and are less likely to re-release malodorous components, but they are only effective against specific types of malodorous compounds, such as fatty acid compounds, and tend to have difficulty deodorizing different types of malodorous compounds, such as amine compounds. Physical deodorization methods are easy to deodorize different types of malodorous compounds, but have a small deodorizing capacity and are more likely to re-release malodorous components. Biological deodorization methods not only limit the types of bacteria for which antibacterial agents are effective, but also take time to inhibit or prey on bacterial growth and have a relatively small deodorizing capacity. Sensory deodorization methods do not fundamentally remove malodorous components, so the masking effect weakens over time and the deodorizing effect does not last long.

[0006] The present inventors and applicants manufacture and sell deodorants that use chemical deodorizing methods to eliminate malodors from fatty acid compounds, amine compounds, and sulfur compounds.

[0007] The market size of commercially available household and commercial deodorizers is overwhelmingly dominated by those using chemical deodorization methods. For example, Patent Document 1 discloses a gel-like deodorizer obtained by mixing an aqueous solution of a deodorizer containing zinc sulfate, magnesium sulfate, aluminum sulfate, and potassium hydrogen sulfate as its main ingredients with an aqueous solution of a mixed acrylamide and N,N-methylenebisacrylamide as a gel-like component, and polymerizing the mixture using a persulfate or a redox catalyst as a catalyst.

[0008] Zinc sulfate, magnesium sulfate, aluminum sulfate, and potassium hydrogen sulfate are all soluble in water and dissociate to form sulfate ions (SO4 2- As a deodorizing ingredient, sulfate ions are anions derived from strong acids, but from the viewpoints of environmental conservation, consumer peace of mind, and safety, there is a demand for deodorizers that use salts or complexes of naturally occurring anionic species and safe metal cation species.

[0009] Patent Document 2 discloses a safe deodorizing, disinfecting, and cleaning agent having a pH of 3.0 to 5.0, which contains a) a weakly acidic citrate buffer solution consisting of citric acid and sodium citrate and / or potassium citrate, b) green tea extract, c) an amphoteric surfactant, and d) a cationic surfactant.

[0010] As a result of investigations by the present inventors, it was found that citric acid, sodium citrate, etc. were insufficient to effectively and balancedly deodorize malodors from fatty acid compounds, amine compounds, sulfur compounds, and neutral compounds. However, through intensive research and development, the inventors discovered a highly safe deodorizer that effectively and balancedly deodorizes these malodors, thereby completing the present invention. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Publication No. 8-308916 [Patent Document 2] Japanese Patent Publication No. 2022-165881 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made to solve the above-mentioned problems, and aims to provide a deodorizer that can effectively deodorize malodors from fatty acid compounds, amine compounds, sulfur compounds, and neutral compounds in a balanced manner, that uses naturally occurring anions, does not contain sulfate ions or chloride ions, contributes to environmental conservation, is water-soluble, is safe even when used repeatedly, and gives end consumers a sense of security. [Means for solving the problem]

[0013] The deodorant made to achieve the above object is characterized by containing at least one zinc citrate complex selected from zinc monohydrogen citrate and zinc dihydrogen citrate.

[0014] This deodorant is preferably an aqueous solution, gel, or sol containing the zinc citrate complex, or a carrier impregnated with any of these.

[0015] It is preferable that the deodorant contains the zinc citrate complex in an amount of 0.01 to 0.5% by mass in the aqueous solution.

[0016] It is more preferable that the deodorant contains the zinc citrate complex in the form of zinc monohydrogen citrate in an amount of 0.05 to 0.5% by mass in the aqueous solution.

[0017] This deodorant may contain the zinc citrate complex in the form of zinc dihydrogen citrate in an amount of 0.025 to 0.2 mass % in the aqueous solution.

[0018] This deodorizer has the property of reducing the odor of ammonia by at least 70%, the odor of hydrogen sulfide by at least 70%, and / or the odor of acetic acid by at least 70%, for example, in accordance with the SEK Mark textile product certification standard (deodorizing test) of the Japan Textile Evaluation Technology Council.

[0019] In this deodorant, the aqueous solution may contain a zinc ion component.

[0020] It is even more preferable that this deodorant be an aqueous solution, gel, or sol containing the zinc citrate complex, or a carrier impregnated with any of these, thereby serving as an antiallergic agent, antiviral agent, deodorizer, and / or sterilizer, disinfectant, disinfectant, or antibacterial agent.

[0021] Specifically, the antiallergic effect of this deodorant as an antiallergic agent is a reduction rate of Dermatophagoides farine allergens of at least 80% and / or a reduction rate of Japanese cedar pollen allergens of at least 50% in accordance with ISO 4333, the antiviral effect as the antiviral agent is such that the antiviral activity value against influenza virus in accordance with JIS 1922:2016 is 3.0 or more, and / or The antibacterial activity as an antibacterial agent has the property that the antibacterial activity value against Staphylococcus aureus is at least 2.0 and / or the antibacterial activity value against Escherichia coli is at least 2.0 according to the test method of JIS L1902. [Effects of the Invention]

[0022] The deodorant of the present invention uses, as a deodorizing ingredient, zinc monohydrogen citrate and / or zinc dihydrogen citrate, which are zinc citrate complexes of naturally occurring citrate anions and zinc cations. Because both of these zinc citrate complexes, which are deodorizing ingredients, are water-soluble, their aqueous solutions can be easily prepared and used as deodorants. This deodorant uses citric acid, a natural hydroxy acid found in citrus fruits and other fruits that does not produce sulfate ions upon dissociation and is also a component of the citric acid cycle in vivo, as the anion, and zinc, which has extremely low toxicity, as the cation, without polluting the environment even when used over a wide area or repeatedly, thereby contributing to environmental conservation.

[0023] This deodorant not only has the effect of deodorizing malodors derived from fatty acid compounds, amine compounds, and sulfur compounds, but also exhibits antiallergic, antiviral, deodorizing, and / or disinfecting, bactericidal, or antibacterial effects, so that in addition to these effects, it can also deodorize malodors derived from neutral compounds.

[0024] This deodorizer is highly safe and can be used repeatedly as needed over a wide range of surfaces, including furniture, floors, walls, futons, cushions, mattresses, toilets, rooms, shoe cabinets, pet hygiene products, kitchens, patient rooms in hospitals and private rooms in nursing homes, linens in hospitals and nursing homes, accommodation and entertainment facilities, car, train and airplane seats, rooms where people have died alone, properties where accidents have occurred, so-called garbage houses, collapsed facilities where multiple animals are kept, and fire sites, so workers can use it with confidence on the users and animals of these facilities, and end consumers can feel at ease when using it. DETAILED DESCRIPTION OF THE INVENTION

[0025] Although the embodiments for carrying out the deodorant of the present invention will be described in detail, the scope of the present invention is not limited to these embodiments.

[0026] This deodorant is made of an aqueous solution containing, for example, 0.01 to 0.5 mass % of at least one zinc citrate complex selected from zinc monohydrogen citrate and zinc dihydrogen citrate.

[0027] When the zinc citrate complex is zinc monohydrogen citrate as an active ingredient, this deodorant contains 0.05 to 0.5 mass %, preferably 0.1 to 0.5 mass %, more preferably 0.1 to 0.3 mass %, even more preferably 0.15 to 0.25 mass %, and even more preferably 0.2 mass % in an aqueous solution.

[0028] When the zinc citrate complex is zinc dihydrogen citrate as an active ingredient, this deodorant contains 0.025 to 0.2 mass %, preferably 0.05 to 0.2 mass %, and more preferably 0.1 mass % in an aqueous solution.

[0029] There are three types of zinc citrate complexes: zinc monohydrogen citrate, represented by the following chemical formula (1), in which one molar equivalent of citrate ions with two carboxylate groups and one molar equivalent of zinc ions are complexed together, with two carboxylate groups and two water molecules coordinating to one zinc ion; zinc dihydrogen citrate, represented by the following chemical formula (2), in which two molar equivalents of citrate ions with one carboxylate group and one molar equivalent of zinc ions are complexed together, with two carboxylate groups from the two citrate ions coordinating to one zinc ion; and zinc citrate, represented by the following chemical formula (2), in which two molar equivalents of citrate ions with three carboxylate groups and three molar equivalents of zinc ions are complexed together, with two carboxylate groups each coordinating to three zinc ions. This deodorant uses zinc monohydrogen citrate and / or zinc dihydrogen citrate, which have carboxyl groups, as the active deodorizing ingredient. [ka]

[0030] The deodorant may be in the form of a homogeneous aqueous solution, a gel, or a sol, or may be one impregnated into a carrier. The carrier may be any substrate made of a fibrous material, a polymeric compound, or a natural material, such as fabric, nonwoven fabric, paper, felt, sponge, polymer such as a superabsorbent polymer, or wood.

[0031] Since zinc monohydrogen citrate and / or zinc dihydrogen citrate have an antiallergic effect, an antiviral effect, a disinfecting or bactericidal effect, an antibacterial effect, and / or a deodorizing effect in addition to a deodorizing effect, this deodorant also functions as an antiallergic agent, an antiviral agent, a deodorizing agent, and / or a disinfecting agent, bactericidal agent, or an antibacterial agent.

[0032] Zinc monohydrogen citrate and zinc dihydrogen citrate have 1 molar equivalent and 2 molar equivalents of free carboxylic acid groups remaining, respectively. As organic acid groups, they donate hydrogen ions to amine compounds such as ammonia, trimethylamine, and indole, skatole, and pyridine, thereby ionically binding and trapping them, thereby eliminating odors. Similarly to zinc citrate, the zinc ions ionically bind to sulfur compounds, such as hydrogen sulfide and acidic mercapto compounds, such as methyl mercaptan, and trap sulfur compounds. Zinc monohydrogen citrate and zinc dihydrogen citrate, which are used in food and have a high level of safety, exhibit excellent deodorizing effects through a two-step deodorizing reaction: neutralization of odor molecules by the citric acid component, followed by complexation of odor molecules by the zinc ion component.

[0033] On the other hand, zinc monohydrogen citrate and zinc dihydrogen citrate can deodorize malodors derived from fatty acid compounds such as acetic acid and valeric acid, as well as neutral compounds such as dimethyl sulfide and nonenal, the source of body odor associated with aging. Although the details of the mechanism are unclear, their antibacterial properties suggest that they also have deodorizing properties against malodorous substances such as acetic acid and valeric acid produced by microorganisms. Therefore, it is speculated that some action of zinc monohydrogen citrate and zinc dihydrogen citrate can prevent malodors to a similar or greater extent without the use of adsorbent deodorizers such as activated carbon. Furthermore, zinc monohydrogen citrate and zinc dihydrogen citrate can simultaneously exhibit sterilizing, disinfecting, antibacterial, or antimicrobial effects, as well as inhibiting the production of neutral malodorous compounds and exerting antiallergic effects, through ionic bonding and complex formation between zinc ions and allergenic proteins.

[0034] This deodorant has the following properties: ammonia odor reduction rate of at least 70%, preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, even more preferably 99% or more, and even more preferably 99.5% or more, hydrogen sulfide odor reduction rate of at least 70%, more preferably 75% or more, even more preferably 80% or more, even more preferably 95% or more, and even more preferably 98% or more, and / or acetic acid odor reduction rate of at least 70%, preferably 80% or more, more preferably 85% or more, and even more preferably 87% or more, as determined by a deodorizing test in accordance with the SEK Mark textile product certification standard of the Japan Textile Evaluation Technology Council.

[0035] On the other hand, zinc monohydrogen citrate and zinc dihydrogen citrate can also simultaneously exert an antiviral effect that reduces the number of viruses such as influenza viruses.

[0036] The antiallergic activity of this deodorant, when measured in accordance with the ISO 4333 test method (test for evaluating the activity of reducing proteins derived from pollen, dust mites, etc.), is such that it reduces allergens such as live or dead bodies of Dermatophagoides farinae (allergy-derived protein Derf2) or excrement (Derf1) and house dust such as Dermatophagoides pteronyssinus excrement (Derp1) by at least 80%. And / or, when measured in accordance with the same test method, it reduces allergens such as Japanese cedar pollen allergen Crytomeria japonica (protein derived from the surface of pollen is Cryj1, and protein derived from the interior of pollen is Cryj2) by at least about 50%.

[0037] When the antiviral activity of this deodorant as an antiviral agent is measured in accordance with JIS 1922:2016 (Testing method for antiviral activity of textile products), the antiviral activity value against influenza viruses (e.g., H3N2 type) is 3.0 or higher, preferably 4.0 or higher, and more preferably 4.4 or higher.

[0038] The antibacterial activity of this deodorant as an antibacterial agent, when measured in accordance with JIS L1902 (Antibacterial activity test methods and antibacterial effects for textile products), is at least 2.0, preferably 2.2 or higher, against Staphylococcus aureus, an intestinal bacterium that is a normal inhabitant of the skin and digestive tracts of humans and animals and that causes various superficial skin infections such as abscesses, food poisoning, and potentially fatal infectious diseases such as inflammations including pneumonia, meningitis, and sepsis. And / or, when measured in accordance with JIS L1902, the antibacterial activity of this deodorant is at least 2.0, preferably 2.2 or higher, against Escherichia coli, a gram-negative bacillus that is a facultative anaerobic bacterium, some of which are phenotypic and can cause serious food poisoning.

[0039] This deodorant contains an aqueous solution of the zinc citrate complex, which is the active ingredient of zinc monohydrogen citrate and / or zinc dihydrogen citrate, that is odorless and colorless, and the active ingredient is highly stable, does not become cloudy, can be stored stably for a long period of time, and does not lose its efficacy even when used after storage.

[0040] This deodorant preferably uses at least one of zinc monohydrogen citrate and zinc dihydrogen citrate as an active ingredient.

[0041] As long as this deodorant contains a zinc citrate complex, which is zinc monohydrogen citrate and / or zinc dihydrogen citrate, as an active ingredient, it may also contain other citrate complexes or citrate salts, such as sodium monohydrogen citrate, which has a high odor reduction rate for amine compound-based malodors and fatty acid compound-based malodors, or sodium dihydrogen citrate, which has a high odor reduction rate for fatty acid compound-based malodors even at lower concentrations.

[0042] This deodorant may contain a zinc ion component other than the zinc citrate complex. Examples of such zinc ion components include those derived from inorganic zinc salts such as zinc chloride, zinc sulfate, zinc iodide, and zinc phosphate, and those derived from organic acid zinc complexes or organic acid zinc salts such as zinc lactate and zinc oleate. The inclusion of a zinc ion component other than the zinc citrate complex can improve the deodorizing ability of the deodorant against malodors from sulfur-based compounds such as hydrogen sulfide, which is specific to zinc ion components.

[0043] This deodorant may contain various additives commonly used in foods, beverages, and pharmaceuticals, such as antioxidants, preservatives, pH adjusters, surfactants, binders, and / or gelling agents.

[0044] This deodorant can be produced, for example, as follows. Zinc monohydrogen citrate can be prepared by dissolving citric acid and zinc oxide in pure water in a molar ratio of 1:1, while zinc dihydrogen citrate can be prepared by dissolving citric acid and zinc oxide in pure water in a molar ratio of 2:1. This deodorant can be obtained by diluting zinc monohydrogen citrate or zinc dihydrogen citrate with pure water to a predetermined concentration.

[0045] This deodorizer can be used, for example, as follows: The deodorizer in aqueous solution, gel, or sol form can be sprayed, applied, or wiped onto the object to be deodorized to remove the malodorous components, or the deodorizer can be impregnated into a carrier to support the object and remove the malodorous components, thereby eliminating the malodor. [Example]

[0046] Examples to which the present invention is applied and comparative examples to which the present invention is not applied will be described in detail below.

[0047] (Preparation Example 1-1: Preparation of zinc monohydrogen citrate stock solution) 6.60 g (0.0344 mol) of citric acid and 2.80 g (0.0344 mol) of zinc oxide were dissolved in 90.6 g of pure water and stirred for 30 minutes or more to prepare 100 g of a 10 mass % concentration zinc monohydrogen citrate stock solution.

[0048] (Preparation Example 1-2: Preparation of a deodorant containing an aqueous solution of zinc monohydrogen citrate) The zinc monohydrogen citrate stock solution was diluted with water to a predetermined concentration to prepare deodorants consisting of aqueous zinc monohydrogen citrate solutions with the desired concentrations of 0.1 mass%, 0.2 mass%, 0.5 mass%, 1.0 mass%, 5 mass%, and 10 mass%.

[0049] (Preparation Example 2-1: Preparation of zinc dihydrogen citrate stock solution) 11.92 g (0.062 mol) of citric acid and 2.53 g (0.031 mol) of zinc oxide were dissolved in 135.55 g of water and stirred for 30 minutes or more to prepare 150 g of a 10 mass % zinc dihydrogen citrate stock solution.

[0050] (Preparation Example 2-2: Preparation of a deodorant containing an aqueous zinc dihydrogen citrate solution) The zinc dihydrogen citrate stock solution was diluted with water to a predetermined concentration to prepare deodorants consisting of aqueous zinc dihydrogen citrate solutions with the desired concentrations of 0.01 mass%, 0.05 mass%, 0.1 mass%, 0.5 mass%, 1.0 mass%, 5 mass%, and 10 mass%.

[0051] (Comparative Preparation Example 1) A deodorant consisting of an aqueous solution of sodium monohydrogen citrate with a concentration of 0.2% by mass was prepared.

[0052] (Comparative Preparation Example 2) A deodorant was prepared from an aqueous zinc chloride solution so that the zinc molar concentration (6.88 mmol / kg) was the same as that of 0.2% by mass of zinc monohydrogen citrate.

[0053] (Comparative Preparation Example 3) A deodorant consisting of an aqueous solution of monosodium dihydrogen citrate with a concentration of 0.05% by mass was prepared.

[0054] (Comparative Preparation Example 4) A deodorant was prepared from an aqueous zinc chloride solution so that the zinc molar concentration (1.00 mmol / kg) was the same as that of zinc dihydrogen citrate at a concentration of 0.05% by mass.

[0055] Next, the obtained deodorant was subjected to various tests to evaluate its performance.

[0056] (Comparative Examples 1 to 3) For comparison, different types of commercially available deodorants from companies A, B, and C were used.

[0057] (Usability test) The deodorants of various concentrations made of aqueous zinc monohydrogen citrate solutions obtained in Preparation Example 1-2 and the deodorants of various concentrations made of aqueous zinc dihydrogen citrate solutions obtained in Preparation Example 2-2 were sprayed onto cotton fabric, dried, and then observed. It was found that the solids of the 10% by mass deodorants had dried and the fibers had hardened, making them too concentrated to be used as spray products.

[0058] (Deodorizing performance evaluation test) The deodorizing test was conducted in accordance with Chapter 6-4 Deodorizing Test of the SEK Mark Textile Product Certification Standards (revised April 1, 2024) compiled by the Product Certification Department of the Japan Textile Evaluation Technology Council, and measured deodorizing performance using ammonia, acetic acid, and hydrogen sulfide as odor components. The measurement method is outlined below. The deodorization test method was the detector tube method. 1 cc of each deodorant was applied to a cotton fabric and dried to prepare a test sample. Test samples treated with deodorants of various concentrations consisting of aqueous zinc monohydrogen citrate solutions obtained in Preparation Example 1-2, deodorants of various concentrations consisting of aqueous zinc dihydrogen citrate solutions obtained in Preparation Example 2-2, and deodorants obtained in Preparation Comparative Examples 1 to 4 and Comparative Examples 1 to 3 were placed in 5L Tedlar bags, and malodorous gases of predetermined concentrations (initial ammonia concentration 100 ppm, initial acetic acid concentration 30 ppm, initial hydrogen sulfide concentration 4 ppm) were injected to start the test. After injecting malodorous gas into each Tedlar bag and leaving it for 2 hours, the concentrations (ppm) of ammonia, acetic acid, and hydrogen sulfide were measured using the gas detector. As a control blank test, ammonia, acetic acid, and hydrogen sulfide were measured using the detector tubes in the same manner except that no deodorant was used. The following formula (1) was used.

number

[0059] [Table 1]

[0060] [Table 2]

[0061] [Table 3]

[0062] [Table 4]

[0063] [Table 5]

[0064] As is clear from Tables 1 and 3, the deodorizer composed of zinc monohydrogen citrate aqueous solution in Preparation Example 1-2, at concentrations of 0.1 to 0.2 mass%, exceeded the 70% evaluation standard for sufficient odor reduction against ammonia, acetic acid, and hydrogen sulfide, as defined by the SEK Mark textile product certification standards. On the other hand, the 0.2 mass% concentration of disodium monohydrogen citrate in Comparative Preparation Example 1 exceeded the same evaluation standard against ammonia and acetic acid, but fell well below the standard against hydrogen sulfide. However, the aqueous solution of zinc chloride in Comparative Preparation Example 2, at 7.97 mmol / L (the same zinc molar concentration as that of 0.2 mass% zinc monohydrogen citrate), exceeded the same evaluation standard against ammonia, acetic acid, and hydrogen sulfide, but zinc chloride is a designated deleterious chemical.

[0065] As is clear from Tables 2 and 4, the deodorant composed of an aqueous zinc dihydrogen citrate solution in Preparation Example 2-2, at a concentration of 0.1% by mass, exceeded the evaluation standard for ammonia and acetic acid, but was slightly below the evaluation standard for hydrogen sulfide. Meanwhile, the monosodium dihydrogen citrate solution in Comparative Preparation Example 3, at a concentration of 0.05% by mass, exceeded the evaluation standard for acetic acid, but was significantly below the evaluation standard for ammonia and hydrogen sulfide. Meanwhile, the monosodium dihydrogen citrate solution in Comparative Preparation Example 3, at a concentration of 0.05% by mass, exceeded the evaluation standard for acetic acid, but was significantly below the evaluation standard for ammonia and hydrogen sulfide. However, the aqueous solution composed of a 1.13 mmol / L aqueous zinc chloride solution (the same zinc molar concentration as that of 0.05% zinc dihydrogen citrate) in Comparative Preparation Example 4 exceeded the evaluation standard for acetic acid and hydrogen sulfide, but was slightly below the evaluation standard for ammonia.

[0066] In contrast, as is clear from Table 5, all commercially available deodorants fell well below the evaluation standards for ammonia and hydrogen sulfide.

[0067] From the results of these deodorizing performance evaluation tests, the deodorizers of Preparation Examples 1-2 and 2-2 to which the present invention is applied are superior in deodorizing effect and safety to the deodorizers of Comparative Preparation Examples 1 to 4 to which the present invention is not applied and the commercially available Comparative Examples 1 to 3.

[0068] (Anti-allergy evaluation test 1: Dermatophagoides farinae allergen) The anti-allergic evaluation test was conducted in accordance with ISO 4333 (measurement of activity to reduce proteins derived from pollen mites, etc.). The results are shown in Table 6-1.

[0069] [Table 6-1]

[0070] (Anti-allergy evaluation test 2: Japanese cedar pollen allergen) Measurements and calculations were carried out in the same manner as in Antiallergic Evaluation Test 1, except that the allergen, Cryj1, a protein derived from the surface of Japanese cedar pollen (Cryotomeria japonica), was used instead of the protein solution derived from Dermatophagoides farinae allergen. The results are shown in Table 6-2.

[0071] [Table 6-2]

[0072] As is clear from Table 6, both the deodorizer consisting of an aqueous solution of zinc monohydrogen citrate and the deodorizer consisting of an aqueous solution of zinc dihydrogen citrate showed a reduction rate of approximately 80 to 96% against Dermatophagoides farinae allergens and approximately 50 to 52% against Japanese cedar allergens, demonstrating their anti-allergic properties.

[0073] (Antiviral evaluation test 1: influenza virus) The antiviral evaluation test was performed in accordance with JIS L 1922:2016 (antiviral test method for textile products). Specifically, the virus infectivity titer was measured using a plaque assay against influenza A virus (H3N2): ATCC VR-1679. The results are shown in Table 7. [Table 7]

[0074] As is clear from Table 7, both the deodorant made from an aqueous solution of zinc monohydrogen citrate and the deodorant made from an aqueous solution of zinc dihydrogen citrate exhibited a high antiviral activity value of approximately 4.4 against influenza viruses, demonstrating excellent antiviral properties.

[0075] (Antibacterial test 1: Staphylococcus aureus) When the antibacterial activity of Staphylococcus aureus was measured using the bacterial liquid absorption method of JIS L 1902:2015 (antibacterial test method and antibacterial effect of textile products), the standard fabric growth value was 2.7, and the antibacterial activity of the standard fabric was 2.7 when 100 mL / m of 1% by mass zinc hydrogen citrate aqueous solution was measured. 2 Treated cotton fabric, 100 mL / m of 1% by mass aqueous solution of zinc dihydrogen citrate 2 The antibacterial activity value for both treated cotton fabrics was 5.8.

[0076] (Antibacterial Test 2: Escherichia coli) The antibacterial activity of Escherichia coli was measured in the same manner as in Antibacterial Test 1, except that Escherichia coli was used. The standard fabric growth value was 3.3, and the antibacterial activity of the deodorant, which was a 1% by mass aqueous solution of zinc hydrogen citrate, at 100 mL / m 2 Treated cotton fabric, 100 mL / m of deodorant made of 1% by mass of zinc dihydrogen citrate aqueous solution 2 The antibacterial activity value for both treated cotton fabrics was 6.4.

[0077] As is clear from the results of the antibacterial test, both the aqueous zinc monohydrogen citrate solution and the aqueous zinc dihydrogen citrate solution exhibited high antibacterial activity.

[0078] (Skin irritation evaluation test) The acute skin irritation evaluation test in rabbits was conducted in accordance with OECD (Organization for Economic Co-operation and Development) Test Guideline TG404 for the testing of chemicals. The criteria for judgment were based on OECD TG404, with erythema / eschar: 0 - 4 points and edema: 0 - 4 points. The evaluation criteria were to calculate the primary irritation index (P.I.I.) by averaging the average scores of erythema and edema 24 and 72 hours after application. When P.I.I. = 0, it was considered a non-irritant; when 0 < P.I.I. ≤ 2, it was a weak irritant; when 2 < P.I.I. ≤ 5, it was a moderate irritant; when 5 < P.I.I. ≤ 8, it was a strong irritant. For the safety evaluation, no skin irritation reaction was observed for either the zinc hydrogen citrate aqueous solution or the zinc dihydrogen citrate aqueous solution, and the P.I.I. was 0. The evaluation category was non-irritant.

[0079] As is clear from the results of the skin irritation evaluation test, neither the deodorant composed of an aqueous solution with a 1% by mass concentration of zinc hydrogen citrate nor the deodorant composed of an aqueous solution with a 1% by mass concentration of zinc dihydrogen citrate showed acute skin irritation and was safe. No abnormalities in body weight and general condition were observed in the test rabbits. Therefore, it is extrapolated that even deodorants with a concentration lower than 1% by mass are free of acute skin irritation.

[0080] (Eye Irritation Evaluation Test) The eye irritation evaluation test is a change using as indicators the redness, swelling, secretions of the conjunctiva, changes in the iris, and cloudiness of the cornea caused by directly contacting the test substance with the eye. The eye irritation test is conducted to predict the damage to the conjunctiva, iris, and cornea that occurs when a human applies a test substance to the mucosa or accidentally gets it into the eye. When the eye irritation evaluation test was conducted by determining the irritation reaction to the eye mucosa 1, 24, 48, and 72 hours after administration in rabbits, neither the deodorant composed of an aqueous solution with a 1% by mass concentration of zinc hydrogen citrate nor the deodorant composed of an aqueous solution with a 1% by mass concentration of zinc dihydrogen citrate showed eye irritation and was safe. No abnormalities in body weight and general condition were observed in the test rabbits. Therefore, it is extrapolated that even deodorants with a concentration lower than 1% by mass are free of acute skin irritation.

[0081] (Acute oral toxicity evaluation test) In the acute oral toxicity evaluation test, the test substance was orally administered at 300 mg / kg and 2000 mg / kg, and mortality was measured and general conditions were observed. No deaths were observed with either the deodorant consisting of a 1% by mass aqueous solution of zinc monohydrogen citrate or the deodorant consisting of a 1% by mass aqueous solution of zinc dihydrogen citrate. 50 It was estimated that the concentration of chlorine in the air was more than 2000 mg / kg, and it was recognized as Category 5 / Not classified in the GHS classification. Therefore, it was confirmed that it is neither a deleterious substance nor a poisonous substance in light of the handling standards for poisonous and deleterious substances, and is extremely safe.

[0082] As is clear from the above results, the deodorant to which the present invention is applied has a superior deodorizing effect compared to conventional deodorants, and can effectively deodorize malodors of fatty acid compounds, amine compounds, sulfur compounds, and neutral compounds in a balanced manner. In addition to deodorizing function, the deodorant has anti-allergic function, antiviral function, deodorizing function, and / or sterilizing function, disinfecting function, bacteria-removing function, or antibacterial function, and is non-irritating to the skin and eyes, making it safe, and not only does it contribute to environmental conservation, but it has also been shown to be safe even when used repeatedly, providing peace of mind to end consumers. [Industrial Applicability]

[0083] The deodorizer to which the present invention is applied can also be used as a chemical agent with a wide range of deodorizing effects, such as deodorizing furniture, especially living room furniture, and houses, cleaning linens in hospitals and nursing homes, deodorizing during cleaning and dry cleaning in hospitals, nursing homes, and factories, and deodorizing during special cleaning.

Claims

1. A deodorant characterized by containing at least one zinc citrate complex selected from zinc monohydrogen citrate and zinc dihydrogen citrate.

2. 2. The deodorant according to claim 1, wherein the deodorant is an aqueous solution, gel, or sol containing the zinc citrate complex, or a carrier impregnated with any of these.

3. 2. The deodorant according to claim 1, wherein the aqueous solution contains the zinc citrate complex in an amount of 0.01 to 0.5% by mass.

4. 2. The deodorant according to claim 1, wherein the zinc citrate complex is in the form of zinc monohydrogen citrate and is contained in the aqueous solution in an amount of 0.05 to 0.5% by mass.

5. 2. The deodorant according to claim 1, wherein the zinc citrate complex is zinc dihydrogen citrate and is contained in the aqueous solution in an amount of 0.025 to 0.2% by mass.

6. 2. The deodorizer according to claim 1, characterized in that it reduces the odor of ammonia by at least 70%, the odor of hydrogen sulfide by at least 70%, and / or the odor of acetic acid by at least 70%, in accordance with the SEK Mark textile product certification standard (deodorization test) of the Japan Textile Evaluation Technology Council.

7. 2. The deodorant according to claim 1, wherein the aqueous solution contains a zinc ion component.

8. 2. The deodorizer according to claim 1, wherein the deodorizer is an aqueous solution, gel, or sol containing the zinc citrate complex, or a carrier impregnated with any of these, and thereby serves as an antiallergic agent, antiviral agent, deodorizer, and / or sterilizer, disinfectant, disinfectant, or antibacterial agent.

9. the antiallergic effect as the antiallergic agent is a reduction rate of Dermatophagoides farine allergens in accordance with ISO 4333 of at least 80% and / or a reduction rate of Japanese cedar pollen allergens in accordance with ISO 4333 of at least 50%; the antiviral effect as the antiviral agent is such that the antiviral activity value against influenza virus in accordance with JIS 1922:2016 is 3.0 or more, and / or The antibacterial activity as an antibacterial agent is at least 2.0 against Staphylococcus aureus and / or at least 2.0 against Escherichia coli, as determined by the test method of JIS L1902.

9. The deodorant according to claim 8.

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