Method for suppressing the generation of malodor and agent for suppressing the generation of malodor

Abstract

To provide a method of suppressing generation of odor capable of suppressing generation of the odor, by suppressing proliferation of microbes by a simple method, in a piping on a drainage water side of a toilet apparatus.SOLUTION: A method for suppressing odor generated from a piping of a drainage side of a toilet apparatus, which comprises generating a gas in water using a foaming agent and an organic acid, and causing a water-soluble antimicrobial agent introduce into the water by the gas to reach the piping, and, as the foaming agent, a foaming agent containing 60 mass% or larger of particles of particle size of 63 μm or larger of the entire foaming agent is used, and, as the organic acid, an organic acid containing 25 mass% or larger of particles of a particle size of 300 μm or larger of the whole organic acid is used.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for suppressing the generation of malodors, and more particularly to a method for suppressing the generation of malodors in the drainage side piping of a toilet apparatus. [Background technology]

[0002] Well-known odor components in toilets include hydrogen sulfide and methyl mercaptan derived from feces, and ammonia resulting from scattered urine, but there are many other odor components present in the toilet space. The unpleasant odor that lingers in the toilet space when entering the toilet can be said to be a complex odor made up of a mixture of components from these various sources.

[0003] Conventionally, in order to keep toilet bowls and toilet spaces clean, various products such as cleaning agents, disinfectants, deodorizers, and air fresheners have been used, and are commercially available. Among these, cleaning agents and disinfectants are products that address the source of the odor and suppress the generation of the odor.

[0004] For example, Patent Document 1 proposes a foaming detergent as a cleaning agent for cleaning toilet bowls, in which a cleaning composition is contained in a water-soluble packaging material, the cleaning composition contains (A) an acid, (B) a bicarbonate, and (C) a surfactant, and the proportion of particles of the bicarbonate smaller than 180 μm is 30% by weight or more. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-2295 Summary of the Invention [Problem to be solved by the invention]

[0006] In toilet systems, microorganisms grow due to water and dirt, and they also produce foul odors. In particular, the drainage pipes of toilet systems (hereinafter sometimes referred to as "drain pipes") have trap structures that bend the pipes into S, U, P, and other shapes to prevent sewage odors from rising up the drain pipes, making it difficult for cleaning agents to reach them, creating an environment where microorganisms can easily grow.

[0007] The cleaning agent described in Patent Document 1 is intended to clean the water pool in the toilet bowl and the inner surface of the toilet bowl, but cannot clean the drain pipe.

[0008] In order to treat the trap and the piping behind it with an antimicrobial agent to remove microorganisms that have grown in the drain pipe at the back of the toilet bowl of a toilet device, the water in the bowl must usually be drained, which is a large-scale operation that is not easily carried out in an average household.

[0009] Therefore, an object of the present invention is to provide a method for suppressing the generation of bad odors, which can suppress the growth of microorganisms in a simple manner and suppress the generation of bad odors, for example, in the drain pipe of a toilet device. [Means for solving the problem]

[0010] As a result of extensive research, the inventors discovered that the above-mentioned problems could be solved by introducing a water-soluble antimicrobial agent into water and using a gas generated by a foaming agent and an organic acid as a carrier to deliver the agent to the drain pipe of a toilet device, thereby completing the present invention.

[0011] That is, the present invention is achieved by the following (1) and (2). (1) A method for suppressing foul odors emanating from the drainage pipe of a toilet system, comprising generating gas in water using a foaming agent and an organic acid, and using the gas to transport a water-soluble antimicrobial agent added to the water to the pipe, wherein the foaming agent contains particles with a particle diameter of 63 μm or more in an amount of 60% by mass or more of the foaming agent, and the organic acid contains particles with a particle diameter of 300 μm or more in an amount of 25% by mass or more of the organic acid. (2) The method for suppressing the generation of malodor according to (1) above, characterized in that the foaming agent contains particles with a particle diameter of 63 μm or more in an amount of 60% by mass or more of the total foaming agent, and particles with a particle diameter of less than 63 μm in an amount of 5% by mass or more of the total foaming agent. [Effects of the Invention]

[0012] According to the present invention, simply adding a water-soluble antimicrobial agent to water causes the carrier gas to diffuse the agent and reach the drainage pipe (drain pipe) of the toilet device, thereby easily suppressing the proliferation of microorganisms in the drain pipe of the toilet device. This suppresses the generation of foul odors and is hygienic. Furthermore, because the gas is generated on the water surface side of the puddle, it can also disinfect the surface of the toilet bowl that comes into contact with the water. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a schematic diagram of a flush toilet bowl for illustrating the method for suppressing the generation of malodor of the present invention. [Figure 2] This is a diagram for explaining the test method for the bubble diffusion test, where the upper figure is a side view of the bubble adhesion test device and the lower figure is a bottom view of the bubble adhesion test device. [Figure 3] 1A and 1B are diagrams for explaining a test method for testing the suppression of the generation of offensive odors, in which (a) is a perspective view of an odor confirmation test device, and (b) is a side view of the odor confirmation test device. [Figure 4] FIG. 1 is a schematic diagram showing the configuration of a sterilization test device used in a sterilization test. [Figure 5]1A and 1B are graphs showing the results of the test to confirm the malodor suppression effect in Test Example 5, where (a) is a graph showing the results of Example 2, (b) is a graph showing the results of Comparative Example 2, and (c) is a graph showing the results of Comparative Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in further detail below.

[0015] The method for suppressing the generation of malodors of the present invention is a method for suppressing malodors generated from the drainage-side piping (discharge pipe) of a toilet apparatus, and comprises generating gas in water using a foaming agent and an organic acid, and using the gas to transport a water-soluble antimicrobial agent added to the water to the piping. The foaming agent and the organic acid are each an aggregate of particles, and the foaming agent contains particles with a particle diameter of 63 μm or more in 60% by mass or more of the total foaming agent, and the organic acid contains particles with a particle diameter of 300 μm or more in 25% by mass or more of the total organic acid.

[0016] The foaming agent and organic acid react in water to generate carbon dioxide. When a foaming agent containing particles 63 μm or larger in diameter accounts for 60% or more by mass of the total foaming agent, and an organic acid containing particles 300 μm or larger in diameter accounts for 25% or more by mass of the total organic acid, are added to water. The foaming agent and organic acid sink to a certain extent before dissolving and reacting, allowing the generated gas to easily spread along the bottom of the water. Because the drain pipe of a toilet system is typically located close to the bottom of the water, the generated gas reaches the entrance of this drain pipe. As the gas moves, the components dissolved in the water are carried along by the water current, allowing the water-soluble antimicrobial agent added to the water to also reach the drain pipe. Once the water-soluble antimicrobial agent reaches the drain pipe, it acts on the microorganisms in the pipe, inhibiting bacterial growth and thereby suppressing the generation of odors.

[0017] In the method of the present invention, the depth (water depth) of the water pool into which the foaming agent, organic acid, and water-soluble antimicrobial agent are added is preferably 100 cm or less. If the water depth is too deep, gas bubbles may occur at a position far from the bottom of the water, and the generated gas may not reach the drain pipe. The water depth is more preferably in the range of 75 cm or less, and even more preferably 50 cm or less. There is no particular lower limit to the water depth, but it is preferably 3 cm or more. For example, the general water depth in toilet devices is 10 to 15 cm, and the method of the present invention is most suitable for use with a water depth in this range.

[0018] Examples of foaming agents include carbonates, bicarbonates, percarbonates, and perborates, and it is preferable to contain at least one selected from the group consisting of these. Of these, it is preferable to use carbonates and bicarbonates because of their excellent foaming properties. The foaming agent is in particulate form.

[0019] Examples of carbonates include sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, and ammonium carbonate. Examples of bicarbonates include sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, and ammonium bicarbonate. These carbonates and bicarbonates may be used alone or in combination of two or more. Among these, sodium carbonate, potassium carbonate, sodium bicarbonate, and calcium bicarbonate are preferred because of their excellent foaming properties and versatility.

[0020] In the present invention, the foaming agent is used in a state where particles having a particle diameter of 63 μm or more account for 60% by mass or more of the total foaming agent. In other words, a foaming agent is used such that when the foaming agent is sieved through a sieve with a mesh size of 63 μm, 60% by mass or more of the particles of the total foaming agent remain on the sieve. By using a foaming agent in which particles having a particle diameter of 63 μm or more account for 60% by mass or more of the total foaming agent, when the foaming agent is introduced into water, the foaming agent dissolves near the bottom of the water and reacts with organic acids. The generated gas is more likely to move to the drain pipe, so the water-soluble antimicrobial agent can be moved to the drain pipe along with the gas. The content of particles with a particle diameter of 63 μm or more is preferably 65% ​​by mass or more of the entire blowing agent. There is no particular upper limit, and all of the particles (100% by mass) of the blowing agent may have a particle diameter of 63 μm or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0021] It is also preferable to use a blowing agent containing particles with a particle diameter of less than 63 μm at 5% by mass or more of the total blowing agent, which improves the diffusibility of the generated gas. The content of particles having a particle diameter of less than 63 μm is more preferably 10% by mass or more, even more preferably 20% by mass or more, and the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less. Specifically, the content of particles having a particle diameter of less than 63 μm is more preferably in the range of 5 to 40% by mass, even more preferably 10 to 40% by mass, and particularly preferably 20 to 35% by mass of the entire blowing agent.

[0022] The upper limit of the particle size of the foaming agent particles is not particularly limited, but it is preferable to use particles of 1000 μm or less, for example.

[0023] In this specification, the particle size can be confirmed by a method in which a particle size distribution is determined using a sieve and the particle size is calculated from the particle size distribution.

[0024] The foaming agent is preferably used in the range of 15 to 100 g per 1 L of water. If too little foaming agent is used, the amount of gas generated by the reaction with the organic acid will be small, and the water-soluble antimicrobial agent may not be able to reach the drain. If too much foaming agent is used, the pH may rise too much, causing the foaming agent to ionize and reducing the amount of gas generated. It is more preferable to use 25 to 70 g of foaming agent per 1 L of water.

[0025] Examples of organic acids include citric acid, malic acid, fumaric acid, tartaric acid, ascorbic acid, succinic acid, malonic acid, pyrrolidonecarboxylic acid, and maleic acid. These organic acids may be used alone or in combination of two or more. In the present invention, from the viewpoint of foaming properties, it is preferable to use citric acid and malic acid. The organic acid is in a particulate form.

[0026] The organic acid is used in a state where it contains particles with a particle size of 300 μm or more at 25% by mass of the total organic acid. In other words, when the organic acid is sieved through a sieve with 300 μm mesh openings, 25% by mass or more of the particles of the total organic acid remain on the sieve. If the organic acid contains 25% by mass or more of particles with a particle size of 300 μm or more, when it is added to water, it dissolves near the bottom and can react with the foaming agent. This also prevents the pH from dropping too low locally, which would cause carbon dioxide gas to dissolve in the water and reduce the foaming amount. The content of particles having a particle size of 300 μm or more is preferably 35% by mass or more, more preferably 45% by mass or more, and even more preferably more than 55% by mass of the total organic acid.

[0027] There is no particular upper limit to the particle size of the organic acid. However, if the particle size is too large, foaming may be insufficient, and foaming may be slow because it takes time to dissolve in water. Therefore, the particle size is preferably 2000 μm or less, more preferably 1700 μm or less, and even more preferably 850 μm or less.

[0028] It is preferable that the organic acid dissolves in water before the foaming agent does, since dissolving the organic acid before the foaming agent makes the water acidic, improving the solubility of the foaming agent and facilitating the generation of carbon dioxide gas.

[0029] The organic acid is preferably used in the range of 20 to 120 g per 1 L of water. If too little organic acid is used, the amount of gas generated by reaction with the foaming agent will be small, and the water-soluble antimicrobial agent may not be able to reach the drain. If too much is used, the pH of the water may drop too much, causing carbon dioxide gas to dissolve in the water and reducing the amount of gas generated. The organic acid is more preferably used in the range of 40 to 100 g per 1 L of water.

[0030] In the present invention, the amount of organic acid used relative to the foaming agent is preferably organic acid / foaming agent (mass ratio) of 0.5 to 6. When the ratio of the amount of foaming agent to the amount of organic acid used is within the above range, almost all of the foaming agent and organic acid can be reacted, and a sufficient amount of gas can be generated. The organic acid / foaming agent ratio is more preferably 0.7 to 2.5, and even more preferably 0.8 to 2.0.

[0031] The amount of gas generated by the reaction between the foaming agent and the organic acid is preferably 3.5 L or more per generation, which improves the diffusibility of the gas in water and facilitates the transfer of the water-soluble antimicrobial agent. The amount of gas generated in one generation is more preferably 7 L or more, even more preferably 10 L or more, and particularly preferably 15 L or more.

[0032] The amount of gas generated can be appropriately adjusted by adjusting the amounts of the foaming agent and organic acid used, the ratio between the amounts of the foaming agent and organic acid used, and the like.

[0033] Examples of water-soluble antimicrobial agents include chlorine-based disinfectants, oxygen-based disinfectants, imidazole-based disinfectants, quaternary ammonium-based disinfectants, isothiazolinone-based disinfectants, and biguanide-based disinfectants. Examples of chlorine-based disinfectants include dichloroisocyanurate, trichloroisocyanurate, hypochlorite, chlorite, and chlorine dioxide. Examples of oxygen-based disinfectants include percarbonate and perborate. Examples of imidazole-based disinfectants include enilconazole. Examples of quaternary ammonium-based disinfectants include benzalkonium chloride and benzethonium chloride. Examples of isothiazolinone-based disinfectants include 5-chloro-2-methyl-4-isothiazolyl-3-one. Examples of biguanide-based disinfectants include polyhexamethylene biquanide and polyaminopropyl biguanide. These may be used alone or in combination of two or more.

[0034] Among these, from the viewpoint of the effect of removing microorganisms, it is preferable to use a chlorine-based disinfectant as the water-soluble antimicrobial agent, and it is more preferable to use dichloroisocyanurate or chlorite.

[0035] The amount of the water-soluble antimicrobial agent used can be adjusted appropriately depending on the type of water-soluble antimicrobial agent used. For example, when dichloroisocyanurate is used as the water-soluble antimicrobial agent, it is preferable to use 1 g or more, more preferably 2.5 g or more, per 1 L of water. When the amount of dichloroisocyanurate used is 1 g or more, it can exhibit a disinfecting effect in drainage pipes, inhibit the growth of microorganisms, and suppress the generation of foul odors. Furthermore, if the amount used is too large, a specific irritation can be felt, so it is preferable to use 75 g or less.

[0036] The temperature of the water during use is not particularly limited and can be used at room temperature, preferably in the range of, for example, 5 to 35° C. If the water temperature is lower than 5° C., the solubility of the foaming agent and the organic acid decreases and the reaction is delayed, causing the timing of gas generation to become irregular and reducing the amount of gas generated. Therefore, if the water temperature becomes too low, it is preferable to adjust the water temperature by adding hot water, for example.

[0037] After adding the foaming agent, organic acid, and water-soluble antimicrobial agent, it is preferable to leave it for 30 minutes or more. By leaving it for 30 minutes or more, the generated gas reaches the drain pipe, allowing the water-soluble antimicrobial agent to act sufficiently against microorganisms. The longer the leaving time, the more effective it becomes, but considering the frequency of toilet use, it is preferable to leave it for 600 minutes or less. The standing time is more preferably 30 to 120 minutes, and even more preferably 30 to 60 minutes.

[0038] After leaving it for a predetermined time, water can be poured into the drain pipe to clean the inside of the drain pipe.

[0039] The foaming agent, organic acid, and water-soluble antimicrobial agent may be added to the water simultaneously or separately. When added separately, it is preferable to add the foaming agent and organic acid after adding the water-soluble antimicrobial agent. It is preferable to add the foaming agent, organic acid, and water-soluble antimicrobial agent to water simultaneously, since this allows for simple, one-time treatment. It is particularly preferable to add the foaming agent, organic acid, and water-soluble antimicrobial agent to water as a mixed solid agent.

[0040] The foaming agent is preferably contained in the solid agent in an amount of 20 to 65% by mass, more preferably 25 to 60% by mass, and even more preferably 30 to 50% by mass.

[0041] The organic acid is preferably contained in the solid preparation in a range of 30 to 75% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 65% by mass.

[0042] The water-soluble antimicrobial agent is contained in the solid preparation in an amount of preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.01 to 10% by mass.

[0043] In the present invention, other components may be added to the water together with the foaming agent, organic acid, and water-soluble antimicrobial agent, as long as the effects of the present invention are not impaired. Examples of other components include various known additives such as surfactants, thickeners, pH adjusters, colorants, fragrances, fluidity improvers, anti-caking agents, enzymes, and specific gravity adjusters. For example, when a surfactant is used, it can be used as a cleaning agent.

[0044] Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Examples of anionic surfactants include alkyl sulfates, alkyl ethoxy sulfates, alkyl sulfoacetates, olefin sulfonates, alkyl benzene sulfonates, lauryl sulfates, alkyl sarcosinates, N-acyltaurine salts, methyl ester sulfonates, and fatty acid salts. Examples of nonionic surfactants include alkyl glycosides, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkyl ethers, and fatty acid monoglycerides. Examples of cationic surfactants include alkyl ammonium salts and alkyl benzyl ammonium salts. Examples of amphoteric surfactants include lecithin, betaine acetate amphoteric surfactants such as alkyl dimethyl amino acetate betaines, and alkyl amino diacetates. These surfactants may be used alone or in combination of two or more. Among these, one or more anionic surfactants and nonionic surfactants are preferred from the viewpoints of foam generation amount and foam duration.

[0045] The surfactant content in the solid formulation is preferably 0.5 to 10% by mass, more preferably 1.0 to 5.0% by mass, and even more preferably 1.5 to 4.0% by mass. If the surfactant content is too low, little foam is generated, the foaming duration is shortened, and the desired cleaning effect may not be achieved, so the content is preferably 0.5% by mass or more.

[0046] The thickener dissolves quickly when the solid agent is added to water, increasing the viscosity of the water, and when the solid agent contains a surfactant, it can improve foam retention. Examples of thickeners include cellulose-based thickeners such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and salts thereof; vinyl-based thickeners such as polyvinyl alcohol and polyvinylpyrrolidone; polysaccharides and derivatives thereof such as pullulan, xanthan gum, carrageenan, guar gum, locust bean gum, gellan gum, tragacanth gum, tamarind gum, agar, agarose, mannan, curdlan, alginic acid or its salts, pectin, starch, chondroitin sulfate or its salts, and chitosan and its derivatives; polyacrylic acid and its salts; polyethylene glycols; polyethylene oxides; and resins containing carbamoyl groups. These thickeners may be used alone or in combination of two or more. Among these, hydroxypropylmethylcellulose, polyacrylic acid, carboxymethylcellulose, and their salts are preferred from the viewpoints of superior foam generation and foam duration.

[0047] The thickener is preferably contained in the solid formulation in an amount of 0.1 to 3.0% by mass, more preferably 0.15 to 2.5% by mass, and even more preferably 0.2 to 2.0% by mass.

[0048] The pH adjuster adjusts the pH of the water containing the dissolved solid agent to a level suitable for gas generation. When 10 g of the solid agent is dissolved in 100 g of water, the pH is preferably in the range of 3.0 to 8.0. If the pH of the water is in this range, the foaming agent dissolves efficiently, increasing the amount of gas generated. The pH at the time of dissolution is more preferably 4.0 to 7.0, and even more preferably 4.5 to 6.5.

[0049] Examples of pH adjusters include borate buffers such as boric acid and borate salts; phosphate buffers such as phosphoric acid and phosphate salts; carbonate buffers such as carbonic acid and carbonate salts; citrate buffers such as citric acid and citrate salts; acetate buffers such as acetic acid and acetate salts; and inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and sodium phosphate.

[0050] Examples of pigments include Red No. 2 (Amaranth), Red No. 3 (Erythrosine), Red No. 102 (New Coccine), Red No. 104 (1) (Phloxine B), Red No. 105 (1) (Rose Bengal), Red No. 106 (Acid Red), Yellow No. 4 (Tartrazine), Yellow No. 5 (Sunset Yellow FCF), Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmiso), Green No. 3 (Fast Green FCF), Red No. 201 (Lithol Rubin B), Red No. 205 (Lithol Red), Red No. 213 (Rhodamine B), Red No. 214 (Rhodamine B Acetate), Red No. 219 (Brilliant Lake Red R), Red No. 227 (Fast Acid Magenta), Red No. 230 (1) (Eosin YS), Red No. 230 (2) (Eosin YSK), Red No. 231 (Phloxine BK), Red No. 232 (Rose Bengal K), Orange No. 207 (Erythrosine Quinoline Yellow NA), Yellow 202 (2) (Uranine K), Yellow 203 (Quinoline Yellow WS), Green 205 (Light Green SF Yellow), Blue 202 (Patent Blue NA), Blue 203 (Patent Blue CA), Blue 205 (Alphazurine FG), Brown 201 (Resorcinol Brown), Red 401 (Violamin R), Red 502 (Ponceau 3R), Red 503 (Ponceau R), Red 504 (Ponceau SX), Examples include Red No. 506 (Fast Red S), Orange No. 402 (Orange I), Yellow No. 402 (Polar Yellow 5G), Yellow No. 403 (1) (Naphthol Yellow S), Yellow No. 406 (Notanyl Yellow), Yellow No. 407 (Fast Light Yellow 3G), Green No. 401 (Naphthol Green B), Green No. 402 (Guinea Green B), Purple No. 401 (Arizrol Purple), and Black No. 401 (Naphthol Blue Black).

[0051] Examples of fragrances include essential oils extracted from lemon, orange, bergamot, grapefruit, lavender, rosemary, jasmine, rose, peppermint, eucalyptus, camphor, etc.; limonene, linalool, linalool acetate, borneol, citral, citronellal, menthol, cineole, menthyl acetate, geranyl acetate, phenethyl acetate, etc.

[0052] Examples of fluidity improvers include liquid paraffin, kerosene, silicone oil, and silicates.

[0053] Examples of anti-caking agents include magnesium stearate and calcium stearate.

[0054] Examples of enzymes include proteases, lipases, amylases, pectinases, cellulases, and lysozymes.

[0055] Examples of the specific gravity adjuster include sodium sulfate.

[0056] The dosage form of the solid preparation of the present invention is not particularly limited, and examples thereof include powders, granules, tablets, capsules, and divided packets. Each component incorporated into the solid preparation is preferably in a solid form, and a solid preparation consisting of a mixture of components molded into a powder, granules, granules, or the like is more preferred. These dosage forms can be obtained by following known manufacturing methods.

[0057] When adding the solid agent to water, it is sufficient to add 40 g or more of the solid agent per 1 L of water, preferably 50 g or more, more preferably 60 g or more. If the amount of the solid agent added is too small, sufficient foaming may not be obtained, and the desired effect may not be achieved. There is no particular upper limit to the amount of the solid agent added.

[0058] The method for suppressing malodor generation of the present invention can be applied to toilets. The method of the present invention generates gas in the water stored in the toilet bowl of a toilet using a foaming agent and an organic acid, and then allows a water-soluble antimicrobial agent added to the water in the toilet bowl to reach the drain pipe, thereby suppressing the generation of malodor in the drain pipe at the back of the toilet bowl. The method of suppressing malodor generation of the present invention can also be applied to drains in kitchens and bathrooms, as well as drains in bathtubs and washing machines.

[0059] The method of use in the toilet device will now be described. FIG. 1 is a schematic diagram of a toilet bowl in a toilet apparatus to which the method for suppressing the generation of bad odors of the present invention can be applied. The flush toilet 1 is a known Western-style toilet, and includes a toilet seat 13, a bowl 11, and a drainage pipe (drain pipe) 15 that is connected to the bowl 11. The drain pipe 15 is connected to the bowl 11, and the drain pipe 15 has a trap 17 that seals the drain pipe 15 with water using a pool of water W in the bowl 11. The pool of water W in the bowl 11 forms a water surface P.

[0060] In the method for suppressing the generation of malodor of the present invention, a foaming agent, an organic acid, and a water-soluble antimicrobial agent are added to a pool of water W, and the foaming agent and the organic acid are reacted near the bottom of the water to generate gas, which then carries the water-soluble antimicrobial agent to the drain pipe 15. The generated gas also transports the water-soluble antimicrobial agent to the drain pipe 15, and the water-soluble antimicrobial agent eliminates microorganisms in the drain pipe 15.

[0061] When the foaming agent, organic acid, and water-soluble antimicrobial agent are added as solid agents, the amount of solid agent used is approximately 70 to 250 g for a typical toilet bowl water volume of approximately 1.8 L. After adding the solid agent, the toilet is left as is for approximately 30 to 600 minutes, and then flushed with water to remove microorganisms in the drain pipe 15. Removal of microorganisms in the drain pipe 15 inhibits their proliferation, thereby suppressing the generation of foul odors. [Example]

[0062] The present invention will be further described below with reference to the following examples, but the present invention is not limited to these examples.

[0063] The components used in the following examples and comparative examples are as follows:

[0064] <Organic acid> Anhydrous citric acid A: A substance with a particle size in the range of 75 to 850 μm, containing 25% by mass or more of particles of 300 μm or larger ("Fuso Citric Acid (Anhydrous) M" (trade name) manufactured by Fuso Chemical Co., Ltd.) Anhydrous citric acid B: Particle size less than 300 μm (Fuso Citric Acid (Anhydrous) MP80 (product name) manufactured by Fuso Chemical Co., Ltd.) Anhydrous citric acid C: A substance with a particle size in the range of 75 to 355 μm, containing less than 20% by mass of particles of 300 μm or larger ("Fuso Citric Acid (Anhydrous) MS" (trade name) manufactured by Fuso Chemical Co., Ltd.) <Foaming agent> Sodium bicarbonate A: "Sodium bicarbonate KF" (product name) manufactured by AGC Corporation Sodium bicarbonate B: "Sodium bicarbonate KG" (product name) manufactured by AGC Corporation Sodium bicarbonate C: "Sodium bicarbonate KP" (product name) manufactured by AGC Corporation Sodium carbonate: "Soda Ash Light" (product name) manufactured by Tokuyama Corporation <Surfactant> Sodium α-olefin sulfonate: "Lipolan PJ-400CJ" (product name) manufactured by Lion Specialty Chemicals Co., Ltd. Sodium lauryl sulfate A: "Emeral 10PHD" (product name) manufactured by Kao Corporation Sodium lauryl sulfate B: "Emeral 10PT" (product name) manufactured by Kao Corporation <Thickener> Sodium polyacrylate A: "Aronvis SX" (trade name) manufactured by Toagosei Co., Ltd. Sodium polyacrylate B: "Aqualic DL-100" (product name) manufactured by Nippon Shokubai Co., Ltd.

[0065] (Test Example 1) (Examples 1 to 3, Comparative Examples 1 to 3) According to the formulation shown in Table 1, the components were mixed uniformly to prepare a solid formulation (powder).

[0066] <Measurement of the proportion of foaming agent particles of a given size> The particle size distribution of the blowing agent was determined using a sieve, and from the particle size distribution, the proportion of particles with a particle size of 63 μm or more and the proportion of particles with a particle size of less than 63 μm were calculated. The results are shown in Table 1.

[0067] <Measurement of bubble adhesion area ratio> As shown in Figure 2, a partition plate 23 was installed vertically in the axial center of a 5 L beaker 21 to divide the inside of the beaker 21 into a first storage section 25 and a second storage section 27, thereby producing a bubble adhesion test device 2. The partition plate 23 was plate-shaped, and was installed so that the vertical side portion of the partition plate 23 was close to the inner peripheral surface of the beaker 21, and the bottom 23a of the partition plate 23 was positioned 5 cm from the bottom of the beaker 21. 4 L of water 3 at 20 to 25° C. was placed in a beaker 21 (water depth: approximately 18 cm), and a solid agent 4 was added from the first storage section 25 side in an amount of 10% by weight of the composition shown in Table 1. Thirty seconds after adding the solid formulation 4, a photograph of the bottom of the beaker 21 was taken. The portion of the photograph on the second storage section 27 side was cut out to separate the foam portion from the other portion, and the weights of each were measured. The foam adhesion area ratio (%) of the foam that had passed under the partition plate 23 and spread from the bottom surface 25a of the first storage section 25 to the bottom surface 27a of the second storage section 27 was calculated using the following formula (1). Foam adhesion area ratio (%) = (weight of the photograph of the foam part) / (weight of the photograph of the foam part + weight of the photograph of the other parts) × 100 (1) It can be determined that the higher the rate at which bubbles penetrate into the bottom surface 27a of the second storage section 27, the more the generated gas has moved along the bottom surface of the bubble adhesion test device 2. The results are shown in Table 1.

[0068] [Table 1]

[0069] The results in Table 1 show that in Examples 1 to 3, bubbles covered more than 50% of the bottom surface of the second container of the beaker in the bubble adhesion test device, and gas was generated near the bottom of the beaker and moved to the second container. Comparing Example 1 and Comparative Example 1, Comparative Example 1, which used a foaming agent with a low content of particles of 63 μm or more, showed no bubbles adhering to the bottom surface of the second storage section (0%), whereas in Example 1, the entire bottom surface of the second storage section was covered with bubbles (100%). Comparing Example 2 with Comparative Examples 2 and 3, Comparative Example 2, which used an organic acid with a particle size of less than 300 μm, and Comparative Example 3, which used an organic acid with a particle size of 300 μm or more of less than 20% by mass, showed no bubbles adhering to the bottom surface of the second storage section (0%), whereas in Example 2, the entire bottom surface of the second storage section was covered with bubbles (100%).

[0070] (Test Example 2) (Examples 4 to 7, Comparative Example 4) A solid preparation (powder) was prepared by uniformly mixing the components according to the formulation shown in Table 2. Example 4 has the same formulation as Example 2.

[0071] <Odor suppression test (verification of odor reduction)> 1. Preparation of test bacteria solution The test strains used were Microbacterium oxydans (Mo, NBRC15586), Bacillus subtilis (Bs, NBRC3134), and Staphylococcus aureus (Sa, NBRC12732). Mo and Bs were smeared on SCD agar medium and cultured at 25°C to form colonies. Bacteria were picked from each colony and suspended in sterilized ion-exchanged water to obtain bacterial suspension A containing Mo and bacterial suspension B containing Bs. The viable cell count in the suspension was estimated at 1 x 10 7 It was expressed as CFU / mL. Sa was smeared on SCD agar medium and cultured at 36°C to form colonies. Bacteria were picked from the colonies and suspended in sterilized ion-exchanged water to obtain bacterial suspension C. The viable cell count of the suspension was 1 x 10 8 It was expressed as CFU / mL. Bacterial suspension A and 0.3% BSA aqueous solution, bacterial suspension B and 0.3% BSA aqueous solution, and bacterial suspension C and 0.3% BSA aqueous solution were mixed at a 1:1 (mass ratio) to obtain test bacterial solutions.

[0072] 2. Test Method 10 μL of the test bacteria solution was dropped into 9 separate drops onto a 20 mm diameter stainless steel plate to obtain a plate with bacteria attached. Next, an odor confirmation test device 5 was fabricated, which imitates the drain pipe (piping having a trap) of a toilet device, as shown in FIGS. 3(a) and (b). 1500 g of sterilized ion-exchanged water 6 was placed in a first container 51 (approximately 18 cm long x 25 cm wide x 12.5 cm high, volume approximately 5.6 L) with an open top. The water depth was approximately 3 cm. The opening of the first container 51 was covered with a plate 55 so that approximately half of the length was covered, and a bacterial cell-attached plate 57 with a test bacterial solution attached thereto was placed on top of the plate 55. A second container 53 of the same size as the first container 51 was placed over the first container 51 with its opening facing downwards, covering the plate material 55 on which the bacterial cell attachment plate 57 was placed. At this time, the second container 53 was placed offset from the first container 51, and an air flow path was provided as shown by arrow X in Figure 3(b). The entire amount of the prepared solid dosage form 4 was poured into the first container 51 through the opening, and left to stand for 1 hour. Thereafter, the bacterial cell adhesion plate 57 was placed in a sample tube containing 30 mL of toilet water, and cultured at 30° C. and 100 rpm for 3 days.

[0073] After three days, the odor in the sample tube was checked and the odor intensity was evaluated using the following six-point scale. The evaluation was performed by five subjects, and the average value was calculated. As a control, the same procedure was carried out without adding any solid preparation, and the odor intensity was evaluated. The odor reduction rate was calculated by subtracting the odor intensity (average value) in the sample treatment (treated) from the odor intensity (average value) in the control (untreated). The results are shown in Table 2. [Evaluation criteria] 5: Strong odor 4: Strong odor 3: Easily detectable odors 2: A faint smell that you can tell what it is 1: A smell that can finally be detected 0: Odorless

[0074] <Calculating the amount of gas generated> The amount of gas generated was calculated from the amount of substance (mol) added, assuming that the foaming agent and organic acid reacted completely according to the chemical reaction formula. In the calculation, the generated gas was treated as an ideal gas. The results are shown in Table 2.

[0075] <Measurement of viable bacteria count> The bacterial cell-attached plate treated with the solid preparation in the same manner as in the odor suppression test above was placed in 10 mL of SCDLP medium containing 0.1% sodium thiosulfate, and the bacterial cells were washed out. This was then appropriately diluted with physiological saline, and 0.1 mL was smeared on SCD agar medium and cultured at 25°C for 3 days, and the number of colonies was counted. From these results, the number of viable bacteria remaining on the bacterial cell-attached plate was calculated. The difference in the Log viable cell count was calculated compared to an untreated sample. The results are shown in Table 2.

[0076] [Table 2]

[0077] From the results in Table 2, it was found that in Examples 4 to 7, carbon dioxide (carbonic acid gas) and hypochlorous acid were generated, and confirmation of odor intensity for Mo revealed that the greater the amount of carbon dioxide generated, the greater the odor reduction and Log viable bacterial count reduction value. It was also found that the viable bacterial count could be reduced for Bs and Sa, and odor could be reduced. This is thought to have resulted in the hypochlorous acid diffusing into the space along with the generated gas, thereby achieving a sterilization effect.

[0078] (Test Example 3) A sterilization test was carried out using the solid preparation of Example 2 prepared in Test Example 1.

[0079] 1. Preparation of test bacteria solution The test strains used were Staphylococcus aureus (Sa, NBRC12732) and Escherichia coli (Ec, NBRC3972). Sa and Ec were each smeared on SCD agar medium and cultured at 36°C for 24 hours to allow colony formation. Bacteria were picked from each colony and suspended in sterilized ion-exchanged water to obtain a bacterial suspension. The viable cell count of the bacterial suspension was 1 to 2 × 10 8 It was expressed as CFU / mL. Each bacterial suspension was mixed with a 0.3% BSA aqueous solution at a mass ratio of 1:1 to obtain each test bacterial solution.

[0080] 2. Test Method 10 μL of the test bacteria solution was dropped into 9 separate drops onto a 20 mm diameter stainless steel plate to obtain a plate with bacteria attached. Next, a sterilization test device 7 was created that mimics the drain pipe of a toilet device, as shown in Figure 4. In the sterilization test device 7, a drain pipe 15 is continuously connected to the bowl part 11 of a flush toilet, and a slit part 71 is provided midway along the drain pipe 15, and a bacterial cell attachment plate 73 is detachably attached to this slit part 71. The sterilization test device 7 was installed in a test room. At this time, the inner surface of the sterilization test device 7 was wiped with a 70% ethanol aqueous solution and allowed to dry thoroughly. The test room was adjusted to a room temperature of 20 to 25°C and a humidity of 100%. The opening of the slit portion 71 was sealed with tape, and approximately 1.5 L of sterilized ion-exchanged water was poured into the bowl portion 11 of the sterilization test device 7. The water depth was approximately 13 cm. Then, the entire amount of the solid agent was poured into the bowl portion 11. After the flow of bubbles toward the drain pipe 15 subsided, the mesh on which the bacterial cell adhesion plate 73 was placed was attached to the slit portion 71, and the gap of the slit portion 71 after attachment was sealed with tape. The mesh was left in this state, and after 30 minutes, the bacterial cell adhesion plate 73 was collected.

[0081] 10 mL of SCDLP medium containing 5.0% 0.1 mol / L sodium thiosulfate solution was placed in a 50 mL centrifuge tube, and the collected bacterial cell-attached plate was placed in it and washed in an ultrasonic cleaner for 10 minutes. The washed liquid was appropriately diluted with physiological saline and smeared on an SCDA plate medium. After that, it was cultured at 36°C for 40 hours, and the number of colonies was counted. From this result, the number of viable bacteria remaining on the bacterial cell-attached plate was calculated.

[0082] As an untreated sample, the plate with attached bacteria was placed in a test room at a room temperature of 25°C and a humidity of 100% for 30 minutes. As described above, the plate was washed with SCDLP medium containing 5.0% of a 0.1 mol / L aqueous solution of sodium thiosulfate, and then cultured on SCDA plate medium, and the number of colonies was counted.

[0083] The difference in the Log viable cell count compared to the untreated sample was calculated, and the results are shown in Table 3.

[0084] [Table 3]

[0085] The results in Table 3 show that the method of the present invention significantly reduced the viable cell counts of both Sa (Staphylococcus aureus) and Ec (Escherichia coli), and was therefore able to suppress the generation of malodors originating from these microorganisms.

[0086] (Test Example 4) A field test was carried out using the solid preparation of Example 2 prepared in Test Example 1.

[0087] <Odor suppression effect confirmation test 1> The solid preparation of Example 2 was applied to flush toilets in the homes of two test subjects in Ako City, Hyogo Prefecture, who experience a foul odor, and to one flush toilet in the Sakae Plant of Earth Chemical Co., Ltd., and the generation of a foul odor was confirmed over time. The flush toilets used in the test were all standard seat-type flush toilets with a water depth of 10 to 15 cm, as shown in Figure 1. The entire amount of the solid preparation was poured into the toilet bowl, left for 30 minutes, and then flushed once. Immediately after that, the toilet room was smelled to confirm whether or not there was a foul odor. Each inspection was performed by one subject. After that, the toilet was used as usual and checked for odor every week. The results are shown in Table 4.

[0088] [Table 4]

[0089] The results in Table 4 show that in both toilets, microorganisms were removed immediately after treatment with the solid preparation of Example 2, and no foul odor was detected. Because factory toilets are used more frequently than residential toilets, a weak odor was detected after two weeks. On the other hand, it was confirmed that there was no odor even after three weeks in the toilet of the first subject's home. This suggests that although repeated use of the toilet generates a foul odor, the generation of foul odor can be prevented while the growth of microorganisms in the toilet is suppressed.

[0090] (Test Example 5) Field tests were carried out using the solid preparations of Example 2 and Comparative Example 2 prepared in Test Example 1, and Comparative Example 4 prepared in Test Example 2.

[0091] <Odor suppression effect confirmation test 2> The solid preparations of Example 2, Comparative Example 2 and Comparative Example 4 were applied to the flush toilets of test subjects' homes in Ako City, Hyogo Prefecture, where a foul odor is felt, and the generation of foul odor was confirmed over time. The flush toilets used in the test were all ordinary seat-type flush toilets with a water depth of 10 to 15 cm, as shown in Figure 1. The entire amount of the solid preparation was poured into the toilet bowl puddle, left for 30 minutes, and then flushed once. Immediately afterwards, the toilet room was smelled and the presence or absence of a foul odor was confirmed according to the following evaluation criteria. The confirmation was carried out by one subject in each home. The toilet was then used as usual, and the presence or absence of an odor was confirmed every day for two weeks. For each example, the test was carried out in the homes of two subjects, and the average of the subjects' evaluation scores was calculated. The results are shown in Figures 5(a) to 5(c). [Evaluation criteria] 5: Strong odor 4: Strong odor 3: Easily detectable odors 2: A faint smell that you can tell what it is 1: A smell that can finally be detected 0: Odorless

[0092] As can be seen from Figure 5(a), when the solid preparation of Example 2 was used, an excellent malodor generation suppression effect was obtained immediately after treatment, and this effect was sustained for about two weeks. In contrast, as can be seen from Figure 5(b), when the solid preparation of Comparative Example 2 was used, an excellent malodor generation suppression effect was obtained immediately after treatment, but the malodor generated every day, and within 10 days the evaluation was equivalent to the initial level. Furthermore, as can be seen from Figure 5(c), when the solid preparation of Comparative Example 4 was used, the malodor generation suppression effect immediately after treatment was small, and this effect could not be sustained. [Explanation of symbols]

[0093] 1 toilet 11 Bowl section 11a Veranda 13 Toilet seat 15 Drainage side piping (exhaust pipe) 17 Trap section 2. Foam adhesion test equipment 21 Beaker 23 Partition 23a Bottom of the partition 25 First storage compartment 25a Bottom surface of first storage section 27 Second storage compartment 27a Bottom surface of second storage section 3 water 4 Solid dosage forms 5. Odor confirmation test equipment 51 1st container 53 Second container 55 Board material 57 Bacterial cell adhesion plate 6. Sterile ion-exchanged water 7. Sterilization test equipment 71 Slit section 73 Bacterial cell adhesion plate W Puddle P Draft surface

Claims

1. A method for suppressing bad odors emanating from a drainage pipe of a toilet device, comprising: The method comprises generating gas in water using a foaming agent and an organic acid, and using the gas to cause the water-soluble antimicrobial agent introduced into the water to reach the piping; A method for suppressing the generation of malodor, characterized in that the foaming agent used contains particles with a particle diameter of 63 μm or more in an amount of 60% by mass or more of the total foaming agent and particles with a particle diameter of less than 63 μm in an amount of 5% by mass or more of the total foaming agent, and the organic acid used contains particles with a particle diameter of 300 μm or more in an amount of 25% by mass or more of the total organic acid.

2. An odor generation inhibitor for suppressing odors generated from piping on the drain side of a toilet apparatus, comprising a foaming agent, an organic acid, and a water-soluble antimicrobial agent, wherein the foaming agent contains particles with a particle diameter of 63 μm or more in an amount of 60% by mass or more of the total foaming agent and particles with a particle diameter of less than 63 μm in an amount of 5% by mass or more of the total foaming agent, and the organic acid contains particles with a particle diameter of 300 μm or more in an amount of 25% by mass or more of the total organic acid.

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