JP2022186650A - Cleaner for indoor water use sites - Google Patents

Abstract

To provide a cleaner for indoor water use sites that is capable of suppressing slime.SOLUTION: A cleaner for indoor water use sites contains at least one selected from the group consisting of hydrolyzable tannin comprising ester bonds of glucose and a plurality of gallic acids, and salts thereof.SELECTED DRAWING: None

Description

FIELD OF THE DISCLOSURE The present disclosure relates to cleaning agents for indoor water use areas and the like.

In places where water is used indoors (places where water is used indoors) such as kitchens, bathrooms, toilets, kitchens, and lavatories, stains are caused by microorganisms propagated in the presence of water. In these places, slime typically caused by biofilm formation by microorganisms is a problem, and it is desirable to suppress it from the viewpoint of hygiene and appearance.

Sodium hypochlorite, which is a chlorine-based cleaning agent, is known as a cleaning agent for places where water is used indoors (Non-Patent Document 1). However, sodium hypochlorite is highly corrosive and oxidizing, and may react with acidic detergents to generate toxic chlorine gas.

Satoshi Fukusaki, "Theory and Practice of Cleaning and Sterilization Using Sodium Hypochlorite", Cooked Food and Technology, Japan Cooked Food Research Association, 2010, Vol. 16, No. 1, p1-14

An object of the present disclosure is to provide an indoor water-using place cleaning agent capable of suppressing sliminess.

As a result of extensive research in view of the above problems, the present inventors have found that at least one selected from the group consisting of hydrolyzable tannins formed by ester bonding of glucose and a plurality of gallic acids, and salts thereof, is slimy. It was found to have an inhibitory action. Based on this knowledge, the inventor of the present invention has completed the invention of the present disclosure as a result of further research. That is, the present disclosure includes the following aspects.

Section 1. A cleaning agent for a place where water is used indoors, containing at least one selected from the group consisting of hydrolyzable tannins formed by ester-bonding glucose and a plurality of gallic acids, and salts thereof.

Section 2. The place of indoor water use is selected from the group consisting of residences, factories, offices, lodging facilities, hospitals, stores, schools, restaurants, airport facilities, stations, bus terminals, service areas, exercise facilities, and meeting places. Item 1. The cleaning agent according to Item 1, which is at least one indoor water use place.

Item 3. Item 3. The cleaning agent according to Item 1 or 2, wherein the indoor water usage location is a plumbing area.

Section 4. Item 4. The cleaning agent according to any one of Items 1 to 3, wherein the indoor water use place is at least one selected from the group consisting of kitchen, kitchen, bathroom, toilet, kitchen, washroom and water circulation equipment.

Item 5. Item 5. The cleaning agent according to any one of Items 1 to 4, wherein the hydrolyzable tannin is tannic acid.

Item 6. Item 6. The cleaning agent according to any one of Items 1 to 5, which contains a solvent.

Item 7. Item 7. The cleaning agent according to item 6, wherein the content of the hydrolyzable tannin and its salt per 1 mL of the solvent is 5000 µg or less.

Item 8. Item 8. The cleaning agent according to Item 6 or 7, wherein the solvent has a pH of 2.0 to 12.0.

Item 9. the solvent is alcohol and water,
Item 8. The cleaning agent according to item 6 or 7, which contains a weak acid pH adjuster and the solvent has a pH of 2.0 to 4.0.

Item 10. Item 10. The cleaning agent according to Item 9, containing an antiseptic/antifungal agent and a surfactant.

Item 11. Item 11. The cleaning agent according to Item 10, wherein the surfactant is a nonionic surfactant.

Item 12. Item 12. A cleaning agent according to Item 11, wherein the surfactant is a polyoxyethylene alkyl ether.

Item 13. Item 13. The cleaning agent according to any one of Items 1 to 12, wherein the hydrolyzable tannin is used at a concentration that does not substantially exhibit a growth-inhibiting effect on bacteria belonging to the genus Methylobacterium.

Item 14. Item 14. The cleaning agent according to any one of Items 1 to 13, which is used in contact with slime derived from microorganisms in a place where indoor water is used.

Item 15. Item 15. The cleaning agent according to any one of Items 1 to 14, which is for suppressing sliminess derived from microorganisms.

Item 16. Item 16. The cleaning agent according to item 14 or 15, wherein the microorganism is at least one selected from the group consisting of bacteria of the genus Methylobacterium, bacteria of the genus Brevundimonas, bacteria of the genus Pseudomonas, bacteria of the genus Xanthomonas, bacteria of the genus Sphingomonas, and bacteria of the genus Rhodococcus. .

Item 17. Item 17. The cleaning agent according to any one of items 14 to 16, wherein the microorganism is a bacterium belonging to the genus Methylobacterium.

Item 18. Item 18. A method for suppressing sliminess, comprising contacting the cleaning agent according to any one of Items 1 to 17 with a water-using surface in an indoor water-using location.

Item 19. Item 19. The method according to Item 18, comprising contacting the cleaning agent according to any one of Items 1 to 18 with slime derived from microorganisms in a place where indoor water is used.

Item 20. Item 14. A deodorizing method comprising contacting the cleaning agent according to any one of Items 1 to 13 with an off-flavor substance.

Item 21. Item 14. A method for solubilizing fatty acid calcium, comprising contacting the detergent according to any one of Items 1 to 13 with fatty acid calcium.

According to the present disclosure, it is possible to provide an indoor water-using place cleaning agent capable of suppressing sliminess.

1 is a diagram showing that in Experiment 1, tannic acid inhibited biofilm formation of Methylobacterium, which is a representative bacterium for slimy plumbing.

As used herein, the expressions "contain" and "include" include the concepts "contain", "include", "consist essentially of" and "consist only of".

In one aspect, the present disclosure contains at least one selected from the group consisting of hydrolyzable tannins formed by ester bonding of glucose and a plurality of gallic acids, and salts thereof, for indoor water-use cleaning. agent (also referred to herein as the “cleaning agent of the present disclosure”). This will be explained below.

1. Ingredients The cleaning agent of the present disclosure contains at least one selected from the group consisting of hydrolyzable tannins formed by ester bonding of glucose and multiple gallic acids, and salts thereof (herein referred to as "active ingredient"). ) is included.

The hydrolyzable tannin is not particularly limited as long as it is formed by ester-bonding glucose and multiple gallic acids.

Glucose is not particularly limited. Glucose can be any of pyranose type (glucopyranose), furanose type (glucofuranose) and linear type, preferably pyranose type. Also, glucose can be either D-type or L-type, preferably D-type. Also, glucose can be either α-type or β-type, preferably β-type. Glucose includes preferably glucopyranose, more preferably D-glucopyranose, still more preferably β-D-glucopyranose, and the like.

The ester bond is an ester bond between a hydroxyl group derived from glucose and a carboxy group derived from gallic acid, and is not particularly limited in this respect. In addition, another gallic acid may be linked to gallic acid linked to glucose. More specifically, the hydrolyzable tannin has at least one (preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more) hydroxyl groups possessed by glucose, It is a hydrolyzable tannin formed by ester bonding with a carboxy group of gallic acid or a linker of gallic acid.

Here, the linked form of gallic acid means two or more (preferably 2 to 6, more preferably 2 to 5, still more preferably 2 to 4, even more preferably 2 to 3, particularly preferably 2) gallic acid linked by an ester bond (that is, an ester bond between a hydroxyl group derived from one gallic acid and a carboxy group derived from another gallic acid). The hydroxyl group that forms an ester bond may be either a hydroxyl group at the meta position or a hydroxyl group at the para position, but is preferably a hydroxyl group at the meta position. In addition, linked products composed of three or more gallic acids are those in which gallic acids are linked in a straight chain (i.e., only one of the three hydroxyl groups of gallic acid is used for ester bond formation. ), or gallic acid linked in a branched chain (that is, for at least one gallic acid, of the three hydroxyl groups of gallic acid, two hydroxyl groups are used for ester bond formation. may be one or more), but it is preferably a linear linker.

Examples of gallic acid conjugates include conjugates represented by the following formulas.

The hydrolyzable tannin is preferably tannic acid. As tannic acid, for example, general formula (1):

[In the formula, R ¹ , R ² , R ⁴ and R ⁵ are the same or different and represent a group obtained by removing the hydroxyl group in the carboxy group from gallic acid or a linker of gallic acid. R ³ represents a hydrogen atom, or a group obtained by removing the hydroxyl group in the carboxy group from gallic acid or a linker of gallic acid. ]
Hydrolyzable tannins represented by

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and are groups obtained by removing the hydroxyl group in the carboxyl group from gallic acid or a linker of gallic acid. and more preferably, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and are a group obtained by removing the hydroxyl group in the carboxyl group from a linker of gallic acid.

Preferred specific examples of tannic acid include two compounds represented by the following formulas.

Another preferred specific example of tannic acid is plant-derived tannic acid such as quintuple tannin and gallic tannin.

The molecular weight of the hydrolyzable tannin is, for example, 300-2500, preferably 800-2200, more preferably 1200-2000, still more preferably 1500-1900.

The origin and form of the hydrolyzable tannin are not particularly limited, and examples include partially purified hydrolyzable tannins such as plant extracts, hydrolyzable tannins isolated from plants, and artificially synthesized tannins. Hydrolyzable tannins and the like can be used and they can be used alone or in combination.

The salt of hydrolyzable tannin is not particularly limited as long as it is a pharmaceutically acceptable salt and can be used as a cleaning agent for places where water is used indoors. , salts with alkaline earth metals such as calcium and magnesium, and salts with amines such as ammonium and triethylamine.

The active ingredient can be used singly or in combination of two or more.

The cleaning agents of the present disclosure can contain only active ingredients, or can contain active ingredients and other ingredients. The content of the active ingredient in the cleaning agent of the present disclosure is, for example, 0.00001 to 100% by mass, and the upper and lower limits thereof may be, for example, a range formed by any combination of two of the following numerical values. Can: 100% by mass, 90% by mass, 70% by mass, 50% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.01 mass %, 0.001 mass %, 0.0001 mass %.

Other components that can be included in the detergent of the present disclosure are not particularly limited as long as the hydrolyzable tannin is stable. For example, whether or not hydrolyzable tannin is stable in a liquid preparation can be determined by measuring the residual ratio of hydrolyzable tannin or by quantifying gallic acid, which is a hydrolyzate of hydrolyzable tannin. For example, when the content of hydrolyzable tannin in the solution is 0.25%, it can be evaluated as stable if the initial rate of gallic acid formation is less than 500 (μg/mL/day), preferably 100 (μg/mL/day). day), more preferably less than 10 (μg/mL/day), even more preferably less than 1.0 (μg/mL/day), most preferably less than 0.1 (μg/mL/day). Alternatively, the ratio (%) of hydrolyzed gallic acid in the liquid formulation can be obtained by setting the quantitative value of gallic acid when the hydrolyzable tannin is completely hydrolyzed with tannase as 100%.

Other ingredients include solvents. Examples of the solvent include nonpolar solvents and polar solvents, with polar solvents being preferred.

Polar solvents include polar aprotic solvents such as methylene chloride, tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, and dimethylsulfoxide; - Polar protic solvents such as propanol, ethanol, methanol, formic acid, water.

Alcohol or water is preferred as the polar protic solvent. As the alcohol, lower alcohols having 5 or less carbon atoms such as 1,3-butanediol, glycerol, 2-propanol, 1-propanol and ethanol are preferable, and alcohols having 3 or less carbon atoms such as 2-propanol, 1-propanol and ethanol are preferred. Lower alcohols are more preferred. By using such an alcohol, the hydrolyzable tannin in the cleaning agent can be more stably retained. Also, such alcohol can be used by mixing with water. When mixed with water, the content ratio of alcohol to the entire solvent is, for example, 0.00001 to 100% by mass, and the upper and lower limits are, for example, a range obtained by combining any two of the following numerical values. Can be: 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass , 0.1% by weight, 0.01% by weight, 0.001% by weight, 0.0001% by weight.

The pH of the solvent can be appropriately set by those skilled in the art according to its effect. The pH of the solvent is, for example, 2.0-12.0. The pH of the solvent may be, for example, an acidic pH of 2.0 to 3.0, a weakly acidic pH of 3.0 to 6.0, a neutral pH of 6.0 to 8.0, or a weakly alkaline pH of 8.0 to 10.0. However, from the viewpoint of the stability of the hydrolyzable tannin contained in the cleaning agent, the pH of the solvent is preferably 2.0 to 6.0, more preferably 2.0 to 4.0. preferable. The cleaning agent of the present disclosure does not generate chlorine gas or the like even under acidic conditions, for example, and is gentle on the body and the environment and can suppress sliminess. In order to adjust the pH to the above, it is preferable to contain a pH adjuster. Although the pH adjuster is not particularly limited, it is preferably a weak acid pH adjuster. Weak acid pH adjusters include citric acid, gluconic acid, tartaric acid, lactic acid, acetic acid, malic acid, and the like. The content of the pH adjuster can be appropriately adjusted within the range of 0.0001% by mass to 2% by mass, depending on the desired pH.

When the cleaning agent of the present disclosure contains a solvent, the content of the active ingredient per 1 mL of the solvent is, for example, 2 μg or more, 5 μg or more, 20 μg or more, 100 μg or more, 500 μg or more, 1000 μg or more, 50000 μg or less, 40000 μg or less, 5000 μg or less. can be:

In addition to the solvent, other components include, for example, antibacterial/antifungal agents, antiseptic antifungal agents, aromatic sulfonic acid compounds, antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, biofouling inhibitors, Additives such as deodorants, organic acids, fatty acid metals, metal compounds, polyvalent metal ion scavengers, cyclodextrins, porous body constituents, pigments, surfactants, and thickeners are included.

Examples of antibacterial and antifungal agents include methyl-2,4-dihydroxy-6-methylbenzoate, ethyl-2,4-dihydroxy-6-methylbenzoate, methyl-2,4-dihydroxy-3,6-dimethylbenzoate , isopropyl-2,4-dihydroxy-6-methylbenzoate, 3-methoxy-5-methylphenyl-2,4-dihydroxy-6-methylbenzoate, ethyl-2,4-dihydroxy-3,6-dimethylbenzoate, ethyl -3-formyl-2,4-dihydroxy-6-methylbenzoate, isopropyl-3-formyl-2,4-dihydroxy-6-methylbenzoate, 3-hydroxy-5-methylphenyl-2,4-dihydroxy-6- methyl benzoate, 3-hydroxy-5-methylphenyl-2-dihydroxy-4-methoxy-6-methylbenzoate, 3-methoxy-5-methylphenyl-2-hydroxy-4-methoxy-6-methylbenzoate, 3-chloro - phenol-alcohol antibacterial and antifungal agents such as 2,6-dihydroxy-4-methylbenzoate;
(2-Pyridylthio-1-oxide) sodium, nalidixic acid, gatifloxacin, pyrithione copper, pyrithione zinc, and other pyridine-quinoline antibacterial and antifungal agents;
Triazine-based antibacterial/antifungal agents such as hexahydro-1,3,5-tris(2-hydroxyethyl)-S-triazine;
1,2-benzisothiazolin-3one, 2-methyl-5-chloro-4-isothiazolone complex, octylisothiazolinone, methylisothiazolinone, chloromethylisothiazolinone, dichlorooctylisothiazolinone, benzisothiazolinone, etc. isothiazolone-based antibacterial and antifungal agents;
Anilide-based antibacterial/antifungal agents such as 4'-hydroxyacetanilide, N-(3-hydroxyphenyl)benzenecarboxamide, and N-(3-hydroxyphenyl)benzamide;
Nitrile-based antibacterial/antifungal agents such as monobromocyanoacetamide, dibromocyanoacetamide, 1,2-dibromo-2,4-dicyanobutane, and tetrachlorophthalonitrile;
2-(4-thiazolyl)benzimidazole, 2-benzimidazole methylcarbamate, 1-(butylcarbamoyl)-2-benzimidazole methylcarbamate and other imidazole/thiazole antibacterial/antifungal agents;
Aldehyde-based antibacterial/antifungal agents such as dehydroacetic acid;
Carboxylic acid-based antibacterial/antifungal agents such as acetic acid, formic acid, and sorbic acid;
Ester-based antibacterial/antifungal agents such as paraoxybenzoic acid ester;
Disulfide compounds such as dithio-2,2-bis(benzmethylamide), tetramethylthiuram disulfide, dimethylphenylsulfamide;
thiocarbamate compounds such as mancozeb, maneb, zineb, polycarbamate;
Nitro compounds such as 1,1-dibromo-1-nitropropanol, 1,1-dibromo-1-nitro-2-acetoxypropane;
quaternary ammonium salts such as benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, cetrimonium chloride, dophanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, domiphen bromide;
biguanides such as metformin, buformin, phenformin, proguanil, chloroproguanil, chlorhexidine, alexidine, polyaminopropyl biguanide, polyhexanide;
Surfactants such as sodium alkylbenzene sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearylamine, lauryldimethylbenzylammonium chloride;
Inorganic antibacterial agents such as silver-supported zeolite, copper-supported zeolite, zinc-supported zeolite, silver-supported calcium phosphate, copper-supported calcium phosphate, zinc-supported calcium phosphate, and titanium oxide;

In addition, antibacterial/antifungal agents include other ingredients classified above or ingredients not classified above, such as thiabendazole, triclosan, chlorhexidine, zinc pyrithione, chlorxylenol, chitosan, catechin, thymol, hinokitiol, Naturally derived antibacterial ingredients such as moso bamboo extract, mustard essential oil, wasabi essential oil, and the like are included.

Examples of antiseptic and antifungal agents include paraoxybenzoic acid esters (parabens), 2-phenoxyethanol, benzoic acid and its salts, salicylic acid and its salts, sorbic acid and its salts, dehydroacetic acid and its salts, p-toluenesulfone. Acids and their salts, alcohols such as ethanol and isopropanol, quaternary ammonium salts such as benzalkonium chloride, polyhydric alcohols that are raw materials with antiseptic properties, medium-chain fatty acids and their esters, glycerin derivatives, and chelating agents such as EDTA.

Examples of aromatic sulfonic acid compounds include methoxybenzenesulfonic acid, methoxybenzenedisulfonic acid, dimethoxybenzenesulfonic acid, dimethoxybenzenedisulfonic acid, ethoxybenzenesulfonic acid, ethoxybenzenedisulfonic acid, diethoxybenzenesulfonic acid, and diethoxybenzenedisulfone. acid, propoxybenzenesulfonic acid, propoxybenzenedisulfonic acid, butoxybenzenesulfonic acid, butoxybenzenedisulfonic acid, methylmethoxybenzenesulfonic acid, methylmethoxybenzenedisulfonic acid, methoxynaphthalenesulfonic acid, methoxynaphthalenedisulfonic acid, dimethoxynaphthalenesulfonic acid, dimethoxy Naphthalene disulfonic acid, ethoxynaphthalene sulfonic acid, ethoxynaphthalene disulfonic acid, diethoxynaphthalene sulfonic acid, diethoxynaphthalenedisulfonic acid, sodium, potassium, lithium, calcium salts thereof, and the like.

Examples of antioxidants include phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, hindered amine antioxidants, and the like.

Phenolic antioxidants include, for example, N-octadecyl-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2 ,2-thio-diethylene-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tri-ethylene glycol-bis-[3-(3-tert-butyl-5- methyl-4-hydroxyphenyl)propionate], 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2 ,4,8,10-tetraoxaspiro[5.5]undecane, tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid} pentaerythrityl ester, 2-tert- Butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4 ,6-di-tert-pentylphenyl acrylate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5- di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2, 4,6-(1H,3H,5H)-trione, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol -le), 4,4'-thiobis(6-tert-butyl-3-methylphenol) and the like.

Examples of sulfur-based antioxidants include 3,3'-thiodipropionic acid di-N-dodecyl ester, 3,3'-thiodipropionic acid di-N-tetradecyl ester, 3,3-thiodipropionate acid di-N-octadecyl ester, tetrakis(3-dodecylthiopropionic acid) pentaerythrityl ester and the like.

Examples of phosphorus antioxidants include tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6 -di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4, 4'-biphenylenediphosphonite, bis-[2,4-di-tert-butyl,(6-methyl)phenyl]ethylphosphite and the like.

Examples of hindered amine antioxidants include sebacate bis(2,2,6,6-tetramethyl-4-piperidyl) ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, poly[{ 6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl)imino} -1,6-hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}] and the like.

Examples of rust inhibitors include alkanolamines, quaternary ammonium salts, alkanethiols, imidazolines, sodium metavanadate, bismuth citrate, phenol derivatives, polyalkenylamines, alkylimidazoline derivatives, dianoalkylamines, carboxylic acid amides, alkylene Diamines, pyrimidines and their carboxylic acids, naphthenic acids, sulfonic acid complexes, calcium nitrites, alkylamines and esters, polyalcohols, polyphenols, alkanolamines, sodium molybdate, sodium tungstate, sodium nitrite, sodium phosphonate, Sodium chromate, sodium silicate, gelatin, polymers of carboxylic acids, aliphatic amines, aliphatic diamines, aromatic amines, aromatic diamines, ethoxylated amines, imidazoles, benzimidazoles, nitro compounds, formaldehyde, acetylenic alcohols, aliphatics thiols, aliphatic sulfides, aromatic thiols, aromatic sulfides, sulfoxides, thiourea, acetylenic alcohols, 2-mercaptobenzimidazoles, mixtures of amines or quaternary ammonium salts and halogen ions, acetylenithiols and sulfides, dibenzyl sulfoxide, Mixture of alkylamine and potassium iodide, dicyclohexylamine nitrite, cyclohexylamine benzoate, benzotriazole, mixture of tannin and sodium phosphate, mixture of triethanolamine, laurylsarcosine and benzotriazole, alkylamine, benzotriazole and nitrite. A mixture of sodium nitrate and sodium phosphate and the like can be mentioned.

UV absorbers and light stabilizers include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]- 2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, methyl -3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol, hydroxyphenylbenzotriazole derivatives, 2-(4,6-diphenyl-1, 3,5-triazin-2-yl)-5[(hexyl)oxy]-phenol, 2-ethoxy-2'-ethyl-oxalic acid bisanilide and the like.

Examples of biofouling agents include tetramethylthiuram disulfide, zinc bis(N,N-dimethyldithiocarbamate), 3-(3,4-dichlorophenyl)-1,1-dimethylurea, dichloro-N-(( dimethylamino)sulfonyl)fluoro-N-(P-tolyl)methanesulfenamide, pyridine-triphenylborane, N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)sulfamide, thiocyanate Copper, cuprous oxide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylenebisdithiocarbamate, 2,3,5,6-tetrachloro-4-(methylsulfonyl ) pyridine, N-(2,4,6-trichlorophenyl)maleimide, bis(2-pyridinethiol-1-oxide) zinc salt, bis(2-pyridinethiol-1-oxide) copper salt, 2-methylthio-4 -tert-butylamino-6-cyclopropylamino-S-triazine, alkylpyridine compounds, gramine compounds, isotonyl compounds and the like.

Examples of deodorants include organic acids, fatty acid metals, metal compounds, cyclodextrins, and porous materials.

Examples of organic acids include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediaminepolyacetic acid, alkane-1,2-dicarboxylic acids, alkene-1,2-dicarboxylic acids, cycloalkane-1 ,2-dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid, naphthalenesulfonic acid and the like.

Examples of fatty acid metals include zinc undecylenate, zinc 2-ethylhexanoate, and zinc ricinoleate.

Examples of metal compounds include iron oxide, iron sulfate, zinc oxide, zinc sulfate, zinc chloride, silver oxide, steel oxide, metals (iron, copper, etc.) sodium chlorophyllin, metals (iron, copper, cobalt, etc.) phthalocyanine, metals (Iron, copper, cobalt, etc.) phthalocyanine tetrasulfonate, titanium dioxide, visible light responsive titanium dioxide (nitrogen-doped type, etc.), and the like.

Examples of polyvalent metal ion scavengers include nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DPTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), hydroxyethylidene diphosphonic acid (HEDP), Amino trimethylene phosphonic acid (ATMP), salts thereof, and the like are included.

Cyclodextrins include, for example, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, their methyl derivatives, hydroxypropyl derivatives, glucosyl derivatives, maltosyl derivatives and the like.

Examples of porous body constituents include polyunsaturated carboxylic acids, aromatic polymers, chitin, chitosan, activated carbon, silica gel, activated alumina, zeolite, and ceramics.

Examples of pigments include carbon black, titanium oxide, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene pigments, perine pigments, quinophthalone pigments, diketopyrrolo-pyrrole pigments, dioxazine pigments, and disazo condensation pigments. pigments, penzimidazolone-based pigments, and the like.

Examples of surfactants include cationic surfactants, amphoteric surfactants, anionic surfactants, and nonionic surfactants.

Cationic surfactants include, for example, quaternary ammonium salts, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, pyridine derivatives and the like.

Examples of amphoteric surfactants include betaine type surfactants, carboxylic acid derivatives, imidazoline derivatives and the like.

Examples of anionic surfactants include alkyl phosphate surfactants, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, olefin sulfates, fatty alcohol sulfates, and alkyl sulfates. , fatty acid ethylsulfonates, alkylnaphthalenesulfonates, alkylbenzenesulfonates, sulfonic acid estersulfonates, phosphoric acid ester salts, and the like.

Nonionic surfactants include, for example, partial fatty acid esters of polyhydric alcohols, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty amino or fatty acid amides, and ethylene oxide adducts of alkylphenols. , ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, polyethylene glycols, polyoxyethylene alkyl ethers, alkyl glucosides, fatty acid alkanolamides, and the like. From the viewpoint of the stability of the hydrolyzable tannin contained in the detergent, polyoxyethylene alkyl ethers, alkyl glucosides and fatty acid alkanolamides are preferred, polyoxyethylene alkyl ethers and alkyl glucosides are more preferred, and polyoxyethylene alkyl ethers are preferred. Especially preferred. Such surfactants are preferable in that they are easy to handle even in an acidic solvent, and that hydrolysis of hydrolyzable tannins is suppressed or within an allowable range when mixed with hydrolyzable tannins.

Polyoxyethylene alkyl ethers include, for example, polyethylene glycol monododecyl ether, polyethylene glycol monocetyl ether, coconut oil alkyl ethoxylate, polyethylene glycol (degree of polymerization: 10) tridecyl ether, polyethylene glycol (degree of polymerization: 12) tridecyl ether, polyethylene Glycol (polymerization degree 18) tridecyl ether and the like. Alkylglucosides include, for example, n-octyl-β-D-glucopyranoside, n-heptyl-β-D-thioglucoside, n-octyl-β-D-thioglucoside and the like.

The content of the surfactant in the cleaning agent of the present disclosure is, for example, 0.00001 to 60% by mass, and the upper and lower limits thereof are, for example, a range formed by any combination of two of the following numerical values. Can be: 60% by mass, 50% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, 0.01% by mass, 0.001% by mass , 0.0001% by mass.

Examples of thickeners include oxides or hydroxides of magnesium, calcium and the like.

Additives, which are other components, include other components that overlap with the above classifications, or components that are not classified above, such as sticking agents, dispersants, wetting agents, stabilizers, propellants, penetration enhancers, and fragrances. agents, fragrances, dissolution modifiers, colorants, gelling agents, kneading resins, non-volatile oils, pH adjusters, biorepellents, antibiotics, antiviral agents, flame retardants, foaming agents, emulsifiers, brighteners, Binders, inorganic salts, oily ingredients, macromolecular substances, medicinal ingredients, enzymes, fragrances, essential oils, pigments, whitening ingredients, pigments, sulfurs, sebum secretion promoting ingredients, vitamins, Examples include seaweed extracts, cooling substances, and moisturizing ingredients.

When the cleaning agent of the present disclosure contains additives, the content of the active ingredient in the cleaning agent of the present disclosure is, for example, 0.000001 to 50% by mass, and the upper and lower limits are, for example, within the following numerical values. The range can be any combination of the two: 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass. , 0.1% by weight, 0.01% by weight, 0.001% by weight, 0.0001% by weight, 0.00001% by weight, 0.000001% by weight.

2. Form and Application The form of the cleaning agent of the present disclosure is not particularly limited, and is a form that enables cleaning indoor water use places. It is not particularly limited as long as it can be brought into contact with the surface. Examples of the form of the detergent of the present disclosure include liquids (oils, emulsions, aqueous solutions, etc.), powders, granules, granules, fine granules, tablets, block agents, baits, pastes, gels, and water. It can be used by preparing formulations such as blends, foam formulations, foam formulations, aerosol formulations, spray formulations, smoking formulations, coating formulations, etc., or carrying them on carriers. These product forms may be in a form adjusted to the working concentration, or may be in a form of high concentration and diluted for use.

The indoor water use place has a place where water (preferably tap water) is used indoors of various buildings, i.e., a surface that can come into contact with water (herein, sometimes referred to as a "water use surface"). It is a place, and it is not particularly limited as long as it is. Such locations may be slimy and are suitable for use with the cleaners of the present disclosure. Examples of buildings include residences, factories, offices, accommodation facilities, hospitals, shops, schools, restaurants, airport facilities, stations, bus terminals, service areas, exercise facilities, and the like. Factories include printing factories, paper and pulp factories, chemical factories, petrochemical factories, machinery factories, metal factories, steel factories, construction factories, housing factories, food factories, beverage factories, automobile factories, auto parts factories, motorcycle factories, Pharmaceutical factories, cosmetics factories, semiconductor factories, electronics factories, home appliance factories, personal computer factories, distribution factories, etc. are not particularly limited, but paper and pulp factories are preferred.

Specific examples of indoor water use locations include kitchens, kitchens, bathrooms, toilets, kitchens, washrooms, and water circulation facilities. As a water circulation facility in which sliminess is likely to occur, for example, a white water circulation facility in the papermaking process of a paper/pulp factory can be mentioned. The cleaning agent of the present disclosure is particularly suitable for cleaning "around the water" represented by the above specific examples.

Cleaning may be to remove all or part of foreign matter from the water-using surface, or may be to suppress adhesion or increase of foreign matter on the water-using surface. The surface on which water is used is not particularly limited as long as it is a target to which foreign matter adheres. Examples include surfaces provided on the substrate, and specific examples include plastics, ceramics, metals, glass, and the like. Examples of plastic include fiber reinforced plastic (FRP), polyvinyl chloride, polypropylene, polyethylene, ABS, polyamide, acrylic, polystyrene, and the like. Examples of ceramics include various nitrides, carbonitrides, oxides, and the like. Examples of metals include iron, stainless steel, aluminum, zinc, silver, and copper.

A foreign object means an object that should not exist, and a foreign object in an indoor water use place means an object that should not enter an indoor water use place. Examples of foreign matter in a place where indoor water is used include foreign matter derived from microorganisms, foreign matter derived from animals, and foreign matter derived from minerals. Examples of foreign substances derived from microorganisms include slime derived from microorganisms (hereinafter sometimes referred to as biofilm). "Microorganism-derived slime" refers to substances that have formed a structure by producing biological substances such as polysaccharides, proteins, and nucleic acids from within the microbial cells during the process of microorganisms adhering to and multiplying on a solid surface. A structure containing biological material. Foreign matter to which the cleaning agent of the present disclosure removes or suppresses adhesion is preferably foreign matter derived from microorganisms, and slime derived from microorganisms is preferable. Since the cleaning agent of the present disclosure is particularly effective in suppressing slime derived from microorganisms, it can be used for suppressing slime or in contact with slime.

Microorganisms are not particularly limited, such as bacteria and fungi (molds and yeasts), but from the viewpoint of efficiently suppressing sliminess, bacteria are preferred, and bacteria having an outer membrane-like membrane on the outside of the cell wall are preferred. More preferred, Gram-negative bacteria, more preferred Methylobacterium genus. Examples of the outer membrane-like membrane include the outer membrane of Gram-negative bacteria, the mycolic acid membrane of bacteria of the genus Rhodococcus, and the like.

細菌としては、例えば、Methylobacterium adhaesivum、Methylobacterium aerolatum、Methylobacterium aminovorans、Methylobacterium aquaticum、Methylobacterium brachiatum、Methylobacterium brachythecii、Methylobacterium bullatum、Methylobacterium cerastii、Methylobacterium chloromethanicum、Methylobacterium crusticola、Methylobacterium currus、Methylobacterium dankookense、Methylobacterium dichloromethanicum、Methylobacterium durans、Methylobacterium extorquens 、Methylobacterium frigidaeris、Methylobacterium fujisawaense、Methylobacterium funariae、Methylobacterium gnaphalii、Methylobacterium goesingense、Methylobacterium gossipiicola、Methylobacterium gregans、Methylobacterium haplocladii、Methylobacterium hispanicum、Methylobacterium indicum、Methylobacterium iners、Methylobacterium isbiliense、Methylobacterium jeotgali、Methylobacterium komagatae、Methylobacterium longum、Methylobacterium lusitanum、Methylobacterium marchantiae, Methylobacterium mesophilicum, Methylobacterium nodulans, Methylobacterium nonmethylotrophicum, Methylobac terium organophilum、Methylobacterium oryzae、Methylobacterium oryzihabitans、Methylobacterium oxalidis、Methylobacterium persicinum、Methylobacterium phyllosphaerae、Methylobacterium phyllostachyos、Methylobacterium planium、Methylobacterium platani、Methylobacterium podarium、Methylobacterium populi、Methylobacterium pseudosasae、Methylobacterium pseudosasicola、Methylobacterium radiora、Methylobacterium radiotolerans、Methylobacterium rhodesianum、Methylobacterium rhodinum 、Methylobacterium rhodos、Methylobacterium salsuginis、Methylobacterium segetis、Methylobacterium soli、Methylobacterium suomiense、Methylobacterium symbioticum、Methylobacterium tardum、Methylobacterium tarhaniae、Methylobacterium terrae、Methylobacterium terricola、Methylobacterium thiocyanatum、Methylobacterium thuringiense、Methylobacterium trifolii、Methylobacterium variabile、Methylobacterium zatmanii等のMethylobacterium属、 Pseudomonas genus such as Pseudomonas aeruginosa and Pseudomonas putida, Escherichia genus such as Escherichia coli, Serratia marces Gram-negative bacteria such as the genus Serratia such as cens, the genus Brevundimonas such as Brevundimonas dimuta, the genus Xanthomonas such as Xanthomonas campestris, the genus Sphingomonas such as Sphingomonas paucimobilis; Gram-positive bacteria such as Bacillus genus such as Bacillus cereus and Bacillus lentus, Staphylococcus genus such as Staphylococcus aureus and Staphylococcus epidermidis, and Rhodococcus genus such as Rhodococcus rhodochrous.

Examples of fungi include Cladosporium genus such as Cladosporium cladosporioides, Penicillium genus such as Penicillium citrinum, Aspergillus genus such as Aspergillus brasiliensis, Alternaria alternata) and other genus Alternaria, Fusarium genus such as Fusariumsolani, Eurotium genus such as Eurotium herbariorum, red yeast such as Rhodotorula mucilaginosa, Aureobasidium (A ureobasidium genus, black yeasts such as Exophiala genus, Phoma genus, Candida genus, Saccharomyces genus, and the like.

The cleaning agent of the present disclosure is preferably used for suppressing slime derived from microorganisms such as bacteria belonging to the genus Methylobacterium, bacteria belonging to the genus Brevundimonas, bacteria belonging to the genus Pseudomonas, bacteria belonging to the genus Xanthomonas, bacteria belonging to the genus Sphingomonas, bacteria belonging to the genus Rhodococcus, etc. can be used by The cleansing agent of the present disclosure is suitable for bacteria of the genus Methylobacterium, which have a particularly high frequency of occurrence among slime-causing bacteria, and is more suitable for Methylobacterium fujisawaense, which easily forms slime, among the bacteria of the genus Methylobacterium. .

Among bacteria, bacteria belonging to the genus Methylobacterium are known to cause pink or red slime. Therefore, the cleaning agent of the present disclosure is suitable for suppressing pink or red slime among slimes.

"Biological substances of microorganisms" is a general term for chemical substances existing in the body of living organisms, including biopolymers such as nucleic acids, proteins, and polysaccharides, and biopolymer components such as nucleotides, nucleosides, amino acids, sugars, and lipids. , alcohols, amino acids, nucleic acids, antioxidants, organic acids, polyols, vitamins, metabolites of hormones, and the like.

The cleaning agent of the present disclosure is preferably used at a concentration that does not substantially inhibit the growth of Methylobacterium bacteria. The concentration that does not substantially exhibit a growth-inhibiting effect is, for example, the number of bacteria of the genus Methylobacterium when the cleaning agent of the present disclosure is not used, and the number of bacteria of the genus Methylobacterium when the cleaning agent of the present disclosure is used. means a range of concentrations that are essentially equivalent to each other. Whether the concentrations are in substantially the same range can be determined by comparing the number of bacteria of the genus Methylobacterium when the detergent is not used and the number of bacteria of the genus Methylobacterium when the detergent is used. As a method for such comparison, the method of Experiment 2 in Examples described later is adopted. If the ratio of Methylobacterium genus bacteria when detergent is used to Methylobacterium genus bacteria when detergent is not used is 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more It can be said that the concentration does not actually show growth inhibition. The concentration at the time of use of the cleaning agent of the present disclosure (that is, when the cleaning agent of the present disclosure is used as it is without dilution, the concentration of the active ingredient in the cleaning agent of the present disclosure, and the cleaning agent of the present disclosure is diluted or diluted with running water, the concentration of the active ingredient in the resulting diluted solution) is, for example, 300 μg/mL or less, 200 μg/mL or less, 100 μg/mL or less, 50 μg/mL Hereinafter, concentrations of 20 μg/mL or less and 10 μg/mL or less can be said to be concentrations that do not substantially inhibit proliferation.

The type of cleaning agent of the present disclosure is not particularly limited, and varies depending on the target indoor water usage location, application, form, and method of use. The cleaning agents of the present disclosure include, for example, household cleaning agents, kitchen/kitchen cleaning agents, industrial cleaning agents, slime removers, anti-sliming agents, kitchen drain cleaning agents, bathroom cleaning agents, and toilet cleaning agents. Examples include detergents, in-tank agents, on-tank agents, automatic flush toilet cleaners, drain pipe cleaners, dishwasher cleaners, bath cleaners, bath kettle cleaners, and the like.

The method for producing the cleaning agent of the present disclosure is not particularly limited, and includes, for example, a method of mixing active ingredients and other ingredients blended as necessary. A suitable method can be adopted depending on the form, type, etc. of the detergent.

There is no particular limitation on the method of using the cleaning agent of the present disclosure when cleaning indoor water-using places. By way of example, the cleaning agents of the present disclosure may be applied directly to the water-used surface, or the application may be performed by dripping the cleaning agents of the present disclosure onto the water-used surface, using wet wipes. It may be carried out by discharging the cleaning agent of the present disclosure onto a sponge or the like, and then spreading it over the wetted surface. Alternatively, the cleaner of the present disclosure may be filled into a pump container or aerosol container and then dispensed onto a wetted surface. Furthermore, the cleaning agent of the present disclosure is placed at or around a water discharge portion (faucet, etc.) in an indoor water usage location, and the cleaning agent of the present disclosure is diluted with the water discharged from the water discharge portion to obtain The water-using surface can also be cleaned by contacting the water-using surface with a diluent (which is also one aspect of the cleaning agent of the present disclosure).

According to the cleaning agent of the present disclosure, it is possible to suppress sliminess in an indoor place where water is used. Therefore, in one aspect, the present disclosure provides a method for suppressing sliminess (hereinafter referred to as "method for suppressing sliminess of the present disclosure") comprising contacting a cleaning agent of the present disclosure with a water-using surface in an indoor water-using location. ), regarding.

The target water-using surface may be a surface on which sliminess already exists or a surface on which sliminess has not yet been formed. In the former case, by bringing the cleaning agent of the present disclosure into contact with slime derived from microorganisms, it is possible to suppress an increase in sliminess or reduce the sliminess itself. In the latter case, the formation of slime can be inhibited by contacting the wetted surface with the cleaner of the present disclosure.

If slime is present on the water-used surface, the slime control method of the present disclosure may include removing the slime prior to contacting the water-used surface with a cleaning agent according to one aspect of the present invention. The step of removing the sliminess is not particularly limited, and the sliminess may be removed by a physical method or a chemical method. By removing the slime in advance and then using the cleaning agent of the present disclosure, slime formation can be suppressed more efficiently.

According to the sliminess suppression method of the present disclosure, sliminess can be suppressed safely and environmentally friendly.

Conditions for the contact step are not particularly limited. The step may be performed, for example, at a temperature of 20 to 35°C or 25 to 30°C. The pH at the time of use may be acidic from 2.0 to 3.0, weakly acidic from 3.0 to 6.0, neutral from 6.0 to 8.0, or weakly alkaline from 8.0 to 10.0. well, it may be 10.0 to 12.0 alkaline. For example, it does not generate chlorine gas or the like even under acidic conditions, and it is gentle on the body and the environment and can suppress sliminess.

The amount of detergent used in the method for suppressing sliminess of the present disclosure can be appropriately set in consideration of the type and concentration of sliminess, the volume of the reaction system, the reaction temperature, and the like. Specifically, in the case of slime derived from Methylobacterium that occurs in drains, etc., the concentration of the active ingredient at the time of contact with the slime may be 2 μg/mL or more and 300 μg/mL or less, or 5 μg/mL or more and 250 μg. /mL or less, 10 μg/mL or more and 200 μg/mL or less, or 20 μg/mL or more and 100 μg or less. When the cleaning agent exhibits a bactericidal action, the sterilized dead bacteria serve as a scaffold to form the next slime. Therefore, within such a concentration range, slimy formation can be suppressed without exhibiting a bactericidal action, so that slimy can be efficiently suppressed.

Whether sliminess is suppressed by the sliminess suppression method of the present disclosure can be determined, for example, by the following method. First, bacteria are cultured for a period of time in the presence or absence of detergents of the present disclosure. After the culture is completed, the culture medium is removed, and the formed slime is stained with a staining solution such as Crystal Violet. SDS is added to the stained slime, and the absorbance of the solution after dissolving the slime is measured. By comparing the absorbance in the presence of the detergent and in the absence of the detergent, if the absorbance in the presence of the detergent is lower than that in the absence of the detergent, it can be determined that the sliminess is suppressed. As bacteria to be used, Methylobacterium, which is considered to be a major cause of sliminess around water, is preferable.

The slime formation rate is preferably small, and the biofilm formation rate calculated in the examples described later is 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20%. These include:

3. Additional Effect: Deodorizing Action According to the cleaning agent of the present disclosure, it is also possible to deodorize offensive odor substances that pose a problem in places where water is used indoors. Therefore, in one aspect, the present disclosure relates to a deodorizing method (hereinafter referred to as "deodorizing method of the present disclosure") comprising contacting the cleaning agent of the present disclosure with an off-flavor substance.

Offensive odor substances that cause problems in indoor water use include N-based substances such as ammonia, trimethylamine and pyridine, S-based substances such as hydrogen sulfide, methyl mercaptan, methyl sulfide, methyl disulfide and propanethiol, acetic acid, and propionic acid. , n-butyric acid, isocitric acid, and caproic acid. By bringing the cleaning agent of the present disclosure into contact with offensive odor substances, offensive odor substances can be reduced or removed.

The conditions of the contact step are not particularly limited, and include the conditions described in the step of contacting the sliminess. From the viewpoint of the stability of hydrolyzable tannin, the pH at the time of use is preferably 2.0 to 6.0, more preferably 2.0 to 4.0.

Whether or not the offensive odor substance is deodorized by the deodorizing method of the present disclosure can be determined, for example, by the following method. First, after contacting an off-flavor substance in an aqueous solution for a certain period of time in the presence or absence of the cleaning agent of the present disclosure, the off-flavor substance in the aqueous solution is quantified. Comparing the quantified values of off-flavor substances in the presence of detergent and in the absence of detergent, and if the quantified value in the presence of detergent is lower than the quantified value in the absence of detergent, it is determined that the off-flavor substances have been deodorized. be able to.

4. Additional effect: Fatty acid calcium solubilization action In places where indoor water is used, fatty acids, which are components of soap, may react with calcium in tap water, depositing unnecessary fatty acid calcium in the water. The detergent of the present disclosure can also solubilize such fatty acid calcium. Therefore, in one aspect, the present disclosure provides a method for solubilizing fatty acid calcium (hereinafter referred to as "method for solubilizing fatty acid calcium of the present disclosure"), which comprises contacting the detergent of the present disclosure with fatty acid calcium. , concerning.

Examples of fatty acid calcium that poses a problem in places where indoor water is used include, for example, calcium salts of fatty acids in soap components. Such fatty acid calcium is not particularly limited as long as it is a calcium salt of fatty acid contained in the soap component, and may be saturated fatty acid calcium or unsaturated fatty acid calcium. Such fatty acid calcium is preferably straight-chain fatty acid calcium having 10 to 20 carbon atoms, more preferably straight-chain fatty acid calcium having 12 to 18 carbon atoms. Examples of such fatty acid calcium include calcium laurate, calcium mystate, calcium palmitate, calcium stearate, and calcium oleate. The fatty acid calcium can be solubilized by contacting the detergent of the present disclosure with the fatty acid calcium.

The conditions of the contact step are not particularly limited, and include the conditions described in the step of contacting the sliminess. From the viewpoint of the stability of hydrolyzable tannin, the pH at the time of use is preferably 2.0 to 6.0, more preferably 2.0 to 4.0.

Whether the fatty acid calcium is solubilized by the solubilization method of the present disclosure can be determined, for example, by visually observing the amount of insoluble fatty acid calcium after contacting the fatty acid calcium in an aqueous solution for a certain period of time in the presence or absence of the detergent of the present disclosure. can be determined by a method of confirming with , or a method of quantifying by image analysis. The amounts of fatty acid calcium in the presence of detergent and in the absence of detergent are compared, and if the amount of fatty acid calcium in the presence of detergent is lower than the amount of fatty acid calcium in the absence of detergent, it can be determined that the fatty acid has been solubilized. can.

Further, whether fatty acid calcium is solubilized by the solubilization method of the present disclosure can also be determined, for example, by a method of quantifying fatty acid or calcium derived from solubilized fatty acid calcium. Examples of such methods include LC analysis, GC analysis, elemental analysis, and a method using a calcium quantification kit. For example, using a calcium quantification kit, the concentration of free calcium in the presence of detergent is compared with that in the absence of detergent. It can be determined that it has dissolved.

An embodiment of the present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

Experiment 1. Inhibition of biofilm (BF) formation by Methylobacterium by tannic acid (Material)
- Methylobacterium fujisawaense NBRC15843; (hereafter, NBRC15843 strain) - R2A medium - Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

"Tannic acid" used in the examples is manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. and has the following structural formula.

(Method)
A glycerol stock solution of NBRC15843 strain was added at a ratio of 100 μL/50 mL-R2A medium, and cultured at 30° C. and 150 rpm for 3 days to prepare a pre-culture solution. The turbidity (OD600) of the preculture solution was measured with a turbidity meter (CO80000 cell density meter; WPA biowave).

Cell dilutions (OD600=0.2) were prepared by diluting the pre-culture solution with R2A medium, and sample serial dilutions were prepared by serially diluting the sample to a predetermined concentration. 100 μL/well of the bacterial cell dilution and the sample serial dilution were each added to a 96-well PS plate (manufactured by Thermo Fisher Scientific) (200 μL/well in total), and static culture was performed at 30° C. for 10 days. The medium was replaced after 72 hours and 144 hours on the way. After the culture was completed, the culture medium was removed, 200 μL/well of 0.2% Crystal Violet solution was added, and the cells were stained at room temperature for about 60 minutes. After completion of staining, the cells were washed twice with 200 μL/well of dH ₂ O, added with 200 μL/well of 2% SDS solution, and allowed to stand for about 30 minutes to dissolve the cells. Transfer 150 μL/well of the cell lysate to another measurement plate and measure the absorbance at 575 nm using a plate reader (SpectraMax 340PC; Molecular Devices). Based on the calculated BF formation rate, it was judged as A to C according to the following criteria.
Formula 1: BF formation rate (%) = (specimen - BG) / (negative control - BG) x 100
Sample: Measured value when sample is added.
Negative control: measured value without addition of sample.
BG: measurements of medium only.
A: 0% or more and less than 30%.
B: 30% or more and less than 70%.
C: 70% or more.

(result)
Table 1 shows the results. The addition of tannic acid inhibited biofilm formation derived from the NBRC15843 strain in a concentration-dependent manner. The 50% inhibitory concentration (hereinafter referred to as IC50) was 2.8 μg/mL.

Experiment 2. Inhibitory effect of tannic acid on growth of Methylobacterium genus bacteria (material)
- NBRC15843 strain - R2A medium - Tannic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

(Method)
A cultured preculture medium was used in the same manner as in Experiment 1. Cell dilutions were prepared by diluting the preculture solution with R2A medium so that OD600 = 0.2, and sample serial dilutions were prepared by serially diluting the sample to a predetermined concentration. Add 1 mL/well each of the cell dilution and sample serial dilution to 48-well deep wells (manufactured by Thermo Fisher Scientific) (total 2 mL/well), and measure the turbidity (OD600) after culturing for 24 hours. From the obtained turbidity, the growth rate was calculated by the following formula 2, and judged as A to C according to the following criteria.
Formula 2: Proliferation rate (%) = (specimen - BG) / (negative control - BG) x 100
Sample: Turbidity when sample is added.
Negative control: measured value without addition of sample.
BG: Turbidity for medium only.
A: More than 90%.
B: 50% or more and less than 90%.
C: 0% or more and less than 50%.

(result)
Table 2 shows the results. The growth of NBRC15843 strain was not inhibited even at a concentration of 200 μg/mL of tannic acid. Combined with the results of Experiment 1, tannic acid did not inhibit the growth of bacteria of the genus Methylobacterium in the range of 2.5-200 μg/mL, and was thought to inhibit BF formation.

Experiment 3. Inhibitory effect of sodium hypochlorite on biofilm formation of Methylobacterium bacteria (material)
・NBRC15843 strain ・R2A medium ・Sodium hypochlorite (manufactured by Nacalai Tesque).

(Method)
The BF formation rate was calculated in the same manner as in Experiment 1, except that sodium hypochlorite was used as the sample to be evaluated.

(result)
Table 3 shows the results. The addition of sodium hypochlorite slightly suppressed biofilm formation derived from the NBRC15843 strain, but the IC50 was higher than that of tannic acid (IC50 > 20 μg/mL), so the BF formation inhibitory activity was lower than that of tannic acid.

Experiment 4. Biofilm formation inhibitory activity of Methylobacterium genus bacteria by various samples (materials)
- NBRC15843 strain - R2A medium - Compounds listed in Table 4.

(Method)
IC50 was calculated from the BF formation rate in the same manner as in Experiment 1, except that the compounds listed in Table 4 were used as specimens to be evaluated, and classified into A to C according to the following criteria.
A: less than 5 μg/mL.
B: ≥5 μg/mL and <10 μg/mL.
C: 10 μg/mL or more.

(result)
Table 4 shows the results. Among these samples, tannic acid and 1,2,3,4,6-pentagaloylglucose particularly effectively inhibited biofilm formation of Methylobacterium. The structural formula of 1,2,3,4,6-pentagaloylglucose is shown below.

Experiment 5. Inhibitory effect of tannic acid on biofilm formation against various bacteria (material)
· Bacteria listed in Table 5 · R2A medium · Tannic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

(Method)
The IC50 was calculated from the BF formation rate in the same manner as in Experiment 1, except that the cells for forming BF and the conditions shown in Table 5 were used as the BF formation time, and classified into A to D according to the following criteria.
A: <3 μg/mL.
B: ≥3 μg/mL and less than 10 μg/mL.
C: 10 μg/mL or more and less than 20 μg/mL.
D: 20 μg/mL or more.

(result)
Table 5 shows the results. Tannic acid inhibited biofilm formation of any of the bacteria listed in Table 5. In particular, it effectively inhibited biofilm formation of bacteria with an outer membrane-like membrane (outer membrane or mycolic acid membrane), and more effectively inhibited biofilm formation of NBRC15843.

Experiment 6. Biofilm formation inhibitory effect by tannic acid solution (pH 2-12) (material)
- NBRC15843 strain - R2A medium - Tannic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

(Method)
A tannic acid solution was prepared by dissolving tannic acid in a solution adjusted to pH 2 to 12 with 1M sodium hydroxide or 1M hydrochloric acid (tannic acid solution). After shaking the prepared tannic acid solution at room temperature for 24 hours, IC50 was calculated from the BF formation rate in the same manner as in Experiment 1, and classified into A to D according to the following criteria.
A: <3 μg/mL.
B: ≥3 μg/mL and less than 10 μg/mL.
C: 10 μg/mL or more and less than 20 μg/mL.
D: 20 μg/mL or more.

(result)
Table 6 shows the results. The tannic acid solution inhibited biofilm formation no matter what pH solution was used to dissolve the tannic acid.

Experiment 7. Stability of tannic acid in tannic acid solutions (pH 2-12 ) (materials)
- Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

(Method)
A tannic acid solution was prepared by dissolving tannic acid in a solution adjusted to pH 2-12 with 1M sodium hydroxide or 1M hydrochloric acid. The prepared tannic acid solution was stored at room temperature in the dark for 3 months and then subjected to HPLC analysis.

流量：1.0ｍｌ／分
カラム温度：40℃
検出：280 nm HPLC analysis conditions:
Column: SUMIPAX ODS A-211 (4.6 mmφ×25 cm, 5 μm) (manufactured by Sumika Analysis Center)
Mobile phase: A solution 0.1w/v% phosphoric acid aqueous solution, B solution 0.1w/v% phosphoric acid-containing methanol Elution method: Gradient

Flow rate: 1.0ml/min Column temperature: 40°C
Detection: 280 nm

The residual tannic acid ratio was calculated by the following formula 3, and judged as A to D according to the following criteria.
Formula 3: Tannic acid residual rate (%) = Area value of tannic acid in sample after 3 months/Area value of tannic acid in sample immediately after solution preparation × 100
Retention time of tannic acid: 10 to 25 minutes
A: 80% or more
B: 60% or more, less than 80%
C: 40% or more, less than 60%
D: less than 40%

The gallic acid production rate was calculated by the following formula 4, and judged as A to D according to the following criteria.
Formula 4: Gallic acid production rate (%) = Area value of gallic acid in sample / Area value of gallic acid produced during complete hydrolysis with tannase × 100
Gallic acid retention time: 4.3 minutes
A: Less than 20%
B: 20% or more, less than 40%
C: 40% or more, less than 60%
D: less than 60%

(result)
Table 8 shows the results. Tannic acid remained in the aqueous solution at any pH. Especially in the pH range of 2-6, the tannic acid residual rate is 80% or more and the gallic acid production rate is less than 20%, and in the pH range of 2-4, the tannic acid residual rate is 90% or more and the gallic acid is Production rate: Since it was less than 5%, tannic acid was considered to exist particularly stably.

Experiment 9. Stability of tannic acid when mixed with pH adjuster (material)
・Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- Compounds listed in Table 9

(Method)
A tannic acid solution was prepared by mixing tannic acid as described in Table 9. The prepared tannic acid solution was stored at room temperature for 24 hours and then subjected to HPLC analysis.
The initial rate of gallic acid formation was calculated by the following formula 5, and judged as A to E according to the following criteria. Formula 5: Initial rate of gallic acid production (μg/mL/day) = ([Gallic acid (Day 1)] - [Gallic acid (Day 0)]) / (1 - 0)
[Gallic acid (Day 1)]: Gallic acid concentration on day 1 (μg/mL)
[Gallic acid (day 0)]: Gallic acid concentration on day 0 (μg/mL)
A: Less than 1.0 (μg/mL/day)
B: 1.0 (μg/mL/day) or more and less than 10 (μg/mL/day)
C: 10 (μg/mL/day) or more and less than 100 (μg/mL/day)
D: 100 (μg/mL/day) or more and less than 500 (μg/mL/day)
E: 500 (μg/mL/day) or more

(result)
Table 9 shows the results. The initial rate of gallic acid production decreased in samples mixed with any pH adjuster, suggesting that the addition of pH adjusters improves the stability of tannic acid.

Experiment 10. Stability of tannic acid when mixed with alcohol (material)
- Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
・Alcohol listed in Table 10

(Method)
A tannic acid solution was prepared by mixing tannic acid as described in Table 10. After storing the prepared tannic acid solution at room temperature for 24 hours, the amount of gallic acid was quantified in the same manner as in Experiment 9, and classified into S to E according to the following criteria.
S: less than 0.1 (μg/mL/day)
A: 0.1 (μg/mL/day) or more and less than 1.0 (μg/mL/day)
B: 1.0 (μg/mL/day) or more and less than 10 (μg/mL/day)
D: 100 (μg/mL/day) or more and less than 500 (μg/mL/day)
E: 500 (μg/mL/day) or more

(result)
Table 10 shows the results. Since the initial rate of gallic acid production decreased in samples mixed with any alcohol, it was considered that the stability of tannic acid was improved by mixing alcohol.

Experiment 11. Stability of tannic acid when mixed with antibacterial, antifungal, antiseptic and antifungal agents (material)
・Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Compounds listed in Table 11

(Method)
A tannic acid solution was prepared by mixing tannic acid as described in Table 11. After storing the prepared tannic acid solution at room temperature for 24 hours, the amount of gallic acid was quantified in the same manner as in Experiment 9, and classified into A to E according to the following criteria.
A: Less than 1.0 (μg/mL/day)
B: 1.0 (μg/mL/day) or more and less than 10 (μg/mL/day)
C: 10 (μg/mL/day) or more and less than 100 (μg/mL/day)
D: 100 (μg/mL/day) or more and less than 500 (μg/mL/day)
E: 500 (μg/mL/day) or more

(result)
Table 11 shows the results. Samples mixed with acetic acid or phenoxyethanol decreased the initial rate of gallic acid formation, suggesting that the stability of tannic acid is improved. In addition, in samples mixed with sodium dehydroacetate, sodium benzoate, or sodium formate, the initial rate of gallic acid formation increased, but it was within the allowable range, so it was considered possible to mix with tannic acid.

Experiment 12. Stability of tannic acid when mixed with surfactant (polyoxyethylene alkyl ether) (material)
- Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
・Compounds listed in Table 12

(Method)
A tannic acid solution was prepared by mixing tannic acid as described in Table 12. After storing the prepared tannic acid solution at room temperature for 24 hours, the amount of gallic acid was quantified in the same manner as in Experiment 9, and classified into A to E according to the following criteria.
A: Less than 1.0 (μg/mL/day)
B: 1.0 (μg/mL/day) or more and less than 10 (μg/mL/day)
C: 10 (μg/mL/day) or more and less than 100 (μg/mL/day)
D: 100 (μg/mL/day) or more and less than 500 (μg/mL/day)
E: 500 (μg/mL/day) or more

(result)
Table 12 shows the results. In samples mixed with polyoxyethylene alkyl ether-based surfactants, the initial rate of gallic acid formation decreased, suggesting that the stability of tannic acid is improved.

Experiment 13. Stability of tannic acid when mixed with surfactant (alkyl glucoside) (material)
- Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
・Compounds listed in Table 13

(Method)
A tannic acid solution was prepared by mixing tannic acid as described in Table 13. After storing the prepared tannic acid solution at room temperature for 24 hours, the amount of gallic acid was quantified in the same manner as in Experiment 9, and classified into A to E according to the following criteria.
A: Less than 1.0 (μg/mL/day)
B: 1.0 (μg/mL/day) or more and less than 10 (μg/mL/day)
C: 10 (μg/mL/day) or more and less than 100 (μg/mL/day)
D: 100 (μg/mL/day) or more and less than 500 (μg/mL/day)
E: 500 (μg/mL/day) or more

(result)
Table 13 shows the results. The initial rate of gallic acid production was decreased in samples mixed with alkylglucoside surfactants, suggesting that the stability of tannic acid was improved. Samples mixed with n-heptyl-β-D-thioglucoside or n-octyl-β-D-thioglucoside decreased the initial rate of gallic acid formation, suggesting that the stability of tannic acid is improved. rice field. In addition, in the sample mixed with n-octyl-β-D-glucopyranoside, although the initial rate of gallic acid formation increased, it was within the allowable range, so it was considered possible to mix with tannic acid.

Experiment 14. Preparation and use of tannic acid-containing detergents (materials)
・Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・NBRC15843 strain ・R2A medium

(Method)
A tannic acid-containing detergent was prepared by mixing 0.25% tannic acid, 0.5% phenoxyethanol, 0.5% acetic acid, 50% ethanol, and the balance pure water. BF formation inhibition was evaluated in the same manner as in Experiment 1 using the prepared detergent.
(result)
The prepared tannic acid-containing detergent inhibited biofilm formation at low concentrations. The 50% inhibitory concentration (IC50) was 0.78 µg/mL in terms of tannic acid.

Experiment 15. Additional effect of tannic acid aqueous solution (1): Deodorizing action (material)
- Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
・Methyl mercaptan Na (manufactured by Tokyo Chemical Industry Co., Ltd.)
・5,5'-Dithiobis (2-nitrobenzoic acid) (DTNB ; Tokyo Chemical Industry)

(Method)
0.1 M phosphate buffer (pH 6.3), tannic acid and sodium methyl mercaptan (0.01% final concentration) were added to a screw cap test tube and shaken at 200 rpm and 25° C. for 6 hours. After 6 hours, 50 μL of the shaking solution, 200 μL of 100 mM phosphate buffer (pH 8.0), 750 μL of pure water and 20 μL of 10 mM DTNB were mixed and allowed to stand for 1 hour. After standing for 1 hour, the solution was transferred to a 1 mL cuvette and the absorbance at 412 nm was measured with a spectrophotometer. The methyl mercaptan residual rate was calculated by the following formula 6 and classified into A to E according to the following criteria.
Formula 6: Methyl mercaptan residual rate (%) = (absorbance of specimen - absorbance of BG) / (absorbance of negative control - absorbance of BG) x 100
Specimen: tannic acid added negative control: no tannic acid added.
A: Less than 20%
B: 20% or more, less than 40%
C: 40% or more, less than 60%
D: 60% or more, less than 80%
E: 80% or more

(result)
The results are shown in Table 14. Addition of the aqueous tannic acid solution reduced the concentration of methyl mercaptan, which is an off-flavour substance. From this, it was considered that the tannic acid aqueous solution also has a deodorizing effect that is different from the sliminess suppressing effect.

Experiment 16. Additional effect of tannic acid aqueous solution (2): Fatty acid calcium solubilization effect (1)
(material)
・Tannic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Calcium assay kit (Calcium Assay Kit, QuantiChrom; manufactured by Funakoshi Co., Ltd.)
・ Fatty acid calcium described in Table 15

(Method)
After the fatty acid calcium was dispensed into a 6-well plate, an aqueous tannic acid solution was added (final concentration: fatty acid calcium: 0.2%, tannic acid: 2%). Perform overnight shaking culture at room temperature using a plate shaker (BioShaker M-BR-024, manufactured by TAITEC), visually observe the degree of solubilization of fatty acid calcium, and classify into A to D according to the following criteria. did.
A: Totally solubilized
B: mostly solubilized
C: Partially solubilized
D: Insoluble

(result)
Table 15 shows the results. Addition of the aqueous tannic acid solution promoted the solubilization of fatty acid calcium. From this, it was considered that the tannic acid aqueous solution has an effect of solubilizing fatty acid calcium, which is different from the effect of suppressing sliminess.

Experiment 17. Additional effect of tannic acid aqueous solution (2): Fatty acid calcium solubilization effect (2)
(material)
・Mixture of fatty acid calcium and tannic acid described in Experiment 16 ・Calcium assay kit (Calcium Assay Kit, QuantiChrom; manufactured by Funakoshi Co., Ltd.)

(Method)
Take 1.0 mL of the mixture of fatty acid calcium and tannic acid described in Experiment 16, remove insoluble components by centrifugation (2,0000 g × 10 minutes), and use a calcium quantification kit to measure free Calcium was quantified. The ratio of free calcium was calculated by the following formula 7 and classified into A to E according to the following criteria.
Formula 7: Free calcium (%) = (Quantitative value of free calcium) / (Theoretical value of calcium calculated from the amount of fatty acid calcium added) x 100
A: 40% or more
B: 30% or more, less than 40%
C: 20% or more, less than 30%
D: 10% or more, less than 20%
E: less than 10%

(result)
The results are shown in Table 16. Addition of the aqueous tannic acid solution increased the concentration of free calcium in the supernatant, suggesting that the aqueous tannic acid solution has an effect of solubilizing fatty acid calcium, which is different from the sliminess suppressing effect.

Claims (21)

A cleaning agent for a place where water is used indoors, containing at least one selected from the group consisting of hydrolyzable tannins formed by ester-bonding glucose and a plurality of gallic acids, and salts thereof. The place of indoor water use is selected from the group consisting of residences, factories, offices, lodging facilities, hospitals, stores, schools, restaurants, airport facilities, stations, bus terminals, service areas, exercise facilities, and meeting places. 2. The cleaning agent of claim 1, which is at least one indoor water use location. 2. The cleaning agent according to claim 1, wherein said indoor water usage location is a plumbing area. 2. The cleaning agent according to claim 1, wherein said indoor water use place is at least one selected from the group consisting of kitchen, kitchen, bathroom, toilet, kitchen, washroom and water circulation equipment. A cleaning agent according to claim 1, wherein said hydrolyzable tannin is tannic acid. 2. A cleaning agent according to claim 1, containing a solvent. The cleaning agent according to claim 6, wherein the content of said hydrolyzable tannin and its salt per 1 mL of said solvent is 5000 µg or less. The cleaning agent according to claim 6, wherein the solvent has a pH of 2.0 to 12.0. the solvent is alcohol and water,
7. The cleaning agent according to claim 6, which contains a weak acid pH adjuster and the solvent has a pH of 2.0 to 4.0. 10. The cleaning agent according to claim 9, which contains an antiseptic antifungal agent and a surfactant. The cleaning agent according to claim 10, wherein the surfactant is a nonionic surfactant. 12. A cleaning agent according to claim 11, wherein said surfactant is a polyoxyethylene alkyl ether. The cleaning agent according to any one of claims 1 to 12, wherein the hydrolyzable tannin is used at a concentration that does not substantially exhibit growth-inhibiting action on bacteria belonging to the genus Methylobacterium. The cleaning agent according to any one of claims 1 to 12, which is used in contact with slime derived from microorganisms in a place where indoor water is used. The cleaning agent according to any one of claims 1 to 12, which is for suppressing sliminess derived from microorganisms. The cleaning agent according to claim 14, wherein the microorganism is at least one selected from the group consisting of Methylobacterium, Brevundimonas, Pseudomonas, Xanthomonas, Sphingomonas, and Rhodococcus. The cleaning agent according to claim 14, wherein the microorganism is Methylobacterium. A method for suppressing sliminess, comprising contacting the cleaning agent according to any one of claims 1 to 12 with a water-using surface in an indoor water-using location. 19. The method of claim 18, comprising contacting the cleansing agent of any one of claims 1-12 with microbial slime from an indoor water use site. A deodorizing method comprising contacting the cleaning agent according to any one of claims 1 to 12 with an off-flavor substance. A method for solubilizing fatty acid calcium, comprising contacting the detergent according to any one of claims 1 to 12 with fatty acid calcium.

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