Components of the agent for biofilm removal.

Abstract

DEPCT69 Provide the components of the biofilm removal agent and the method for biofilm removal. Using similar excellence in its ability to remove biofilms adhering to target objects. It can be exported, especially textile products. The composition of the biofilm removal agent contains the following components (a) and (b): One or more of the following components (a) are selected from (a1) quaternary salts. Ammonium compounds with long alkyl chains are represented by the general formulas (a1) and (a2). Bispyridinium, and Ingredient(b): anionic surfactant;

Description

Biofilm remover composition

[0001] The present invention relates to a biofilm remover composition and a method for removing a biofilm.

[0002] BACKGROUND ART Once bacteria attach to an object, they multiply and form a biofilm. Biofilms, also known as biofilms or slimes, generally refer to three-dimensional structures formed by microorganisms such as bacteria, enveloping them with polymeric substances such as polysaccharides, proteins, and nucleic acids produced by the microorganisms as they attach to and multiply on the surface of a material. Biofilms are a problem for individuals in a variety of situations. For example, they cause unpleasant slimy stains and foul odors in household wet environments such as kitchens, sinks, and bathroom drains. Biofilms are also prone to forming and causing problems not only in these direct water environments, but also in situations where water, moisture, and dirt coexist, such as scratches on cutting boards, the inside of dishwashing sponges, washing machine drums, and fabric products such as clothing, dish towels, dustcloths, and foot mats. Furthermore, detergents containing various surfactants are widely used to clean textile products such as clothing. In recent years, with increasing hygiene awareness among consumers, interest in bacteria and viruses adhering to the surfaces of textile products has also increased. As a result, consumers take the extra effort and expense of washing items such as socks and sweaty clothing, which are prone to bacterial growth, by soaking them in cleaning solution for a while, or by using disinfectants or bleach in combination with textile cleaners.

[0003] US Patent No. 5,728,667 discloses germicidal light-duty dishwashing detergent compositions, either gel or liquid, containing dioctyldimethylammonium salts and alkyl ether carboxylate salts.

[0004] Biofilms attached to target articles, particularly textile products, are extremely difficult to remove because the polymers that make up the biofilm function as a protective barrier that protects bacteria from various substrates. The present invention provides a biofilm remover composition that is excellent at removing biofilms attached to target articles, particularly textile products, and a method for removing biofilms using the same.

[0005] The present invention relates to a biofilm remover composition containing the following components (a) and (b): Component (a): (a1) a compound represented by the following general formula (a1) (hereinafter referred to as component (a1)), and (a2) one or more compounds selected from bispyridinium compounds (hereinafter referred to as component (a2)):

[0006]

[0007] [In general formula (a1), R １ａ and R ２ａ are each independently a linear or branched alkyl group having 6 to 12 carbon atoms, R ３ａ and R ４ａ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － is an anion.] Component (b): Anionic surfactant

[0008] The present invention also relates to a method for removing a biofilm, which comprises contacting an object on which a biofilm is present with the biofilm remover composition of the present invention or a treatment liquid prepared by diluting the biofilm remover composition with water.

[0009] The present invention also relates to a method for removing a biofilm, which comprises contacting a treatment liquid containing the above-mentioned components (a) and (b) with an object on which a biofilm is present.

[0010] The present invention also relates to use of a composition containing the components (a) and (b) for removing a biofilm from an object to which the biofilm is attached.

[0011] According to the present invention, there are provided a biofilm remover composition that is excellent in removing biofilms attached to target articles, particularly textile products, and a method for removing biofilms using the same.

[0012] Modes for Carrying Out the Invention The reason why the biofilm remover composition of the present invention and the biofilm removal method using the same are excellent at removing biofilms attached to target objects, particularly textile products, is not entirely clear, but is presumed to be as follows. Extracellular polysaccharides, a type of polymer that constitutes biofilms, function as a protective barrier that protects bacteria from various bases, making biofilm removal extremely difficult. In the present invention, it is believed that the combined use of a specific cationic surfactant (component (a)) and an anionic surfactant (component (b)) relaxes and disperses the dense structure of the extracellular polysaccharide, thereby enabling biofilm removal. Specifically, the biofilm remover composition of the present invention uses a specific cationic surfactant (component (a)) and an anionic surfactant (component (b)) in combination, forming a loose ion complex between (a) and (b) that does not cancel each other out. It is believed that the ion complex acts on the extracellular polysaccharide when the excess anionic surfactant that does not form an ion complex disperses the extracellular polysaccharide, thereby removing the extracellular polysaccharide. Preferably, a more excellent biofilm removal effect can be obtained when the biofilm removing composition of the present invention contains a specific cationic surfactant as component (a) and an anionic surfactant as component (b) in a mass ratio (a) / (b) of less than 1. However, the present invention is not limited to the above-mentioned mechanism of action.

[0013] [Biofilm Remover Composition] <Component (a)> The biofilm remover composition of the present invention contains, as component (a), one or more compounds selected from (a1) a compound represented by the following general formula (a1) (hereinafter referred to as component (a1)), and (a2) a bispyridinium compound (hereinafter referred to as component (a2)):

[0014]

[0015] [In general formula (a1), R １ａ and R ２ａ are each independently a linear or branched alkyl group having 6 to 12 carbon atoms, R ３ａ and R ４ａare each independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － is an anion.]

[0016] In the compound of general formula (a1) which is the component (a1), R １ａ and R ２ａ are each independently a linear or branched alkyl group, preferably a linear alkyl group, having 6 or more, preferably 8 or more, and 12 or less, preferably 10 or less, carbon atoms, from the viewpoint of biofilm removal. １ａ and R ２ａ are preferably the same as each other. ３ａ and R ４ａ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a group selected from a methyl group, an ethyl group, and a propyl group. － is an anion. From the viewpoint of biofilm removal, the anion is preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. Examples of halogen ions include chloride ions, bromine ions, and iodine ions. X － From the viewpoint of biofilm removal, chloride ion is preferred. Examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion.

[0017] The component (a1) may be used alone or in combination of two or more.

[0018] The component (a2) is a bispyridinium compound. Examples of the bispyridinium compound include those described in British Patent No. 1533952, Japanese Patent Laid-Open No. 52-105228, and International Publication No. 2014 / 100807. Specifically, from the viewpoint of biofilm removal, the bispyridinium compound is preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (a21) and compounds represented by the following general formula (a22):

[0019]

[0020] wherein Y is an alkylene or alkenylene group having 4 to 18 carbon atoms; R ５ａ each represents an alkyl group having 6 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a phenyl group with or without halogen substitution; A is an anion; q is 1 or 2, r is 1 or 2, and q×r=2.

[0021] A is a monovalent or divalent anion, such as chloride, bromide, phosphate, orthosilicate, an organic acid, such as a compound of formula R ６ａ It can be an anion from a compound such as an organic acid having —COO— or an alkyl (having 1 to 40 carbon atoms) sulfonic acid. ６ａ is hydrogen, hydroxyl, or an alkyl group having from 1 to 40 carbon atoms.

[0022] Examples of organic acids corresponding to the anion of A include acetic acid, propionic acid, phosphoric acid, glycolic acid, pyruvic acid, oxalic acid, maleic acid, malonic acid, succinic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, glycyrrhizic acid, salicylic acid, stearic acid, phosphonic acid, trifluoroacetic acid, cyanoacetic acid, 4-cyanobenzoic acid, 2-chlorobenzoic acid, 2-nitrobenzoic acid, phenoxyacetic acid, and benzenesulfonic acid.

[0023] From the viewpoint of biofilm removal, preferred bispyridinium compounds are compounds of general formula (a22), and further octenidine dihydrochloride (in general formula (a22), R ５ａ are n-octyl groups, Y is n-decenyl groups, A is Cl, q is 1, and r is 2; CAS number: 70775-75-6). The component (a2) may be used alone or in combination of two or more.

[0024] From the viewpoint of biofilm removal, the component (a) is preferably the component (a1), more preferably one or more compounds selected from dioctylmethylethylammonium salt and dioctyldimethylammonium salt, and even more preferably dioctyldimethylammonium salt.

[0025] <Component (b)> The biofilm remover composition of the present invention contains an anionic surfactant as component (b). From the viewpoint of biofilm removal, component (b) is preferably an anionic surfactant containing one or more compounds selected from (b1) a compound represented by the following general formula (b1) (hereinafter referred to as component (b1)), (b2) a compound represented by the following general formula (b2) (hereinafter referred to as component (b2)), and (b3) an internal olefin sulfonate having from 14 to 20 carbon atoms (hereinafter referred to as component (b3)). R １ｂ -O-[(PO) ｐ / (EO) ｑ ]-SO ３ M (b1) [In general formula (b1), R １ｂ is a hydrocarbon group having from 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, " / " is a symbol indicating that the bonding order of PO and EO does not matter, p is the average number of moles of PO added and is a number from 0 to 10, q is the average number of moles of EO added and is a number from 0 to 25, and M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1 / 2 atom), an ammonium ion, or an organic ammonium ion.] R ２ｂ -B-SO ３ M (b2) [In general formula (b2), R ２ｂ represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, and M represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1 / 2 atom), an ammonium ion, or an organic ammonium ion. ２ｂ The sulfonic acid group is bonded to the ortho, meta, or para position.

[0026] In the compound of the general formula (b1) of the component (b1), R １ｂis a hydrocarbon group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 22 or less, preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less, preferably a linear or branched alkyl group or a linear or branched alkenyl group, more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group, from the viewpoint of biofilm removal. p is the average number of moles of PO added, and from the viewpoint of biofilm removal, it is a number that is 0 or more, preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 1 or more, even more preferably 2 or more, and 10 or less, preferably 8 or less, more preferably 5 or less, even more preferably 3 or less, and even more preferably 2.5 or less. q is the average number of moles of EO added, and from the viewpoint of biofilm removal, it is a number that is 0 or more, preferably 0.5 or more, more preferably 1 or more, even more preferably 2 or more, and 25 or less, preferably 8 or less, more preferably 5 or less, even more preferably 3 or less, and even more preferably 1.5 or less. M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (half an atom), an ammonium ion, or an organic ammonium ion. Examples of the alkali metal ion include a sodium ion or a potassium ion, examples of the alkaline earth metal ion (half an atom) include a calcium ion or a magnesium ion, and examples of the organic ammonium ion include alkanolamines having 1 to 3 alkanol groups each having 2 or 3 carbon atoms (e.g., monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

[0027] In the compound of the general formula (b2) of the component (b2), R ２ｂ From the viewpoint of biofilm removal, represents an alkyl group having 3 or more carbon atoms, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, still more preferably 12 or more, and 21 or less, preferably 18 or less, more preferably 16 or less, even more preferably 14 or less. B represents a benzene ring, and R bonded to B ２ｂ On the other hand, sulfonic acid groups (-SO ３M) is bonded at the ortho-, meta-, or para-position. M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (half atom), an ammonium ion, or an organic ammonium ion. Examples of the alkali metal ion include a sodium ion or a potassium ion, examples of the alkaline earth metal ion (half atom) include a calcium ion or a magnesium ion, and examples of the organic ammonium ion include alkanolamines having 1 to 3 alkanol groups each having 2 or 3 carbon atoms (e.g., monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

[0028] Component (b3) is an internal olefin sulfonate. From the viewpoint of biofilm removal, the number of carbon atoms in the internal olefin sulfonate in component (b3) is preferably 14 or more, more preferably 16 or more, and preferably 24 or less, more preferably 20 or less, and even more preferably 18 or less. The number of carbon atoms in the internal olefin sulfonate in component (b3) represents the number of carbon atoms in the internal olefin to which the sulfonate is covalently bonded.

[0029] The internal olefin sulfonate (b3) is a sulfonate obtained by sulfonating, neutralizing, and hydrolyzing a raw material internal olefin (an olefin having a double bond within the olefin chain) preferably having 10 or more carbon atoms, more preferably 14 or more carbon atoms, and preferably 20 or less, more preferably 18 or less carbon atoms. Such internal olefins also include those containing trace amounts of so-called alpha olefins (hereinafter also referred to as α-olefins), in which the double bond is located at position 1 of the carbon chain. Furthermore, sulfonation of internal olefins quantitatively produces β-sultone, and a portion of the β-sultone is converted to γ-sultone and olefin sulfonic acid. These are further converted to hydroxyalkanesulfonate and olefin sulfonate in the neutralization and hydrolysis steps (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). The hydroxy group of the resulting hydroxyalkanesulfonate is located within the alkane chain, while the double bond of the olefin sulfonate is located within the olefin chain. The resulting product is primarily a mixture of these compounds, and may contain trace amounts of hydroxyalkanesulfonates having a hydroxy group at the end of the carbon chain or olefinsulfonates having a double bond at the end of the carbon chain. In this specification, these products and their mixtures are collectively referred to as internal olefinsulfonates (component (b3)). Hydroxyalkanesulfonates are also referred to as hydroxy forms of internal olefinsulfonates (hereinafter also referred to as HAS forms), and olefinsulfonates are also referred to as olefin forms of internal olefinsulfonates (hereinafter also referred to as IOS forms). The mass ratio of the HAS form to the IOS form of the compounds in component (b3) can be measured using a high-performance liquid chromatography mass spectrometer (hereinafter abbreviated as HPLC-MS). Specifically, the mass ratio can be determined from the HPLC-MS peak area of ​​component (b3).

[0030] Examples of salts of internal olefin sulfonates include alkali metal salts, alkaline earth metal (half atom) salts, ammonium salts, and organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamine and having from 2 to 6 carbon atoms.

[0031] As is clear from the above production method, the sulfonic acid group of the internal olefin sulfonate of component (b3) is present within the carbon chain of the internal olefin sulfonate, i.e., the olefin chain or alkane chain, and a small amount of the internal olefin sulfonate may contain a sulfonic acid group at the end of the carbon chain.

[0032] In component (b3), the content of internal olefin sulfonates in which the sulfonic acid group is present at the 5th position or higher, preferably at the 5th or higher and 9th or lower positions, is preferably 5% by mass or higher, more preferably 10% by mass or higher, even more preferably 15% by mass or higher, still more preferably 20% by mass or higher, and preferably 60% by mass or lower, more preferably 55% by mass or lower, even more preferably 45% by mass or lower, and still more preferably 40% by mass or lower, from the viewpoint of biofilm removal.

[0033] In component (b3), the mass ratio of the content of internal olefin sulfonates [hereinafter sometimes referred to as (IO-1S)] in which the sulfonic acid group is located at position 2 or more and position 4 or less to the content of internal olefin sulfonates [hereinafter sometimes referred to as (IO-2S)] in which the sulfonic acid group is located at position 5 or more, preferably position 5 or more and position 9 or less, (IO-1S) / (IO-2S), is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1.0 or more, still more preferably 1.5 or more, still more preferably 2 or more, still more preferably 2.5 or more, still more preferably 3 or more, still more preferably 4 or more, still more preferably 4.5 or more, and from the viewpoint of biofilm removal, is preferably 10 or less, more preferably 8 or less, even more preferably 6 or less. The contents of compounds in component (b3) in which the sulfonic acid group is located at different positions can be measured by HPLC-MS. In this specification, the content of each compound having a sulfonic acid group at a different position is determined as a mass ratio based on the HPLC-MS peak area of ​​the compound having the sulfonic acid group at each position in the total HAS form of component (b3).

[0034] The content of olefin sulfonate salts in which the sulfonic acid group is present at position 1 in component (b3) is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less in component (b3) from the viewpoint of biofilm removal, and is preferably 0.01% by mass or more from the viewpoint of reducing production costs and improving productivity. The position of the sulfonic acid group in these compounds is a position in the olefin chain or alkane chain.

[0035] The internal olefin sulfonate may be a mixture of a hydroxyl form and an olefin form. The mass ratio of the content of the olefin form in the internal olefin sulfonate to the content of the hydroxyl form in the internal olefin sulfonate (olefin form / hydroxyl form) in component (b3) may be 0 / 100 or more, further 5 / 95 or more, and may be 50 / 50 or less, further 40 / 60 or less, further 30 / 70 or less, or further 25 / 75 or less.

[0036] Examples of anionic surfactants other than components (b1), (b2), and (b3) include one or more selected from α-olefin sulfonic acids, alkanesulfonic acids, saturated or unsaturated fatty acids, alkyl or alkenyl ether carboxylic acids, α-sulfofatty acids, N-acylamino acids, mono- or diester phosphates, sulfosuccinate esters, and salts thereof. The alkyl or alkenyl group of these anionic surfactants may have, for example, from 8 to 22 carbon atoms. Examples of salts of these anionic surfactants include alkali metal salts, alkaline earth metal (half atom) salts, ammonium salts, and organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamine and having from 2 to 6 carbon atoms.

[0037] In the biofilm remover composition of the present invention, the contents of the (b1), (b2), and (b3) components in the (b) component are preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, more preferably 100% by mass, from the viewpoint of biofilm removal. The contents of the (b1), (b2), and (b3) components in the (b) component do not necessarily require that the (b1), (b2), and (b3) components are all essential components; it is sufficient that at least one of the components is contained. From the viewpoint of biofilm removal, the (b) component is preferably one or more selected from the (b1), (b2), and (b3) components, and more preferably one or more selected from the (b1) and (b3) components in the general formula (b1) where p is 0.1 or more. From the viewpoint of biofilm removal, the component (b) is a component (b1) in which p is 0.1 or more and 10 or less and q is 0 or more and 25 or less, and R ２ｂ is preferably an anionic surfactant containing one or more compounds selected from the group consisting of a (b2) component having from 8 to 18 carbon atoms and a (b3) component of an internal olefin sulfonate salt of an alkyl group having from 8 to 18 carbon atoms and from 16 to 18 carbon atoms.

[0038] The (b) component may be used alone or in combination of two or more. From the viewpoint of biofilm removal, two or more types of the (b) component are preferred. From the viewpoint of biofilm removal, the (b) component is preferably two or more types including a (b1) component in which p in the general formula (b1) is 0.1 or more, and more preferably two types of the (b1) component and a (b3) component in which p in the general formula (b1) is 0.1 or more.

[0039] <Composition, etc.> From the viewpoint of biofilm removal, the biofilm remover composition of the present invention contains component (a) in an amount of preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, still more preferably 10% by mass or less, and still more preferably 5% by mass or less. In the present invention, when component (a1) is contained as component (a), the mass of component (a1) is used as the value converted into the chlorine salt, and when component (a2) is contained as component (a), the mass of component (a2) is used as the value converted into the hydrochloride salt.

[0040] From the viewpoint of biofilm removal, the biofilm remover composition of the present invention contains component (b) in an amount of preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 1% by mass or more, still more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 12% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 18% by mass or less. In the present invention, the mass of component (b) is expressed as a value converted into the sodium salt.

[0041] In the biofilm remover composition of the present invention, the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is, from the viewpoint of biofilm removal, preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, still more preferably 0.02 or more, still more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.12 or more, still more preferably 0.15 or more, and preferably 7 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1.5 or less, still more preferably less than 1, still more preferably 0.99 or less, still more preferably 0.97 or less, still more preferably 0.95 or less, still more preferably 0.5 or less, and still more preferably 0.3 or less.

[0042] The biofilm remover composition of the present invention can promote biofilm removal when it contains other components such as water-soluble solvents, chelating agents, pH adjusters, preservatives, colorants, fragrances, hydrotropes, anti-redeposition agents such as polymers, dispersants, enzymes, antibacterial agents, antioxidants, antifoaming agents, etc. (however, components (a) and (b) are excluded).

[0043] The biofilm remover composition of the present invention contains water. Ion-exchanged water, tap water, purified water, etc. can be used as the water. Water can be used as the remainder of the composition in an amount such that the total composition is 100% by mass. The biofilm remover composition of the present invention contains water in an amount of preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less.

[0044] From the viewpoint of biofilm removal, the pH of the biofilm remover composition of the present invention at 25°C is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, even more preferably 6 or more, and preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less. The pH is a value measured at 25°C using a glass electrode. Specifically, it was measured by the following method. <pH Measurement Method> A pH electrode (BlueLine 17 pH, manufactured by SI Analytics) mounted on a Consort multi-parameter analyzer C3010 is calibrated in advance with Reagecon pH4.000 High Resolution Color Coded Buffer Solution or Reagecon pH 7.000 High Resolution Color Coded Buffer Solution, and the electrode is then thoroughly rinsed with ion-exchanged water. The pH electrode calibrated and cleaned as described above is placed in the cleaning composition whose temperature has been adjusted to 25°C, and measurement is continued using the AUTO HOLD mode of the pH meter until the measured value becomes constant.

[0045] The biofilm removing composition of the present invention may be a biofilm removing composition comprising component (a) and component (b), and may further comprise water and other components. The matters described for the biofilm removing composition of the present invention can be applied to this biofilm removing composition as appropriate, and the contents and mass ratios of the components described above can be applied by replacing them with the amounts of the components.

[0046] The biofilm remover composition of the present invention can be suitably used for textile products or hard articles, and more preferably for textile products.

[0047] The fibers of the textile product may be either hydrophobic or hydrophilic. Examples of hydrophobic fibers include protein-based fibers (such as milk protein casein fiber and Promix), polyamide-based fibers (such as nylon), polyester-based fibers (such as polyester), polyacrylonitrile-based fibers (such as acrylic), polyvinyl alcohol-based fibers (such as vinylon), polyvinyl chloride-based fibers (such as polyvinyl chloride), polyvinylidene chloride-based fibers (such as vinylidene), polyolefin-based fibers (such as polyethylene and polypropylene), polyurethane-based fibers (such as polyurethane), polyvinyl chloride / polyvinyl alcohol copolymer-based fibers (such as polycrelal), polyalkylene paraoxybenzoate-based fibers (such as benzoate), and polyfluoroethylene-based fibers (such as polytetrafluoroethylene). Examples of hydrophilic fibers include seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), palm fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silkworm silk, wild silkworm silk), feathers, cellulosic fibers (rayon, polynosic, cupra, acetate, etc.), etc. In the present invention, the term "textile products" refers to fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics made using the hydrophobic or hydrophilic fibers, as well as products obtained using the same, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, bedding, textile products for bedding (sheets, pillowcases, etc.), knitwear, socks, underwear, tights, and masks. Preferred textile products are woven fabrics such as woven fabrics and knitted fabrics, and from the viewpoint of biofilm removal, preferred textile products are textile products containing hydrophobic fibers.

[0048] Examples of hard articles include washing machines, washing machine tubs, washing machine inlets, washing machine lint filters, washing machine drain pipes, tableware, hard articles around the kitchen, and / or hard articles in living environments such as bathrooms, toilet areas, and floors, drainage ditches, water pipes, food manufacturing or beverage manufacturing plants, cooling water systems such as industrial cooling towers, endoscopes, catheters, medical equipment for artificial dialysis, etc. Examples of materials for hard articles include plastics (including silicone resins, etc.) such as polyethylene and polypropylene, metals, ceramics, wood, and combinations thereof.

[0049] [Biofilm Removal Method] The present invention relates to a method for removing a biofilm, which involves contacting a target article on which a biofilm is present with the biofilm remover composition of the present invention or a treatment solution obtained by diluting the biofilm remover composition with water (hereinafter also referred to as the treatment solution of the present invention). The treatment solution of the present invention is prepared by diluting the biofilm remover composition of the present invention with water, and therefore contains the components (a) and (b). That is, the present invention relates to a method for removing a biofilm, which involves contacting a target article on which a biofilm is present with a treatment solution containing components (a), (b), and water (hereinafter also referred to as the treatment solution of the present invention). Hereinafter, both the treatment solution obtained by diluting the biofilm remover composition of the present invention with water and the treatment solution containing components (a), (b), and water will be referred to as the treatment solution of the present invention. In a preferred method of the biofilm removal method of the present invention, the biofilm remover composition of the present invention or the treatment solution of the present invention is contacted with a target article on which a biofilm is present, and then the target article to which the biofilm remover composition of the present invention or the treatment solution of the present invention has adhered is wiped or rinsed with water to remove the biofilm remover composition of the present invention or the treatment solution of the present invention from the target article. A preferred wiping method is to wipe the target object with a fiber sheet, fabric, or the like. A preferred rinsing method is to rinse the target object to which a biofilm that has come into contact with the biofilm remover composition of the present invention or the treatment solution of the present invention is attached by contacting it with water. Specifically, preferred rinsing methods include continuously applying water to the target object or immersing the target object in water. The biofilm removal method of the present invention is carried out using the biofilm remover composition of the present invention or the treatment solution of the present invention, and the embodiments described for the biofilm remover composition of the present invention can be applied as appropriate.

[0050] The target article of the biofilm removal method of the present invention is a textile product or a hard article, preferably a textile product. The aspects of the target textile product and hard article are the same as those described for the biofilm remover composition of the present invention.

[0051] Methods for contacting the biofilm removing composition of the present invention or the treatment liquid of the present invention with a target article on which a biofilm exists include spraying or applying the biofilm removing composition of the present invention or the treatment liquid of the present invention to the target article on which a biofilm exists or is thought to exist, or immersing the target article, such as a textile product, in the biofilm removing composition of the present invention or the treatment liquid of the present invention. Alternatively, the biofilm removing composition of the present invention or the treatment liquid of the present invention may be impregnated into a nonwoven fabric and then contacted with the target article.

[0052] When the biofilm remover composition of the present invention or the treatment liquid of the present invention is sprayed or applied to a target object, the biofilm remover composition of the present invention or the treatment liquid of the present invention may be filled into a container equipped with a sprayer and sprayed in the form of droplets or foam, or the biofilm remover composition of the present invention or the treatment liquid of the present invention may be poured from the container onto the target object and applied with a brush or the like. Examples of containers equipped with a sprayer include manual spray devices that do not use propellants, such as trigger-type spray containers and pump-type spray containers, and aerosols that use propellants. The container equipped with a sprayer is preferably a trigger-type spray that can spray the contents in the form of droplets or foam, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in the form of droplets or a trigger-type spray equipped with a mechanism for forming foam (foam-forming mechanism).

[0053] When a target article, such as a textile product, is immersed in the biofilm remover composition of the present invention or the treatment solution of the present invention, the target article and the biofilm remover composition of the present invention or the treatment solution of the present invention may be left to stand or stirred during immersion. Stirring may be performed by hand or using a rotary agitator. A rotary agitator is an apparatus that stirs the target article and the biofilm remover composition of the present invention or the treatment solution of the present invention by rotating them around a certain axis of rotation. A rotary agitator may perform stirring in one direction only or in the opposite direction. Furthermore, stirring can be performed continuously or intermittently. Examples of rotary agitators available to users include pulsator-type washing machines, agitator-type washing machines, and drum-type washing machines. The biofilm removal method of the present invention preferably involves immersing a textile product on which a biofilm is present in the treatment solution of the present invention and stirring using a rotary agitator.

[0054] In the biofilm removal method of the present invention, when the target article is a hard article, the biofilm remover composition of the present invention or the treatment liquid of the present invention may be allowed to stand or be fluidized after contact, with fluidization being preferred from the viewpoint of further enhancing biofilm removal. Preferred embodiments of the method of fluidizing the biofilm remover composition of the present invention or the treatment liquid of the present invention over a hard article include, for example, a method of continuously or intermittently spraying the biofilm remover composition or the treatment liquid of the present invention over the surface of a stationary hard article, and a method of fluidizing the biofilm remover composition or the treatment liquid of the present invention in which a hard article has been immersed. Embodiments of fluidizing the biofilm remover composition or the treatment liquid of the present invention in which a hard article has been immersed include, for example, a method of fluidizing the biofilm remover composition or the treatment liquid of the present invention in which a hard article has been immersed by applying an external force such as stirring, or a method of rotating or shaking the hard article immersed in the biofilm remover composition or the treatment liquid of the present invention.

[0055] When the biofilm remover composition of the present invention is diluted with water to prepare the treatment solution of the present invention, the dilution ratio is, for example, from the viewpoint of biofilm removal, 100,000 times or less, further 50,000 times or less, further 10,000 times or less, further 3,000 times or less, and then 10 times or more, further 50 times or more, and further 100 times or more.

[0056] From the viewpoint of biofilm removal, the content of component (a) in the treatment solution of the present invention is preferably 0.001 ppm or more, more preferably 0.01 ppm or more, even more preferably 0.1 ppm or more, even more preferably 1 ppm or more, and preferably 150,000 ppm or less, more preferably 100,000 ppm or less, even more preferably 50,000 ppm or less, even more preferably 10,000 ppm or less, even more preferably 5,000 ppm or less, even more preferably 1,000 ppm or less, even more preferably 500 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less.

[0057] From the viewpoint of biofilm removal, the content of component (b) in the treatment solution of the present invention is preferably 0.001 ppm or more, more preferably 0.01 ppm or more, even more preferably 0.1 ppm or more, even more preferably 1 ppm or more, and preferably 5,000,000 ppm or less, more preferably 1,000,000 ppm or less, even more preferably 500,000 ppm or less, even more preferably 100,000 ppm or less, even more preferably 500,000 ppm or less, even more preferably 100,000 ppm or less, even more preferably 50,000 ppm or less, even more preferably 10,000 ppm or less, even more preferably 5,000 ppm or less, even more preferably 1,000 ppm or less, even more preferably 500 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less.

[0058] In the treatment liquid of the present invention, the range of mass ratios of each component described in the biofilm removing composition of the present invention can be directly applied to the range of mass ratios of each component in the treatment liquid of the present invention.

[0059] From the viewpoint of biofilm removal, the pH of the treatment solution of the present invention is preferably 1 or higher, more preferably 3 or higher, even more preferably 5 or higher, still more preferably 6 or higher, and preferably 14 or lower, more preferably 12 or lower, and even more preferably 10 or lower. The pH is a value measured at 25°C using a glass electrode. The pH measurement method is the same as the method described above.

[0060] From the viewpoint of biofilm removal, the hardness of the water used to prepare the treatment solution of the present invention is, on the German hardness scale, preferably 0° dH or more, more preferably 1° dH or more, even more preferably 3° dH or more, and preferably 30° dH or less, more preferably 25° dH or less, even more preferably 20° dH or less, still more preferably 10° dH or less, and even more preferably 5° dH or less. The hardness of the treatment solution of the present invention may be within the above-mentioned range.

[0061] Here, the German hardness (° dH) in this specification is the concentration of calcium and magnesium in water expressed as CaCO ３German hardness refers to the converted concentration of 1 mg / L (ppm) = approximately 0.056°dH (1°dH = 17.8 ppm). The calcium and magnesium concentrations for this German hardness are determined by chelate titration using disodium ethylenediaminetetraacetic acid. The specific method for measuring the German hardness of water in this specification is shown below. <Method for Measuring German Water Hardness> [Reagents] 0.01 mol / L EDTA 2Na solution: 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01 M EDTA-2Na, manufactured by Sigma-Aldrich) Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories, Inc.) Ammonia buffer solution for hardness measurement (solution prepared by dissolving 67.5 g of ammonium chloride in 570 ml of 28 w / v% aqueous ammonia and adding ion-exchanged water to a total volume of 1000 ml) [Hardness Measurement] (1) Using a volumetric pipette, place 20 ml of sample water into a conical beaker. (2) Add 2 ml of ammonia buffer solution for hardness measurement. (3) Add 0.5 ml of Universal BT indicator. Confirm that the solution after addition is reddish purple. (4) While shaking the conical beaker well, add 0.01 mol / L EDTA 2Na solution dropwise from the burette, and the end point of the titration is when the sample water turns blue. (5) Calculate the total hardness using the following formula: Hardness (°dH) = T x 0.01 x F x 56.0774 x 100 / A T: Titration volume (mL) of 0.01 mol / L EDTA 2Na solution A: Sample volume (20 mL, volume of sample water) F: Factor of 0.01 mol / L EDTA 2Na solution

[0062] When a textile product having a biofilm is immersed in the treatment solution of the present invention, the immersion (contact) time of the textile product is preferably 10 seconds or more, more preferably 1 minute or more, even more preferably 5 minutes or more, and preferably 1 day or less, more preferably 15 hours or less, even more preferably 5 hours or less, from the viewpoint of biofilm removal. After immersion, the textile product is rinsed with water and dried. Rinsing may be performed using water according to known methods such as washing textile products. The water used for rinsing in the present invention is not particularly limited, but examples include tap water, well water, ion-exchanged water, sterilized water, and distilled water.

[0063] When the biofilm remover composition of the present invention or the treatment liquid of the present invention is sprayed or applied to a target article, the amount of the biofilm remover composition of the present invention or the treatment liquid of the present invention used is not particularly limited. For example, ２ From the viewpoint of biofilm removal, the amount of component (a) is preferably 0.0001 g or more, more preferably 0.001 g or more, and preferably 100 g or less, more preferably 10 g or less, per 100g of water.

[0064] When the biofilm remover composition of the present invention or the treatment solution of the present invention is sprayed or applied to a target object, the time for which the biofilm remover composition of the present invention or the treatment solution of the present invention is contacted with the target object on which a biofilm is present (the time for which it is left to stand) is preferably 10 seconds or more, more preferably 1 minute or more, even more preferably 5 minutes or more, from the viewpoint of biofilm removal, and preferably 1 day or less, more preferably 15 hours or less, even more preferably 5 hours or less. After contact, the biofilm remover composition of the present invention may be dried as is, wiped off with a clean cloth, or rinsed with water. When rinsing, an external force (physical force) may be applied using a sponge or the like, or simply rinsed with a water stream, but rinsing with water is preferred from the viewpoint of biofilm removal.

[0065] When a nonwoven fabric is impregnated with the biofilm removing composition of the present invention or the treatment solution of the present invention and brought into contact with a target article, the nonwoven fabric can be processed into a sheet, and the fibers constituting the nonwoven fabric are preferably composed of one or more types of fibers selected from the hydrophilic fibers and hydrophobic fibers described above. The method for contacting the target article involves pressing a nonwoven fabric impregnated with the biofilm removing composition of the present invention or the treatment solution of the present invention against the target article, applying an external force within a range that does not damage the target article, and transferring the biofilm removing composition of the present invention impregnated in the nonwoven fabric, or the treatment solution obtained by diluting it with water, to the target article and bringing it into contact with the target article, and this may be done by any of rubbing, kneading, or tapping.

[0066] The biofilm remover composition of the present invention is suitable for use in removing a biofilm from a target object to which the biofilm is attached. That is, the present invention provides use of a composition containing the components (a) and (b) for removing a biofilm from a target object to which the biofilm is attached. The composition containing the components (a) and (b) is the same as the biofilm remover composition of the present invention, and specific aspects of the components (a) and (b) are also the same. Specific aspects of the composition can be appropriately applied from the aspects described for the biofilm remover composition of the present invention. Furthermore, aspects described for the biofilm removal method of the present invention can be appropriately applied from the aspects of using the composition.

[0067] In addition to the above-described embodiment, the present invention discloses the following aspects.

[0068] <1> A biofilm remover composition containing the following components (a) and (b): Component (a): (a1) a compound represented by the following general formula (a1) (hereinafter referred to as component (a1)), and (a2) one or more compounds selected from a bispyridinium compound (hereinafter referred to as component (a2)):

[0069]

[0070] [In general formula (a1), R １ａ and R ２ａare each independently a linear or branched alkyl group having 6 to 12 carbon atoms, R ３ａ and R ４ａ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － is an anion.] Component (b): Anionic surfactant

[0071] <2> The biofilm removing agent composition according to <1>, wherein the component (b) is an anionic surfactant containing one or more compounds selected from (b1) a compound represented by the following general formula (b1) (hereinafter referred to as the component (b1)), (b2) a compound represented by the following general formula (b2) (hereinafter referred to as the component (b2)), and (b3) an internal olefin sulfonate having from 14 to 20 carbon atoms (hereinafter referred to as the component (b3)). １ｂ -O-[(PO) ｐ / (EO) ｑ ]-SO ３ M (b1) [In general formula (b1), R １ｂ is a hydrocarbon group having from 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, " / " is a symbol indicating that the bonding order of PO and EO does not matter, p is the average number of moles of PO added and is a number from 0 to 10, q is the average number of moles of EO added and is a number from 0 to 25, and M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1 / 2 atom), an ammonium ion, or an organic ammonium ion.] R ２ｂ -B-SO ３ M (b2) [In general formula (b2), R ２ｂ represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, and M represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1 / 2 atom), an ammonium ion, or an organic ammonium ion. ２ｂ The sulfonic acid group is bonded to the ortho, meta, or para position.

[0072] <3> In the general formula (b1) of the component (b1), R １ｂis a hydrocarbon group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 22 or less, preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less, preferably a linear or branched alkyl group or a linear or branched alkenyl group, more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group; p is a number of 0 or more, preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 1 or more, even more preferably 2 or more, and 10 or less, preferably 8 or less, more preferably 5 or less, even more preferably 3 or less, and even more preferably 2.5 or less; q is a number of 0 or more, preferably 0.5 or more, more preferably 1 or more, even more preferably 2 or more, and 25 or less, preferably 8 or less, more preferably 5 or less, and even more preferably 3 or less; The biofilm remover composition according to <2> above, wherein M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (half an atom), an ammonium ion, or an organic ammonium ion, and is preferably a hydrogen ion, a sodium ion, a potassium ion, a calcium ion, a magnesium ion, or an alkanolamine having 1 to 3 alkanol groups having 2 or 3 carbon atoms (preferably monoethanolamine, diethanolamine, or triethanolamine).

[0073] <4> In the general formula (b1) of the component (b1), R １ｂis a linear or branched alkyl group or a linear or branched alkenyl group having from 12 to 16 carbon atoms, more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group, p is a number of 0.3 or more, more preferably 0.5 or more, even more preferably 1 or more, even more preferably 2 or more, and 8 or less, more preferably 5 or less, even more preferably 3 or less, and even more preferably 2.5 or less, q is a number of 0 or more, preferably 0.5 or more, more preferably 1 or more, even more preferably 2 or more, and 25 or less, preferably 8 or less, more preferably 5 or less, and even more preferably 3 or less, The biofilm remover composition according to <2> or <3>, wherein M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (half an atom), an ammonium ion, or an organic ammonium ion, and is preferably a hydrogen ion, a sodium ion, a potassium ion, a calcium ion, a magnesium ion, or an alkanolamine having 1 to 3 alkanol groups having 2 or 3 carbon atoms (preferably monoethanolamine, diethanolamine, or triethanolamine).

[0074] <5> R in general formula (b1) of component (b1) １ｂ is a linear or branched alkyl group having from 12 to 16 carbon atoms, more preferably a linear alkyl group; p is a number of from 0.3 to 8, preferably from 0.3 to 5, more preferably from 0.5 to 3, and even more preferably from 0.5 to 2.5; q is a number of from 0 to 8, preferably from 0 to 5, more preferably from 0 to 3, and even more preferably from 0 to 2.5; and M is a hydrogen ion, ammonium ion, sodium ion, potassium ion, calcium ion, magnesium ion, or an alkanolamine having 1 to 3 alkanol groups having 2 or 3 carbon atoms (preferably monoethanolamine, diethanolamine, or triethanolamine).

[0075] <6> The biofilm removing composition according to any one of <2> to <5>, wherein the component (b3) is an internal olefin sulfonate having 16 to 18 carbon atoms.

[0076] <7> The component (b) is a compound represented by the general formula (b1) in which p is 0.1 or more and 10 or less, and q is 0 or more and 25 or less, and R ２ｂ is an anionic surfactant containing one or more compounds selected from the group consisting of a (b2) component having 8 to 18 carbon atoms, and an (b3) component of an internal olefin sulfonate salt of an alkyl group having 8 to 18 carbon atoms and 16 to 18 carbon atoms.

[0077] <8> The biofilm remover composition according to any one of <2> to <7>, wherein the content of the component (b1), the component (b2), and the component (b3) in the component (b) is 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more and 100% by mass or less.

[0078] <9> The biofilm removing composition according to any one of <2> to <8>, wherein the component (a2) is octenidine dihydrochloride.

[0079] <10> The biofilm remover composition according to any one of <1> to <9>, wherein the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) in the biofilm remover composition is 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, still more preferably 0.02 or more, still more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.12 or more, still more preferably 0.15 or more, and 7 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1.5 or less, still more preferably less than 1, still more preferably 0.95 or less, still more preferably 0.5 or less, still more preferably 0.95 or less, still more preferably 0.5 or less, still more preferably 0.3 or less.

[0080] <11> The biofilm disinfectant composition further contains water, and the content of the component (a) in the biofilm disinfectant composition is 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and 80% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, still more preferably 10% by mass or less, and still more preferably 5% by mass or less, and the content of the component (b) is 0.001% by mass or more, more preferably 0.01% by mass or more, The biofilm remover composition according to any one of <1> to <10> above, which is preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 12% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0081] <12> The biofilm removing composition according to any one of <1> to <11>, which is for use in textile products.

[0082] <13> A method for removing a biofilm, comprising contacting a target article on which a biofilm is present with the biofilm remover composition according to any one of <1> to <12> or a treatment liquid obtained by diluting the biofilm remover composition with water.

[0083] <14> The method for removing a biofilm according to <13>, wherein the biofilm remover composition or the treatment liquid is brought into contact with a target article on which a biofilm is present, and then the target article to which the biofilm remover composition or the treatment liquid has adhered is wiped off or rinsed with water to remove the biofilm remover composition or the treatment liquid from the target article.

[0084] <15> The method for removing a biofilm according to <13> or <14>, wherein the target article is a textile product.

[0085] <16> A method for removing a biofilm, comprising contacting a target article on which a biofilm is present with a treatment liquid containing the following components (a) and (b), and water: Component (a): (a1) one or more compounds selected from the group consisting of a compound represented by the following general formula (a1) (hereinafter referred to as component (a1)), and (a2) a bispyridinium compound (hereinafter referred to as component (a2)):

[0086]

[0087] [In general formula (a1), R １ａ and R ２ａ are each independently a linear or branched alkyl group having 6 to 12 carbon atoms, R ３ａ and R ４ａ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － is an anion.] Component (b): Anionic surfactant

[0088] <17> The method for removing a biofilm according to <16>, wherein the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) in the treatment solution is 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, still more preferably 0.02 or more, still more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.12 or more, still more preferably 0.15 or more, and 7 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1.5 or less, still more preferably less than 1, still more preferably 0.95 or less, still more preferably 0.5 or less, still more preferably 0.95 or less, still more preferably 0.5 or less, still more preferably 0.3 or less.

[0089] <18> The method for removing a biofilm according to <16> or <17>, wherein the treatment liquid is brought into contact with the target object on which a biofilm is present, and then the target object to which the treatment liquid has adhered is wiped or rinsed with water to remove the treatment liquid from the target object.

[0090] <19> Use of a composition containing the following components (a) and (b) for removing a biofilm from an object to which the biofilm is attached: Component (a): (a1) one or more compounds selected from a compound represented by the following general formula (a1) (hereinafter referred to as component (a1)), and (a2) a bispyridinium compound (hereinafter referred to as component (a2)):

[0091]

[0092] [In general formula (a1), R １ａ and R ２ａ are each independently a linear or branched alkyl group having 6 to 12 carbon atoms, R ３ａ and R ４ａ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － is an anion.] Component (b): Anionic surfactant

[0093] <20> Use of the composition according to <19>, wherein the component (b) is an anionic surfactant containing one or more compounds selected from (b1) a compound represented by the following general formula (b1) (hereinafter referred to as the component (b1)), (b2) a compound represented by the following general formula (b2) (hereinafter referred to as the component (b2)), and (b3) an internal olefin sulfonate having from 14 to 20 carbon atoms (hereinafter referred to as the component (b3)), for removing a biofilm from an object to which the biofilm is attached. １ｂ -O-[(PO) ｐ / (EO) ｑ ]-SO ３ M (b1) [In general formula (b1), R １ｂ is a hydrocarbon group having from 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, " / " is a symbol indicating that the bonding order of PO and EO does not matter, p is the average number of moles of PO added and is a number from 0 to 10, q is the average number of moles of EO added and is a number from 0 to 25, and M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1 / 2 atom), an ammonium ion, or an organic ammonium ion.] R ２ｂ -B-SO ３M (b2) [In general formula (b2), R ２ｂ represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, and M represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion (1 / 2 atom), an ammonium ion, or an organic ammonium ion. ２ｂ The sulfonic acid group is bonded to the ortho, meta, or para position.

[0094] <21> In the general formula (b1) of the component (b1), R １ｂ is a linear or branched alkyl group having from 12 to 16 carbon atoms, more preferably a linear alkyl group; p is a number of from 0.3 to 8, preferably from 0.3 to 5, more preferably from 0.5 to 3, and even more preferably from 0.5 to 2.5; q is a number of from 0 to 8, preferably from 0 to 5, more preferably from 0 to 3, and even more preferably from 0 to 2.5; and M is a hydrogen ion, ammonium ion, sodium ion, potassium ion, calcium ion, magnesium ion, or an alkanolamine having 1 to 3 alkanol groups having 2 or 3 carbon atoms (preferably monoethanolamine, diethanolamine, or triethanolamine), for removing a biofilm from a target object to which the biofilm is attached.

[0095] <22> Use of the composition according to any one of <19> to <21>, wherein the component (b3) is an internal olefin sulfonate having 16 to 18 carbon atoms, for removing a biofilm from an object to which the biofilm is attached.

[0096] <23> The component (b) is a compound represented by the general formula (b1) in which p is 0.1 or more and 10 or less, and q is 0 or more and 25 or less, and R ２ｂis an anionic surfactant containing one or more compounds selected from the group consisting of a (b2) component having from 8 to 18 carbon atoms, and a (b3) component of an internal olefin sulfonate salt of an alkyl group having from 8 to 18 carbon atoms and from 16 to 18 carbon atoms, for use in removing a biofilm from an object to which the biofilm is attached.

[0097] <24> Use of the composition according to any one of <19> to <23>, wherein the contents of the components (b1), (b2), and (b3) in the component (b) are 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less, for removing a biofilm from an object to which the biofilm is attached.

[0098] <25> Use of the composition according to any one of <19> to <23>, wherein the component (a2) is octenidine dihydrochloride, for removing a biofilm from an object to which the biofilm is attached.

[0099] <26> Use of the composition according to any of <19> to <25> above for removing a biofilm from a target article to which a biofilm is attached, wherein the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) in the composition is 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, still more preferably 0.02 or more, still more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.12 or more, still more preferably 0.15 or more, and is 7 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1.5 or less, still more preferably less than 1, still more preferably 0.95 or less, still more preferably 0.5 or less, still more preferably 0.95 or less, still more preferably 0.5 or less, and still more preferably 0.3 or less.

[0100] Examples [Components] The following components were used in the examples and comparative examples. <Component (a)> Q-D08: dioctyldimethylammonium chloride, in which R １ａ and R２ａ is an alkyl group having 8 carbon atoms, and R ３ａ and R ４ａ is a methyl group, and X － is a chloride ion, component (a1) C10DMAB: didecyldimethylammonium bromide, in general formula (a1), R １ａ and R ２ａ is an alkyl group having 10 carbon atoms, and R ３ａ and R ４ａ is a methyl group, and X － is a bromo ion, component (a1), trade name "Didecyldimethylammonium Bromide", manufactured by Tokyo Chemical Industry Co., Ltd. Q-D10: didecyldimethylammonium chloride, in the general formula (a1), R １ａ and R ２ａ is an alkyl group having 10 carbon atoms, and R ３ａ and R ４ａ is a methyl group, and X － is a chloride ion, component (a1) octenidine: octenidine dihydrochloride, in general formula (a22), R ５ａ are n-octyl groups, Y is n-decenyl groups, A is Cl, q is 1, and r is 2. Component (a2), a compound having the trade name "Octenidine Dihydrochloride" manufactured by Tokyo Chemical Industry Co., Ltd. <Component (b)> C16IOS: potassium salt of an internal olefin sulfonate having 16 carbon atoms, component (b3) ApS: partial PO-added alkyl ether sulfate, in general formula (b1), R １ｂ is an alkyl group having 8 to 12 carbon atoms, p is 0.6, q is 0, and M is a sodium ion, component (b1) AS: alkyl sulfate ester salt, in general formula (b1), １ｂ is an alkyl group having 12 carbon atoms, p is 0, q is 0, and M is a sodium ion, component (b1), trade name "sodium dodecyl sulfate", manufactured by Tokyo Chemical Industry Co., Ltd. ES: polyoxyethylene alkyl ether sulfate, in the general formula (b1), R １ｂis an alkyl group having 10 to 16 carbon atoms, p is 0, q is 2, and M is a sodium ion, component (b1) C12APES: a polyoxypropylene polyoxyethylene alkyl ether sulfate having an alkyl group having 12 carbon atoms, １ｂ is an alkyl group having 12 carbon atoms, p is 2, q is 2, and M is monoethanolammonium, component (b1) LAS (linear alkylbenzene sulfonate), component (b2), product name "Neopelex G-25", manufactured by Kao Corporation

[0101] [Preparation of Biofilm Remover Compositions] The biofilm remover compositions shown in Tables 1 to 6 were prepared as follows. A 3 cm long Teflon stirrer piece was placed in a 200 mL glass beaker, followed by 10 g of ion-exchanged water and the components (a) and (b) in the formulations shown in Tables 1 to 6. The mixture was stirred at 100 r / min for 10 minutes, and 95% by mass of the ion-exchanged water needed to bring the total to 100 g was added. After stirring at 100 r / min for 5 minutes, the pH (25 ° C.) was adjusted to 8 with monoethanolamine or hydrochloric acid (Examples 38 and 39 in Table 6 were adjusted to the pH listed in the table). Ion-exchanged water was added so that the total amount was 100 g. After stirring at 100 r / min for 15 minutes, the biofilm remover compositions shown in Tables 1 to 6 were prepared. After preparation, the pH was confirmed again, and the pH of each biofilm remover composition in Tables 1 to 6 was unchanged from the pH at the time of adjustment. The amounts of each component in each biofilm remover composition shown in Tables 1 to 6 are all active ingredients. For Example 33 in Table 4, the amounts of each component in the diluted test treatment solution are shown below.

[0102] [Biofilm Removal Evaluation] (1-1) Preparation of Biofilm-Formed Fabrics Glycerol stock solutions of Rhodotorula mucilaginosa (clothing isolate) and Methylobacterium variable (clothing isolate) were smeared on potato dextrose agar medium (manufactured by Difco Laboratories) and statically cultured for 2 days at 30 ° C. A glycerol stock solution of Moraxella osloensis (clothing isolate) was smeared on SCD agar medium (Shiotani MS Co., Ltd., SCD agar medium "Daigo", for general bacterial testing) and statically cultured for 1 day at 37 ° C. After culturing, the bacterial cells were scraped off with a disposable loop (As One Corporation, Disposable Loop 10) and suspended in R2A medium (Shiotani MS Co., Ltd., R2A medium "Daigo"). The turbidity (OD600) of each bacterial suspension was measured using a spectrophotometer (Apel Co., Ltd., Model No. PD-303S), and the bacterial suspension was diluted to an OD600 of 0.2 for R. mucilaginosa and 0.01 for M. variable and M. osloensis. Hiraori cotton cloth (Cotton 2003, manufactured by Tanigashira Shoten) cut into 3 x 3 cm pieces (PE faille (Polyester Faille, manufactured by Tanigashira Shoten) was used in Example 4) was autoclaved under pressure in an autoclave (High-pressure steam sterilizer Lab Autoclave, model number: MLS-3781, manufactured by PHC Corporation). After sterilization, the Hiraori cotton cloth or PE faille was placed in a No. 6 screw tube (No. 6 screw tube bottle, manufactured by Maruemu Corporation), and 1 mL of each of the above three bacterial strains and 7 mL of R2A medium were added. The tubes were then capped and sealed, and cultured with shaking for 2 days at 30°C and 200 rpm in a small constant-temperature shaking incubator Bioshaker (Model number: BR-23FP, manufactured by TAITEC Corporation). After culturing, the Hiraori cotton cloth or PE faille was transferred to a new No. The resulting tissue was transferred to a No. 6 screw tube and 10 mL of autoclave-sterilized ion-exchanged water was added. The tissue was washed by shaking at 25°C and 150 rpm for 3 minutes in a small constant temperature shaking incubator, a bioshaker. After washing, the Hiraori cotton cloth or PE faille cloth was air-dried for 1 hour in a safety cabinet to obtain a biofilm-forming cloth.Biofilm formation on the fabric was confirmed by loosening the fabric into threads with tweezers, staining the threads, and observing them with a confocal laser scanning microscope (LSM880 ZEN, manufactured by Carl Zeiss KK). The threads to be observed were stained with a dye for staining live cells (C375-Cellstain™-CFSE, manufactured by Dojindo Laboratories, Inc.), a dye for staining dead cells (P378-Cellstain™-PI solution, manufactured by Dojindo Laboratories, Inc.), a dye for staining cellulose (Calcofluor White staining solution, manufactured by Sigma-Aldrich), a dye for staining sugars (Lectin PNA From Arachis hypogaea (peanut), Alexa Fluor™ 647 Conjugate, manufactured by Thermo Fisher Scientific Co., Ltd.), a dye for staining sugars (Concanavalin Alexa Fluor™ 647, manufactured by Thermo Fisher Scientific Co., Ltd.), and a dye for staining sugars (Lectin PNA From Arachis hypogaea (peanut), Alexa Fluor™ 647 Conjugate, manufactured by Thermo Fisher Scientific Co., Ltd.). The cells were stained with HCl (Conjugate) for 30 minutes.

[0103] (1-2) Preparation of biofilm-forming hard surfaces For Example 37 in Table 5, 0.3 mL of each of the three bacterial strains and 2.1 mL of R2A medium were added per well of a polystyrene 6-well plate (Corning Falcon Cell Culture 6-well multiwell plate with flat bottom lid), and the plate was sealed with a lid and allowed to stand at 30 °C for 2 days. After incubation, the upper layer of the 6-well plate was absorbed and air-dried for 1 hour in a safety cabinet to form a biofilm-forming hard surface. Biofilm formation on the hard surface was confirmed by observation with a digital microscope (Keyence Corporation VHX-7000).

[0104] (2) Biofilm Removal Test (Biofilm Removal Evaluation) The prepared biofilm-formed cloth was cut into a 1.5 × 1.5 cm piece, and the sterilized Hiraori cotton cloth was cut into a 1.5 × 3 cm piece. A total of three pieces (one cut biofilm-formed cloth and two cut sterilized Hiraori cotton cloths) were stacked and placed in a 5 mL tube (Eppendorf Tube 5.0 mL, model number: 0030 119.401, manufactured by Eppendorf Co., Ltd.). To this was added 3 mL of a test treatment solution prepared by diluting each of the biofilm remover compositions shown in Tables 1 to 6 3000 times with model tap water (4° dH). (For Examples 5 to 7 in Table 1, the hardness of the model tap water used for the 3000-fold dilution was changed to that shown in the table to prepare the test treatment solution. In addition, in Table 4, for Example 33, the diluted test treatment solution at the concentration shown in the table was used, and for Examples 34 and 35, the test treatment solution was used as is without dilution at the concentration shown in the table.) The solution was washed by shaking in a small constant temperature shaking incubator, a bioshaker, at 25°C and 150 rpm for 10 minutes, which was the washing step. After washing, the cloth was transferred to a 5 mL tube containing 3 mL of model tap water and washed by shaking for 3 minutes under the same conditions, which was the rinsing step. After rinsing, only the biofilm-formed cloth was removed and air-dried for 30 minutes in a safety cabinet. The same treatment was also performed using model tap water (4° dH) as the test treatment solution instead of each biofilm remover composition, and a biofilm-formed cloth after treatment with model tap water was obtained. For biofilm-forming hard surfaces, 3 mL of a test treatment solution prepared by diluting the biofilm remover composition of Example 37 in Table 5 30,000 times with model tap water (4 ° dH) was added per well, and the wells were shaken and washed for 10 minutes at 25 ° C and 150 rpm in a small constant temperature shaking incubator bioshaker. This was the washing step. After washing, the test treatment solution in the bioshaker was aspirated with a micropipette (Eppendorf Research (R) plus, manufactured by Eppendorf Co., Ltd.), and 3 mL of model tap water was added. The rinse step involved shaking and washing for 3 minutes under the same conditions. The model tap water in the bioshaker after rinsing was aspirated with a micropipette, and the rinsed biofilm-forming hard surface was air-dried for 30 minutes in a safety cabinet.The same treatment was also carried out using model tap water (4° dH) as the test treatment liquid instead of the biofilm removal composition of Example 37, and a biofilm-formed hard surface was obtained after treatment with the model tap water.

[0105] (Extraction of EPS (Extracellular Polysaccharide)) After air drying, the biofilm-formed fabric was placed in a 1.5 mL tube (Eppendorf Co., Ltd., Eppendorf Tube 1.5 mL, model number: 0030 125.150) containing 600 μL of 1.5 M sodium chloride (Fujifilm Wako Pure Chemical Industries, Ltd., sodium chloride) aqueous solution. The lid was closed and the fabric was placed in an ultrasonic cleaner (Emerson Japan Co., Ltd., tabletop ultrasonic cleaner, model number: 2510JDTH) on cold ice for 2 hours to extract the EPS remaining on the fabric. EPS (Extracellular Polysaccharide) is the main component of biofilms. After stirring the liquid for 5 minutes in a Cute Mixer (Tokyo Rikakikai Co., Ltd., model number: CUTE MIXER CM-1000), the liquid and biofilm-formed fabric were filtered using a filter (ADVANTEC, model number: DISMIC-25CS) and a syringe (Terumo Corporation, model number: SS-02SZ2.5ML). The filtrate was collected in a 2.0 mL tube (Eppendorf Co., Ltd., Eppendorf Tube 2.0 mL, model number: 0030 121.597), and 1.2 mL of ethanol (Fujifilm Wako Pure Chemical Industries, Ltd., ethanol (99.5)) pre-cooled to -30 ° C was added. The lid was closed, the mixture was mixed by inversion, and the mixture was left to stand at -30 ° C to precipitate EPS. After cooling, the tubes were centrifuged at 4 ° C and 13,000 rpm for 15 minutes in a centrifuge (Eppendorf High-Speed ​​Centrifuge Model: Centrifuge 5430) and the supernatant was removed and air-dried for 1 hour. 200 μL of ion-exchanged water was added to the air-dried tubes and stirred for 5 minutes with a cute mixer to dissolve the precipitated EPS in ion-exchanged water. Furthermore, for the biofilm-formed hard surfaces after air-drying, 2 mL of 1.5 M sodium chloride aqueous solution was added per well and pipetted 20 times with a micropipette to disperse the biofilm in the sodium chloride aqueous solution. The biofilm dispersion was placed in a 5 mL tube, the lid was closed, and the tube was placed in an ultrasonic cleaner on cold ice for 2 hours to extract the EPS remaining on the hard surface. The filtrate was collected in a 0.6 mL tube, and EPS was precipitated using the same method as above and dissolved in ion-exchanged water.

[0106] (Quantification of EPS) 100 μL of the EPS aqueous solution obtained in the previous step was placed in a glass test tube (Corning Inc., disposable glass test tube, model number: 99445-16), and 100 μL of a 5% aqueous solution of phenol (Fujifilm Wako Pure Chemical Industries, Ltd., phenol) was added thereto. After stirring for 3 seconds with a vortex mixer, 500 μL of concentrated sulfuric acid (Fujifilm Wako Pure Chemical Industries, Ltd., sulfuric acid) was added, and the mixture was further stirred for 3 seconds with a vortex mixer (AS ONE Corporation, vortex mixer, model number: VTX-3000L). After leaving to stand for 30 minutes, 200 μL was dispensed into a 96-well plate (AGC Technoglass Co., Ltd., Model No. 3815-012-MYP Microplate), and the absorbance (492 nm) of the reaction solution was measured using a microplate reader (TECAN, Fluorescence, Absorbance, and Luminescence Plate Reader, Model No. Infinite M200 PRO). Based on the amount of remaining EPS quantified in terms of glucose, the EPS removal rate was calculated using formula (1). A higher EPS removal rate indicates better biofilm removal. The results are shown in Tables 1 to 6. EPS removal rate (%) = [(W1 - W2) / W1] x 100 (1) W1: Amount of EPS remaining on the biofilm-formed fabric or biofilm-formed hard surface after treatment with model tap water W2: Amount of EPS remaining on the biofilm-formed fabric or biofilm-formed hard surface after treatment with each test treatment solution

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

Claims

DEPCT691. The composition of an agent for biofilm removal consisting of the following components (a) and (b): Component (a): one or more compounds selected from (a1) compounds represented by the following general formula (a1) (hereinafter referred to as component (a1)) and (a2) a bispyridinium compound (hereinafter referred to as component (a2)), (chemical formula) X-(a1) in which, in the general formula (a1), R1a and R2a each independently represent linear or branched alkyl groups of 6 or more carbon atoms. a- and 12 or fewer carbon atoms, R3a and R4a each independently being linear or branched alkyl groups with 1 or more carbon atoms and 3 or fewer carbon atoms, and X- being an anion and component(b): anionic surfactant.2.Component of the biofilm removal agent according to claim1, where component(b) is anionic surfactant which includes one or more compounds selected from(b1) compounds represented by the following general formula(b1) (hereinafter referred to as component(b1)),(b2)The compound represented by the following general formula (b2) (hereinafter referred to as component (b2)) and (b3)the intrinsic olefin sulfonate containing 14 or more carbon atoms and 20 or fewer carbon atoms (hereinafter referred to as component (b3)),R1b-O-[(PO)p / (EO)q]-SO3M(b1), where in the general formula (b1), R1b is the hydrocarbon group containing 8 or more carbon atoms and 22 or fewer carbon atoms, PO is the propylene oxy group, EO is the ethylene oxy group, “ / ” is a symbol indicating the sequence in which the PO and EO bonds are not restricted, p is the average number of carbon atoms. The number of moles of added PO₂ and is 0 or more and 10 or less, q is the average number of moles of added EO and is 0 or more and 25 or less, and M is hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom), ammonium ion or organic ammonium ion, and R2b-B-SO₃M(b2) where in the general formula(b2), R2b represents an alkyl group with 3 or more carbon atoms and 21 or fewer, B represents the benzene ring, M is hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom),Ammonium ions or organic ammonium ions and sulfonic acid groups bonded at the ortho, meta, or para positions relative to R2b bonded to B3. Composition of the biofilm removal agent under claim 2, where component (b) is an anionic surfactant comprising one or more compounds selected from component (b1) of the general formula (b1) in which p is 0.1 or greater and 10 or less and q is 0 or greater and 25 or less, component (b2) of the general formula (b1). 2) in which R2b contains 8 or more carbon atoms and 18 or fewer carbon atoms, and an alkyl group containing 8 or more carbon atoms and 18 or fewer carbon atoms, and an intra-sulfonate olefin of component (b3) containing 16 or more carbon atoms and 18 or fewer carbon atoms.

4. The composition of the biofilm removal agent under claim 2 or 3, in which the amounts of components (b1), (b2) and (b3) in component (b) are 70% by mass or more and 100% by mass or less.

5. The composition of the biofilm removal agent under any one of claims 1 through 4,where component (a2) is octenidine dihydrochloride; 6. Components of the biofilm removal agent under any of claims 1 to 5, where the mass ratio of the amount of component (a) to the amount of component (b), (a) / (b), is 0.001 or more and 7 or less; 7. Components of the biofilm removal agent under any of claims 1 to 6, where the components are additionally mixed with water, and the amount of component (a) is 0.001% by mass or more and 50% by mass or less and the amount of component (a) (b) is 0.001% by mass or more and 80% by mass or less.

8. The composition of the biofilm removal agent under any of the claims 1 through 7, where the composition is used for textile products.

9. The biofilm removal method which includes the composition of the biofilm removal agent under any of the claims 1 through 7 or the treatment liquid which is an aqueous dilute solution of the composition and comes into contact with the target object containing biofilm.

10. The biofilm removal method under claim 9,Where, after the biofilm removal agent or treatment fluid is brought into contact with a biofilm-containing target object, the target object to which the biofilm removal agent or treatment fluid adheres is wiped or washed with water to remove the biofilm removal agent or treatment fluid from the target object.

11. Methods for biofilm removal under claim 9 or 10, where the target object is a textile product.

12. Methods for biofilm removal which involve the contact of a treatment fluid with a biofilm-containing target object, the treatment fluid consisting of the following components (a) and (b) and water, component (a): one or more compounds selected from (a1) compounds represented by the following general formula (a1) (hereinafter referred to as component (a1)) and (a2) bispyridinium compounds (hereinafter referred to as component (a2)), (chemical formula) X-(a1) where in the general formula (a1), each R1a and R2a independently are linear or branched alkyl groups of 6 or more carbon atoms and 12 or fewer carbon atoms,R3a and R4a each independently represent linear or branched alkyl groups with one or more carbon atoms and three or fewer carbon atoms, and X- is an anion and component (b): anionic surfactant.

13. Method for biofilm removal according to claim 12, where the mass ratio of the amount of component (a) to the amount of component (b) in the treatment fluid, (a) / (b), is 0.001 or greater and 7 or less.

14. Method for biofilm removal according to claim 12 or 13, where after the treatment fluid is introduced into contact with the target object containing biofilm, the object 15. Using a composition consisting of the following components (a) and (b) for the removal of biofilm from the target object on which the biofilm is attached, component (a): one or more compounds selected from (a1) compounds represented by the following general formula (a1) (hereinafter referred to as component (a1)) and (a2) a bispyridinium compound (hereinafter referred to as component (a2)), (chemical formula) X-(a1) in which in the general formula (a1),Each independent R1a and R2a is a linear or branched alkyl group with 6 or more carbon atoms and 12 or fewer carbon atoms, each independent R3a and R4a is a linear or branched alkyl group with 1 or more carbon atoms and 3 or fewer carbon atoms, and X- is an anion and component (b): anionic surfactant.

16. Use of the components under claim 15 for the removal of biofilm from a target object on which the biofilm is attached, where component (b) is anionic surfactant which includes one or more of the compounds. More than selected from (b1) compounds represented by the following general formula (b1) (hereinafter referred to as component (b1)), (b2) compounds represented by the following general formula (b2) (hereinafter referred to as component (b2)) and (b3) intrinsic olefin sulfonates containing 14 or more carbon atoms and 20 or fewer carbon atoms (hereinafter referred to as component (b3)) R1b-O-[(PO)p / (EO)q]-SO3M(b1) where in the general formula (b1), R1b is the hydrocarbon group containing 8 or more carbon atoms and 22 or fewer carbon atoms, PO is the propylene oxy group, EO is the ethylene oxy group,“ / ” is a symbol indicating the sequence in which the bonded PO and EO are not restricted, p is the average number of moles of PO added and is 0 or more and 10 or less, q is the average number of moles of EO added and is 0 or more and 25 or less, and M is hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom), ammonium ion or organic ammonium ion, and R2b-B-SO3M(b2) in which in the general formula(b2), R2b represents the alkyl group with 3 or more carbon atoms and 21 or fewer, B represents the benzene ring, M is hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom), ammonium ion or organic ammonium ion and the sulfonic acid group bonded at the ortho, meta or para positions relative to the bonded R2b with B;