Methods for killing bacteria present in biofilms

Abstract

The present invention provides a method for sterilizing bacteria present in a biofilm, and a liquid composition used therein, which exhibits excellent bactericidal properties for bacteria present in the biofilm. [Solution] A method for killing bacteria present in a biofilm, comprising contacting the biofilm with a liquid composition containing the following components (a) and (b), and water. (a) Components: Quaternary ammonium salt having one long-chain alkyl group represented by general formula (a1) (b) Components: Compounds having an aliphatic hydrocarbon group with 8 to 18 carbon atoms, and a group selected from a sulfate ester group, a sulfonic acid group, and salts thereof.

Description

[Technical Field]

[0001] This invention relates to a method for killing bacteria present in a biofilm, and to a liquid composition used therefor. [Background technology]

[0002] Once bacteria adhere to an object, they multiply and form a biofilm. A biofilm, also known as a biomembrane or slime, generally refers to a three-dimensional structure formed when microorganisms such as bacteria adhere to the surface of a material and multiply, enveloping the microorganisms with macromolecular substances such as polysaccharides, proteins, and nucleic acids produced by the microorganisms. Biofilms pose a problem for ordinary people in various situations. For example, in household water-related environments such as kitchens, sinks, and around bathroom drains, they cause unpleasant slime buildup and foul odors. Biofilms are also likely to form in situations where water, moisture, and dirt coexist, not just in these direct water-related areas, but also in scratches on cutting boards, inside dishwashing sponges, washing machine drums, and even on fabric products such as clothing, dishcloths, rags, and bath mats.

[0003] Patent Document 1 discloses a biofilm removal composition containing a quaternary amine compound having a linear or branched alkyl group having 1 to 18 carbon atoms, with a total of 16 to 38 carbon atoms in the alkyl group. Patent Document 2 discloses a disinfectant composition containing a quaternary ammonium salt having one aliphatic hydrocarbon group with 12 to 16 carbon atoms, a polyoxyalkylene sulfate ester salt, and any sulfate ester salt or fatty acid salt. Patent Document 3 describes a bactericide composition having a compound having one or more groups selected from a quaternary ammonium salt having one aliphatic hydrocarbon group with 9 to 11 carbon atoms and a sulfate ester or sulfonate. Patent Document 4 describes a biofilm remover composition for hard surfaces containing 1% by mass or more and 40% by mass or less of an internal olefin sulfonate with 16 to 22 carbon atoms.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] Biofilms are difficult to sterilize the bacteria present therein because the polymers constituting the biofilm function as a protective barrier to protect bacteria from various substrates. In particular, it has been difficult to sterilize the bacteria present in the biofilm formed inside a structure having voids.

[0006] The present invention provides a method for sterilizing bacteria present in a biofilm, which is excellent in bactericidal property against the bacteria present in the biofilm, and a liquid composition used therefor.

Means for Solving the Problems

[0007] The present invention is a method for sterilizing bacteria present in a biofilm, which comprises bringing a liquid composition containing the following component (a), component (b), and water into contact with the biofilm. Component (a): A compound represented by the following general formula (a1)

[0008]

Chemical Formula

[0009] [In general formula (a1), R 1a is an aliphatic hydrocarbon group having 10 to 14 carbon atoms, R2a , R 3a and R 4a Each of these is independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X - It is an anion. (b) Components: Compounds having an aliphatic hydrocarbon group with 8 to 18 carbon atoms, and a group selected from a sulfate ester group, a sulfonic acid group, and salts thereof.

[0010] Furthermore, the present invention relates to a liquid composition containing component (a), component (b), and water, and is a liquid composition for killing bacteria present in a biofilm.

[0011] Furthermore, the present invention relates to a product for a liquid composition for sterilizing bacteria present in a biofilm, comprising the above-mentioned component (a), component (b), and water. [Effects of the Invention]

[0012] The present invention provides a method for sterilizing bacteria present in a biofilm, which is highly effective in sterilizing bacteria present in the biofilm, and a liquid composition used therein. [Modes for carrying out the invention]

[0013] The reason why the method for killing bacteria present in a biofilm and the liquid composition used therein, according to the present invention, are excellent at killing bacteria present in biofilms, particularly those located inside microstructures, is not entirely clear, but it is presumed to be as follows. In this invention, we believe that by using a specific compound as component (a) and a specific compound as component (b) in combination, the base material penetrates into the biofilm and acts to kill bacteria present within the biofilm. Specifically, a specific compound (a) and a specific compound (b) form a loose aggregate in a water-containing liquid composition. This prevents the bactericidal component (a) from non-specifically adsorbing to the biofilm surface, while allowing the aggregate of components (a) and (b) to penetrate into the biofilm. In addition, the penetrated aggregate is thought to have a moderate cationic property, which acts on bacteria and enables sterilization. Furthermore, in environments where biofilms are formed and organic matter stains coexist, there is room for improvement in methods for sterilizing bacteria present within biofilms. The inventors have revealed that in environments where biofilms are formed, such as inside a washing machine, when there is a large amount of organic matter stains derived from fatty acids, sebum, or proteins, the organic matter stains in the washing tub are released into the water, causing the quaternary ammonium compound to adsorb to the stains and making it difficult for it to act on the biofilm. However, the method for sterilizing bacteria present within biofilms of the present invention, and the liquid composition used therein, can exhibit an excellent bactericidal effect against bacteria present within biofilms even in environments where biofilms and organic matter stains coexist, as the aggregate of component (a) and component (b). However, the present invention is not limited to the mechanism of action described above.

[0014] [Methods for killing bacteria present in biofilms] The present invention relates to a method for sterilizing bacteria present in a biofilm, comprising contacting the biofilm with a liquid composition containing component (a), component (b), and water (hereinafter referred to as the liquid composition of the present invention). The liquid composition of the present invention can be suitably used in a method for sterilizing bacteria present in a biofilm. That is, the liquid composition of the present invention may be a liquid composition for sterilizing bacteria present in a biofilm. First, the liquid composition of the present invention will be described below.

[0015] [Liquid composition] <(a) Components> The liquid composition of the present invention contains, as component (a), one or more compounds selected from the compounds represented by the following general formula (a1). (a) Component: A compound represented by the following general formula (a1)

[0016] [Chemical formula]

[0017] [In general formula (a1), R 1a is an aliphatic hydrocarbon group having 10 to 14 carbon atoms, R 2a , 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.]

[0018] In general formula (a1), R 1a is an aliphatic hydrocarbon group which, together with the component (b) described above, forms an aggregate that adsorbs to the biofilm, and from the viewpoint of enhancing the bactericidal property of the bacteria present in the biofilm by making it easier for the component (a1) to penetrate into the biofilm from the aggregate adsorbed to the biofilm, is preferably an aliphatic hydrocarbon group having 10 or more and 14 or less, preferably 12 or less carbon atoms, preferably a linear or branched alkyl group. R 1a is particularly preferably a linear alkyl group having 10 to 12 carbon atoms from the above viewpoint. R 2a , R 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 groups selected from a methyl group, an ethyl group, and a propyl group. X - is an anion. From the viewpoint of enhancing the bactericidal effect of the bacteria present in the biofilm, the anion is preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. Examples of the halogen ion include a chlorine ion, a bromo ion, or an iodine ion. X -Chlorine ions are preferred from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm. Examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, or propyl sulfate ions. The component (a) contained in the liquid composition may be used alone or in combination of two or more components.

[0019] <(b) Component> The liquid composition of the present invention contains, as component (b), a compound having an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and a group selected from a sulfate ester group, a sulfonic acid group, and salts thereof. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm when used together with component (a) above, component (b) of the present invention is preferably one or more compounds selected from the following: a compound represented by the following general formula (b1) (hereinafter referred to as component (b1)), an olefin sulfonate or salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms (hereinafter referred to as component (b2)), and an alkane sulfonate or salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms (hereinafter referred to as component (b3)). <(b1) component> R 1b -O-(AO) p -SO3M (b1) [In general formula (b1), R 1b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, AO is an alkylene oxy group having 2 to 3 carbon atoms, p is the average number of moles of AO added, a number between 0 and 10, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom), ammonium ion, or organic ammonium ion.

[0020] (b1) In a compound of general formula (b1) of component R 1bFrom the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, the aliphatic hydrocarbon group has 8 or more carbon atoms, preferably 10 or more carbon atoms, more preferably 11 or more carbon atoms, even more preferably 12 or more carbon atoms, and from the same viewpoint, 18 or fewer carbon atoms, preferably 16 or fewer carbon atoms, more preferably 15 or fewer carbon atoms, and even more preferably 14 or fewer carbon atoms. (b) Total R of component 1b The proportion of aliphatic hydrocarbon groups with 12 to 14 carbon atoms is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm. This proportion may also be 100% by mass. 1b Examples of hydrocarbon groups include alkyl groups and alkenyl groups. R 1b The hydrocarbon group is 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 further enhancing the bactericidal effect on bacteria present in the biofilm. The AO group is one or more groups selected from alkylene oxy groups having 2 to 3 carbon atoms. The alkylene oxy group with 2 carbon atoms may be an ethylene oxy group, and the alkylene oxy group with 3 carbon atoms may be a propylene oxy group. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, the AO group is preferably an alkylene oxy group having 2 to 3 carbon atoms and containing an ethylene oxy group, and more preferably an ethylene oxy group. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, p is a number of 0 or more, and 10 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. M is a hydrogen ion, alkali metal ion, alkaline earth metal ion (half atom), ammonium ion, or organic ammonium ion. Examples of alkali metal ions include sodium ions or potassium ions, examples of alkaline earth metal ions (half atom) include calcium ions or magnesium ions, and examples of organic ammonium ions include alkanolamines having 1 to 3 alkanol groups with 2 or 3 carbon atoms (e.g., monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

[0021] In general formula (b1), (AO) p More specifically, “(EO) p1 (PO) p2 The group may be represented by ". PO is a propyleneoxy group, EO is an ethyleneoxy group, and " / " is a symbol indicating that the bonding order of PO and EO does not matter. p1 is the average number of moles of EO added, a number between 0 and 10, p2 is the average number of moles of PO added, a number between 0 and 10, and the sum of p1 and p2 is between 0 and 10. In other words, component (b1) may be a compound represented by the following general formula (b11) (hereinafter referred to as component (b11)). R 1b -O-[(EO) p1 (PO) p2 ]-SO3M (b11) [In general formula (b11), R 1b EO, PO, p1, p2, or M can be applied in the same manner as described above. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, p1 is preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, even more preferably 3 or less, and 0 or more. On the other hand, the R of component (a) 1aHowever, when using a compound that is an aliphatic hydrocarbon group having 11 or 12 carbon atoms, p1 is preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, even more preferably 3 or less, and preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 1 or more, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, p2 is preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, even more preferably 3 or less, even more preferably 2 or less, even more preferably 1.5 or less, even more preferably 1.0 or less, even more preferably 0.9 or less, even more preferably 0.8 or less, and preferably 0.2 or more, more preferably 0.4 or more, and even more preferably 0.5 or more.

[0022] In the general formula (b11) above, when a compound with p2 of 2 or less is used, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, p1 is preferably 1.5 or less, more preferably 1.0 or less, even more preferably 0.8 or less, even more preferably 0.6 or less, even more preferably 0.4 or less, even more preferably 0.2 or less, and even more preferably 0 or more. p1 may be 0.

[0023] In the above general formula (b11), from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, the ratio of the number of p1s to the number of p2s, p1 / p2, is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, even more preferably 1 or less, even more preferably less than 1, even more preferably 0.9 or less, even more preferably 0.8 or less, even more preferably 0.6 or less, even more preferably 0.5 or less, even more preferably 0.3 or less, even more preferably 0.1 or less, and 0 or more. p1 / p2 may be 0.

[0024] <(b2) component> Component (b2) of the present invention is an olefin sulfonate or a salt thereof having an aliphatic hydrocarbon group with 8 to 18 carbon atoms. Component (b2) may be one or more selected from internal olefin sulfonates or salts thereof, and α-olefin sulfonates or salts thereof. The number of carbon atoms in the internal olefin sulfonate or its salt is preferably 14 or more, more preferably 16 or more, and 18 or less, and particularly preferably 16, from the viewpoint of biofilm sterilization. (b2) The number of carbon atoms in the internal olefin sulfonate or its salt in component (b2) represents the number of carbon atoms in the internal olefin to which the sulfonate or its salt is covalently bonded.

[0025] (b2) The internal olefin sulfonate or its salt is a sulfonate obtained by sulfonating, neutralizing, and hydrolyzing an internal olefin (an olefin having a double bond inside the olefin chain) which preferably has 14 or more carbon atoms and 18 or fewer carbon atoms, and preferably 16 or fewer carbon atoms, as a raw material. Such internal olefins may also contain trace amounts of so-called alpha-olefins (hereinafter also called α-olefins), in which the double bond is located at position 1 of the carbon chain. Furthermore, when an internal olefin is sulfonated, β-sartone is quantitatively produced, and a portion of the β-sartone is converted into γ-sartone and olefin sulfonate, which are further converted into hydroxyalkane sulfonate or its salt and olefin sulfonate or its salt in the neutralization and hydrolysis process (for example, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxyl group of the obtained hydroxyalkane sulfonate is inside the alkane chain, and the double bond of the olefin sulfonate is inside the olefin chain. Furthermore, the resulting product is mainly a mixture of these, and may also contain trace amounts of hydroxyalkanesulfonic acid or its salts having a hydroxyl group at the end of the carbon chain, or olefin sulfonic acid or its salts having a double bond at the end of the carbon chain. In this specification, each of these products and mixtures thereof are collectively referred to as internal olefin sulfonate or its salt. Furthermore, hydroxyalkane sulfonates are referred to as the hydroxy derivative of internal olefin sulfonates (hereinafter also referred to as the HAS derivative), and olefin sulfonates are referred to as the olefin derivative of internal olefin sulfonates (hereinafter also referred to as the IOS derivative). The mass ratio of the HAS and IOS forms of a compound can be measured using high-performance liquid chromatography-mass spectrometry (HPLC-MS). Specifically, the mass ratio can be determined from the HPLC-MS peak area of ​​component (b2).

[0026] Examples of salts of internal olefin sulfonic acid include alkali metal salts, alkaline earth metal (half atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0027] (b2) As is clear from the above manufacturing method, the sulfonic acid groups of the internal olefin sulfonic acid or its salt are located inside the carbon chain of the internal olefin sulfonic acid or its salt, i.e., inside the olefin chain or alkane chain, and in some cases, trace amounts of sulfonic acid groups may be present at the ends of the carbon chain.

[0028] (b2) The content of internal olefin sulfonic acid in the component, where the sulfonic acid group is located at position 5 or higher, preferably at position 5 to 9, is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 45% by mass or less, and even more preferably 42% by mass or less.

[0029] (b2) The mass ratio (IO-1S) / (IO-2S) of the content of internal olefin sulfonic acid [hereinafter sometimes referred to as (IO-1S)] in the component, in which the sulfonic acid group is located at position 2 to 4, and the content of internal olefin sulfonic acid [hereinafter sometimes referred to as (IO-2S)] in which the sulfonic acid group is located at position 5 or higher, preferably at position 5 to 9, is preferably 0.5 or higher, more preferably 0.8 or higher, even more preferably 1.0 or higher, and even more preferably 1.5 or higher, and even more preferably 10 or lower, more preferably 8 or lower, even more preferably 6 or lower, even more preferably 4 or lower, even more preferably 3 or lower, even more preferably 2.5 or lower, and even more preferably 2 or lower. Furthermore, the content of each compound with different sulfonic acid group positions in component (b2) can be measured by HPLC-MS. In this specification, the content of each compound with different sulfonic acid group positions shall be determined as the mass ratio based on the HPLC-MS peak area of ​​the compounds with sulfonic acid groups at each position in the total HAS mixture of component (b2).

[0030] (b2) When the component is internal olefin sulfonate or a salt thereof, the content of the olefin sulfonate with the sulfonic acid group at position 1 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 the internal olefin sulfonate from the viewpoint of killing bacteria in the biofilm, and 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 within the olefin chain or the alkane chain.

[0031] The aforementioned internal olefin sulfonic acid may be a mixture of hydroxy and olefin compounds. The mass ratio (olefin / hydroxy) of the olefin content to the hydroxy content in the internal olefin sulfonic acid may be 0 / 100 or more, more specifically 5 / 95 or more, and then 50 / 50 or less, more specifically 40 / 60 or less, more specifically 30 / 70 or less, and more specifically 25 / 75 or less.

[0032] (b2) In the α-olefin sulfonic acid or salt thereof of component (b2), the number of carbon atoms in the aliphatic hydrocarbon group constituting the α-olefin is preferably 12 or more, preferably 16 or less, and more preferably 14 or less, from the viewpoint of further enhancing the bactericidal effect against bacteria present in the biofilm. Examples of salts of α-olefin sulfonic acid include alkali metal salts, alkaline earth metal (half atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0033] <(b3) component> Component (b3) of the present invention includes alkanesulfonic acid or a salt thereof having an aliphatic hydrocarbon group with 8 to 18 carbon atoms. The aliphatic hydrocarbon group constituting the alkane is preferably a secondary alkyl group. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 10 or more, more preferably 12 or more, and preferably 16 or less. (b3) Examples of salts of component (b3) include alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0034] Component (b) is one or more selected from components (b1), (b2), and (b3) from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, wherein component (b1) is preferably a compound represented by the general formula (b11), and is one or more compounds selected from components (b1) and (b2), wherein component (b1) is a compound in the general formula (b11) in which p1 is 0 or more and p2 is 0.2 or more and 4 or less, and component (b2) is more preferably an internal olefin sulfonate having 16 or more carbon atoms and 18 or less, or a salt thereof. Furthermore, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, it is preferable that in the general formula (b11), the ratio of the number of p1s to the number of p2s, p1 / p2, is 0 or greater and 1 or less.

[0035] As component (b) other than components (b1) to (b3), the liquid composition of the present invention may contain alkylbenzene sulfonates having a linear alkyl group with 8 to 18 carbon atoms, but this may inhibit the effects of the present invention. The mass ratio of the content of alkylbenzene sulfonates (LAS) having a linear alkyl group with 8 to 18 carbon atoms to the content of component (b) in the liquid composition of the present invention or the product for the liquid composition described later, LAS / component (b), is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.3 or less, even more preferably 0.25 or less, even more preferably 0.2 or less, even more preferably 0.15 or less, even more preferably 0.1 or less, even more preferably 0.05 or less, and 0% by mass or more, and may be 0% by mass (counterions are on a sodium basis).

[0036] <Composition, etc.> [Liquid composition] The liquid composition of the present invention contains, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, preferably, 2 mg / kg or more, more preferably 2.2 mg / kg or more, even more preferably 2.4 mg / kg or more, even more preferably 2.5 mg / kg or more, even more preferably 2.6 mg / kg or more, even more preferably 2.7 mg / kg or more, even more preferably 2.8 mg / kg or more, even more preferably 3 mg / kg or more, even more preferably 3.5 mg / kg or more, even more preferably 4 mg / kg or more, even more preferably 5 mg / kg or more, even more preferably 6 mg / kg or more, even more preferably 7 mg / kg or more, even more preferably 8 mg / kg or more, even more preferably 10 mg / kg or more, and even more preferably 1 It contains 5 mg / kg or more, and from the same viewpoint, preferably 50,000 mg / kg or less, more preferably 30,000 mg / kg or less, even more preferably 20,000 mg / kg or less, even more preferably 10,000 mg / kg or less, even more preferably 5,000 mg / kg or less, even more preferably 3,000 mg / kg or less, even more preferably 1,000 mg / kg or less, even more preferably 500 mg / kg or less, even more preferably 300 mg / kg or less, even more preferably 200 mg / kg or less, even more preferably 100 mg / kg or less, even more preferably 80 mg / kg or less, even more preferably 50 mg / kg or less, even more preferably 40 mg / kg or less, even more preferably 30 mg / kg or less, and even more preferably 20 mg / kg or less. In this invention, the mass of component (a) shall be the value converted to the chlorine salt.

[0037] The liquid composition of the present invention contains, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, preferably 5 mg / kg or more, more preferably 10 mg / kg or more, even more preferably 15 mg / kg or more, even more preferably 17 mg / kg or more, even more preferably 20 mg / kg or more, even more preferably 23 mg / kg or more, even more preferably 25 mg / kg or more, even more preferably 27 mg / kg or more, even more preferably 30 mg / kg or more, even more preferably 35 mg / kg or more, even more preferably 37 mg / kg or more, even more preferably 40 mg / kg or more, even more preferably 45 mg / kg or more, even more preferably 47 mg / kg or more, even more preferably 50 mg / kg or more, even more preferably 53 mg / kg or more, and even more preferably 55 mg / kg or more. From the same viewpoint as above, it preferably contains 300,000 mg / kg or less, more preferably 200,000 mg / kg or less, even more preferably 100,000 mg / kg or less, even more preferably 50,000 mg / kg or less, even more preferably 30,000 mg / kg or less, even more preferably 20,000 mg / kg or less, even more preferably 10,000 mg / kg or less, even more preferably 5,000 mg / kg or less, even more preferably 3,000 mg / kg or less, even more preferably 1,000 mg / kg or less, even more preferably 500 mg / kg or less, even more preferably 300 mg / kg or less, even more preferably 200 mg / kg or less, even more preferably 150 mg / kg or less, even more preferably 100 mg / kg or less, even more preferably 70 mg / kg or less, and even more preferably 60 mg / kg or less. In this invention, the mass of component (b) shall be the value converted to the sodium salt.

[0038] In the liquid composition of the present invention, the mass ratio of the content of component (b) to the content of component (a), component (b) / component (a), is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.2 or more, even more preferably 1.5 or more, even more preferably 1.8 or more, even more preferably 2 or more, even more preferably 2.2 or more, even more preferably 2.5 or more, even more preferably 3 or more, even more preferably 4 or more, and from the same viewpoint, preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, even more preferably 15 or less, even more preferably 12 or less, even more preferably 10 or less, even more preferably 9 or less, even more preferably 8 or less, even more preferably 7 or less, even more preferably 6 or less, even more preferably 5 or less, and even more preferably 4 or less.

[0039] In the liquid composition of the present invention, when the above-mentioned component (b) is component (b1) and a compound in general formula (b11) in which p2 is 0 is used, in the general formula (a1) of component (a), R 1a The maximum number of carbon atoms and the general formula (b11) of component (b1), R 1b If there is no combination in which the sum of the maximum number of carbon atoms is 24 or more, the mass ratio of the content of component (b1) to the content of component (a), component (b1) / component (a), is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.2 or more, even more preferably 1.5 or more, even more preferably 1.8 or more, even more preferably 2 or more, even more preferably 2.2 or more, even more preferably 2.4 or more, and from the same viewpoint, preferably 40 or less, more preferably 30 or less, even more preferably 25 or less, even more preferably 20 or less, even more preferably 10 or less, even more preferably 9 or less, even more preferably 8 or less, even more preferably 6 or less, even more preferably 4 or less, and even more preferably 3.0 or less.

[0040] Furthermore, in the liquid composition of the present invention, if the above-mentioned component (b) is component (b1) and a compound in general formula (b11) in which p2 is 0 is used, then in the general formula (a1) of component (a), R 1a The maximum number of carbon atoms and the general formula (b11) of component (b1), R 1b If the combination has a total of 24 or more maximum carbon atoms, the mass ratio of the content of component (b1) to the content of component (a), (b1) / (a), is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, even more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.2 or more, even more preferably 1.5 or more, even more preferably 1.8 or more, even more preferably 2 or more, and from the same viewpoint, preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, even more preferably 10 or less, even more preferably 8 or less, even more preferably 6 or less, even more preferably 5 or less, even more preferably 4 or less, and even more preferably 3.5 or less.

[0041] In the liquid composition of the present invention, when the above-mentioned component (b) is component (b1) and a compound in which p2 is greater than 0 is used, the mass ratio of the content of component (b1) to the content of component (a), component (b1) / component (a), from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.2 or more, even more preferably 1.5 or more, even more preferably 1.8 or more, even more preferably 2 or more, even more preferably 2.2 or more, even more preferably 2.5 or more, even more preferably 3 or more, even more preferably 4 or more, and from the same viewpoint, preferably 40 or less, more preferably 35 or less, even more preferably 30 or less, even more preferably 25 or less, even more preferably 20 or less, even more preferably 15 or less, even more preferably 10 or less, even more preferably 9 or less, even more preferably 8 or less, even more preferably 7 or less, even more preferably 6.5 or less, and even more preferably 6.0 or less.

[0042] In the liquid composition of the present invention, when component (b) is component (b2) or component (b3), the mass ratio of the content of component (b2) or component (b3) to the content of component (a) [component (b2) or component (b3)] / component (a) is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, even more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.2 or more, even more preferably 1.5 or more, even more preferably 1.8 or more, even more preferably 2 or more, and from the same viewpoint, preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, even more preferably 10 or less, even more preferably 8 or less, even more preferably 6 or less, even more preferably 5 or less, even more preferably 4 or less, and even more preferably 3.0 or less.

[0043] The liquid composition of the present invention or the product for the liquid composition described later can promote the killing of bacteria in the biofilm if it contains, among other components, for example, a water-soluble solvent, a chelating agent, a pH adjuster, a preservative, a coloring agent, a fragrance, a hydrotrope, a re-decontamination inhibitor and dispersant such as a polymer, an enzyme, an antibacterial agent, an antioxidant, an antifoaming agent, etc. (except for those corresponding to components (a) and (b)).

[0044] The liquid composition of the present invention or the product for the liquid composition described later may contain cationic surfactants other than component (a) and anionic surfactants other than component (b) to an extent that does not impair the effects of the present invention. For example, as a cationic surfactant other than component (a), in the compound represented by the general formula (a1) above, R 1aOne or more compounds selected from compounds whose group is a linear aliphatic hydrocarbon group having 16 to 20 carbon atoms and alkylbenzyldimethylammonium chloride having a linear alkyl group having 8 to 18 carbon atoms [component (a)] may inhibit the effects of the present invention, and care should be taken with the amount used. The content of component (a) in the liquid composition of the present invention or the product for the liquid composition described later is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.8 parts by mass or less, even more preferably 0.5 parts by mass or less, even more preferably 0.2 parts by mass or less, even more preferably 0.1 parts by mass or less, and even 0 parts by mass or more, and may be 0 parts by mass (counterions are calculated on a chloride basis).

[0045] The liquid composition of the present invention or the product for the liquid composition described later may contain a quaternary ammonium compound having one aliphatic hydrocarbon group with 8 to 18 carbon atoms other than component (a) above [component (a')], to the extent that it does not impair the effects of the present invention. For example, one or more compounds selected from the compounds represented by the following general formula (a'1) can be used as component (a'). (a') Component: Compound represented by the following general formula (a'1)

[0046] [ka]

[0047] [In general formula (a'1), R 5a This refers to aliphatic hydrocarbon groups having 8 to 18 carbon atoms (excluding aliphatic hydrocarbon groups having 10 to 14 carbon atoms), R 6a , R 7a and R 8a Each of these is independently a linear or branched alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and X - It is an anion.

[0048] In general formula (a'1), R 5aThis refers to an aliphatic hydrocarbon group having 8, 9, 15, 16, or 18 carbon atoms, more specifically, a linear or branched alkyl group having 8, 9, 15, 16, or 18 carbon atoms. R 6a , R 7a and R 8a Each of these is independently a linear or branched alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include groups selected from methyl, ethyl, and propyl groups. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include 2-hydroxyalkyl groups, 2-hydroxypropyl groups, or 3-hydroxypropyl groups. X - This is an anion. Preferred anions are halogen ions or alkyl sulfate ions having 1 to 3 carbon atoms. Examples of halogen ions include chlorine ions, bromo ions, or iodide ions. Examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, or propyl sulfate ions. The component (a') contained in the liquid composition of the present invention or the product for the liquid composition described later may be used alone or in combination of two or more types.

[0049] From the viewpoint of not inhibiting the bactericidal effect on bacteria present in the biofilm of the present invention, the mass ratio of the content of component (a') to the total amount of the content of component (a) and component (a') in the liquid composition or product for the liquid composition of the present invention, (a') / [(a)+(a')], is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.3 or less, even more preferably 0.2 or less, even more preferably 0.1 or less, even more preferably 0.05 or less, and even more preferably 0.

[0050] The liquid composition of the present invention contains water. The water can be deionized water, tap water, purified water, water containing hardness components, etc. In the case of water containing hardness components, the hardness of the water is preferably 0°dH or higher, more preferably 1°dH or higher, even more preferably 3°dH or higher, and preferably 30°dH or lower, more preferably 25°dH or lower, even more preferably 20°dH or lower, even more preferably 10°dH or lower, and even more preferably 5°dH or lower, in terms of German hardness, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm. Herein, German hardness (°dH) as used herein refers to the concentration of calcium and magnesium in water, expressed as a CaCO3 equivalent concentration of 1 mg / L (ppm) = approximately 0.056°dH (1°dH = 17.8 ppm). The calcium and magnesium concentrations required for this German hardness can be determined by chelation titration using disodium ethylenediaminetetraacetate. The specific method for measuring the German hardness of water used in this specification is shown below. <Method for measuring water hardness in Germany> 〔reagent〕 • 0.01 mol / l EDTA-2Na solution: A 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 Kagaku Kenkyusho Co., Ltd.) • Ammonia buffer solution for hardness measurement (a solution made by dissolving 67.5g of ammonium chloride in 570ml of 28w / v% ammonia water and diluting the total volume to 1000ml with deionized water). [Measuring hardness] (1) Take 20 ml of water to be used as a sample into a conical beaker using a volumetric pipette. (2) Add 2 ml of ammonia buffer solution for hardness measurement. (3) Add 0.5 ml of Universal BT indicator. Confirm that the solution is reddish-purple after adding the indicator. (4) While thoroughly shaking the conical beaker, slowly add the 0.01 mol / l EDTA·2Na solution from the burette. The end point of the titration is the moment when the water sample turns blue. (5) The total hardness is determined by the following calculation formula. Hardness (°dH) = T × 0.01 × F × 56.0774 × 100 / A T: Titration volume of 0.01 mol / l EDTA·2Na solution (mL) A: Sample volume (20 mL, volume of the water sample) F: Factor of 0.01 mol / l EDTA·2Na solution

[0051] In the liquid composition of the present invention, water can be used in an amount such that the composition of the whole composition becomes 100% by mass as the remainder of the composition. The liquid composition of the present invention contains water in the composition, preferably 1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less.

[0052] From the viewpoint of enhancing the bactericidal effect of the bacteria present in the biofilm, the pH of the liquid composition of the present invention at 25°C is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, even more preferably 6 or more, even more preferably 7 or more, and preferably 14 or less, more preferably 12 or less, still more preferably 10 or less, even more preferably 9 or less. The pH is a value measured at 25°C using a glass electrode. Specifically, it is measured by the following method. <Measurement method of pH> The pH electrode (SI Analytics BlueLine 17 pH) of the Consort C3010 multi-parameter analyzer is pre-calibrated with Reagecon pH 4.000 High Resolution Colour Coded Buffer Solution and Reagecon pH 7.000 High Resolution Colour Coded Buffer Solution, and then thoroughly rinsed with deionized water. The pH electrode, calibrated and washed as described above, is placed in a liquid composition adjusted to a temperature of 25°C, and measurements are taken using the AUTO HOLD mode of the pH meter until the measured value stabilizes.

[0053] The liquid composition of the present invention may be a liquid composition comprising component (a) and component (b), and may further contain water or other components. The matters described in the liquid composition of the present invention can be appropriately applied to this liquid composition, and the content and mass ratio of each component can be replaced with the amount of each component to be blended.

[0054] The liquid composition of the present invention can be suitably used for biofilms attached to textile products or rigid articles, and more preferably for biofilms present inside textile products or rigid articles. "Present inside textile products or rigid articles" means that the textile product or rigid article has a three-dimensional structure and voids throughout the structure, and that the biofilm exists in the voids within that structure. The structure may be a structure formed from a continuous rigid material, or it may be a composite structure formed by the overlapping of multiple single-unit structures. "The interior of a composite structure formed by the overlapping of multiple single-unit structures" may refer to a portion of one of the internal structures forming the composite structure.

[0055] The fibers used in textile products 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 Polycloral), polyalkylene parahydroxybenzoate-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, cannabis, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), coconut fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuña, angora, etc.), silk fibers (domestic silk, wild silk), feathers, and cellulose fibers (rayon, polynosic, cupro, acetate, etc.).

[0056] In the present invention, "textile products" refers to fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics using the aforementioned hydrophobic and hydrophilic fibers, and products obtained using them, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, bedding, textile products for bedding (sheets, pillowcases, etc.), knits, socks, underwear, tights, and masks. Preferred textile products are woven fabrics such as woven fabrics and knitted fabrics, and woven textile products. Furthermore, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, preferred textile products are textile products containing hydrophobic fibers.

[0057] Examples of hard materials include washing machines, washing tubs, washing machine inlets, washing machine lint filters, washing machine drain pipes, tableware, hard materials around the kitchen, and / or hard materials in the living environment such as bathrooms, toilets, and floors, drains, water pipes, cooling water systems such as food or beverage manufacturing plants and industrial cooling towers, and medical devices such as endoscopes, catheters, and hemodialysis equipment. Examples of materials for rigid articles include plastics such as polyethylene and polypropylene (including silicone resin), metals, ceramics, wood, and combinations thereof.

[0058] Because the liquid composition of the present invention exhibits excellent bactericidal properties against bacteria present in biofilms, it can be used for sterilizing textile products or hard articles used not only in general households but also in medical and nursing care settings. The bacteria targeted by the liquid composition of the present invention include, for example, bacteria of the genera Moraxella, Micrococcus, Methylobacterium, Acinetobacter, Pseudomonas, Bacillus, Sphingomonas, Ralstonia, Cupriavidus, and Cyclobacter (Ps This includes one or more species selected from the following genera: bacteria of the genus *Chorobacter*, *Serratia*, *Escherichia*, *Staphylococcus*, *Burkholderia*, *Listeria*, *Shigella*, *Vibrio*, *Klebsiella*, *Salmonella*, and *Enterobacter*.

[0059] [Products for liquid compositions] The liquid composition of the present invention can be prepared by diluting a product for liquid compositions (stock solution) containing component (a) and component (b) (hereinafter referred to as the product for liquid compositions of the present invention) with water. The product for the liquid composition of the present invention may further contain water. Furthermore, the product for the liquid composition of the present invention may contain, in addition to components (a) and (b), other optional components described in the description of the liquid composition of the present invention. The specific embodiments of component (a) and component (b) are the same as those described in the liquid composition of the present invention, and the other optional components are also the same as those described in the liquid composition of the present invention. The liquid composition product of the present invention can be suitably used in the preparation of a liquid composition for killing bacteria present in a biofilm. That is, the liquid composition product of the present invention may be a product for a liquid composition for killing bacteria present in a biofilm. Products for the liquid composition of the present invention can be appropriately adapted to the embodiments described for the liquid composition of the present invention.

[0060] The product for the liquid composition of the present invention contains component (a) in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, even more preferably 2% by mass or more, even more preferably 3.5% by mass or more, and from the same viewpoint, preferably 10% by mass or less, more preferably 9% by mass or less, and even more preferably 8% by mass or less. In this invention, the mass of component (a) shall be the value converted to the chlorine salt.

[0061] The product for the liquid composition of the present invention contains, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, component (b) in the product for the liquid composition, preferably in an amount of 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 6% by mass or more, even more preferably 7% by mass or more, even more preferably 8% by mass or more, even more preferably 9% by mass or more, even more preferably 10% by mass or more, even more preferably 12% by mass or more, even more preferably 14% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 18% by mass or less. In this invention, the mass of component (b) shall be the value converted to the sodium salt.

[0062] In the product for the liquid composition of the present invention, the mass ratio of the content of component (b) to the content of component (a) (b) / (a), the mass ratio of the content of component (b1) to the content of component (a) (b1) / (a), and the mass ratio of the content of component (b2) or component (b3) to the content of component (a) [(b2) or (b3)] / (a) can be appropriately applied within the ranges described for the liquid composition of the present invention.

[0063] When preparing the liquid composition of the present invention by diluting the product for the liquid composition of the present invention with water, the dilution ratio is, for example, 100,000 times or less, further 50,000 times or less, further 10,000 times or less, further 3,000 times or less, and 10 times or more, further 50 times or more, and further 100 times or more.

[0064] [Methods for killing bacteria present in biofilms] The present invention relates to a method for sterilizing bacteria present in a biofilm by bringing the liquid composition of the present invention into contact with the biofilm. A preferred method for sterilizing bacteria present in a biofilm according to the present invention is to bring the liquid composition of the present invention into contact with the biofilm and then leave it for a predetermined time.

[0065] The aforementioned "leaving for a predetermined time" refers to bringing the liquid composition of the present invention into contact with the biofilm and maintaining that contact for a predetermined period of time. From the viewpoint of maximizing the bactericidal effect on bacteria present in the biofilm, the predetermined time is preferably 10 seconds or more, more preferably 30 seconds or more, even more preferably 1 minute or more, even more preferably 3 minutes or more, even more preferably 5 minutes or more, and preferably 1 hour or less, more preferably 50 minutes or less, even more preferably 40 minutes or less, even more preferably 30 minutes or less, and even more preferably 20 minutes or less.

[0066] The present invention provides a method for sterilizing bacteria present in a biofilm, and it is preferable to bring the liquid composition of the present invention into contact with a textile product in which the biofilm is formed inside a textile product having voids between the constituent materials of the textile product, or with a hard article in which the biofilm is formed inside a hard article having voids between the constituent materials of the hard article. The sterilization method of the present invention has an excellent sterilizing effect not only on the surface of the target article but also on bacteria present in biofilms formed inside the target article having voids and a complex structure.

[0067] Methods for bringing the liquid composition of the present invention into contact with a biofilm include spraying or coating the liquid composition of the present invention onto a target article in which a biofilm is present or is suspected to be present, or immersing the target article, such as a textile product, in the liquid composition of the present invention. Alternatively, the liquid composition of the present invention may be impregnated into a nonwoven fabric and then brought into contact with the target article.

[0068] When spraying or applying the liquid composition of the present invention to a target article, the liquid composition 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 liquid composition of the present invention may be poured from the container onto the target article and applied with a brush or the like. Examples of containers equipped with a sprayer include trigger-type spray containers, pump-type spray containers and other manual spraying devices that do not use propellants, and aerosols that use propellants. The container equipped with the sprayer is preferably a trigger-type spray capable of spraying the contents in droplet or foam form, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in droplet form or a mechanism for forming foam (foam-forming mechanism).

[0069] When immersing an article, such as a textile product, in the liquid composition of the present invention, the article and the liquid composition may be left undisturbed or stirred. In the case of stirring, any means are acceptable as long as one or both of the liquid composition and the biofilm or the article on which the biofilm is formed are in motion. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, it is preferable to use a rotary agitator for stirring. Examples of rotary agitators include washing machines such as pulsator-type washing machines, agitator-type washing machines, or drum-type washing machines, or shakers in which the article on which the biofilm is formed moves in a circular motion. A preferred method for sterilizing biofilms according to the present invention involves immersing a textile product containing a biofilm in the liquid composition of the present invention and stirring it using a rotary agitator.

[0070] In the biofilm sterilization method of the present invention, when the target article is a hard article, the liquid composition of the present invention may be left to stand or flowed after contact, and flowing is preferred from the viewpoint of further enhancing biofilm sterilization. Preferred embodiments of the method for flowing the liquid composition of the present invention onto a hard article include, for example, a method of continuously or intermittently spraying the liquid composition of the present invention so that it passes over the surface of a hard article that is left to stand, or through the inside of a hard article having voids, and a method of flowing the liquid composition of the present invention in which a hard article is immersed. Embodiments of flowing the liquid composition of the present invention in which a hard article is immersed include, for example, a method of flowing the liquid composition of the present invention in which a hard article is immersed by applying an external force such as stirring, or a method of rotating or shaking the hard article immersed in the liquid composition of the present invention.

[0071] After immersing a textile product or hard article in the liquid composition of the present invention, the textile product or hard article may be rinsed with water. After rinsing with water, the textile product or hard article may be dried. Rinsing may be carried out using water in accordance with known methods, such as washing textile products. The water used for rinsing in the present invention is not particularly limited, but examples include water containing hardness components, tap water, well water, ion-exchanged water, sterilized water, and distilled water. From the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, the hardness of the water containing hardness components is preferably 0°dH or higher, more preferably 1°dH or higher, even more preferably 3°dH or higher, and preferably 30°dH or lower, more preferably 25°dH or lower, even more preferably 20°dH or lower, even more preferably 10°dH or lower, and even more preferably 5°dH or lower, in German hardness. Furthermore, the hardness of the liquid composition of the present invention may be within the aforementioned range.

[0072] When spraying or applying the liquid composition of the present invention to a target article, the amount of the liquid composition used is not particularly limited, but for example, per unit area of ​​1 cm² of the target article 2 In terms of the amount of component (a), from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm, it is preferably 0.0001 g or more, more preferably 0.001 g or more, and preferably 100 g or less, and more preferably 10 g or less.

[0073] When spraying or applying the liquid composition of the present invention to a target article, the time for which the liquid composition of the present invention is in contact with the target article containing a biofilm (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, and preferably 1 day or less, more preferably 15 hours or less, and even more preferably 5 hours or less, from the viewpoint of further enhancing the bactericidal effect on bacteria present in the biofilm. After contact, you can let it dry as is, wipe it with a clean cloth, or rinse it with water. When rinsing, you can apply external force (physical force) with a sponge or simply rinse it with water.

[0074] When the liquid composition of the present invention is impregnated into a nonwoven fabric and brought into contact with a target article, the nonwoven fabric can be processed into a sheet, and it is preferable that the fibers constituting the nonwoven fabric consist of one or more fibers selected from the hydrophilic fibers and hydrophobic fibers described above. The method for bringing the liquid composition of the present invention into contact with the target article involves pressing a nonwoven fabric impregnated with the liquid composition of the present invention against the target article, applying external force within a range that does not damage the article, and transferring the liquid composition of the present invention impregnated in the nonwoven fabric, or a treatment solution obtained by diluting it with water, to the target article and bringing it into contact with it. This can be done by rubbing, kneading, or tapping.

[0075] [Organic matter stains] The present invention provides an excellent method for sterilizing bacteria present in a biofilm, even when the biofilm and organic contaminants coexist. Therefore, it is preferable to bring the liquid composition of the present invention into contact with the biofilm in the presence of both the biofilm and organic contaminants. Organic matter in organic contaminants includes one or more selected from fatty acids, oils and fats, proteins, and carbohydrates such as starch. These contaminants are found in environments where biofilms are formed, such as in water or attached to the aforementioned objects to which biofilms are attached.

[0076] [Liquid composition for killing bacteria present in biofilms] The liquid composition of the present invention is preferably a liquid composition for killing bacteria present in a biofilm. In other words, the present invention provides a liquid composition containing component (a), component (b), and water, which is a liquid composition for killing bacteria present in a biofilm. The liquid composition for killing bacteria present in a biofilm according to the present invention is the same as the liquid composition of the present invention, and the embodiments described for the liquid composition of the present invention can be applied as appropriate. Furthermore, the liquid composition of the present invention is not limited to the sterilization of bacteria present in biofilms. For example, this does not preclude the liquid composition of the present invention from having a cleaning effect on textile products and hard articles. [Examples]

[0077] [Ingredients] The following components were used in the examples and comparative examples. <(a) Components> • (a-1)C10TMAC: Decyltrimethylammonium chloride, in general formula (a1), R 1a is an alkyl group having 10 carbon atoms, and R 2a , R 3a and R 4a is a methyl group, X - This is a compound that is a chloride ion. • (a-2)C12TMAC: Lauryltrimethylammonium chloride, in general formula (a1), R 1a is an alkyl group with 12 carbon atoms, and R 2a , R 3a and R 4a is a methyl group, X - This is a compound that is a chloride ion. • (a-3)C14TMAC: Myristyltrimethylammonium chloride, in general formula (a1), R 1a is an alkyl group with 14 carbon atoms, and R 2a , R 3a and R 4a is a methyl group, X - This is a compound that is a chloride ion.

[0078] <(a') component (comparative component of (a) component)> • (a'-1)C8TMAC: Octyltrimethylammonium chloride, in general formula (a1), R 1a is an alkyl group with 8 carbon atoms, and R 2a , R 3a and R 4a is a methyl group, X - This is a compound that is a chloride ion.

[0079] <(b) Component> • (b-1)AS: Alkyl sulfate salt, in general formula (b1), R 1bA compound in which C12 is an alkyl group, AO is an ethylene oxy group, p is 0, and M is a sodium ion. ·(b-2)ES: In general formula (b1), R 1b A mixture of compounds in which C1 is an alkyl group with 10 to 16 carbon atoms (10 / 12 / 14 / 16 carbon atoms = 1 / 72 / 26 / 1 (mass ratio)), AO is an ethylene oxy group, p is 2, and M is a sodium ion. ·(b-3)APS: In general formula (b11), R 1b Compounds in which C1 is an alkyl group having 8 to 12 carbon atoms, p1 is 0, p2 is 0.6, and M is a sodium ion. ·(b-4)C12APES: In general formula (b11), R 1b A compound in which is a C12 alkyl group, p1 is 2, p2 is 2, the PO group and EO group are sulfate ester salts of a compound obtained by adding a PO group to lauryl alcohol followed by the addition of an EO group, and M is a monoethanolammonium ion. • (b-5) C16IOS: C16 internal olefin sulfonate potassium salt obtained by the following manufacturing method. • (b-6)LAS: Sodium alkylbenzene sulfonate having a linear alkyl group with 10 to 14 carbon atoms.

[0080] <Example of production of C16IOS (potassium internal olefin sulfonate) with 16 carbon atoms> C16IOS was obtained using an internal olefin with 16 carbon atoms, with reference to the method described in the production example of Japanese Patent Application Publication No. 2014-76988. The mass ratio of the olefin (potassium olefin sulfonate) to the hydroxyl (potassium hydroxyalkanesulfonate) in the potassium internal olefin sulfonate salt of the obtained C16IOS was 17 / 83. The mass percentage of the positional distribution of the sulfonic acid groups of the hydroxyl group in C16IOS was 1st / 2nd / 3rd / 4th / 5th / 6th-8th = 2.3 mass% / 23.6 mass% / 18.9 mass% / 17.5 mass% / 13.7 mass% / 24 mass% (total 100 mass%). Also, (IO-1S) / (IO-2S) ≈ 1.7 (mass ratio). (IO-1S) / (IO-2S) is the mass ratio of the content of internal olefin sulfonates [(IO-1S)] where the sulfonic acid group is located between the 2nd and 4th positions, and the content of internal olefin sulfonates [(IO-2S)] where the sulfonic acid group is located at the 5th position or higher.

[0081] <Optional ingredients> • Benzalkonium chloride: Alkyldimethylbenzylammonium chloride having an alkyl group with 12 to 16 carbon atoms.

[0082] [Preparing sebum stains] A 3cm long Teflon stirrer piece was placed in a 200mL glass beaker. Then, 10g of deionized water, 16.8g of oleic acid (manufactured by Eiken Chemical Co., Ltd.), 9.3g of triolein (manufactured by Eiken Chemical Co., Ltd.), 0.9g of cholesterol (manufactured by Eiken Chemical Co., Ltd.), 1.5g of squalene (manufactured by Eiken Chemical Co., Ltd.), and 4.2g of gelatin (manufactured by Eiken Chemical Co., Ltd.) were added. The mixture was stirred at 100 r / min for 10 minutes, and then deionized water was added until the total volume reached 100g. After stirring at 100 r / min for 15 minutes, a masterbatch of sebum stains (3000 times concentrated) was obtained.

[0083] [Preparation of protein stains] A 3cm long Teflon stirrer piece was placed in a 200mL glass beaker, then 10g of deionized water and 37.5mL of horse serum (Horse Serum, heat inactivated, New Zealand origin, manufactured by Thermo Fisher Scientific Co., Ltd.) were added. The mixture was stirred at 100 r / min for 10 minutes, and then more deionized water was added until the total volume reached 100g. The mixture was then stirred at 100 r / min for 15 minutes to obtain a protein-contaminated masterbatch (300-fold concentrate).

[0084] [Preparation of model tap water] A 5cm long Teflon stirrer piece was placed in a 1L glass beaker. Then, 500mL of deionized water, 0.067g of sodium bicarbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.5mL of 0.1mol / L HCl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.0893g of calcium chloride dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.02902g of magnesium chloride hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. The mixture was stirred at 100 r / min for 10 minutes. Deionized water was then added until the total volume reached 1000mL, and the mixture was stirred at 100 r / min for 15 minutes to obtain the model tap water. The hardness of the model tap water was 4°DH, and its alkalinity was 34.47.

[0085] [Preparation of products for liquid compositions] The preparation method for the liquid composition products (stock solutions) shown in Tables 1-6 is as follows: A 3cm long Teflon stirrer piece was placed in a 200mL glass beaker. Then, 10g of deionized water, component (a) or (a'), component (b), and any optional components as shown in Tables 1-6 were added. The mixture was stirred at 100 r / min for 10 minutes. Additional deionized water equivalent to 95% by mass was added to reach a total volume of 100g. The mixture was stirred at 100 r / min for 5 minutes. The pH (25°C) was then adjusted to 8 with monoethanolamine or hydrochloric acid. Deionized water was added to reach a total volume of 100g. The mixture was stirred at 100 r / min for 15 minutes to obtain the liquid composition products shown in Tables 1-6. After preparation, the pH was checked again, and the pH of the liquid composition products in Tables 1-6 remained unchanged from the pH at the time of adjustment. Note that in the products for each liquid composition listed in Tables 1-6, the amounts of each component are all for the effective portion.

[0086] [Method for evaluating the bactericidal activity of bacteria present within biofilms] (1) Preparation of biofilm-forming fabric Glycerol stock solutions of Rhodotorula mucilaginosa (clothing isolate) and Methylobacterium variable (clothing isolate) were streaked onto potato dextrose agar (Difco Laboratories) and incubated statically at 30°C for 2 days. Glycerol stock solution of Moraxella osloensis (clothing isolate) was streaked onto SCD agar (Shioya MS Co., Ltd., SCD agar medium "Daigo", for general bacterial testing) and incubated statically at 37°C for 1 day. After incubation, the bacterial cells were scraped off using a disposable loop (AS ONE Corporation, Disposable Loop Type 10) and suspended in R2A medium (Shioya MS Co., Ltd., R2A medium "Daigo"). The turbidity (OD600) of each bacterial suspension was measured using a spectrophotometer (Apere Co., Ltd., model number: PD-303S). The bacterial suspensions were diluted so that R. mucilaginosa had an OD600 of 0.2, and M. variable and M. osloensis had an OD600 of 0.01. Flat-woven cotton cloth (Cotton 2003, manufactured by Tanigashira Shoten), cut to 3 x 3 cm, was sterilized under pressure in an autoclave (High-pressure steam sterilizer, Lab Autoclave, model number: MLS-3781, manufactured by PHC Corporation). The sterilized flat-woven cotton cloth was placed in No. 6 screw-cap bottles (Screw-cap bottles No. 6, manufactured by Maruemu Co., Ltd.), and 1 mL of bacterial suspension of each of the three bacterial species and 7 mL of R2A medium were added. The bottles were sealed and incubated with shaking for 2 days at 30°C and 200 rpm in a small constant-temperature shaking incubator, Bio Shaker (manufactured by TAITEC Corporation, model number: BR-23FP). After incubation, the flat-woven cotton cloth was transferred to a new No. 6 screw-cap bottle, and 10 mL of autoclaved deionized water was added. The cloth was washed by shaking for 3 minutes at 25°C and 150 rpm in a small constant-temperature shaking incubator, Bio Shaker. The washed, flat-woven cotton fabric was air-dried in a safety cabinet for one hour to form a biofilm. Biofilm formation on the fabric was confirmed by unraveling the fabric into threads with tweezers, staining the threads, and observing them with a confocal laser scanning microscope (LSM880 ZEN, Carl Zeiss). The threads observed were stained for 30 minutes with a dye for live cells (C375-Cellstain(TM)-CFSE, Dojin Chemical Laboratories Co., Ltd.), a dye for dead cells (P378-Cellstain(TM)-PI solution, Dojin Chemical Laboratories Co., Ltd.), a dye for cellulose (Calcofluor White, Sigma-Aldrich), a dye for sugars (Lectin PNA From Arachis hypogaea (peanut), Alexa Fluor(TM) 647 Conjugate, Thermo Fisher Scientific K.K.), and a dye for sugars (Concanavalin Alexa Fluor(TM) 647 Conjugate, Thermo Fisher Scientific K.K.).

[0087] (2) Test method for the bactericidal activity of bacteria present in biofilms (Sterilization method 1: No organic matter contamination) The prepared biofilm-forming cloth was cut to 1.5 × 1.5 cm, and the sterilized flat-woven cotton cloth was cut to 1.5 × 3 cm. One piece of cut biofilm-forming cloth was sandwiched between two pieces of sterilized flat-woven cloth (3 mm thick), and while maintaining this stacked state of three pieces, it was placed at the bottom of a 5 mL tube (Eppendorf Tube 5.0 mL, model number: 0030 119.401, manufactured by Eppendorf Co., Ltd.). 0.1 g of the product for each liquid composition listed in Tables 1-3 and Table 5, and 299.9 g of model tap water were placed in a 300 mL glass beaker containing a 6 cm long Teflon stirrer piece, and stirred with a magnetic stirrer at 50 r / m for 5 minutes to prepare each liquid composition listed in Tables 1-3 and Table 5. 3 mL of the obtained liquid composition was added to a 5 mL tube containing the evaluation cloth described above, and the cloth was shaken and washed in a small constant-temperature shaking incubator (bioshaker) at 25°C and 150 rpm for 10 minutes; this was considered the contact step. After contact, the cloth was transferred to a 5 mL tube containing 3 mL of model tap water, and shaken under the same conditions for 3 minutes; this was considered the rinsing step. After repeating this contact step and rinsing step alternately four times, only the biofilm-forming cloth was removed and air-dried in a safety cabinet for 30 minutes. The three cloths remained stacked throughout the period from the contact step to the end of the rinsing step.

[0088] (Sterilization method 2: Organic matter contamination present) The prepared biofilm-forming cloth was cut to 1.5 × 1.5 cm, and the sterilized flat-woven cotton cloth was cut to 1.5 × 3 cm. One piece of cut biofilm-forming cloth was sandwiched between two pieces of sterilized flat-woven cloth (3 mm thick), and while maintaining this stacked state of three pieces, it was placed at the bottom of a 5 mL tube (Eppendorf Tube 5.0 mL, model number: 0030 119.401, manufactured by Eppendorf Co., Ltd.). 0.1 g of the product for each liquid composition listed in Tables 4 and 6, 0.1 g of the sebum stain masterbatch, 1 g of the protein stain masterbatch, and 298.9 g of model tap water were placed in a 300 mL glass beaker containing a 6 cm long Teflon stirrer piece, and stirred with a magnetic stirrer at 50 r / m for 5 minutes to prepare each liquid composition listed in Tables 4 and 6 while incorporating organic stains. 3 mL of the obtained liquid composition containing organic matter stains was added to a 5 mL tube containing the evaluation cloth described above, and the cloth was shaken and washed in a small constant-temperature shaking incubator, a bioshaker, at 25°C and 150 rpm for 10 minutes. This was designated as the contact step. After contact, the cloth was transferred to a 5 mL tube containing 3 mL of model tap water, and shaken for 3 minutes under the same conditions. This was designated as the rinsing step. After repeating this contact step and rinsing step alternately four times, only the biofilm-forming cloth was removed and air-dried in a safety cabinet for 30 minutes. The three cloths remained stacked throughout the period from the contact step to the end of the rinsing step. Sterilization method 2 is an evaluation method that assumes, for example, normal washing using a washing machine in a typical household. It modelly represents a method of washing and sterilizing textile products to which biofilms have been attached using a liquid composition in which organic matter stains attached to the washing machine tub are detached and mixed when the product for the liquid composition and water are mixed in the washing machine tub to prepare the liquid composition (i.e., washing and sterilization in a state where organic matter stains and biofilms coexist).

[0089] (Residual viable bacteria count measurement) The air-dried biofilm-forming cloth and the biofilm-forming cloth before contact with the test treatment solution were each placed in a 1.5 mL tube (Eppendorf Tube 1.5 mL, Model No.: 0030 125.150, manufactured by Eppendorf Co., Ltd.) containing 1 mL of LP diluent (LP diluent "Daigo," manufactured by Shioya MS Co., Ltd.). With the lids closed, the tubes were placed in an ultrasonic cleaner (Tabletop ultrasonic cleaner, Model No.: 2510JDTH, manufactured by Emerson Japan Co., Ltd.) for 15 minutes to disperse any remaining bacteria on the cloth into the LP diluent. After stirring the solution for 3 seconds with a vortex mixer (Vortex mixer, Model No.: VTX-3000L, manufactured by AS ONE Corporation), this bacterial solution was diluted with LP diluent for 10 minutes. The solution was serially diluted by 2:1 and dispensed into 100 μL portions in petri dishes (AS ONE Corporation's Azunol petri dish, 90 mm in diameter, 15 mm in height). Approximately 15 mL of SCD agar medium was added to each, the lid was closed, and after light mixing, the mixture was left to stand at room temperature until the agar solidified. After static incubation at 37°C for 1 day, the number of remaining viable M. variable cells was counted using a colony counter pen (AS ONE Corporation's Colony Counter Pen Type, Model No.: 2-5764-01).

[0090] (Method for calculating bactericidal activity value) The bactericidal activity value was determined using the following formula. The results are shown in Tables 1-6. A higher bactericidal activity value indicates superior bactericidal effect against bacteria present in the biofilm. A bactericidal activity value of 1.0 or higher is preferable. Biofilm bactericidal activity value = LogA - LogB A: Average value of the number of remaining viable bacteria before contact with the test treatment solution. B: Average number of remaining viable bacteria after contact with the test treatment solution

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3]

[0094] Table 4

[0095] Table 5

[0096] Table 6

Claims

1. A method for sterilizing bacteria present in a biofilm, comprising contacting the biofilm with a liquid composition containing the following components (a) and (b), and water. (a) Component: Compound represented by the following general formula (a1) 【Chemistry 1】 [In general formula (a1), R １ａ R is an aliphatic hydrocarbon group having 10 to 14 carbon atoms. ２ａ , R ３ａ and R ４ａ Each of these is independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － It is an anion. (b) Component: A compound having an aliphatic hydrocarbon group with 8 to 18 carbon atoms, and a group selected from a sulfate ester group, a sulfonic acid group, and salts thereof.

2. (b) A method for killing bacteria present in a biofilm according to claim 1, wherein component (b) is a compound represented by the following general formula (b11). ( １ｂ _____________________ ｐ１ / (!) ｐ２ ___ ３ * (()) [In general formula (b11), R １ｂ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, PO is a propylene oxy group, EO is an ethylene oxy group, and " / " is a symbol indicating that the bonding order of PO and EO does not matter. p1 is the average number of moles of EO added, between 0 and 10, p2 is the average number of moles of PO added, between 0 and 10, the sum of p1 and p2 is between 0 and 10, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom), ammonium ion, or organic ammonium ion.

3. (b) A method for killing bacteria present in a biofilm according to claim 1, wherein the component is one or more compounds selected from olefin sulfonic acid or a salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and alkane sulfonic acid or a salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms.

4. A method for sterilizing bacteria present in a biofilm according to claim 1 or 2, wherein the mass ratio of the content of component (b) to the content of component (a) in the liquid composition, i.e., component (b) / component (a), is 0.1 or more and 40 or less.

5. A method for sterilizing bacteria present in a biofilm according to claim 1 or 2, wherein the liquid composition contains 2 mg / kg or more and 50,000 mg / kg or less of component (a), and contains 5 mg / kg or more and 300,000 mg / kg or less of component (b).

6. A method for sterilizing bacteria present in a biofilm according to claim 1 or 2, wherein the liquid composition is brought into contact with the biofilm in the presence of the biofilm and organic matter contaminants.

7. The method for sterilizing bacteria present in a biofilm according to claim 6, wherein the organic matter in the organic matter stain is one or more selected from fatty acids, oils and fats, proteins, and carbohydrates.

8. A liquid composition containing the following components (a) and (b), and water, for sterilizing bacteria present in a biofilm. (a) Component: Compound represented by the following general formula (a1) 【Chemistry 2】 [In general formula (a1), R １ａ R is an aliphatic hydrocarbon group having 10 to 14 carbon atoms. ２ａ , R ３ａ and R ４ａ Each of these is independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － It is an anion. (b) Component: A compound having an aliphatic hydrocarbon group with 8 to 18 carbon atoms, and a group selected from a sulfate ester group, a sulfonic acid group, and salts thereof.

9. A liquid composition for killing bacteria present in a biofilm according to claim 8, wherein component (b) is one or more compounds selected from a compound represented by the following general formula (b11) (hereinafter referred to as component (b1)), an olefin sulfonic acid or a salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms (hereinafter referred to as component (b2)), and an alkane sulfonic acid or a salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms (hereinafter referred to as component (b3)). ( １ｂ _____________________ ｐ１ / (!) ｐ２ ___ ３ * (()) [In general formula (b1), R １ｂ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, PO is a propylene oxy group, EO is an ethylene oxy group, and " / " is a symbol indicating that the bonding order of PO and EO does not matter. p1 is the average number of moles of EO added, between 0 and 10, p2 is the average number of moles of PO added, between 0 and 10, the sum of p1 and p2 is between 0 and 10, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom), ammonium ion, or organic ammonium ion.

10. A liquid composition for killing bacteria present in a biofilm, according to claim 8 or 9, wherein the mass ratio of the content of component (b) to the content of component (a) in the liquid composition, i.e., component (b) / component (a), is 0.1 or more and 40 or less.

11. A bactericidal composition for bacteria present in a biofilm according to claim 8 or 9, wherein the liquid composition contains 2 mg / kg or more and 50,000 mg / kg or less of component (a), and contains 5 mg / kg or more and 300,000 mg / kg or less of component (b).

12. A product for a liquid composition for killing bacteria present in a biofilm, comprising the following components (a) and (b), and water. (a) Component: Compound represented by the following general formula (a1) 【Transformation 3】 [In general formula (a1), R １ａ R is an aliphatic hydrocarbon group having 10 to 14 carbon atoms. ２ａ , R ３ａ and R ４ａ Each of these is independently a linear or branched alkyl group having 1 to 3 carbon atoms, and X － It is an anion. (b) Component: One or more compounds selected from the following: compounds represented by the general formula (b11) below (hereinafter referred to as component (b1)), olefin sulfonic acid or salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms (hereinafter referred to as component (b2)), and alkane sulfonic acid or salt thereof having an aliphatic hydrocarbon group having 8 to 18 carbon atoms (hereinafter referred to as component (b3)). ( １ｂ _____________________ ｐ１ / (!) ｐ２ ___ ３ * (()) [In general formula (b1), R １ｂ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, PO is a propylene oxy group, EO is an ethylene oxy group, and " / " is a symbol indicating that the bonding order of PO and EO does not matter. p1 is the average number of moles of EO added, between 0 and 10, p2 is the average number of moles of PO added, between 0 and 10, the sum of p1 and p2 is between 0 and 10, and M is a hydrogen ion, alkali metal ion, alkaline earth metal ion (1 / 2 atom), ammonium ion, or organic ammonium ion.

13. The product for the liquid composition described above, wherein the mass ratio of the content of component (b) to the content of component (a), i.e., component (b) / component (a), is 0.1 or more and 40 or less, is the product for the liquid composition described above.

14. A product for a liquid composition for sterilizing bacteria present in a biofilm, according to claim 12 or 13, wherein the content of component (a) in the product is 0.5% by mass or more and 10% by mass or less, and the content of component (b) is 1% by mass or more and 30% by mass or less.

Images