Biofilm remover composition
A biofilm remover composition using a cationic and anionic surfactant combination disrupts the polysaccharide barrier in biofilms, effectively removing them from textile products.
Patent Information
- Application Number
- JP2024049139
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-06-30
- Filing Date
- 2024-03-26
- Publication Date
- 2025-01-20
AI Technical Summary
Biofilms attached to target articles, especially textile products, are difficult to remove due to the protective barrier formed by extracellular polysaccharides, making conventional cleaning methods ineffective.
A biofilm remover composition comprising a specific cationic surfactant and an anionic surfactant, which disrupts the dense structure of extracellular polysaccharides by forming a loose ionic complex, facilitating biofilm removal.
The composition effectively removes biofilms from textile products by disrupting the protective barrier of extracellular polysaccharides, enhancing cleaning efficacy.
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Abstract
Description
[Technical field]
[0001] The present invention relates to a biofilm removing agent composition and a method for removing a biofilm. [Background technology]
[0002] Once bacteria attach to a target object, the bacteria grow on the target object and form a biofilm. A biofilm is also called a biofilm or slime, and generally refers to a three-dimensional structure formed by microorganisms such as bacteria attaching to the surface of a material and growing, and enveloping the microorganisms with polymeric substances such as polysaccharides, proteins, and nucleic acids produced by the microorganisms. Biofilms are a problem for ordinary people in various situations. For example, they cause unpleasant slimy dirt and bad odors in household water environments such as the kitchen, sinks, and around the drains in the bathroom. Biofilms form not only in direct water environments, but also in scratches on cutting boards, inside dishwashing sponges, washing machine drums, and even in fabric products such as clothing, dish towels, dusters, and foot mats, and are prone to cause problems in situations where water, moisture, and dirt coexist. In addition, detergents containing various surfactants are widely used for cleaning textile products such as clothing. In recent years, as consumers have become more hygienic, there has been growing interest in bacteria and viruses attached to the surface of textile products. For this reason, consumers take extra time and cost to clean such products by soaking socks and sweaty clothes, which are prone to bacterial growth, in a cleaning solution for a while, or by using disinfectants or bleach in combination with textile cleaning agents.
[0003] US Patent No. 5,399,633 discloses a germicidal light-duty dishwashing detergent composition, either gel or liquid, containing a dioctyldimethylammonium salt and an alkyl ether carboxylate salt. [Prior art documents] [Patent documents]
[0004] [Patent Document 1] U.S. Pat. No. 5,728,667 Summary of the Invention [Problem to be solved by the invention]
[0005] Biofilms that adhere to target objects, especially textile products, are extremely difficult to remove because the polymers that compose the biofilm act as a protective barrier that protects bacteria from various substrates. The present invention provides 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. [Means for solving the problem]
[0006] The present invention relates to a biofilm removing composition comprising the following component (a) and component (b): 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)):
[0007] [ka]
[0008] [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; - is an anion.] (b) Component: Anionic surfactant
[0009] The present invention also relates to a method for removing a biofilm, which comprises contacting a target article on which a biofilm is present with the biofilm remover composition of the present invention or a treatment liquid obtained by diluting the composition with water.
[0010] 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 a target article on which a biofilm exists.
[0011] The present invention also relates to use of a composition containing the above-mentioned components (a) and (b) for removing a biofilm from a target article to which the biofilm is attached. Effect of the Invention
[0012] 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] The reason why the biofilm remover composition of the present invention and the biofilm removal method using the same are excellent in removing biofilms attached to target objects, particularly textile products, is not entirely clear, but is presumed to be as follows. Extracellular polysaccharides, which are a type of polymer that constitutes biofilms, function as a protective barrier that protects bacteria from various bases, making it very difficult to remove biofilms. In the present invention, it is believed that the combination of a specific cationic surfactant as component (a) and an anionic surfactant as component (b) relaxes and disperses the dense structure of the extracellular polysaccharides, thereby making it possible to remove biofilms. Specifically, the biofilm remover composition of the present invention uses a specific cationic surfactant as component (a) and an anionic surfactant as component (b) in combination, forming a loose ion complex in which (a) and (b) do not cancel each other out, and 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, when the biofilm remover composition of the present invention contains the specific cationic surfactant as component (a) and the anionic surfactant as component (b) in a mass ratio (a) / (b) of less than 1, a better biofilm removal effect can be obtained. However, the present invention is not limited to the above-mentioned mechanism of action.
[0014] [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)).
[0015] [ka]
[0016] [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; - is an anion.]
[0017] 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 having 6 or more, preferably 8 or more, and 12 or less, preferably 10 or less, carbon atoms, preferably a linear alkyl group, from the viewpoint of biofilm removal. 1a and R 2a are preferably identical to each other. R 3a and R 4a are each independently a straight-chain or branched-chain alkyl group having from 1 to 3 carbon atoms. Examples of the alkyl group having from 1 to 3 carbon atoms include groups selected from a methyl group, an ethyl group, and a propyl group. X - X 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 the halogen ion include a chloride ion, a bromide ion, and an iodide ion. - 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.
[0018] The component (a1) may be used alone or in combination of two or more.
[0019] The component (a2) is a bispyridinium compound. Examples of bispyridinium compounds include those described in British Patent No. 1533952, Japanese Patent Publication No. 52-105228, and International Publication No. 2014 / 100807. Specifically, from the viewpoint of biofilm removal, the bispyridinium compound is preferably one or more selected from the compounds represented by the following general formula (a21) and the compounds represented by the following general formula (a22).
[0020] [ka]
[0021] [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, and A is an anion. q is 1 or 2, r is 1 or 2, and q×r=2.
[0022] A is a monovalent or divalent anion, for example, chloride, bromide, phosphate, orthosilicate, an organic acid, for example, a compound of the 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. Here, R 6a is hydrogen, hydroxyl, or an alkyl group having from 1 to 40 carbon atoms.
[0023] 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.
[0024] From the viewpoint of biofilm removal, the preferred bispyridinium compound is a compound of general formula (a22), and further, octenidine dihydrochloride (in general formula (a22), R 5a is an n-octyl group, Y is an n-decenyl group, 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.
[0025] 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.
[0026] <(b) Component> The biofilm removing composition of the present invention contains an anionic surfactant as component (b). From the viewpoint of biofilm removal, the 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 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)). R 1b -O-[(PO) p / (EO) q ]-SO 3 M (b1) [In general formula (b1), R 1b is a hydrocarbon group having 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 of 0 to 10, q is the average number of moles of EO added and is a number of 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. R bonded to B 2b In contrast, the sulfonic acid group is bonded to the ortho, meta or para position.
[0027] In the compound of the general formula (b1) of the component (b1), R 1b From the viewpoint of biofilm removal, is 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 straight-chain or branched-chain alkyl group, or a straight-chain or branched-chain alkenyl group, more preferably a straight-chain or branched-chain alkyl group, and even more preferably a straight-chain alkyl group. p is the average number of moles of PO added, and from the viewpoint of biofilm removal, 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, even more preferably 0.5 or more, even more preferably 1 or more, even more preferably 2 or more, and is 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, 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 (1 / 2 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 (1 / 2 atom) include a calcium ion or a magnesium ion, and examples of the organic ammonium ion include an alkanolamine having 1 to 3 alkanol groups having 2 or 3 carbon atoms (e.g., monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).
[0028] 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, the sulfonic acid group (-SO 3 M) is attached at the ortho, meta or para position. 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. Examples of the alkali metal ion include a sodium ion or a potassium ion, examples of the alkaline earth metal ion (1 / 2 atom) include a calcium ion or a magnesium ion, and examples of the organic ammonium ion include an alkanolamine having 1 to 3 alkanol groups having 2 or 3 carbon atoms (e.g., monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).
[0029] The component (b3) is an internal olefin sulfonate. From the viewpoint of biofilm removal, the number of carbon atoms in the internal olefin sulfonate in the 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 the component (b3) refers to the number of carbon atoms in the internal olefin to which the sulfonate is covalently bonded.
[0030] The internal olefin sulfonate of component (b3) is a sulfonate obtained by sulfonating, neutralizing and hydrolyzing an internal olefin (an olefin having a double bond inside the olefin chain) having a carbon number of preferably 10 or more, more preferably 14 or more, and preferably 20 or less, more preferably 18 or less as a raw material. Such internal olefins include those containing a trace amount of so-called alpha olefins (hereinafter also referred to as α-olefins) in which the double bond is located at the first position of the carbon chain. Furthermore, when an internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are further converted to hydroxyalkanesulfonate and olefin sulfonate in the neutralization and hydrolysis process (for example, J. Am.Oil Chem. Soc. 69, 39(1992)). Here, the hydroxy group of the obtained hydroxyalkanesulfonate is inside the alkane chain, and the double bond of the olefin sulfonate is inside the olefin chain. Furthermore, the obtained product is mainly a mixture of these, and some of the products 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 mixtures thereof are collectively referred to as internal olefin sulfonate (component (b3)). Furthermore, hydroxyalkanesulfonate is referred to as hydroxy form of internal olefin sulfonate (hereinafter also referred to as HAS form), and olefin sulfonate is referred to as olefin form of internal olefin sulfonate (hereinafter also referred to as IOS form). The mass ratio of the HAS form and the IOS form of the compound in component (b3) can be measured by a high performance liquid chromatography mass spectrometer (hereinafter abbreviated as HPLC-MS). Specifically, the mass ratio can be calculated from the HPLC-MS peak area of component (b3).
[0031] Examples of the salt of the internal olefin sulfonate include an alkali metal salt, an alkaline earth metal (1 / 2 atom) salt, an ammonium salt, and an organic ammonium salt. Examples of the alkali metal salt include a sodium salt and a potassium salt. Examples of the organic ammonium salt include an alkanol ammonium salt having 2 to 6 carbon atoms, including an alkanolamine.
[0032] 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 some of them may have a sulfonic acid group at the end of the carbon chain.
[0033] The content of internal olefin sulfonate salts in which sulfonic acid groups are present at the 5th position or higher, preferably from the 5th to the 9th positions, in component (b3) is, from the viewpoint of biofilm removal, preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, still more preferably 20 mass% or more, and preferably 60 mass% or less, more preferably 55 mass% or less, even more preferably 45 mass% or less, and still more preferably 40 mass% or less.
[0034] In component (b3), the mass ratio of the content of internal olefin sulfonate salts [hereinafter sometimes referred to as (IO-1S)] in which the sulfonic acid group is present at position 2 or more and position 4 or less to the content of internal olefin sulfonate salts [hereinafter sometimes referred to as (IO-2S)] in which the sulfonic acid group is present at position 5 or more, preferably position 5 or more and position 9 or less, (IO-1S) / (IO-2S), is, from the viewpoint of biofilm removal, 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, preferably 10 or less, more preferably 8 or less, even more preferably 6 or less. The content of each compound having a sulfonic acid group at a different position in the (b3) component 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 a sulfonic acid group at each position in the total HAS body of the (b3) component.
[0035] The content of olefin sulfonate in component (b3) in which a sulfonic acid group is present at position 1 is preferably 10 mass% or less in component (b3) from the viewpoint of biofilm removal, more preferably 7 mass% or less, even more preferably 5 mass% or less, and even more preferably 3 mass% or less, and from the viewpoint of reducing production costs and improving productivity, it is preferably 0.01 mass% or more. The position of the sulfonic acid group in these compounds is a position in the olefin or alkane chain.
[0036] The internal olefin sulfonate may be a mixture of a hydroxyl group and an olefin group. The mass ratio of the content of the olefin group in the internal olefin sulfonate to the content of the hydroxyl group in the internal olefin sulfonate in the component (b3) (olefin group / hydroxyl group) may be 0 / 100 or more, further 5 / 95 or more, and 50 / 50 or less, further 40 / 60 or less, further 30 / 70 or less, further 25 / 75 or less.
[0037] Examples of the anionic surfactant other than the 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 di-phosphate esters, sulfosuccinate esters, and salts thereof. The alkyl or alkenyl group of these anionic surfactants has, for example, 8 to 22 carbon atoms. Examples of the salts of these anionic surfactants include alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, and organic ammonium salts. Examples of the alkali metal salts include sodium salts and potassium salts. Examples of the organic ammonium salts include alkanol ammonium salts containing alkanolamine and having 2 to 6 carbon atoms.
[0038] In the biofilm remover composition of the present invention, the contents of the components (b1), (b2), and (b3) in the component (b) 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 components (b1), (b2), and (b3) in the component (b) do not necessarily require that the components (b1), (b2), and (b3) are all essential components, and it is sufficient if at least any one of the components is contained. From the viewpoint of biofilm removal, the (b) component is preferably one or more selected from the (b1) component, the (b2) component, and the (b3) component, and more preferably one or more selected from the (b1) component and the (b3) component, in which p in the general formula (b1) 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 8 to 18 carbon atoms, and a (b3) component of an internal olefin sulfonate salt having an alkyl group having 8 to 18 carbon atoms and 16 to 18 carbon atoms.
[0039] The (b) component may be used alone or in combination of two or more. From the viewpoint of biofilm removal, two or more (b) components are preferred. From the viewpoint of biofilm removal, the (b) component is preferably two or more including a (b1) component in which p in the general formula (b1) is 0.1 or more, and more preferably two components, a (b1) component and a (b3) component in which p in the general formula (b1) is 0.1 or more.
[0040] <Composition, etc.> From the viewpoint of biofilm removal, the biofilm remover composition of the present invention contains component (a) in a concentration 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 expressed as a value converted into a chlorine salt, and when component (a2) is contained as component (a), the mass of component (a2) is expressed as a value converted into a hydrochloride salt.
[0041] 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, 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. In the present invention, the mass of component (b) is expressed as a value converted into a sodium salt.
[0042] 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, even more preferably 0.02 or more, even more preferably 0.05 or more, even more preferably 0.1 or more, even more preferably 0.12 or more, even more preferably 0.15 or more, and preferably 7 or less, more preferably 5 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 less than 1, even more preferably 0.99 or less, even more preferably 0.97 or less, even more preferably 0.95 or less, even more preferably 0.5 or less, and even more preferably 0.3 or less.
[0043] The biofilm remover composition of the present invention can promote biofilm removal by containing 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).
[0044] The biofilm remover composition of the present invention contains water. As the water, ion-exchanged water, tap water, purified water, etc. can be used. The water can be used in an amount such that, as the remainder of the composition, the total composition of the whole composition becomes 100% by mass. The biofilm remover composition of the present invention contains water in the composition, preferably 0.1% 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.
[0045] The pH of the biofilm remover composition of the present invention at 25°C is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, still more preferably 6 or more, and preferably 14 or less, more preferably 12 or less, still more preferably 10 or less, from the viewpoint of biofilm removal. The pH is a value measured at 25°C using a glass electrode. Specifically, it is measured by the following method. <Method for Measuring pH> Calibrate the pH electrode (BlueLine 17 pH manufactured by SI Analytics) of the Consort multi-parameter analyser C3010 in advance with Reagecon pH4.000 High Resolution Colour Coded Buffer Solution and Reagecon pH 7.000 High Resolution Colour Coded Buffer Solution, and rinse thoroughly with ion-exchanged water. Put the pH electrode calibrated and washed as described above into the detergent composition adjusted to 25°C, and measure using the AUTO HOLD mode of the pH meter until the measured value becomes constant.
[0046] The biofilm remover composition of the present invention may be a biofilm remover composition containing component (a) and component (b), and may further contain water and other components. The matters described in the biofilm remover composition of the present invention can be appropriately applied to this biofilm remover composition, and the content of each component and each mass ratio can be applied by replacing them with the blending amounts of each component.
[0047] The biofilm remover composition of the present invention can be suitably used for textile products or hard articles, and more preferably for textile products.
[0048] The fibers of the textile product may be either hydrophobic or hydrophilic. Examples of hydrophobic fibers include protein fibers (milk protein casein fibers, promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride / polyvinyl alcohol copolymer fibers (polycral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), and polyfluoroethylene fibers (polytetrafluoroethylene, etc.). 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 silk, wild silk), feathers, and cellulosic fibers (rayon, polynosic, cupra, acetate, etc.). In the present invention, the textile product refers to fabrics such as woven fabrics, knitted fabrics, nonwoven fabrics, etc. using the hydrophobic fibers or hydrophilic fibers, and 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, masks, etc. Preferred textile products are woven fabrics such as woven fabrics and knitted fabrics, and woven textile products, such as textile products containing hydrophobic fibers, from the viewpoint of biofilm removal.
[0049] Examples of hard articles include washing machines, washing tubs, washing machine inlets, washing machine lint filters, washing machine drain pipes, tableware, hard articles around the kitchen, and / or hard articles in the living environment such as bathrooms, toilet areas, and floors, drains, water pipes, food manufacturing or beverage manufacturing plants, cooling water systems such as industrial cooling towers, endoscopes, catheters, medical equipment such as artificial dialysis, and the like. Examples of materials for hard articles include plastics such as polyethylene and polypropylene (including silicone resins), metals, ceramics, wood, and combinations thereof.
[0050] [How to remove biofilm] The present invention relates to a method for removing a biofilm, which comprises contacting a target object on which a biofilm is present with the biofilm remover composition of the present invention or a treatment liquid obtained by diluting the biofilm remover composition with water (hereinafter also referred to as the treatment liquid of the present invention). The treatment liquid of the present invention is prepared by diluting the biofilm remover composition of the present invention with water, and therefore contains the above-mentioned components (a) and (b). That is, the present invention relates to a method for removing a biofilm, which comprises contacting a treatment liquid containing component (a), component (b), and water (hereinafter also referred to as the treatment liquid of the present invention) with a target object on which a biofilm exists. Hereinafter, the treatment liquid obtained by diluting the biofilm remover composition of the present invention with water, and the treatment liquid containing component (a), component (b), and water will both be described as the treatment liquid 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 liquid of the present invention 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 of the present invention or the treatment liquid of the present invention has been attached is wiped or rinsed with water to remove the biofilm remover composition of the present invention or the treatment liquid of the present invention from the target article. A preferred method for wiping is to wipe the target object with a sheet, fabric, or the like made of fibers. A preferred method for rinsing is to rinse the target object to which the biofilm that has been in contact with the biofilm remover composition of the present invention or the treatment liquid of the present invention is attached by contacting the biofilm remover composition with water. Specifically, preferred rinsing methods include a method of continuously applying water to the target object or a method of immersing the target object in water. The biofilm removal method of the present invention is carried out using the biofilm removing agent composition of the present invention or the treatment liquid of the present invention, and the aspects described for the biofilm removing agent composition of the present invention can be appropriately applied.
[0051] The target article for 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 articles, that is, textile products and hard articles, are the same as those described for the biofilm removing composition of the present invention.
[0052] Examples of a method 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 a method of spraying or applying the biofilm removing composition of the present invention or the treatment liquid of the present invention to a target article on which a biofilm exists or is thought to exist, and a method of 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. The biofilm removing composition of the present invention or the treatment liquid of the present invention may also be impregnated into a nonwoven fabric and contacted with the target article.
[0053] When the biofilm removing composition of the present invention or the treatment liquid of the present invention is sprayed or applied to a target article, the biofilm removing 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 removing composition of the present invention or the treatment liquid 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 manual spray devices that do not use a propellant, such as trigger-type spray containers and pump-type spray containers, and aerosols that use a propellant. The container equipped with the 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).
[0054] When a target object, such as a textile product, is immersed in the biofilm remover composition of the present invention or the treatment liquid of the present invention, the target object and the biofilm remover composition of the present invention or the treatment liquid of the present invention may be left stationary or may be stirred during immersion. When stirring, stirring may be performed by hand or a rotary stirrer may be used. A rotary stirrer is a device that rotates the target object and the biofilm remover composition of the present invention or the treatment liquid of the present invention around a certain rotation axis to stir. The rotary stirrer may perform stirring in only one direction or in the opposite direction. In addition, stirring may be performed continuously or intermittently. Rotary agitators available to consumers include, for example, pulsator type washing machines, agitator type washing machines, or drum type washing machines. The method for removing a biofilm of the present invention preferably involves immersing a textile product on which a biofilm is present in the treatment liquid of the present invention and stirring the product using a rotary stirrer.
[0055] 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 left stationary or flowed after contact, and from the viewpoint of further enhancing biofilm removal, flowing is preferred. Preferred embodiments of the method of flowing the biofilm remover composition of the present invention or the treatment liquid of the present invention to the hard article include, for example, a method of continuously or intermittently spraying the biofilm remover composition or the treatment liquid of the present invention to the surface of a stationary hard article, and a method of flowing the biofilm remover composition in which a hard article is immersed or the treatment liquid of the present invention. Examples of embodiments of flowing the biofilm remover composition in which a hard article is immersed or the treatment liquid of the present invention include, for example, a method of flowing the biofilm remover composition in which a hard article is immersed or the treatment liquid of the present invention by applying an external force such as stirring to flow the biofilm remover composition in which a hard article is immersed or the treatment liquid of the present invention, or a method of rotating or shaking the hard article immersed in the biofilm remover composition or the treatment liquid of the present invention.
[0056] When the biofilm remover composition of the present invention is diluted with water to prepare the treatment liquid of the present invention, 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 then 10 times or more, further 50 times or more, and further 100 times or more, from the viewpoint of biofilm removal.
[0057] From the viewpoint of biofilm removal, the content of component (a) in the treatment liquid 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 5000 ppm or less, even more preferably 1000 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] From the viewpoint of biofilm removal, the content of component (b) in the treatment liquid 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 5000 ppm or less, even more preferably 1000 ppm or less, even more preferably 50 ppm or less.
[0059] In the treatment liquid of the present invention, the range of mass ratios of each component described in the biofilm removing agent 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.
[0060] From the viewpoint of biofilm removal, the pH of the treatment solution of the present invention is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, still 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 using a glass electrode at 25° C. The method for measuring the pH is the same as that described above.
[0061] From the viewpoint of biofilm removal, the hardness of the water used to prepare the treatment solution of the present invention is 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, even more preferably 10°dH or less, and even more preferably 5°dH or less, on the German hardness scale. The hardness of the treatment liquid of the present invention may be within the above range.
[0062] Here, the German hardness (°dH) in this specification is the concentration of calcium and magnesium in water expressed as CaCO 3 This refers to the converted concentration expressed as 1 mg / L (ppm) = approximately 0.056°dH (1°dH = 17.8 ppm). The calcium and magnesium concentrations for the German hardness scale are determined by chelate titration using disodium salt of ethylenediaminetetraacetic acid. A specific method for measuring the German hardness of water in this specification is shown below. <Method of measuring water hardness in Germany> 〔reagent〕 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 Co., Ltd.) Ammonia buffer solution for hardness measurement (67.5 g of ammonium chloride dissolved in 570 ml of 28 w / v% ammonia water, and then made up to 1000 ml with ion-exchanged water) [Measurement of hardness] (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 and confirm that the solution is reddish purple after addition. (4) While shaking the conical beaker well, add 0.01 mol / l EDTA·2Na solution from the burette, and the end point of the titration is when the sample water turns blue. (5) The total hardness is calculated using the following formula. Hardness (°dH)=T×0.01×F×56.0774×100 / A T:0.01mol / l Titration amount of EDTA・2Na solution (mL) A: Sample volume (20 mL, volume of sample water) F: Factor of 0.01mol / l EDTA·2Na solution
[0063] When a textile product on which a biofilm is present is immersed in the treatment solution of the present invention, the time for which the textile product is immersed (contacted) is, from the viewpoint of biofilm removal, preferably at least 10 seconds, more preferably at least 1 minute, even more preferably at least 5 minutes, and preferably at most 1 day, more preferably at most 15 hours, even more preferably at most 5 hours. After immersion, the textile product is rinsed with water and dried. Rinsing may be performed using water in accordance with a known method such as washing textile products. The water used for rinsing in the present invention is not particularly limited, but may include tap water, well water, ion-exchanged water, sterilized water, distilled water, etc.
[0064] 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.
[0065] 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 time for which the biofilm remover composition of the present invention or the treatment liquid of the present invention is contacted with the target article on which a biofilm is present (the time for which it is left standing) is, from the viewpoint of biofilm removal, 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. After contact, the surface 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 with a sponge or the like, or simply rinsed with a water flow. From the viewpoint of removing biofilm, rinsing with water is preferable.
[0066] When the biofilm removal agent composition of the present invention or the treatment liquid of the present invention is impregnated into a nonwoven fabric and brought into contact with a target article, the nonwoven fabric may 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 of contacting the target article can be any of rubbing, kneading, or tapping, by pressing a nonwoven fabric impregnated with the biofilm remover composition of the present invention or the treatment liquid of the present invention against the target article and applying an external force within a range that does not damage the target article, thereby transferring the biofilm remover composition of the present invention impregnated in the nonwoven fabric, or the treatment liquid obtained by diluting it with water, to the target article.
[0067] The biofilm remover composition of the present invention is suitable for use in removing a biofilm from a target article to which the biofilm is attached. That is, the present invention provides use of a composition containing the above-mentioned components (a) and (b) for removing a biofilm from a target article 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 the specific aspects of the components (a) and (b) are also the same. The specific aspects of the composition can be appropriately applied to the aspects described in the biofilm remover composition of the present invention. In addition, the use aspects of the composition can be appropriately applied to the aspects described in the biofilm removal method of the present invention. EXAMPLES
[0068] [Ingredients] In the examples and comparative examples, the following components were used. <Component (a)> Q-D08: Dioctyldimethylammonium chloride, in the general formula (a1), R 1a and R 2a is an alkyl group having 8 carbon atoms, and R 3a and R 4a is a methyl group, and X - is a compound that is a chloride ion, component (a1) CDMAB: 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 compound that is a chloride ion, component (a1) Octenidine: Octenidine dihydrochloride, in the general formula (a22), R 5a are n-octyl groups, Y is n-decenyl groups, A is Cl, q is 1, and r is 2. The compound (a2) component is available under the trade name "Octenidine Dihydrochloride" from Tokyo Chemical Industry Co., Ltd. <(b) Component> C16IOS: Potassium salt of internal olefin sulfonate having 16 carbon atoms, component (b3) ApS: partial PO-added alkyl ether sulfate, in the 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; AS: alkyl sulfate salt, in the general formula (b1), R 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 1b is an alkyl group having 10 to 16 carbon atoms, p is 0, q is 2, and M is a sodium ion; C12APES: polyoxypropylene polyoxyethylene alkyl ether sulfate having an alkyl group with 12 carbon atoms. In the general formula (b1), R 1b is an alkyl group having 12 carbon atoms, p is 2, q is 2, and M is monoethanolammonium; LAS (linear alkylbenzene sulfonate), component (b2), product name "Neopelex G-25", manufactured by Kao Corporation
[0069] [Preparation of biofilm remover composition] The preparation method of the biofilm remover composition shown in Tables 1 to 6 is as follows. A 3 cm long Teflon stirrer piece is put into a 200 mL capacity glass beaker, then 10 g of ion-exchanged water and the (a) and (b) components are put in according to the formulations shown in Tables 1 to 6, and the mixture is stirred at 100 r / min for 10 minutes. An amount of ion-exchanged water equivalent to 95% by mass of the amount of additional water required to make the total amount 100 g is added, and the mixture is stirred at 100 r / min for 5 minutes. The pH (25 ° C.) is adjusted to 8 with monoethanolamine or hydrochloric acid (Examples 38 and 39 in Table 6 were adjusted to the pH shown in the table). The ion-exchanged water is added so that the total amount is 100 g, and the mixture is stirred at 100 r / min for 15 minutes to obtain each biofilm remover composition having the formulation shown in Tables 1 to 6. After preparation, the pH was checked again, and the pH of each biofilm remover composition in Tables 1 to 6 did not change from the pH at the time of adjustment. The amounts of each component in each biofilm removing composition shown in Tables 1 to 6 are all active ingredients. For Example 33 in Table 4, the amounts of each component in the test treatment liquid after dilution are shown, as described later.
[0070] [Biofilm removal evaluation] (1-1) Preparation of biofilm-formed fabric Glycerol stock solutions of Rhodotorula mucilaginosa (clothing isolate) and Methylobacterium variable (clothing isolate) were smeared on potato dextrose agar medium (Difco Laboratories) and cultured statically at 30°C for 2 days. Glycerol stock solutions of Moraxella osloensis (clothing isolate) were smeared on SCD agar medium (Shioya MS Co., Ltd. SCD agar medium "Daigo", for general bacterial testing) and cultured statically at 37°C for 1 day. After culture, the bacterial cells were scraped off with a disposable loop (As One Co., Ltd. Disposable Loop 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 (Model: PD-303S, manufactured by APEL Co., Ltd.), and the bacterial suspension was diluted so that R. mucilaginosa had an OD600 of 0.2, and M. variable and M. osloensis had an OD600 of 0.01. Hiraori cotton cloth (Cotton 2003, Tanigashira Shoten) cut to 3 x 3 cm (PE faille (Polyester faille, Tanigashira Shoten) was used in Example 4) was sterilized by pressure in an autoclave (High pressure steam sterilizer Lab Autoclave, model number: MLS-3781, PHC Corporation). The sterilized Hiraori cotton cloth or PE faille was placed in a No. 6 screw tube (No. 6 screw tube, Maruemu Corporation), and 1 mL of each of the above three bacterial strains and 7 mL of R2A medium were added. The tube was then sealed with a lid and cultured with shaking at 30°C and 200 rpm for 2 days in a small constant temperature shaking incubator Bioshaker (Model number: BR-23FP, TAITEC Corporation). After the culture, the Hiraori cotton cloth or PE faille was transferred to a new No. 6 screw tube, and 10 mL of autoclave-sterilized ion-exchanged water was added. The cloth was washed by shaking at 25°C and 150 rpm for 3 minutes in a small constant temperature shaking incubator, Bioshaker. After washing, the Hiraori cotton cloth or PE faille was air-dried for 1 hour in a safety cabinet to prepare a biofilm-formed 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, Carl Zeiss, Inc.). The threads observed were stained for 30 minutes with a live cell staining dye (C375-Cellstain(TM)-CFSE, Dojindo Laboratories, Inc.), a dead cell staining dye (P378-Cellstain(TM)-PI solution, Dojindo Laboratories, Inc.), a cellulose staining dye (Calcofluor White staining solution, Sigma-Aldrich, Inc.), a sugar staining dye (Lectin PNA From Arachis hypogaea (peanut), Alexa Fluor(TM) 647 Conjugate, Thermo Fisher Scientific, Inc.), and a sugar staining dye (Concanavalin Alexa Fluor(TM) 647 Conjugate, Thermo Fisher Scientific, Inc.).
[0071] (1-2) Preparation of biofilm-supported hard surfaces For Example 37 in Table 5, 0.3 mL of each of the above three bacterial species and 2.1 mL of R2A medium were added per well of a polystyrene 6-well plate (Corning Co., Ltd. Falcon Cell Culture 6-well multi-well plate, flat bottom, with lid), the plate was sealed with a lid, and then cultured stationarily for 2 days at 30° C. After culture, the moisture in the upper layer of the 6-well plate was sucked off and air-dried for 1 hour in a safety cabinet to form a hard surface for biofilm formation. The formation of biofilms on hard surfaces was confirmed by observation using a digital microscope (Keyence Corporation, VHX-7000).
[0072] (2) Biofilm removal test (Biofilm removal evaluation) The prepared biofilm-formed cloth was cut to 1.5 x 1.5 cm, and the sterilized flat-woven cotton cloth was cut to 1.5 x 3 cm. One cut biofilm-formed cloth and two sterilized flat-woven cloths were stacked together (a total of three pieces) and placed in a 5 mL tube (Eppendorf Tube 5.0 mL, model number: 0030 119.401, manufactured by Eppendorf Co., Ltd.). Thereto, 3 mL of a test treatment solution prepared by diluting each of the biofilm remover compositions in Tables 1 to 6 with model tap water (4 ° dH) 3000 times (for Examples 5 to 7 in Table 1, the hardness of the model tap water for diluting 3000 times was changed to that shown in the table to prepare a test treatment solution. In addition, in Table 4, for Example 33, the test treatment solution after dilution at the concentration shown in the table was used, and for Examples 34 and 35, the test treatment solution was used without dilution at the concentration shown in the table.) was added, and shaking washing was performed for 10 minutes at 25 ° C. and 150 rpm in a small constant temperature shaking incubator bioshaker, which was used as is as a washing step. The washed cloth was transferred to a 5 mL tube containing 3 mL of model tap water, and shaking washing was performed for 3 minutes under the same conditions as above, which was used as a rinsing step. After rinsing, only the biofilm-formed cloth was taken out and air-dried for 30 minutes in a safety cabinet. The same treatment was also performed for a test treatment solution in which model tap water (4 ° dH) was used instead of each biofilm remover composition, and a biofilm-formed cloth after treatment with model tap water was obtained. For the biofilm-formed hard surface, 3 mL of a test treatment liquid obtained 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 shaking washing was performed for 10 minutes at 25 ° C. and 150 rpm in a small constant temperature shaking incubator bioshaker, which was used as a washing step. The test treatment liquid in the bioshaker after washing was sucked up with a micropipette (Eppendorf Research (R) plus manufactured by Eppendorf Co., Ltd.), 3 mL of model tap water was added, and shaking washing was performed for 3 minutes under the same conditions, which was used as a rinsing step. The model tap water in the bioshaker after rinsing was sucked up with a micropipette, and the biofilm-formed hard surface after rinsing was air-dried for 30 minutes in a safety cabinet. The same treatment was also performed on a test treatment liquid in which model tap water (4 ° dH) was used instead of the biofilm remover composition of Example 37, and a biofilm-formed hard surface after treatment with model tap water was obtained.
[0073] (Extraction of EPS (Extracellular Polysaccharide)) The biofilm-formed cloth after air drying was placed in a 1.5 mL tube (Eppendorf Tube 1.5 mL, model number: 0030 125.150, manufactured by Eppendorf Co., Ltd.) 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 cloth was placed in an ultrasonic cleaner (Emerson Japan, Ltd., tabletop ultrasonic cleaner, model number: 2510JDTH) on cold ice for 2 hours to extract the EPS remaining on the cloth. EPS (Extracellular Polysaccharide) is the main component of biofilm. After stirring the liquid for 5 minutes with a cute mixer (Tokyo Rikakikai Co., Ltd., model number: CUTE MIXER CM-1000), the liquid and the biofilm-formed cloth were filtered using a filter (ADVANTEC, model number: DISMIC-25CS) and a syringe (Terumo, 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 Co., Ltd., ethanol (99.5)) that had been cooled to -30°C in advance 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 tube was centrifuged at 4°C and 13,000 rpm for 15 minutes using a centrifuge (Eppendorf high-speed centrifuge, model number: Centrifuge 5430), the supernatant was removed, and the tube was air-dried for 1 hour. 200 μL of ion-exchanged water was added to the tube after air-drying, and the tube was stirred for 5 minutes using a cute mixer to dissolve the precipitated EPS in the ion-exchanged water. For the hard surfaces with biofilms formed after air drying, 2 mL of 1.5 M sodium chloride solution was added per well and pipetted 20 times with a micropipette to disperse the biofilms in the sodium chloride 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 in the same manner as above and dissolved in ion-exchanged water.
[0074] (EPS quantification) 100μL of the EPS aqueous solution obtained in the previous step was placed in a glass test tube (Corning, disposable glass test tube, model number: 99445-16), and 100μL of 5% phenol (Fujifilm Wako Pure Chemical Industries, Ltd., phenol) aqueous solution was added. After stirring for 3 seconds with a vortex, 500μL 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 (As One Corporation, vortex mixer, model number: VTX-3000L). After leaving it for 30 minutes, 200μL was dispensed into a 96-well plate (AGC Technoglass, model number: 3815-012-MYP microplate), and the absorbance (492nm) of the reaction solution was measured with a microplate reader (TECAN, fluorescence, absorbance, and luminescence plate reader, model number: infinite M200 PRO). Based on the residual amount of EPS quantified in terms of glucose, the EPS removal rate was calculated using formula (1). It can be said that the higher the EPS removal rate, the better the biofilm removal ability. The results are shown in Tables 1 to 6. EPS removal rate (%)=[(W1-W2) / W1]×100...(1) W1: Amount of EPS remaining on biofilm-formed fabric or biofilm-formed hard surface after treatment with model tap water W2: Amount of EPS remaining on biofilm-formed fabric or biofilm-formed hard surface after treatment with each test treatment solution
[0075] [Table 1]
[0076] [Table 2]
[0077] [Table 3]
[0078] [Table 4]
[0079]
Table 5
[0080]
Table 6
Claims
1. A biofilm removing composition comprising the following components (a) and (b): 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)) 【Chemistry 1】 [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; - is an anion.] Component (b): Anionic surfactant
2. The biofilm remover composition according to claim 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 14 to 20 carbon atoms (hereinafter referred to as the component (b3)). R 1b -O-[(POO) p / (EO) q ]-SO 3 M (b1) [In general formula (b1), R 1b is a hydrocarbon group having 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 of 0 to 10, q is the average number of moles of EO added and is a number of 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 In contrast, the sulfonic acid group is bonded to the ortho, meta or para position.
3. 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 The biofilm remover composition according to claim 2, which 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 a (b3) component of an internal olefin sulfonate salt having an alkyl group carbon number of 16 to 18.
4. The biofilm remover composition according to claim 2 or 3, wherein the contents of the components (b1), (b2) and (b3) in the component (b) are 70% by mass or more and 100% by mass or less.
5. The biofilm removing composition according to claim 1 or 2, wherein the component (a2) is octenidine dihydrochloride.
6. The biofilm remover composition according to claim 1 or 2, wherein the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is 0.001 or more and 7 or less.
7. The biofilm remover composition according to claim 1 or 2, further comprising water, the content of component (a) being 0.001% by mass or more and 50% by mass or less, and the content of component (b) being 0.001% by mass or more and 80% by mass or less.
8. The biofilm removing composition according to claim 1 or 2, which is for use on textile products.
9. A method for removing a biofilm, comprising contacting a target object on which a biofilm is present with the biofilm remover composition according to claim 1 or 2, or a treatment liquid obtained by diluting the biofilm remover composition with water.
10. The method for removing a biofilm according to claim 9, wherein the biofilm removing 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 removing composition or the treatment liquid is attached is wiped or rinsed with water to remove the biofilm removing composition or the treatment liquid from the target article.
11. The method for removing a biofilm according to claim 9, wherein the target article is a textile product.
12. 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 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)) 【Chemistry 2】 [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; - is an anion.] Component (b): Anionic surfactant
13. The method for removing a biofilm according to claim 12, wherein the mass ratio (a) / (b) of the content of component (a) to the content of component (b) in the treatment liquid is 0.001 or more and 7 or less.
14. The method for removing a biofilm according to claim 12 or 13, wherein the treatment liquid is brought into contact with a target object on which a biofilm is present, and then the target object to which the treatment liquid is attached is wiped or rinsed with water to remove the treatment liquid from the target object.
15. Use of a composition comprising the following components (a) and (b) for removing a biofilm from a target 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)) 【Chemistry 3】 [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; - is an anion.] Component (b): Anionic surfactant
16. Use of the composition described in claim 15, 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 14 to 20 carbon atoms (hereinafter referred to as the component (b3)), for removing a biofilm from a target article to which the biofilm is attached. R 1b -O-[(POO) p / (EO) q ]-SO 3 M (b1) [In general formula (b1), R 1b is a hydrocarbon group having 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 of 0 to 10, q is the average number of moles of EO added and is a number of 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 In contrast, the sulfonic acid group is bonded to the ortho, meta or para position.
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US5728667A