Method for inhibiting biofilm formation

Abstract

To provide a method for inhibiting biofilm formation in fibers.SOLUTION: A method for inhibiting biofilm formation comprises bringing (a) a treatment medium comprising at least one of (a1)-(a3) into contact with fibers. (a1) a compound represented by formula (a-1): R1-O-[(PO)m / (EO)n]-SO3M (a-1) [where R1 denotes a C8-22 alkyl group, PO and EO each have a block bond or a random bond, m and n each denote an average number of added moles of PO and EO, and M denotes a hydrogen atom, an alkali metal, an alkaline-earth metal (1 / 2 atom), ammonium, or organic ammonium]. (a2) a compound represented by formula (a-2): R2-B-SO3M (a-2) [where R2 denotes a C3-21 alkyl group, B denotes a benzene ring, and M denotes a hydrogen atom, an alkali metal, an alkaline-earth metal (1 / 2 atom), ammonium, or organic ammonium. (a3) a C14-24 internal olefin sulfonate.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for inhibiting biofilm formation. [Background technology]

[0002] A biofilm is a structure formed by a community of microorganisms such as bacteria and mold attached to the surface of a solid or liquid together with secretions. Biofilms that occur in drainage systems and water circulation systems in homes and factories can cause slime and clogging of pipes and foul odors. Biofilms also cause deterioration of facilities, such as corrosion of sewer pipes. The adverse effects of biofilm formation are also a problem in reverse osmosis membranes used in seawater desalination plants and piping equipment in paper factories. Furthermore, biofilms can cause microbial contamination. Biofilms that occur in hot spring facilities can cause infectious diseases. In the medical field, biofilms formed on medical instruments such as tubes for dialysis, endoscopes, and contact lenses can be a source of infection. Biofilm formation on the skin and in the oral cavity can also cause diseases. In the food field, biofilms formed on food or cooking utensils can cause spoilage and food poisoning.

[0003] In addition to techniques for removing biofilms that have developed on various articles by methods such as cleaning, techniques for suppressing the formation of biofilms themselves have also been proposed. For example, Patent Document 1 discloses a method for inhibiting biofilm formation, in which a composition containing a compound represented by a specific general formula, a surfactant, and a solvent is applied to an object and used without rinsing. Furthermore, Patent Document 2 discloses a biofilm control agent composition containing a specific nonionic surfactant, an enzyme, and optionally an anionic surfactant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-78205 A [Patent Document 2] JP 2008-156331 A Summary of the Invention [Problem to be solved by the invention]

[0005] Among the objects on which biofilms form, biofilms may form not only on the surface of fibers but also inside the three-dimensional structure. Biofilms formed inside the three-dimensional structure of fibers are difficult to remove by normal washing because sufficient mechanical force is not applied. Therefore, it is desirable to suppress the formation of biofilms on fibers. When suppressing the formation of biofilms on fibers, unlike hard objects such as drainage equipment and the oral cavity, it is necessary to consider the surface and internal structures and cleaning mechanisms, and an approach different from the conventionally proposed methods for suppressing biofilm formation is required. The present invention provides a method for inhibiting biofilm formation, which can effectively inhibit the formation of a biofilm on a fiber. [Means for solving the problem]

[0006] The present invention relates to (a) a method for inhibiting biofilm formation, which comprises contacting fibers with a treatment medium containing one or more compounds selected from the following components (a1) to (a3) ​​(hereinafter referred to as component (a)): Component (a1): a compound represented by the following general formula (a-1): R 1 -O-[(PO) m / (EO) n ]-SO3M (a-1) [In formula (a-1), R 1represents an alkyl group having 8 to 22 carbon atoms, PO represents a propyleneoxy group, EO represents an ethyleneoxy group, PO and EO are block bonds or random bonds, / is a symbol indicating that the order of bonding of PO and EO does not matter, m and n are the average number of moles added of PO and EO, m is 0 to 5, n is 0 to 10, m and n are not 0 at the same time, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium. Component (a2): a compound represented by the following general formula (a-2): R 2 -B-SO3M (a-2) [In formula (a-2), R 2 represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium. 2 In contrast, the sulfonic acid group is bonded to the ortho, meta or para position. (a3) Component: Internal olefin sulfonate having 14 to 24 carbon atoms Effect of the Invention

[0007] According to the present invention, there is provided a method for inhibiting biofilm formation, which can effectively inhibit the formation of a biofilm on a fiber. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In the method for inhibiting biofilm formation of the present invention, a treatment medium (hereinafter also referred to as the treatment medium of the present invention) containing one or more compounds selected from the components (a1) to (a3) ​​as component (a) is contacted with fibers.

[0009] The component (a1) may be a compound represented by the following general formula (a1-1) (hereinafter referred to as component (a1-1)). R 1 -O-(EO) n1 -SO3M (a1-1) [In formula (a1-1), R1 represents an alkyl group having 8 to 22 carbon atoms, EO represents an ethyleneoxy group, n1 is the average number of moles of EO added, n1 is greater than 0 and is 10 or less, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium.

[0010] The content of the component (a1-1) in the present invention is based on the amount of the compound converted into a sodium salt, i.e., the concentration (ppm) or mass ratio is calculated based on the amount of the compound in which M in general formula (a1-1) is sodium.

[0011] From the viewpoint of inhibiting biofilm formation, in formula (a1-1), R 1 represents an alkyl 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.

[0012] In formula (a1-1), EO represents an ethyleneoxy group. In formula (a1-1), n1 is the average number of moles of EO added, and from the viewpoint of inhibiting biofilm formation, is a number greater than 0, preferably 0.5 or more, more preferably 1 or more, and 10 or less, preferably 8 or less, more preferably 5 or less, and even more preferably 3 or less.

[0013] In formula (a1-1), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium, and from the viewpoint of inhibiting biofilm formation, M is preferably an alkali metal or an alkanolammonium having 2 to 6 carbon atoms. Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the organic ammonium include alkanolammonium such as monoethanolammonium, diethanolammonium, and triethanolammonium.

[0014] The component (a1) may be a compound represented by the following general formula (a1-2) (hereinafter referred to as component (a1-2)). R 2 -O-[(PO) m1 / (EO) n2 ]-SO3M (a1-2) [In formula (a1-2), R 2 represents an alkyl group having 8 to 22 carbon atoms, PO represents a propyleneoxy group, / is a symbol indicating that the order of bonding between PO and EO does not matter, EO represents an ethyleneoxy group, EO and PO are block-type bonds or random-type bonds, m1 and n2 are the average molar numbers of PO and EO added, m1 is 0.5 to 5, n2 is 0 to 10, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium.

[0015] The content of the (a1-2) component in the present invention is based on the amount of the compound converted into a sodium salt when n2 is 0, or into a monoethanolamine salt when n2 exceeds 0. That is, the concentration (ppm) and mass ratio are calculated based on the amount of the compound in which M is sodium when n2 in general formula (a1-2) is 0, or based on the amount of the compound in which M is monoethanolammonium when n2 in general formula (a1-2) exceeds 0.

[0016] In the formula (a1-2), from the viewpoint of inhibiting biofilm formation, R 2 represents an alkyl 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, even more preferably 16 or less, and still more preferably 14 or less.

[0017] In formula (a1-2), PO represents a propyleneoxy group, EO represents an ethyleneoxy group, and EO and PO are bonded in a block or random manner. In formula (a1-2), the order of bonding between PO and EO is not important. 2 A compound having a structure in which PO is bonded to --O-- is one of the preferred embodiments. In formula (a1-2), m1 and n2 are the average numbers of moles of PO and EO added. In formula (a1-2), from the viewpoint of inhibiting biofilm formation, m1 is a number of 0.5 or more, preferably 1.5 or more, more preferably 2 or more, and 5 or less, preferably 4 or less, more preferably 3 or less, and even more preferably 2.5 or less. In formula (a1-2), from the viewpoint of inhibiting biofilm formation, n2 is a number that is 0 or more, preferably 0.5 or more, more preferably 1 or more, even more preferably 1.5 or more, still more preferably 2 or more, and 10 or less, preferably 8 or less, more preferably 5 or less, and even more preferably 3 or less.

[0018] In formula (a1-2), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium, and from the viewpoint of inhibiting biofilm formation, M is preferably an alkali metal or an alkanolammonium having 2 to 6 carbon atoms. Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the organic ammonium include alkanolammonium such as monoethanolammonium, diethanolammonium, and triethanolammonium.

[0019] In the present invention, the content of the component (a1) other than the components (a1-1) and (a1-2) can be based on the amount of the compound converted to a sodium salt, i.e., the concentration (ppm) or mass ratio can be calculated based on the amount of the compound in which M in the general formula (a-1) is sodium.

[0020] The component (a1) may be one or more compounds selected from the components (a1-1) and (a1-2).

[0021] The component (a2) is a compound represented by the following general formula (a-2). R 2 -B-SO3M (a-2) [In formula (a-2), R 2represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium. 3 In contrast, the sulfonic acid group is bonded to the ortho, meta or para position.

[0022] The content of the compound represented by component (a2) in the present invention is based on the amount of the compound converted into a sodium salt, i.e., the concentration (ppm) or mass ratio is calculated based on the amount of the compound in which M in general formula (a2) is sodium.

[0023] In formula (a-2), from the viewpoint of inhibiting biofilm formation, R 2 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.

[0024] In formula (a-2), B represents a benzene ring, and R 2 In contrast, the sulfonic acid group (-SO3M) is attached at the ortho, meta or para position.

[0025] In formula (a-2), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium, and is preferably an alkali metal or an alkanolammonium having 2 to 6 carbon atoms from the viewpoint of inhibiting biofilm formation. Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the organic ammonium include alkanolammonium such as monoethanolammonium, diethanolammonium, and triethanolammonium.

[0026] The component (a3) ​​is an internal olefin sulfonate having 14 or more and 24 or less carbon atoms. The carbon number of the (a3) ​​component is the carbon number of the olefin portion, and from the viewpoint of inhibiting biofilm formation, is 14 or more, preferably 16 or more, and 24 or less, preferably 20 or less.

[0027] Examples of the salt of component (a3) ​​include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, and organic ammonium salts, for example, alkanol ammonium salts such as monoethanol ammonium, diethanol ammonium, triethanol ammonium, etc. From the viewpoint of inhibiting biofilm formation, alkaline earth metals and alkanol ammonium salts having 2 to 6 carbon atoms are preferred.

[0028] The content of the component (a3) ​​in the present invention is based on the amount of the compound converted into a potassium salt.

[0029] From the viewpoint of inhibiting biofilm formation, the component (a) is preferably one or more compounds containing the component (a1). From the viewpoint of inhibiting biofilm formation, the component (a1) is preferably the component (a1-2).

[0030] From the viewpoint of inhibiting biofilm formation, the component (a) may be two or more compounds selected from the components (a1) to (a3), or even two compounds. From the viewpoint of inhibiting biofilm formation, two or more compounds selected from the components (a1) and (a2) are preferred. In this case, it is also preferred that the component (a) contains the component (a1). As the component (a1), from the viewpoint of inhibiting biofilm formation, the component (a1-2) is preferred.

[0031] According to one embodiment, the treatment medium of the present invention contains, from the viewpoint of suppressing biofilm formation, preferably 10 ppm or more, more preferably 25 ppm or more, even more preferably 50 ppm or more, even more preferably 100 ppm or more, even more preferably 150 ppm or more, even more preferably 250 ppm or more, even more preferably 350 ppm or more, even more preferably 450 ppm or more, even more preferably 550 ppm or more, and preferably 800 ppm or less, more preferably 700 ppm or less, even more preferably 600 ppm or less of the component (a). This content is preferable, for example, when the treatment medium of the present invention is immersed in the fiber and contacted with the fiber.

[0032] According to another embodiment, the treatment medium of the present invention contains, from the viewpoint of inhibiting biofilm formation, preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less of component (a). This content is preferable, for example, when the treatment medium of the present invention is sprayed or applied to contact with fibers.

[0033] The treatment medium of the present invention may optionally contain (b) a nonionic surfactant (hereinafter referred to as component (b)).

[0034] As component (b), from the viewpoint of inhibiting biofilm formation, one or more nonionic surfactants selected from fatty alcohol alkoxylates and fatty ester alkoxylates are preferred, and one or more nonionic surfactants selected from fatty acid methyl ester ethoxylates are more preferred.

[0035] Examples of the aliphatic alcohol alkoxylates include alkylene oxide adducts of aliphatic alcohols and their terminal methyl ether adducts. From the viewpoint of inhibiting biofilm formation, the aliphatic alcohol is preferably an aliphatic alcohol having an aliphatic hydrocarbon group having a carbon number of preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less. From the viewpoint of inhibiting biofilm formation, the aliphatic alcohol is preferably a primary alcohol. From the viewpoint of inhibiting biofilm formation, the aliphatic hydrocarbon group may be an alkyl group or an alkenyl group, with an alkyl group being preferred. From the viewpoint of inhibiting biofilm formation, the aliphatic hydrocarbon group is linear or branched, and linear is preferred. From the viewpoint of inhibiting biofilm formation, the alkylene oxide is preferably at least one selected from ethylene oxide and propylene oxide. When the alkylene oxide contains ethylene oxide and propylene oxide, it may be of block bond type or random bond type. From the viewpoint of inhibiting biofilm formation, the average number of moles added of the alkylene oxide is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 70 or less, more preferably 50 or less, even more preferably 30 or less.

[0036] Furthermore, examples of the aliphatic ester alkoxylates include alkylene oxide adducts of fatty acids and their terminal methylated products. From the viewpoint of inhibiting biofilm formation, the fatty acids include fatty acids having an aliphatic hydrocarbon group having preferably 9 or more carbon atoms, more preferably 10 or more carbon atoms, even more preferably 12 or more carbon atoms, even more preferably 14 or more carbon atoms, even more preferably 16 or more carbon atoms, and preferably 20 or less carbon atoms, more preferably 18 or less carbon atoms. From the viewpoint of inhibiting biofilm formation, the aliphatic hydrocarbon group may be an alkyl group or an alkenyl group, with an alkyl group being preferred. From the viewpoint of inhibiting biofilm formation, the aliphatic hydrocarbon group is linear or branched, and linear is preferable. From the viewpoint of inhibiting biofilm formation, the alkylene oxide is preferably at least one selected from ethylene oxide and propylene oxide, more preferably ethylene oxide. When the alkylene oxide contains ethylene oxide and propylene oxide, it may be of block bond type or random bond type. From the viewpoint of inhibiting biofilm formation, the average number of moles of the alkylene oxide added is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 50 or less, more preferably 35 or less, even more preferably 20 or less. As the aliphatic ester alkoxylate, fatty acid methyl ester ethoxylate is preferred from the viewpoint of inhibiting biofilm formation.

[0037] Examples of the component (b) include nonionic surfactants represented by the following general formula (b-1). R 1b -(CO) p O-(AO) q -R 2b (b-1) [In the formula, R 1b is an aliphatic hydrocarbon group having 9 to 18 carbon atoms, R 2b is a hydrogen atom or a methyl group, CO is a carbonyl group, p is a number of 0 or 1, and AO is one or more alkyleneoxy groups selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. When AO contains an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, the alkyleneoxy group having 2 carbon atoms and the alkyleneoxy group having 3 carbon atoms may be bonded in a block type or random type. q is the average number of moles added and is a number of 1 to 70.

[0038] R 1b From the viewpoint of inhibiting biofilm formation, the carbon number of is 9 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less. R 2bFrom the viewpoint of inhibiting biofilm formation, the aliphatic hydrocarbon group may be a straight chain or a branched chain, and is preferably a straight chain. From the viewpoint of biofilm formation inhibition, R 2b is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0039] In formula (b-1), p is a number of 0 or 1, and from the viewpoint of inhibiting biofilm formation, p is preferably 1.

[0040] In formula (b-1), q is 1 or more, preferably 5 or more, more preferably 10 or more, and is 70 or less, preferably 50 or less, more preferably 25 or less, from the viewpoint of inhibiting biofilm formation.

[0041] In formula (b-1), AO is one or more alkyleneoxy groups selected from alkyleneoxy groups having 2 carbon atoms and alkyleneoxy groups having 3 carbon atoms. When AO contains an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, the alkyleneoxy group having 2 carbon atoms and the alkyleneoxy group having 3 carbon atoms may be bonded in a block type or random type.

[0042] From the viewpoint of inhibiting biofilm formation, component (b) has an average degree of polymerization (also referred to as the average number of moles added) of the alkyleneoxy group having two carbon atoms, i.e., the ethyleneoxy group (hereinafter sometimes referred to as the EO group), of preferably 3 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 70 or less, more preferably 50 or less, even more preferably 25 or less.

[0043] From the viewpoint of inhibiting biofilm formation, component (b) has an average degree of polymerization (also referred to as the average number of moles added) of the alkyleneoxy group having 3 carbon atoms, i.e., the propyleneoxy group (hereinafter sometimes referred to as the PO group), of preferably 0 or more, more preferably 1 or more, even more preferably 2 or more, and preferably 5 or less, more preferably 4 or less.

[0044] When the (b) component contains an EO group and a PO group, the EO group and the PO group may be randomly or block-bonded, and from the viewpoint of inhibiting biofilm formation, a block bond is preferable, and a block bond in the order of EOPOEO or POEO to alkyl ether is more preferable.

[0045] When the treatment medium of the present invention contains the component (b), from the viewpoint of inhibiting biofilm formation, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) in the treatment medium is preferably 0.4 or more and preferably 4 or less. However, when the component (b) is one or more nonionic surfactants selected from fatty acid methyl ester ethoxylates, from the viewpoint of inhibiting biofilm formation, (a) / (b) is preferably more than 0 and preferably 4 or less, more preferably 2.5 or less, even more preferably 1 or less, still more preferably 0.75 or less, and even more preferably 0.5 or less.

[0046] When the treatment medium of the present invention contains the component (b), in one embodiment, the treatment medium contains the component (b) in an amount of preferably 500 ppm or less from the viewpoint of inhibiting biofilm formation. This content is preferable, for example, when the treatment medium of the present invention is immersed in the treatment medium and contacted with fibers. In addition, when the treatment medium of the present invention contains the component (b), in another embodiment, the treatment medium contains the component (b) in an amount of preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more from the viewpoint of suppressing biofilm formation, and preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 5% by mass or less from the viewpoint of detergency. This content is preferable, for example, when the treatment medium of the present invention is sprayed or applied to contact with fibers.

[0047] From the viewpoint of inhibiting biofilm formation, the treatment medium of the present invention may contain (c) an antibacterial compound having an aromatic ring (hereinafter referred to as component (c)). Component (c) may be, for example, a nonionic antibacterial compound having an aromatic ring.

[0048] Regarding component (c), the antibacterial compound may be, for example, a compound that shows a zone of inhibition when an antibacterial test is performed according to JIS L 1902 "Antibacterial test method for textile products" using a cotton cloth #2003 with 1% by mass of the compound evenly applied thereto.

[0049] Examples of the (c) component include antibacterial compounds having a diphenyl ether skeleton, antibacterial compounds selected from phenol derivatives, and antibacterial compounds selected from benzoic acid derivatives. From the viewpoint of inhibiting biofilm formation, antibacterial compounds having a diphenyl ether skeleton, for example, antibacterial compounds containing a halogen atom and having a diphenyl ether skeleton, are preferred. Specific compounds include diclosan, triclosan, benzoic acid, paraben, etc., and from the viewpoint of inhibiting biofilm formation, diclosan and triclosan are preferred, and further from the viewpoint of inhibiting biofilm formation, diclosan is more preferred.

[0050] When the treatment medium of the present invention contains component (c), from the viewpoint of inhibiting biofilm formation, the treatment medium contains component (c) in an amount of preferably 0.1 ppm or more, more preferably 0.25 ppm or more, even more preferably 0.5 ppm or more, even more preferably 1 ppm or more, and preferably 10 ppm or less, more preferably 5 ppm or less, and even more preferably 2.5 ppm or less.

[0051] The treatment medium of the present invention may contain the following components (d1) to (d8) as optional components other than the components (b) and (c). (d1) Anti-redeposition agents and dispersants such as polyacrylic acid, polymaleic acid, and carboxymethyl cellulose (d2) Bleaching agents such as hydrogen peroxide, sodium percarbonate, or sodium perborate (d3) Bleaching activators such as tetraacetylethylenediamine and bleaching activators represented by general formulas (I-2) to (I-7) of JP-A-6-316700 (d4) one or more enzymes selected from cellulase, amylase, pectinase, protease, and lipase (d5) Fluorescent dyes, for example, fluorescent dyes commercially available as Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) (d6) Antioxidants such as butylated hydroxytoluene, distyrenated cresol, sodium sulfite, and sodium hydrogen sulfite (d7) Antifoaming agents such as colorants, fragrances, and silicones (d8) Surfactants other than components (a) and (b)

[0052] The treatment medium of the present invention may contain water. The treatment medium of the present invention may be a liquid composition containing component (a) and water. The water is used in an amount that is the remainder of the treatment medium of the present invention. From the viewpoint of suppressing biofilm formation, water that does not contain impurities and is appropriately purified is preferably used, but well water and industrial water can also be used. From the viewpoint of suppressing biofilm formation, tap water, purified water, and ion-exchanged water are preferred.

[0053] The pH of the treatment medium of the present invention may be, for example, 4 or more, further 5 or more, and 10 or less, further 8 or less. This pH may be the pH at the temperature of the treatment medium of the present invention when it is contacted with the fibers. It may also be the pH at 25°C measured by the following method. From the viewpoint of inhibiting biofilm formation, the lower the pH of the treatment medium of the present invention, the better.

[0054] [Method of measuring pH (25℃)] A composite electrode for pH measurement (HORIBA glass ground sleeve type) is connected to a pH meter (HORIBA pH / ion meter F-23) and the power is turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) is used as the internal solution of the pH electrode. Next, a 100 mL beaker is filled with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution), and the beaker is immersed in a thermostatic bath at 25°C for 30 minutes. The pH measurement electrode is immersed in the thermostatically adjusted standard solution for 3 minutes, and the calibration operation is performed in the order of pH 6.86 → pH 9.18 → pH 4.01. The sample (treatment medium) to be measured is adjusted to 25°C, the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

[0055] The treatment medium of the present invention may have a temperature of, for example, 5° C. or higher, further 20° C. or higher, and 40° C. or lower, further 30° C. or lower. This temperature may be the temperature of the treatment medium of the present invention when it is contacted with the fibers. From the viewpoint of inhibiting biofilm formation, a higher temperature is preferable.

[0056] The method for contacting the treatment medium of the present invention with the fibers is not particularly limited, but examples thereof include immersion, spraying, coating, and the like.

[0057] The method of spraying or applying the treatment medium of the present invention to fibers is preferably a method of filling a container with the treatment medium of the present invention and spraying the treatment medium onto the fibers to bring the treatment medium into contact with the fibers. When applying the treatment medium of the present invention to fibers, the treatment medium of the present invention may be applied directly to the fibers, or the treatment medium of the present invention may be supported on an applicator such as a cloth or a brush and applied to the fibers to bring the treatment medium into contact with the fibers.

[0058] Since a biofilm is a structure formed by a community of microorganisms such as bacteria and mold attached to the surface of a solid or liquid together with secretions, etc., in the present invention, it is preferable to contact the (a) component with a fiber under conditions in which the microorganisms act on the fiber, for example, to contact the (a) component with a fiber in the presence of the microorganisms. Therefore, the present invention may be a method for inhibiting the formation of a biofilm, in which a treatment medium containing the (a) component is contacted with a fiber in the presence of the microorganisms. The microorganisms may be present in any state, such as, for example, on the fiber (on the surface of the fiber and / or inside the fiber structure), in the treatment medium, in the biofilm, or in a combination thereof. When the treatment medium contains water, the microorganisms may be present in the water used to prepare the treatment medium. Also, the microorganisms may be present by being mixed in a state in which the treatment medium containing the (a) component is in contact with the fiber. Also, in the present invention, the treatment medium containing the (a) component may be contacted with a fiber in an environment in which the microorganisms can come into contact. Examples of the microorganisms include Rhodotorula, Methylobacterium, Roseomonas, Moraxella, Staphylococcus aureus, and Micrococcus.

[0059] The time for contacting the treatment medium of the present invention with the fibers may be, for example, 5 minutes or more, even 10 minutes or more, even 1 hour or more, and up to 1 day, even 15 hours or less, even 5 hours or less.

[0060] The fibers to be used in the present invention may be either hydrophobic or hydrophilic, but from the viewpoint of inhibiting biofilm formation, it is preferable to use hydrophobic fibers. 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.), 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.).

[0061] The fibers of interest in the present invention may be so-called textile products, such as fabrics, knitted fabrics, nonwoven fabrics, etc., using the hydrophobic or hydrophilic fibers, and products obtained using the same, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitted clothing, socks, underwear, tights, sheets, pillowcases, masks, etc.

[0062] In the present invention, from the viewpoint of inhibiting biofilm formation, the mass ratio of the amount of fiber to the amount of component (a), that is, fiber / component (a), is preferably from 20 to 400. It is preferable to adjust the contact amount of the treatment medium of the present invention and the concentration of component (a) in the treatment medium so as to achieve this mass ratio.

[0063] After contacting the fibers with the treatment medium of the present invention, the fibers may be appropriately rinsed with water, dried, and the like. EXAMPLES

[0064] The inhibitory effect of biofilm formation on fibers was evaluated using the following components (a), (a’), (b), and (c).

[0065] Component (a) · ES: Sodium polyoxyethylene alkyl (C10 - C16) ether sulfate, a compound represented by the general formula (a1 - 1), and the average number of moles of ethyleneoxy groups (EO) added is 2 moles. · APES: Polyoxyalkylene alkyl (C12 - C14) ether monoethanolamine salt, a compound represented by the general formula (a1 - 2). The alkyleneoxy group has an average addition mole number of 2 moles of propyleneoxy groups (PO) and 2 moles of ethyleneoxy groups (EO). R in the general formula (a1 - 2) 2 -O- is a compound in which PO and EO are block - bonded in this order · ApS: Sodium polyoxypropylene alkyl (C8 - C12) ether sulfate, a compound represented by the general formula (a1 - 2), and the average number of moles of propyleneoxy groups (PO) added is 0.6 moles · LAS: Sodium dodecylbenzenesulfonate, Neoperex G - 25 (Kao Corporation) · Cumene sulfonic acid: A mixture of Teikatox 565 (Teika Co., Ltd.) and KUALIMATE CSA 65 (Milligram Chemical Co., Ltd.) · C16IOS: Potassium salt of internal olefin sulfonic acid with 16 carbon atoms obtained in the following production example <Production example of C16IOS> C16IOS was obtained by using an internal olefin having a carbon number of 16, with reference to the method described in the manufacturing example of JP 2014-76988 A. The mass ratio of the olefin body (potassium olefin sulfonate) / hydroxy body (potassium hydroxyalkanesulfonate) in the obtained internal olefin sulfonate potassium salt of C16IOS was 17 / 83. The mass ratio of the position distribution of the sulfonic acid group of the hydroxy body in C16IOS was 1st position / 2nd position / 3rd position / 4th position / 5th position / 6th to 9th position=2.3% / 23.6% / 18.9% / 17.5% / 13.7% / 11.2% / 6.4% / 6.4% / 0% (total 100% by mass). In addition, (IO-1S) / (IO-2S)≒1.6 (mass ratio). Here, (IO-1S) / (IO-2S) is the mass ratio of the content of internal olefin sulfonate [(IO-1S)] in which the sulfonic acid group is located at the 2nd or more and the 4th or less position, to the content of internal olefin sulfonate [(IO-2S)] in which the sulfonic acid group is located at the 5th or more position. · C18IOS: Sodium salt of internal olefin sulfonate with 18 carbon atoms (The mass ratio of olefin form (sodium olefin sulfonate) / hydroxy form (sodium hydroxyalkanesulfonate) is 16 / 84. The mass ratio of the position distribution of sulfonic acid groups of the HAS form in (a-1) is as follows: 1st / 2nd / 3rd / 4th / 5th / 6th-9th = 1.5 / 22.1 / 17.2 / 21.8 / 13.5 / 23.9. In addition, (IO-1S) / (IO-2S) ≒ 1.6 (mass ratio).)

[0066] Component (a') (comparison component of component (a)) AS: Sodium alkyl (carbon number 12) sulfate ester

[0067] (b) Component C12E6: Polyoxyethylene (average number of moles added: 6) alkyl (carbon number: 12) ether C12 / C14E10: polyoxyethylene mixed alkyl ether, a mixed alkyl group in which the alkyl group has 12 carbon atoms / the alkyl group has 14 carbon atoms (7 / 3, mass ratio), the average number of moles of oxyethylene groups added is 10 moles MEE: Fatty acid methyl ester ethoxylate, fatty acid carbon number 16 to 18, average number of added ethyleneoxy groups 15 moles APE: polyoxypropylene-polyoxyethylene mixed alkyl ether, the alkyl group being a mixed alkyl group of alkyl group having 12 carbon atoms / alkyl group having 14 carbon atoms (7 / 3, mass ratio), polyoxypropylene group and polyoxyethylene group are block-bonded to the mixed alkyl group in this order, the average number of moles of oxypropylene group added is 3.7 moles, and the average number of moles of oxyethylene group added is 16.5 moles.

[0068] (c) Component Dichlosan: 4,4'-dichloro-2-hydroxydiphenyl ether

[0069] [Evaluation of biofilm formation inhibition effect] <Reagents used> Potato dextrose agar medium "Nissui" (Nihon Pharmaceutical Co., Ltd.) R2A medium "Daigo" (Nihon Pharmaceutical Co., Ltd.) Sodium chloride (FUJIFILM Wako Pure Chemical Corporation) 99.5% ethanol (FUJIFILM Wako Pure Chemical Industries, Ltd.)

[0070] <Bacterial strain used> Methylobacterium variabile B1 (Isolated from clothing)

[0071] <Equipment used> No.5 screw pipe (Maruem) Cotton plain weave fabric (Cotton 2003 (made by Tanigashira Shoten)) Chemical plain weave fabric (polyester faille (made by Tanigashira Shoten)) Spectrophotometer (APEL Co., Ltd. PD-303S) Constant temperature shaking incubator (TITEC) 0.20μm sterilized filter (ADVANTEC DISMIC-25CS) High-speed centrifuge (HIMAC manufactured by HITACHI) Microplate reader (TECAN Infinite (registered trademark) 200PRO)

[0072] <Experimental Method> (1) Pre-culture of the strain to be used 0.1 mL of a 10% glycerol suspension of the above strain stored at -80°C was smeared onto potato dextrose agar medium, spread with a Conlarge stick, and cultured at 30°C for 24 hours.

[0073] (2) Preparation of liquid medium 3.2 g of R2A liquid medium (Nihon Pharmaceutical Co., Ltd.) was dissolved in 1 L of ion-exchanged water, and the mixture was autoclaved at 121° C. for 15 minutes.

[0074] (3) Preparation of fabric Cloth (cotton 2003 (Tanigaishi Shoten) or synthetic fiber (polyester faille (Tanigaishi Shoten))) autoclaved at 121°C for 15 minutes was cut into a 3 cm square.

[0075] (4) Main operation Calcium chloride and magnesium chloride were added to the autoclaved R2A liquid medium in a mass ratio of 8:2 to adjust the hardness to 4°dH. 10mL of the R2A liquid medium with the hardness adjusted was placed in a No.5 screw tube (Maruemu), and the components in Tables 1 and 2 (hereinafter referred to as added components) were added so that the concentration in the medium was the treatment concentration in Tables 1 and 2. Colonies of the pre-cultured strain were scraped off and suspended in the R2A liquid medium with the hardness adjusted, and the turbidity was adjusted to 3.0 at a wavelength of 600 nm using a spectrophotometer (PD-303S), and 0.1mL of the bacteria were inoculated. One piece of cloth (0.1g) was placed in each screw tube with tweezers, the lid was closed, and the tube was placed in a thermostatic shaking incubator (TITEC), and cultured at 30°C, 200 rpm, for 15 hours.

[0076] <German hardness measurement method> The German hardness was measured by the following method. 〔reagent〕 0.01 mol / L EDTA·2Na solution: 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01M EDTA-Na2, 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) [Method of measuring hardness] First, 20 ml of the sample (autoclaved R2A liquid medium mixed with calcium chloride and magnesium chloride) was taken into a conical beaker with a volumetric pipette, and 2 ml of ammonia buffer solution for hardness measurement was added. Furthermore, 0.5 ml of Universal BT indicator was added, and it was confirmed that the solution after the addition was reddish purple. While shaking the conical beaker well, 0.01 mol / l EDTA·2Na solution was dropped from the burette, and the end point of the titration was when the sample turned blue. The total hardness in the sample was calculated from the titration volume T (mL) of the EDTA·2Na solution 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, sample volume) F: Factor of 0.01mol / L EDTA·2Na solution

[0077] (5) Washing and collection of fabric The cultured cloth was placed in a new No. 5 screw tube containing 10 mL of ion-exchanged water whose hardness had been adjusted to 4°dH in the same manner as above, and then placed in a thermostatic shaking incubator (TITEC) and washed at 25°C, 200 rpm for 5 minutes. The cloth was then removed and placed on a paper towel to remove excess water, and then dried in a safety cabinet for 1 hour.

[0078] (6) Calculation of the inhibition rate (%) of extracellular polymeric substances (EPS) formation The dried cloth was transferred to a 15 ml centrifuge tube, 2 mL of 1.5 M NaCl aqueous solution was added, and ultrasonic extraction was performed for 3 hours. The extract was filtered through a 0.20 μm sterilized filter (DISMIC-25CS), 3 mL of 99.5% ethanol that had been cooled to -80°C was added, and after mixing by inversion, it was cooled at -28°C for 1 hour. The cloth was centrifuged at 18,000 rpm, 4°C, for 15 minutes using a high-speed centrifuge (HIMAC). After discarding the supernatant, it was air-dried for 15 minutes, and 0.3 mL of ion-exchanged water was added to suspend the precipitate.

[0079] An equal amount of 5% aqueous phenol solution was added to 0.2 mL of the suspension, and the mixture was mixed using a vortex mixer. 1 mL of concentrated sulfuric acid was added, and the mixture was further mixed using a vortex mixer. The absorbance of the reaction solution at an excitation light of 492 nm was measured using a microplate reader (Infinite (registered trademark) 200PRO). At this time, a calibration curve of the glucose aqueous solution was prepared to determine the total sugar amount, which was used as the amount of extracellular polymeric substances (EPS). From the obtained amount of EPS, the EPS formation inhibition rate (%) was calculated using the following formula, and the biofilm formation inhibition effect was evaluated. The results are shown in Tables 1 and 2. In this evaluation, the higher the value of the EPS formation inhibition rate (%), the better the biofilm formation inhibition effect. EPS formation inhibition rate (%) = 100 - [(EPS amount with added ingredients) / (EPS amount without added ingredients) x 100]

[0080] [Table 1]

[0081] [Table 2]

[0082] Table 3 shows examples of the formulation of the treatment medium used by spraying and contacting the fibers. The components used in the formulation examples in Table 3 are as follows. Component (a): Sodium polyoxyethylene alkyl ether sulfate (alkyl group carbon number 10 to 16, average number of moles of oxyethylene added 2.4) Polyoxyethylene alkyl ether (alkyl group carbon number 6-16, average number of moles of oxyethylene added 4) Alkylamine oxide (alkyl group with carbon number of 10 to 18) pH adjuster: phosphate buffer

[0083] [Table 3]

Claims

1. (a) A method for inhibiting the formation of a biofilm on a fiber, comprising contacting a treatment medium containing one or more compounds selected from the following components (a1) to (a3), including component (a1) [hereinafter referred to as component (a)], with the fiber in the presence of microorganisms: Component (a1): a compound represented by the following general formula (a1-2): R 2 -O-[(PO) m1 / (EO) n2 ]-SO 3 M (a1-2) [In formula (a1-2), R2 represents an alkyl group having 8 to 22 carbon atoms, PO represents a propyleneoxy group, EO represents an ethyleneoxy group, PO and EO are block-type bonds or random-type bonds, / is a symbol indicating that the bonding order of PO and EO does not matter, m1 and n2 are the average molar numbers of PO and EO added, m1 is 0.5 to 5, n2 is 0 to 10, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium.] Component (a2): a compound represented by the following general formula (a-2): R ２ -B-SO ３ M (a-2) [In formula (a-2), R ２ represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium. ２ In contrast, the sulfonic acid group is bonded to the ortho, meta or para position. Component (a3): Internal olefin sulfonate having 14 to 24 carbon atoms

2. The method for inhibiting biofilm formation according to claim 1, wherein the component (a) is two or more compounds selected from the components (a1) to (a3) ​​and including the component (a1).

3. 3. The method for inhibiting biofilm formation according to claim 1 or 2, wherein the component (a) is selected from the component (a1) and the component (a2) and is two or more compounds including the component (a1).

4. The method for inhibiting biofilm formation according to claim 1, wherein in the general formula (a-2) of the component (a2), R 2 is an alkyl group having 8 to 21 carbon atoms.

5. A method for inhibiting the formation of a biofilm as described in claim 1 or 2, wherein the treatment medium contains component (a) at 10 ppm or more and 800 ppm or less.

6. The method for inhibiting biofilm formation according to claim 1 or 2, wherein the treatment medium contains (c) an antibacterial compound having an aromatic ring.

7. A method for inhibiting the formation of a biofilm as described in claim 6, wherein the antibacterial compound having an aromatic ring (c) is an antibacterial compound having a diphenyl ether skeleton, and the treatment medium contains the component (c) in an amount of 0.1 ppm or more and 10 ppm or less.

8. A method for inhibiting biofilm formation as described in claim 7, wherein the antibacterial compound having a diphenyl ether skeleton is diclosan.

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