JP2023066355A - Method for inhibiting biofilm formation - Google Patents

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

The present invention relates to a biofilm formation suppression method.

A biofilm is a structure formed by colonies of microorganisms such as bacteria and fungi adhering to the surfaces of solids and liquids together with secretions and the like. Biofilms generated in domestic or industrial drainage facilities, water circulation systems, etc. cause sliminess and clogging of pipes and bad odors. Biofilms also cause deterioration of equipment, such as corrosion of sewage pipes. In reverse osmosis membranes used in seawater desalination plants, piping equipment in paper mills, and the like, the harmful effects of biofilm formation are being viewed as a problem. Additionally, biofilms are a source of microbial contamination. Biofilms generated in hot spring facilities may cause infectious diseases. In the medical field, biofilms formed on medical instruments such as dialysis tubes, endoscopes, contact lenses and the like may become a source of infection. Biofilm formation on the skin and oral cavity can also cause disease. In the food industry, biofilms formed on food or cooking utensils can cause spoilage and food poisoning.

In addition to techniques for removing biofilms generated on various articles by methods such as washing, techniques for suppressing the formation of biofilms have been conventionally proposed.
For example, Patent Document 1 discloses a biofilm formation suppression method 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. ing.
In addition, US Pat. No. 6,200,000 discloses biofilm control agent compositions containing certain nonionic surfactants, enzymes, and optionally anionic surfactants.

JP 2009-78205 A JP 2008-156331 A

Among objects on which biofilms are formed, fibers may have biofilms formed not only on their surfaces but also inside their three-dimensional structures. 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, it is necessary to consider the surface and internal structure, cleaning mechanism, etc., unlike hard objects such as drainage equipment and the oral cavity. A different approach is required from the method of suppressing the formation of
The present invention provides a biofilm formation suppression method capable of effectively suppressing biofilm formation on fibers.

The present invention provides a method for inhibiting biofilm formation, wherein (a) a treatment medium containing one or more compounds selected from the following components (a1) to (a3) [hereinafter referred to as component (a)] is brought into contact with fibers. Regarding.
Component (a1): Compound R ¹ —O—[(PO) _m /(EO) _n ]—SO ₃ M (a-1) represented by the following general formula (a-1)
[In formula (a-1), R ¹ represents an alkyl group having 8 to 22 carbon atoms; PO represents a propyleneoxy group; EO represents an ethyleneoxy group; / is a symbol indicating that the bonding order of PO and EO does not matter, m and n are the average number of added moles of PO and EO, m is 0 or more and 5 or less, n is 0 or more and 10 m and n are never 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): Compound R ² —B—SO ₃ M (a-2) represented by the following general formula (a-2)
[In formula (a-2), R ² represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, M represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom), Indicates ammonium or organic ammonium. The sulfonic acid group is attached at the ortho-, meta- or para-position relative to ^R2 , which is attached to B. ]
(a3) component: internal olefin sulfonate having 14 to 24 carbon atoms

ADVANTAGE OF THE INVENTION According to this invention, the formation suppression method of the biofilm which can suppress effectively the formation of the biofilm in a fiber is provided.

In the biofilm formation suppression method of the present invention, a treatment medium containing one or more compounds selected from the above-mentioned (a1) to (a3) components as the component (a) (hereinafter also referred to as the treatment medium of the present invention). contact the fibers.

Examples of the component (a1) include compounds represented by the following general formula (a1-1) [hereinafter referred to as component (a1-1)].
R ¹ —O—(EO) _n1 —SO ₃ M (a1-1)
[In the formula (a1-1), R ¹ represents an alkyl group having 8 to 22 carbon atoms, EO represents an ethyleneoxy group, n1 is the average number of added moles of EO, and n1 is more than 0 and 10 and M represents a hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium, or organic ammonium. ]

The content of component (a1-1) in the present invention is based on the amount of the compound converted to sodium salt. That is, the concentration (ppm) and mass ratio are calculated from the amount of the compound in which M in the general formula (a1-1) is sodium.

From the viewpoint of suppressing biofilm formation, in formula (a1-1), R ¹ has 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. , more preferably 16 or less alkyl groups.

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

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 suppressing biofilm formation, preferably an alkali metal, the number of carbon atoms 2 or more and 6 or less alkanolammonium. Alkali metals include sodium and potassium. Alkaline earth metals include calcium and magnesium. Organic ammonium includes alkanolammonium such as monoethanolammonium, diethanolammonium and triethanolammonium.

Examples of the component (a1) include compounds represented by the following general formula (a1-2) [hereinafter referred to as component (a1-2)].
R ² —O—[(PO) _m1 /(EO) _n2 ]—SO ₃ M (a1-2)
[In the formula (a1-2), R ² represents an alkyl group having 8 to 22 carbon atoms; PO represents a propyleneoxy group; EO represents an ethyleneoxy group, EO and PO are a block type bond or a random type bond, m1 and n2 are the average addition mole numbers of PO and EO, m1 is 0.5 or more and 5 or less, n2 is 0 greater than or equal to 10, and M represents a hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium, or organic ammonium. ]

The content of component (a1-2) in the present invention is based on the amount of the compound in terms of sodium salt when n2 is 0, and monoethanolamine salt when n2 exceeds 0. That is, when n2 in general formula (a1-2) is 0, it is a compound in which M is sodium, and when n2 in general formula (a1-2) exceeds 0, M is monoethanolammonium. Concentration (ppm) and mass ratio are calculated from the amount of the compound.

In formula (a1-2), from the viewpoint of suppressing biofilm formation, R ² has 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. , more preferably 16 or less, even more preferably 14 or less.

In formula (a1-2), PO represents a propyleneoxy group, EO represents an ethyleneoxy group, and EO and PO are block-type bonds or random-type bonds. In formula (a1-2), PO and EO may be bonded in any order. A compound having a structure in which PO is bonded to R ² —O— in formula (a1-2) is one of preferred embodiments.
In formula (a1-2), m1 and n2 are the average added mole numbers of PO and EO.
In formula (a1-2), m1 is 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, from the viewpoint of suppressing biofilm formation. Below, it is more preferably a number of 2.5 or less.
In formula (a1-2), n2 is 0 or more, preferably 0.5 or more, more preferably 1 or more, still 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, still more preferably 3 or less.

In formula (a1-2), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), ammonium or organic ammonium, and from the viewpoint of suppressing biofilm formation, preferably an alkali metal having 2 carbon atoms. It is an alkanolammonium of more than or equal to 6 or less. Alkali metals include sodium and potassium. Alkaline earth metals include calcium and magnesium. Organic ammonium includes alkanolammonium such as monoethanolammonium, diethanolammonium and triethanolammonium.

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

Component (a1) may be one or more compounds selected from components (a1-1) and (a1-2).

Component (a2) is 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, M represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom), Indicates ammonium or organic ammonium. The sulfonic acid group is attached at the ortho-, meta- or para-position relative to ^R3 , which is attached to B. ]

The content of the compound represented by component (a2) in the present invention is based on the amount of the compound converted to sodium salt. That is, the concentration (ppm) and mass ratio are calculated from the amount of the compound in which M in the general formula (a2) is sodium.

In formula (a-2), from the viewpoint of suppressing biofilm formation, R ² has 3 or more carbon atoms, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, and It represents an alkyl group of 21 or less, preferably 18 or less, more preferably 16 or less, still more preferably 14 or less.

In formula (a-2), B represents a benzene ring, and the sulfonic acid group (--SO ₃ M) is bonded at the ortho-, meta- or para-position with respect to R ² bonding to B.

In formula (a-2), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), ammonium or organic ammonium, and from the viewpoint of suppressing biofilm formation, preferably an alkali metal having 2 carbon atoms. It is an alkanolammonium of more than or equal to 6 or less. Alkali metals include sodium and potassium. Alkaline earth metals include calcium and magnesium. Organic ammonium includes alkanolammonium such as monoethanolammonium, diethanolammonium and triethanolammonium.

Component (a3) is an internal olefin sulfonate having 14 to 24 carbon atoms.
The number of carbon atoms in component (a3) is the number of carbon atoms in the olefin portion, and is 14 or more, preferably 16 or more, and 24 or less, preferably 20 or less, from the viewpoint of suppressing biofilm formation.

Salts of component (a3) include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, organic ammonium salts, alkanols such as monoethanolammonium, diethanolammonium and triethanolammonium. Ammonium salts are mentioned. From the viewpoint of suppressing biofilm formation, alkaline earth metals and alkanolammonium having 2 to 6 carbon atoms are preferable.

In addition, content of the (a3) component in this invention is based on the amount of the compound converted into potassium salt.

From the viewpoint of suppressing biofilm formation, the component (a) is preferably one or more compounds containing the component (a1). As the component (a1), the component (a1-2) is preferable from the viewpoint of suppressing biofilm formation.

The component (a) may be two or more compounds selected from the components (a1) to (a3), or two or more compounds from the viewpoint of suppressing biofilm formation. Two or more compounds selected from components (a1) and (a2) are preferable from the viewpoint of biofilm formation suppression. Also in this case, it is preferable that the component (a1) is included as the component (a). As the component (a1), the component (a1-2) is preferable from the viewpoint of suppressing biofilm formation.

According to one aspect, the treatment medium of the present invention contains component (a) in an amount of preferably 10 ppm or more, more preferably 25 ppm or more, still more preferably 50 ppm or more, and even more preferably 100 ppm, from the viewpoint of suppressing biofilm formation. more preferably 150 ppm or more, still more preferably 250 ppm or more, still more preferably 350 ppm or more, still more preferably 450 ppm or more, still more preferably 550 ppm or more, and preferably 800 ppm or less, more preferably 700 ppm or less, More preferably, it contains 600 ppm or less. This content is preferred, for example, when the treatment medium of the invention is brought into immersion contact with the fibers.

According to another aspect, the treatment medium of the present invention preferably contains component (a) in an amount of 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 5% by mass, from the viewpoint of suppressing biofilm formation. % or more, preferably 15% by mass or less, more preferably 10% by mass or less. This content is preferred, for example, when the treatment medium of the invention is brought into contact with the fibers by spraying or painting them.

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

As the component (b), from the viewpoint of suppressing biofilm formation, one or more nonionic surfactants selected from fatty alcohol alkoxylates and aliphatic ester alkoxylates are preferred, and one selected from fatty acid methyl ester ethoxylates. The above nonionic surfactants are more preferred.

Examples of fatty alcohol alkoxylates include alkylene oxide adducts of fatty alcohols and their terminal methyl ether adducts.
From the viewpoint of suppressing biofilm formation, the aliphatic alcohol preferably has 9 or more carbon atoms, more preferably 10 or more carbon atoms, still more preferably 12 or more carbon atoms, and preferably 18 or less, more preferably 16 or less, and further Aliphatic alcohols having 14 or less aliphatic hydrocarbon groups are preferred. From the viewpoint of suppressing biofilm formation, the aliphatic alcohol is preferably a primary alcohol.
From the viewpoint of suppressing biofilm formation, the aliphatic hydrocarbon group includes an alkyl group or an alkenyl group, preferably an alkyl group.
From the viewpoint of suppressing biofilm formation, the aliphatic hydrocarbon group is linear or branched, preferably linear.
From the viewpoint of suppressing biofilm formation, the alkylene oxide is preferably one or more selected from ethylene oxide and propylene oxide. When the alkylene oxide contains ethylene oxide and propylene oxide, it may be block-bonded or random-bonded.
From the viewpoint of suppressing biofilm formation, the average number of added moles of the alkylene oxide is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, and preferably 70 or less, more preferably 50 or less, and further Preferably it is 30 or less.

Examples of aliphatic ester alkoxylates include alkylene oxide adducts of fatty acids and terminal methylated products thereof.
From the viewpoint of suppressing biofilm formation, the fatty acid preferably has 9 or more carbon atoms, more preferably 10 or more carbon atoms, still more preferably 12 or more carbon atoms, still more preferably 14 or more carbon atoms, and even more preferably 16 or more carbon atoms, and Fatty acids having preferably 20 or less, more preferably 18 or less aliphatic hydrocarbon groups are mentioned.
From the viewpoint of suppressing biofilm formation, the aliphatic hydrocarbon group includes an alkyl group or an alkenyl group, preferably an alkyl group.
From the viewpoint of suppressing biofilm formation, the aliphatic hydrocarbon group is linear or branched, preferably linear.
From the viewpoint of suppressing biofilm formation, the alkylene oxide is preferably one or more selected from ethylene oxide and propylene oxide, and more preferably ethylene oxide. When the alkylene oxide contains ethylene oxide and propylene oxide, it may be block-bonded or random-bonded.
From the viewpoint of suppressing biofilm formation, the average added mole number of the alkylene oxide is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, and preferably 50 or less, more preferably 35 or less, and further It is preferably 20 or less.
As the aliphatic ester alkoxylate, fatty acid methyl ester ethoxylate is preferable from the viewpoint of suppressing biofilm formation.

Component (b) includes nonionic surfactants represented by the following general formula (b-1).
R ^1b —(CO) _p O—(AO) _q —R ^2b (b-1)
[Wherein, 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 the number of 0 or 1, 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 a block type bond or a random type bond. good. q is the average number of added moles and is a number of 1 or more and 70 or less. ]

The carbon number of R ^1b 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, from the viewpoint of suppressing biofilm formation.
From the viewpoint of suppressing biofilm formation, R ^2b includes an alkyl group or an alkenyl group, preferably an alkyl group. From the viewpoint of suppressing biofilm formation, the aliphatic hydrocarbon group may be linear or branched, preferably linear.
From the viewpoint of suppressing biofilm formation, ^R2b is a hydrogen atom or a methyl group, preferably a hydrogen atom.

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

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

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 a block type bond or a random type bond. good.

Component (b) is an alkyleneoxy group having 2 carbon atoms, that is, an ethyleneoxy group (hereinafter sometimes referred to as an EO group) from the viewpoint of suppressing biofilm formation, the average degree of polymerization (or the average number of moles added). is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and preferably 70 or less, more preferably 50 or less, still more preferably 25 or less.

Component (b) is the average degree of polymerization (or the average number of added moles) of the alkyleneoxy group having 3 carbon atoms, that is, the propyleneoxy group (hereinafter sometimes referred to as the PO group) from the viewpoint of suppressing biofilm formation. is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more, and preferably 5 or less, more preferably 4 or less.

(b) When the component contains an EO group and a PO group, the EO group and the PO group may be a random or block bond, and from the viewpoint of suppressing biofilm formation, preferably a block bond, more preferably an alkyl ether EOPOEO order or POEO order block join.

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

When the treatment medium of the present invention contains the (b) component, according to one aspect, the treatment medium preferably contains 500 ppm or less of the (b) component from the viewpoint of suppressing biofilm formation. This content is preferred, for example, when the treatment medium of the invention is brought into immersion contact with the fibers.
Further, when the treatment medium of the present invention contains the (b) component, according to another aspect, the treatment medium contains the (b) component, preferably 0.1% by mass, from the viewpoint of suppressing biofilm formation. Above, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and from the viewpoint of detergency, preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 5% by mass or less contains. This content is preferred, for example, when the treatment medium of the invention is brought into contact with the fibers by spraying or painting them.

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

Regarding the component (c), the antibacterial compound is, for example, a cotton gold cloth #2003 that is uniformly coated with 1% by mass of the corresponding compound and tested for antibacterial properties by the method of JIS L 1902 "Antibacterial test method for textile products". It may be a compound that has been tested and shows a growth inhibition zone.

Component (c) includes an antibacterial compound having a diphenyl ether skeleton, an antibacterial compound selected from phenol derivatives, an antibacterial compound selected from benzoic acid derivatives, and the like. From the viewpoint of suppressing biofilm formation, an antibacterial compound having a diphenyl ether skeleton, for example, an antibacterial compound containing a halogen atom and having a diphenyl ether skeleton is preferred. Specific compounds include diclosan, triclosan, benzoic acid, paraben, and the like. Diclosan and triclosan are preferred from the viewpoint of suppressing biofilm formation, and diclosan is more preferred from the viewpoint of suppressing biofilm formation. .

When the treatment medium of the present invention contains component (c), the treatment medium preferably contains component (c) of 0.1 ppm or more, more preferably 0.25 ppm or more, from the viewpoint of suppressing biofilm formation. It is preferably 0.5 ppm or more, more preferably 1 ppm or more, and preferably 10 ppm or less, more preferably 5 ppm or less, and still more preferably 2.5 ppm or less.

The treatment medium of the present invention can contain the following components (d1) to (d8) as optional components other than components (b) and (c).
(d1) Anti-soil 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) Tetraacetylethylenediamine, JP-A-6- Bleach activators such as bleach activators represented by general formulas (I-2) to (I-7) of No. 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) Butylhydroxytoluene, distyrenated cresol, sulfurous acid Antioxidants such as sodium and sodium bisulfite (d7) Antifoaming agents such as dyes, perfumes and silicones (d8) Surfactants other than components (a) and (b)

The treatment medium of the present invention can contain water. The treatment medium of the present invention may be a liquid composition containing component (a) and water. Water is used in the balance amount of the treatment medium of the present invention. From the viewpoint of suppressing biofilm formation, water that is moderately purified without containing impurities is preferably used, but well water and industrial water can also be used. Water is preferably tap water, purified water, or ion-exchanged water from the viewpoint of suppressing biofilm formation.

The treatment medium of the present invention may have a pH of, for example, 4 or higher, further 5 or higher, and 10 or lower, further 8 or lower. This pH may be the pH at the temperature of the treatment medium of the invention when it contacts the fiber. Moreover, it may be the pH at 25° C. measured by the following method. From the viewpoint of suppressing biofilm formation, the treatment medium of the present invention preferably has a low pH.

[Method for measuring pH (25°C)]
A pH meter (pH/ion meter F-23, manufactured by HORIBA) is connected to a combined electrode for pH measurement (glass-sliding sleeve type, manufactured by HORIBA), and the power is turned on. A saturated potassium chloride aqueous solution (3.33 mol/L) is used as the pH electrode internal liquid. Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) are each filled in a 100 mL beaker, and 25 C. for 30 minutes. A pH measuring electrode is immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibrated in the order of pH 6.86→pH 9.18→pH 4.01. A 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.

The treatment medium of the present invention may have a temperature of, for example, 5° C. or higher, even 20° C. or higher, and 40° C. or lower, even 30° C. or lower. This temperature may be at the temperature of the treatment medium of the invention when it contacts the fibers. From the viewpoint of suppressing biofilm formation, the higher the temperature, the better.

The method of bringing the treatment medium of the present invention into contact with the fibers is not particularly limited, but includes, for example, methods such as immersion, spraying, and coating.

The method of spraying or applying the treatment medium of the present invention to the fibers is preferably a method of filling the treatment medium of the present invention in a container with a sprayer and spraying the treatment medium onto the fibers to bring the treatment medium into contact with the fibers. . When the treatment medium of the present invention is applied 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 applied to the fibers by applying the treatment medium of the present invention to an applicator such as a cloth or brush. The treatment medium may be brought into contact with the fibers by application.

A biofilm is a structure formed by a colony of microorganisms such as bacteria and fungi adhering to the surface of a solid or liquid together with secretions. ) component is contacted with the fiber, for example, component (a) is preferably contacted with the fiber in the presence of microorganisms. Therefore, the present invention may also be a method for inhibiting biofilm formation, comprising bringing a treatment medium containing the component (a) into contact with fibers in the presence of microorganisms. Microorganisms are present in any state, e.g., present on the fiber (on the surface of the fiber and/or within the fiber structure), present in the treatment medium, present in biofilms, present in combinations thereof, and the like. You may have If the treatment medium contains water, the microorganisms may be present in the water used to prepare the treatment medium. In addition, the microbes may be present when the fibers are in contact with the treatment medium containing the component (a). Further, in the present invention, the treatment medium containing the component (a) may be brought into contact with the fibers in an environment where microorganisms can come into contact.
Examples of microorganisms include Rhodotorula, Methylobacterium, Roseomonas, Moraxella, Staphylococcus aureus, and Micrococcus.

The duration of contact of the treatment medium of the invention with the fibers may be, for example, 5 minutes or more, even 10 minutes or more, even 1 hour or more, and 1 day or less, even 15 hours or less, even 5 hours or less.

The fibers targeted by the present invention may be either hydrophobic fibers or hydrophilic fibers, but from the viewpoint of suppressing biofilm formation, hydrophobic fibers are preferably included. Examples of hydrophobic fibers include protein fibers (milk protein casein fiber, Promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers, etc. 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 (such as polycleral) are exemplified. Hydrophilic fibers include, for example, seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (manila hemp, sisal hemp, etc.), palm fibers, rush, Straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silk, wild silk), feathers, cellulose fibers (rayon, polynosic, cupra, acetate, etc.), etc. exemplified.

Also, the fibers targeted by the present invention may be so-called textile products. Textile products include fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics using the above-mentioned hydrophobic fibers and hydrophilic fibers, and undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, and towels obtained using the same. , knitted clothing, socks, underwear, tights, sheets, pillowcases, masks and other products.

In the present invention, the mass ratio of the amount of fiber to the amount of component (a), that is, fiber/(a) component, is preferably 20 or more and 400 or less from the viewpoint of suppressing biofilm formation. 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.

After contact with the treatment medium of the present invention, the fibers may be rinsed with water, dried, etc., as appropriate.

The following components (a), (a'), (b), and (c) were used to evaluate the effect of suppressing biofilm formation on fibers.

(a) Component ES: Polyoxyethylene alkyl (C 10-16) ether sulfate sodium salt, compound represented by general formula (a1-1), average number of added moles of ethyleneoxy group (EO): 2 mol ,
・APES: polyoxyalkylene alkyl (12 to 14 carbon atoms) ether sulfate monoethanolamine salt, a compound represented by the general formula (a1-2), wherein the alkyleneoxy group is the average addition of the propyleneoxy group (PO) A compound having a mole number of 2 moles, an average added mole number of ethyleneoxy groups (EO) of 2 moles, and having PO and EO block-bonded to R ² —O— in the general formula (a1-2) in this order. ApS: polyoxypropylene alkyl (carbon number 8-12) ether sulfate sodium salt, compound represented by general formula (a1-2), average added mole number of propyleneoxy group (PO) is 0.6 mol LAS: Sodium dodecylbenzenesulfonate, Neopelex G-25 (Kao Corporation)
・Cumene sulfonic acid: a mixture of Teikatox 565 (Tayka Corporation) and KUALIMATE CSA 65 (Kyoke Chemical Co., Ltd.) ・C16IOS: internal olefin sulfonic acid potassium salt having 16 carbon atoms obtained in the following production example <C16IOS Production example of>
C16IOS was obtained by using an internal olefin having 16 carbon atoms and referring to the method described in the production example of JP-A-2014-76988. The mass ratio of olefin (potassium olefinsulfonate)/hydroxy (potassium hydroxyalkanesulfonate) in the internal olefinsulfonate potassium salt of C16IOS obtained was 17/83. The mass ratio of the positional distribution of the sulfonic acid group of the hydroxy form in C16IOS is 1-position/2-position/3-position/4-position/5-position/6-9-position=2.3%/23.6%/18.9. %/17.5%/13.7%/11.2%/6.4%/6.4%/0% (100% by mass in total). Also, (IO-1S)/(IO-2S)≈1.6 (mass ratio). (IO-1S)/(IO-2S) is the content of the internal olefin sulfonate [(IO-1S)] in which the sulfonic acid group is present at the 2-position or higher and the 4-position or lower, and the content of the sulfonic acid group is 5 It is the mass ratio to the content of the internal olefin sulfonate [(IO-2S)] present at the position or higher.
C18IOS: Sodium salt of internal olefin sulfonate having 18 carbon atoms [The mass ratio of olefin (sodium olefin sulfonate)/hydroxy (sodium hydroxyalkanesulfonate) is 16/84. The mass ratio of the positional distribution of the sulfonic acid group 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. Also, (IO-1S)/(IO-2S)≈1.6 (mass ratio). ]

(a′) component (comparative component of (a) component)
・AS: Alkyl (12 carbon atoms) sulfate sodium salt

(b) Component C12E6: polyoxyethylene (average addition number of moles 6) alkyl (carbon number 12) ether C12/C14E10: polyoxyethylene mixed alkyl ether, alkyl group having 12 carbon atoms / Mixed alkyl group of alkyl groups (7/3, mass ratio), average addition mole number of oxyethylene group is 10 mol MEE: fatty acid methyl ester ethoxylate, fatty acid with 16 to 18 carbon atoms, average addition of ethyleneoxy group 15 moles APE: polyoxypropylene/polyoxyethylene mixed alkyl ether, wherein the alkyl group is a mixed alkyl group of an alkyl group having 12 carbon atoms/an alkyl group having 14 carbon atoms (7/3, mass ratio), A polyoxypropylene group and a polyoxyethylene group are block-bonded to the mixed alkyl group in that order, and the average number of added moles of the oxypropylene group is 3.7 moles and the average number of added moles of the oxyethylene group is 16.5 moles.

(c) Component Diclosan: 4,4'-dichloro-2-hydroxydiphenyl ether

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

<Bacterial strain used>
Methylobacterium variabile B1 (clothing isolate)

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

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

(2) Preparation of Liquid Medium 3.2 g of R2A liquid medium (Nihon Pharmaceutical Co., Ltd.) was dissolved in 1 L of deionized water, and autoclaved at 121° C. for 15 minutes.

(3) Preparation of cloth
A cloth (cotton 2003 (manufactured by Tanigashira Shoten) or synthetic fiber (polyester faille (manufactured by Tanigashira Shoten)) autoclaved at 121° C. for 15 minutes was cut into 3 cm squares.

(4) Main operation Calcium chloride and magnesium chloride were added to an autoclaved R2A liquid medium at a mass ratio of 8:2 to adjust the hardness to 4°dH. Put 10 mL of R2A liquid medium with adjusted hardness into No.5 screw tube (manufactured by Maruem), and adjust the concentration in the medium to the treatment concentration shown in Tables 1 and 2. ) was added. A colony of the pre-cultured strain was scraped off, suspended in R2A liquid medium with adjusted hardness, adjusted to a turbidity of 3.0 at a wavelength of 600 nm using a spectrophotometer (PD-303S), and inoculated in 0.1 mL increments. . One piece of cloth (0.1 g) was put into each screw tube with tweezers, the lid was closed, the tube was placed in a constant temperature shaking incubator (manufactured by TITEC), and cultured at 30° C., 200 rpm for 15 hours.

<Method for measuring German hardness>
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 (solution for titration, 0.01 MEDTA-Na, manufactured by SIGMA-ALDRICH)
・Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories)
- Ammonia buffer solution for hardness measurement (solution of 67.5 g of ammonium chloride dissolved in 570 ml of 28 w/v% ammonia water and made up to 1000 ml with deionized water)
[Method for measuring hardness]
First, 20 ml of a sample (a mixture of calcium chloride and magnesium chloride in an autoclaved R2A liquid medium) was collected in a conical beaker with a whole pipette, and 2 ml of ammonia buffer for hardness measurement was added. Furthermore, 0.5 ml of UniversalBT indicator was added, and it was confirmed that the solution after the addition was reddish purple.
While shaking the conical beaker well, a 0.01 mol/l EDTA.2Na solution was added dropwise from a burette, and the titration was terminated when the sample turned blue. From the titration amount T (mL) of the EDTA/2Na solution, the total hardness in the sample was determined by the following formula.
Hardness (°dH) = (T x 0.01 x F x 56.0774 x 100)/A
T: Titration volume (mL) of 0.01mol/L EDTA/2Na solution
A: sample volume (20 mL, sample volume)
F: Factor of 0.01mol/L EDTA/2Na solution

(5) Washing and recovery of the cloth The cloth after culture is put into a new No. 5 screw tube containing 10 mL of deionized water whose hardness has been adjusted to 4 ° dH by the same method as above, and the constant temperature shaking incubator ( TITEC) and washed at 25°C, 200 rpm for 5 minutes. The cloth was removed, placed on a paper towel to remove excess moisture, and dried in a safety cabinet for 1 hour.

(6) Calculation of Extracellular Polymeric Substance (EPS) Formation Inhibition Rate (%) 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 sterilizing filter (DISMIC-25CS), 3 mL of 99.5% ethanol cooled at −80° C. was added, mixed by inversion, and then cooled at −28° C. for 1 hour. Centrifugation was performed 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.

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

Table 3 shows formulation examples 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 with 10 to 16 carbon atoms, average number of moles of oxyethylene added: 2.4)
・Polyoxyethylene alkyl ether (alkyl group with 6 to 16 carbon atoms, average number of added moles of oxyethylene: 4)
- Alkylamine oxide (alkyl group with 10 to 18 carbon atoms)
・pH adjuster: Phosphate buffer

Claims (5)

(a) A method for inhibiting biofilm formation, comprising 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): Compound R ¹ —O—[(PO) _m /(EO) _n ]—SO ₃ M (a-1) represented by the following general formula (a-1)
[In formula (a-1), R ¹ represents an alkyl group having 8 to 22 carbon atoms; PO represents a propyleneoxy group; EO represents an ethyleneoxy group; / is a symbol indicating that the bonding order of PO and EO does not matter, m and n are the average number of added moles of PO and EO, m is 0 or more and 5 or less, n is 0 or more and 10 m and n are never 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): Compound R ² —B—SO ₃ M (a-2) represented by the following general formula (a-2)
[In formula (a-2), R ² represents an alkyl group having 3 to 21 carbon atoms, B represents a benzene ring, M represents a hydrogen atom, an alkali metal, or an alkaline earth metal (1/2 atom), Indicates ammonium or organic ammonium. The sulfonic acid group is attached at the ortho-, meta- or para-position relative to ^R2 , which is attached to B. ]
(a3) component: internal olefin sulfonate having 14 to 24 carbon atoms The method for inhibiting biofilm formation according to claim 1, wherein the component (a) is two or more compounds selected from components (a1) to (a3). The method for inhibiting biofilm formation according to claim 1 or 2, wherein the component (a) is two or more compounds selected from components (a1) and (a2). The biofilm formation suppression method according to any one of claims 1 to 3, wherein the component (a1) is a compound represented by the following general formula (a1-2).
R ² —O—[(PO) _m1 /(EO) _n2 ]—SO ₃ M (a1-2)
[In the formula (a1-2), R ² represents an alkyl group having 8 to 22 carbon atoms; PO represents a propyleneoxy group; EO represents an ethyleneoxy group, EO and PO are a block type bond or a random type bond, m1 and n2 are the average addition mole numbers of PO and EO, m1 is 0.5 or more and 5 or less, n2 is 0 greater than or equal to 10, and M represents a hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium, or organic ammonium. ] The biofilm formation suppression method according to any one of claims 1 to 4, wherein the treatment medium contains (c) an antibacterial compound having an aromatic ring.