Agent for suppressing airborne deposition of bacteria and / or viruses

Abstract

To provide an agent for suppressing airborne deposition, which is capable of suppressing the airborne deposition of bacteria and / or viruses to the surface of an object when applied thereto, as well as a method for suppressing the airborne deposition of bacteria and / or viruses using the agent for suppressing airborne deposition.SOLUTION: The present invention provides an agent for suppressing the airborne deposition of bacteria and / or viruses that comprises particles composed of pseudo-polyrotaxane and / or polyrotaxane, as well as a method for suppressing the airborne deposition of bacteria and / or viruses using the agent for suppressing airborne deposition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an agent for inhibiting airborne adhesion of bacteria and / or viruses. [Background technology]

[0002] When bacteria and / or viruses adhere to a solid surface, the bacteria and / or viruses adhered to the solid surface grow and form a biofilm. Since the work of removing bacteria and / or viruses adhered to a solid surface and a biofilm formed on a solid surface is time-consuming and costly, there is an increasing demand for an adhesion inhibitor that can suppress the adhesion of bacteria and / or viruses to a solid surface. For example, Patent Document 1 discloses a microbial adhesion inhibitor that contains a polymer having pendant groups in its side chains that contain at least carbon, hydrogen, and oxygen atoms and have a total atomic weight of 100 or more, with the aim of providing a microbial adhesion inhibitor that has excellent microbial adhesion inhibitory ability, has little impact on the environment, and can be manufactured at low cost. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2012-1694 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the technology of Patent Document 1 does not consider the inhibition of adhesion of bacteria and / or viruses in the air. An object of the present invention is to provide an under-air adhesion inhibitor that can be applied to a surface of an object to inhibit adhesion of bacteria and / or viruses to the surface of an object in the air, and a method for inhibiting adhesion of bacteria and / or viruses in the air using the under-air adhesion inhibitor. [Means for solving the problem]

[0005] The present inventors have found that the above problems can be solved by an agent for inhibiting adhesion of bacteria and / or viruses using particles composed of pseudopolyrotaxane and / or polyrotaxane. That is, the present invention provides the following [1] and [2]. [1] An agent for inhibiting airborne adhesion of bacteria and / or viruses, which contains particles composed of pseudopolyrotaxane and / or polyrotaxane. [2] A method for inhibiting airborne adhesion of bacteria and / or viruses, comprising applying the airborne adhesion inhibitor of bacteria and / or viruses described in [1] to a target surface. Here, the air-under-air adhesion inhibitor of bacteria and / or viruses of the present invention can inhibit adhesion of bacteria and / or viruses under air (atmospheric pressure) to the surface of an object to which the air-under-air adhesion inhibitor is applied. Therefore, the airborne adhesion inhibitor of bacteria and / or viruses of the present invention is an adhesion inhibitor of bacteria and / or viruses that is applied to the surface of a target object, and is different from an inhibitor that inhibits adhesion of bacteria and / or viruses in a liquid to the surface of a target object to which the adhesion inhibitor is applied. Effect of the Invention

[0006] The present invention provides an air-based adhesion inhibitor that can be applied to the surface of an object to inhibit adhesion of bacteria and / or viruses to the surface of the object in the air, and a method for inhibiting air-based adhesion of bacteria and / or viruses using the air-based adhesion inhibitor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Hereinafter, an embodiment of the present invention will be described. In this specification, "X to Y" indicating a range means "X or more and Y or less". In this specification, the upper and lower limits of the numerical range can be arbitrarily combined. In this specification, when there are a plurality of substituents or linking groups, etc., indicated by specific symbols (hereinafter referred to as "substituents, etc."), the respective substituents, etc. may be the same or different from each other. In this specification, the components contained in the air-borne adhesion inhibitor of bacteria and / or viruses (essential components) and the components that may be contained therein (optional components) may be used alone or in combination of two or more.

[0008] [An agent for inhibiting airborne adhesion of bacteria and / or viruses] The air-based adhesion inhibitor of bacteria and / or viruses of the present invention contains pseudopolyrotaxane and / or particles composed of polyrotaxane. Hereinafter, the "air-based adhesion inhibitor of bacteria and / or viruses" may be simply referred to as the "air-based adhesion inhibitor." By applying the adhesion inhibitor under air of the present invention to the surface of an object under air, it is possible to inhibit adhesion of bacteria and / or viruses to the surface of the object under air. The mechanism by which such an effect is exerted is not clear, but is presumed to be as follows. Particles formed by associating pseudopolyrotaxanes and / or polyrotaxanes by crystallizing cyclic molecules constituting the pseudopolyrotaxanes and / or polyrotaxanes have dense chain polymers constituting the pseudopolyrotaxanes and / or polyrotaxanes. When the particles are applied to the surface of a target object, one end of the chain polymer conforms to the shape of the target surface to form a thin polymer film that is firmly attached to the surface, and it is presumed that the other end of the chain polymer can contribute to inhibiting airborne adhesion of bacteria and / or viruses.

[0009] [Particles composed of pseudopolyrotaxane and / or polyrotaxane] The air-based adhesion inhibitor of the present invention contains particles composed of pseudopolyrotaxane and / or polyrotaxane. The "particles composed of pseudopolyrotaxane and / or polyrotaxane" refer to particles in which pseudopolyrotaxane and / or polyrotaxane cyclic molecules are crystallized and pseudopolyrotaxane and / or polyrotaxane form an aggregate (particles which are aggregates of pseudopolyrotaxane and / or polyrotaxane). The term "pseudopolyrotaxane" refers to a supramolecular polymer in which a single chain polymer threads multiple cyclic molecules, and includes a molecule in which a bulky moiety (blocking group) is bonded to only one end of the chain polymer, and a supramolecular polymer in which no bulky moieties (blocking groups) are bonded to both ends of the chain polymer. "Polyrotaxane" refers to a supramolecular polymer in which a single chain polymer threads multiple cyclic molecules, and bulky moieties (blocking groups) are bonded to both ends of the chain polymer, preventing the chain polymer from detaching from the cyclic molecule due to steric hindrance. From the viewpoint of inhibiting adhesion of bacteria and / or viruses in the air, the air-based adhesion inhibitor of the present invention preferably contains particles composed of a pseudopolyrotaxane, and more preferably contains particles composed of a pseudopolyrotaxane that does not have blocking groups at both ends.

[0010] Specific examples of blocking groups include a dinitrophenyl group, a cyclodextrin group, an adamantane group, a trityl group, a fluorescein group, and a pyrene group. The blocking group can be introduced into the chain polymer by a conventional method.

[0011] Examples of the shape of the particles composed of the pseudopolyrotaxane and / or polyrotaxane include a spherical shape, a cylindrical shape, an elliptical shape, a substantially cubic shape, a polygonal shape, a columnar shape, a plate shape, and a needle shape. From the viewpoint of improving the adhesion and tracking ability to the target surface and more effectively suppressing the adhesion of bacteria and / or viruses to the target surface in air, a plate shape is preferred. The maximum diameter of the particles composed of pseudopolyrotaxane and / or polyrotaxane is preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 1.5 μm or more, and is preferably 15 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, from the viewpoint of improving the adhesion and tracking ability to the target surface and more effectively suppressing the adhesion of bacteria and / or viruses to the target surface in air. The maximum diameter is a value obtained by the measurement method described in the Examples.

[0012] When the particles composed of pseudopolyrotaxane and / or polyrotaxane are plate-shaped, they are preferably nanosheets from the viewpoint of improving the adhesion and tracking ability to the target surface and more effectively suppressing the adhesion of bacteria and / or viruses to the target surface in air. Hereinafter, the nanosheet composed of pseudopolyrotaxane and / or polyrotaxane is also simply referred to as "nanosheet". In this specification, "nanosheet" means a plate-shaped particle having a thickness of 200 nm or less and an aspect ratio of 5 or more.

[0013] The thickness of the nanosheet is 200 nm or less, and from the viewpoint of improving the adhesion and tracking ability to the target surface and more effectively suppressing adhesion of bacteria and / or viruses to the target surface in air, the thickness is preferably 2 nm or more, more preferably 6 nm or more, even more preferably 10 nm or more, and is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 20 nm or less. The thickness of the nanosheet is a value obtained by the measurement method described in the Examples. With the z-axis direction being the thickness direction of the nanosheet, the longest length in the x- and y-axis directions of the nanosheet is preferably 0.1 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, and is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less. The longest length in the x- and y-axis directions is a value obtained by the measurement method described in the Examples. The aspect ratio of the nanosheet (the value obtained by dividing the longest length of the nanosheet in the x and y axes by the nanosheet's thickness (length in the z axis direction) (longest length of the nanosheet in the x and y axes directions / thickness of the nanosheet (length in the z axis direction))) is 5 or more, and from the viewpoint of improving adhesion and tracking to the target surface and more effectively suppressing adhesion of bacteria and / or viruses to the target surface in air, it is preferably 50 or more, more preferably 100 or more, and is preferably 1500 or less, more preferably 900 or less, and even more preferably 500 or less. The aspect ratio of the nanosheet is a value obtained by the measurement method described in the Examples. In addition, when the nanosheet is, for example, a plate-like sheet with a thickness of 20 nm, a length of 3 μm, and a width of 2 μm (xy plane is rectangular), the length of the diagonal of the rectangle (3.6 μm) is the longest length in the xy axis directions of the nanosheet, and the aspect ratio is 180. In addition, when the nanosheet is, for example, a plate-like sheet with a thickness of 20 nm and an xy plane that is an ellipse with a longest diameter of 3 μm, the longest diameter of 3 μm is the longest length in the xy axis directions, and the aspect ratio is 150.

[0014] <Cyclic molecules> Examples of cyclic molecules constituting the pseudopolyrotaxane and polyrotaxane include cyclodextrin, crown ether, pillararene, calixarene, cyclophane, cucurbituril, and cyclic amide, as well as derivatives thereof. From the viewpoint of ease of production of particles composed of the pseudopolyrotaxane and / or polyrotaxane, cyclodextrin is preferred.

[0015] Specific examples of cyclodextrin include α-cyclodextrin (α-CD, number of hydroxyl groups: 18) in which six D-glucose units are bound, β-cyclodextrin (β-CD, number of hydroxyl groups: 21) in which seven D-glucose units are bound, and γ-cyclodextrin (γ-CD, number of hydroxyl groups: 24) in which eight D-glucose units are bound.

[0016] The term "cyclodextrin derivative" refers to a compound having a structure in which a part of the cyclodextrin molecule is substituted with another organic group. As the cyclodextrin derivative, a compound in which at least one of the hydroxyl groups selected from the 2-, 3-, and 6-positions of the D-glucose constituting the cyclodextrin is substituted with a substituent is preferred. Examples of the substituent include hydroxyalkyl groups such as a hydroxyethyl group and a hydroxypropyl group, alkyl groups such as a methyl group and an ethyl group, amino groups, quaternary ammonium groups such as a trimethylammonium group and a trimethylammoniummethyl group, aminoalkyl groups such as an aminomethyl group, carboxymethyl groups, sulfoxyl groups, sulfoxyethyl groups, saturated or unsaturated acyl groups, and glucosyl groups.

[0017] Specific examples of β-cyclodextrin derivatives include maltosyl β-CD (G2-β-CD) and hydroxypropyl-β-CD (HP-β-CD), in which one or more glucose residues, galactosyl groups, hydroxypropyl groups, etc. are linked to β-CD as side chains. Specific examples of γ-cyclodextrin derivatives include alkylated γ-CDs such as 2,6-di-O-methyl-γ-cyclodextrin, 2,3,6-tri-O-methyl-γ-cyclodextrin, 2,6-di-O-ethyl-γ-cyclodextrin, and 2,3,6-tri-O-ethyl-γ-cyclodextrin; hydroxyalkylated γ-CDs such as 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, and 2,3-dihydroxypropyl-γ-cyclodextrin; acylated γ-CDs such as 2,3,6-tri-O-acetyl-γ-cyclodextrin; sugar-modified γ-CDs such as 6-O-α-D-glucosyl-γ-cyclodextrin and 6-O-α-maltosyl-γ-cyclodextrin; and polymers such as poly-γ-cyclodextrin.

[0018] Among these, from the viewpoints of ease of production of particles composed of pseudopolyrotaxane and / or polyrotaxane, and suppression of adhesion in air, β-cyclodextrin and γ-cyclodextrin are preferred.

[0019] The cyclodextrin or its derivative may be a commercially available product, or may be synthesized by a known production method described in various publications, etc. The cyclodextrin or its derivative may be used alone or in combination of two or more kinds.

[0020] <Chain polymer> The pseudopolyrotaxane and the linear polymer constituting the polyrotaxane are not particularly limited as long as they can form the pseudopolyrotaxane or the polyrotaxane by penetrating the cyclic molecule. From the viewpoint of suppressing adhesion of bacteria and / or viruses in air, it is preferable that the linear polymer constituting the pseudopolyrotaxane has a triblock structure of (A1) block-(B) block-(A2) block, and the linear polymer constituting the polyrotaxane has a triblock structure of (A'1) block-(B') block-(A'2) block.

[0021] The (A1) block, the (A2) block, the (A'1) block and the (A'2) block may be either an organic chain (a molecular chain made of an organic substance) or an inorganic chain (a molecular chain made of an inorganic substance), with the organic chain being preferred. Specific examples of the compound that leads to an organic chain include polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyethyleneimine, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylpyrrolidone, polymethacryloyloxyethyl phosphorylcholine, polymethacryloyloxyethyl carboxybetaine, and poly 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid, of which polyethylene glycol and polypropylene glycol are preferred, and polyethylene glycol is more preferred. The above compounds may be used alone or in combination of two or more. When the (A1) block, the (A2) block, the (A'1) block and the (A'2) block are organic chains and the compound leading to the organic chains contains an ethyleneoxy group, the average number of moles of ethyleneoxy groups added in the organic chain is, from the viewpoint of suppressing adhesion of bacteria and / or viruses in the air, preferably 2 or more, more preferably 5 or more, even more preferably 10 or more, and is preferably 200 or less, more preferably 150 or less, even more preferably 100 or less.

[0022] Compounds which lead to the (B) block and the (B') block include polyethylene glycol, polyoxytrimethylene, polytetrahydrofuran, polypropylene glycol, polymethylvinyl ether, polyethylvinyl ether, polyethyleneimine, polyiminoundecamethylene, polyε-lysine, polyboranephiphile, polyviologen, polyethylene adipate, polytrimethylene adipate, poly1,4-butylene adipate, polyε-caprolactone, polyε-lactide, polyethylvinyl ether, poly3-hydroxybutyrate, polyε-caprolactone-block-ester, poly(3-hydroxybutyrate), ... Examples of the block copolymer include ethylene oxide-block-ε-caprolactone, polyε-caprolactone-block-lactic acid, polyε-caprolactone-block-polypropylene glycol-block-ε-caprolactone, oligoethylene, polypropylene, polyisobutene, squalane, polybutadiene, polyisoprene, nylon 11, nylon 6, polydialkylsiloxane such as polydimethylsiloxane, polydimethylsilane, poly(meth)acrylic acid ester, poly(meth)acrylic acid amide, and derivatives thereof, with polypropylene glycol and polydialkylsiloxane being preferred. The number average molecular weight of these compounds is preferably 500 or more, more preferably 1000 or more, even more preferably 1500 or more, and is preferably 1,000,000 or less, more preferably 100,000 or less, even more preferably 20,000 or less. The above compounds may be used alone or in combination of two or more.

[0023] It is preferable that "(A1) block-(B) block-(A2) block" is in a form in which "a compound leading to an organic chain", "a compound leading to a (B) block", and "a compound leading to an organic chain" are covalently bonded. It is also preferable that "(A'1) block-(B') block-(A'2) block" is in a form in which "a compound leading to an organic chain", "a compound leading to a (B') block", and "a compound leading to an organic chain" are covalently bonded.

[0024] From the viewpoint of more firmly adhering the adhesion inhibitor of the present invention under air to the surface of an object and more effectively suppressing adhesion of bacteria and / or viruses to the surface of an object under air, it is preferable that the chain polymer constituting the pseudopolyrotaxane and polyrotaxane has a functional group at one end or both ends, preferably at both ends. Specific examples of the functional group include a hydroxy group, a methoxy group, a carboxy group, a sulfo group, a phosphate group, an amino group, a quaternary ammonium group, and a betaine group (e.g., a sulfobetaine group, a carboxybetaine group), and a carboxy group is preferable. The functional groups at the ends of each chain polymer may be the same or different.

[0025] In the adhesion inhibitor under air of the present invention, from the viewpoint of inhibiting adhesion of bacteria and / or viruses under air, the pseudopolyrotaxane and / or the linear polymer constituting the polyrotaxane is preferably a compound represented by the following general formula (1) or (2). Furthermore, in a form in which the adhesion inhibitor under air of the present invention contains a dispersion medium, from the viewpoint of inhibiting adhesion of bacteria and / or viruses under air and from the viewpoint of maintaining the ability to inhibit adhesion under air of particles composed of the pseudopolyrotaxane and / or polyrotaxane for a long period of time, the linear polymer constituting the pseudopolyrotaxane and / or polyrotaxane is more preferably a compound represented by the following general formula (1).

[0026] [ka]

[0027] In general formula (1), R 1 ~R 6each independently represents an alkyl group having 1 to 3 carbon atoms; R 7 and R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxy group, a sulfo group, a phosphate group, an amino group, a quaternary ammonium group, or a betaine group. 1 and L 2 each independently represents an alkylene group having 2 to 5 carbon atoms. t, a1, b1, a2, and b2 each independently represent the average number of moles added of each unit, where t is 1 to 200, a1 and a2 each independently represent 0 to 20, and b1 and b2 each independently represent 2 to 100. When there are a plurality of units to which t is added, the units may have the same structure or different structures. R 7 and R 8 is preferably a carboxy group. L 1 and L 2 Among the alkylene groups which may be taken, the alkylene group having 3 to 5 carbon atoms may be either linear or branched. t is preferably 3-150, and more preferably 5-100. a1 and a2 are preferably 0 to 10, more preferably 0 to 5, and further preferably 0 to 3. b1 and b2 are preferably 5-50, and more preferably 5-20. The propylene in the propyleneoxy group may be linear or branched. The bonds of the ethyleneoxy group ("-OC2H4-" or "-C2H4O-") and the propyleneoxy group ("-OC3H6-" or "-C3H6O-") may be random or block. The same applies to the propyleneoxy group and the ethyleneoxy group in the following general formula (2).

[0028] [ka]

[0029] In the general formula (2), l, m, and n represent the average number of moles added of each unit, l and n are each independently 30 to 130, and m is 5 to 50. Each of l and n is preferably 50-110, and more preferably 70-90. m is preferably 10-45, and more preferably 15-40. R 9 and R 10 are each independently R 7 The same definition and preferred form are also the same.

[0030] In the adhesion inhibitor of the present invention, from the viewpoint of inhibiting adhesion of bacteria and / or viruses under air, a combination of cyclodextrin and a compound represented by general formula (1) or (2) is preferred as a combination of the cyclic molecule and linear polymer constituting the pseudopolyrotaxane and / or polyrotaxane, and a combination of γ-cyclodextrin and a compound represented by general formula (1) and a combination of β-cyclodextrin and a compound represented by general formula (2) are more preferred. In addition, from the viewpoint of inhibiting adhesion of bacteria and / or viruses under air and maintaining the ability to inhibit adhesion of particles composed of pseudopolyrotaxane and / or polyrotaxane under air for a long period of time when the adhesion inhibitor of the present invention contains a dispersion medium, a combination of cyclic molecule and linear polymer constituting the pseudopolyrotaxane and / or polyrotaxane is preferred as a combination of cyclodextrin and a compound represented by general formula (1), and a combination of γ-cyclodextrin and a compound represented by general formula (1) is more preferred.

[0031] In the pseudopolyrotaxane and / or polyrotaxane, the mass ratio of the linear polymer to the cyclic molecules is not limited as long as the pseudopolyrotaxane or polyrotaxane structure can be formed, and the mass of the linear polymer to 100 parts by mass of the cyclic molecules is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and is preferably 125 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 75 parts by mass or less.

[0032] In the solid content contained in the air-based adhesion inhibitor of the present invention, the content of particles composed of pseudopolyrotaxane and / or polyrotaxane is preferably 80 mass% or more, more preferably 85 mass% or more, even more preferably 90 mass% or more, still more preferably 95 mass% or more, and is 100 mass% or less, preferably 100 mass%.

[0033] <Dispersion medium> The air-under-adhesion inhibitor of the present invention preferably contains a dispersion medium so that it can be uniformly applied to the surface of the target object, that is, particles composed of pseudopolyrotaxane and / or polyrotaxane are preferably dispersed in the dispersion medium. Examples of the dispersion medium include water and organic solvents, and a mixed solvent of water and a water-soluble organic solvent can also be used. Examples of the organic solvent include alcohol solvents, ester solvents, nitrile solvents, ether solvents, hydrocarbon solvents, and ketone solvents. The adhesion inhibitor under air of the present invention preferably contains water, and the content of water in the dispersion medium is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and is 100% by mass or less, preferably 100% by mass. When the adhesion inhibitor under air of the present invention contains a dispersion medium, the solids concentration in the adhesion inhibitor under air is, from the viewpoint of uniformly applying the adhesion inhibitor under air to the surface of the target object, preferably 0.01 mass % or more, more preferably 0.1 mass % or more, even more preferably 0.2 mass % or more, even more preferably 0.3 mass % or more, and is preferably 50 mass % or less, more preferably 10 mass % or less, even more preferably 2 mass % or less.

[0034] <Other ingredients> The air-submerged adhesion inhibitor of the present invention may contain components (other components) other than the pseudopolyrotaxane and / or the particles composed of polyrotaxane and the dispersion medium, within the range not impairing the effects of the present invention. Examples of the other components include a thickener. The content of other components in the solid content contained in the air-based adhesion inhibitor of the present invention is preferably 5 mass % or less, more preferably 3 mass % or less, even more preferably 1 mass % or less, and is 0 mass %.

[0035] [Method of manufacturing the airborne adhesion inhibitor] The particles composed of pseudopolyrotaxane and / or polyrotaxane contained in the adhesion inhibitor under air of the present invention can be produced by a conventional method, for example, by referring to JP-A-2022-117199. In the present invention, for example, the particles composed of the obtained pseudopolyrotaxane and / or polyrotaxane can be combined with a dispersion medium as necessary to form an adhesion inhibitor under air. In addition, the dispersion medium used in the manufacturing process of the particles composed of pseudopolyrotaxane and / or polyrotaxane may be used as the dispersion medium contained in the adhesion inhibitor under air.

[0036] [Method for inhibiting airborne adhesion of bacteria and / or viruses] The method for inhibiting adhesion of bacteria and / or viruses under air of the present invention can inhibit adhesion of bacteria and / or viruses to a surface of a target object under air by applying an agent for inhibiting adhesion of bacteria and / or viruses under air to the surface of the target object. Hereinafter, the "method for inhibiting adhesion of bacteria and / or viruses under air" will also be simply referred to as the "method for inhibiting adhesion under air".

[0037] [How to apply] In the method for inhibiting adhesion under air of the present invention, the method for applying the inhibition of adhesion under air to the surface of an object is not limited as long as it can be applied to the surface of the object to which the ability to inhibit adhesion of bacteria and / or viruses is to be imparted, and examples of the method include dip coating, painting, spray coating, spin coating, etc.

[0038] [Target surface treatment] The method for inhibiting adhesion under air of the present invention preferably includes a step of introducing a functional group onto the surface of the object, from the viewpoint of more firmly adhering the adhesion inhibitor of the present invention under air to the surface of the object and more effectively inhibiting adhesion of bacteria and / or viruses to the surface of the object under air. The functional group is preferably a functional group that reacts with the functional group at the end of the chain polymer to form a covalent bond, such as a hydroxyl group, a methoxy group, a carboxyl group, a sulfo group, a phosphate group, an amino group, a quaternary ammonium group, and a betaine group, and is preferably an amino group. These functional groups can be introduced to the surface of the object alone or in combination of two or more. The functional groups can be introduced onto the surface of the object by using a known surface treatment agent, such as a silane coupling agent, alkanethiols, amphiphilic molecules, or polymers having any of the functional groups.

[0039] [Object] The target object may be an object whose surface is at least made of one or more materials selected from plastics, ceramics, metals, semiconductors including Si wafers, wood, glass, rubber, carbon materials, etc. Examples of plastics include acrylic resin, polyamide, polycarbonate, melamine, polyvinyl chloride, polyester, polystyrene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene copolymer resin (ABS), FRP (fiber reinforced plastic), etc. Examples of metals include alloys such as stainless steel, aluminum, and iron such as steel for automobiles. Examples of rubbers include natural rubber and diene-based synthetic rubber. Examples of woods include woods used for flooring, etc. Woods used for flooring, etc. may be surface-treated. Specific examples of the object include indoor electric switches, desks, chairs, shelves, doorknobs, writing implements, mobile phones, medical instruments, home appliances, and hanging straps. The environment in which the object is used is not particularly limited, but may be, for example, a temperature of 10 to 50°C and a relative humidity of 20 to 99%, and the airborne adhesion inhibitor of bacteria and / or viruses of the present invention can be applied to the surface of the object to effectively inhibit adhesion of bacteria and / or viruses to the surface of the object under the above conditions. The temperature may be 15°C or higher, 20°C or higher, and 40°C or lower, or 30°C or lower. The relative humidity may be 50% or higher, 80% or higher, and 98% or lower.

[0040] [Contact angle on the surface of the object] The contact angle of water on the surface of an object to which adhesion inhibition under air has been applied is preferably 0° or more, more preferably 5° or more, and is preferably 90° or less, more preferably 40° or less, from the viewpoint of more effectively inhibiting adhesion of bacteria and / or viruses to the surface of the object under air. The contact angle is a value obtained by the measurement method described in the Examples.

[0041] [Bacteria and / or viruses] Examples of the bacterial species that are the subject of adhesion inhibition include fungi such as those of the genus Rhodotorula, such as Rhodotorula mucilaginosa, those of the genus Saccharomyces, and those of the genus Pichia; molds such as those of the genus Candida, such as Cladosporium, Aspergillus, and Candida parapsilosis, those of the genus Penicillium, Alternaria, Phoma, and Aureobasidium; and fungi such as those of the genus Pseudomonas aeruginosa and Pseudomonas putida. putida and other species, Moraxella osloensis and other species, Ralstonia, Burkholderia, Escherichia, Cupriavidus, Psychorobacter, Alcaligenes, Klebsiella, Proteus, Serratia, Roseomonas, Methylobacterium variabile and other species, variabile and other gram-negative bacteria represented by the genera Methylobacterium, Acinetobacter, and Sphingomonas;Examples of such bacteria include gram-positive bacteria such as Bacillus cereus, Bacillus coagulans, Lactobacillus, Micrococcus, Staphylococcus aureus, and Staphylococcus aureus; Viral species that can be subject to attachment inhibition include enveloped viruses such as arenaviruses, Ebola viruses, smallpox viruses, nairoviruses, Marburg viruses, coronaviruses, monkeypox viruses, betacoronaviruses, influenza viruses, respiratory syncytial viruses, herpes viruses, mumps viruses, varicella-zoster viruses, rubella viruses, and measles viruses, as well as non-enveloped viruses such as enteroviruses, adenoviruses, coxsackie viruses, noroviruses, and rotaviruses. EXAMPLES

[0042] The features of the present invention will be described in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below. Unless otherwise specified, the following operations were performed at room temperature (25°C).

[0043] Production Example 1 Synthesis of carboxy-terminated polyether-modified silicone (compound represented by general formula (1)) 9.0 g of polyether-modified silicone (KF-6123, manufactured by Shin-Etsu Chemical Co., Ltd.), 2.7 g of 2,2,6,6-tetramethylpiperidine 1-oxyl, and 2.7 g of sodium bromide were dissolved in 373 mL of water. While stirring the obtained solution, 12 mL of 5 mass% aqueous sodium hypochlorite solution was added over 90 minutes. After the entire amount of the aqueous sodium hypochlorite solution was added, the mixture was stirred for another 70 minutes, and 33 mL of ethanol was added to stop the reaction. Then, 0.5 mol / L hydrochloric acid was added to the mixture so that the pH became 2, and the mixture was extracted with 150 mL of dichloromethane. The dichloromethane layer was washed twice with 0.01 mol / L hydrochloric acid, washed once with saturated saline, dried over sodium sulfate, and then filtered to remove sodium sulfate. After dichloromethane was distilled off, the mixture was vacuum-dried at 30°C overnight to obtain the desired polyether-modified silicone with a carboxyl group terminal.

[0044] Production Example 2 Synthesis of Carboxy-Terminated Polyoxyethylene Polyoxypropylene Glycol (Compound Represented by General Formula (2)) A carboxyl-terminated polyoxyethylene polyoxypropylene glycol was obtained in the same manner as in Production Example 1, except that the polyether-modified silicone was changed to 33.5 g of polyoxyethylene polyoxypropylene glycol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., Pluronic (registered trademark) F-68, average number of moles of ethyleneoxy groups added: 160, average number of moles of propyleneoxy groups added: 30, weight average molecular weight: 8350).

[0045] Example 1 (Preparation of Air-Deposition Inhibitors 1-1 and 1-2) 2.0 g of γ-cyclodextrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 110 mL screw tube bottle, and 16 g of ion-exchanged water was added to dissolve γ-cyclodextrin, to obtain solution (1). 1.1 g of the carboxy-terminated polyether-modified silicone obtained in Production Example 1 was placed in another screw tube bottle, and 15 g of ion-exchanged water and 1.2 g of a 1 mol / L aqueous sodium hydroxide solution were added and homogenized to obtain solution (2). The mixture obtained by adding solution (2) to solution (1) was shaken (shaking speed: 140 times / min) at room temperature using a medium-sized shaker (reciprocating shaker NR-10, manufactured by Taitec Co., Ltd.) for 3 days. During shaking, the mixture became cloudy over time. The mixture was then centrifuged (3000 rpm, 60 minutes) to remove the supernatant. The same amount of water as the removed supernatant was added. The resulting precipitate was diluted with ion-exchanged water to obtain an air-based adhesion inhibitor 1-1 (solid content concentration 1% by mass) containing a nanosheet. In the same manner, an air-based adhesion inhibitor 1-2 (solid content concentration 0.5% by mass) containing a nanosheet was obtained. The nanosheet had a thickness of 11 nm, a maximum length in the xy axis direction of 4.5 μm, and an aspect ratio of 409. The concentration was measured using an infrared moisture meter (Kett Electric Laboratory).

[0046] Example 2 (Preparation of Air-Deposition Inhibitor 2-1) 0.55 g of β-cyclodextrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 110 mL screw tube bottle, and 32 g of ion-exchanged water was added to dissolve the β-cyclodextrin. Next, 0.14 g of carboxy-terminated polyoxyethylene polyoxypropylene glycol obtained in Production Example 2 was added to the mixture, which was then shaken (shaking speed: 140 times / min) at room temperature for 3 days using a medium-sized shaker (reciprocating shaker NR-10, manufactured by Taitec Co., Ltd.). During shaking, the mixture became cloudy over time. The mixture was then centrifuged (3000 rpm, 60 minutes) to remove the supernatant. The same amount of water as the removed supernatant was added. The resulting precipitate was diluted with ion-exchanged water to obtain an airborne adhesion inhibitor 2-1 (solid content concentration 1% by mass) containing nanosheets. The nanosheets had a thickness of 15 nm, a maximum length in the xy axis direction of 2.8 μm, and an aspect ratio of 187.

[0047] -Observation and measurement of particle morphology- (1) Shape of particles composed of pseudopolyrotaxane and / or polyrotaxane Based on atomic force microscope (AFM) images, it was confirmed that the particles composed of pseudopolyrotaxane and / or polyrotaxane contained in the air-based adhesion inhibitor were nanosheets. (2) Based on the AFM height profile (length in the z-axis direction), the height difference between the top and bottom surfaces of the nanosheet was calculated. Ten randomly selected nanosheets were measured, and the average value was taken as the thickness of the nanosheet. (3) The longest length in the xy axis direction and the aspect ratio of the nanosheet In the planar direction of the AFM image, the length of the longest part of 10 randomly selected nanosheets was measured using the scale bar as a reference. The average of the measured values ​​was calculated as the longest length. The aspect ratio of the nanosheet was calculated according to the following formula. Aspect ratio of a nanosheet = maximum length of the nanosheet / thickness of the nanosheet

[0048] <Virus attachment inhibition test> (Preparation of surface-treated substrate) A silicon wafer was cut into 1 cm x 1 cm pieces, ultrasonically cleaned in ethanol for 30 minutes, and cleaned with a UV ozone cleaner for 30 minutes (this is called the Si wafer (blank)). After that, it was immersed in a 2% by mass toluene solution of 3-aminopropyltriethoxysilane (APTES) for 15 minutes, and then the substrate was washed with toluene and dried (this is called the APTES-treated Si wafer). The APTES-treated Si wafer was immersed in the air-conditioned adhesion inhibitor 1-1 or 2-1 (solid content concentration: 1% by mass) for 8 minutes, and then excess liquid was removed with nitrogen. The wafer was then left to dry overnight at 25°C to prepare a dip-coated substrate. 100 μL of adhesion inhibitor 1-2 (solid content concentration: 0.5 mass %) in air was dropped onto the APTES-treated Si wafer, and then the wafer was left to stand overnight at 25° C. to dry, thereby preparing a substrate that had been subjected to cast film treatment. As a comparative example, an APTES-treated Si wafer was used instead of the surface-treated substrate (Comparative Example 1).

[0049] -Contact angle measurement- For the substrate surface (treated surface) treated with the adhesion inhibitor 1-1, 1-2 or 2-1 in air, the contact angle when 1 μL of water was dropped was measured by the θ / 2 method using a fully automatic contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.), and the average value of 5 measurements was taken as the contact angle (°) of the water droplet on the treated surface. For the APTES-treated Si wafer of the comparative example, the contact angle was measured in the same manner as above for randomly selected surfaces. The results are shown in Table 1.

[0050] (Preparation of virus-treated substrate) Cut the ABS board into 1cm x 1cm pieces and 3 x 10 10 After applying 10 μL of PFU / mL MS2 phage suspension, the plate was dried by standing for 30 minutes or more at 25°C in a safety cabinet (HITACHI SCV-1609ECIIA2).Then, the ABS plate was left for 30 minutes or more at 25°C where the relative humidity was controlled to 97% using a saturated aqueous solution of potassium sulfate, and then used for the test.

[0051] (Evaluation of virus attachment inhibition ability) The virus-treated substrate was placed on a balance with the virus-treated surface facing up, and the surface-treated substrate was placed so that the virus-treated surface of the virus-treated substrate was in contact with the surface-treated surface of the surface-treated substrate, and the balance was pressed for 10 seconds so that it indicated 500 g. Then, each substrate was immersed in 1.5 mL of LP dilution solution ("Daigo" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to extract the MS2 phage. An Escherichia coli suspension adjusted to OD = 0.4 was prepared. 30 μL of MS2 phage extract diluted to a concentration suitable for plaque counting was mixed with 270 μL of Escherichia coli suspension, 1.5 mL of soft agar medium was added, and the mixture was layered on the agar medium and cultured at 37 ° C overnight, and the number of plaques was counted. The number of plaques was multiplied by the dilution factor of the MS2 phage extract to calculate the number of plaques in the original solution. The virus adhesion rate of the surface-treated substrate was calculated by dividing the number of plaques in the stock solution of the surface-treated substrate by the sum of the number of plaques in the stock solution of the surface-treated substrate and the number of plaques in the stock solution of the virus-treated substrate. The results are shown in Table 1. A smaller adhesion rate means that the adhesion of viruses to the target surface in air is more suppressed. For the APTES-treated Si wafer of the comparative example, the APTES-treated Si wafer was placed so that the virus-treated surface of the virus-treated substrate was in contact with the surface of the APTES-treated Si wafer on which the contact angle was measured, and the balance was pressed for 10 seconds until it indicated 500 g.

[0052] [Table 1]

[0053] As is clear from Table 1, compared to the APTES-treated Si wafer surface to which the air-based adhesion inhibitor of the present invention was not applied (Comparative Example 1), it can be seen that virus adhesion in air is suppressed on the object surface to which the air-based adhesion inhibitor of the present invention was applied (Examples 1 and 2).

[0054] <Virus adhesion inhibition performance maintenance test> Air-borne adhesion inhibitor 1-1 from Example 1 was diluted with ion-exchanged water to prepare air-borne adhesion inhibitor 1-3 (solids concentration 0.2% by mass), which was then allowed to stand at 25°C for 24 hours. Thereafter, the turbidity was measured at a wavelength of 600 nm with an optical path length of 10 mm. Air-borne adhesion inhibitor 2-1 from Example 2 was also diluted with ion-exchanged water to prepare air-borne adhesion inhibitor 2-2 (solids concentration 0.2% by mass), and the turbidity was measured. The results are shown in Table 2. The smaller the turbidity, the more the nanosheets disintegrate in water, meaning that the virus adhesion inhibitory performance is reduced.

[0055] [Table 2]

[0056] From Table 2, it can be seen that aerated adhesion inhibitor 1-3, in which the linear polymer constituting the pseudo-polyrotaxane is a compound represented by general formula (1), when made into a dispersion containing water, can maintain virus adhesion inhibition performance for a longer period of time than aerated adhesion inhibitor 2-2, in which the linear polymer constituting the pseudo-polyrotaxane is a compound represented by general formula (2).

Claims

1. An agent for inhibiting adhesion of bacteria and / or viruses in the air, comprising particles composed of pseudopolyrotaxane and / or polyrotaxane.

2. a linear polymer constituting the pseudopolyrotaxane has a triblock structure of (A1) block-(B) block-(A2) block, the (A1) block and the (A2) block being organic chains; The agent for inhibiting adhesion of bacteria and / or viruses in air according to claim 1, wherein the linear polymer constituting the polyrotaxane has a triblock structure of (A'1) block-(B') block-(A'2) block, and the (A'1) block and the (A'2) block are organic chains.

3. 3. The agent for inhibiting adhesion of bacteria and / or viruses in air according to claim 1 or 2, wherein the particles composed of the pseudopolyrotaxane and / or polyrotaxane are nanosheets having a thickness of 2 nm or more and 200 nm or less and an aspect ratio of 5 or more and 1,500 or less.

4. 4. The agent for inhibiting adhesion of bacteria and / or viruses in air according to claim 1, wherein particles composed of pseudopolyrotaxane and / or polyrotaxane are dispersed in a dispersion medium.

5. A method for inhibiting airborne adhesion of bacteria and / or viruses, comprising applying the airborne adhesion inhibitor of bacteria and / or viruses according to any one of claims 1 to 4 to a surface of an object.

Images