Antibacterial and antiviral agent, antibacterial and antiviral coating composition, laminate, antibacterial and antiviral resin composition, and molded article

Abstract

To provide an antiviral agent having high resin compatibility as well as high antibacterial and antiviral activity, and capable of reducing the influence on the appearance of the application target.SOLUTION: The present invention provides an antibacterial and antiviral agent containing a bismuth fatty acid salt and a rare earth fatty acid salt.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an antibacterial and antiviral agent, an antibacterial and antiviral coating composition, a laminate, an antibacterial and antiviral resin composition, and a molded article.

Background Art

[0002] Due to the spread of coronavirus disease, people's awareness of hygiene has rapidly increased. Even in daily necessities, the need for "antibacterial and antiviral" to reduce the possibility of infection by pathogenic bacteria and viruses is expanding worldwide. For example, the surfaces of the exteriors of smartphones, smartphone touch panels, handrails, doorknobs, washbasins, various push buttons such as elevator buttons, and the interiors of public transportation are expected to be used multiple times a day, so strong measures against antibacterial and antiviral are strongly demanded.

[0003] As antibacterial and antiviral agents, photocatalyst systems (TiO 2 etc.) and metal systems (Ag, Cu, etc.) are known (for example, Patent Document 1), and these metals alone or metal compounds are directly applied to the application target, or mixed with a binder resin to form a coating composition, and the composition is applied to the application target for use.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When an inorganic metal compound, which is a conventional antibacterial and antiviral agent, is directly applied to an object to be applied, there is a problem that the touch feeling of the object to be applied becomes rough. Further, even when it is a coating composition of an inorganic metal compound and a binder resin, the coating layer obtained from the coating composition is not only turbid in color due to the inorganic metal compound, but also has a problem that its transparency is impaired when the binder resin is a transparent resin. In addition, in a composition containing an inorganic metal compound, since the inorganic compound is generally a powder, dispersion treatment is required, and there is also a problem from the viewpoint of productivity.

[0006] The problem to be solved by the present invention is to provide an antibacterial and antiviral agent having high compatibility with a resin and high antibacterial and antiviral activity, and reduced influence on the appearance of an object to be applied. Another problem to be solved by the present invention is to provide an antibacterial and antiviral coating composition capable of antibacterial and antiviral coating without impairing the surface appearance and surface touch feeling. Another problem to be solved by the present invention is to provide a laminate and a molded body capable of exhibiting antibacterial and antiviral properties without impairing the surface appearance and surface touch feeling.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that an antibacterial and antiviral agent containing a fatty acid bismuth salt and a fatty acid rare earth salt has high compatibility with a resin and also exhibits high antibacterial and antiviral activity, and completed the present invention.

[0008] That is, the present invention relates to the following antibacterial and antiviral agents and the like. 1. An antibacterial and antiviral agent containing a fatty acid bismuth salt and a fatty acid rare earth salt. 2. The antibacterial and antiviral agent according to 1, wherein the fatty acid bismuth salt is a bismuth salt of a fatty acid having 1 to 22 carbon atoms. 3. The antibacterial and antiviral agent according to 1 or 2, wherein the fatty acid bismuth salt is a bismuth salt of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid, naphthenic acid, lauric acid, stearic acid, oleic acid, palmitic acid or myristic acid. 4. The antibacterial and antiviral agent according to any one of 1 to 3, wherein the rare earth fatty acid salt is a neodymium salt of a fatty acid having 1 to 22 carbon atoms. 5. The antibacterial and antiviral agent according to any one of 1 to 4, wherein the rare earth fatty acid salt is a neodymium salt of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid, naphthenic acid, lauric acid, stearic acid, oleic acid, palmitic acid or myristic acid. 6. The antibacterial and antiviral agent according to any one of 1 to 5, which contains 1 to 200 moles of rare earth in the rare earth fatty acid salt per 1 mole of bismuth in the fatty acid bismuth salt. 7. An antibacterial and antiviral coating composition containing the antibacterial and antiviral agent according to any one of 1 to 6 and a binder resin. 8. The antibacterial and antiviral coating composition according to 7, wherein the binder resin is at least one selected from the group consisting of acrylic resin, vinyl acetate resin, styrene resin, vinyl chloride resin, olefin resin, urethane resin, urea resin, urethane-urea resin, epoxy resin, melamine resin, phenol resin, polyester resin, alkyd resin, silicone resin, acrylonitrile / styrene copolymer resin and acrylonitrile / butadiene copolymer resin. 9. The antibacterial and antiviral coating composition according to 7 or 8, which contains the metal derived from the antibacterial and antiviral agent in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin solid content. 10. The antibacterial and antiviral coating composition according to any one of 7 to 9, which contains the bismuth metal derived from the antibacterial and antiviral agent in the range of 1 part by mass or less with respect to 100 parts by mass of the resin solid content. 11. A laminate having a coating layer and a substrate of the antibacterial and antiviral coating composition according to any one of 11.7 to 10. 12. The laminate according to 11, wherein the coating layer is transparent. 13. An antibacterial and antiviral resin composition containing an antibacterial and antiviral agent and a resin according to any one of 1 to 6. 14. A molded article obtained by molding the antibacterial and antiviral resin composition according to 13.

Effects of the Invention

[0009] According to the present invention, an antibacterial and antiviral agent having high compatibility with a resin and high antibacterial and antiviral activity and reducing the influence on the appearance of an application target can be provided. According to the present invention, an antibacterial and antiviral coating composition capable of antibacterial and antiviral coating without impairing the surface appearance and touch can be provided. According to the present invention, a laminate and a molded article capable of exhibiting antibacterial and antiviral properties without impairing the surface appearance and surface touch can be provided.

Modes for Carrying Out the Invention

[0010] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments and can be implemented with appropriate modifications without impairing the effects of the present invention. In addition, the compounds in this specification may be derived from fossil resources or may be derived from biological resources.

[0011] [Antibacterial and Antiviral Agent] The antibacterial and antiviral agent of the present invention contains a fatty acid bismuth salt and a fatty acid rare earth salt. Among fatty acid metal salts, bismuth fatty acid salts can exhibit high antibacterial and antiviral properties on their own. However, bismuth fatty acid salts are compounds whose usage amount is restricted in certain antibacterial and antiviral certification tests, and it was difficult to obtain sufficient antibacterial and antiviral properties due to this restriction. On the other hand, rare earth fatty acid salts, when compared at the same addition amount, cannot exhibit antibacterial and antiviral properties as high as those of bismuth fatty acid salts, and there were limitations to their antibacterial and antiviral properties. In the antibacterial and antiviral agent of the present invention, by combining a bismuth fatty acid salt with a rare earth fatty acid salt, it is possible to exhibit antibacterial and antiviral properties higher than those of the bismuth fatty acid salt alone.

[0012] In the present invention, "antibacterial" means including the effects of reducing the number of bacteria, inactivating bacteria, reducing the infectivity of bacteria, etc.

[0013] The bacteria targeted for antibacterial in the present invention are not particularly limited, and may be either bacteria or fungi. Examples of bacteria include Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, Legionella; Gram-positive bacteria such as Staphylococcus aureus, Clostridium bacteria, etc. Examples of fungi include yeasts such as Candida, Rhodotorula, baker's yeast; molds such as Aspergillus, Penicillium, etc.

[0014] In the present invention, "antiviral" means including the effects of reducing the number of viruses, inactivating viruses, reducing the infectivity of viruses, etc. The viruses targeted for antiviral are not particularly limited, and may be any of known enveloped viruses (viruses having an envelope) and non-enveloped viruses (viruses not having an envelope).

[0015] Examples of the above-mentioned enveloped viruses include, for example, coronavirus, influenza virus, rubella virus, Ebola virus, measles virus, varicella-zoster virus, herpes virus, mumps virus, arbovirus, RS virus, SARS virus, hepatitis virus (e.g., hepatitis A virus, hepatitis B virus, hepatitis C virus, hepatitis D virus, hepatitis E virus, etc.), yellow fever virus, AIDS virus, rabies virus, hantavirus, dengue virus, Nipah virus, lyssavirus, etc.

[0016] Examples of the above-mentioned non-enveloped viruses include, for example, adenovirus, norovirus, rotavirus, human papillomavirus, poliovirus, enterovirus, coxsackievirus, human parvovirus, encephalomyocarditis virus, polyomavirus, BK virus, rhinovirus, feline calicivirus, etc.

[0017] Hereinafter, the antibacterial and antiviral agent of the present invention will be described.

[0018] (Fatty acid bismuth salt and fatty acid rare earth salt) Both the fatty acid bismuth salt and the fatty acid rare earth salt contained in the antibacterial and antiviral agent of the present invention are compounds represented by, for example, the following general formula (1).

[0019] [Chemical formula] (In the general formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 21 carbon atoms, n1 is an integer in the range of 1 to 4, M 1 is bismuth or a rare earth. )

[0020] In the general formula (1), when n1 is an integer of 2 or more, a plurality of R 1 may be the same as or different from each other.

[0021] R 1 The alkyl group having 1 to 21 carbon atoms of R may be a straight-chain alkyl group, a branched alkyl group, or may contain an alicyclic structure.

[0022] R 1 The hydrogen atom or the alkyl group having 1 to 21 carbon atoms of R corresponds to the carboxylic acid residue obtained by removing the carboxyl group (COOH) from the carboxylic acid having 1 to 22 carbon atoms represented by R 1 COOH. Examples of the carboxylic acid residue include formic acid residue, acetic acid residue, propionic acid residue, butanoic acid residue, pentanoic acid residue, hexanoic acid residue, 2-ethylbutyric acid residue, heptanoic acid residue, octanoic acid residue, acrylic acid residue, methacrylic acid residue, octylic acid residue (2-ethylhexanoic acid residue), neodecanoic acid residue, naphthenic acid residue, isononanoic acid residue, eleostearic acid residue, tall oil fatty acid residue, coconut oil fatty acid residue, soybean oil fatty acid residue, linseed oil fatty acid residue, safflower oil fatty acid residue, dehydrated castor oil fatty acid residue, camellia oil fatty acid residue, lauric acid residue, myristic acid residue, palmitic acid residue, stearic acid residue, isostearic acid residue, oleic acid residue, etc.

[0023] R 1 The alkyl group having 1 to 21 carbon atoms of R is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 11 carbon atoms. R 1 is preferably formic acid residue, acetic acid residue, propionic acid residue, butanoic acid residue, pentanoic acid residue, hexanoic acid residue, 2-ethylbutyric acid residue, heptanoic acid residue, octanoic acid residue, 2-ethylhexanoic acid residue, isononanoic acid residue, neodecanoic acid residue, naphthenic acid residue, stearic acid residue, oleic acid residue, palmitic acid residue or myristic acid residue.

[0024] n1 is a numerical value determined by the valence of the metal atom of M 1 For example, when M 1 is bismuth, n1 is 3, and when M 1 is neodymium, n1 is 3.

[0025] In the present invention, the rare earth means one or more selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

[0026] The rare earth fatty acid salt contained in the antibacterial and antiviral agent of the present invention may be a single kind or two or more kinds of rare earth fatty acid salts having different structures from each other.

[0027] The bismuth fatty acid salt contained in the antibacterial and antiviral agent of the present invention is preferably a bismuth salt of a fatty acid having 1 to 22 carbon atoms, more preferably a bismuth salt of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid, naphthenic acid, lauric acid, stearic acid, or oleic acid.

[0028] The rare earth fatty acid salt contained in the antibacterial and antiviral agent of the present invention is preferably a neodymium salt of a fatty acid having 1 to 22 carbon atoms, more preferably a neodymium salt of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid, naphthenic acid, lauric acid, stearic acid, or oleic acid.

[0029] In the antibacterial and antiviral agent of the present invention, the content of each of the fatty acid bismuth salt and the rare earth fatty acid salt may be set, for example, so that the rare earth in the rare earth fatty acid salt is contained in the range of 1 to 200 moles per 1 mole of bismuth in the fatty acid bismuth salt. The content of the rare earth fatty acid salt is preferably in the order of 1 to 100 moles, 1 to 30 moles, 1 to 20 moles, and 1 to 10 moles of rare earth in the rare earth fatty acid salt per 1 mole of bismuth in the fatty acid bismuth salt.

[0030] The antibacterial and antiviral agent of the present invention only needs to contain a fatty acid bismuth salt and a rare earth fatty acid salt, and may substantially consist of, for example, a fatty acid bismuth salt and a rare earth fatty acid salt. Here, "substantially consisting of" means that the total content of the fatty acid bismuth salt and the rare earth fatty acid salt is 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the total amount of the antibacterial and antiviral agent of the present invention.

[0031] The fatty acid bismuth salt and the rare earth fatty acid salt can be produced by known methods, and commercially available products may also be used.

[0032] (Metal complex) Both the fatty acid bismuth salt and the rare earth fatty acid salt may be in the form of a metal complex coordinated with a heteroatom-containing ligand.

[0033] The heteroatom-containing ligand that forms the metal complex may be a ligand having one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus in the molecule. Examples of the heteroatom-containing ligand include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2] Octane (DABCO), 4-dimethylaminoamine (DMAP), dicyandiamide (DICY), tri-n-butylamine, dimethylbenzylamine, butylamine, 1,2-propanediamine, 1,2-cyclohexanediamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, 2-[[(2-dimethylamino)ethyl]methylamino]ethanol, picolinic acid, 2,2’-[propane-1,2-diylbis(azanilylidene methanilylidene)]diphenol, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, 8-quinolinol, 5-chloro-8-quinolinol, 2,2’-bipyridyl and its derivatives, 2,2’-[propane-1,2-diylbis(azanilylidene methanilylidene)]diphenol and its derivatives, 2,2’-methylenebis〔6-(2h-benzotriazol-2-yl)-4-tert-octylphenol〕 and other amine compounds; quaternary ammonium salts such as trioctylmethylammonium chloride, trioctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, benzylphosphonium chloride; sulfur-based compounds such as thiolactic acid, 2-aminothiophenol, 2,2’-dithiodianiline, etc.

[0034] The heteroatom-containing ligand is preferably at least one amine ligand selected from picolinic acid, 2-{[(2-dimethylamino)ethyl]methylamino}ethanol, 1,2-propanediamine, 1,2-cyclohexanediamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 8-quinolinol, 5-chloro-8-quinolinol, 2,2'-bipyridyl and its derivatives, and 2,2'-[propane-1,2-diylbis(azanilylidene methanilylidene)]diphenol and its derivatives.

[0035] The heteroatom-containing ligand forming the metal complex may be a single kind or two or more kinds having different structures from each other.

[0036] In the metal complex, the ratio (molar ratio) of the fatty acid bismuth salt or fatty acid rare earth salt to the heteroatom-containing ligand is in the range of, for example, 0.1 to 12 moles of the heteroatom-containing ligand per 1 mole of the metal atom of the fatty acid bismuth salt or fatty acid rare earth salt, preferably in the range of 0.3 to 10 moles, and more preferably in the range of 0.5 to 10 moles.

[0037] The metal complex of the fatty acid bismuth salt or fatty acid rare earth salt and the heteroatom-containing ligand can be produced by a known method, and can be produced by reacting the fatty acid bismuth salt or fatty acid rare earth salt with the heteroatom-containing ligand. Also, a commercially available product may be used as the metal complex.

[0038] [Coating Composition] The coating composition of the present invention contains the antibacterial and antiviral agent of the present invention and a binder resin. Since the antibacterial and antiviral agent of the present invention has high compatibility with the binder resin, the coating layer obtained from the coating composition containing the antibacterial and antiviral agent of the present invention can reduce the influence on the appearance such as the transparency being impaired by the antibacterial and antiviral agent while the coating layer exhibits antibacterial and antiviral properties.

[0039] The content of the antibacterial and antiviral agent of the present invention in the coating composition of the present invention is not particularly limited. For example, the amount of metal derived from the antibacterial and antiviral agent (total amount of bismuth metal and rare earth metal) is preferably contained in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.01 to 10 parts by mass, still more preferably in the range of 0.01 to 5 parts by mass, and even more preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the resin solid content. Here, the "resin solid content" means the total amount of solid components such as binder resin other than the solvent contained in the coating composition.

[0040] The content of bismuth metal derived from the antibacterial and antiviral agent of the present invention in the coating composition of the present invention is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 part by mass or less with respect to 100 parts by mass of the resin solid content. Regarding the content of the above bismuth metal, the lower limit of the content of bismuth metal is not particularly limited, but is, for example, 0.001 part by mass, 0.005 part by mass, 0.01 part by mass, 0.05 part by mass or 0.1 part by mass.

[0041] Regarding the binder resin contained in the coating composition of the present invention, its curing characteristics are not particularly limited. For example, when the binder resin is an acrylic resin, the acrylic resin may be a thermosetting acrylic resin or an active energy ray-curable acrylic resin. Furthermore, the form of the binder resin is not particularly limited. It may be an emulsion resin or a latex resin.

[0042] The binder resin may be either an aqueous resin or a water-insoluble resin (solvent-based resin). In the present application, the "water-soluble resin" means that the amount of water required to dissolve 1 g of the resin at 20°C is less than 10 ml. The "water-insoluble resin" refers to a resin other than the "water-soluble resin".

[0043] Specific examples of the binder resin include acrylic resin, vinyl acetate resin, styrene resin, vinyl chloride resin, olefin resin, urethane resin, urea resin, urethane-urea resin, acrylic-urethane resin, epoxy resin, melamine resin, phenol resin, polyester resin, alkyd resin, silicone resin, polyphenylene sulfide resin, acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene copolymer resin, and acrylonitrile / butadiene / styrene copolymer (ABS) resin, etc. The binder resin also includes those obtained by modifying the above resins. For example, in the case of a phenol resin, it includes a rosin-modified phenol resin.

[0044] The binder resin contained in the coating composition of the present invention may be a single type or two or more types.

[0045] The content of the binder resin in the coating composition of the present invention is not particularly limited, and may be appropriately set, for example, in the range of 10 to 100% by mass based on the total mass of the resin solids of the coating composition.

[0046] The coating composition of the present invention only needs to contain the antibacterial and antiviral agent of the present invention and the binder resin, and may further contain a dispersion medium. The dispersion medium is added for the purpose of adjusting the viscosity of the coating composition, and may be either an aqueous medium or an oily medium.

[0047] Specific examples of the dispersion medium include water, monohydric alcohols such as 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, etc., polyhydric alcohols such as various diols and glycerin, diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, propylene glycol, 1,2-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-methyl-1,3-propanediol, 1,2-hexanediol, dipropylene glycol, diethylene glycol, aromatic diols which are adducts of bisphenol A and alkylene oxides having 2 or 3 carbon atoms (average addition mole number is 1 or more and 16 or less) of bisphenol A, alicyclic diols such as hydrogenated bisphenol A, polyoxypropylene-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-isobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-isobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, γ-butyrolactone, various fatty acids, etc.

[0048] The dispersion medium contained in the coating composition of the present invention may be a single type or two or more types.

[0049] The content of the dispersion medium in the coating composition of the present invention is not particularly limited, and it may be appropriately set, for example, so that the solid content concentration of the coating composition is in the range of 30 to 80% by mass.

[0050] The coating composition of the present invention may further contain a plasticizer. By adding a plasticizer to the coating composition, flexibility can be imparted to the resulting coating layer, and the followability to the substrate can be improved.

[0051] The plasticizer is not particularly limited, and examples thereof include phthalic acid esters, non-aromatic dibasic acid esters, aliphatic esters, esters of polyalkylene glycols, phosphate esters, trimellitic acid esters, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, etc., and phthalic acid esters are preferred. Specific examples of the plasticizer include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, benzyl epoxy stearate, etc.

[0052] The plasticizer contained in the coating composition of the present invention may be a single type or two or more types.

[0053] The content of the plasticizer in the coating composition of the present invention is not particularly limited, and it may be appropriately set, for example, in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin solid content of the coating composition.

[0054] The coating composition of the present invention may contain the antibacterial and antiviral agent of the present invention, a binder resin, and optionally a dispersion medium and / or a plasticizer, and may contain other additives as long as the effects of the present invention are not impaired. Examples of the other additives include pigments, matting agents, curing agents, curing accelerators, defoaming agents, dispersants, leveling agents, thickeners, antioxidants, weathering agents, flame retardants, antistatic agents, lubricants, preservatives, and the like.

[0055] The coating composition of the present invention can be applied to the surface of a substrate, and a coating layer can be formed by applying a curing method (such as heat curing or active energy ray curing) suitable for the binder resin to the obtained coating film.

[0056] Regarding the coating method of the coating composition, any known and publicly available coating method can be used. Examples include methods such as roll coaters, electrostatic coating, bar coaters, gravure coaters, knife coaters, dipping coating, and spray coating.

[0057] The substrate to be coated is not particularly limited, and examples include paper, synthetic paper, steel plates, aluminum foils, glass, wood, woven fabrics, knitted fabrics, non-woven fabrics, gypsum boards, wooden boards, resin substrates, and the like.

[0058] Specific examples of the resin base material include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low-density polyethylene film, HDPE: high-density polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polycarbonate film, polyethylene terephthalate film, polymethyl methacrylate film, polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose resin film, polyvinyl alcohol film, ABS resin film, norbornene resin film, cyclic olefin resin film, polyimide resin film, polyvinyl fluoride resin film, polyvinylidene fluoride resin film, ethylene-vinyl acetate copolymer film, etc. The resin base material to be used may be subjected to surface treatment such as corona treatment.

[0059] [Resin composition] The resin composition of the present invention contains the antibacterial and antiviral agent of the present invention and a resin. The resin composition containing the antibacterial and antiviral agent of the present invention can be made into a molded article exhibiting antibacterial and antiviral properties not only for coating applications but also by molding the composition itself.

[0060] The resin contained in the resin composition of the present invention can be the same as the binder resin contained in the coating composition of the present invention. Further, the resin composition of the present invention can contain the same components as those that can be contained in the coating composition of the present invention.

[0061] The molding method of the resin composition of the present invention may employ a molding method suitable for the resin to be used, and examples include melt molding methods such as injection molding, extrusion molding, compression molding (press molding), pressure air molding, and vacuum molding, and casting methods.

[0062] The coating layer obtained using the coating composition of the present invention and the molded article obtained using the resin composition of the present invention can be suitably used for places touched by human hands as materials having antibacterial and antiviral activities. As applicable uses, there are a wide range of uses such as smartphone exteriors, personal computer exteriors, touch panels, handrails, doorknobs, washbasins, push buttons such as elevator buttons, interior decorations (wallpapers, floorings, etc.), various packaging materials, various fiber products, medical equipment (medical gloves, medical glasses, etc.), surface coatings of printed materials (books, magazines, business cards, etc.), nursing care supplies (supporters, corsets, rehabilitation shoes, etc.).

Examples

[0063] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the following Examples.

[0064] (Synthesis Example 1: Preparation of fatty acid metal salt (Bi)) 330.6 parts by mass of 2-ethylhexanoic acid and 125.0 parts by mass of bismuth oxide were reacted at 130°C, and after dehydration under reduced pressure at 130°C, 439.5 parts by mass of a bismuth 2-ethylhexanoate solution (fatty acid metal salt (Bi)) was obtained. The bismuth content in the obtained fatty acid metal salt (Bi) was 25% by mass.

[0065] (Synthesis Example 2: Preparation of fatty acid metal salt (Nd)) 224.8 parts by mass of neodecanoic acid and 60.0 parts by mass of neodymium oxide were reacted at 130°C, and after dehydration under reduced pressure at 130°C, 306.9 parts by mass of cyclohexane was added to obtain 570.0 parts by mass of a neodymium neodecanoate solution (fatty acid metal salt (Nd)). The neodymium content in the obtained fatty acid metal salt (Nd) was 8.8% by mass.

[0066] (Synthesis Example 3: Preparation of fatty acid metal salt (Zr)) 212.3 parts by mass of 2-ethylhexanoic acid and 220.0 parts by mass of zirconium oxide were reacted at 110 °C. After dehydration under reduced pressure at 90 °C, 277.5 parts by mass of petroleum hydrocarbon was added to obtain 555.0 parts by mass of a zirconium 2-ethylhexanoate solution (fatty acid metal salt (Zr)). The zirconium content in the obtained fatty acid metal salt (Zr) was 12% by mass.

[0067] (Examples 1-8 and Comparative Examples 1-4: Production of Urethane Resin Coated Substrate and Antiviral Property Evaluation) An antibacterial and antiviral agent shown in Table 1 was added to a urethane resin ("Barnock 16-416" manufactured by DIC Corporation) in the amounts shown in Table 1 to prepare coating compositions respectively. The prepared coating compositions were applied onto a glass substrate using an applicator so that the wet film thickness became 152 μm. After that, the obtained coated substrate was dried at room temperature for 12 hours and further dried at 80 °C for 60 minutes to produce a urethane resin antibacterial and antiviral coated substrate composed of a urethane resin coating layer and a glass substrate. Regarding the produced antibacterial and antiviral coated substrate, the following antiviral property test and transparency test were conducted. The results are shown in Table 1.

[0068] (Influenza Virus Antiviral Property Test) The antiviral property evaluation was carried out according to ISO21702 (Mesurement of antiviral activity on plastics and other non-porous surfaces). Specifically, a virus suspension of influenza virus (H3N2) prepared to be 1×10 7 ~5×10 7 PFU / ml was dropped in an amount of 0.4 ml onto a test piece (antiviral coating test piece) obtained by cutting the coated substrate into 50 mm×50 mm, and covered with a polyethylene film from above. It was left standing at a temperature of 25 °C for 24 hours. Then, 10 mL of eluent was added to recover the virus from the test piece, and the virus infectious titer (common logarithm value) (PFU / cm 2) was determined. Similar viral infectivity titers were also evaluated for blank test pieces, which were glass substrates without the coating composition.

[0069] For the obtained viral infectivity titers, antiviral activity values were calculated using the following calculation formula. A higher antiviral activity value means higher antiviral properties. V = Log(A / B) = Log(A) - Log(B) V: Antiviral activity value Log(A): Viral infectivity titer of the blank test piece (common logarithm value) Log(B): Infectivity titer of the antiviral coating test piece (common logarithm value)

[0070] (Transparency test) Regarding the coating layer of the coated substrate produced in the influenza virus antiviral test, its transparency was visually confirmed and evaluated according to the following criteria. ○: No turbidity was confirmed. ×: Turbidity was confirmed.

[0071]

Table 1

[0072] In Table 1, "antibacterial and antiviral agent addition amount" means the mass part of the metal derived from the antibacterial and antiviral agent (fatty acid metal salt) relative to 100 mass parts of the urethane resin solid content. For example, in Example 1, it means that the fatty acid metal salt (Bi) and the fatty acid metal salt (Nd) were added to the urethane resin so as to contain 0.31 mass part of bismuth derived from the fatty acid metal salt (Bi) and 0.88 mass part of neodymium derived from the fatty acid metal salt (Nd) with respect to 100 mass parts of the urethane resin. The following Tables 2 and 3 have the same meaning.

[0073] Examples 1 - 5 of the present application show antiviral activity values equal to or higher than those of Comparative Example 1 of the present application, which contains 1.25 parts by mass of bismuth with respect to 100 parts by mass of the urethane resin, even though the amount of bismuth is small, being 0.063 to 0.31 parts by mass with respect to 100 parts by mass of the urethane resin. Comparative Example 2 is an antibacterial and antiviral agent containing only a bismuth fatty acid salt, and Comparative Example 3 is an antibacterial and antiviral agent containing only a neodymium fatty acid salt. However, Examples 1 - 5, which contain both of these in equal amounts or less, show antiviral activity values higher than the sum of the antiviral activity values (0.8 and 0.7) of Comparative Examples 2 and 3. These facts indicate that a high antiviral activity value can be obtained by the synergistic effect of containing both a bismuth fatty acid salt and a rare earth fatty acid salt. Regarding Examples 5 - 8 of the present application as well, a similar synergistic effect can be observed. Even though the amount of bismuth is extremely small, being 0.0125 to 0.0312 parts by mass with respect to 100 parts by mass of the urethane resin, they show antiviral activity values higher than the sum of the antiviral activity values (0.8 and 0.7) of Comparative Examples 2 and 3. Also, Comparative Example 4 is an antibacterial and antiviral agent containing both a bismuth fatty acid salt and a zirconium fatty acid salt, but it has not obtained a high antiviral activity value. It can be seen that the combination of a bismuth fatty acid salt and a rare earth fatty acid salt is important.

[0074] (Examples 9 - 10 and Comparative Examples 5 - 7: Production of Urethane Resin Coated Substrate and Antiviral Property Evaluation) To the urethane resin ("Barnock 16 - 416" manufactured by DIC Corporation), the antibacterial and antiviral agents shown in Table 2 were added in the amounts shown in Table 2, and coating compositions were prepared respectively. The prepared coating compositions were applied onto a glass substrate using an applicator so that the wet film thickness became 152 μm. After that, the obtained coated substrate was dried at room temperature for 12 hours and then further dried at 80°C for 60 minutes to produce a urethane resin antibacterial and antiviral coated substrate composed of a urethane resin coating layer and a glass substrate. Regarding the produced antibacterial and antiviral coated substrates, the following antiviral property tests were conducted. The results are shown in Table 2.

[0075] (Feline calicivirus antiviral test) An antiviral test was conducted in the same manner as the influenza virus antiviral test, except that feline calicivirus (F-9) was used instead of influenza virus (H3N2).

[0076]

Table 2

[0077] The results in Table 2 are also the same as those in Table 1, indicating that the combination of fatty acid bismuth salts and fatty acid rare earth salts is important.

[0078] (Examples 11 - 12 and Comparative Examples 8 - 11: Production of urethane resin-coated substrate and antibacterial property evaluation) An antibacterial and antiviral agent shown in Table 3 was added to urethane resin (“Barnock 16 - 416” manufactured by DIC Corporation) in the amounts shown in Table 3 to prepare coating compositions respectively. The prepared coating compositions were applied onto a glass substrate using an applicator to a wet film thickness of 152 μm. After that, the obtained coated substrate was dried at room temperature for 12 hours and then further dried at 80°C for 60 minutes to produce a urethane resin antibacterial and antiviral coated substrate composed of a urethane resin coating layer and a glass substrate. The following antibacterial test was conducted on the produced antibacterial and antiviral coated substrate. The results are shown in Table 3.

[0079] (Antibacterial test) The antibacterial property evaluation was carried out with reference to JIS Z2801:2012. Specifically, the concentration of the inoculated bacteria (Staphylococcus aureus (NBRC12732)) was 2.5×10 5 ~10×10 5The test bacterial solution adjusted to 10^6 CFU / mL was dropped in an amount of 0.4 mL onto a test piece (antibacterial coating test piece) obtained by cutting out a coating substrate into a size of 50 mm × 50 mm, and a reinforced polyethylene film was covered thereon from above. The sample covered with the reinforced polyethylene film was allowed to stand at a temperature of 35°C and a relative humidity of 90% or more for 24 hours. Then, 10 mL of the eluate was added to recover the test bacteria from the test piece, and the viable cell count was determined by the agar plate culture method. The viable cell count was similarly evaluated for a blank test piece, which was a glass substrate without the coating composition applied.

[0080] Regarding the obtained viable cell count, the antibacterial activity value was determined using the following calculation formula. A higher antibacterial activity value indicates greater antibacterial properties. Antibacterial activity value R: R = U t -A t U t : Logarithm of the viable cell count per unit area after the reaction of the unprocessed test piece A t : Logarithm of the viable cell count per unit area after the reaction of the antibacterial processed test piece

[0081] TIFF2025080741000004.tif68155

[0082] The results in Table 3 also show the same results as those in Tables 1 and 2, indicating that the combination of fatty acid bismuth salts and fatty acid rare earth salts is important.

Claims

1. An antibacterial and antiviral agent containing a fatty acid bismuth salt and a fatty acid rare earth salt.

2. 2. The antibacterial and antiviral agent according to claim 1, wherein the fatty acid bismuth salt is a bismuth salt of a fatty acid having 1 to 22 carbon atoms.

3. The antibacterial and antiviral agent according to claim 1, wherein the fatty acid bismuth salt is a bismuth salt of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid, naphthenic acid, lauric acid, stearic acid, oleic acid, palmitic acid, or myristic acid.

4. 2. The antibacterial and antiviral agent according to claim 1, wherein the fatty acid rare earth salt is a neodymium salt of a fatty acid having 1 to 22 carbon atoms.

5. 2. The antibacterial and antiviral agent according to claim 1, wherein the fatty acid rare earth salt is a neodymium salt of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid, naphthenic acid, lauric acid, stearic acid, oleic acid, palmitic acid, or myristic acid.

6. 2. The antibacterial and antiviral agent according to claim 1, wherein the fatty acid rare earth salt contains 1 to 200 moles of rare earth per mole of bismuth in the fatty acid bismuth salt.

7. An antibacterial and antiviral coating composition comprising the antibacterial and antiviral agent according to any one of claims 1 to 6 and a binder resin.

8. 8. The antibacterial and antiviral coating composition according to claim 7, wherein the binder resin is at least one selected from the group consisting of acrylic resins, vinyl acetate resins, styrene resins, vinyl chloride resins, olefin resins, urethane resins, urea resins, urethane urea resins, epoxy resins, melamine resins, phenolic resins, polyester resins, alkyd resins, silicone resins, acrylonitrile / styrene copolymer resins, and acrylonitrile / butadiene copolymer resins.

9. The antibacterial and antiviral coating composition according to claim 7, containing the metal derived from the antibacterial and antiviral agent in a range of 0.01 to 5 parts by mass per 100 parts by mass of resin solids.

10. 8. The antibacterial and antiviral coating composition according to claim 7, containing bismuth metal derived from the antibacterial and antiviral agent in an amount of 1 part by mass or less per 100 parts by mass of resin solids.

11. A laminate having a coating layer of the antibacterial and antiviral coating composition according to claim 7 and a substrate.

12. The laminate of claim 11 , wherein the coating layer is transparent.

13. An antibacterial and antiviral resin composition comprising the antibacterial and antiviral agent according to any one of claims 1 to 6 and a resin.

14. A molded article obtained by molding the antibacterial and antiviral resin composition according to claim 13.

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