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

Abstract

Provided is an antibacterial and antiviral agent having antibacterial and antiviral activity, which reduces the influence on the appearance of the application subject. Specifically, an antibacterial and antiviral agent, which is a fatty acid metal salt and / or a metal complex, wherein the metal of the aforementioned fatty acid metal salt and the aforementioned metal complex is each independently lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or a rare earth metal.

Description

Technical Field

[0001] This invention relates to antibacterial and antiviral agents, antibacterial and antiviral coating compositions, laminates, antibacterial and antiviral resin compositions, and molded articles. Background Technology

[0002] With the spread of COVID-19, people's awareness of hygiene has rapidly increased. The demand for "antibacterial and antiviral" products that reduce the possibility of infection by pathogens and viruses is expanding globally. For example, surfaces such as smartphone casings, touch panels, handrails, door handles, washbasins, elevator buttons, and the interiors of public transportation equipment are expected to be used multiple times a day; therefore, there is a strong demand for antibacterial and antiviral properties.

[0003] As antibacterial and antiviral agents, photocatalytic (TiO2, etc.) and metal (Ag, etc.) are known (for example, Patent Document 1). These metal elements or metal compounds are directly coated onto the object of application or mixed in an adhesive resin to form a coating composition, which is then coated onto the object of application for use.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-182846 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] When inorganic metal compounds, which are existing antibacterial and antiviral agents, are directly applied to the target object, the following problems arise: the color of the target object changes, and the surface becomes rough. Furthermore, when a coating composition of an inorganic metal compound and a binder resin is formed, the following problems also exist: the coating layer obtained from this composition becomes cloudy due to the inorganic metal compound, and its transparency is compromised if the binder resin is transparent. Moreover, in compositions containing inorganic metal compounds, the inorganic compound is usually in powder form, thus requiring dispersion processing, which raises concerns about productivity.

[0009] The problem this invention aims to solve is to provide an antibacterial and antiviral agent that has high compatibility with resins and antibacterial and antiviral activity, and reduces the impact on the appearance of the application object.

[0010] Solution for solving the problem

[0011] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by forming antibacterial and antiviral agents into fatty acid metal salts or metal complexes, the impact on the appearance of the application object can be reduced, thus completing the present invention.

[0012] That is, the present invention relates to an antibacterial and antiviral agent, which is selected from one or more of the group consisting of fatty acid metal salts, metal complexes containing heteroatom ligands and metal ions, and metal complexes containing heteroatom ligands and fatty acid metal salts, wherein the metals of the aforementioned fatty acid metal salts, the aforementioned metal complexes containing heteroatom ligands and metal ions, and the aforementioned metal complexes containing heteroatom ligands and fatty acid metal salts are each independently lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth metals.

[0013] The effects of the invention

[0014] According to the present invention, an antibacterial and antiviral agent having high compatibility with resins and antibacterial and antiviral activity, and reducing the impact on the appearance of the application object, can be provided. Detailed Implementation

[0015] Hereinafter, one embodiment of the present invention will be described. The present invention is not limited to the following embodiment, and can be appropriately modified and implemented within the scope that does not impair the effects of the present invention.

[0016] [Antibacterial and antiviral agents]

[0017] The antibacterial and antiviral agent of the present invention is selected from one or more of the group consisting of fatty acid metal salts, metal complexes containing heteroatom ligands and metal ions, and metal complexes containing heteroatom ligands and fatty acid metal salts, wherein the metal in the aforementioned fatty acid metal salts, the aforementioned metal complexes containing heteroatom ligands and metal ions, and the aforementioned metal complexes containing heteroatom ligands and fatty acid metal salts are each independently lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth metals.

[0018] The antibacterial and antiviral agent of the present invention is in the form of a fatty acid metal salt or a metal complex. It is believed that by adding the antibacterial and antiviral properties of the metal and the high compatibility of the fatty acid or complex ligand with organic matter to a coating composition containing a binder resin, the resulting coating layer can be endowed with antibacterial and antiviral properties while reducing the impact on appearance, such as damage to the transparency of the coating layer due to the antibacterial and antiviral agent.

[0019] In this invention, "antibacterial" encompasses the effects of reducing the number of bacteria, inactivating bacteria, and reducing the infectivity of bacteria. Similarly, in this invention, "antiviral" encompasses the effects of reducing the number of viruses, inactivating viruses, and reducing the infectivity of viruses.

[0020] The bacteria used as antimicrobial targets in this invention are not particularly limited and can be either bacteria or fungi. Examples of bacteria include Gram-negative bacteria such as *Escherichia coli*, *Pseudomonas aeruginosa*, *Salmonella*, *Moraxella osloi*, and *Legionella*; and Gram-positive bacteria such as *Staphylococcus aureus* and *Clostridium*. Examples of fungi include yeasts such as *Candida*, *Rhodotorula rubrum*, and *Bakery's yeast*; and molds such as *Russula rubrum* and *Russula nigra*.

[0021] The virus used as the antiviral target in this invention is not particularly limited and can be either a known enveloped virus (a virus with a coronavirus) or a non-enveloped virus (a virus without a coronavirus).

[0022] Examples of enveloped viruses mentioned above include coronaviruses, influenza viruses, rubella viruses, Ebola viruses, measles viruses, varicella / zoster viruses, herpes viruses, mumps viruses, vector-borne viruses, RS viruses, SARS viruses, hepatitis viruses (such as hepatitis A, hepatitis B, hepatitis C, hepatitis D, hepatitis E, etc.), yellow fever viruses, HIV, rabies viruses, Hantavirus, dengue viruses, Nipah viruses, and Lyssa viruses.

[0023] Examples of non-enveloped viruses mentioned above include adenovirus, norovirus, rotavirus, HPV, poliovirus, enterovirus, Coxsackievirus, human parvovirus, encephalomyelitis virus, polyomavirus, BK virus, rhinovirus, and feline calicivirus.

[0024] The antibacterial and antiviral agents of the present invention will be described below.

[0025] (Fatty acid metal salts)

[0026] The fatty acid metal salts used as antibacterial and antiviral agents of the present invention are, for example, compounds represented by the following general formula (1).

[0027] (R 1 COO) n1 M 1 (1)

[0028] (In the aforementioned general formula (1),

[0029] R 1 It is an alkyl group having 1 to 21 hydrogen atoms or carbon atoms.

[0030] n1 is an integer in the range of 1 to 4.

[0031] M 1 It can be lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth metals.

[0032] In the aforementioned general formula (1), when n1 is an integer greater than or equal to 2, multiple R 1 Choose whether they are the same or different from each other.

[0033] R 1 The alkyl group having 1 to 21 carbon atoms can be a straight-chain alkyl group, a branched alkyl group, or an alicyclic structure.

[0034] R 1 The hydrogen atoms or alkyl groups having 1 to 21 carbon atoms correspond to R used in the manufacture of fatty acid metal salts. 1 Carboxylic acid residues obtained by removing the carboxyl group (COOH) from carboxylic acids with 1 to 22 carbon atoms (represented by COOH). Examples of such carboxylic acid residues include formic acid residues, acetic acid residues, propionic acid residues, butyric acid residues, valeric acid residues, hexanoic acid residues, 2-ethylbutyric acid residues, heptanoic acid residues, octanoic acid residues, acrylic acid residues, methacrylic acid residues, octanoic acid residues (2-ethylhexanoic acid residues), neodecanoic acid residues, naphthenic acid residues, isononanoic acid residues, tung oil acid residues, tall oil fatty acid residues, coconut oil fatty acid residues, soybean oil fatty acid residues, linseed oil fatty acid residues, safflower oil fatty acid residues, dehydrated castor oil fatty acid residues, tung oil fatty acid residues, lauric acid residues, myristic acid residues, palmitic acid residues, stearic acid residues, isostearic acid residues, and oleic acid residues.

[0035] From the perspective of substrate adhesion, as discussed later, R 1 The alkyl group having 1 to 21 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 11 carbon atoms.

[0036] R 1 Preferred residues include formic acid residues, acetic acid residues, propionic acid residues, butyric acid residues, valeric acid residues, hexanoic acid residues, 2-ethylbutyric acid residues, heptanoic acid residues, octanoic acid residues, 2-ethylhexanoic acid residues, isononanoic acid residues, neodecanoic acid residues, cycloalkyl acid residues, stearic acid residues, or oleic acid residues.

[0037] M 1 The metal is lithium, sodium, potassium, rubidium, cesium, boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, silver, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth metals, preferably bismuth, neodymium, magnesium, cobalt, copper, silver, zinc, lead, yttrium, lanthanum, praseodymium, samarium, or gadolinium, and more preferably bismuth, neodymium, magnesium, cobalt, silver, copper, lead, yttrium, lanthanum, praseodymium, samarium, or gadolinium.

[0038] If the metal in the fatty acid metal salt is bismuth, neodymium, magnesium, lanthanum, gadolinium, or samarium, it is less likely to cause coloration due to the addition of antibacterial and antiviral agents.

[0039] It should be noted that, in this invention, rare earth metals refer to 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).

[0040] n1 is based on M 1 The value is determined by the ionic valence of the metal atom, for example, M. 1 If it is boron, then n1 becomes 3, M 1 If it is cobalt, then n1 becomes 2.

[0041] The fatty acid metal salts used as antibacterial and antiviral agents of the present invention also include fatty acid borate metal salts. These fatty acid borate metal salts are, for example, compounds represented by the following general formula (2).

[0042] (R 2 COO-M 2 -O)3B (2)

[0043] (In the aforementioned general formula (2),

[0044] R 2 It is an alkyl group having 1 to 21 hydrogen atoms or carbon atoms.

[0045] M 2 It can be boron, magnesium, aluminum, calcium, manganese, iron, cobalt, nickel, tin, antimony, copper, zinc, molybdenum, vanadium, strontium, zirconium, barium, bismuth, lead, gold, platinum, or rare earth metals.

[0046] In the aforementioned general formula (2), R 2 Alkyl groups with 1 to 21 carbon atoms and R of the aforementioned general formula (1) 1 The alkyl groups with 1 to 21 carbon atoms are the same. Similarly, in the aforementioned general formula (2), M 2 The metal and the M of the aforementioned general formula (1) 1 The metals are the same.

[0047] When using fatty acid metal salts as the antibacterial and antiviral agents of the present invention, the fatty acid metal salts used can be a single type or two or more fatty acid metal salts with different structures.

[0048] Fatty acid metal salts can be manufactured using known methods or commercially available products.

[0049] (Metal complex)

[0050] The metal complexes of heteroatom-containing ligands and metal ions and the metal complexes of heteroatom-containing ligands and fatty acid metal salts used as antibacterial and antiviral agents of the present invention are compounds in which metal ions or fatty acid metal salts form complexes with heteroatom-containing ligands through coordination bonds.

[0051] The metal ion that forms a metal complex as a heteroatom-containing ligand can be the same metal ion as the fatty acid metal salt described as the antibacterial and antiviral agent of the present invention.

[0052] As a fatty acid metal salt that forms a metal complex with heteroatom-containing ligands, the same fatty acid metal salt described as the antibacterial and antiviral agent of the present invention can be used.

[0053] The heteroatom-containing ligand for forming a metal complex only needs to be a ligand having one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus within the molecule. Examples of such heteroatom-containing ligands 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, and monobutylamine. Ethanolamine, diethanolamine, triethanolamine, 2-[[(2-dimethylamino)ethyl]methylamino]ethanol, pyridinecarboxylic acid, N,N'-disalicyl-1,2-propanediamine (2,2'-[Propane-1,2-diylbis(azanylylidenemethanylylidene)]diphenol), imidazole, 1-methylimidazolium, 2-methylimidazolium, 4-methylimidazolium, 2,4-dimethylimidazolium, 1,4-diethyl Imidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, 8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, 2,2'-bipyridine and its derivatives, N,N'-bis(salicylic acid)-1,2-propanediamine and its derivatives, 2,2'-methylenebis[6- Amine compounds such as (2h-benzotriazol-2-yl)-4-tert-octylphenol; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphine salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; thiolactic acid, 2-aminobenzylthiophenol, and 2,2'-dithiodiphenylamine, etc.

[0054] The heteroatom-containing ligand is preferably one or more amine ligands selected from pyridinecarboxylic acid, 2-{[(2-dimethylamino)ethyl]methylamino}ethanol, 1,2-propanediamine, 1,2-cyclohexanediamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazolium, 2-methylimidazolium, 4-methylimidazolium, 2,4-dimethylimidazolium, 1,4-diethylimidazolium, 8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, 2,2'-bipyridine and its derivatives, and N,N'-bis(salicyl)-1,2-propanediamine and its derivatives.

[0055] The heteroatom-containing ligands that form metal complexes can be a single type or two or more types with different structures.

[0056] In metal complexes, the ratio (molar ratio) of metal ions or fatty acid metal salts to heteroatom-containing ligands is, for example, 0.1 to 12 moles of heteroatom-containing ligands, preferably 0.3 to 10 moles, and more preferably 0.5 to 10 moles, relative to 1 mole of metal atoms in the metal ions or fatty acid metal salts.

[0057] When the metal ion in the metal complex is an aluminum ion, the aluminum complex is preferably selected from one or more aluminum chelate compounds shown in general formula (3-1) and general formula (3-2).

[0058]

[0059] (In the aforementioned general formulas (3-1) and (3-2),

[0060] R 311 ~R 316 and R 321 ~R 326 Each is independently an alkyl group having 1 to 22 carbon atoms or an alkoxy group having 1 to 22 carbon atoms.

[0061] R 311 ~R 316 and R 321 ~R 326 The alkyl group having 1 to 22 carbon atoms and the alkylene group having 1 to 22 carbon atoms can be straight-chain, branched, or contain alicyclic structures. R 311 ~R 316 and R 321 ~R 326 The alkyl and alkoxy alkylene moieties preferably have 1 to 9 carbon atoms.

[0062] R 311 ~R 316 and R 321 ~R 326 The alkyl group having 1 to 22 carbon atoms is preferably methyl or ethyl.

[0063] R 311 ~R 316 and R 321 ~R 326 The alkoxy group with 1 to 22 carbon atoms is preferably methoxy, ethoxy, or oleyloxy.

[0064] Specific examples of aluminum chelating compounds include tri(aluminum acetylacetonate), tri(ethyl acetoacetate)aluminum, monoacetylacetonate aluminum bis(ethyl acetoacetate), monoacetylacetonate aluminum dioleyl acetoacetate, ethyl aluminum acetoacetate diisopropyl, and alkyl aluminum acetoacetate diisopropyl.

[0065] The antibacterial and antiviral agent of the present invention is preferably a non-water-soluble antibacterial and antiviral agent. Because the antibacterial and antiviral agent is non-water-soluble, its antibacterial and antiviral properties remain excellent even when exposed to everyday rain or other water.

[0066] It should be noted that in this application, "non-water-soluble" means that the amount of water required to dissolve 1g of the antibacterial and antiviral agent at 20°C is more than 10ml.

[0067] Metal complexes of heteroatom-containing ligands with metal ions and metal complexes of heteroatom-containing ligands with fatty acid metal salts, which are used as antibacterial and antiviral agents, can be manufactured by known methods, such as reacting a metal element or a fatty acid metal salt with a heteroatom-containing ligand. Alternatively, commercially available products can also be used.

[0068] [Coating Composition]

[0069] The coating composition of the present invention contains: the antibacterial and antiviral agent of the present invention and the adhesive resin.

[0070] The antibacterial and antiviral agent of the present invention exhibits high compatibility with adhesive resins. Therefore, coatings obtained from coating compositions containing the antibacterial and antiviral agent of the present invention can reduce the impact on appearance, such as impaired transparency, caused by the antibacterial and antiviral agent. Furthermore, the antibacterial and antiviral agent of the present invention can demonstrate a adhesion-promoting effect with the substrate, and coatings containing the antibacterial and antiviral agent of the present invention can exhibit high adhesion to the substrate. Therefore, the coating of the laminate of the substrate and the coating layer stacked on the substrate exhibits antibacterial and antiviral properties, while also exhibiting high adhesion between the substrate and the coating layer.

[0071] 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, it is preferable to contain the metal source of the antibacterial and antiviral agent in the range of 0.01 to 30 parts by weight relative to 100 parts by weight of the resin solids, more preferably in the range of 0.01 to 15 parts by weight relative to 100 parts by weight of the resin solids, more preferably in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the resin solids, and even more preferably in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the resin solids.

[0072] Here, "solid resin content" refers to the total amount of solid components such as adhesive resin contained in the coating composition.

[0073] The antibacterial and antiviral agents contained in the coating composition of the present invention may be a single agent or two or more agents.

[0074] The binder resin contained in the coating composition of the present invention is not particularly limited, and for example, any type of emulsion resin, latex resin, thermosetting resin, or active energy ray curable resin can be used.

[0075] The adhesive resin can be either water-based or non-water-soluble (solvent-based) resin.

[0076] It should be noted that, in this application, "water-soluble resin" refers to resin for which less than 10 ml of water is required to dissolve 1 g of resin at 20°C. "Insoluble resin" refers to resin that is not the aforementioned "water-soluble resin".

[0077] Specific examples of adhesive resins include acrylic resins, vinyl acetate resins, styrene resins, vinyl chloride resins, olefin resins, urethane resins, urea resins, urethane urethane resins, acrylate urethane resins, epoxy resins, melamine resins, phenolic resins, polyester resins, alkyd resins, silicone resins, polyphenylene sulfide resins, acrylonitrile / styrene copolymer resins, acrylonitrile / butadiene copolymer resins, and acrylonitrile / butadiene / styrene copolymer (ABS) resins.

[0078] The term "adhesive resin" also includes those modified from the aforementioned resins; for example, if it is a phenolic resin, it also includes rosin-modified phenolic resin.

[0079] The adhesive resin contained in the coating composition of the present invention may be a single type or two or more types.

[0080] The content of the binder resin in the coating composition of the present invention is not particularly limited, and can be appropriately set in the range of 10 to 100% by mass relative to the total mass of the resin solids in the coating composition.

[0081] The coating composition of the present invention only needs to contain the antibacterial and antiviral agent and the binder resin of the present invention, and may also contain a dispersion medium. The dispersion medium is added for the purpose of adjusting the viscosity of the coating composition, and therefore can be an aqueous medium or an oil-based medium, either is acceptable.

[0082] Specific examples of dispersion media include: water, 1-butanol, isobutanol, 1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, methyl ethyl ketone, methanol, ethanol, n-propanol, isopropanol, and other monofunctional alcohols; various glycols, glycerol, and other polyols; 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, and other glycols; bisphenol A, and the carbon source of bisphenol A. Aromatic diols, hydrogenated bisphenol A, and other alicyclic diols, such as 2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane, cyclohexanediol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, ethyl carbitol, γ-butyrolactone, and various fatty acids.

[0083] The dispersion medium contained in the coating composition of the present invention may be a single type or two or more types.

[0084] The content of the dispersion medium in the coating composition of the present invention is not particularly limited, and can be appropriately set, for example, so that the concentration of the solid component of the coating composition is in the range of 30 to 80% by mass.

[0085] The coating composition of the present invention may also contain a plasticizer.

[0086] By adding a plasticizer to the coating composition, the resulting coating layer can be made more flexible, thus improving its conformability to the substrate.

[0087] There are no particular limitations on plasticizers, but examples include phthalates, non-aromatic diesters, aliphatic esters, esters of polyalkylene glycols, phosphate esters, trimellitates, chlorinated paraffins, hydrocarbon oils, processing oils, polyethers, epoxy plasticizers, and polyester plasticizers, with phthalates being preferred.

[0088] Specific examples of plasticizers 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, and benzyl epoxidized stearate.

[0089] The plasticizer contained in the coating composition of the present invention may be a single type or two or more types.

[0090] The content of plasticizer in the coating composition of the present invention is not particularly limited, and can be appropriately set in the range of 0.1 to 50 parts by weight relative to 100 parts by weight of the resin solids component of the coating composition.

[0091] The coating composition of the present invention only needs to contain the antibacterial and antiviral agent of the present invention, the binder resin, and optionally a dispersing medium and / or a plasticizer. Other additives may also be included without impairing the effects of the present invention. Examples of such other additives include pigments, matting agents, curing agents, curing accelerators, defoamers, dispersants, leveling agents, thickeners, antioxidants, weathering agents, flame retardants, antistatic agents, lubricants, and preservatives.

[0092] The coating composition of the present invention is applied to the surface of a substrate, and the resulting coating film is cured by a curing method suitable for the adhesive resin (thermal curing, active energy radiation curing, etc.) to form a coating layer.

[0093] For the coating method of the coating composition, any known and commonly used coating method can be used, such as roller coating, electrostatic coating, bar coating, gravure coating, doctor blade coating, dip coating, spraying and other methods.

[0094] There are no particular limitations on the substrate to be coated, and examples include paper, synthetic paper, steel plate, aluminum foil, glass, wood, woven fabric, knitted fabric, non-woven fabric, gypsum board, wood board, resin substrate, etc.

[0095] Specific examples of the aforementioned resin substrates 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 oriented 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, cellulose triacetate resin film, polyvinyl alcohol film, ABS resin film, norbornene resin film, cyclic olefin resin film, polyimide resin film, ethylene fluoride resin film, polyvinylidene fluoride resin film, and ethylene-vinyl acetate copolymer film.

[0096] The resin substrate used can also undergo surface treatments such as corona treatment.

[0097] [Resin Composition]

[0098] The resin composition of the present invention contains: the antibacterial and antiviral agent of the present invention and the resin.

[0099] Resin compositions containing the antibacterial and antiviral agents of the present invention can be used not only for coating purposes, but also to form molded articles that exhibit antibacterial and antiviral properties by molding them.

[0100] The resin contained in the resin composition of the present invention may be the same as the adhesive resin contained in the coating composition of the present invention. Furthermore, the resin composition of the present invention may contain the same components as those contained in the coating composition of the present invention.

[0101] The molding method of the resin composition of the present invention can be any molding method suitable for the resin used, such as injection molding, extrusion molding, compression molding, pneumatic molding, vacuum molding, and other melt molding and casting methods.

[0102] The coating 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 as materials with antibacterial and antiviral activity for parts that come into contact with human hands. As applications, it can be used in a wide range of applications, including smartphone casings, personal computer casings, touch panels, handrails, door handles, washbasins, elevator buttons, interior decorations (wallpaper, flooring, etc.), various packaging materials, various fiber products, and medical equipment (medical handbags, medical eyeglasses, etc.).

[0103] Example

[0104] The present invention will now be specifically described through examples and comparative examples.

[0105] It should be noted that the present invention is not limited to the following embodiments.

[0106] (Synthesis Example 1: Preparation of Fatty Acid Metal Salt (Cu))

[0107] 217.1 parts by mass of neodecanoic acid and 36.0 parts by mass of sodium hydroxide were reacted at 80°C, and then 100.0 parts by mass of copper sulfate were added, followed by reaction at 80°C. The byproduct sodium sulfate was washed with water and then dehydrated under reduced pressure at 130°C. 76.2 parts by mass of petroleum hydrocarbons were added to obtain 301.6 parts by mass of a copper neodecanoate solution (fatty acid metal salt (Cu)). The copper content in the obtained fatty acid metal salt (Cu) was 8% by mass.

[0108] (Synthesis Example 2: Preparation of Fatty Acid Metal Salt (Co))

[0109] 319.0 parts by mass of 2-ethylhexanoic acid and 100.0 parts by mass of cobalt hydroxide were reacted at 130°C. After dehydration under reduced pressure at 130°C, 134.2 parts by mass of petroleum-based hydrocarbons were added to obtain 502.3 parts by mass of a cobalt 2-ethylhexanoate solution (fatty acid metal salt (Co)). The cobalt content in the obtained fatty acid metal salt (Co) was 12% by mass.

[0110] (Synthetic Example 3: Preparation of Fatty Acid Metal Salt (Nd))

[0111] 224.8 parts by mass of neodecanoic acid and 60.0 parts by mass of neodymium oxide were reacted at 130°C. After dehydration under reduced pressure at 130°C, 306.9 parts by mass of cyclohexane were added to obtain 570.0 parts by mass of neodymium neodecanoate solution (fatty acid metal salt (Nd)). The neodymium content in the obtained fatty acid metal salt (Nd) was 8.8% by mass.

[0112] (Synthetic Example 4: Preparation of Fatty Acid Metal Salts (Bi))

[0113] 330.6 parts by mass of 2-ethylhexanoic acid and 125.0 parts by mass of bismuth oxide were reacted at 130°C. 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.

[0114] (Synthetic Example 5: Preparation of Fatty Acid Metal Salt (Mg))

[0115] 461.4 parts by mass of 2-ethylhexanoic acid, 71.9 parts by mass of magnesium hydroxide, and 411.4 parts by mass of petroleum hydrocarbons were reacted at 110°C. After dehydration under reduced pressure at 90°C, 35.9 parts by mass of butyl diethylene glycol were added to obtain 1000 parts by mass of a magnesium 2-ethylhexanoate solution (fatty acid metal salt (Mg)). The magnesium content in the obtained fatty acid metal salt (Mg) was 3.0% by mass.

[0116] (Synthetic Example 6: Preparation of Fatty Acid Metal Salt (La))

[0117] 83.1 parts by mass of neodecanoic acid and 21.5 parts by mass of lanthanum oxide were reacted at 130°C. After dehydration under reduced pressure at 130°C, 107.6 parts by mass of cyclohexane were added to obtain 208.5 parts by mass of a lanthanum neodecanoic acid solution (fatty acid metal salt (La)). The lanthanum content in the obtained fatty acid metal salt (La) was 8.8% by mass.

[0118] (Synthesis Example 7: Preparation of Fatty Acid Metal Salt (Pr))

[0119] 166.6 parts by mass of neodecanoic acid and 45.0 parts by mass of praseodymium oxide were reacted at 130°C. After dehydration under reduced pressure at 130°C, 220.0 parts by mass of cyclohexane were added to obtain 422.0 parts by mass of a praseodymium neodecanoate solution (fatty acid metal salt (Pr)). The praseodymium content in the obtained fatty acid metal salt (Pr) was 8.8% by mass.

[0120] (Synthetic Example 8: Preparation of Fatty Acid Metal Salt (Sm))

[0121] 137.1 parts by mass of neodecanoic acid and 37.6 parts by mass of samarium oxide were reacted at 130°C. After dehydration under reduced pressure at 130°C, 196.3 parts by mass of cyclohexane were added to obtain 364.7 parts by mass of samarium neodecanoate solution (fatty acid metal salt (Sm)). The samarium content in the obtained fatty acid metal salt (Sm) was 8.8% by mass.

[0122] (Synthetic Example 9: Preparation of Fatty Acid Metal Salt (Gd))

[0123] 149.3 parts by mass of neodecanoic acid and 43.0 parts by mass of gadolinium oxide were reacted at 130°C. After dehydration under reduced pressure at 130°C, 230.2 parts by mass of cyclohexane were added to obtain 415.1 parts by mass of a gadolinium neodecanoate solution (fatty acid metal salt (Gd)). The gadolinium content in the obtained fatty acid metal salt (Gd) was 8.8% by mass.

[0124] (Synthetic Example 10: Preparation of Fatty Acid Metal Salt (Nd2))

[0125] 192.8 parts by mass of 2-ethylhexanoic acid and 60.0 parts by mass of neodymium oxide were reacted at 130°C. After dehydration under reduced pressure at 130°C, 338.5 parts by mass of cyclohexane were added to obtain 581.6 parts by mass of a neodymium 2-ethylhexanoate solution (fatty acid metal salt (Nd2)). The neodymium content in the obtained fatty acid metal salt (Nd2) was 8.8% by mass.

[0126] (Synthetic Example 11: Preparation of Metal Complex (Mn))

[0127] 50 parts by mass of 8-hydroxyquinoline were added to a solution of 291 parts by mass of manganese neodecanoate solution (Mn: 6.5 wt%) and 1235 parts by mass of benzyl alcohol, and the mixture was reacted at 50 °C for 1 hour to obtain 1576 parts by mass of a complex solution of manganese neodecanoate and 8-hydroxyquinoline (metal complex (Mn)). The manganese content in the obtained metal complex (Mn) was 1.2 wt%.

[0128] In addition to the above, commercially available products of yttrium 2-ethylhexanoate (Y), lead 2-ethylhexanoate (Pb), and silver 2-ethylhexanoate (Ag) were prepared respectively (yttrium 2-ethylhexanoate was manufactured by FUJIFILM Wako Chemicals Corporation, lead 2-ethylhexanoate by DIC Corporation, and silver 2-ethylhexanoate by FUJIFILM Wako Chemicals Corporation).

[0129] (Examples 1-13 and Comparative Examples 1-2: Preparation of urethane resin coated substrates)

[0130] Antibacterial and antiviral agents as shown in Tables 1 and 2 were mixed into urethane urea resin (Burnock EPL-925 manufactured by DIC Co., Ltd.) such that the metal content of the antibacterial and antiviral agents was 1% by mass of the solid component of the aforementioned urethane urea resin, and coating compositions were prepared accordingly. In Comparative Example 1, no antibacterial and antiviral agents were added. In Comparative Example 2, an inorganic silver compound (Novaron IV1000 (manufactured by Toa Synthetic Co., Ltd.)) was added in an amount equal to the solid component content (NV. 51% by mass) of the fatty acid metal salt (Cu) of Example 1, and coating compositions were prepared accordingly.

[0131] Using a smearer, the prepared coating composition is applied to a glass substrate to achieve a wet film thickness of 152 μm. The resulting coated substrate is then dried at room temperature for 12 hours, followed by further drying at 80°C for 60 minutes to produce a urethane urea resin coated substrate formed by the urethane urea resin coating layer and the glass substrate.

[0132] (Examples 14-16 and Comparative Example 3: Preparation of waterborne acrylic resin coated substrates)

[0133] Antibacterial and antiviral agents as shown in Table 3 were mixed into an aqueous acrylic resin (Bonkote CG-6150 manufactured by DIC Corporation) such that the metal content of the antibacterial and antiviral agents was 1% by mass of the solid component of the aforementioned aqueous acrylic resin, and coating compositions were prepared accordingly. Using an applicator, the prepared coating compositions were applied to a glass substrate to achieve a wet film thickness of 152 μm. The resulting coated substrate was dried at room temperature for 12 hours, and then further dried at 80°C for 60 minutes to produce an aqueous acrylic resin coated substrate formed by the aqueous acrylic resin coating layer and the glass substrate.

[0134] (Example 17 and Comparative Example 4: Preparation of urethane acrylate resin coated substrate)

[0135] Antibacterial and antiviral agents as shown in Table 4 were mixed into urethane acrylate resin (Luxydir 17-806 manufactured by DIC Corporation) such that the metal content of the antibacterial and antiviral agents was 1% by mass of the solid component of the aforementioned urethane acrylate resin. Irgacure 184 photoinitiator was further mixed in such a way that it constituted 5% by mass of the resin solid component. The mixtures were diluted with solvent to prepare coating compositions. Using a rod coater, the prepared coating compositions were coated onto a glass substrate to a wet film thickness of 30 μm. The resulting coated substrate was then dried at 60°C for 5 minutes and subjected to irradiation at a nitrogen atmosphere with a radiation dose of 200 mJ / cm². 2 The process involves curing to create a coated substrate consisting of a urethane acrylate resin coating and a glass substrate.

[0136] For the manufactured coated substrates, Comparative Examples 1, 3, and 4 were used as blank test pieces that substantially contained no antibacterial or antiviral agents, and Examples 1-17 and Comparative Example 2 were used as antibacterial and antiviral coated test pieces. The following antiviral and antibacterial tests were conducted. The results are shown in Tables 1-4.

[0137] (Antiviral test)

[0138] Antiviral efficacy was evaluated as follows: using the membrane closure method of JIS R1706:2020 as a reference, and bacteriophage Qβ as the target.

[0139] The inoculation conditions for viruses on the surfaces of blank test pieces and antibacterial / antiviral coated test pieces were set to 4 hours at 25°C in the dark. Based on the phage Qβ infection titers of the blank test pieces and antibacterial / antiviral coated test pieces after 4 hours of reaction, the antiviral activity value was calculated using the following formula. The results are shown in Table 1. An antiviral activity value of 2.0 or higher was considered to indicate an antiviral effect.

[0140] V = Log(A / B) = Log(A) - Log(B)

[0141] V: Antiviral activity value

[0142] Log(A): A commonly used logarithmic value of the infection titer 4 hours after the reaction of the blank test strip.

[0143] Log(B): A commonly used logarithmic value of the infection titer of an antibacterial or antiviral coating test strip 4 hours after reaction.

[0144] (Antibacterial test)

[0145] Antimicrobial activity was evaluated using San-ai biochecker FC (manufactured by San-ai Petroleum Co., Ltd.). Well water that had been left to stand at room temperature for one week was dropped onto the surface of the San-ai biochecker culture medium, brought into contact with the coating layer of the substrate, and fixed with masking tape. The sample was incubated at 30°C for 2 days. Cases where colonies formed in any culture medium were marked as ×, and cases where no colonies formed in any culture medium were marked as ○.

[0146] (Transparency Test)

[0147] The transparency of the coating layer on the manufactured coated substrate is visually confirmed and evaluated based on the following criteria.

[0148] ○: No turbidity detected

[0149] ×: Confirmed turbidity

[0150] [Table 1]

[0151]

[0152] [Table 2]

[0153]

[0154] [Table 3]

[0155]

[0156] [Table 4]

[0157]

[0158] As shown in Tables 1-4, in Comparative Examples 1, 3 and 4, the coating layer does not contain antibacterial or antiviral agents (the coating layer is composed only of adhesive resin). In contrast, in Examples 1-17 of this application, antibacterial properties are obtained without compromising transparency by adding the antibacterial and antiviral agents of the present invention.

[0159] The antibacterial and antiviral agent in Comparative Example 2 was Novaron IV1000 (manufactured by Toa Synthetic Co., Ltd.), an inorganic silver compound. Since the antibacterial and antiviral agent in Comparative Example 2 was an inorganic compound, it was incompatible with urethane resin. Therefore, a disperser was used in the composition preparation to disperse the antibacterial and antiviral agent. A white turbidity was observed in the coating obtained in Comparative Example 2, indicating that the transparency of the coating was impaired.

[0160] (Examples 18-19 and Comparative Example 5: Manufacturing of Printed Materials)

[0161] A coating composition was prepared by adding the antibacterial and antiviral agents shown in Table 5 to a base coating consisting of 15.0 g of urethane urea resin, 30.0 g of white ink mill base, and 36.0 g of mixed organic solvent (EtAc / IPA = 60 / 40 (mass ratio)). The amount of metal in the antibacterial and antiviral agents was 0.5% by mass of the solid components of the base coating.

[0162] Using a gravure correction machine equipped with a 35 μm deep gravure plate, the prepared coating composition was printed onto a corona-treated biaxially stretched polypropylene film (hereinafter referred to as OPP film), and dried at 45°C to obtain the printed material. The obtained printed material was evaluated as follows.

[0163] (Fitness assessment)

[0164] After the printed material has been left for 1 day, a transparent tape is applied to the printed surface, and the appearance of the printed film is visually judged when it is quickly peeled off according to the following criteria.

[0165] A: The printed coating was not completely peeled off.

[0166] B: 50-80% of the printed coating remains on the film.

[0167] C: Less than 50% of the printed coating remains on the film.

[0168] [Table 5]

[0169]

[0170] As can be seen from the results in Table 5, the adhesion between the coating layer and the substrate is improved by adding the antibacterial and antiviral agent of the present invention.

Claims

1. An antibacterial and antiviral composition comprising an antibacterial and antiviral agent and a binder resin, wherein the antibacterial and antiviral agent is a fatty acid metal salt, wherein... The metal of the fatty acid metal salt is bismuth, neodymium, lanthanum, praseodymium, samarium, or gadolinium. The fatty acids in the fatty acid metal salt are propionic acid, butyric acid, valeric acid, hexanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, isononanoic acid, and neodecanoic acid.

2. The antiviral composition according to claim 1, wherein, The adhesive resin is selected from one or more of the following groups: acrylic resin, vinyl acetate resin, styrene resin, vinyl chloride resin, olefin resin, urethane resin, urea resin, urethane urea resin, epoxy resin, melamine resin, phenolic resin, polyester resin, alkyd resin, silicone resin, acrylonitrile-styrene copolymer resin, and acrylonitrile-butadiene copolymer resin.

3. The antiviral composition according to claim 1 or 2, wherein, The metal containing the antibacterial and antiviral agent is in the range of 0.01 to 30 parts by weight relative to 100 parts by weight of the resin solids.

4. A laminate having a coating layer and a substrate of the antibacterial and antiviral composition according to any one of claims 1 to 3.

5. The laminate according to claim 4, wherein The coating is transparent.

6. A molded article obtained by molding the antibacterial and antiviral composition of claim 1.

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