Coating material imparting resistance to lower alcohols, laminate, partition and antibacterial member

Abstract

To provide a lower alcoholic property resistance-imparting coat agent capable of imparting excellent lower alcoholic property resistance, a laminate, a partition and an antiviral member.SOLUTION: A coating material for imparting lower alcohol resistance contains a copolymer of a monomer composition containing a nitrile group-containing unsaturated ethylenic monomer, and / or a benzene ring-containing unsaturated ethylenic monomer, and a carboxyl group-containing unsaturated ethylenic monomer, and an aqueous solvent dissolving and / or dispersing the copolymer. With respect to a total amount of the monomer composition, when the nitrile group-containing unsaturated ethylenic monomer is contained, a content ratio of the nitrile group-containing unsaturated ethylenic monomer is 10 mass% or more and 70 mass% or less, when the benzene ring-containing unsaturated ethylenic monomer is contained, a content ratio of the benzene ring-containing unsaturated ethylenic monomer is 5 mass% or more and 66 mass % or less, and a content ratio of the carboxylic group-containing unsaturated ethylenic monomer is 1 mass% or more and 10 mass% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a coating material imparting resistance to lower alcohols, a laminate, a partition, and an antibacterial member. [Background technology]

[0002] In recent years, partitions have been proposed to prevent droplet infection as a measure against viruses and the like (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Utility Model Registration No. 3228065 Summary of the Invention [Problem to be solved by the invention]

[0004] However, such partitions need to be disinfected with alcohol, and repeated disinfection of the partitions with alcohol can cause deterioration of the partitions.

[0005] The present invention relates to a lower alcohol resistance-imparting coating material that can impart excellent lower alcohol resistance, a laminate having a coating layer of the lower alcohol resistance-imparting coating material, a partition including the laminate, and an antibacterial member including the laminate. [Means for solving the problem]

[0006] The present invention [1] includes a lower alcohol-resistant coating material comprising a copolymer of a monomer composition containing a nitrile group-containing unsaturated ethylenic monomer and / or a benzene ring-containing unsaturated ethylenic monomer and a carboxyl group-containing unsaturated ethylenic monomer, and an aqueous solvent for dissolving and / or dispersing the copolymer, wherein, relative to the total amount of the monomer composition, if the nitrile group-containing unsaturated ethylenic monomer is contained, the content of the nitrile group-containing unsaturated ethylenic monomer is 10% by mass or more and 70% by mass or less, and if the benzene ring-containing unsaturated ethylenic monomer is contained, the content of the benzene ring-containing unsaturated ethylenic monomer is 5% by mass or more and 66% by mass or less, and the content of the carboxyl group-containing unsaturated ethylenic monomer is 1% by mass or more and 10% by mass or less.

[0007] The present invention [2] is characterized in that the glass transition temperature of the copolymer is 10°C or higher and 100°C or lower. The coating material for imparting resistance to lower alcohols described in [1] above is included.

[0008] The present invention [3] includes the lower alcohol-resistant coating material according to the above [1] or [2], which further contains a crosslinking agent.

[0009] The present invention [4] includes a laminate comprising a member and a coating layer of the lower alcohol resistance-imparting coating material described in any one of [1] to [3] above, formed on at least one side of the member.

[0010] The present invention [5] includes the laminate according to the above [4], and includes a partition in which the member is a plastic substrate.

[0011] The present invention [6] includes the laminate described in the above [4], and includes an antibacterial member in which the member has been subjected to an antibacterial treatment. [Effects of the Invention]

[0012] The lower alcohol-resistant coating material of the present invention contains a copolymer of a monomer composition containing a nitrile group-containing unsaturated ethylenic monomer and / or a benzene ring-containing unsaturated ethylenic monomer and a carboxyl group-containing unsaturated ethylenic monomer in a predetermined ratio, and therefore can form a coating layer (coating layer) with excellent lower alcohol resistance.

[0013] The laminate of the present invention has a coating layer of a lower alcohol resistance-imparting coating material that has excellent lower alcohol resistance, and therefore the laminate of the present invention has excellent lower alcohol resistance.

[0014] The partition of the present invention includes a laminate having excellent resistance to lower alcohols, and therefore the partition of the present invention has excellent resistance to lower alcohols.

[0015] The antibacterial member of the present invention includes a laminate having excellent resistance to lower alcohols, and therefore the antibacterial member of the present invention has excellent resistance to lower alcohols. DETAILED DESCRIPTION OF THE INVENTION

[0016] The coating material of the present invention that provides resistance to lower alcohols contains a copolymer of a monomer composition and an aqueous solvent that dissolves and / or disperses the copolymer.

[0017] The copolymer of the monomer composition is, for example, a (meth)acrylic polymer, where (meth)acrylic refers to acrylic and / or methacrylic (the same applies hereinafter).

[0018] The monomer composition contains a hard monomer as an essential component. The hard monomer is a monomer whose homopolymer has a relatively high glass transition temperature (calculated by the FOX formula (same applies hereinafter)) (for example, 20°C or higher, preferably 200°C or lower).

[0019] The hard monomer contains, as an essential component, a nitrile group-containing unsaturated ethylenic monomer and / or a benzene ring-containing unsaturated ethylenic monomer. In other words, the monomer composition contains, as an essential component, a nitrile group-containing unsaturated ethylenic monomer and / or a benzene ring-containing unsaturated ethylenic monomer. More specifically, the monomer composition contains, as an essential component, either a nitrile group-containing unsaturated ethylenic monomer or a benzene ring-containing unsaturated ethylenic monomer. Furthermore, the monomer composition may contain both a nitrile group-containing unsaturated ethylenic monomer and a benzene ring-containing unsaturated ethylenic monomer.

[0020] Examples of the nitrile group-containing unsaturated ethylenic monomer include nitrile group-containing vinyl monomers. Examples of the nitrile group-containing vinyl monomer include (meth)acrylonitrile. (Meth)acrylonitrile is acrylonitrile and / or methacrylonitrile. These can be used alone or in combination of two or more. From the viewpoint of lower alcohol resistance, the nitrile group-containing unsaturated ethylenic monomer is preferably a nitrile group-containing vinyl monomer, more preferably (meth)acrylonitrile, and even more preferably acrylonitrile.

[0021] When the monomer composition contains a nitrile group-containing unsaturated ethylenic monomer, the content of the nitrile group-containing unsaturated ethylenic monomer is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total amount of the monomer composition. If the content of the nitrile group-containing unsaturated ethylenic monomer is higher than the above lower limit, better resistance to lower alcohols can be obtained.

[0022] Furthermore, when the monomer composition contains a nitrile group-containing unsaturated ethylenic monomer, the content of the nitrile group-containing unsaturated ethylenic monomer is 70 mass % or less, preferably 65 mass % or less, more preferably 60 mass % or less, and particularly preferably 57.5 mass % or less, based on the total amount of the monomer composition. If the content of the nitrile group-containing unsaturated ethylenic monomer is below the above upper limit, better lower alcohol resistance can be obtained.

[0023] Examples of the benzene ring-containing unsaturated ethylenic monomer include styrene-based vinyl monomers. Examples of the styrene-based vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and chlorostyrene. These can be used alone or in combination of two or more. Examples of the benzene ring-containing unsaturated ethylenic monomer include preferably styrene-based vinyl monomers, and more preferably styrene.

[0024] When the monomer composition contains a benzene ring-containing unsaturated ethylenic monomer, the content of the benzene ring-containing unsaturated ethylenic monomer relative to the total amount of the monomer composition is, from the viewpoint of resistance to lower alcohols, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 29% by mass or more, even more particularly preferably 40% by mass or more, and most preferably 50% by mass or more.

[0025] Furthermore, when the monomer composition contains a benzene ring-containing unsaturated ethylenic monomer, the content of the benzene ring-containing unsaturated ethylenic monomer relative to the total amount of the monomer composition is, for example, 70 mass% or less, preferably 66 mass% or less, and more preferably 60 mass% or less, from the viewpoint of resistance to lower alcohols.

[0026] When the monomer composition contains both a nitrile group-containing unsaturated ethylenic monomer and a benzene ring-containing unsaturated ethylenic monomer, the content of the nitrile group-containing unsaturated ethylenic monomer relative to the total amount of the nitrile group-containing unsaturated ethylenic monomer and the benzene ring-containing unsaturated ethylenic monomer is, for example, 60 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more, and for example, less than 100 mass%.

[0027] When the monomer composition contains both a nitrile group-containing unsaturated ethylenic monomer and a benzene ring-containing unsaturated ethylenic monomer, the content of the benzene ring-containing unsaturated ethylenic monomer relative to the total amount of the nitrile group-containing unsaturated ethylenic monomer and the benzene ring-containing unsaturated ethylenic monomer is, for example, more than 1 mass%, preferably 2 mass% or more, more preferably 3 mass% or more, and for example, 40 mass% or less, preferably 20 mass% or less, more preferably 10 mass% or less.

[0028] The content of the nitrile group-containing unsaturated ethylenic monomer and the benzene ring-containing unsaturated ethylenic monomer (total amount when used in combination) is, for example, 70 mass% or more, preferably 80 mass% or more, relative to the total amount of the hard monomers.

[0029] The content of the nitrile group-containing unsaturated ethylenic monomer and the benzene ring-containing unsaturated ethylenic monomer (total amount when used in combination) is, for example, 100 mass% or less, preferably 95 mass% or less, and more preferably 90 mass% or less, relative to the total amount of hard monomers.

[0030] The hard monomer may optionally contain methyl methacrylate, in other words, the monomer composition may optionally contain methyl methacrylate.

[0031] When the monomer composition contains methyl methacrylate, the content of methyl methacrylate relative to the total amount of the monomer composition is, from the viewpoint of copolymerizability, for example, 1 mass% or more, preferably 2 mass% or more, and more preferably 5 mass% or more.

[0032] Furthermore, when the monomer composition contains methyl methacrylate, the content of methyl methacrylate relative to the total amount of the monomer composition is, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, from the viewpoint of resistance to lower alcohols.

[0033] Methyl methacrylate is preferably used in combination with a nitrile group-containing unsaturated ethylenic monomer. That is, when the monomer composition contains a nitrile group-containing unsaturated ethylenic monomer, methyl methacrylate is also contained. On the other hand, when the monomer composition contains a benzene ring-containing unsaturated ethylenic monomer but does not contain a nitrile group-containing unsaturated ethylenic monomer, methyl methacrylate is not contained.

[0034] The content of the hard monomer relative to the total amount of the monomer composition is, for example, 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more, from the viewpoint of resistance to lower alcohols.

[0035] The content of the hard monomer relative to the total amount of the monomer composition is, from the viewpoint of film-forming properties, for example, 90 mass % or less, preferably 80 mass % or less, and more preferably 70 mass % or less.

[0036] The monomer composition may also contain a soft monomer as an optional component. The soft monomer is a monomer whose homopolymer has a relatively low glass transition temperature (for example, less than 20° C., preferably 0° C. or lower).

[0037] Examples of soft monomers include alkyl (meth)acrylates other than methyl methacrylate, where (meth)acrylate refers to acrylate and / or methacrylate (the same applies hereinafter).

[0038] Examples of alkyl(meth)acrylates include alkyl(meth)acrylates (excluding methyl methacrylate) having an alkyl moiety with 1 to 30 carbon atoms. More specifically, examples of alkyl(meth)acrylates include methyl acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, s-butyl(meth)acrylate, t-butyl(meth)acrylate, pentyl(meth)acrylate, neopentyl(meth)acrylate, isoamyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate. Examples of the acrylates include methyl (meth)acrylate, ...

[0039] The alkyl(meth)acrylate is preferably an alkyl(meth)acrylate having an alkyl moiety having 2 to 10 carbon atoms, more preferably butyl(meth)acrylate and 2-ethylhexyl(meth)acrylate, and even more preferably butyl acrylate and 2-ethylhexyl acrylate.

[0040] When the monomer composition contains a soft monomer, the content of the soft monomer relative to the total amount of the monomer composition is, from the viewpoint of film-forming property, for example, 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more. That is, from the viewpoint of lower alcohol resistance, the monomer composition preferably contains a soft monomer.

[0041] Furthermore, when the monomer composition contains a soft monomer, the content of the soft monomer relative to the total amount of the monomer composition is, for example, 60 mass% or less, preferably 50 mass% or less, and more preferably 45 mass% or less, from the viewpoint of resistance to lower alcohols.

[0042] The monomer composition also contains a copolymerizable monomer. The copolymerizable monomer is a monomer that can be copolymerized with the hard monomer and / or the soft monomer. The copolymerizable monomer includes an essential copolymerizable monomer and an optional copolymerizable monomer.

[0043] The copolymerizable essential monomer is contained as an essential component in the monomer composition. Examples of the copolymerizable essential monomer include a carboxyl group-containing unsaturated ethylenic monomer. In other words, the monomer composition contains a carboxyl group-containing unsaturated ethylenic monomer as an essential component.

[0044] Examples of carboxyl group-containing unsaturated ethylenic monomers include carboxyl group-containing vinyl monomers. Examples of carboxyl group-containing vinyl monomers include α,β-unsaturated carboxylic acids and their salts. Examples of α,β-unsaturated carboxylic acids include α,β-unsaturated monocarboxylic acids and α,β-unsaturated dicarboxylic acids. Examples of α,β-unsaturated monocarboxylic acids include (meth)acrylic acid and crotonic acid. Examples of α,β-unsaturated dicarboxylic acids include itaconic acid, maleic acid, fumaric acid, itaconic anhydride, maleic anhydride, and fumaric anhydride. Examples of salts include sodium salts, potassium salts, and ammonium salts. These can be used alone or in combination of two or more. From the viewpoint of lower alcohol resistance, the carboxyl group-containing unsaturated ethylenic monomer is preferably a carboxyl group-containing vinyl monomer, more preferably an α,β-unsaturated monocarboxylic acid, even more preferably (meth)acrylic acid, and particularly preferably methacrylic acid.

[0045] The content of the carboxyl group-containing unsaturated ethylenic monomer is 0.5% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, based on the total amount of the monomer composition, from the viewpoint of lower alcohol resistance. If the content of the carboxyl group-containing unsaturated ethylenic monomer is higher than the lower limit, better film-forming properties and lower alcohol resistance can be obtained.

[0046] Furthermore, the content of the carboxyl group-containing unsaturated ethylenic monomer is 20% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less, based on the total amount of the monomer composition, from the viewpoint of lower alcohol resistance. If the content of the carboxyl group-containing unsaturated ethylenic monomer is below the upper limit, better film-forming properties and lower alcohol resistance can be obtained.

[0047] The optional copolymerizable monomer is a copolymerizable monomer contained in the monomer composition as needed. Examples of the optional copolymerizable monomer include other functional group-containing copolymerizable monomers.

[0048] The other functional group-containing copolymerizable monomer is a functional group-containing copolymerizable monomer other than the carboxy group-containing unsaturated ethylenic monomer. Examples of the other functional group-containing copolymerizable monomer include a hydroxyl group-containing vinyl monomer, an amide group-containing vinyl monomer, a glycidyl group-containing vinyl monomer, an amino group-containing vinyl monomer, an acetoacetoxy group-containing vinyl monomer, a phosphate group-containing vinyl monomer, and a sulfonic acid group-containing vinyl monomer.

[0049] Examples of hydroxyl group-containing vinyl monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Examples of amide group-containing vinyl monomers include (meth)acrylamide and methylenebis(meth)acrylamide. Examples of glycidyl group-containing vinyl monomers include glycidyl (meth)acrylate. Examples of amino group-containing vinyl monomers include 2-aminoethyl (meth)acrylate, 2-(N-methylamino)ethyl (meth)acrylate, and 2-(N,N-dimethylamino)ethyl (meth)acrylate. Examples of acetoacetoxy group-containing vinyl monomers include acetoacetoxyethyl (meth)acrylate. Examples of phosphate group-containing vinyl monomers include 2-(meth)acryloxyethyl acid phosphate. Examples of sulfonic acid group-containing vinyl monomers include allyl sulfonic acid, methallyl sulfonic acid, acrylamido t-butyl sulfonic acid, and styrene sulfonate. Examples of salts include sodium salts, potassium salts, and ammonium salts.

[0050] The other functional group-containing copolymerizable monomers can be used alone or in combination of two or more kinds.

[0051] As the other functional group-containing copolymerizable monomer, preferably, a hydroxyl group-containing vinyl monomer and an amide group-containing vinyl monomer are used in combination with a benzene ring-containing unsaturated ethylenic monomer. That is, when the monomer composition contains a benzene ring-containing unsaturated ethylenic monomer but does not contain a nitrile group-containing unsaturated ethylenic monomer, the other functional group-containing copolymerizable monomer is contained.

[0052] Further examples of the optional copolymerizable monomer include vinyl esters, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halide compounds, α-olefins, dienes, and crosslinkable vinyl monomers.

[0053] Examples of vinyl esters include vinyl acetate and vinyl propionate. Examples of N-substituted unsaturated carboxylic acid amides include N-methylol(meth)acrylamide. Examples of heterocyclic vinyl compounds include vinylpyrrolidone. Examples of halogenated vinylidene compounds include vinylidene chloride and vinylidene fluoride. Examples of α-olefins include ethylene and propylene. Examples of dienes include butadiene. Examples of crosslinkable vinyl monomers include methylenebis(meth)acrylamide, divinylbenzene, polyethylene glycol chain-containing di(meth)acrylate, trimethylolpropane tetraacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. These can be used alone or in combination of two or more.

[0054] The content of the optional copolymerizable monomer is appropriately determined depending on the purpose and application.

[0055] For example, when the monomer composition contains a hydroxyl group-containing vinyl monomer, the content of the hydroxyl group-containing vinyl monomer relative to the total amount of the monomer composition is, for example, 0.5 mass% or more, preferably 1 mass% or more, and more preferably 1.5 mass% or more, from the viewpoint of resistance to lower alcohols.

[0056] Furthermore, for example, when the monomer composition contains a hydroxyl group-containing vinyl monomer, the content of the hydroxyl group-containing vinyl monomer is, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, from the viewpoint of lower alcohol resistance.

[0057] Furthermore, for example, when the monomer composition contains an amide group-containing vinyl monomer, the content of the amide group-containing vinyl monomer relative to the total amount of the monomer composition is, from the viewpoint of resistance to lower alcohols, for example, 0.1 mass% or more, preferably 0.25 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more.

[0058] Furthermore, for example, when the monomer composition contains an amide group-containing vinyl monomer, the content of the amide group-containing vinyl monomer is, for example, 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less, from the viewpoint of lower alcohol resistance.

[0059] The copolymer of the monomer composition can be obtained by polymerizing the above-mentioned monomer composition by a known method. More specifically, for example, the monomer composition and a polymerization initiator are mixed in an aqueous solvent, and the monomer composition is polymerized.

[0060] The polymerization initiator is not particularly limited, and examples thereof include water-soluble initiators and oil-soluble initiators. Examples of water-soluble initiators include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, and organic hydroperoxides. Examples of oil-soluble initiators include benzoyl peroxide and azobisisobutyronitrile. Further, known redox initiators can also be used. These can be used alone or in combination of two or more. Preferred examples of the polymerization initiator include water-soluble initiators, more preferably potassium persulfate and ammonium persulfate. More preferably, potassium persulfate is used.

[0061] The blending ratio of the polymerization initiator relative to 100 parts by mass of the monomer composition is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.25 parts by mass or more, and for example, 3 parts by mass or less, preferably 2 parts by mass or less.

[0062] Examples of aqueous solvents include water and hydrophilic solvents. Examples of hydrophilic solvents include alcohols, ketones, esters, ethers, ether alcohols, ether alcohol acetates, and nitriles. Examples of alcohols include methanol and ethanol. Examples of ketones include acetone. Examples of esters include ethyl acetate and butyl acetate. Examples of ethers include dioxane and tetrahydrofuran. Examples of ether alcohols include cellosolve and carbitol. Examples of ether alcohol acetates include cellosolve acetate and carbitol acetate. Examples of nitriles include acetonitrile. These can be used alone or in combination of two or more. A preferred aqueous solvent is water.

[0063] When water is used as the aqueous solvent, an emulsifier is preferably blended with the monomer composition, and the monomer composition is emulsion polymerized in water.

[0064] Examples of emulsifiers include anionic surfactants and nonionic surfactants. Examples of anionic surfactants include alkyl sulfate ester salts, aliphatic sulfonates, alkylbenzene sulfonates, and alkyl diphenyl ether sulfonates. Examples of nonionic surfactants include alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, and alkyl ethers of polyethylene glycol. These can be used alone or in combination of two or more. The blending ratio of the emulsifier is appropriately set depending on the purpose and application. More specifically, the blending ratio of the emulsifier is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, per 100 parts by mass of the monomer composition. The blending ratio of the emulsifier is, for example, 2.0 parts by mass or less, preferably 1.8 parts by mass or less, per 100 parts by mass of the monomer composition.

[0065] The polymerization conditions are appropriately set depending on the purpose and application. For example, the pressure conditions are normal pressure. The polymerization temperature is, for example, 30°C or higher, preferably 50°C or higher. The polymerization temperature is, for example, 95°C or lower, preferably 85°C or lower. The polymerization time is, for example, 0.5 hours or higher, preferably 1.5 hours or higher. The polymerization time is, for example, 20 hours or shorter, preferably 10 hours or shorter.

[0066] In addition, in the polymerization, known additives can be blended in appropriate proportions from the viewpoint of improving production stability. Examples of additives include pH adjusters, metal ion sequestering agents, molecular weight modifiers, and chain transfer agents. The additives may be added to the monomer composition before polymerization, to the reaction liquid during polymerization, or to the reaction-terminated liquid after polymerization.

[0067] This causes the monomer composition to copolymerize in the aqueous solvent to produce a copolymer of the monomer composition. As a result, a lower alcohol-resistant coating material is obtained that contains the aqueous solvent and the copolymer dissolved and / or dispersed in the aqueous solvent. More specifically, when water is used as the aqueous solvent, the lower alcohol-resistant coating material is obtained as a resin emulsion in which the copolymer is dispersed in water.

[0068] In the above polymerization, a neutralizing agent is preferably added to the reaction-terminated liquid to adjust the pH. Examples of the neutralizing agent include ammonia. The neutralizing agent is preferably added to the reaction-terminated liquid after polymerization. If necessary, the reaction-terminated liquid is maintained for a predetermined period of time. The pH of the reaction-terminated liquid after adding the neutralizing agent is, for example, 5 or more, preferably 7 or more, and more preferably 8 or more. The pH of the reaction liquid is, for example, 11 or less, and more preferably 10 or less. The copolymer is hydrated in the reaction-terminated liquid by the neutralizing agent, and is swelled and softened.

[0069] In the polymerization, the monomer composition may be polymerized in one step or in multiple steps. For example, core-shell particles can be formed by polymerizing the monomer composition in multiple steps.

[0070] More specifically, a portion of the monomer composition (primary composition) is first polymerized to synthesize a primary polymer, and then the remainder of the monomer composition (secondary composition) is polymerized in the presence of the primary polymer to synthesize a secondary polymer (multi-stage polymerization). This results in core-shell particles of a copolymer comprising a core made of the primary polymer and a shell made of the secondary polymer that coats the primary polymer. The order of reaction of the portion of the monomer composition and the remainder may be reversed.

[0071] The copolymer contains repeating units derived from a nitrile group-containing unsaturated ethylenic monomer and / or repeating units derived from a benzene ring-containing unsaturated ethylenic monomer, and repeating units derived from a carboxy group-containing unsaturated ethylenic monomer.

[0072] In the copolymer, the content of the repeating units derived from the nitrile group-containing unsaturated ethylenic monomer is the same as the content of the nitrile group-containing unsaturated ethylenic monomer in the monomer composition.

[0073] That is, the content of repeating units derived from the nitrile group-containing unsaturated ethylenic monomer is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total amount of the copolymer. Furthermore, the content of repeating units derived from the nitrile group-containing unsaturated ethylenic monomer is 70% by mass or less, preferably 65% ​​by mass or less, more preferably 60% by mass or less, and particularly preferably 57.5% by mass or less, based on the total amount of the copolymer. When the content of repeating units derived from the nitrile group-containing unsaturated ethylenic monomer is within the above range, better resistance to lower alcohols can be obtained.

[0074] The content of repeating units derived from benzene ring-containing unsaturated ethylenic monomers is 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 29% by mass or more, even more particularly preferably 40% by mass or more, and most preferably 50% by mass or more, based on the total amount of the copolymer. Furthermore, the content of repeating units derived from benzene ring-containing unsaturated ethylenic monomers is 70% by mass or less, preferably 66% by mass or less, and more preferably 60% by mass or less, based on the total amount of the copolymer. When the content of repeating units derived from benzene ring-containing unsaturated ethylenic monomers is within the above range, better resistance to lower alcohols can be obtained.

[0075] In addition, the content of the repeating units derived from the carboxyl group-containing unsaturated ethylenic monomer in the copolymer is the same as the content of the carboxyl group-containing unsaturated ethylenic monomer in the monomer composition.

[0076] That is, the content of repeating units derived from the carboxyl group-containing unsaturated ethylenic monomer is 0.5% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, based on the total amount of the copolymer. Furthermore, the content of repeating units derived from the carboxyl group-containing unsaturated ethylenic monomer is 20% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less, based on the total amount of the copolymer. When the content of repeating units derived from the carboxyl group-containing unsaturated ethylenic monomer is within the above range, better resistance to lower alcohols can be obtained.

[0077] The weight-average molecular weight of the copolymer is, for example, 5,000 or more, preferably 10,000 or more, and more preferably 30,000 or more. The weight-average molecular weight of the copolymer is, for example, 1,000,000 or less, preferably 800,000 or less, and more preferably 500,000 or less. The weight-average molecular weight is a polystyrene-equivalent molecular weight determined by gel permeation chromatogram.

[0078] The copolymer has a glass transition temperature of, for example, 5° C. or higher, preferably 10° C. or higher, from the viewpoints of lower alcohol resistance and blocking resistance of the coated surface. The copolymer has a glass transition temperature of, for example, 200° C. or lower, preferably 100° C. or lower, more preferably 80° C. or lower, from the viewpoints of lower alcohol resistance and film-forming properties. The glass transition temperature is calculated using the FOX formula (the same applies hereinafter).

[0079] In the lower alcohol-resistant coating material, the solids concentration of the copolymer is, for example, 3% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more.

[0080] In the coating material imparting resistance to lower alcohols, the solid content of the copolymer is appropriately adjusted by adding or removing an aqueous solvent, as required.

[0081] Furthermore, the lower alcohol resistance-imparting coating material can contain additives in appropriate proportions as needed. Examples of additives include crosslinkers, fillers, antioxidants, UV absorbers, thermoplastic resins, thermosetting resins, lubricants, thickeners, wetting agents, antifoaming agents, and pH adjusters. These can be used alone or in combination. A preferred additive is a crosslinker.

[0082] Examples of crosslinking agents include isocyanate-based crosslinking agents, carbodiimide-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, and oxazoline-based crosslinking agents. These can be used alone or in combination of two or more. Preferred crosslinking agents include isocyanate-based crosslinking agents and carbodiimide-based crosslinking agents.

[0083] The blending ratio of the crosslinking agent is not particularly limited and is appropriately set depending on the purpose and application. More specifically, the blending ratio of the crosslinking agent is, for example, 1 part by mass or more, preferably 5 parts by mass or more, relative to 100 parts by mass of the total amount of the copolymer. Furthermore, the blending ratio of the crosslinking agent is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of the copolymer.

[0084] If the coating material for imparting lower alcohol resistance contains a crosslinking agent, better lower alcohol resistance and film-forming properties can be obtained.

[0085] The lower alcohol-resistant coating material contains a copolymer of a monomer composition containing a predetermined proportion of a nitrile group-containing unsaturated ethylenic monomer and / or a benzene ring-containing unsaturated ethylenic monomer and a carboxy group-containing unsaturated ethylenic monomer. Therefore, the lower alcohol-resistant coating material can form a coating layer with excellent lower alcohol resistance. Examples of lower alcohols include methanol, ethanol, and isopropyl alcohol. Ethanol and isopropyl alcohol are preferred. Furthermore, the lower alcohol-resistant coating material uses an aqueous solvent, which reduces the environmental impact compared to when organic solvents are used. Additionally, the coating layer formed from the lower alcohol-resistant coating material exhibits excellent adhesion to the substrate.

[0086] In other words, the lower alcohol-resistant coating material can form a lower alcohol-resistant layer with excellent adhesion as a coating layer while reducing the environmental impact. The lower alcohol-resistant coating material can be applied to various members that require lower alcohol resistance.

[0087] The member is not particularly limited as long as it is resistant to lower alcohols. Examples of the material of the member include plastic, paper, wood, ceramic, and metal. The shape of the member is also not particularly limited.

[0088] The above-mentioned lower alcohol resistance imparting coating material is applied to one surface of a member that requires resistance to lower alcohols, and is dried by heating as necessary.

[0089] The method for applying the lower alcohol resistance-imparting coating material is not particularly limited, and any known coating method can be used, such as a gravure coater, a small-diameter gravure coater, a reverse roll coater, a transfer roll coater, a kiss coater, a dip coater, a microgravure coater, a knife coater, an air doctor coater, a blade coater, a rod coater, a squeeze coater, a cast coater, a die coater, a screen printing method, or a spray coating method.

[0090] The drying conditions are not particularly limited and are appropriately set depending on the purpose and application. For example, the drying temperature is 40° C. or higher. The drying temperature is 200° C. or lower. The drying time is appropriately set depending on the purpose and application.

[0091] As a result, a coating layer of the lower alcohol resistance-imparting coating material is formed on one surface of the member.

[0092] The thickness of the coating layer (after drying) is not particularly limited and is appropriately set depending on the purpose and use. For example, the thickness of the coating layer (after drying) is, for example, 1 μm or more, preferably 3 μm or more. In addition, the thickness of the coating layer (after drying) is, for example, 10 μm or less, preferably 8 μm or less.

[0093] As a result of the above, a laminate is obtained which comprises a member and a coating layer of the above-mentioned lower alcohol resistance-imparting coating material placed on the surface of the member.

[0094] In such a laminate, the coating layer (exposed surface) has resistance to lower alcohols, and therefore such a laminate is used in applications where the coating layer (exposed surface) frequently comes into contact with lower alcohols.

[0095] Such applications include, for example, partitions and antibacterial components.

[0096] The partition includes a laminate including a plastic substrate and a coating layer disposed on one surface of the plastic substrate. The coating layer may be disposed on the other surface of the plastic substrate. Such a laminate has, for example, a flat plate shape of an appropriate size, and is assembled into a shape appropriate for the intended use and used as a partition.

[0097] The antibacterial member includes a laminate including a member whose surface is antibacterially treated and which requires frequent disinfection with a lower alcohol, and a coating layer disposed on one surface of the member. Note that the member is not limited to a member whose surface is antibacterially treated, but also includes, for example, a member into which an antibacterial agent is mixed. Examples of antibacterial-treated members include members that come into contact with an unspecified number of people, specifically doorknobs, handrails, and straps.

[0098] Furthermore, in the partition or antibacterial member including the laminate, the coating layer (exposed surface) of the laminate is resistant to lower alcohols, so that deterioration of the exposed surface is suppressed even if the laminate is frequently disinfected with lower alcohols.

[0099] In the above description, a coating layer of a lower alcohol-resistant coating material is disposed on one or both surfaces of the member. However, for example, an optional intermediate layer (undercoat layer) may be interposed between the member and the coating layer. Furthermore, if necessary, a known top coat layer (overcoat layer) may be laminated on the coating layer of the above-mentioned lower alcohol-resistant coating material. In such cases, the coating layer of the lower alcohol-resistant coating material also provides a substrate with excellent lower alcohol resistance. [Example]

[0100] Specific numerical values ​​of blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0101] 1. Preparation of coating material with resistance to lower alcohols refer to Example 1 A separable flask equipped with a stirrer and reflux condenser was charged with 230 g of ion-exchanged water and 1.5 g of sodium dodecyl diphenyl ether disulfonate, and the atmosphere in the flask was purged with nitrogen gas. The flask was then heated to 75°C. 0.5 g of potassium persulfate was then added to the flask and dissolved. The emulsion of the monomer composition was then continuously added to the flask over approximately 5 hours. The emulsion of the monomer composition contained 56 g of acrylonitrile, 5 g of styrene, 5 g of methyl methacrylate, 26 g of n-butyl acrylate, 8 g of methacrylic acid, 0.1 g of n-dodecyl mercaptan, 0.2 g of sodium dodecyl diphenyl ether disulfonate, and 56 g of ion-exchanged water.

[0102] The mixture was then maintained at the above temperature for 4 hours to complete the polymerization. After that, aqueous ammonia was added to the flask to make it alkaline, and the temperature was maintained for 2 hours. This resulted in the hydration, swelling, and softening of the copolymer. The flask was then cooled to room temperature, and deionized water was added to the flask. This resulted in a copolymer resin emulsion with a solids concentration of approximately 20% by mass, yielding a coating material with resistance to lower alcohols.

[0103] The glass transition temperatures (Tg) of the copolymers were calculated using the following FOX formula (the same applies hereinafter). The glass transition temperatures (Tg) of the copolymers are shown in Table 1 (the same applies hereinafter).

[0104] 1 / Tg=W1 / Tg1+W2 / Tg2++W n / Tg n (1) [Wherein, Tg is the glass transition temperature of the copolymer (unit: K), Tg i (i=1, 2, . . . n) is the glass transition temperature (unit: K) when monomer i forms a homopolymer, W i (i=1, 2,...n) represents the mass fraction of monomer i in all monomers.]

[0105] refer to Example 2 A separable flask equipped with a stirrer and reflux condenser was charged with 80 g of ion-exchanged water and 0.1 g of sodium dodecyl diphenyl ether disulfonate, and the atmosphere in the flask was purged with nitrogen gas. The flask was then heated to 72°C. 0.5 g of potassium persulfate was then added to the flask and dissolved. The emulsion of the monomer composition was then continuously added to the flask over approximately 5 hours. The emulsion of the monomer composition contained 57 g of styrene, 39 g of 2-ethylhexyl acrylate, 2 g of methacrylic acid, 2 g of acrylamide, 0.1 g of t-dodecyl mercaptan, 0.1 g of sodium dodecyl diphenyl ether disulfonate, and 44 g of ion-exchanged water.

[0106] The temperature was then maintained for 4 hours to complete the polymerization. The resulting aqueous emulsion was then cooled to room temperature, and deionized water and an aqueous ammonium solution were added to the flask. The solid content was adjusted to 45% by weight and the pH to 7.0 to obtain a coating material with low alcohol resistance.

[0107] Example 3 refer to An aqueous emulsion was obtained in the same manner as in Example 2. A carbodiimide crosslinking agent (V-02-L2, manufactured by Nisshinbo Chemical Inc.) was added to the aqueous emulsion in an amount of 10 parts by weight per 100 parts by weight of the monomer composition to obtain a coating material imparting resistance to lower alcohols.

[0108] Example 4 refer toAn aqueous emulsion was obtained in the same manner as in Example 2. An isocyanate-based crosslinking agent (WD-725, manufactured by Mitsui Chemicals, Inc.) was added to the aqueous emulsion in an amount of 10 parts by weight per 100 parts by weight of the monomer composition to obtain a coating material imparting resistance to lower alcohols.

[0109] refer to Example 5 A separable flask equipped with a stirrer and reflux condenser was charged with 80 g of ion-exchanged water and 0.1 g of sodium dodecylbenzenesulfonate, and the atmosphere in the flask was purged with nitrogen gas. The flask was then heated to 75°C. 0.3 g of potassium persulfate was then added to the flask and dissolved. The emulsion of the monomer composition was then continuously added to the flask over approximately 5 hours. The emulsion of the monomer composition contained 52 g of styrene, 43.6 g of 2-ethylhexyl acrylate, 2 g of methacrylic acid, 1.8 g of hydroxyethyl methacrylate, 0.6 g of acrylamide, 0.3 g of sodium dodecylbenzenesulfonate, and 44 g of ion-exchanged water.

[0110] The temperature was then maintained for 4 hours to complete the polymerization. The resulting aqueous emulsion was then cooled to room temperature, and deionized water and an aqueous ammonium solution were added to the flask. The solid content was adjusted to 40% by weight and the pH to 8.0 to obtain a coating material with low alcohol resistance.

[0111] Example 6 refer to An aqueous emulsion was obtained in the same manner as in Example 5. A carbodiimide crosslinking agent (V-02-L2, manufactured by Nisshinbo Chemical Inc.) was added to the aqueous emulsion in an amount of 10 parts by weight per 100 parts by weight of the monomer composition to obtain a coating material imparting resistance to lower alcohols.

[0112] Example 7 refer to An aqueous emulsion was obtained in the same manner as in Example 5. An isocyanate-based crosslinking agent (WD-725, manufactured by Mitsui Chemicals, Inc.) was added to the aqueous emulsion in an amount of 10 parts by weight per 100 parts by weight of the monomer composition to obtain a coating material imparting resistance to lower alcohols.

[0113] refer to Example 8 A separable flask equipped with a stirrer and a reflux condenser was charged with 230 g of ion-exchanged water and 1.5 g of sodium dodecyl sulfate, and the atmosphere in the flask was replaced with nitrogen gas. The flask was then heated to 75°C. 1.0 g of potassium persulfate was then added to the flask and dissolved. The emulsion of the monomer composition was then continuously added to the flask over approximately 5 hours. The emulsion of the monomer composition contained 45 g of acrylonitrile, 10 g of methyl methacrylate, 40 g of n-butyl acrylate, 5 g of methacrylic acid, 0.2 g of sodium dodecyl sulfate, and 56 g of ion-exchanged water.

[0114] Next, after maintaining the temperature for 2 hours, 0.2 g of ammonium persulfate was added, and the temperature was maintained for 2 hours to complete the polymerization. Ammonia water was then added to the flask to make it alkaline, and the temperature was maintained for 3 hours. This resulted in hydration, swelling, and softening of the copolymer. The flask was then cooled to room temperature, and deionized water was added to the flask. This resulted in a resin emulsion of the copolymer with a solids concentration of approximately 20% by mass, which provided a coating material with low alcohol resistance.

[0115] refer to Example 9 A separable flask equipped with a stirrer and reflux condenser was charged with 230 g of ion-exchanged water and 1.5 g of sodium dodecyl sulfate, and the atmosphere in the flask was replaced with nitrogen gas. The flask was then heated to 75°C. 1.0 g of potassium persulfate was then added to the flask and dissolved. An emulsion of the monomer composition was then continuously added to the flask over approximately 5 hours. The emulsion of the monomer composition contained 45 g of acrylonitrile, 10 g of methyl methacrylate, 40 g of n-butyl acrylate, 5 g of acrylic acid, 0.2 g of sodium dodecyl sulfate, and 56 g of ion-exchanged water.

[0116] Next, after maintaining the temperature for 2 hours, 0.2 g of ammonium persulfate was added, and the temperature was maintained for 2 hours to complete the polymerization. Ammonia water was then added to the flask to make it alkaline, and the temperature was maintained for 3 hours. This resulted in hydration, swelling, and softening of the copolymer. The flask was then cooled to room temperature, and deionized water was added to the flask. This resulted in a resin emulsion of the copolymer with a solids concentration of approximately 20% by mass, which provided a coating material with low alcohol resistance.

[0117] Comparative Example 1 A separable flask equipped with a stirrer and reflux condenser was charged with 57 g of ion-exchanged water and 0.3 g of sodium dodecyl diphenyl ether disulfonate, and the atmosphere inside the flask was purged with nitrogen gas. The flask was then heated to 72°C. 0.3 g of potassium persulfate was then added to the flask and dissolved. The emulsion of the monomer composition was then continuously added to the flask over approximately 4 hours. The emulsion of the monomer composition contained 51 g of methyl methacrylate, 44 g of 2-ethylhexyl acrylate, 2 g of methacrylic acid, 2 g of 2-hydroxyethyl methacrylate, 1 g of acrylamide, 0.1 g of t-dodecyl mercaptan, 0.3 g of sodium dodecyl diphenyl ether disulfonate, and 40 g of ion-exchanged water.

[0118] The temperature was then maintained for 4 hours to complete the polymerization. The resulting aqueous emulsion was then cooled to room temperature, and deionized water and an aqueous ammonium solution were added to the flask. The solid content was adjusted to 50% by weight and the pH to 8.0.

[0119] To the aqueous emulsion obtained above, an isocyanate-based crosslinking agent (WD-725, manufactured by Mitsui Chemicals) was added in an amount of 10 parts by weight per 100 parts by weight of the monomer composition, to obtain a coating material imparting resistance to lower alcohols.

[0120] 2. Evaluation <Laminate> A plastic substrate (polyethylene terephthalate substrate) was prepared as a member. A lower alcohol-resistant coating material was applied to one surface of the plastic substrate to a dry film thickness of 4 μm, and the coating was dried at 90°C. This resulted in a coating layer (4 μm) of the lower alcohol-resistant coating material being formed on the plastic substrate. In other words, a laminate comprising a plastic substrate and a coating layer of the lower alcohol-resistant coating material was produced.

[0121] <Adhesion> An adhesive tape (product name: Cellotape (registered trademark) CT405AP-24, manufactured by Nichiban Co., Ltd.) was applied to the coating layer of the low-alcohol resistance-imparting coating material, and a 2 kg roller was rolled back and forth once. The adhesive tape was then peeled off, and the surface was evaluated according to the following criteria.

[0122] ◯: No peeling of the coating layer was observed, or material destruction of the coating layer was observed. Δ: A part of the coating layer peeled off from the substrate. ×: The entire coating layer peeled off from the substrate.

[0123] <Rubbing test (lower alcohol resistance)> A drop of 80% or 100% ethanol solution was dropped onto the coating layer of the low-alcohol-resistant coating material, and a rubbing test was performed with a cloth (1 kg load, 50 strokes back and forth). The results were evaluated according to the following criteria.

[0124] ◯: No change in the coating layer was observed. △: Roughness was observed in the coating layer. ×: The coating layer was dissolved.

[0125] The higher the evaluation of the coating layer in the rubbing test, the more the coating layer can suppress deterioration of the surface of the laminate.

[0126] [Table 1]

Claims

1. a nitrile group-containing unsaturated ethylenic monomer and / or a benzene ring-containing unsaturated ethylenic monomer, a carboxyl group-containing unsaturated ethylenic monomer, and a copolymer of a monomer composition containing an amide group-containing vinyl monomer; an aqueous solvent that dissolves and / or disperses the copolymer; Crosslinking agent Including, relative to the total amount of the monomer composition In the case where the nitrile group-containing unsaturated ethylenic monomer is contained, the content of the nitrile group-containing unsaturated ethylenic monomer is 10% by mass or more and 70% by mass or less, In the case where the benzene ring-containing unsaturated ethylenic monomer is contained, the content of the benzene ring-containing unsaturated ethylenic monomer is 5% by mass or more and 66% by mass or less, the content of the carboxyl group-containing unsaturated ethylenic monomer is 1% by mass or more and 10% by mass or less, the content of the amide group-containing vinyl monomer is 0.1% by mass or more and 10% by mass or less, The coating material is resistant to lower alcohols, and the crosslinking agent contains at least one selected from the group consisting of an isocyanate crosslinking agent and a carbodiimide crosslinking agent.

2. The glass transition temperature of the copolymer is 10°C or higher and 100°C or lower. The coating material according to claim 1 which provides resistance to lower alcohols.

3. The components and a coating layer of the lower alcohol resistance imparting coating material according to claim 1 or 2 formed on at least one side of the member; A laminate comprising:

4. The laminate according to claim 3, A partition, wherein the member is a plastic substrate.

5. The laminate according to claim 3, Antibacterial material.

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