Article having resin film

Abstract

[Problem] To provide an article having a resin film comprising an environmentally friendly non-fluorine-based water- and oil-repellent material that can exhibit excellent water- and oil-repellency without using a fluorine-containing functional group that causes a problem of diffusion into the environment.　[Solution] An article comprising a resin film and characterized in that the resin film, which comprises a cured product of an ultraviolet-curable acrylic resin composition containing silane-modified particles, is laminated on a base material, the article having a surface with fine irregularities with the arithmetic mean roughness Sa of the surface of the resin film being 0.03-0.50 μm, the kurtosis (degree of sharpness) Sku being 1.00-6.00, and the skewness (degree of deviation) Ssk being 0.10-2.00.

Description

Article having a resin film

[0001] The present invention relates to an environmentally friendly, non-fluorinated water- and oil-repellent resin film that can exhibit excellent water- and oil-repellent properties without using fluorine-containing functional groups, and to an article having the resin film.

[0002] It is known that applying fluorine-containing functional groups is extremely effective in producing water-repellent and oil-repellent properties, and conventionally, methods such as laminating or coating articles with resin films made of fluorine-containing resin materials have been frequently used as means of imparting water-repellent and oil-repellent properties to articles.

[0003] However, fluorine-containing resin films pose a problem due to the diffusion of fluorine into the environment during decomposition and disposal. Therefore, there is a need for the development of resin materials that do not contain fluorine and can impart excellent water and oil repellency to products. Furthermore, from the perspective of SDGs, there is a demand for environmentally friendly water and oil repellent resin materials.

[0004] On the other hand, UV-curable acrylic resin materials are known as materials that can form resin films on articles. Patent Document 1 discloses a composition containing UV-curable unsaturated monomers and / or oligomers and colloidal silica containing organosilane compounds, which, when applied to a plastic support, forms a scratch-resistant film.

[0005] Patent Document 2 discloses an ultraviolet-curable resin composition containing a hydrocarbon polymer having a (meth)acryloyloxy group and hydrophobic fine particles, which can be used as a masking agent or protective sheet, and it is stated that this composition has excellent peelability after curing. However, none of these are resin materials that can form a resin film on an article and impart high water-repellent and oil-repellent properties.

[0006] Japanese Patent Publication No. 1-315403 Japanese Patent Publication No. 2015-174940

[0007] The present invention aims to provide an article with excellent water and oil repellency, having a resin film made of an environmentally friendly, non-fluorinated water and oil repellent material that can exhibit excellent water and oil repellency without using functional groups containing fluorine, which poses a problem in terms of diffusion into the environment.

[0008] As a result of diligent research, the inventors have discovered that by forming a resin film using an ultraviolet-curable resin composition containing particles of non-fluorine material (organic particles, inorganic particles) that are imparted with water-repellent and oil-repellent properties, it is possible to obtain an article with a laminated resin film that has significantly improved water-repellent and oil-repellent properties and surface characteristics that allow water and organic matter (oil) to easily slide off even at low angles of sliding. This led to the completion of the present invention.

[0009] In other words, the present invention relates to an article having the following resin film: (1) An article having a resin film, wherein a resin film made of a cured product of an ultraviolet-curable acrylic resin composition containing silane-modified particles is laminated on a substrate, and the resin film surface has a surface micro-irregular shape with an arithmetic mean roughness: Sa of 0.03 μm or more and 0.50 μm or less, a kurtosis (sharpness): Sk of 1.00 or more and 6.00 or less, and a skewness (deviation): Ssk of 0.10 or more and 2.00 or less.

[0010] (2) The article according to (1), wherein the ultraviolet-curable acrylic resin composition comprises at least an ultraviolet-curable acrylic oligomer, an ultraviolet-curable monomer, a photopolymerization initiator, and silane-modified particles.

[0011] (3) The article according to (1) or (2), wherein the silane-modified particles are modified with an alkyltrialkoxysilane having a linear alkyl group having 1 to 18 carbon atoms.

[0012] (4) The article according to (1) or (2), wherein the silane-modified particles are inorganic or organic particles having a primary particle size of 1 to 1000 nm.

[0013] (5) The article according to (2), characterized in that at least one of the UV-curable acrylic oligomer and the UV-curable monomer has a hydrophilic group. (6) The article according to (2), wherein the UV-curable monomer comprises at least a cyclizable monomer.

[0014] (7) The article according to (1) or (2), wherein the content of the silane-modified particles is 1 to 50% by mass with respect to the total amount of the ultraviolet-curable acrylic resin composition. (8) The article according to (1) or (2), wherein the thickness of the resin film is 0.1 to 5 μm.

[0015] (9) A method for producing an article having a resin film as described in (1), comprising the following steps A to C: Step A: A step of forming a film on an article consisting of an ultraviolet-curable acrylic resin composition solution containing at least an ultraviolet-curable acrylic oligomer, an ultraviolet-curable monomer, a photopolymerization initiator, silane-modified particles, and a solvent. Step B: A step of irradiating the film obtained in step A with ultraviolet light to pre-cure it and form a pre-cured film having a phase separation structure. Step C: A step of fully curing the pre-cured film obtained in step B.

[0016] (10) The method for producing a product according to (9), wherein the ultraviolet-curable monomer comprises at least a cyclizable monomer. (11) The method for producing a product according to (9) or (10), wherein the solvent is a monohydric alcohol having 2 to 12 carbon atoms. (12) The method for producing a product according to (9), wherein step C is a step of heat-treating the pre-cured film obtained in step B.

[0017] According to the present invention, by forming a resin film using an ultraviolet-curable resin composition containing particles (organic particles, inorganic particles) of a non-fluorine material that has been given water-repellent and oil-repellent properties, an article can be obtained in which a resin film has significantly improved water-repellent and oil-repellent properties and surface characteristics that allow water and organic matter (oil) to easily slide off even at a low angle of sliding.

[0018] The aforementioned UV-curable acrylic resin composition can be used as an inkjet ink and, by laminating it onto the surface of articles made of various materials, can impart high water and oil repellency, and can be used, for example, for stain-resistant processing.

[0019] The resin film formed by the cured product of the UV-curable acrylic resin composition of the present invention exhibits significantly improved water and oil repellency despite not using fluorine-containing functional groups. Therefore, it eliminates problems such as the decomposition of fluorine-containing water and oil repellent films and the diffusion of fluorine into the environment during disposal, and is also useful as an environmentally friendly material from the perspective of SDGs.

[0020] The resin film laminated on the article of the present invention is formed from a cured product of an ultraviolet-curable acrylic resin composition.

[0021] 1. UV-curable acrylic resin composition The UV-curable acrylic resin composition contains at least UV-curable acrylic oligomers and silane-modified particles, and may also optionally contain UV-curable monomers, photopolymerization initiators, etc., and may further contain thiol compounds, etc.

[0022] Furthermore, the acrylic polymer produced by curing the UV-curable acrylic resin composition of the present invention preferably contains hydrophilic groups. Examples of hydrophilic groups include hydroxyl groups, amino groups such as tertiary amino groups, and quaternary ammonium groups. Therefore, it is preferable that at least one of the UV-curable acrylic oligomer and UV-curable monomer contained in the UV-curable acrylic resin composition has hydrophilic groups.

[0023] Furthermore, in the resin film formation process, the UV-curable acrylic resin composition may contain a solvent as needed. Hereinafter, the UV-curable acrylic resin composition with a solvent added may be referred to as the "UV-curable acrylic resin composition solution."

[0024] <UV-curable acrylic oligomers> Examples of UV-curable acrylic oligomers of the present invention include (meth)acrylate oligomers such as urethane, acrylic, polycarbonate, epoxy, polyether, and polyester. These compounds can be used individually or in combination of two or more.

[0025] Examples of urethane-based (meth)acrylate oligomers include urethane (meth)acrylate obtained by reacting a polyol (meth)acrylate having at least one hydroxyl group in its molecule with a diisocyanate compound or a triisocyanate compound, or tris(2-hydroxyethyl) isocyanurate (meth)acrylate obtained by reacting tris(2-hydroxyethyl) isocyanuric acid with (meth)acrylic acid or (meth)acrylic acid ester.

[0026] Examples of acrylic (meth)acrylate oligomers include polymers of alkyl (meth)acrylates such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate; copolymers of the above monomers with vinyl carboxylic acid compounds such as maleic acid, itaconic acid, crotonic acid, and fumaric acid; glycidyl group-containing vinyl compounds such as glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, and glycidyl crotonic acid; hydroxyethyl (meth)acrylate, vinyl acetate, (meth)acrylonitrile, (meth)acrylate chloride, and N-(meth)acryloylmorpholine.

[0027] Other examples include aminoalkyl (meth)acrylates having a tertiary amino group, and quaternary ammonium alkyl (meth)acrylates having a quaternary ammonium group.

[0028] Examples of polycarbonate-based (meth)acrylate oligomers include oligomers obtained by reacting polycarbonate polyols, polyisocyanates, and ethylenically unsaturated monomers with hydroxyl functional groups.

[0029] Examples of epoxy-based (meth)acrylate oligomers include epoxy (meth)acrylate obtained by reacting epoxy resin with (meth)acrylic acid.

[0030] Examples of polyether-based (meth)acrylate oligomers include polyol (meth)acrylates in which at least one of the hydroxyl groups of polyhydric alcohols such as polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol is replaced with a (meth)acryloyloxy group.

[0031] Examples of polyester-based (meth)acrylate oligomers include esters of polyester diols composed of adipic acid and 1,6-hexanediol with acrylic acid.

[0032] Among these, the UV-curable acrylic oligomer of the present invention is preferably a bifunctional urethane (meth)acrylate oligomer having a urethane bond and a (meth)acrylic group in its molecule, given its excellent flexibility of the film after curing.

[0033] The aforementioned urethane (meth)acrylate oligomers are typically obtained by the reaction of isocyanate compounds, polyol compounds, and hydroxyl group-containing (meth)acrylic monomers, and depending on the polyol compound used, they can be of the polyester, polycarbonate, or polyether type.

[0034] The average molecular weight of the urethane (meth)acrylate oligomer is not particularly limited, but the weight-average molecular weight (Mw) is preferably 1,000 to 20,000, more preferably 3,000 to 10,000.

[0035] The UV-curable acrylic oligomer content is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more, based on the total amount of the UV-curable acrylic resin composition. There is no particular upper limit to the content, but it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0036] Furthermore, the UV-curable acrylic oligomer content is preferably 0.5% by mass or more, more preferably 1% by mass or more, relative to the total amount of the UV-curable acrylic resin composition solution including the solvent. There is no particular upper limit to the content, but it is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0037] <UV-curable monomers> The UV-curable acrylic resin composition of the present invention contains UV-curable monomers. Examples of UV-curable monomers include acrylate compounds, ether compounds, ester compounds, urethane compounds, and the like. These UV-curable monomers can be used individually or in combination of two or more.

[0038] Examples of the acrylate compound include (meth)acrylic acid esters of polyhydric alcohols and hydroxy acids. Specific examples of the acrylate compounds include phenoxypolyethylene glycol (meth)acrylate, epoxy (meth)acrylate, oligoester (meth)acrylate, urethane (meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. A cyclopolymerizable monomer such as methyl 2-[(allyloxy)methyl]acrylate can also be used.

[0039] Examples of the ether compound include alkylene glycols, polyalkylene glycols, and compounds in which one or both ends of these are blocked with an alkyl group, alkenyl group, aryl group, acyl group, or a combination thereof. Examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and compounds in which one or both ends of these are blocked with an alkyl group such as a methyl group, an alkenyl group such as an allyl group, an aryl group such as a phenyl group, an acyl group such as an acetyl group or a (meth)acryloyl group, or a combination thereof.

[0040] Examples of the ester compound include polyester oligomers such as ε-caprolactone (meth)acrylate and polycaprolactone oligomer, and compounds in which one or both ends of these are blocked with an alkyl group such as a methyl group, an alkenyl group such as an allyl group, an aryl group such as a phenyl group, an acyl group such as an acetyl group or a (meth)acryloyl group, or a combination thereof.

[0041] Examples of the urethane compound include reaction products of hydroxy (meth) acrylate compounds such as hydroxyethyl (meth) acrylate and glycerin dimethacrylate, compounds having an isocyanate group such as methylene diisocyanate, and polyols (e.g., polyester polyol, polyether polyol, etc.).

[0042] The content of the ultraviolet curable monomer is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, based on the total amount of the ultraviolet curable acrylic resin composition. The upper limit of the content is not particularly limited, but is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

[0043] Also, the content of the ultraviolet curable monomer is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total amount of the ultraviolet curable acrylic resin composition solution containing a solvent. The upper limit of the content is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

[0044] More preferably, the ultraviolet curable monomer is composed of a combination of one or more monomers containing at least a cyclopolymerizable monomer. By blending a cyclopolymerizable monomer into the ultraviolet curable acrylic resin composition, a desired micro-roughness shape can be formed on the surface of the resin film during curing in combination with a monohydric alcohol solvent having 2 to 12 carbon atoms, which is preferably used in the present invention described later, and a resin film having high water and oil repellency can be obtained.

[0045] Since cyclizable monomers can be dissolved in monohydric alcohol solvents having 2 to 12 carbon atoms, which are preferably used in the present invention, incorporating cyclizable monomers into an ultraviolet-curable acrylic resin composition solution makes other polymerization components contained in the resin composition solution soluble in the solvent. Subsequently, when the resin composition solution is cured to start polymerization, the compatibility with the solvent decreases as the molecular weight increases, inducing phase separation, and a micro-irregular shape is formed on the surface of the resin film obtained by removing the solvent. Therefore, in the present invention, it is desirable to include at least a cyclizable monomer as the ultraviolet-curable monomer.

[0046] In the present invention, a cyclizable monomer refers to a polymerizable monomer in which an intramolecular cyclization reaction can occur during polymerization (curing reaction). From the viewpoint of physical properties such as hardness and toughness, and compatibility, α-allyloxymethylacrylic acid ester is preferred as the cyclizable monomer.

[0047] Examples of α-allyloxymethylacrylic acid esters include methyl α-allyloxymethylacrylate, ethyl α-allyloxymethylacrylate, n-propyl α-allyloxymethylacrylate, i-propyl α-allyloxymethylacrylate, n-butyl α-allyloxymethylacrylate, s-butyl α-allyloxymethylacrylate, t-butyl α-allyloxymethylacrylate, n-hexyl α-allyloxymethylacrylate, 2-ethylhexyl α-allyloxymethylacrylate, methoxyethyl α-allyloxymethylacrylate, and α-allyloxymethylacrylate. Methoxyethoxyethyl, α-Allyloxymethylacrylate methoxyethoxyethoxyethyl, α-Allyloxymethylacrylate 3-Methoxybutyl, α-Allyloxymethylacrylate ethoxyethyl, α-Allyloxymethylacrylate ethoxyethoxyethyl, α-Allyloxymethylacrylate phenoxyethyl, α-Allyloxymethylacrylate phenoxyethoxyethyl, α-Allyloxymethylacrylate hydroxyethyl, α-Allyloxymethylacrylate hydroxypropyl, α-Allyloxymethylacrylate hydroxybutyl, α-Allyloxymethylacrylate 2,Examples include 3-dihydroxypropyl, α-allyloxymethylacrylate dimethylaminoethyl, α-allyloxymethylacrylate diethylaminoethyl, α-allyloxymethylacrylate acetamidoethyl, α-allyloxymethylacrylate N-methylacetamidoethyl, α-allyloxymethylacrylate propioamide ethyl, α-allyloxymethylacrylate pyrrolidonyl ethyl, α-allyloxymethylacrylate cyclohexyl, α-allyloxymethylacrylate isobornyl, α-allyloxymethylacrylate tetrahydrofurfuryl, α-allyloxymethylacrylate tetrahydrofurfuryloxyethyl, α-allyloxymethylacrylate tetrahydrofurfuryloxyethoxyethyl, α-allyloxymethylacrylate tetrahydropyranyl, α-allyloxymethylacrylate (5-methyl-5-m-dioxanyl)methyl, α-allyloxymethylacrylate phenyl, α-allyloxymethylacrylate benzyl, and α-allyloxymethylacrylate naphthyl.

[0048] Among these, α-allyloxymethyl acrylic acid ester or α-allyloxymethyl acrylate (2-[(allyloxy)methyl]acrylate) is more preferred from the viewpoint of availability. When α-allyloxymethyl acrylic acid ester is included in the UV-curable resin composition, polymerization forms a polymer having a tetrahydrofuran ring in the main chain.

[0049] These cyclopolymerizable monomers can also be commercially available (2-[(allyloxy)methyl]methyl acrylate; trade name "AOMA"; manufactured by Nippon Shokubai Co., Ltd.).

[0050] The content of cyclizable monomers is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of UV-curable monomers. The upper limit of the content is not particularly limited, but is preferably 80% by mass or less, and more preferably 70% by mass or less.

[0051] Furthermore, the content of cyclizable monomers is preferably 1.5% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, based on the total amount of the UV-curable acrylic resin composition solution containing the solvent. There is no particular upper limit to the content, but it is preferably 7% by mass or less, more preferably 6% by mass or less, and particularly preferably 5% by mass or less.

[0052] Furthermore, the content of cyclizable monomers is preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more, based on the total amount of the UV-curable acrylic resin composition. There is no particular upper limit to the content, but it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0053] <Thiol Compounds> The UV-curable acrylic resin composition of the present invention may optionally contain thiol compounds. By incorporating thiol compounds, the film properties such as flexibility and elasticity when formed into a resin film can be improved. There are no particular restrictions on the thiol compound, and conventionally known primary or secondary thiols can be used, but secondary thiols are more preferably used in that they do not make the reactivity of the UV-curable resin composition too high.

[0054] More preferably, as secondary thiols, trifunctional or tetrafunctional secondary thiols selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), and 1,3,5-tris[2-(3-mercaptobutanoyloxy)ethyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are used. These may be used alone or in combination of two or more.

[0055] The content of the thiol compound is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and especially preferably 5% by mass or more, based on the total amount of the UV-curable acrylic resin composition. The upper limit of the content is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0056] Furthermore, the thiol compound content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more, based on the total amount of the UV-curable acrylic resin composition solution containing the solvent. There is no particular upper limit to the content, but it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less.

[0057] <Photopolymerization Initiator> The UV-curable acrylic resin composition of the present invention preferably contains a photopolymerization initiator in order to cure it appropriately by ultraviolet light. The photopolymerization initiator is not particularly limited, but examples include photocationic polymerization initiators and radical polymerization initiators. Furthermore, it is preferable to use a photocationic polymerization initiator and a radical polymerization initiator in combination.

[0058] Examples of radical fusion initiators include alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, titanocene compounds, benzoic acid ester compounds, and acridine compounds.

[0059] As photocationic polymerization initiators, any known and conventional ones that generate Brønsted acid upon ultraviolet irradiation and can polymerize polymerizable compounds can be used. Examples of such photocationic polymerization initiators include those in which the cation portion is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, etc., and the anion portion is BF ４ － , PF ６ － SbF ６ － [BX ４ ] － Examples of onium salts include those composed of (where X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups).

[0060] Examples of alkylphenone compounds include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0061] Examples of benzophenone compounds include benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone.

[0062] Examples of benzoin compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0063] Examples of thioxanthone compounds include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.

[0064] Examples of halomethylated triazine compounds include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-sec-triazine, and 2-(4-ethoxycarbokynylnaphthyl)-4,6-bis(trichloromethyl)-sec-triazine.

[0065] Examples of halomethylated oxadiazole compounds include 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0066] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0067] Examples of oxime ester compounds include 1-[4-(phenylthio)-,2-(O-benzoyl oxime)]-1,2-octanedione and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime)ethanone.

[0068] Examples of titanocene compounds include bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium.

[0069] Examples of benzoic acid ester compounds include p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid. Examples of acridine compounds include 9-phenylacridine.

[0070] Preferably, onium salts include those in which the anionic portion is tetrakis(pentafluorophenyl)borate (TFPB) and the cation portion is triarylsulfonium, which is an aromatic sulfonium. Specific examples of onium salts with TFPB as the anion that are available on the market include the trade names "IRGACURE 270" (manufactured by BASF Japan Ltd.), "IRGACURE 290" (manufactured by BASF Japan Ltd.), and "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.).

[0071] These photopolymerization initiators may be used individually or in combination of two or more. The content of the photopolymerization initiator is not particularly limited, but it is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, in the UV-curable acrylic resin composition solution. There is no particular upper limit to the content of the photopolymerization initiator, but it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, in the UV-curable acrylic resin composition solution. By having a photopolymerization initiator content within the above range, the UV-curable acrylic resin composition is easily cured by ultraviolet light.

[0072] Furthermore, a radical polymerization initiator and a photocationic polymerization initiator can be used in combination as the photopolymerization initiator. When used in combination, the proportion of the photocationic polymerization initiator to the total amount of the photopolymerization initiator is not particularly limited, but it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more. The upper limit of the content of the photocationic polymerization initiator in the photopolymerization initiator is not particularly limited, but it is preferably 100% by mass or less, more preferably 80% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0073] <Solvent> The UV-curable acrylic resin composition may contain an appropriate solvent as needed during the resin film formation process. The solvent is not particularly limited, but water or an organic solvent may be used. Preferably, an organic solvent is included as a liquid component for dissolving the UV-curable acrylic oligomer.

[0074] The type of organic solvent is not particularly limited, but examples include aromatic hydrocarbon solvents such as xylene and toluene; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol, and 1-hexanol; ketone solvents such as methyl ethyl ketone; and others such as glycol ether solvents, acetate solvents, ester solvents, hydrocarbon solvents, and fatty acid ester solvents. These organic solvents can be used in combination as appropriate.

[0075] Of these, monohydric alcohols having 2 to 12 carbon atoms are particularly preferred. Examples of monohydric alcohols include ethanol, isopropyl alcohol, 1-butanol, 1-hexanol, 1-octanol, and 1-dodecanol, with 1-hexanol being particularly preferred.

[0076] In the present invention, by combining a monohydric alcohol solvent having 2 to 12 carbon atoms with a cyclopolymerizable monomer as an ultraviolet-curable monomer, it becomes possible to form a desired micro-irregular shape on the surface of the resin film during curing, resulting in a resin film with high water-repellent and oil-repellent properties.

[0077] Since cyclopolymerizable monomers can be dissolved in monohydric alcohol solvents having 2 to 12 carbon atoms, by incorporating cyclopolymerizable monomers into an ultraviolet-curable acrylic resin composition solution and using the above monohydric alcohol as the solvent, other polymerization components contained in the resin composition solution become soluble in the solvent. Subsequently, when the resin composition solution is cured to begin polymerization, the compatibility with the solvent decreases as the molecular weight increases, inducing phase separation, and a micro-rough surface is formed on the resin film obtained by removing the solvent.

[0078] While it is not impossible to use a solvent capable of dissolving the polymer after the polymerization reaction, using a monohydric alcohol with 2 to 12 carbon atoms as the solvent makes it easier to achieve the exceptional effects of the present invention.

[0079] The solvent content is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, and especially preferably 50% by mass or more, relative to the total amount of the UV-curable acrylic resin composition solution containing the solvent. There is no particular upper limit to the content, but is preferably 90% by mass or less, more preferably 80% by mass or less, and especially preferably 70% by mass or less. If the amount of solvent used is within the above range, uneven coating and uneven thickness can be prevented.

[0080] <Optional Components> In addition to the above-mentioned UV-curable acrylic oligomer and optionally blended UV-curable monomer, photopolymerization initiator, thiol, and organic solvent, the UV-curable acrylic resin composition of the present invention may also contain inorganic pigments, organic pigments, surfactants (excluding fluorine-containing surfactants), and the like.

[0081] The viscosity of the UV-curable acrylic resin composition used in the present invention is not particularly limited, but the viscosity at 25°C is preferably 1 mPa·s or more, more preferably 3 mPa·s or more, and particularly preferably 5 mPa·s or more. The upper limit of viscosity is not particularly limited, but is preferably 100 mPa·s or less, more preferably 30 mPa·s or less, and particularly preferably 10 mPa·s or less.

[0082] (2) Silane-modified particles The ultraviolet-curable acrylic resin composition contains silane-modified particles. The silane-modified particles may be either inorganic particles or organic particles.

[0083] <Inorganic Particles> Specific examples of inorganic particles to be modified with silane include silica, alumina, zeolite, and titanium oxide. Of these, silica is preferred. The average particle size of the inorganic particles is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more. The upper limit of the average particle size is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less, even more preferably 200 nm or less, and especially preferably 150 nm or less. Note that the particle size hardly changes even when these inorganic particles are modified with silane.

[0084] <Organic Particles> Specific examples of organic particles that are modified with silane include particles made of silicone resin. For example, polymethylsilsesquioxane, a polymer of methyltrimethoxysilane, can be used. Polymethylsilsesquioxane is a silicone resin polymerized by crosslinking methyltrimethoxysilane in a three-dimensional network structure, and it is a spherical microparticle. Commercially available products can be used for these.

[0085] The average particle size of the organic particles is not particularly limited, but is preferably 10 nm or more, more preferably 100 nm or more, even more preferably 200 nm or more, and especially preferably 300 nm or more. The upper limit of the average particle size is not particularly limited, but is preferably 1000 nm or less, more preferably 800 nm or less, even more preferably 600 nm or less, and especially preferably 500 nm or less. Note that the particle size hardly changes even when these organic particles are modified with silane.

[0086] <Silane Modification> The silane-modified particles are obtained by modifying (coating, surface treating, or hydrophobicizing) part or all of the surface of the inorganic or organic particles (hereinafter sometimes simply referred to as "particles") with silane. More preferably, they are obtained by treating and coating part or all of the silanol groups on the surface of the silica particles with silane.

[0087] <Silane> Examples of silanes used for modification include alkylsilanes, arylsilanes, arylalkylsilanes, olefinylsilanes, and alkylalkoxysilanes. Of these, alkylalkoxysilanes are preferred. Preferably, alkylalkoxysilanes are alkyltrialkoxysilanes having a linear alkyl group with 1 to 18 carbon atoms and a linear alkoxy group with 1 to 2 carbon atoms.

[0088] Examples of linear alkyl groups having 1 to 18 carbon atoms include methyl, hexyl, decyl, and octadecyl groups. A preferred example of a linear alkoxy group having 1 to 2 carbon atoms is a methoxy group.

[0089] Particularly preferred silanes for modification include octadecyltrimethoxysilane, methyltrimethoxysilane, and hexyltrimethoxysilane. These may be used individually or in combination of two or more.

[0090] <Preparation Method> The silane-modified inorganic or organic particles used in this invention can be prepared by mixing the particles with silane and, if necessary, a dispersant, dispersion medium, etc., and stirring. This yields a particle dispersion containing silane-modified particles. For example, if silica is used as the particles, a silane-modified silica sol is obtained.

[0091] While there are no particular limitations on the dispersant, examples include polyfunctional comb-type functional polymers (polyfunctional comb-type surfactants) having ionic groups in the main chain and polyoxyalkylene chains in the graft chains. By shortening the length of the main chain, excellent dispersibility is exhibited, especially for fine particles of about 1 μm or less.

[0092] The dispersion medium is not particularly limited, but water or an organic solvent can be used, and an organic solvent is preferred. The organic solvent is not particularly limited, but examples include aromatic hydrocarbon solvents such as xylene and toluene; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, and 1-hexanol; and ketone solvents such as methyl ethyl ketone, and these can be used in combination as appropriate.

[0093] The particle content in the particle dispersion is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by weight of the particle dispersion. The upper limit of the particle content is not particularly limited, but is preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

[0094] The silane content per 100 parts by weight of the particle dispersion is not particularly limited, but is preferably 1 part by mass or more, more preferably 3 parts by mass or more. The upper limit of the silane content is not particularly limited, but is preferably 20 parts by mass or less, more preferably 8 parts by mass or less.

[0095] The amount of dispersant per 100 parts by weight of the particle dispersion is not particularly limited, but is preferably 1 part by mass or more, more preferably 2 parts by mass or more. The upper limit of the dispersant content is not particularly limited, but is preferably 20 parts by mass or less, more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less.

[0096] The content of the dispersion medium per 100 parts by weight of the particle dispersion is not particularly limited, but is preferably 10 parts by mass or more, more preferably 35 parts by mass or more, and especially preferably 54 parts by mass or more. The upper limit of the dispersion medium content is not particularly limited, but is preferably 90 parts by mass or less, and more preferably 84 parts by mass or less.

[0097] The stirring method after mixing the particles, silane, and dispersant, dispersion medium, etc., as needed, is not particularly limited, but commercially available dispersers or other devices that can perform homogeneous mixing and dispersion in a short time can be used. For example, the product name "Paint Conditioner 1400-0H" (manufactured by Red Devil Co., Ltd.) can be cited.

[0098] While there are no particular restrictions on the stirring conditions, examples include a stirring temperature of 23-28°C (room temperature), an vibration speed of 600 times / minute or more, and a stirring time of approximately 1-5 hours. Furthermore, beads such as zirconia beads used in grinding and dispersion bead mills can be incorporated for mixing and dispersion. Beads with a diameter of approximately φ0.3-2.0 mm are preferably used.

[0099] <Primary Particle Size> The silane-modified particles have a primary particle size of preferably 1 to 1000 nm. Specifically, the primary particle size is 1 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more. There is no particular upper limit to the primary particle size, but it is preferably 1000 nm or less, more preferably 800 nm or less, even more preferably 600 nm or less, and particularly preferably 500 nm or less. The primary particle size referred to here is the size (particle diameter) of the unit particle that is recognized as the smallest unit of particle based on its external geometric shape, and can be measured using the laser diffraction scattering method.

[0100] <Inorganic Particles> The primary particle diameter of silane-modified inorganic particles is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more. The upper limit of the primary particle diameter is not particularly limited, but is preferably 1000 nm or less, more preferably 500 nm or less, even more preferably 200 nm or less, and especially preferably 150 nm or less.

[0101] <Organic Particles> The primary particle size of the silane-modified organic particles is not particularly limited, but is preferably 10 nm or larger, more preferably 100 nm or larger, even more preferably 200 nm or larger, and especially preferably 300 nm or larger. The upper limit of the primary particle size is not particularly limited, but is preferably 1000 nm or smaller, more preferably 800 nm or smaller, even more preferably 600 nm or smaller, and especially preferably 500 nm or smaller.

[0102] <Content of particle dispersion> The content of the particle dispersion containing silane-modified particles is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more, based on the total amount of the UV-curable acrylic resin composition solution containing the solvent. There is no particular upper limit to the content, but it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0103] (3) Preparation of UV-curable acrylic resin composition solution The UV-curable acrylic resin composition solution of the present invention is obtained by placing a predetermined amount of a particle dispersion containing the above-mentioned UV-curable acrylic oligomer and silane-modified particles, as well as materials such as UV-curable monomers, photopolymerization initiators, thiol compounds, and solvents, which are added as needed, into a container and stirring. The UV-curable acrylic resin composition solution obtained in this way can be used in inkjet printing as an inkjet ink, as described later, to form a resin film.

[0104] (4) Resin film The resin film of the present invention is composed of an ultraviolet-curable acrylic resin cured product obtained by curing the ultraviolet-curable acrylic resin composition by irradiating it with ultraviolet light. Despite not containing fluorine, the surface of the resin film of the present invention has extremely high water-repellent and oil-repellent properties.

[0105] The UV-curable acrylic resin cured product contains silane-modified particles. The silane-modified particle content is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more, based on the total amount of the UV-curable acrylic resin cured product. There is no particular upper limit to the content, but it is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less. In the UV-curable acrylic resin cured product, the solvent used in the ink and the dispersion medium used in the particle dispersion are removed during the curing process.

[0106] If the content of silane-modified particles is too low, the water-repellent and oil-repellent properties of the resin film may decrease, and if it is too high, the resin film may turn white.

[0107] The resin film obtained by curing the above-mentioned ultraviolet-curable resin composition of the present invention has a micro-uneven surface that satisfies the following physical properties. By laminating such a resin film onto an article, a micro-uneven surface that satisfies the following physical properties can be formed on the surface of the article, thereby imparting high water-repellent and oil-repellent properties to the article.

[0108] <Arithmetic mean roughness: Sa> The arithmetic mean roughness: Sa of the resin film surface is 0.03 μm or more and 0.50 μm or less, preferably 0.05 μm or more and 0.40 μm or less. <Curtosis (sharpness): Sku> The curtosis (sharpness): Sku of the resin film surface is 1.00 or more and 6.00 or less, preferably 2.00 or more and 5.60 or less. <Skewness (deviation): Ssk> The skewness (deviation): Ssk of the resin film surface is 0.10 or more and 2.00 or less, preferably 0.10 or more and 1.85 or less.

[0109] The arithmetic mean roughness, crustosis (sharpness), and skewness (bias) described above can all be determined by photographing the surface of the resin film with a laser microscope (product name "VK-X3000"; manufactured by Keyence Corporation) using a 150x objective lens, thereby acquiring a surface image that includes height information. That is, after capturing the surface image, the analysis application attached to the laser microscope is used to analyze the surface roughness from the obtained surface image, and from there the arithmetic mean surface roughness: Sa, crustosis (sharpness): Sku, and skewness (bias): SSk of the resin cured product surface can be calculated.

[0110] <Resin film thickness> The thickness of the resin film is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.3 μm or more. The upper limit of the film thickness is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 2.5 μm or less.

[0111] 2. Articles Having a Resin Film A resin film composed of a cured product obtained by curing the ultraviolet-curable resin composition of the present invention can be laminated onto an article (substrate) to create an article having a resin film. The shape of the substrate on which the resin film can be laminated is not particularly limited, and various shapes of substrates can be used, such as film-like, plate-like, and 3D-shaped substrates. Preferably, the substrate is in the form of a film. Specifically, examples include articles used in applications such as antifouling processing where high water-repellent and oil-repellent properties are required.

[0112] Examples of film-like articles (substrates) include those made of materials such as synthetic resins, metals, paper, and glass. Preferably, the film is made of synthetic resin, and more preferably, polyester film, urethane film, acrylic film, polyimide film, etc. Of these, polyester film such as polyethylene terephthalate (PET) is even more preferred.

[0113] The film thickness is not particularly limited and can be set according to the application, but is preferably about 50 to 1000 μm. The thickness of the resin film laminated on the surface of the substrate is the same as the thickness of the resin film itself as described above.

[0114] 3. Method for Manufacturing Articles Having a Resin Film The method for manufacturing articles having a resin film according to the present invention is not particularly limited, but as an example, it can be manufactured by a method including the following steps A to C.

[0115] Step A: A step of forming a film on an article consisting of a UV-curable acrylic resin composition solution containing at least a UV-curable acrylic oligomer, a UV-curable monomer, a photopolymerization initiator, silane-modified particles, and a solvent. Step B: A step of irradiating the film obtained in Step A with ultraviolet light to pre-cure it and form a pre-cured film having a phase separation structure. Step C: A step of fully curing the pre-cured film obtained in Step B.

[0116] (1) Step A: In Step A of the manufacturing method of the present invention, a film (coated film) made of an ultraviolet-curable acrylic resin composition solution containing at least an ultraviolet-curable acrylic oligomer, an ultraviolet-curable monomer, silane-modified particles, and a solvent is formed on the surface of the target article (substrate). The above-mentioned substrates are examples of articles (substrates) to which the resin film is laminated.

[0117] There are no particular limitations on the method for forming a film made of an ultraviolet-curable acrylic resin composition solution on a substrate, but a printing method using an ink made of an ultraviolet-curable acrylic resin composition solution is preferred. Known printing methods such as gravure printing, screen printing, photolithography, gravure offset printing, xerography, stamping, flexographic printing, painting, airbrushing, and inkjet printing can be applied.

[0118] Of these, screen printing and inkjet printing are more preferred, and inkjet printing is particularly preferred. It is preferable to prepare an ink consisting of an ultraviolet-curable acrylic resin composition solution in advance and apply a coating film to the substrate by inkjet printing using this ink. The thickness of the coating film formed in this way is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 50 μm, and particularly preferably 3 to 25 μm.

[0119] An ink consisting of an ultraviolet-curable acrylic resin composition solution (hereinafter simply referred to as "ink") can be prepared by pre-mixing an ultraviolet-curable acrylic oligomer, an ultraviolet-curable monomer, a dispersion of silane-modified particles, a solvent, and optionally a photopolymerization initiator, a thiol compound, etc.

[0120] Preferably, the solvent is an organic solvent that can be used in the above-mentioned UV-curable acrylic resin composition solution, but more preferably a monohydric alcohol having 2 to 12 carbon atoms is used. Specifically, examples include ethanol, isopropyl alcohol, 1-butanol, 1-hexanol, 1-octanol, 1-dodecanol, and the like, with 1-hexanol being particularly preferred.

[0121] In the present invention, by combining a monohydric alcohol solvent having 2 to 12 carbon atoms with a cyclopolymerizable monomer as an ultraviolet-curable monomer, it becomes possible to form a desired micro-irregular shape on the surface of the resin film during curing, resulting in a resin film with high water-repellent and oil-repellent properties.

[0122] The amount of solvent used is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of ink. There is no particular upper limit to the amount used, but it is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less. If the amount of solvent used is within the above range, uneven coating and uneven thickness can be prevented.

[0123] Furthermore, while the viscosity of the ink is not particularly limited, in the case of inkjet ink, the viscosity at 25°C is preferably 1 mPa·s or more, more preferably 3 mPa·s or more, and even more preferably 5 mPa·s or more. The upper limit of the viscosity of the ink at 25°C is not particularly limited, but is preferably 30 mPa·s or less, more preferably 25 mPa·s or less, and even more preferably 15 mPa·s or less.

[0124] Details regarding the UV-curable acrylic oligomer, UV-curable monomer, silane-modified particles, solvent, and other additives such as photopolymerization initiators and thiol compounds included in the aforementioned ink are as described above.

[0125] As the UV-curable acrylic oligomer contained in the ink, it is preferable to use a bifunctional urethane (meth)acrylate oligomer having a urethane bond and a (meth)acrylic group in its molecule, since the cured film has excellent flexibility.

[0126] Preferably, the UV-curable monomer contained in the ink includes one or a combination of two or more monomers, including a cyclizable monomer.

[0127] When cyclizable monomers are used in combination with other UV-curable monomers, they are preferably present in amounts of 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of UV-curable monomers. There is no particular upper limit to the content, but it is preferably 80% by mass or less, and more preferably 70% by mass or less.

[0128] Furthermore, the cyclizable monomer is preferably present in an amount of 1.5% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the total amount of ink. There is no particular upper limit to the content, but it is preferably 7% by mass or less, more preferably 6% by mass or less, and particularly preferably 5% by mass or less.

[0129] The total amount of ultraviolet-curable monomers contained in the ink is preferably 3% by mass or more, more preferably 5% by mass or more, relative to the total amount of ink. There is no particular upper limit to the amount, but it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0130] The ink preferably contains a thiol compound. The thiol compound is preferably present in an amount of 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of ink. There is no particular upper limit to the content, but it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less.

[0131] (2) Step B In Step B, the film (coated film) formed in Step A is subjected to ultraviolet irradiation to pre-cure it, forming a pre-cured film having a phase separation structure. The irradiation in Step B is a pre-irradiation, which prevents the ultraviolet-curable acrylic resin composition from being completely cured, leaving it in a pre-cured state, and simultaneously inducing phase separation.

[0132] The above-mentioned ink (UV-curable acrylic resin composition solution) is a homogeneous solution in which, at the stage of the mixed solution obtained by mixing each component (coating solution before UV irradiation), the UV-curable acrylic oligomer and UV-curable monomer are compatible, and organic or inorganic particles are uniformly dispersed. However, after preliminary irradiation with UV light, it is thought that solvent-insoluble components (polymers) are generated by photopolymerization, and these components separate from the solvent, forming a phase-separated structure in which these components are dispersed in the solvent, with organic or inorganic particles further uniformly dispersed within it.

[0133] The criterion for semi-curing is not particularly limited. However, it can be determined that phase separation between the solvent and the polymer is induced in the coating film when a transparent film becomes opaque (whitened) after ultraviolet irradiation before the irradiation.

[0134] Ultraviolet irradiation in step B can preferably be carried out using an ultraviolet light source having a peak at 365 to 410 nm, more preferably a UV lamp having a peak at 365 nm. The integrated light quantity is not particularly limited, but is preferably 100 to 4000 mJ / cm ２ , more preferably 500 to 2500 mJ / cm ２ , particularly preferably 1000 to 1500 mJ / cm ２ By irradiating ultraviolet rays so as to obtain the desired semi-cured film.

[0135] (3) Step C In step C, the semi-cured film obtained in step B is fully cured. Examples of the method for full curing include heat treatment, re-irradiation with ultraviolet rays, etc. Heat treatment is preferably used. By heating, the solvent in the semi-cured film is removed to obtain a fully cured film. The method of heat treatment is not particularly limited, and examples include conventionally known methods such as leaving it standing in a dryer. The heating temperature is preferably 50 to 150 °C, more preferably 60 to 100 °C, and the heating time is preferably 5 to 60 minutes, more preferably about 10 to 30 minutes.

[0136] In the present invention, by devising the ink composition, it is possible to induce phase separation in the curing treatment step to form a surface micro-roughness structure, thereby dramatically improving the water and oil repellency of the resin film surface. The ultraviolet-curable acrylic oligomer and ultraviolet-curable monomer capable of forming a polymer by a curing reaction can be made soluble in a solvent by including a cyclopolymerizable monomer in the ultraviolet-curable monomer and using a monohydric alcohol having 2 to 12 carbon atoms as the solvent. When an ink having a combination of these specific components is cured to initiate polymerization, as the molecular weight of the polymer increases, the compatibility with the solvent decreases, and phase separation is induced. It is considered that micro-roughness is formed on the surface of the resin film by this.

[0137] Therefore, in the present invention, it is particularly preferable to include a cyclopolymerizable monomer as an ultraviolet-curable monomer in the components of the ink, and to use a monohydric alcohol solvent such as hexanol, in order to improve the water-repellent and oil-repellent properties of the resin film.

[0138] However, articles having the resin film of the present invention are not limited to these specific compositions, and may have a surface micro-roughness that satisfies a certain range of arithmetic mean roughness, kurtosis (sharpness), and skewness (bias) of the resin film surface. Furthermore, articles having the resin film of the present invention are not limited to the above manufacturing method, and may be manufactured by other methods as long as they possess the physical properties unique to the present invention.

[0139] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the preceding and following descriptions, and all such modifications are included within the technical scope of the present invention.

[0140] <Preparation of Silane-Modified Particle Dispersions> The components shown in Table 1 below were prepared in the mixing ratios (parts by mass) shown in Table 1. Using 0.5 mm zirconia beads, the dispersions were stirred for 3 hours in a stirrer (product name "Paint Conditioner 1400-0H"; manufactured by Red Devil Co., Ltd.) (vibration speed: 1725 revolutions per minute at a frequency of 60 Hz, temperature 25°C) to obtain particle dispersions A to D. The primary particle diameters of the silane-modified particles were A: 30 nm, B: 110 nm, C: 500 nm, and D: 30 nm.

[0141]

[0142] - Product names "QSG-30, QSG-100" (manufactured by Shin-Etsu Chemical Co., Ltd.) - Product name "MSP-SN05" (manufactured by Nikko Rica Co., Ltd.) - 1-Hexanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) - Product name "Marialim SC-0505K" (manufactured by NOF Corporation) - Octadecyltrimethoxysilane (manufactured by Tokyo Chemical Industries, Ltd.) - Hexyltrimethoxysilane (manufactured by Tokyo Chemical Industries, Ltd.)

[0143] <Preparation of Inks 1-5> The components shown in Table 2 were mixed in the proportions (parts by mass) shown in Table 2 to prepare inks 1-7, which consist of an ultraviolet-curable acrylic resin composition.

[0144]

[0145] The viscosities of each ink (1-7) are as follows: Ink 1: 5.2 mPa·s, Ink 2: 5.2 mPa·s, Ink 3: 5.5 mPa·s, Ink 4: 5.2 mPa·s, Ink 5: 5.4 mPa·s, Ink 6: 5.1 mPa·s, Ink 7: 5.3 mPa·s

[0146] • Product name "CN996": Urethane acrylate oligomer (manufactured by Sartomer) • Product name "SR-444": Pentaerythritol triacrylate (manufactured by Sartomer) • Product name "DPHA": Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) • Product name "SR-257": Stearyl acrylate (manufactured by Sartomer) • Product name "4-HBA": 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) • Product name "AOMA": Cyclopolymerizable monomer (manufactured by Nippon Shokubai Co., Ltd.)

[0147] • Product name "PE-1": Pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonaq Corporation) • Product name "BD-1": 1,4-bis(3-mercaptobutyryloxy)butane (manufactured by Resonaq Corporation)

[0148] • Product name "Omnirad 184": 1-Hydroxycyclohexyl-phenyl ketone; IGM Resins B. V.

[0149] [Examples 1-6, Comparative Examples 1-2] The following PET films (all manufactured by Toray Industries, Inc., size = 80 x 300 mm) were used as substrates: • Product name "Lumirror #50-S10" (thickness: 50 μm) • Product name "Lumirror #100-U46" (thickness: 100 μm)

[0150] Inks 1 to 7 were applied to the substrate by an inkjet method to obtain a coated film with a wet film thickness of 5 to 20 μm. Subsequently, the coated film was cured by ultraviolet irradiation using a high-pressure mercury lamp having a peak at 365 nm to obtain a cured film.

[0151] Next, the cured film was heat-treated in a dryer at 60°C for 15 minutes to remove the solvent and obtain the cured film. The cumulative amount of ultraviolet irradiation during curing in each example and comparative example (unit: mJ / cm) ２ The temperature at 365 nm was 1250. After curing, an article (resin film laminated film) with a resin film coated onto the film was obtained. The thickness of the resin film in the obtained article was 0.5 to 2.0 μm.

[0152] [Measurement Method] <Water Repellency> The water contact angle (degrees; °) on the resin film surface was measured using the θ / 2 method in accordance with ISO 19403. <Slip Angle> 20 μl of water was dropped onto the resin film coated on the film, and the angle at which the water slipped off the film was measured. <Oil Repellency> Measured using the AATCC 118 method, with the average value of n=3 being used. The results are expressed in reagent grade. The grades are divided from 1 to 8, with grade 8 being the highest grade (highest oil repellency).

[0153] <Surface Irregularities> The surface of the resin film on the obtained articles was photographed using a laser microscope (product name "VK-X3000"; manufactured by Keyence Corporation) with an objective lens of x150 to obtain a surface image including height information.

[0154] Next, using the analysis application included with the aforementioned product name "VK-X3000" (manufactured by Keyence Corporation), surface roughness was analyzed from the obtained surface image, and from this, the arithmetic mean surface roughness: Sa, kurtosis (sharpness): Sku, and skewness (bias): SSk of the resin cured product surface were calculated.

[0155]

[0156] The UV-curable acrylic resin composition of the present invention can be used as an inkjet ink or the like, and by laminating it onto the surface of articles made of various materials, it can impart a resin film with high water-repellent and oil-repellent properties.

[0157] The resin film formed by the cured product of the UV-curable acrylic resin composition of the present invention exhibits excellent water and oil repellency despite not using fluorine-containing functional groups, and can therefore be used, for example, for anti-fouling treatment. Thus, by laminating such a resin film onto an article, problems such as the decomposition of fluorine-containing water and oil repellent films and the diffusion of fluorine into the environment during disposal are eliminated, and environmentally friendly articles can be provided from the perspective of SDGs.

Claims

1. An article having a resin film, wherein a resin film made of a cured product of an ultraviolet-curable acrylic resin composition containing silane-modified particles is laminated on a substrate, and the resin film surface has a surface micro-irregularity shape with an arithmetic mean roughness: Sa of 0.03 μm or more and 0.50 μm or less, a kurtosis (sharpness): Sk of 1.00 or more and 6.00 or less, and a skewness (deviation): Ssk of 0.10 or more and 2.00 or less.

2. The article according to claim 1, wherein the ultraviolet-curable acrylic resin composition comprises at least an ultraviolet-curable acrylic oligomer, an ultraviolet-curable monomer, a photopolymerization initiator, and silane-modified particles.

3. The article according to claim 1 or 2, wherein the silane-modified particles are modified with an alkyltrialkoxysilane having a linear alkyl group having 1 to 18 carbon atoms.

4. The article according to claim 1 or 2, wherein the silane-modified particles are inorganic or organic particles having a primary particle diameter of 1 to 1000 nm.

5. The article according to claim 2, characterized in that at least one of the ultraviolet-curable acrylic oligomer and the ultraviolet-curable monomer has a hydrophilic group.

6. The article according to claim 2, wherein the ultraviolet-curable monomer comprises at least a cyclizable monomer.

7. The article according to claim 1 or 2, wherein the content of the silane-modified particles is 1 to 50% by mass relative to the total amount of the ultraviolet-curable acrylic resin composition.

8. The article according to claim 1 or 2, wherein the thickness of the resin film is 0.1 to 5 μm.

9. A method for producing an article having a resin film as described in claim 1, comprising the following steps A to C: Step A: A step of forming a film on an article consisting of an ultraviolet-curable acrylic resin composition solution containing at least an ultraviolet-curable acrylic oligomer, an ultraviolet-curable monomer, a photopolymerization initiator, silane-modified particles, and a solvent. Step B: A step of irradiating the film obtained in step A with ultraviolet light to pre-cure it and form a pre-cured film having a phase separation structure. Step C: A step of fully curing the pre-cured film obtained in step B.

10. The manufacturing method according to claim 9, wherein the ultraviolet-curable monomer comprises at least a cyclizable monomer.

11. The manufacturing method according to claim 9 or 10, wherein the solvent is a monohydric alcohol having 2 to 12 carbon atoms.

12. The manufacturing method according to claim 9, wherein step C is a step of heat-treating the pre-cured film obtained in step B.

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