Method for producing substrate having cured film

Abstract

To provide a production method for a substrate having a hardened film, excellent in adhesiveness and long-term acid resistance on a wide substrate, particularly in adhesiveness on inorganic substrates such as glass and superior in adhesiveness even in a case used under high-humidity conditions.SOLUTION: A production method for a substrate having a hardened film comprises carrying out sequentially the following processes 1 and 2: process 1 of forming the hardened film by coating on the substrate, an active energy ray curable composition (hereinafter referred to as a composition 1) including (A) cationic polymerizable silane coupling agent and (B) cationic photopolymerization initiator and by irradiating a coated surface with the active energy ray to form the hardened film; and process 2 of forming a final hardened film by coating on the hardened film obtained by process 1, the active energy ray curable composition including (B) cationic photopolymerization initiator, (C) oxetane compound and (D) oxirane compound and by irradiating the coated surface with the active energy ray.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a substrate having a cured film. The cured film obtained by the production method of the present invention has excellent adhesion to inorganic substrates, particularly to glass substrates, and can be used to form ink layers and coating layers on glass substrates. In addition, by applying the cured film to the end face of a glass substrate that has been subjected to metal vapor deposition, it can prevent water intrusion and form a protective cured film that prevents corrosion of the vapor-deposited film, and these technical fields belong to this invention. [Background technology]

[0002] Active energy ray-curable compositions can be cured by short-term irradiation with active energy rays such as ultraviolet rays, visible light, and electron beams, and are widely used as inks and coating agents for various substrates due to their high productivity.

[0003] However, while conventional active energy ray-curable compositions can relatively easily achieve desired substrate adhesion when the substrate is made of a surface-treated plastic material such as poly(ethylene terephthalate) resin (PET resin), polycarbonate (PC), polystyrene (PS), or polymethyl methacrylate (PMMA), there has been a problem in that they are unable to achieve good adhesion to inorganic substrates such as metals and glass.

[0004] As a method for imparting adhesion to inorganic substrates such as metals and glass, an active energy ray-curable composition containing a phosphate ester (A) having two or more (meth)acryloyl groups in one molecule, a polyfunctional (meth)acrylate (B) excluding (A), and a photopolymerization initiator (C) is known (Patent Document 1). However, although this composition can provide a certain degree of initial adhesion, when used as a coating agent for products that require water resistance, such as those used in wet areas, the water resistance of the cured film is insufficient, and there is a problem that the cured film easily peels off when immersed in warm water, for example.

[0005] Known active energy ray-curable compositions intended to improve adhesion to glass substrates include an active energy ray-curable composition containing a compound (A) having one or more (meth)acryloyloxy groups, a (co)polymer (B) obtained by homopolymerizing a simple ethylenically unsaturated compound or copolymerizing a mixture thereof, a silane coupling agent (C), and a photopolymerization initiator (D) (Patent Document 2). However, there is a limit to the range of polymer (B) that can be used due to the balance between compatibility and coatability, and in order to expand this range, all of the examples in Patent Document 2 use solvent-based compositions, which poses issues of reduced productivity and environmental impact due to drying of the solvent.

[0006] As an example other than the above, there is known an active energy ray-curable composition containing an acrylic resin (A), an unsaturated compound (B) containing two or more ethylenically unsaturated groups, a phosphoric acid group-containing ethylenically unsaturated compound (C), a silane coupling agent (D), and a fluorine-based compound (E) (Patent Document 3). However, since the condensation reaction of component (D) in the composition is accelerated under acidic conditions, the coexistence of component (C), which has acidity, significantly impairs the storage stability of the composition. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-155470 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-93893 [Patent Document 3] Japanese Patent Application Laid-Open No. 2015-83658 [Patent Document 4] Patent Application No. 2020-155840 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0008] The present inventors have conducted extensive research to find an active energy ray-curable composition that produces a cured film that has excellent adhesion to a wide range of substrates, particularly to inorganic substrates such as glass, that does not lose adhesion even when used under high humidity conditions, and that also has excellent water resistance and acid resistance. As a result, they have proposed an active energy ray-curable composition that includes component (A): a compound having an oxetane ring, component (B): a compound having an oxirane ring, component (C): a silane coupling agent, and component (D): a compound that initiates cationic polymerization upon irradiation with active energy rays (Patent Document 4). A cured film of this composition exhibited excellent adhesion to inorganic substrates such as glass under high humidity conditions, and also had excellent acid resistance and water resistance. However, in environments where the composition is used, such as around a bathroom, where the composition is exposed to high humidity for long periods of time, the cured film did not exhibit sufficient adhesion performance.

[0009] The present inventors have conducted extensive research to find a method for producing a substrate having a cured film which exhibits excellent adhesion to a wide range of substrates and long-term acid resistance, particularly excellent adhesion to inorganic substrates such as glass, and which also exhibits excellent adhesion even when used under high humidity conditions, and in particular a method for producing a substrate having a cured film on which a coating layer and an ink layer can be suitably formed. [Means for solving the problem]

[0010] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a production method in which a composition of a silane coupling agent and a compound that initiates cationic polymerization upon irradiation with active energy rays is applied to a substrate, the composition is cured with active energy rays, and a composition of a compound that initiates cationic polymerization upon irradiation with active energy rays, a compound having an oxetane ring, and a compound having an oxirane ring is applied to the resulting cured film, and the composition is cured with active energy rays, provides good adhesion to inorganic substrates such as glass, and further provides a cured film with excellent water resistance, thereby completing the present invention. The present invention will be described in detail below. [Effects of the Invention]

[0011] According to the production method of the present invention, the cured film has excellent adhesion to a wide range of substrates, particularly to inorganic substrates such as glass, and also has excellent water resistance. Therefore, the manufacturing method of the present invention can suitably form a protective layer for a metal vapor deposition film formed on glass. By applying the method to the edge of a mirror used in wet areas such as kitchens and bathrooms, it can be used to form a protective agent for glass tiles in bathrooms or a protective layer for semiconductor cleaning treatment tanks. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention relates to a method for producing a substrate having a cured film, which comprises sequentially carrying out the following steps 1 and 2: Step 1: A step of applying an active energy ray-curable composition (hereinafter referred to as "composition 1") containing the following components (A) and (B) to a substrate, and irradiating the coated surface with active energy rays to form a cured film (hereinafter also referred to as "primer layer"). Step 2: A step of applying an active energy ray-curable composition (hereinafter referred to as "composition 2") containing the following components (B), (C), and (D) onto the cured film obtained in step 1, and irradiating the coated surface with active energy rays to form a cured film (hereinafter also referred to as "overcoat layer"). Component (A): Silane coupling agent having a cationically polymerizable group Component (B): a compound that initiates cationic polymerization upon irradiation with active energy rays Component (C): Compound having an oxetane ring Component (D): Compound having an oxirane ring Composition 1, Composition 2, Step 1, Step 2, and uses will be explained below.

[0013] 1. Composition 1 Composition 1 is an active energy ray-curable composition containing components (A) and (B), and is a composition for forming a primer layer, which is a cured film of composition 1, on a substrate. The component (A), the component (B), and the composition 1 will be described in detail below.

[0014] 1-1.(A) Component Component (A) is a silane coupling agent having a cationically polymerizable group, which reacts with water, such as moisture in the air, to improve adhesion to substrates, preferably inorganic substrates, and also improves adhesion to the overcoat layer, which is a cured film of composition 2, by undergoing cationic polymerization together with components (C) and (D) described below.

[0015] Examples of the cationically polymerizable group in component (A) include an epoxy group, a vinyl ether group, and an oxetanyl group, with an epoxy group being preferred.

[0016] The following compounds can be used as component (A). Specific preferred examples include epoxy group-containing silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 8-glycidoxyoctyltriethoxysilane; and oxetanyl group-containing silane coupling agents such as 2-(3,4-oxetanylcyclohexyl)ethyltrimethoxysilane, 3-oxetanylpropyltrimethoxysilane, 3-oxetanylpropylmethyldiethoxysilane, 3-oxetanylpropyltriethoxysilane, and 8-oxetanyloctyltriethoxysilane. Examples of suitable silane coupling agents include oxolanyl group-containing silane coupling agents such as 2-(3,4-oxolanylcyclohexyl)ethyltrimethoxysilane, 3-oxolanylpropyltrimethoxysilane, 3-oxolanylpropylmethyldiethoxysilane, 3-oxolanylpropyltriethoxysilane, and 8-oxolanyloctyltriethoxysilane; and vinyl ether-based silane coupling agents such as vinyl(trimethoxysilyl)ether, vinyl(methyldiethoxysilyl)ether, and vinyl(triethoxysilyl)ether. These compounds may be used alone or in combination of two or more.

[0017] Among these compounds, silane coupling agents having a cationically polymerizable group are preferred because the rate of polymerization propagation is slow. If the rate of polymerization propagation is fast, it becomes difficult to control the curing rate. Preferred silane coupling agents include the above-mentioned epoxy group-containing silane coupling agents, and 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane are particularly preferred.

[0018] 1-2.(B) Component Component (B) is a compound that initiates cationic polymerization upon irradiation with active energy rays, that is, a compound that generates cationic species or Lewis acids upon irradiation with active energy rays, and is generally known as a photocationic polymerization initiator. As the component (B), various compounds known as photocationic polymerization initiators can be used, including onium salts such as aromatic iodonium salts and aromatic sulfonium salts, aromatic diazonium salts, and iron-allene complexes, with onium salts such as aromatic iodonium salts and aromatic sulfonium salts being preferred. Specific examples of the aromatic iodonium salt and aromatic sulfonium salt in component (B) include the compounds exemplified in JP-A No. 11-246647.

[0019] Specific preferred examples of the component (B) include the following compounds: Examples of aromatic iodonium salts include the following compounds: Examples thereof include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate.

[0020] Examples of aromatic sulfonium salts include the following compounds: Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, 4,4'-bis(diphenylsulfonio)diphenyl sulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenyl sulfide bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenyl sulfide bishexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)sulfonio-diphenyl sulfide tetrakis(pentafluorophenyl)borate, and the like.

[0021] Examples of aromatic diazonium salts include the following compounds: Examples thereof include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

[0022] Examples of iron-allene complexes include the following compounds: xylene-cyclopentadienyliron(II) hexafluoroantimonate, cumene-cyclopentadienyliron(II) hexafluorophosphate, and xylene-cyclopentadienyliron(II)-tris(trifluoromethylsulfonyl)methanide.

[0023] As the component (B), one of the above compounds may be used alone, or two or more of them may be used in combination.

[0024] As the component (B), commercially available products can be used. Specific examples include the trade names "Kayarad PCI-220", "Kayarad PCI-620" (both manufactured by Nippon Kayaku Co., Ltd.), "UVI-6992" (manufactured by The Dow Chemical Company), "Adeka Optomer SP-150", "Adeka Optomer SP-170" (both manufactured by ADEKA Corporation), "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", "CIP-2048S", and "CIP-2064S". [All products are manufactured by Nippon Soda Co., Ltd.] "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105" , "MDS-103", "MDS-105", "DTS-102", "DTS-103" (all manufactured by Midori Chemical Co., Ltd.), "PI-2074" (manufactured by Rhodia), "Omnirad250", "OmniradPAG103", OmniradPAG108", OmniradPAG121", OmniradPAG203" (all manufactured by IGM Resins), "CPI-100P", "CPI-101A", "CPI-200K", "CPI-210S" (all manufactured by San-Apro Ltd.), and the like. Among these, "UVI-6992" manufactured by Dow Chemical Company, and "CPI-100P", "CPI-101A", "CPI-200K", and "CPI-210S" manufactured by San-Apro Co., Ltd., which contain diphenyl[4-(phenylthio)phenyl]sulfonium as a cationic component, are particularly preferred.

[0025] 1-3. Details of Composition 1 Composition 1 is an active energy ray-curable composition containing the components (A) and (B). The composition can be produced by stirring and mixing components (A) and (B), and other components described below as needed, in accordance with conventional methods. In this case, the mixture may be heated and stirred as needed. When the mixture is heated and stirred / mixed, the temperature is preferably in the range of 20 to 70°C.

[0026] The content ratio of the component (A) and the component (B) in the composition 1 may be appropriately set depending on the purpose. The content of component (B) in composition 1 is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, as the active ingredient, per 100 parts by weight of component (A). Here, the term "active ingredient" refers to the solid content of component (B), which is often used as a solution in an organic solvent. By setting the content of component (B) to 0.1 parts by weight or more, component (A) can be cured favorably, and by setting the content of component (B) to 10 parts by weight or less, problems such as corrosion caused by the acid contained in component (B) can be prevented depending on the substrate or product to which it is applied. Depending on the type of component (B), a solution diluted with an organic solvent (hereinafter referred to as "component (B) solution") may be used. In this case, if the active ingredient concentration is 50% by weight, the amount added should be doubled. Even when a component (B) solution is used, if the amount added is large, the amount of organic solvent carried over from the component (B) solution will increase, requiring a separate drying process, the environmental impact of drying the solvent will be a problem, and curing without drying may result in poor appearance due to the organic solvent. Therefore, it is preferable to adjust the content ratio taking into account the degree of curability and any deterioration in the performance of the cured film, etc.

[0027] The viscosity of composition 1 may be appropriately set depending on the base material used, the application, the purpose, etc. The viscosity of composition 1 is preferably 1 to 1,000,000 mPa·s, and more preferably 1 to 10,000 mPa·s. In the present invention, the viscosity refers to a value measured at 25°C using an E-type viscometer (cone-plate type viscometer).

[0028] Composition 1 of the present invention essentially comprises the above-mentioned components (A) and (B), but may also contain various other components as required. A preferred other component is a photoradical polymerization initiator (hereinafter referred to as "component (E)"). The component (E) and other components will be described below. In the following, the components (C) and (D) described below will be referred to as "curable components." As for the other components described below, only one of the exemplified compounds may be used, or two or more of them may be used in combination.

[0029] 1-3-1.(E) Component As the component (E) in the present invention, various known photoradical polymerization initiators can be used. Component (E) is used to increase the curing rate when an aromatic iodonium salt is used as component (B).

[0030] As the component (E), various photoradical initiators can be used, but photocleavage-type photoradical polymerization initiators are preferred because they can generate radicals efficiently regardless of the blending composition. Specific examples of the photocleavage type photoradical polymerization initiator in component (E) include 2,2-dimethoxy-1,2-diphenylethan-1-one, 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-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and diethoxyacetophenone. Acetophenone compounds such as non-, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene compounds;

[0031] The content of component (E) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, and particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable components. Within this range, the composition has excellent curability, and the resulting cured film has excellent scratch resistance.

[0032] 1-3-2. Other ingredients other than those mentioned above As other components other than those mentioned above, various compounds can be mentioned, and preferably known additives used in coating agents can be used. Examples of the components include organic solvents, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, surface modifiers, pigments, dyes, and tackifiers, etc. However, it is preferable that the components other than those mentioned above are not basic, since basic substances inhibit the curing of Composition 1 or 2. Among the other components, the organic solvent, the ultraviolet absorber, the light stabilizer, the acidic substance, the inorganic particles, the antioxidant, and the surface modifier will be described below.

[0033] <Organic solvents> Composition 1 or 2 of the present invention can be used without a solvent, but various organic solvents can be used for the purpose of adjusting the coating viscosity and film thickness. Specific examples of organic solvents include alcohol compounds such as methanol, ethanol, isopropanol, and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatic compounds such as benzene, toluene, and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone.

[0034] It is preferable not to use an organic solvent, and even if one is used, it is necessary to use the minimum amount. If it is unavoidable to use an organic solvent, the content is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of Composition 1 or 2.

[0035] <UV absorber> Specific examples of the ultraviolet absorber include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethylhexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)-1,3,5-triazine, and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4 triazine-based UV absorbers such as 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone-based UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; cyanoacrylate-based UV absorbers such as ethyl-2-cyano-3,3-diphenylacrylate and octyl-2-cyano-3,3-diphenylacrylate; and inorganic particles that absorb UV light such as titanium oxide particles, zinc oxide particles, and tin oxide particles. Among these compounds, benzotriazole-based UV absorbers are particularly preferred. The content of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of the total amount of the curable components.

[0036] In general, it is preferable not to use an ultraviolet absorber for component (B) because of its short absorption wavelength. However, if it is unavoidable to use an ultraviolet absorber, it is preferable to use it in combination with a photosensitizer that enables component (B) to act even at longer wavelengths. Specific examples of photosensitizers include thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone, and anthracene derivatives such as 9,10-dibutoxyanthracene and 9,10-bis(acyloxy)anthracene.

[0037] <Light stabilizer> As the light stabilizer, known light stabilizers can be used, and among them, hindered amine light stabilizers (HALS) are preferred. Specific examples of hindered amine light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, and decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester. Commercially available hindered amine light stabilizers include TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.

[0038] The content of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and even more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the total amount of the curable components.

[0039] <Acidic substances> Composition 1 or 2 of the present invention is excellent in adhesion to substrates such as plastics, and the addition of an acidic substance can further improve adhesion. Examples of the acidic substance include a photoacid generator that generates an acid when irradiated with active energy rays, sulfuric acid, nitric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, and the like. Among these, inorganic acids or organic acids are preferred, organic sulfonic acid compounds are more preferred, aromatic sulfonic acid compounds are even more preferred, and p-toluenesulfonic acid is particularly preferred. The content of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and even more preferably 0.0005 to 0.5 parts by weight, relative to 100 parts by weight of the total amount of the curable components. Within this range, excellent adhesion to the substrate is achieved, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

[0040] <Inorganic particles> As the inorganic particles, metal oxide particles are preferred. Preferred examples of the metal oxide particles include metal oxide particles or composite metal oxide particles made of one or more metals selected from the group consisting of silicon, zirconium, titanium, antimony, tin, cerium, aluminum, zinc, and indium.

[0041] The average particle size of the inorganic particles may be selected depending on the application, but is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and particularly preferably 10 to 100 nm.Within the above range, the transparency and appearance of the cured film are good. In the present invention, the average particle size of inorganic particles means the particle size when the particles are assumed to be spherical particles based on the specific surface area of ​​a sample obtained by the BET method.

[0042] The inorganic particles may be surface-modified particles. As the surface modifier, known agents can be used, and preferred examples include silane coupling agents and titanium coupling agents. Among them, silane coupling agents are more preferred, and compounds having an ethylenically unsaturated group and an alkoxysilyl group are particularly preferred. In the above embodiment, the hardness and curl resistance of the obtained cured film are more excellent. Specific examples of the silane coupling agent include the same compounds as those described below. Furthermore, the amount of surface modification of the inorganic particles is not particularly limited, but it is preferable that the surface modifier is reacted with the inorganic particles in a proportion of 1.0 to 45.0 wt % based on the total weight of the surface modifier and the inorganic particles.

[0043] The content of the inorganic particles is preferably 25 to 400 parts by weight, more preferably 30 to 200 parts by weight, and even more preferably 50 to 150 parts by weight, per 100 parts by weight of the total amount of the curable components. In this embodiment, the resulting cured film has better adhesion, scratch resistance, and curl resistance.

[0044] <Antioxidants> Composition 1 or 2 of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film. Examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Preferred examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available antioxidants include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation. Preferred examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphites, triaryl phosphites, etc. Commercially available derivatives of these compounds include Adeka STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010, all manufactured by Adeka Corporation. Examples of sulfur-based antioxidants include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

[0045] The content of the antioxidant is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the total amount of Composition 1 or 2. In this embodiment, the stability of the composition is excellent.

[0046] <Surface modifier> A surface modifier may be added to composition 1 or 2 of the present invention for the purposes of improving leveling properties during application, increasing the slipperiness of the cured film and improving scratch resistance, etc. Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, an agent for imparting smoothness, an agent for imparting antifouling property, etc., and these known surface modifiers can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. Furthermore, a surface modifier having an oxetane ring or oxirane ring in the molecule may be used for the purpose of improving the durability of the lubricity. The content of the surface modifier is preferably 0.01 to 1.0 part by weight per 100 parts by weight of the total amount of Composition 1 or 2. Within this range, the surface smoothness of the cured film is excellent.

[0047] 2. Composition 2 Composition 2 is an active energy ray-curable composition containing components (B), (C), and (D), and is a composition for forming an overcoat layer, which is a cured film of composition 2, on a primer layer. The components (B), (C), and (D) and composition 2 will be described in detail below.

[0048] 2-1.(B) Component The component (B) is a compound that initiates cationic polymerization upon irradiation with active energy rays, and the details thereof are as explained above.

[0049] 2-2.(C) Component Component (C) is a compound having an oxetane ring. Component (C) is a component that imparts good curability to composition 2 and good flexibility to the cured film, thereby preventing cracking and peeling of the overcoat layer even when the component is subjected to impact. It also controls the curing rate of composition 2 by slowing the initiation of polymerization of oxetane and speeding up the propagation reaction.

[0050] Component (C) can be either a compound having one oxetane ring (hereinafter referred to as "component (C1)") or a compound having two or more oxetane rings (hereinafter referred to as "component (C2)"). Furthermore, either one or more of the following components (C1) and (C2) can be used:

[0051] As the component (C1), various compounds can be used as long as they have one oxetane ring. A preferred compound of the component (C1) is a compound represented by the following formula (1).

[0052] [ka]

[0053] In formula (1), Z represents an oxygen atom or a sulfur atom. 1 R represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. 2means an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an aryl group, an alkylcarbonyl group having 1 to 6 carbon atoms, or an alkoxycarbamoyl group having 1 to 6 carbon atoms. R 1 and R 2 Examples of the alkyl group having 1 to 6 carbon atoms in the formula include a methyl group, an ethyl group, a propyl group, and a butyl group. R 2 Examples of the alkenyl group having 1 to 6 carbon atoms in the formula include a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. R 1 and R 2 Examples of the aryl group in include a phenyl group, a benzyl group, a fluorobenzyl group, a methoxybenzyl group, and a phenoxyethyl group. R 2 Examples of the alkylcarbonyl having 1 to 6 carbon atoms in the above formula include a propylcarbonyl group, a butylcarbonyl group, and a pentylcarbonyl group. R 2 Examples of the alkylcarbamoyl group having 1 to 6 carbon atoms in the formula include an ethoxycarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a butylpentylcarbamoyl group.

[0054] In the present invention, in the above formula (1), Z, R 1 and / or R 2 The compounds shown below are preferred. Z is preferably an oxygen atom. 1 As R, compounds with a lower alkyl group are preferred, and compounds with a methyl group or an ethyl group are preferred. 2 is preferably a hydrogen atom, a butyl group, a 2-ethylhexyl group, or a benzyl group.

[0055] Specific examples of preferred compounds represented by formula (1) include those in which Z is an oxygen atom, R 1 is a lower alkyl group, and R 2is a hydrogen atom, such as 3-ethyl-3-hydroxymethyloxetane. Specific examples of preferred compounds represented by formula (1) include those in which Z is an oxygen atom, R 1 is a lower alkyl group, and R 2 is an alkyl group, such as 3-ethyl-3-butyloxymethyloxetane, 3-ethyl-3-hexyloxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-dodecyloxymethyloxetane, 3-ethyl-3-octadecyloxymethyloxetane, 3-ethyl-3-cyclohexyloxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(nonylphenoxymethyl)oxetane, 3-ethyl-3-(phenylmethoxymethyl)oxetane, 2-[(3-ethyloxetan-3-yl)methoxy]biphenyl, and 4-[(3-ethyloxetan-3-yl)methoxy]biphenyl.

[0056] As the component (C1), a compound having one oxetane ring and one hydroxyl group is more preferred because it has excellent adhesion to the substrate. Specific examples of compounds having one oxetane ring and one hydroxyl group include those in which, in formula (1), Z is an oxygen atom, R 1 is a lower alkyl group, and R 2 is a hydrogen atom, such as 3-ethyl-3-hydroxymethyloxetane.

[0057] Component (C1) is commercially available, and examples thereof include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) [Aron Oxetane OXT-101, manufactured by Toagosei Co., Ltd.] and 2-ethylhexyloxetane [Aron Oxetane OXT-212, manufactured by Toagosei Co., Ltd.].

[0058] By using component (C2), the protective agent swells little even under high humidity conditions, and a cured coating film with good substrate adhesion can be formed. Various compounds containing two or more oxetane rings can be used as component (C2). Specific examples of component (C2) include the compounds exemplified in JP-A-11-246647.

[0059] Specific preferred examples of the component (C2) include the following compounds: 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane, 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene, 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 2,2'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 3,3',5,5'-tetramethyl-4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl phenyl, 2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene, bis[4-{(3-ethyloxetan-3-yl)methoxy}phenyl]methane, bis[2-{(3-ethyloxetan-3-yl)methoxy}phenyl]methane, 2,2-bis[4-{(3-ethyloxetan-3-yl)methoxy}phenyl]propane, etherified products of novolak type phenol-formaldehyde resin with 3-chloromethyl-3-ethyloxetane, 3(4),8(9)-bis[(3-ethyloxetan-3-yl)methoxymethyl]-tricyclo[5.2.1.0 2,6]decane, 2,3-bis[(3-ethyloxetan-3-yl)methoxymethyl]norbornane, 1,1,1-tris[(3-ethyloxetan-3-yl)methoxymethyl]propane, 1-butoxy-2,2-bis[(3-ethyloxetan-3-yl)methoxymethyl]butane, 1,2-bis[{2-(3-ethyloxetan-3-yl)methoxy}ethylthio]ethane, bis[{4-(3-ethyloxetan-3-yl)methyl]propane [(3-ethyloxetan-3-yl)methylthio}phenyl] sulfide, 1,6-bis[(3-ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane, hydrolysis condensation product of 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxysilane, and condensation product of tetrakis[(3-ethyloxetan-3-yl)methyl]silicate.

[0060] As the component (C2), a compound having two oxetane rings is preferred, and specific examples thereof include the compounds listed above.

[0061] Component (C2) is commercially available, and examples thereof include xylylene bisoxetane (Aron Oxetane OXT-121, manufactured by Toagosei Co., Ltd.) and 3-ethyl 3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (Aron Oxetane OXT-221, manufactured by Toagosei Co., Ltd.).

[0062] The proportions of the (C1) and (C2) components in the total amount of the (C1) and (C2) components (100% by weight) can be within any range and can be adjusted depending on the type of substrate. Specifically, the proportions of the (C1) component and the (C2) component are preferably 50 to 100% by weight and 0 to 50% by weight, respectively.

[0063] 2-3.(D) Component Component (D) is a compound having an oxirane ring. The component (D) is a component that, when contained in composition 2, can increase the strength of the overcoat layer, which is a cured film, and can also improve water resistance. As the component (D), any of a monomer, an oligomer, and a polymer can be used.

[0064] Specific examples of the component (D) include conventionally known aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds.

[0065] The aromatic epoxy compound is a di- or polyglycidyl ether produced by reacting a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof with epichlorohydrin. Specific examples of aromatic epoxy compounds include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of brominated bisphenol A; diglycidyl ethers of alkylene oxide adducts of bisphenols, such as diglycidyl ethers of alkylene oxide adducts of bisphenol A, diglycidyl ethers of alkylene oxide adducts of bisphenol F, and diglycidyl ethers of alkylene oxide adducts of brominated bisphenol AF; and Examples include novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins. Other examples include biphenyl epoxy resins, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, epoxidized products of styrene-butadiene copolymers, epoxidized products of styrene-isoprene copolymers, and addition reaction products of carboxylic acid-terminated polybutadiene and bisphenol A epoxy resins. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

[0066] Here, the epoxy resin refers to a compound or polymer that has an average of two or more epoxy groups in the molecule and hardens by reaction. In accordance with the practice in this field, in this specification, even a monomer may be referred to as an epoxy resin as long as it has two or more curable epoxy groups in the molecule.

[0067] Examples of alicyclic epoxy compounds include compounds obtained by epoxidizing a compound having at least one cycloalkene ring such as a cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or a peracid. Specific examples of alicyclic epoxy compounds include compounds having at least one epoxidized cyclohexyl group, such as dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis(3,4-epoxycyclohexylmethyl)adipate, as well as di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts.

[0068] Examples of the aliphatic epoxy compound include di- or polyglycidyl ethers of aliphatic alcohols or their alkylene oxide adducts. Specific examples of such compounds include diglycidyl ethers of alkylene glycols such as diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, and diglycidyl ether of 1,6-hexanediol; Polyglycidyl ethers of polyhydric alcohols, such as di- or triglycidyl ethers of glycerin or its alkylene oxide adducts; and Examples include polyglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, and diglycidyl ethers of polypropylene glycol or its alkylene oxide adducts. Examples of the alkylene oxide include ethylene oxide and propylene oxide. In addition to these compounds, monoglycidyl ethers of aliphatic higher alcohols, which are monomers having one oxirane ring in the molecule, and monoglycidyl ethers of phenol, cresol, or alkylene oxide adducts thereof can also be used.

[0069] As component (D), a compound having two or more oxirane rings [hereinafter referred to as "component (D1)"] is preferred, as this will result in good surface hardness of the resulting cured film and excellent chemical resistance and water resistance. Furthermore, the component (D1) is preferably an aromatic epoxy compound, more preferably an epoxy resin having a bisphenol skeleton, such as bisphenol A, bisphenol F, bisphenol P, and bisphenol Z.

[0070] As the component (D), the above compounds can be used alone or in combination of two or more.

[0071] 2-4. Details of Composition 2 Composition 2 is an active energy ray-curable composition containing components (B), (C), and (D). The method for producing composition 2 includes a method in which components (B), (C) and (D), as well as other components as required, are stirred and mixed in accordance with a conventional method. In this case, the mixture may be heated and stirred as needed. When the mixture is heated and stirred / mixed, the temperature is preferably in the range of 20 to 70°C.

[0072] The proportion of component (B) in composition 2 is preferably 0.01 to 40 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, as the active ingredient, per 100 parts by weight of components (C) and (D) combined. By setting the content of component (B) to 0.1 parts by weight or more, components (C) and (D) can be cured favorably, and by setting the content of component (B) to 10 parts by weight or less, problems such as corrosion caused by the acid contained in component (B) can be prevented depending on the substrate or product to which it is applied.

[0073] The content ratios of the (C) component and the (D) component in the composition 2 are preferably 5 to 40 parts by weight of the (C) component and 95 to 60 parts by weight of the (D) component, and more preferably 10 to 30 parts by weight of the (C) component and 90 to 70 parts by weight of the (D) component, per 100 parts by weight of the (C) component and the (D) component combined. By including the components (C) and (D) in the above proportions, the curing rate of the composition 2 can be improved, and the composition can have excellent adhesion to the substrate.

[0074] The viscosity of the composition 2 may be appropriately set depending on the application and purpose of use. The viscosity of composition 2 is preferably 100 to 20,000 mPa·s, and more preferably 200 to 8,000 mPa·s.

[0075] Composition 2 of the present invention essentially comprises the above-mentioned components (B), (C) and (D), but may contain various other components as required. A preferred example of the other component is component (E). The component (E) and other components include the same compounds as those described above, and are preferably contained in the same proportions as those described above. As for the other components, only one of the exemplified compounds may be used, or two or more of them may be used in combination.

[0076] The composition 2 used in the present invention preferably includes a coating composition and an ink composition. Furthermore, as described above, the production method of the present invention can be preferably applied to inorganic substrates, and examples of composition 2 include an active energy ray-curable coating composition for inorganic substrates and an active energy ray-curable ink composition for inorganic substrates. Furthermore, as the inorganic substrate, the production method of the present invention can be preferably applied to glass, and examples of the inorganic substrate include an active energy ray-curable coating composition for glass and an active energy ray-curable ink composition for glass. Specific applications for glass include coating agents and inks for glass surfaces, and further include printing inks and paints for glass bottles. Applications for glass and metal include mirrors, and more specifically, it can be preferably used as a coating agent to prevent corrosion of a metal vapor deposition layer due to moisture absorption from the edge of a mirror. Furthermore, since the composition 2 used in the present invention has excellent adhesion and water resistance when cured, it can be preferably used as an anti-corrosion coating agent for the edge surfaces of mirrors used mainly in wet areas, and as a printing ink or paint for glass bottles.

[0077] 3. Method for manufacturing a substrate having a cured film The present invention relates to a method for producing a substrate having a cured film, which comprises sequentially carrying out the following steps 1 and 2: Step 1: A step of applying composition 1 to a substrate and irradiating the coated surface with active energy rays to form a cured film. Step 2: A step of applying composition 2 onto the cured film obtained in step 1 and irradiating the coated surface with active energy rays to form a cured film. Steps 1 and 2 will be explained below.

[0078] 3-1. Process 1 Step 1 is a step of applying Composition 1 to a substrate and irradiating the coated surface with active energy rays to form a primer layer, which is a cured film.

[0079] The manufacturing method of the present invention can be applied to a variety of substrates, including inorganic materials, plastics, and paper. Inorganic materials include glass, metal, concrete, and stone. Examples of metals include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resins, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, cyclic polyolefin resins containing cyclic olefins as monomers such as norbornene, polyvinyl chloride, epoxy resins, and polyurethane resins.

[0080] The manufacturing method of the present invention has excellent adhesion to inorganic substrates among these substrates, and therefore can be preferably applied to inorganic materials, specific examples of which are as mentioned above. As inorganic materials, glass and metals can be more preferably applied, and more specific examples include glass plates such as soda glass, and the end faces of mirrors having metal vapor deposition layers. To explain mirrors, mirrors are manufactured by forming a silver film on the back of plated glass using a process known as "silvering," then forming a copper film on top of the silver film using copper plating to protect the silver film from moisture and other factors, and then forming a protective coating on top of this using a protective paint such as alkyd-melamine resin. While the silver film can be protected on the back of the plated glass by the copper film and protective coating, the silver and copper films are exposed on the side surfaces (edges), which can cause corrosion of the metal surfaces on the mirror edges and lead to bleeding on the mirror, so a coating agent suitable for protecting the edges was needed. Composition 1 of the present invention can be preferably used as a coating agent suitable for protecting the mirror end surface, since the cured film has excellent adhesion to glass and metal and excellent water resistance.

[0081] The method for applying composition 1 of the present invention to a substrate may be appropriately determined depending on the purpose, and examples include coating methods using a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, lip coater, spray coater, gravure coater, microgravure coater, etc.

[0082] The thickness of the cured film of Composition 1 on the substrate may be appropriately determined depending on the purpose. The thickness of the cured film may be selected depending on the substrate to be used and the application of the substrate having the produced cured film, but is preferably 5 to 800 μm, more preferably 10 to 500 μm.

[0083] When the composition 1 contains an organic solvent, it is preferable to apply the composition to the substrate, and then heat and dry the composition to evaporate the organic solvent. The drying temperature is not particularly limited as long as it is a temperature below which the substrate to be applied does not suffer from problems such as deformation. A preferred heating temperature is 40 to 100° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 3 minutes.

[0084] The method of irradiating with active energy rays may be any common method known as a conventional curing method. Examples of active energy rays for curing the composition 1 of the present invention include electron beams, ultraviolet rays, and visible light rays, with ultraviolet rays or visible light rays being preferred, and ultraviolet rays being particularly preferred. Examples of ultraviolet ray irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs). The irradiation energy should be set appropriately depending on the type of active energy ray and the compounding composition. For example, when using a high-pressure mercury lamp, the irradiation energy in the UV-A region is 100 to 8,000 mJ / cm. 2 is preferred, and 200 to 3,000 mJ / cm 2 is more preferred. If necessary, heating can be carried out after irradiation with active energy rays.

[0085] In this case, the reaction rate of the polymerizable groups in the composition 1 is preferably 1 to 80%, more preferably 1 to 50%. By setting the reaction rate to 1% or more, composition 1 can be sufficiently cured, and by setting it to 80% or less, it can be sufficiently copolymerized with the overcoat layer, thereby improving the adhesion between the primer layer and the overcoat layer. Furthermore, composition 1 contains a silane coupling agent having an epoxy group as component (A) of composition 1, and the reaction rate of the polymerizable group in composition 1 is preferably 1 to 80%, more preferably 1 to 50%, as calculated from the following formula (1): Curing rate (%)= 100 - (epoxy value of composition 1) ÷ (epoxy value of cured film of composition 1) × 100 ···(1) The epoxy value in the formula (1) means a value measured in accordance with JIS K7236. As a method for controlling the reaction rate of the polymerizable group, for example, a method of irradiating the active energy rays while adjusting the integrated light amount thereof can be mentioned.

[0086] When composition 1 of the present invention is used under high-humidity conditions, defects may occur in the cured film if composition 1 is not sufficiently degassed after application. For example, when a cured film obtained from composition 1 of the present invention is subjected to a hot water immersion test described below, defects may occur in the cured film if composition 1 is not sufficiently degassed after application. To solve this problem, it is preferable to degas the composition by heating it at 40 to 60°C for several minutes, preferably 1 to 30 minutes, after application. However, the amount of bubbles contained in the applied composition 1 varies depending on the application method, so a heating step is not essential.

[0087] Immediately after irradiation with active energy rays, tack may remain on the cured film, but in this case, it will cure completely if left at room temperature for approximately 10 minutes or more. When continuous coating and curing are performed using a device equipped with a conveyor, post-curing by heating in a drying oven may be performed after irradiation with active energy rays. Although there are no temperature restrictions, heating at 40 to 80°C for about 1 to 30 minutes is preferred.

[0088] 3-2. Process 2 Step 2 is a step of applying composition 2 onto the cured film (primer layer) obtained in step 1, and irradiating the coated surface with active energy rays to form a cured film (overcoat layer).

[0089] The method for applying the composition 2 of the present invention to a substrate may be appropriately determined depending on the purpose, and includes the same methods as those described above. The thickness of the cured film (overcoat layer) may be selected depending on the application of the substrate having the cured film, but is preferably 5 to 800 μm, more preferably 10 to 500 μm.

[0090] When composition 2 contains an organic solvent, it is preferable to apply the composition to the substrate and then heat and dry it to evaporate the organic solvent. The drying temperature is not particularly limited as long as it is a temperature below which the substrate to be applied does not suffer from problems such as deformation. A preferred heating temperature is 40 to 100° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 3 minutes.

[0091] As a method for irradiating with active energy rays, a general method known as a conventional curing method may be adopted. Examples of active energy rays for curing the composition 2 of the present invention include electron beams, ultraviolet rays, and visible light rays, with ultraviolet rays or visible light rays being preferred, and ultraviolet rays being particularly preferred. Examples of ultraviolet ray irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs). The irradiation energy is preferably the same as that described above. If necessary, heating can be carried out after irradiation with active energy rays.

[0092] Immediately after irradiation with active energy rays, tack may remain on the cured film, but in this case, it will cure completely if left at room temperature for approximately 10 minutes or more. When continuous coating and curing are performed using a device equipped with a conveyor, post-curing by heating in a drying oven may be performed after irradiation with active energy rays. Although there are no temperature restrictions, heating at 40 to 80°C for about 1 to 30 minutes is preferred.

[0093] 4.Applications The manufacturing method of the present invention can be used for various purposes, and preferred examples include a method for manufacturing a substrate having a coating layer and a method for manufacturing a substrate having an ink layer. Furthermore, as described above, the production method of the present invention can be preferably applied to inorganic substrates, and is a method for producing inorganic substrates having a coating layer and inorganic substrates having an ink layer. Furthermore, the production method of the present invention can be preferably applied to glass as the inorganic substrate, and is more preferably applied to methods for producing glass having a coating layer and glass having an ink layer. Specific applications for glass include the formation of coating layers and ink layers on glass surfaces, and further include the formation of printing ink layers and paint layers for glass bottles. Applications for glass and metal include mirrors, and more specifically, it can be preferably used to form a coating layer that prevents corrosion of a metal vapor deposition layer due to moisture absorption from the end face of a mirror. Furthermore, since the manufacturing method of the present invention produces a cured product with excellent adhesion and water resistance, it can be preferably used for forming an anti-corrosion coating layer on the end surface of a mirror that is mainly used around water, and for forming a printing ink layer or a paint layer on a glass bottle. [Example]

[0094] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" means parts by weight and "%" means % by weight.

[0095] 1. Examples 1 to 5 1) Preparation of the composition The components shown in Table 1 below were stirred and mixed at 30° C. to obtain compositions 1 and 2 used in Examples 1 to 5.

[0096] 2) Process 1 The obtained compositions 1 of Examples 1 to 5 were applied to cut float glass (150 mm x 70 mm x 3 mm) manufactured by Nippon Sheet Glass Co., Ltd. using a bar coater so that the thickness of the cured film (primer layer) was 10 μm. Next, the test specimen was irradiated with ultraviolet light using a high-pressure mercury lamp equipped with a conveyor (H06-L 41 manufactured by Eye Graphics Co., Ltd.) under the conditions of a UV-A illuminance of 80 W / cm and an integrated light amount as shown in Table 1. The resulting cured film was allowed to stand at room temperature and 40% RH for the waiting time shown in Table 1. The cure rate of the resulting cured film (primer layer) was calculated according to the following formula (1). Curing rate (%)= 100 - (epoxy value of composition 1) ÷ (epoxy value of cured film of composition 1) × 100 (1) The epoxy value was measured in accordance with JIS K 7236. The sample used for the epoxy value was prepared by placing the necessary weight of composition 1 in a petri dish-shaped container, irradiating it with ultraviolet light under the same conditions as in step 1, and waiting.

[0097] 3) Process 2 Composition 2 was applied onto the cured films (primer layers) of the compositions of Examples 1 to 5 obtained in step 1 so that the thickness of the cured film (overcoat layer) was 50 μm. Subsequently, ultraviolet light was irradiated at the integrated light dose shown in Table 1 in the same manner as above. The resulting cured film was allowed to stand at room temperature and 40% RH for 24 hours, and the adhesion and appearance of the cured film were evaluated according to the following methods. The results are shown in Table 3.

[0098] 1) Adhesion Two types of test specimens were used for evaluating adhesion: a) the cured film obtained above after 24 hours of curing; and b) the cured film was immersed in a 10% hydrochloric acid aqueous solution for 48 hours, then removed, washed with tap water, and further immersed in 80°C hot water for 10 days, then removed and dried indoors for 24 hours. Two types of test specimens were cut with a cutter knife at 1 mm intervals vertically and horizontally to form 25 1 mm x 1 mm squares. Cellophane tape #405 manufactured by Nichiban Co., Ltd. was attached to the squares and then peeled off forcefully. The number of remaining films after peeling was evaluated. The greater the number of remaining films, the better the adhesion.

[0099] 2) Appearance of cured film The appearance of the same three types of test specimens as those used in the above adhesion test was visually inspected and evaluated according to the following three levels. ◯: A smooth, transparent cured film with no irregularities; △: A slightly uneven, but generally smooth, transparent cured film; ×: Dimples, bulges, or changes such as cloudiness were observed.

[0100] 2. Comparative Examples 1 to 4 1) Preparation of the composition The components shown in Table 2 were stirred and mixed at 30° C. to obtain compositions 1 and 2 used in Comparative Examples 1 to 4. In Comparative Example 1, only Composition 1 was produced, and in Comparative Example 3, only Composition 2 was produced.

[0101] 2) Process 1 The obtained compositions 1 of Comparative Examples 1, 2, and 4 were applied using a bar coater to cut float glass (150 mm × 70 mm × 3 mm) manufactured by Nippon Sheet Glass Co., Ltd., so that the thickness of the cured film (primer layer) was 10 μm. In Comparative Example 4, Composition 2 was used and applied in the same manner as above. Next, the test specimen was irradiated with ultraviolet light using the same high-pressure mercury lamp as in the example under the conditions of a UV-A illuminance of 80 W / cm and an integrated light amount shown in Table 2. The resulting cured film was allowed to stand at room temperature and 40% RH for the waiting time shown in Table 1. The curing rate of the resulting cured film was calculated according to the above formula (1).

[0102] 3) Process 2 Composition 2 was applied onto the cured film (primer layer) of Composition 1 of Comparative Examples 2 and 4 obtained in step 1 so that the thickness of the cured film (overcoat layer) was 50 μm. Subsequently, ultraviolet light was irradiated at the integrated light dose shown in Table 2 in the same manner as above. The resulting cured film was allowed to stand at room temperature and 40% RH for 24 hours, and the adhesion and appearance of the cured film were evaluated according to the methods described above. The results are shown in Table 3.

[0103] [Table 1]

[0104] [Table 2]

[0105] The abbreviations in Tables 1 and 2 have the following meanings: The numbers in parentheses in Tables 1 and 2 indicate the number of parts of each component. Component (A) M3: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) E3: 3-Glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) E2: 3-glycidoxypropylmethyldiethoxysilane (KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.) (B) Component CPI: 50% propylene carbonate solution of triarylsulfonium PF6 salt (CPI-100P, manufactured by San-Apro Co., Ltd.) (C) Component OXA: 3-ethyl-3-hydroxymethyloxetane (Aronoxetane OXT-101, manufactured by Toagosei Co., Ltd.) DOX: 3-ethyl 3[[(3-ethyloxetan-3-yl)methoxy]methyl]oxetane (Aronoxetane OXT-221, manufactured by Toagosei Co., Ltd.) (D) Component jER: Bisphenol A epoxy resin (jER-828, manufactured by Mitsubishi Chemical Corporation)

[0106] [Table 3]

[0107] 3. Evaluation Results As is clear from the results of Examples 1 to 5 in Table 3, the cured films obtained by the production method of the present invention were excellent in adhesion to glass and in long-term acid resistance. In contrast, the manufacturing method of Comparative Example 1 produced a cured film by performing only step 1, in which composition 1 was completely cured, but the initial adhesion to glass and curability were insufficient, and the appearance of the cured film was also poor. In the manufacturing method of Comparative Example 2, composition 2 used in step 2 was a composition that did not contain component (C), and although the effect of component (D) resulted in excellent initial adhesion and appearance, the adhesion and appearance became insufficient after immersion in hydrochloric acid and hot water. Initial adhesion was obtained due to the hardness-increasing effect of component (D), but adhesion after immersion in hot water was not obtained. In addition, the manufacturing method of Comparative Example 3 produced a cured film by carrying out only step 1, in which composition 1 further contained components (C) and (D) and was completely cured, but the adhesion between the substrate and the cured film was insufficient, resulting in peeling. In the manufacturing method of Comparative Example 4, composition 2 used in step 2 was a composition that did not contain component (D), and the hardness of the cured film obtained from composition 2 was insufficient, resulting in insufficient adhesion and a poor appearance of the cured film. [Industrial Applicability]

[0108] The method for producing a substrate having a cured film of the present invention produces a cured film that has excellent adhesion and water resistance to inorganic substrates such as glass, and is preferably used for forming an anti-corrosion coating layer on the end face of a mirror that is used mainly around water, and for forming a printing ink layer or a paint layer for glass bottles.

Claims

1. A method for producing a substrate having a cured film, comprising sequentially carrying out the following steps 1 and 2: Step 1: A step of applying an active energy ray-curable composition (hereinafter referred to as "composition 1") containing the following components (A) and (B) but not the following components (C) and (D) to a substrate, and irradiating the coated surface with active energy rays to form a cured film. Step 2: A step of coating an active energy ray-curable composition (hereinafter referred to as "composition 2") containing the following components (B), (C), and (D) but not containing component (A) on the cured film obtained in step 1, and irradiating the coated surface with active energy rays to form a cured film. Component (A): a silane coupling agent having a cationically polymerizable group Component (B): a compound that initiates cationic polymerization upon irradiation with active energy rays Component (C): Compound having an oxetane ring Component (D): Compound having an oxirane ring

2. The method for producing a substrate having a cured film according to claim 1 , wherein the component (A) comprises a silane coupling agent having an epoxy group.

3. 3. The method for producing a substrate having a cured film according to claim 1 or 2, wherein the component (C) includes a component (C1): a compound having one oxetane ring, and the component (C1) further includes a compound having one oxetane ring and one hydroxyl group.

4. The method for producing a substrate having a cured film according to any one of claims 1 to 3, wherein the component (C) includes a component (C2): a compound having two or more oxetane rings, and the component (C2) further includes a compound having two oxetane rings.

5. The method for producing a substrate having a cured film according to any one of claims 1 to 4, wherein the component (D) comprises a component (D1): a compound having two or more oxirane rings.

6. The method for producing a substrate having a cured film according to claim 5 , wherein the component (D1) comprises an aromatic epoxy compound.

7. The method for producing a substrate having a cured film according to claim 6, wherein the component (D1) is an aromatic epoxy compound having a bisphenol skeleton.

8. The method for producing a substrate having a cured film according to any one of claims 1 to 7, wherein the composition 1 contains 0.01 to 40 parts by weight of the component (B) relative to a total of 100 parts by weight of the component (A).

9. 9. The method for producing a substrate having a cured film according to any one of claims 1 to 8, wherein composition 2 contains 5 to 40 parts by weight of component (C) and 95 to 60 parts by weight of component (D), based on a total of 100 parts by weight of component (C) and component (D).

10. The method for producing a substrate having a cured film according to any one of claims 1 to 9, wherein composition 2 contains 0.01 to 40 parts by weight of component (B) relative to 100 parts by weight of the total of components (C) and (D).

11. The method for producing a substrate having a cured film according to any one of claims 1 to 10, wherein in step 1, the curing is carried out so that the curing rate is 1 to 80%, and then step 2 is carried out.

12. 12. The method for producing a substrate having a cured film according to claim 11, wherein in step 1, a silane coupling agent having an epoxy group is contained as component (A) of composition 1, and composition 1 is cured so that the cure rate represented by the following formula (1) is 1 to 80%, and then step 2 is carried out: Cure rate (%) = 100 - (epoxy value of composition 1) ÷ (epoxy value of cured film of composition 1) × 100 (1)

13. The method for producing a substrate having a cured film according to any one of claims 1 to 12, wherein the composition 1 and the composition 2 are active energy ray-curable coating compositions.

14. The method for producing a substrate having a cured film according to any one of claims 1 to 12, wherein the composition 1 and the composition 2 are active energy ray-curable ink compositions.

15. The method for producing a substrate having a cured film according to any one of claims 1 to 14, wherein the substrate is an inorganic substrate.

16. The method for producing a substrate having a cured film according to claim 15, wherein the substrate is glass.

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