JP2022187440A - Production method for substrate having hardened film - Google Patents

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 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, and particularly has excellent adhesion to glass substrates as inorganic substrates. In addition to being able to form a coating layer, by applying it to the end face of a glass substrate that has undergone metal vapor deposition, it is possible to prevent water from entering and form a protective hardened film to prevent corrosion of the vapor deposited film. .

Active energy ray-curable compositions can be cured by irradiating them with active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short period of time. used.

However, conventional active energy ray-curable compositions include surface-treated poly(ethylene-terephthalate) resins (PET resins), polycarbonate (PC), polystyrene (PS), and polymethyl methacrylate (PMMA). Although the desired adhesion to substrates can be obtained relatively easily in the case of plastic materials such as , there is a problem that good adhesion cannot be obtained to inorganic substrates such as metals and glass.

As a method for imparting adhesion to inorganic substrates such as metals and glass, phosphoric acid esters (A) having two or more (meth)acryloyl groups in one molecule, polyfunctional (meth) ) An active energy ray-curable composition containing an acrylate (B) and a photopolymerization initiator (C) is known (Patent Document 1).
However, although the composition can obtain a certain degree of initial adhesion, when used for a coating agent or the like that requires water resistance such as products around water, the water resistance of the cured film is insufficient. There is a problem that the cured film is easily peeled off by immersion in hot water or the like.

As an active energy ray-curable composition for the purpose of improving adhesion to a glass substrate, a compound (A) having one or more (meth)acryloyloxy groups and an ethylenically unsaturated compound are homopolymerized. Active energy ray-curable compositions containing a (co)polymer (B) obtained by copolymerizing a mixture thereof or a mixture thereof, a silane coupling agent (C), and a photopolymerization initiator (D) are known. (Patent Document 2).
However, there is a limit to the range that can be used in the polymer (B) due to compatibility and coatability. I had it as a thing. As a result, the problem was the decrease in productivity and the burden on the environment due to solvent drying.

Examples other than the above include an acrylic resin (A), an unsaturated compound containing two or more ethylenically unsaturated groups (B), a phosphoric acid group-containing ethylenically unsaturated compound (C), a silane coupling agent ( D) and an active energy ray-curable composition containing a fluorine-based compound (E) is known (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.

JP 2009-155470 A JP 2015-93893 A JP 2015-83658 A Japanese Patent Application No. 2020-155840

The present inventors have found that the cured film has excellent adhesion to a wide range of substrates, particularly excellent adhesion to inorganic substrates such as glass, and does not lose adhesion even when used under high humidity. Furthermore, as a result of intensive studies to find an active energy ray-curable composition having excellent water resistance and acid resistance, component (A): a compound having an oxetane ring, component (B): a compound having an oxirane ring, (C ) component: a silane coupling agent, and (D) component: an active energy ray-curable composition containing a compound that initiates cationic polymerization upon irradiation with an active energy ray (Patent Document 4).
The cured film of the composition has excellent adhesion to inorganic substrates such as glass under high humidity, and has excellent acid resistance and water resistance. In a use environment in which the film is exposed to high humidity for a long time, the cured film does not have sufficient adhesion performance.

The present inventors have found that the cured film has excellent adhesion to a wide range of substrates and long-term acid resistance, particularly excellent adhesion to inorganic substrates such as glass, and has excellent adhesion even when used under high humidity. Extensive studies have been conducted to find out a method for producing a substrate having an excellent cured film, particularly a method for producing a substrate having a cured film that can suitably form a coating layer and an ink layer.

The present inventors have made intensive studies to solve the above problems. As a result, a composition of a compound that initiates cationic polymerization by silane coupling agent and active energy ray irradiation is applied to a substrate and cured by active energy ray. A production method in which a composition of a compound that initiates cationic polymerization upon exposure to active energy rays, a compound that has an oxetane ring, and a compound that has an oxirane ring is applied onto the resulting cured film, and cured by active energy rays. The present inventors have found that the adhesion to inorganic substrates such as glass is good, and that the cured film is excellent in water resistance, thereby completing the present invention.
The present invention will be described in detail below.

According to the production method of the present invention, the cured film has excellent adhesion to a wide range of substrates, particularly excellent adhesion to inorganic substrates such as glass, and is also excellent in water resistance.
Therefore, the manufacturing method of the present invention can suitably form a protective layer for a metal deposition film formed on glass. By applying it to the end faces of mirrors used in water-related products such as kitchens and bathrooms, it is possible to form protective agents for glass tiles in bathrooms and protective layers for semiconductor cleaning tanks.

The present invention relates to a method for producing a substrate having a cured film, in which step 1 and step 2 below are sequentially performed.
- Step 1: An active energy ray-curable composition (hereinafter referred to as "composition 1") containing the following components (A) and (B) is applied to a substrate, and the coated surface is irradiated with an active energy ray. Step of forming a cured film (hereinafter also referred to as “primer layer”) Step 2: On the cured film obtained in Step 1, the following components (B), (C) and (D) are included A step of applying an active energy ray-curable composition (hereinafter referred to as “composition 2”) and irradiating the coated surface with an active energy ray 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 exposure to active energy rays Component (C): A compound having an oxetane ring Component (D): A compound having an oxirane ring Compound Composition 1, Composition 2, Step 1, Step 2, and use are described below.

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.
Details of the component (A), the component (B), and the composition 1 are described below.

1-1. (A) Component (A) is a silane coupling agent having a cationically polymerizable group, the reaction proceeds with water such as moisture in the air, and adhesion to substrates, preferably adhesion to inorganic substrates. and the role of improving adhesion to the overcoat layer, which is a cured film of composition 2, by cationic polymerization of both the components (C) and (D) described later.

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

(A) As a component, the following compounds can be used.
Preferred specific examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane. Epoxy group-containing silane coupling agents such as silane and 8-glycidoxyoctyltriethoxysilane; 2-(3,4-oxetanylcyclohexyl)ethyltrimethoxysilane, 3-oxetanylpropyltrimethoxysilane, 3-oxetanylpropylmethyldi oxetanyl group-containing silane coupling agents such as ethoxysilane, 3-oxetanylpropyltriethoxysilane, 8-oxetanyloctyltriethoxysilane; 2-(3,4-oxolanylcyclohexyl)ethyltrimethoxysilane, 3-oxolanyl oxolanyl group-containing silane coupling agents such as propyltrimethoxysilane, 3-oxolanylpropylmethyldiethoxysilane, 3-oxolanylpropyltriethoxysilane, 8-oxolanyloctyltriethoxysilane; vinyl (trimethoxysilyl ) ether, vinyl (methyldiethoxysilyl) ether, vinyl (triethoxysilyl) ether, and other vinyl ether-based silane coupling agents.
These compounds may be used alone or in combination of two or more.

Among these compounds, a silane coupling agent having a cationic polymerizable group with a slow polymerization growth reaction rate is preferred. If the growth reaction rate is fast, it becomes difficult to control the curing rate.
Preferred silane coupling agents include the epoxy group-containing silane coupling agents described above, and further 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Propyltriethoxysilane is particularly preferred.

1-2. (B) Component (B) is a compound that initiates cationic polymerization upon irradiation with active energy rays, and is a compound that produces cationic species or Lewis acids upon irradiation with active energy rays, and is usually used as a photocationic polymerization initiator. It is a known compound.
As the component (B), various compounds known as photocationic polymerization initiators can be used, and onium salts such as aromatic iodonium salts and aromatic sulfonium salts, aromatic diazonium salts, and iron-allene complexes, etc., and onium salts such as aromatic iodonium salts and aromatic sulfonium salts are preferred.
Specific examples of the aromatic iodonium salt and aromatic sulfonium salt in the component (B) include the compounds exemplified in JP-A-11-246647.

Preferred specific examples of component (B) include the following compounds.
Examples of aromatic iodonium salts include the following compounds.
diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate and the like.

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)diphenylsulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluoroantimonate, 4 , 4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di( p-toluyl)sulfonio]-2-isopropylthioxanthone Tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide Hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4 '-diphenylsulfonio-diphenylsulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)sulfonio-diphenylsulfide tetrakis(pentafluorophenyl)borate and the like.

Examples of aromatic diazonium salts include the following compounds.
benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate and the like.

Examples of iron-allene complexes include the following compounds. xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II)-tris(trifluoromethylsulfonyl) methanide, etc. mentioned.

As the component (B), one type of the above-described compounds may be used alone, or two or more types may be used in combination.

(B) As a component, it is possible to use a commercial item.
Specific examples include, for example, the trade names of "Kayarad PCI-220", "Kayarad PCI-620" [manufactured by Nippon Kayaku Co., Ltd.], and "UVI-6992" (manufactured by Dow Chemical Co., Ltd.). , “Adeka Optomer SP-150”, “Adeka Optomer SP-170” [above, manufactured by ADEKA Co., Ltd.], “CI-5102”, “CIT-1370”, “CIT-1682”, “CIP-1866S” ”, “CIP-2048S”, “CIP-2064S” [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” [manufactured by Midori Chemical Co., Ltd.], “PI-2074” (Rhodia ), “Omnirad250”, “OmniradPAG103”, OmniradPAG108”, OmniradPAG121”, OmniradPAG203” [manufactured by IGM RESINS), “CPI-100P”, “CPI-101A”, “CPI-200K”, “CPI-210S ” [all of which are manufactured by San-Apro Co., Ltd.] and the like.
Among these, in particular, "UVI-6992" manufactured by Dow Chemical Company, "CPI-100P" and "CPI-101A" manufactured by San-Apro Co., Ltd., containing diphenyl[4-(phenylthio)phenyl]sulfonium as a cation component. ”, “CPI-200K”, and “CPI-210S” are preferred.

1-3. Details of Composition 1 Composition 1 is an active energy ray-curable composition containing the components (A) and (B).
Examples of the method for producing the composition include a method of stirring and mixing the components (A) and (B) and, if necessary, other components described later, according to a conventional method.
In this case, if necessary, the mixture may be heated and stirred. The temperature for stirring and mixing with heating is preferably in the range of 20 to 70°C.

The content ratios of the components (A) and (B) in composition 1 may be appropriately set according to the purpose.
The content of component (B) in composition 1 is preferably 0.01 to 40 parts by weight as an active ingredient, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of component (A). Preferably, 0.5 to 5 parts by weight is more preferable.
Here, the "active ingredient" means 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 preferably cured. Due to the influence of the acid contained in the ingredients, problems such as corrosion can be prevented depending on the substrate or product to be coated.
Depending on the type of component (B), a solution diluted with an organic solvent [hereinafter referred to as "(B) component solution"] may be used. If so, double the amount used. Even when the component (B) solution is used, if the blending amount is large, the amount of the organic solvent brought in from the component (B) solution will increase, requiring a separate drying process, and the drying of the solvent will burden the environment. If it is cured without drying, it may cause a poor appearance due to the influence of the organic solvent. .

The viscosity of composition 1 may be appropriately set according to the base material to be used, the application, the purpose, and the like. The viscosity of Composition 1 is preferably 1 to 1000000 mPa·s, more preferably 1 to 10000 mPa·s.
In the present invention, viscosity means a value measured at 25° C. with an E-type viscometer (cone plate type viscometer).

Although the composition 1 of the present invention essentially comprises the components (A) and (B), other various components can be blended as necessary.
Other preferable components include a radical photopolymerization initiator [hereinafter referred to as "component (E)"].
The component (E) and other components are described below.
In the following, the components (C) and (D) described later are referred to as "curable components".
Further, for other components described later, only one kind of the exemplified compounds may be used, or two or more kinds thereof may be used in combination.

1-3-1. (E) Component As the (E) component in the present invention, various known radical photopolymerization initiators can be used.
Component (E) is used for the purpose of increasing the curing rate when an aromatic iodonium salt is used as component (B).

Although various photoradical initiators can be used as the component (E), a photocleavable photoradical polymerization initiator is preferable because it can efficiently generate radicals regardless of the formulation composition.
Specific examples of photocleavable photoradical polymerization initiators in component (E) include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 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, diethoxyacetophenone, oligo{2-hydroxy- 2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl Acetophenone compounds such as propan-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)- Phosphine oxide compounds such as 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;

The content of component (E) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, with respect to 100 parts by weight of the total amount of curable components. ~5 parts by weight is particularly preferred. Within the above range, the curability of the composition is excellent, and the scratch resistance of the resulting cured film is excellent.

1-3-2. Other components other than those mentioned above Examples of other components other than those mentioned above include various compounds, and preferably known additives used in coating agents can be used.
Examples include organic solvents, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, surface modifiers, pigments, dyes, and tackifiers. However, since a basic substance inhibits the curing of composition 1 or 2, other components other than those mentioned above preferably do not have basicity.
The organic solvent, ultraviolet absorber, light stabilizer, acidic substance, inorganic particles, antioxidant, and surface modifier among other components are described below.

<Organic solvent>
The composition 1 or 2 of the present invention can be used without solvent, but various organic solvents can be used for the purpose of adjusting 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; 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; .

It is preferable not to use an organic solvent, and even if it is used, it must be contained in a minimum amount. When it is unavoidably used, the content ratio is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of the total amount of composition 1 or 2. preferable.

<Ultraviolet absorber>
Specific examples of UV absorbers 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-butyroxyphenyl)-6-(2,4-bisbutyroxyphenyl)-1,3,5-triazine, 2-( Triazine UV absorbers such as 2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; 2-(2H-benzo triazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy Benzotriazole UV absorbers such as -5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; cyanoacrylate UV absorbers such as ethyl-2-cyano-3,3-diphenyl acrylate and octyl-2-cyano-3,3-diphenyl acrylate; UV rays such as titanium oxide particles, zinc oxide particles and tin oxide particles; and inorganic particles that absorb Among the above 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 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably 1 to 2 parts by weight.

In general, component (B) has a short absorption wavelength, so it is preferable not to use an ultraviolet absorber. It is preferable to use agents together.
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. .

<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 and 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, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester and the like.
Commercially available hindered amine light stabilizers include TINUVIN 111FDL, TINUVIN123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.

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 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably 1 to 1 part by weight.

<Acidic substances>
The composition 1 or 2 of the present invention is excellent in adhesion to substrates such as plastics, and the adhesion can be further improved by adding an acidic substance.
Examples of acidic substances include photoacid generators that generate acids upon exposure to 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 more preferably 0.0005 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably ~0.5 parts by weight. Within the above range, the adhesiveness to the substrate is excellent, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

<Inorganic particles>
As the inorganic particles, metal oxide particles are preferred.
The metal oxide particles are preferably 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. mentioned.

The average particle diameter 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 cured film has good transparency and appearance.
In the present invention, the average particle size of the inorganic particles means the particle size when assuming true spherical particles from the specific surface area of the sample obtained by the BET method.

The inorganic particles may be surface-modified particles.
As the surface modifier, a known one can be used, and a silane coupling agent, a titanium coupling agent, and the like are preferably used.
Among them, a silane coupling agent is more preferable, and a compound having an ethylenically unsaturated group and an alkoxysilyl group is particularly preferable. In the above mode, the resulting cured film is more excellent in hardness and curl resistance. Specific examples of the silane coupling agent include compounds similar to those described later.
The amount of surface modification of the inorganic particles is not particularly limited, but the ratio of the surface modifier to the inorganic particles is 1.0 to 45.0% by weight with respect to the total weight of the surface modifier and the inorganic particles. It is preferable to react with.

The content of the inorganic particles is preferably 25 to 400 parts by weight, more preferably 30 to 200 parts by weight, and 50 to 150 parts by weight with respect to 100 parts by weight of the total amount of the curable components. is more preferred. In the above mode, the resulting cured film is more excellent in adhesion, scratch resistance and curl resistance.

<Antioxidant>
The 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 antioxidants used in the present invention include phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
Preferable examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70 and AO-80 manufactured by Adeka Corporation.
Preferable examples of phosphorus-based antioxidants include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite. Commercially available products of these derivatives include, for example, Adekastab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A and 3010 manufactured by Adeka Co., Ltd. etc.
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.

The content of the antioxidant is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of the composition 1 or 2. In the above aspect, the composition is excellent in stability.

<Surface modifier>
A surface modifier may be added to the composition 1 or 2 of the present invention for the purpose of improving the leveling property during application, or for the purpose of improving the slipperiness of the cured film to improve the scratch resistance.
Surface modifiers include surface modifiers, surfactants, leveling agents, antifoaming agents, slipperiness imparting agents, antifouling agents and the like, and these known surface modifiers can be used. .
Among them, preferred are silicone-based surface modifiers and fluorine-based surface modifiers. 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, and fluorine-based polymers having a perfluoroalkyl group and a polyalkylene oxide chain. and oligomers, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains.
Also, for the purpose of increasing the durability of lubricity, a surface modifier having an oxetane ring or an oxirane ring in the molecule may be used. The content of the surface modifier is preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the total composition 1 or 2. Within the above range, the surface smoothness of the cured film is excellent.

2. Composition 2
Composition 2 relates to an active energy ray-curable composition containing components (B), (C) and (D), for forming an overcoat layer, which is a cured film of composition 2, on the primer layer. is the composition of
The details of the components (B), (C), (D), and composition 2 are described below.

2-1. (B) Component (B) is a compound that initiates cationic polymerization upon exposure to active energy rays, and the details thereof are as described above.

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

Component (C) includes both a compound having one oxetane ring [hereinafter referred to as "(C1) component"] and a compound having two or more oxetane rings [hereinafter referred to as "(C2) component"]. can be used. Moreover, only one kind of the (C1) component or (C2) component shown below can be used, or two or more kinds can be used.

As the component (C1), various compounds can be used as long as they have one oxetane ring.
Preferred compounds for component (C1) include compounds represented by the following formula (1).

Here, in formula (1), Z means an oxygen atom or a sulfur atom. R ¹ 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. R ² represents 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. do.
Examples of alkyl groups having 1 to 6 carbon atoms for R ¹ and R ² include methyl group, ethyl group, propyl group and butyl group.
Examples of alkenyl groups having 1 to 6 carbon atoms for R ² include 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group and 3-butenyl and the like.
Examples of aryl groups for R ¹ and R ² include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like.
Examples of alkylcarbonyl having 1 to 6 carbon atoms for R ² include propylcarbonyl, butylcarbonyl, pentylcarbonyl and the like.
Examples of the alkylcarbamoyl group having 1 to 6 carbon atoms for R ² include ethoxycarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, butylpentylcarbamoyl group and the like.

In the present invention, compounds in which Z, R ¹ and/or R ² in the above formula (1) are shown below are preferred.
Z is preferably a compound that is an oxygen atom. R ¹ is preferably a compound of a lower alkyl group, preferably a compound of a methyl group or an ethyl group. Further, as R ² , compounds having a hydrogen atom, a butyl group, a 2-ethylhexyl group, or a benzyl group are preferred.

Specific examples of preferred compounds represented by formula (1) include 3-ethyl-3-hydroxymethyloxetane, which is a compound in which Z is an oxygen atom, R ¹ is a lower alkyl group, and R ² is a hydrogen atom. is mentioned.
A specific example of a preferable compound represented by formula (1) is 3-ethyl-3-butyloxymethyloxetane, which is a compound in which Z is an oxygen atom, R ¹ is a lower alkyl group, and R ² is an alkyl group. , 3-ethyl-3-hexyloxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-dodecyloxymethyloxetane, 3-ethyl-3-octadecyloxymethyl Oxetane, 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, 4-[(3-ethyloxetan-3-yl)methoxy]biphenyl and the like.

As the component (C1), a compound having one oxetane ring and one hydroxyl group is more preferable because of excellent adhesion to the substrate.
A specific example of the compound having one oxetane ring and one hydroxyl group is a compound represented by formula (1) in which Z is an oxygen atom, R ¹ is a lower alkyl group, and R ² is a hydrogen atom. -ethyl-3-hydroxymethyloxetane and the like.

Component (C1) is commercially available and includes 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) [Aron oxetane OXT-101 manufactured by Toagosei Co., Ltd.] and 2-ethylhexyloxetane [Aron manufactured by Toagosei Co., Ltd. oxetane OXT-212] and the like.

By using the component (C2) in combination, it is possible to form a cured coating film with low swelling of the protective agent even under high humidity and good adhesion to the substrate. As the component (C2), various compounds can be used as long as they have two or more oxetane rings. Specific examples of the component (C2) include compounds exemplified in JP-A-11-246647.

Preferred specific 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, 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, 3-chloromethyl-3-ethyloxetane etherification modification of novolak type phenol-formaldehyde resin, 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)methylthio}phenyl]sulfide, 1,6-bis[ (3-ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane, 3-[(3-ethyloxetan-3-yl)methoxy]propyl tri Hydrolytic condensates of ethoxysilane, condensates of tetrakis[(3-ethyloxetan-3-yl)methyl]silicate and the like can be mentioned.

Component (C2) is preferably a compound having two oxetane rings, and specific examples thereof include the compounds listed above.

Component (C2) is commercially available, and 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.] and the like.

The ratio of components (C1) and (C2) in the total amount of components (C1) and (C2) of 100% by weight can be within any range, and may be adjusted according to the type of substrate. is preferably 50 to 100% by weight of component (C1) and 0 to 50% by weight of component (C2).

2-3. (D) Component (D) is a compound having an oxirane ring.
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 improve water resistance.
Any of monomers, oligomers, and polymers can be used as component (D).

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

Aromatic epoxy compounds include polyhydric phenols having at least one aromatic nucleus, or di- or polyglycidyl ethers prepared by reacting their alkylene oxide adducts 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;
A diglycidyl ether of an alkylene oxide adduct of bisphenol, such as a diglycidyl ether of an alkylene oxide adduct of bisphenol A, a diglycidyl ether of an alkylene oxide adduct of bisphenol F, and a diglycidyl ether of an alkylene oxide adduct of brominated bisphenol AF. ;and,
Novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins are included.
Examples other than the above include biphenyl-type epoxy resins, hydroquinone diglycidyl ether, resorcin diglycidyl ether, diglycidyl terephthalate, diglycidyl phthalate, epoxidized styrene-butadiene copolymers, and styrene-isoprene copolymers. and an addition reaction product of terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin.
Examples of the alkylene oxide mentioned above include ethylene oxide and propylene oxide.

Here, the term "epoxy resin" refers to a compound or polymer that has an average of two or more epoxy groups in the molecule and is cured 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 its molecule.

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

Aliphatic epoxy compounds include di- or polyglycidyl ethers of aliphatic alcohols or their alkylene oxide adducts.
Specific examples of the compound include diglycidyl ethers of alkylene glycol 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;
Diglycidyl ether of polyethylene glycol or its alkylene oxide adduct, and polyglycidyl ether of polyalkylene glycol such as polypropylene glycol or diglycidyl ether of its alkylene oxide adduct.
Here, alkylene oxide includes ethylene oxide, propylene oxide, and the like.
Furthermore, in addition to these compounds, monoglycidyl ethers of aliphatic higher alcohols, phenols, cresols, or monoglycidyl ethers of these alkylene oxide adducts, which are monomers having one oxirane ring in the molecule, can also be used. can.

As the component (D), a compound having two or more oxirane rings [hereinafter referred to as "component (D1)" is used because the resulting cured film has good surface hardness and excellent chemical resistance and water resistance. ] is preferable.
Furthermore, as component (D1), an aromatic epoxy compound is preferable, and an epoxy resin having a bisphenol skeleton is more preferable. Bisphenol skeletons include bisphenol A, bisphenol F, bisphenol P, bisphenol Z, and the like.

(D) As a component, only 1 type of the said compound can be used, and 2 or more types can also be used together.

2-4. Details of Composition 2 Composition 2 is an active energy ray-curable composition containing components (B), (C) and (D).
Examples of the method for producing composition 2 include a method of stirring and mixing the components (B), (C) and (D), and, if necessary, other components as described above, according to a conventional method.
In this case, if necessary, the mixture may be heated and stirred. The temperature for stirring and mixing with heating is preferably in the range of 20 to 70°C.

The ratio of component (B) in composition 2 is preferably from 0.01 to 40 parts by weight as an active ingredient with respect to a total of 100 parts by weight of components (C) and (D), and 0.1 ~10 parts by weight is more preferred, and 0.5 to 5 parts by weight is even more preferred.
By setting the content of component (B) to 0.1 parts by weight or more, the components (C) and (D) can be preferably cured, and the content of component (B) is set to 10 parts by weight or less. In addition, it is possible to prevent problems such as corrosion depending on the substrate or product to be coated due to the influence of the acid contained in the component (B).

The content of component (C) and component (D) in composition 2 is 5 to 40 parts by weight of component (C) and component (D) in a total of 100 parts by weight of component (C) and component (D). It preferably contains 95 to 60 parts by weight of component, more preferably 10 to 30 parts by weight of component (C) and 90 to 70 parts by weight of component (D).
By setting the content ratios of the components (C) and (D) in the above range, the curing speed of the composition 2 can be improved, and the adhesion to the substrate can be improved.

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

The composition 2 of the present invention essentially comprises the components (B), (C) and (D), but may contain other various components as necessary.
Other preferred components include component (E).
Components (E) and other components include the same compounds as described above, and are preferably contained in the same proportions as described above.
Further, as the other components mentioned above, only one kind of the exemplified compounds may be used, or two or more kinds thereof may be used in combination.

Composition 2 used in the present invention preferably includes a coating agent composition, an ink composition, and the like.
Furthermore, as described above, the production method of the present invention can be preferably applied to inorganic substrates, and composition 2 includes an active energy ray-curable coating composition for inorganic substrates and an active An energy ray-curable ink composition can be mentioned, and the inorganic substrate can be preferably applied to glass. Active energy ray-curable coating composition for glass and active energy ray-curable ink composition for glass is mentioned.
Specific examples of applications for glass include coating agents and inks for glass surfaces, and printing inks and paints for glass bottles.
Applications for glass and metals include mirrors, and more specifically, it can be preferably used as a coating agent for preventing corrosion of metal deposition layers due to moisture absorption from the end faces of mirrors.
Furthermore, composition 2 used in the present invention has excellent adhesiveness and water resistance when cured, so it is more suitable as an anti-corrosion coating agent for the end faces of mirrors that are mainly used around water, and as a printing ink or paint for glass bottles. It can be preferably used.

3. METHOD FOR MANUFACTURING SUBSTRATE HAVING CURED FILM The present invention relates to a method for manufacturing a substrate having a cured film, in which step 1 and step 2 below are sequentially carried out.
- Step 1: A step of applying the composition 1 to a substrate and irradiating the coated surface with an active energy ray to form a cured film - Step 2: On the cured film obtained in step 1, the composition 2 and irradiating the coated surface with an active energy ray to form a cured film. Steps 1 and 2 will be described below.

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.

Substrates to which the production method of the present invention can be applied include various materials such as inorganic materials, plastics, and paper.
Examples of inorganic materials include glass, metals, concrete, and stone materials. 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, polycarbonates, polyarylates, polyether sulfones, norbornene, and the like. cyclic polyolefin resins, polyvinyl chloride, epoxy resins, polyurethane resins and the like, which use cyclic olefins of the above as monomers.

Among these substrates, the production method of the present invention is excellent in adhesion to inorganic substrates, and thus can be preferably applied to inorganic materials. Specific examples thereof are as described above.
As inorganic materials, more preferably glass and metal can be applied, and more specifically, glass plates typified by soda glass, end surfaces of mirrors having metal deposition layers, and the like can be mentioned.
Mirrors are made by forming a silver film on the back side of the plate glass by silver plating called “silver coating”. It is manufactured by forming a copper film with a copper film and then forming a protective coating film with a protective paint such as an alkyd-melamine resin thereon. On the back side of the sheet glass, the silver film can be protected by a copper film and a protective coating, but on the sides (end faces), the silver film and copper film are exposed, so this is the cause of the mirror damage. Since the metal surface of the end face corrodes and the mirror bleeds, etc., there has been a demand for a coating agent suitable for protecting the end face.
The composition 1 of the present invention can be preferably used as a coating agent suitable for protecting the end surface of the mirror because the cured film thereof has excellent adhesion and water resistance to glass and metal.

The method of applying the composition 1 of the present invention to a substrate may be appropriately set according to the purpose, and may be a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, a knife coater, A coating method using a comma coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, a micro gravure coater, or the like can be mentioned.

The film thickness of the cured film of composition 1 with respect to the substrate may be appropriately set according to 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 cured film produced, but is preferably 5 to 800 μm, more preferably 10 to 500 μm. .

When the composition 1 contains an organic solvent, it is preferable to heat and dry the composition after applying it to the substrate to evaporate the organic solvent.
The drying temperature is not particularly limited as long as it is not higher than the temperature at which problems such as deformation of the applied base material do not occur. A preferable 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, preferably 0.5 to 3 minutes.

As for the irradiation method of the active energy ray, a general method known as a conventional curing method may be adopted.
Active energy rays for curing the composition 1 of the present invention include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferred, and ultraviolet rays are particularly preferred. Ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, light emitting diodes (LEDs), and the like.
The irradiation energy should be appropriately set according to the type of active energy ray and composition, but if a high-pressure mercury lamp is used as an example, the irradiation energy in the UV-A region is 100 to 8,000 mJ/. cm ² is preferred, and 200-3,000 mJ/cm ² is more preferred.
Heating can also be performed after irradiating the active energy ray, if necessary.

In this case, the reaction rate of the polymerizable groups in composition 1 is preferably 1 to 80%, more preferably 1 to 50%.
By setting the reaction rate to 1% or more, the composition 1 can be sufficiently cured, and by setting it to 80% or less, it can be sufficiently copolymerized with the overcoat layer, and the primer layer and the overcoat layer can improve the adhesion of.
Furthermore, composition 1 contains a silane coupling agent having an epoxy group as the component (A) of composition 1, and the reaction rate of the polymerizable group in composition 1 is calculated from the following formula (1). The value is preferably 1-80%, more preferably 1-50%.

Curing rate (%) =
100−(epoxy value of composition 1)÷(epoxy value of cured film of composition 1)×100
... (1)

In addition, the epoxy value in Formula (1) means the value measured according to JISK7236.
Examples of the method for adjusting the reaction rate of the polymerizable group include a method of adjusting the integrated light quantity of the active energy ray and irradiating it.

When the composition 1 of the present invention is used under high humidity conditions, defects may occur in the cured film if defoaming of the composition 1 after coating is insufficient. For example, when the cured film obtained from the composition 1 of the present invention is subjected to the hot water immersion test described later, defects may occur in the cured film if the defoaming of the composition 1 after coating is insufficient. . In order to solve this problem, it is preferable to degas by heating at 40 to 60° C. for several minutes, preferably 1 to 30 minutes after application. However, the heating step is not essential because the extent to which air bubbles are contained in the applied composition varies depending on the coating method.

The cured film may remain tacky immediately after the irradiation of the active energy ray, but in this case also, the cured film can be completely cured by standing at room temperature for about 10 minutes or longer.
When coating and curing are performed continuously using an apparatus equipped with a conveyor, post-curing may be performed by heating in a drying oven after irradiation with active energy rays. Although there are no restrictions on the temperature, it is preferable to heat at 40 to 80° C. for about 1 to 30 minutes.

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 an active energy ray to form a cured film (overcoat layer). be.

The method of applying the composition 2 of the present invention to the base material may be appropriately set according to the purpose, and examples thereof include the same methods as those described above.
The thickness of the cured film (overcoat layer) may be selected according to the application of the substrate having the cured film, but is preferably 5 to 800 μm, more preferably 10 to 500 μm.

When the composition 2 contains an organic solvent, it is preferable to heat and dry the composition after applying it to the base material to evaporate the organic solvent.
The drying temperature is not particularly limited as long as it is not higher than the temperature at which problems such as deformation of the applied base material do not occur. A preferable 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, preferably 0.5 to 3 minutes.

As a method for irradiating the active energy ray, a general method known as a conventional curing method may be adopted.
Active energy rays for curing the composition 2 of the present invention include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferred, and ultraviolet rays are particularly preferred. Ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, light emitting diodes (LEDs), and the like.
Irradiation energy is preferably under the same conditions as described above.
Heating can also be performed after irradiating the active energy ray, if necessary.

The cured film may remain tacky immediately after the irradiation of the active energy ray, but in this case also, the cured film can be completely cured by standing at room temperature for about 10 minutes or more.
When coating and curing are performed continuously using an apparatus equipped with a conveyor, post-curing may be performed by heating in a drying oven after irradiation with active energy rays. Although there are no restrictions on the temperature, it is preferable to heat at 40 to 80° C. for about 1 to 30 minutes.

4. Applications The production method of the present invention can be used in various applications, and preferably includes a method for producing a substrate having a coating layer and a method for producing 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 an inorganic substrate having a coating layer and an inorganic substrate having an ink layer. It can be preferably applied to glass, and can be preferably applied to the manufacturing method of glass having a coating layer and glass having an ink layer.
Specific examples of applications for glass include the formation of a coating layer and the formation of an ink layer on the glass surface, and the formation of a printing ink layer and the formation of a paint layer 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 the metal deposition layer due to moisture absorption from the end face of the mirror.
Furthermore, since the cured product has excellent adhesion and water resistance, the production method of the present invention can be used to form an anticorrosive coating layer on the end face of a mirror that is mainly used around water, and to form a printing ink layer for glass bottles. It can be preferably used for forming a paint layer.

EXAMPLES Examples and comparative examples are shown below to describe the present invention more specifically. It should be noted that the present invention is not limited by these examples.
Further, hereinafter, unless otherwise specified, "parts" means parts by weight, and "%" means % by weight.

1. Examples 1 to 5
1) After 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 1-5.

2) Step 1
The obtained composition 1 of Examples 1 to 5 was cut using a bar coater to a float glass (150 mm × 70 mm × 3 mm) manufactured by Nippon Sheet Glass Co., Ltd., and the cured film (primer layer) had a thickness of It was coated so that it would be 10 μm.
Then, using a high-pressure mercury lamp [H06-L 41 manufactured by Eyegraphics Co., Ltd.] equipped with a conveyor, the specimen was irradiated with ultraviolet rays under the conditions of UV-A illuminance of 80 W / cm and integrated light quantity 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 curing rate of the obtained 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 according to JIS K7236. The sample used for the epoxy value was prepared by placing Composition 1 in a weight required for measurement in a petri dish-like container, irradiating with ultraviolet rays under the same conditions as in Step 1, and waiting.

3) Process 2
Composition 2 was applied onto the cured film (primer layer) of the compositions of Examples 1 to 5 obtained in step 1 so that the cured film (overcoat layer) had a thickness of 50 μm.
Subsequently, according to the same method as described above, ultraviolet rays were irradiated at the integrated light amount shown in Table 1.
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.
Those results are shown in Table 3.

1) Adhesion As test specimens for adhesion evaluation, the cured film obtained above was a) after 24 hours of curing, and b) after being immersed in a 10% hydrochloric acid aqueous solution for 48 hours, taken out and washed with tap water. After that, the specimens which had been immersed in hot water at 80° C. for 10 days were taken out and dried in a room for 24 hours.
The two types of test specimens were cut with a cutter knife at intervals of 1 mm in length and width to form 25 squares with a size of 1 mm × 1 mm. After applying it, I peeled it off. The number of remaining films after peeling was evaluated. The larger the number of remaining films, the better the adhesion.

2) Appearance of Cured Film The appearance of the same three specimens used in the adhesion test was visually confirmed and evaluated according to the following three levels.
〇: A smooth cured film with no unevenness is transparent, △: A generally smooth cured film with slight unevenness is transparent, ×: There are dents and swellings, and changes such as cloudiness were observed.

2. Comparative Examples 1 to 4
1) Composition preparation Each component shown in Table 2 was stirred and mixed at 30°C to obtain Compositions 1 and 2 used in Comparative Examples 1-4.
In Comparative Example 1, only composition 1 was produced, and in comparative example 3, only composition 2 was produced.

2) Step 1
The obtained composition 1 of Comparative Examples 1, 2, and 4 was cut using a bar coater to float glass (150 mm × 70 mm × 3 mm) manufactured by Nippon Sheet Glass Co., Ltd., and a cured film (primer layer) was applied. It was coated so that the film thickness of was 10 μm.
In Comparative Example 4, composition 2 was used and coated in the same manner as described above.
Then, using the same high-pressure mercury lamp as in the example, the specimen was irradiated with ultraviolet rays under the conditions of UV-A illuminance of 80 W/cm and integrated light quantity 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 cure rate of the obtained cured film was calculated according to the above formula (1).

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 cured film (overcoat layer) had a thickness of 50 μm. .
Subsequently, according to the same method as described above, ultraviolet rays were irradiated with the integrated light quantity shown in Table 2.
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.
Those results are shown in Table 3.

The abbreviations in Tables 1 and 2 mean the following. Parentheses in Tables 1 and 2 mean the number of parts of each component.
(A) component
・ 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 PF ₆ salt [CPI-100P manufactured by San-Apro Co., Ltd.]
(C) component
- OXA: 3-ethyl-3-hydroxymethyl oxetane [Aron oxetane OXT-101 manufactured by Toagosei Co., Ltd.]
・DOX: 3-ethyl 3[[(3-ethyloxetan-3-yl)methoxy]methyl]oxetane [Aron oxetane OXT-221 manufactured by Toagosei Co., Ltd.]
(D) component
・ jER: bisphenol A type epoxy resin [jER-828 manufactured by Mitsubishi Chemical Corporation]

3. As is clear from the results of Examples 1 to 5 in Evaluation Results Table 3, the cured film obtained by the production method of the present invention was excellent in adhesion to glass and long-term acid resistance.
On the other hand, the production method of Comparative Example 1 is a cured film obtained by performing only step 1, and the composition 1 is completely cured. The properties were insufficient, and the appearance of the cured film was also poor.
In the production method of Comparative Example 2, the composition 2 used in step 2 is a composition that does not contain component (C). Adhesion and appearance became insufficient after immersion in hydrochloric acid and warm 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 production method of Comparative Example 3 is a cured film obtained by performing only step 1, in which the composition 1 further containing components (C) and (D) is completely cured. However, the adhesiveness between the substrate and the cured film was insufficient, resulting in peeling.
In the production method of Comparative Example 4, the composition 2 used in step 2 uses a composition that does not contain the (D) component, and the hardness of the cured film obtained by the composition 2 is insufficient. Adhesion was insufficient, and the appearance of the cured film was also poor.

In the method for producing a substrate having a cured film of the present invention, the resulting cured film has excellent adhesion and water resistance to inorganic substrates such as glass, and is mainly used around water. It can be preferably used to form anti-corrosion coating layers on the end faces of mirrors, and to form printing ink layers or paint layers for glass bottles.

Claims (16)

A method for producing a substrate having a cured film, wherein the following steps 1 and 2 are sequentially performed.
- Step 1: An active energy ray-curable composition (hereinafter referred to as "composition 1") containing the following components (A) and (B) is applied to a substrate, and the coated surface is irradiated with an active energy ray. Forming a cured film Step 2: On the cured film obtained in Step 1, an active energy ray-curable composition containing the following components (B), (C) and (D) (hereinafter referred to as (referred to as "composition 2") and irradiating the coated surface with active energy rays to form a cured film (A) component: silane coupling agent having a cationic polymerizable group (B) component: active Compound that initiates cationic polymerization by irradiation with energy rays Component (C): compound having an oxetane ring Component (D): compound having an oxirane ring The method for producing a substrate having a cured film according to claim 1, wherein the component (B) contains a silane coupling agent having an epoxy group. 1 or claim 1, wherein the component (C) comprises the component (C1): a compound having one oxetane ring, and the component (C1) further comprising a compound having one oxetane ring and one hydroxyl group. Item 3. A method for producing a substrate having a cured film according to item 2. 4. Any one of Claims 1 to 3, wherein the component (C) comprises the component (C2): a compound having two or more oxetane rings, and the component (C2) further comprising a compound having two oxetane rings. 2. A method for producing a substrate having a cured film according to claim 1. The method for producing a substrate having a cured film according to any one of claims 1 to 4, wherein the component (D) contains 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) contains 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. The curing 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) with respect to a total of 100 parts by weight of the component (A). A method for producing a substrate having a membrane. The composition 2 contains 5 to 40 parts by weight of the component (C) and 95 to 60 parts by weight of the component (D) in a total of 100 parts by weight of the components (C) and (D). A method for producing a substrate having a cured film according to any one of claims 1 to 8. Any one of claims 1 to 9, wherein the composition 2 contains 0.01 to 40 parts by weight of the component (B) with respect to a total of 100 parts by weight of the components (C) and (D). 10. A method for producing a substrate having a cured film according to item 1. The method for producing a substrate having a cured film according to any one of claims 1 to 10, wherein step 2 is performed after curing in step 1 so that the curing rate is 1 to 80%. In step 1, the composition 1 contains a silane coupling agent having an epoxy group as the component (A), and after curing so that the curing rate represented by the following formula (1) is 1 to 80%, the step 12. The method for producing a substrate having a cured film according to claim 11, wherein 2 is performed.
Curing rate (%) =
100−(epoxy value of composition 1)÷(epoxy value of cured film of composition 1)×100
... (1) The method for producing a substrate having a cured film according to any one of claims 1 to 12, wherein said composition 1 and composition 2 are active energy ray-curable coating composition. The method for producing a substrate having a cured film according to any one of claims 1 to 12, wherein said composition 1 and composition 2 are active energy ray-curable ink compositions. 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. The method for producing a substrate having a cured film according to claim 15, wherein the substrate is glass.