Resin, curable resin composition, cured product, and article

Abstract

To provide: a resin that gives a cured product having excellent thermostability, elasticity and substrate adhesion; a curable resin composition containing the same; a cured product formed from the curable resin composition; and an article having a coating film composed of the cured product.SOLUTION: A resin has at least one acid radical, and an amide bond and / or imide bond, the resin having a structure represented by any one of general formulae (1)-(6). There is also provided a curable resin composition containing the same.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin having excellent heat resistance, elasticity and substrate adhesion in a cured product, a curable resin composition containing the same, a cured product of the curable resin composition, and an article.

Background Art

[0002] In recent years, curable compositions such as active energy ray curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been widely used in fields such as inks, paints, coating agents, adhesives, and optical members. Among them, as the coating agent use, in general, it is required that it can impart designability to the surfaces of various substrates, has excellent curability, and can form a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, materials having excellent elasticity as well as heat resistance and substrate adhesion of the obtained cured products have been demanded by the industry.

[0003] Conventional curable resins include polyamideimide resins obtained by reacting an isocyanurate type polyisocyanate synthesized from an isocyanate having an aliphatic structure with a tricarboxylic anhydride having an aliphatic structure, and isocyanurate type polyisocyanates synthesized from isocyanates having an aliphatic structure. Alcohol-modified polyamideimide resins obtained by modifying the acid anhydride groups at the terminal of a polyamideimide resin obtained by reacting with a tricarboxylic anhydride with an alcohol compound are known (for example, see Patent Documents 1 and 2 below), but in terms of heat resistance, elasticity and substrate adhesion, they do not satisfy the increasingly demanding characteristics in the future and are not sufficient for current market requirements.

[0004] Therefore, materials having excellent heat resistance, elasticity and substrate adhesion have been demanded.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] International Publication No. 2010 / 107045 [Patent Document 2] International Publication No. 2015 / 068744 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] The problem to be solved by the present invention is to provide a resin having excellent heat resistance, elasticity and substrate adhesion in a cured product, a curable resin composition containing the same, a cured product composed of the curable resin composition, and an article.

[0007] The problem to be solved by the present invention is to provide a resin capable of forming a cured product having excellent heat resistance, elasticity and substrate adhesion, a curable resin composition containing the same, a cured product of the curable resin composition, and an article. [Means for Solving the Problems]

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by having at least one acid group, and have completed the present invention.

[0009] That is, the present invention relates to a resin having at least one acid group and having an amide bond and / or an imide bond, and having a structure represented by any one of the following general formulas (1) to (6), a curable resin composition containing the same, a cured product composed of the curable resin composition, and an article.

[0010] [Chemical Formula] [In formulas (1) to (6), A is independently a benzene ring or an alicyclic ring, X represents any one of the following formulas (x-1) to (x-24), and Y is independently -OR 1 or -NH-X-(Z) lrepresents, n is an integer of 0 or 1 to 3, m is an integer of 0 or 1 to 3, and n + m is 2 or 3. Further, the R 1 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents the following formula (z-1) or (z-2), and l is 1 or 2. In the formulas (1) to (6), (z-1) and (z-2), at least one of Y is -OR 1 and at least one of the R 1 is a hydrogen atom.]

[0011]

Chemical formula

[0012]

Chemical formula

[0013]

Chemical formula

Advantages of the Invention

[0014] Since the resin of the present invention has excellent heat resistance, elasticity, and substrate adhesion in the cured product, it can be suitably used as an insulating material and a resist member. In the present invention, "excellent elasticity" means "high elasticity".

Mode for Carrying Out the Invention

[0015] The resin of the present invention has at least one acid group and has an amide bond and / or an imide bond, and is characterized by having a structure represented by any one of the following general formulas (1) to (6).

[0016]

Chemical formula

[0017]

Chemical formula

[0018]

Chemical formula

[0019] [Chemical formula] [In formula (z-2), A is a benzene ring or an alicyclic ring, and Y is, independently of each other, -OR 1 represents, and said R 1 is, independently of each other, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In formula (z-1), "*" indicates the bonding point with X.]

[0020] As said acid group, a carboxyl group is indicated.

[0021] In formulas (1) to (6), as said X, since a resin capable of forming a cured product excellent in heat resistance, elasticity and substrate adhesion can be obtained, (x-1), (x-2), (x-3), (x-4), (x-8), (x-9), (x-10), (x-13), (x-14), (x-15), (x-16) are preferable, and (x-1), (x-13) are more preferable.

[0022] In formulas (1) to (6), as said Y, since a resin capable of forming a cured product excellent in heat resistance, elasticity and substrate adhesion can be obtained, at least two of Y are -OR 1 and at least one of said R 1 is a hydrogen atom, and it is preferable that at least one is a hydrocarbon group having 1 to 20 carbon atoms.

[0023] Examples of the resin of the present invention include resin (I) having a polyisocyanate compound and a reaction product (1) of a bifunctional polybasic acid anhydride and an alcohol compound as essential raw materials, a reaction product (2) of a polyisocyanate compound and a monofunctional polybasic acid anhydride, and a reaction product (3) obtained by further reacting a monofunctional polybasic acid anhydride with an alcohol compound as an essential raw material, resin (II), etc.

[0024] The production method of the resin (I) is not particularly limited and can be produced by an appropriately known method. For example, the polyisocyanate compound and the bifunctional polybasic acid anhydride are reacted in the temperature range of 100 to 180 ° C in the absence of a catalyst or in the presence of a basic catalyst, and then the alcohol compound is added and produced at 80 to 140 ° C in the presence of a basic catalyst. And the like.

[0025] Examples of the basic catalyst include amine compounds such as N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxylpropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organometallic compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. These basic catalysts can be used alone or in combination of two or more.

[0026] In the production of the resin (I), it may be carried out in an organic solvent if necessary. Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. Also, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials from the viewpoint of good reaction efficiency.

[0027] The method for producing the resin (II) is not particularly limited and can be produced by an appropriately known method. For example, the polyisocyanate compound and the monofunctional polybasic acid anhydride are reacted in the presence of no catalyst or a basic catalyst in a temperature range of 100 to 180°C, and then the monofunctional polybasic acid anhydride is further reacted in the presence of no catalyst or a basic catalyst in a temperature range of 100 to 200°C, and then the alcohol compound is added and reacted at 80 to 140°C in the presence of a basic catalyst.

[0028] As the basic catalyst, the same ones as those exemplified as the above basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.

[0029] In the production of the resin (II), if necessary, it may be carried out in an organic solvent. As the organic solvent, the same solvents as those exemplified as the above-mentioned organic solvents can be used, and the organic solvent can be used alone or in combination of two or more kinds.

[0030] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following formula (7); and isocyanurate-modified products, biuret-modified products, allophanate-modified products, etc. of these. These polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0031]

Chemical formula

[0032] Examples of the bifunctional polybasic acid anhydride include bifunctional aliphatic polybasic acid anhydrides and bifunctional alicyclic polybasic acid anhydrides. In the present invention, the "bifunctional polybasic acid anhydride" refers to a polybasic acid anhydride having two acid anhydride groups. Further, in the present invention, the "alicyclic polybasic acid anhydride" refers to a polybasic acid anhydride containing an alicyclic structure in one molecule.

[0033] Examples of the bifunctional aliphatic polybasic acid anhydride include 1,2,3,4-butanetetracarboxylic dianhydride.

[0034] Examples of the bifunctional alicyclic polybasic acid anhydride include 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, octahydrobiphenylene-4a,8b:4b,8a-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like. These bifunctional alicyclic polybasic acid anhydrides can be used alone or in combination of two or more. Among these, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride is preferred because a resin capable of forming a cured product excellent in heat resistance, elasticity, and substrate adhesion can be obtained.

[0035] The amount of the bifunctional polybasic acid anhydride used is preferably in the range of 0.1 to 5 moles, more preferably in the range of 0.1 to 3 moles, and particularly preferably in the range of 0.15 to 1.5 moles, per mole of the isocyanate groups possessed by the polyisocyanate compound, since a resin capable of forming a cured product excellent in heat resistance, elasticity and substrate adhesion can be obtained.

[0036] Examples of the monofunctional polybasic acid anhydride include monofunctional aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides and the like. Among these, monofunctional aliphatic polybasic acid anhydrides and monofunctional alicyclic polybasic acid anhydrides are preferred since a resin capable of forming a cured product excellent in heat resistance, elasticity and substrate adhesion can be obtained. In the present invention, the "monofunctional polybasic acid anhydride" means a polybasic acid anhydride having one acid anhydride group.

[0037] Examples of the monofunctional aliphatic polybasic acid anhydride include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. Further, as the monofunctional aliphatic polybasic acid anhydride, the aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. These monofunctional aliphatic polybasic acid anhydrides can be used alone or in combination of two or more.

[0038] Examples of the monofunctional alicyclic polybasic acid anhydride include anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, etc. These monofunctional alicyclic polybasic acid anhydrides can be used alone or in combination of two or more.

[0039] Examples of the monofunctional aromatic polybasic acid anhydride include acid anhydrides such as phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. These monofunctional aromatic polybasic acid anhydrides can be used alone or in combination of two or more.

[0040] These monofunctional polybasic acid anhydrides can be used alone or in combination of two or more. Further, these monofunctional polybasic acid anhydrides can be reacted and used as a bifunctional polybasic acid anhydride.

[0041] Examples of the alcohol compound include alcohols having 10 or less carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, and benzyl alcohol; alcohols having 10 or less carbon atoms containing an ether bond such as 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol, and 2-isopropoxyethyl alcohol; alcohols having 10 or less carbon atoms containing a ketone group such as 3-hydroxy-2-butanone; and alcohols having 10 or less carbon atoms containing an ester group such as methyl hydroxyisobutyrate. These alcohol compounds can be used alone or in combination of two or more. Among these, monohydric alcohols having 10 or less carbon atoms are preferred, and monohydric alcohols having 5 or less carbon atoms are more preferred because a resin capable of forming a cured product excellent in heat resistance, elasticity, and substrate adhesion can be obtained.

[0042] In the production of the resin (I) and the resin (II), other compounds other than the essential raw materials can be contained as raw materials as necessary.

[0043] Examples of the other compounds include epoxy resins and the like.

[0044] Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, epoxy compounds of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols, epoxy compounds of 2,2’,6,6’-tetramethylbiphenol, epoxy compounds of 4,4’-methylenebis(2,6-dimethylphenol), epoxies derived from naphthalene skeletons such as novolak modification of naphthol, binaphthol, naphthol or binaphthol, epoxy resins obtained by epoxidizing phenol resins having a fluorene skeleton, aromatic epoxy resins such as phenyl glycidyl ether, etc. Further, aliphatic epoxy resins such as neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis-(3,4-epoxycyclohexyl) adipate, cyclic aliphatic epoxy resins such as 1,2-epoxy-4-(2-oxiranyl) cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxy resins containing a polyalkylene glycol chain in the main chain such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and heterocyclic-containing epoxy resins such as triglycidyl isocyanurate can also be used.Furthermore, epoxy group-containing polymer resins obtained by polymerizing unsaturated groups of epoxy compounds having polymerizable unsaturated double bonds such as (meth)acryloyl groups and vinyl groups, such as glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, 6-hydroxyhexyl (meth)acrylate glycidyl ether, 5-hydroxy-3-methylpentyl (meth)acrylate glycidyl ether, (meth)acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth)acrylic acid-3,4-epoxycyclohexyl, vinylcyclohexene oxide, and copolymers with other monomers having polymerizable unsaturated bonds can also be used. These epoxy resins can be used alone or in combination of two or more.

[0045] Examples of commercially available products of the cyclic aliphatic epoxy resin include "Denacol EX-252" manufactured by Nagase ChemteX Corporation, "EHPE3150", "EHPE3150CE" manufactured by Daicel Corporation, and the like.

[0046] The content of the other compound is preferably less than 50% by mass, more preferably less than 40% by mass in the raw material.

[0047] The curable resin composition of the present invention may contain other resin components other than the resins described above. Examples of the other resin components include resins having acid groups, curable resins, and the like.

[0048] Examples of the resin having an acid group include an epoxy resin having an acid group, a urethane resin having an acid group, an acrylic resin having an acid group, an amide-imide resin having an acid group, an acrylamide resin having an acid group, an ester resin having an acid group, and the like. These resins having an acid group can be used alone or in combination of two or more.

[0049] Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

[0050] The curable resin has a functional group capable of reacting with the acid group of the resin of the present invention. Examples thereof include epoxy resins having one or more epoxy groups in one molecule, compounds having one or more maleimide groups in one molecule, benzoxazine resins, cyanate ester resins, melamine resins, isocyanate compounds, silicates, and alkoxysilane compounds, (meth)acrylic resins, and the like. These curable resins can be used alone or in combination of two or more. Among these, an epoxy resin is preferable because a resin capable of forming a cured product excellent in heat resistance, elasticity, and substrate adhesion can be obtained.

[0051] In addition, the meaning of the above-mentioned and hereinafter-described curable properties described in the present invention includes not only the cured product of the resin of the present invention and the component that reacts therewith, but also the resin alone of the present invention or other resins, additives, inorganic material components, etc. that do not react with the resin of the present invention, and also includes a simply solvent-dried coating film or molded body. Furthermore, the cured product obtained by mixing the resin of the present invention with a curing agent that reacts with heat or light and / or the cured product and its curable properties obtained by curing the additive component itself that does not react with the resin of the present invention by heat, light, etc. are also included in that meaning.

[0052] As the epoxy resin, the same ones as those exemplified as the above-mentioned epoxy resin can be used, and the epoxy resin can be used alone or in combination of two or more.

[0053] Examples of the compound having a maleimide group include N - aliphatic maleimides such as N - cyclohexyl maleimide, N - methyl maleimide, N - n - butyl maleimide, N - hexyl maleimide, N - tert - butyl maleimide; N - aromatic maleimides such as N - phenyl maleimide, N-(p - methylphenyl) maleimide, N - benzyl maleimide; bismaleimides such as 4,4'-diphenylmethane bismaleimide, 4,4'-diphenylsulfone bismaleimide, m - phenylene bismaleimide, bis(3 - methyl - 4 - maleimidophenyl)methane, bis(3 - ethyl - 4 - maleimidophenyl)methane, bis(3,5 - dimethyl - 4 - maleimidophenyl)methane, bis(3 - ethyl - 5 - methyl - 4 - maleimidophenyl)methane, bis(3,5 - diethyl - 4 - maleimidophenyl)methane, etc. These compounds having a maleimide group can be used alone or in combination of two or more. Among them, bismaleimide is preferred because a resin capable of forming a cured product excellent in heat resistance, elasticity and substrate adhesion can be obtained. 4,4'-diphenylmethane bismaleimide, bis(3,5 - dimethyl - 4 - maleimidophenyl)methane, bis(3 - ethyl - 5 - methyl - 4 - maleimidophenyl)methane, bis(3,5 - diethyl - 4 - maleimidophenyl)methane are more preferred.

[0054] Since a resin capable of forming a cured product excellent in heat resistance, elasticity and substrate adhesion can be obtained, the content of the curable resin is preferably in the range of 0.6 to 2 moles, more preferably 0.8 to 1.5 moles, of the number of moles of the functional group capable of reacting with the acid group of the curable resin per mole of the acid group of the resin of the present invention.

[0055] In addition, the curable resin composition of the present invention may contain various additives such as a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler, polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, a storage stabilizer, etc., if necessary.

[0056] As the hardening accelerator, it is something that accelerates the hardening reaction. For example, phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, amine complex salts, etc. can be mentioned. These hardening accelerators can be used alone or in combination of two or more. Also, the addition amount of the hardening accelerator is preferably used in the range of 0.01 to 10% by mass in the solid content of the curable resin composition, for example.

[0057] As the ultraviolet absorber, for example, 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 and other triazine derivatives, 2-(2'-xanthene carboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthene carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. can be mentioned. These ultraviolet absorbers can be used alone or in combination of two or more.

[0058] Examples of the polymerization inhibitor include phenolic compounds such as p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline; quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone; and melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N-(1.(3-dimethylbutyl)-N’-phenyl-p-phenylenediamine, diphenylamine, 4,4’-dicumyl-diphenylamine, 4,4’-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction product of styrenated diphenylamine and 2,4,4-trimethylpentene, amine compounds such as reaction product of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl = bis[3-(dodecylthio)propionate], thioether compounds such as ditridecan-1-yl = 3,3’-sulfanediyldipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitroso benzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc., N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrodimethylamine, p-nitro-N,N-diethylamine, N-nitrosoethanolamine, N-nitroso-di-n-butylamine, N-nitroso-N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, dinitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N-n-propylurethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, ester of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecyl-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5) Phosphite compounds such as undecane, tris(nonylphenyl) phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylene tetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, etc., zinc compounds such as bis(dimethyldithiocarbamato-κ(2)S,S’)zinc, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, etc., nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S’)nickel, etc., 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, sulfur compounds such as dilauryl thiodipropionate, distearyl 3,3’-thiodipropionate, etc. These polymerization inhibitors can be used alone or in combination of two or more.

[0059] As the antioxidant, the same compounds as those exemplified for the polymerization inhibitor can be used, and the antioxidant can be used alone or in combination of two or more.

[0060] In addition, as commercially available products of the polymerization inhibitor and the antioxidant, for example, "Q-1300", "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., "Sumilizer BBM-S", "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd., etc. can be mentioned.

[0061] As the organic solvent, the same solvents as those exemplified as the above-mentioned organic solvents can be used, and the organic solvent can be used alone or in combination of two or more.

[0062] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc.

[0063] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0064] Examples of the inorganic pigment include, for example, white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, ultramarine blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0065] Examples of the white pigment include, for example, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc.

[0066] Examples of the organic pigment include, for example, quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more.

[0067] Examples of the flame retardant include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic phosphorus compounds such as amide phosphate; phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus compounds, and organic phosphorus compounds such as derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glasses. These flame retardants can be used alone or in combination of two or more. When using these flame retardants, it is preferably in the range of 0.1 to 20% by mass in the total resin composition.

[0068] The cured product of the present invention can be obtained by heating the curable resin composition.

[0069] Examples of the method of curing with heat include a method of performing in the range of a curing temperature of 80°C to 300°C, preferably 120°C to 250°C, in the presence of a catalyst for initiating thermal polymerization or an additive. After coating, casting, etc. are performed on the object to be coated, it may be cured by heating, or stepwise curing at various temperatures may be performed. Further, a sheet-like or coating film-like composition semi-cured at a temperature of about 50°C to 170°C may be stored and treated at the above-mentioned curing temperature when necessary.

[0070] The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, interior and exterior automotive materials, and OA equipment, as well as semiconductor devices, display devices, imaging devices, and the like.

Examples

[0071] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. It should be noted that the present invention is not limited to the following Examples.

[0072] (Example 1: Production of Resin (1)) To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 651 parts by mass of propylene glycol monomethyl ether acetate, 244 parts by mass of an isocyanurate-modified product of isophorone diisocyanate ("VESTANAT T-1890 / 100" manufactured by EVONIK, isocyanate group content 17.2% by mass), 250 parts by mass of 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and 1.1 parts by mass of dibutylhydroxytoluene were added and dissolved. Under a nitrogen atmosphere, the reaction was carried out at 140°C for 10 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less, and an amide-imide resin (A1) as an intermediate was obtained. To this amide-imide resin (A1), 43 parts by mass of n-butanol and 1.4 parts by mass of triphenylphosphine were added, and the reaction was carried out at 110°C for 5 hours to obtain the target resin (1). The non-volatile content of this resin (1) was 42% by mass, and the solid acid value was 140 mgKOH / g. The acid value was a value measured by the neutralization titration method of JIS K 0070 (1992). The number of moles of 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride with respect to 1 mole of the isocyanate group of the isocyanurate-modified product of isophorone diisocyanate was 1.03 moles.

[0073] (Example 2: Production of Resin (2)) To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 76 parts by mass of 2-ethylhexanol and 1.5 parts by mass of triphenylphosphine were added to 1086 parts by mass of the amide-imide resin (A1), and the mixture was reacted at 110 °C for 5 hours under a nitrogen atmosphere to obtain the target resin (2). The non-volatile content of this resin (2) was 44% by mass, and the solid acid value was 129 mgKOH / g.

[0074] (Example 3: Production of resin (3)) To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 607 parts by mass of propylene glycol monomethyl ether acetate, 244 parts by mass of an isocyanurate-modified product of isophorone diisocyanate (「VESTANAT T-1890 / 100」manufactured by EVONIK, isocyanate group content 17.2% by mass), 204 parts by mass of 1,2,3,4-butanetetracarboxylic dianhydride, and 1.0 part by mass of dibutylhydroxytoluene were added and dissolved. The mixture was reacted at 140 °C for 15 hours under a nitrogen atmosphere, and it was confirmed that the isocyanate group content was 0.1% by mass or less to obtain an amide-imide resin (A2) as an intermediate. To this amide-imide resin (A2), 43 parts by mass of n-butanol and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 °C for 5 hours to obtain the target resin (3). The non-volatile content of this resin (3) was 42% by mass, and the solid acid value was 164 mgKOH / g. The molar ratio of 1,2,3,4-butanetetracarboxylic dianhydride to 1 mole of the isocyanate groups of the isocyanurate-modified product of isophorone diisocyanate was 1.03 moles.

[0075] (Example 4: Production of resin (4)) To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 70 parts by mass of 2-ethylhexanol and 1.4 parts by mass of triphenylphosphine were added to 1012 parts by mass of the amide-imide resin (A2), and the mixture was reacted at 110 °C for 5 hours under a nitrogen atmosphere to obtain the target resin (4). The non-volatile content of this resin (4) was 44% by mass, and the solid acid value was 141 mgKOH / g.

[0076] (Example 5: Production of resin (5)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 473 parts by mass of diethylene glycol monoethyl ether acetate, 244 parts by mass of an isocyanurate-modified product of isophorone diisocyanate ("VESTANAT T-1890 / 100" manufactured by EVONIK, isocyanate group content 17.2% by mass), 171 parts by mass of 3-methyltetrahydrophthalic anhydride, and 1.1 parts by mass of dibutylhydroxytoluene were added and dissolved. The reaction was carried out at 140 °C for 42 hours under a nitrogen atmosphere. Next, 202 parts by mass of maleic anhydride was added, and after reacting at 200 °C for 5 hours, the pressure was reduced to recover unreacted maleic anhydride, and an amide-imide resin (A3) was obtained. To 1000 parts by mass of the amide-imide resin (A3), 40 parts by mass of n-butanol, 1.6 parts by mass of triphenylphosphine, and 40 parts by mass of diethylene glycol monoethyl ether acetate were added, and the reaction was carried out at 110 °C for 5 hours to obtain the target resin (5). The non-volatile content of this resin (5) was 50% by mass and the solid acid value was 108 mgKOH / g.

[0077] (Example 6: Production of Resin (6)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 43 parts by mass of n-butanol and 1.4 parts by mass of triphenylphosphine were added to 1086 parts by mass of the amide-imide resin (A1), and the reaction was carried out at 110 °C for 5 hours under a nitrogen atmosphere. Then, 126 parts by mass of propylene glycol monomethyl ether acetate and 41 parts by mass of phenyl glycidyl ether were added, and the reaction was carried out at 120 °C for 5 hours to obtain the target resin (6). The non-volatile content of this resin (6) was 40% by mass and the solid acid value was 100 mgKOH / g.

[0078] (Example 7: Production of Resin (7)) Into a flask equipped with a thermometer, a stirrer, and a reflux condenser, 460 parts by mass of propylene glycol monomethyl ether acetate, 74 parts by mass of 1,2,3,4-butanetetracarboxylic dianhydride, 0.9 parts by mass of dibutylhydroxytoluene, 144 parts by mass of trimellitic anhydride, 24 parts by mass of n-butanol, and 0.7 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120 °C for 5 hours under a nitrogen atmosphere. Next, 222 parts by mass of isophorone diisocyanate was added, and the reaction was carried out at 140 °C for 12 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 11 parts by mass of n-butanol and 14 parts by mass of propylene glycol monomethyl ether acetate were added, and the reaction was carried out at 110 °C for 4 hours to obtain the target resin (7). The non-volatile content of this resin (7) was 45% by mass, and the solid acid value was 118 mgKOH / g. The number of moles of 1,2,3,4-butanetetracarboxylic dianhydride per mole of the isocyanate group contained in isophorone diisocyanate was 0.19 mole.

[0079] (Example 8: Production of Resin (8)) To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 460 parts by mass of propylene glycol monomethyl ether acetate, 74 parts by mass of 1,2,3,4-butanetetracarboxylic dianhydride, 0.9 parts by mass of dibutylhydroxytoluene, 144 parts by mass of trimellitic anhydride, 24 parts by mass of n-butanol, and 0.7 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120 °C for 5 hours under a nitrogen atmosphere. Then, 222 parts by mass of isophorone diisocyanate was added, and the mixture was reacted at 140 °C for 12 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 11 parts by mass of n-butanol and 29 parts by mass of propylene glycol monomethyl ether acetate were added, and the mixture was reacted at 110 °C for 4 hours. Then, 13 parts by mass of phenyl glycidyl ether was added, and the mixture was reacted at 110 °C for 4 hours to obtain the target resin (8). The non-volatile content of this resin (8) was 45% by mass, and the solid acid value was 102 mgKOH / g. The number of moles of 1,2,3,4-butanetetracarboxylic dianhydride per mole of the isocyanate group of isophorone diisocyanate was 0.19 mole.

[0080] (Example 9: Production of Resin (9)) To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 820 parts by mass of propylene glycol monomethyl ether acetate, 244 parts by mass of an isocyanurate-modified product of isophorone diisocyanate (「VESTANAT T-1890 / 100」manufactured by EVONIK, isocyanate group content 17.2% by mass), 363 parts by mass of 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and 1.4 parts by mass of dibutylhydroxytoluene were added and dissolved. Under a nitrogen atmosphere, the mixture was reacted at 140 °C for 10 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 126 parts by mass of n-butanol and 2.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110 °C for 5 hours. Then, 69 parts by mass of propylene glycol monomethyl ether acetate and 54 parts by mass of phenyl glycidyl ether were added, and the mixture was reacted at 120 °C for 5 hours to obtain the target resin (9). The non-volatile content of this resin (9) was 45% by mass, and the solid content acid value was 140 mgKOH / g. The number of moles of 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride per mole of the isocyanate group possessed by the isocyanurate-modified product of isophorone diisocyanate was 1.5 moles.

[0081] (Comparative Example 1: Production of Resin (R1)) To a flask equipped with a thermometer, a stirrer, and a reflux condenser, 276 parts by mass of diethylene glycol monomethyl ether acetate, 146 parts by mass of an isocyanurate-modified product of isophorone diisocyanate (「VESTANAT T-1890 / 100」manufactured by EVONIK, isocyanate group content 17.2% by mass), and 125 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. Under a nitrogen atmosphere, the mixture was reacted at 140 °C for 4 hours, and it was confirmed that the isocyanate group content was 0.1% by mass or less. Next, 25 parts by mass of n-butanol was added, and the mixture was reacted at 120 °C for 2 hours to obtain resin (R1). The non-volatile content of this resin (R1) was 50% by mass, and the solid content acid value was 162 mgKOH / g.

[0082] (Example 10: Preparation of curable resin composition (1)) 100 parts by mass of the resin (1) with a nonvolatile content of 42% by mass obtained in Example 1 (42 parts by mass as solid content), 22.2 parts by mass of an epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214), 12 parts by mass of propylene glycol monomethyl ether acetate, and 1.28 parts by mass of imidazole as a thermosetting catalyst were mixed to obtain a curable resin composition (1).

[0083] (Examples 11 to 19: Preparation of curable resin compositions (2) to (10)) Curable resin compositions (2) to (10) were obtained in the same manner as in Example 10 at the compounding ratios shown in Table 1.

[0084] (Comparative Example 2: Preparation of curable resin composition (R1)) 100 parts by mass of the resin (R1) with a nonvolatile content of 50% by mass obtained in Comparative Example 1 (50 parts by mass as solid content), 30.6 parts by mass of an epoxy resin ("EPICLON N-680" manufactured by DIC Corporation, epoxy equivalent: 214), 16.5 parts by mass of propylene glycol monomethyl ether acetate, and 1.61 parts by mass of imidazole as a thermosetting catalyst were mixed to obtain a curable resin composition (R1).

[0085] Using the curable resin compositions obtained in the above Examples and Comparative Examples, the following evaluations were carried out.

[0086] [Evaluation method for heat resistance] The curable resin compositions obtained in each Example and Comparative Example were applied onto a copper foil ("F2-WS", electrolytic copper foil, 18 μm thick, manufactured by Furukawa Electric Co., Ltd.) using an applicator to a film thickness of 50 μm, and heated at 180°C for 2 hours to obtain a cured coating film. Then, the cured coating film was peeled off from the copper foil to obtain a cured product. A test piece of 6 mm × 35 mm was cut out from the cured product, and using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric, tensile method: frequency 1 Hz, heating rate 3°C / min), the temperature at which the change in elastic modulus was maximum was evaluated as the glass transition temperature. Note that the higher the glass transition temperature, the better the heat resistance.

[0087] [Method for Evaluating Adhesion] The adhesion was evaluated by measuring the peel strength. [Preparation of Test Specimen] The curable resin compositions obtained in the examples and comparative examples were applied onto a copper foil (manufactured by Furukawa Electric Co., Ltd., electrolytic copper foil "F2-WS" 18 μm) using a 50-μm applicator, and heated at 180°C for 2 hours to obtain test specimens.

[0088] [Method for Measuring Peel Strength] The test specimens were cut into a size of 1 cm in width and 12 cm in length, and the 90° peel strength was measured using a peel tester ("A&D tensilon" manufactured by A&D Company, Limited, peel rate 50 mm / min).

[0089] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (10) prepared in Examples 10 to 19, and the curable resin composition (R2) prepared in Comparative Example 2.

[0090]

Table 1

[0091] Note that the description of the parts by mass of the resin in Table 1 is based on the solid content value.

[0092] "Epoxy resin" in Table 1 indicates an ortho-cresol novolak type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation).

[0093] "Organic solvent" in Tables 1 and 2 indicates propylene glycol monomethyl ether acetate.

[0094] Examples 10 to 19 shown in Table 1 are examples using resins having at least one acid group and having an amide bond and / or an imide bond, and having a structure represented by any one of general formulas (1) to (6). It was confirmed that the cured product of the curable resin composition containing the resin of the present invention has excellent heat resistance, elasticity, and substrate adhesion.

[0095] On the other hand, Comparative Example 2 is an example using a resin having none of the structures represented by General Formulas (1) to (6). It was confirmed that the cured product of this curable resin composition was extremely insufficient in heat resistance, elasticity, and substrate adhesion.

Claims

Claim 1 A resin having at least one acid group and having an amide bond and / or an imide bond, characterized in that it has a structure represented by any one of the following general formulas (1) to (6). The resin is a resin using a reaction product (1) of a polyisocyanate compound and a bifunctional polybasic acid anhydride and a monohydric alcohol compound having 10 or less carbon atoms as essential raw materials. 【Chemical 1】 [In formulas (1) to (6), each A independently represents a benzene ring or an alicyclic ring, X represents any one of the following formulas (x-1), (x-8), (x-9), (x-13), (x-20), and (x-21), and each Y independently represents -OR １ or -NH-X-(Z) ｌ . n is an integer of 0 or 1 to 3, m is an integer of 0 or 1 to 3, and n + m is 2 or 3. Further, each of the R １ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, Z represents the following formula (z-1) or (z-2), and l is 1 or 2. In formulas (1) to (6), (z-1), and (z-2), at least one of the Ys is -OR １ , and at least one of the R １ is a hydrogen atom.] 【Chemical Formula 2】 [In formulas (x-1), (x-8), (x-9), (x-13), (x-20) and (x-21), "*" indicates a bonding point with a nitrogen atom.] 【Chemical Formula 3】 In formula (z-1), A is a benzene ring or an alicyclic ring, and Y is, independently of each other, -OR １ represents, and the R １ is, independently of each other, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In formula (z-1), "*" indicates the bonding point with X.] 【Chemical Formula 4】 [In formula (z-2), A is a benzene ring or an alicyclic ring, and Y is, independently of each other, -OR １ represents, and the said R １ is, independently of each other, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In formula (z-1), "*" indicates the bonding point with X.] Claim 2 The resin according to claim 1, wherein the bifunctional polybasic acid anhydride is a bifunctional aliphatic polybasic acid anhydride and / or a bifunctional alicyclic polybasic acid anhydride. Claim 3 The resin according to claim 1 or 2, wherein the amount of the bifunctional polybasic acid anhydride used is in the range of 0.1 to 5 moles per mole of the isocyanate group of the polyisocyanate compound. Claim 4 A curable resin composition comprising the resin according to any one of claims 1 to 3 and a curable resin. Claim 5 A cured product of the curable resin composition according to claim 4. Claim 6 An article having a coating film made of the cured product according to claim 5.

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