Polyamideimide (meth)acrylate resin, an active energy ray-curable resin composition using the same, and a cured product thereof

Abstract

To provide a polyamide-imide(meth)acrylate resin having excellent tackiness, hardness, curing shrinkage and moist heat resistance.SOLUTION: There is provided a polyamide-imide(meth)acrylate resin (A) which is obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule with a polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group obtained by the reaction of an alicyclic isocyanurate polyisocyanate (a1) and an alicyclic tricarboxylic acid anhydride (a2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyamideimide (meth) acrylate resin and an active energy ray-curable resin composition using the same. The polyamideimide (meth) acrylate resin of the present invention is suitably used as a binder resin, a crosslinking agent, and a hard coat material.

Background Art

[0002] It is important to form a crosslinked structure and cure a composition or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. The technology is used in various applications such as composite material matrices, casting materials, inks, coating agents, paints, adhesives, etc. in the housing field, civil engineering and construction field, electrical, electronic and information field, transportation field, etc., and is industrially very useful. In such a curable resin composition, by using a compound having a plurality of reactive functional groups, a cured product having a crosslinked structure formed after curing and having a high glass transition point (Tg) and excellent physical properties such as heat resistance and solvent resistance can be obtained.

[0003] Conventionally, (meth) acrylate oligomers and (meth) acrylate monomers have been widely used as curable resins. In particular, the development of epoxy (meth) acrylates and urethane (meth) acrylates has been actively carried out for the purpose of improving the flexibility and elastic modulus of the cured film.

[0004] For example, Patent Document 1 describes that a curable resin using a (meth) acrylate oligomer or a (meth) acrylate monomer is excellent in adhesion to a substrate, transparency, and curability. However, these curable resins have problems such as large curing shrinkage during curing, peeling from the substrate, and deformation of the cured product. Patent Document 2 describes that a curable resin using urethane (meth) acrylate or the like is excellent in suppressing flexibility and curing shrinkage, but has problems in hardness and heat and humidity resistance. Patent Document 3 shows that a cured resin using amideimide (meth) acrylate or the like is excellent in solvent solubility and heat resistance, but has a problem in heat and humidity resistance.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] In view of the above situation, an object of the present invention is to provide a polyamideimide (meth) acrylate resin excellent in tackiness, hardness, curing shrinkage property, and wet and heat resistance.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found that a polyamideimide (meth) acrylate resin (A) obtained by reacting a polyamideimide resin (a3) having a terminal acid group or acid anhydride group obtained by the reaction of an alicyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2) with a (meth) acrylate compound (b) having an epoxy group in one molecule is excellent in tackiness after drying, can be cured by irradiation with active energy rays, and can provide a curable composition having good hardness, curing shrinkage property, and wet and heat resistance after curing, and thus completed the present invention.

[0008] That is, the present invention relates to the following [1] to [5]. [1] A polyamideimide (meth) acrylate resin (A) obtained by reacting a polyamideimide resin (a3) having a terminal acid group or acid anhydride group obtained by the reaction of an alicyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2) with a (meth) acrylate compound (b) having an epoxy group in one molecule. The polyamide-imide (meth)acrylate resin (A) according to [1], wherein the molar ratio ((b) / (a2)) of the alicyclic tricarboxylic anhydride (a2) to the epoxy group-containing methacrylate compound (b) is 0.8 to 2.0. An active energy ray-curable resin composition containing the polyamide-imide (meth)acrylate resin (A) according to [1] or [2], a photopolymerization initiator (B), and an organic solvent (C). The active energy ray-curable resin composition according to [3], which contains a photopolymerizable monomer (D) other than the polyamide-imide (meth)acrylate resin (A). The active energy ray-curable resin composition according to [3] or [4], which is an active energy ray-curable resin composition for a hard coat material. A cured product of the active energy ray-curable resin composition according to any one of [3] to [5]. [Effects of the Invention]

[0009] According to the present invention, a polyamide-imide (meth)acrylate resin excellent in hardness, low curing shrinkage property, and wet heat resistance can be provided. [Embodiments for Carrying Out the Invention]

[0010] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an exemplification for explaining the present invention and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of its gist.

[0011] The present invention relates to a polyamide-imide (meth)acrylate resin (A) obtained by reacting a polyamide-imide resin (a3) having a terminal acid group or acid anhydride group, which is obtained by the reaction of an alicyclic isocyanurate-type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule.

[0012] The alicyclic isocyanurate type polyisocyanate (a1) is obtained by trimerizing a diisocyanate compound containing an alicyclic diisocyanate compound in the presence or absence of a trimerization catalyst.

[0013] In this specification, "alicyclic" means, in the context of the present invention, a compound in which carbon atoms are arranged in a ring (as already suggested by being the same as the description combining the two terms "aliphatic" and "cyclic"). Therefore, "alicyclic" is also a synonym for cycloaliphatic. As a result, alicyclic compounds belong to the group of homocyclic compounds and, in this case, include cycloalkanes, cycloalkenes, and cycloalkynes. Aromatic compounds, heterocyclic compounds, and saturated compounds of heterocyclic compounds are not considered to be alicyclic within the scope of the meaning of the present invention.

[0014] Examples of the diisocyanate compound containing the alicyclic diisocyanate compound include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like.

[0015] Examples of the trimerization catalyst include, without particular limitation, amine compounds such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts of carboxylic acids having 2 to 12 carbon atoms such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate; and quaternary ammonium salts of carboxylic acids. Commercially available products include DABCO P15 (manufactured by Sankyo Air Products), DABCO K15 (manufactured by Sankyo Air Products), PELCAT9540 (manufactured by Perron), DABCO TMR (manufactured by Sankyo Air Products), TOYOCAT TR20 (manufactured by Tosoh), U-CAT 18X (manufactured by San Apro), and the like.

[0016] Examples of the alicyclic isocyanurate type polyisocyanate (a1) include alicyclic isocyanurate type triisocyanates synthesized from isophorone diisocyanate (including polymers such as pentamers), alicyclic isocyanurate type triisocyanates synthesized from hydrogenated tolylene diisocyanate (including polymers such as pentamers), alicyclic isocyanurate type triisocyanates synthesized from hydrogenated xylene diisocyanate (including polymers such as pentamers), isocyanurate type triisocyanates synthesized from norbornane diisocyanate (including polymers such as pentamers), alicyclic isocyanurate type triisocyanates synthesized from hydrogenated diphenylmethane diisocyanate (including polymers such as pentamers), etc. Among them, the alicyclic isocyanurate type isocyanate synthesized from isophorone diisocyanate is preferred. By using the alicyclic isocyanurate type polyisocyanate (a1), a polyamideimide (meth)acrylate resin (A) excellent in tackiness and curing shrinkage can be obtained.

[0017] Examples of the alicyclic tricarboxylic anhydride (a2) include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferred. By using the alicyclic tricarboxylic anhydride (a2), a polyamideimide (meth)acrylate resin (A) excellent in tackiness and curing shrinkage can be obtained.

[0018] The reaction between the alicyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2) preferably satisfies that the total of the acid anhydride group and carboxylic acid is 1 mol or more, more preferably 1.2 mol or more, and still more preferably 1.4 mol or more, per 1 mol of the isocyanate group possessed by the alicyclic isocyanurate-type polyisocyanate (a1). By using 1.4 mol or more, the cured product obtained from the polyamideimide resin (a3) having terminal acid groups or acid anhydride groups has excellent hardness and tackiness. It is considered that this is because when using 1.4 mol or more, since it substantially does not contain urethane bonds, the reaction is easier to control.

[0019] As the (meth)acrylate (b) having an epoxy group in one molecule, other specific structures are not particularly limited as long as they have a (meth)acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. As an example, for instance, glycidyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, glycidyl group-containing (meth)acrylate monomers such as epoxycyclohexylmethyl (meth)acrylate; mono(meth)acrylated products of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, bisphenol diglycidyl ether, etc. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, (meth)acrylate compounds having one epoxy group are preferred because the reaction is easier to control, and glycidyl group-containing (meth)acrylate monomers are preferred from the viewpoints of reactivity and curability.

[0020] In the present invention, for the reaction of reacting the alicyclic isocyanurate type polyisocyanate (a1) with the alicyclic tricarboxylic anhydride (a2) to obtain the polyamideimide resin (a3) used in the present invention (hereinafter, also referred to as the amide-imidation reaction), it is preferable to use an organic solvent such as a solvent-free or an ester-based solvent having no hydroxyl group, a ketone-based solvent having no hydroxyl group, or an ether-based solvent having no hydroxyl group. An alcohol-based solvent having a hydroxyl group is not preferable because it reacts with isocyanate or acid anhydride. Examples of the ester-based solvent having no hydroxyl group include ethyl acetate, propyl acetate, and butyl acetate. Examples of the ketone-based solvent having no hydroxyl group include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Among these, examples of the ether-based solvent having no hydroxyl group include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and triethylene glycol monobutyl ether acetate; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether;Polypropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; Polypropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate; Or dialkyl ethers of copolymer polyether glycols such as low molecular weight ethylene-propylene copolymers, and monoacetate monoalkyl ethers of copolymer polyether glycols; Or alkyl esters of such polyether glycols; Monoalkyl ester monoalkyl ethers of polyether glycols, etc.

[0021] The amidation reaction is preferably carried out by mixing one or more of the alicyclic isocyanurate type polyisocyanates (a1) and one or more of the alicyclic tricarboxylic anhydrides (a2) in a solvent or without a solvent, and heating while stirring.

[0022] The reaction temperature of the amidation reaction is preferably in the range of 50°C to 250°C, particularly preferably in the range of 70°C to 180°C. By setting the reaction temperature in such a range, the reaction rate can be increased. The reaction involves the formation of imide groups from anhydride groups and isocyanate groups with decarboxylation, and the formation of amide groups from carboxylic acid groups and isocyanates. During the reaction, antioxidants, leveling agents, defoaming agents, surfactants, etc. can be used as needed.

[0023] The progress of the amidation reaction can be traced by analytical means such as infrared spectra, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and quantification of isocyanate groups. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm -1 decreases with the reaction, and furthermore, the acid anhydride group having characteristic absorption at 1860 cm -1 and 850 cm -1 decreases. On the other hand, the absorption of the imide group increases at 1780 cm -1 and 1720 cm -1 It is preferable to proceed the reaction until the characteristic absorption of the isocyanate group at 2250 cm -1 disappears, as it is easy to control the reaction.

[0024] The reaction of the polyamideimide resin (a3) having the terminal acid group or acid anhydride group with the (meth)acrylate compound (b) having an epoxy group in one molecule is preferably carried out in the above organic solvent or in the absence of a solvent.

[0025] It is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction during the reaction. The amount is 0.001 to 1 part by mass based on 100 of the total amount of the reaction product obtained by adding the (meth)acrylate compound (b) having an epoxy group in one molecule and a solvent to the polyamideimide resin (a3). Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, and the like.

[0026] Also, it is preferable to use a catalyst to promote the reaction during the reaction. The amount of the catalyst used is 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the reaction product obtained by adding a (meth)acrylate compound (b) having an epoxy group in one molecule and a solvent to the partial polyamideimide resin (a3). The reaction temperature at that time is 60 to 150°C, and the reaction time is preferably 3 to 60 hours. Examples of the catalyst used in this reaction include dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium 2-ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethyl sulfide, diphenyl sulfide, and the like.

[0027] The progress of the reaction can be traced by analytical means such as infrared spectrum, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and quantification of epoxy groups. It is preferable to stop the reaction when the consumption of epoxy groups converted from the epoxy equivalent is 95% or more from the viewpoint of storage stability.

[0028] Also, from the viewpoints of hardness and curability, the molar ratio ((b) / (a2)) of the (meth)acrylate (b) having an epoxy group in one molecule to the alicyclic tricarboxylic anhydride (a2) is preferably 0.8 to 2.0. More preferably, it is 0.9 to 1.80, and even more preferably, it is 1.0 to 1.5. When ((b) / (a2)) is 0.8 to 2.0, a polyamideimide (meth)acrylate resin (A) excellent in curability, hardness, and tackiness can be obtained. On the other hand, when ((b) / (a2)) is less than 0.8, the curability and hardness are likely to decrease, and when ((b) / (a2)) is greater than 2.0, the hardness and tackiness are likely to decrease.

[0029] In the active energy ray-curable resin composition of the present invention, it is more preferable from the viewpoints of hardness and curability that the polyamideimide (meth) acrylate resin (A) is 50 to 100 parts by mass with respect to 100 parts by mass of the solid content in the composition excluding solvents and the like.

[0030] Also, a photopolymerization initiator (B) can be used as necessary. The amount of the photopolymerization initiator used can be 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin composition. Specific examples of the photopolymerization initiator (B) include, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bis(methylamino)benzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0031] In the active energy ray-curable resin composition of the present invention, an organic solvent (C) can be used as necessary. Specifically, in addition to ester solvents, ketone solvents, and ether solvents, alcohols or phenols such as ethanol, isopropanol, and phenol, alkoxy alcohols such as 2-ethoxyethanol and 1-methoxy-2-propanol, glycol oligomers such as diethylene glycol and tripropylene glycol; water-soluble organic solvents such as alkoxy alcohol esters such as 2-ethoxyethyl acetate can also be used.

[0032] In the active energy ray-curable resin composition of the present invention, a photopolymerizable monomer (D) can be used from the viewpoints of curability, plasticity, and solvent compatibility. The polyamideimide (meth)acrylate resin (A) is not included in the photopolymerizable monomer (D). The photopolymerizable monomer (D) can be used in an amount of 0 to 50 parts by mass based on 100 parts by mass of the solid content in the composition excluding solvents and the like.

[0033] The photopolymerizable monomer (D) other than the polyamideimide (meth)acrylate resin (A) includes monomers or oligomers that are cured by ultraviolet rays, heat, etc. to form a resin, and these can be used alone or in combination of two or more.

[0034] Examples of the photopolymerizable monomer (D) include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0035] Examples of the monofunctional (meth)acrylates include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, biphenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethylene glycol (meth)acrylate, 2-ethylhexyl ethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, biphenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclodecyloxyethyl (meth)acrylate, nonylphenoxyethylene glycol (meth)acrylate, nonylphenoxypropylene glycol, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc., (meth)acryloylmorpholine (morpholino(meth)acrylate), (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-isobutyl(meth)acrylamide, N-t-butyl(meth)acrylamide, N-t-octyl(meth)acrylamide, diacetone(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-triphenylmethyl(meth)acrylamide, N,(Meth)acrylamides such as N-dimethyl(meth)acrylamide, aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, butadiene or substituted butadiene compounds such as butadiene, isoprene, ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, acrylonitrile; monomers such as vinyl esters such as vinyl acetate, etc. are included.

[0036] Examples of the polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of ε-caprolactone adduct of hydroxybivalic acid neopentyl glycol, poly(meth)acrylate of reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethanolamine tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, etc.

[0037] Furthermore, various additives may be used as required, for example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, thixotropy imparting agents such as nanosilica, Carboxylic acids such as phthalic acid, adipic acid, succinic acid, phosphoric acid, trimellitic acid, or plasticizers such as their esters, leveling agents such as silicone and fluorine-based agents, defoaming agents, and antistatic agents. Conductive metal oxides selected from the group consisting of titanium, zinc, zirconium, antimony, indium, tin, silicon, and aluminum, and colorants such as phthalocyanine blue, phthalocyanine green, carbon black, and titanium oxide. Polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be added for the purpose of enhancing various properties of the composition.

[0038] The cured product of the present invention is obtained by curing the above resin composition of the present invention by irradiation with energy rays such as ultraviolet rays and electron beams. Curing by irradiation with energy rays such as ultraviolet rays can be carried out by a conventional method. For example, when irradiating ultraviolet rays, an ultraviolet ray generating device such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or an ultraviolet light-emitting laser (excimer laser, etc.) can be used.

[0039] The polyamideimide (meth) acrylate resin of the present invention is excellent in tackiness, hardness, curing shrinkage, and heat and humidity resistance, and is therefore suitably used as a binder resin, a crosslinking agent, and a hard coat material. Applications of the cured product of the present invention include automobiles, home electric appliances such as computers and displays, and portable devices such as mobile phones.

Examples

[0040] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[0041] Production Example 1 Into a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen line, 287.2 g of methyl isobutyl ketone, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (''VESTANATT-1890 / 100'' manufactured by EVONIK, isocyanate group content: 17.3% by mass), and 188.1 g (0.95 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116°C and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1 which is the characteristic absorption of the isocyanate group had completely disappeared. A solid acid value of 160 mgKOH / g and a solution of amide-imide resin intermediate (1) with a number average molecular weight of 1251 and a weight average molecular weight of 3680 based on polystyrene by gel permeation chromatography were obtained. After cooling to 60°C, 332.5 g of methyl isobutyl ketone, 184.6 g (1.30 mol) of glycidyl methacrylate, and 1.7 g of dibutylhydroxytoluene were added and stirred for a while, then 1.7 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was carried out at the same temperature for 10 hours to obtain a polyamide-imide (meth)acrylate resin (I) with a solid acid value of 12 mgKOH / g, a number average molecular weight of 2027, and a weight average molecular weight of 5520 by gel permeation chromatography.

[0042] Production Example 2 Into a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen line, 411.1 g of methyl isobutyl ketone, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (''VESTANATT-1890 / 100'' manufactured by EVONIK, isocyanate group content: 17.3% by mass), and 168.2 g (0.85 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116°C and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1It was confirmed that the absorption of [] had completely disappeared. An amide-imide resin intermediate (1) solution with a number average molecular weight of 1,420 and a weight average molecular weight of 4,120 by gel permeation chromatography using polystyrene as a standard and a solid acid value of 120 mgKOH / g was obtained. After cooling to 60 °C, 188.8 g of methyl isobutyl ketone, 168.3 g (0.95 mol) of glycidyl methacrylate, and 1.7 g of dibutylhydroxytoluene were added and stirred for a while, and then 1.7 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 14 hours to obtain a polyamide-imide (meth)acrylate resin (II) with a solid acid value of 35 mgKOH / g, a number average molecular weight of 2,250, and a weight average molecular weight of 6,840 by gel permeation chromatography.

[0043] Production Example 3 To a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 124.5 g of methyl isobutyl ketone, 65.6 g of an isocyanurate-modified product of isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3 mass%), and 58.8 g (1.1 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116 °C and the reaction was carried out at the same temperature for 24 hours. The absorption at 2250 cm -1 which is the characteristic absorption of the isocyanate group was confirmed to have completely disappeared by infrared spectrum. An amide-imide resin intermediate (1) solution with a number average molecular weight of 1,170 and a weight average molecular weight of 3,520 by gel permeation chromatography using polystyrene as a standard and a solid acid value of 170 mgKOH / g was obtained. After cooling to 60 °C, 75.5 g of methyl isobutyl ketone, 74.2 g (1.4 mol) of 3,4-epoxycyclohexylmethyl methacrylate, and 0.2 g of dibutylhydroxytoluene were added and stirred for a while, and then 0.2 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 14 hours to obtain a polyamide-imide (meth)acrylate resin (III) with a solid acid value of 20 mgKOH / g, a number average molecular weight of 1,820, and a weight average molecular weight of 4,440.

[0044] Production Example 4 To 203.8 g of methyl isobutyl ketone, 56.8 g (0.4 mol) of glycidyl methacrylate, and 1.4 g of dibutylhydroxytoluene were added to the amide-imide resin intermediate (1) obtained in Production Example 1, and the mixture was stirred for a while. Then, 1.4 g of triphenylphosphine was added, and the temperature was raised to 116°C. The reaction was carried out at the same temperature for 10 hours to obtain a polyamide-imide (meth)acrylate resin (IV) with a solid acid value of 142 mgKOH / g, a number average molecular weight of 1560, and a weight average molecular weight of 4050 by gel permeation chromatography.

[0045] Production Example 5 To 179.1 g of methyl isobutyl ketone, 36 g (0.25 mol) of 4-hydroxylbutyl acrylate, and 1.2 g of dibutylhydroxytoluene were added to the amide-imide intermediate obtained in Production Example 1, and the mixture was stirred for a while. Then, the temperature was raised to 100°C. The reaction was carried out at the same temperature for 5 hours to obtain a polyamide-imide (meth)acrylate resin (V) with a solid acid value of 175 mgKOH / g, a number average molecular weight of 1265, and a weight average molecular weight of 3750 by gel permeation chromatography.

[0046] Formulation of Resin Composition and Preparation of Test Films The polyamide-imide (meth)acrylate resins obtained in Production Examples 1 to 5 were formulated in the compositions shown in Table 1 to obtain Examples and Comparative Examples.

[0047]

Table 1

[0048] Each evaluation item will be described in detail. (Tackiness) The resin composition with a solid content concentration of 20% was applied to an easy-adhesion polyester film (manufactured by Toyobo Co., Ltd.: A-4300, film thickness 100 μm) using a bar coater No. 16 and dried in an oven at 105°C for 2 minutes. After drying, the coated film was touched with a finger and evaluated according to the following criteria. Evaluation: No tackiness: ○ The resin adheres to the finger or the coated film deforms: ×

[0049] After drying, it was irradiated with 300 mJ / cm 2 using a conveyor-type UV exposure machine to obtain a coating film with a cured film (5 μm).

[0050] (Pencil hardness) The dried coating film was irradiated with 300 mJ / cm 2 using a conveyor-type UV exposure machine to obtain a coating film with a cured film (5 μm). According to JIS K 5400, the pencil hardness of the coating film was measured using a pencil scratch. That is, on the polyester film with the cured film to be measured, a pencil was scratched at an angle of 45 degrees from above with a load of 1 kg for about 5 mm, and the hardness of the pencil that did not cause scratches was confirmed.

[0051] (Curing shrinkage) The polyester film with the cured film to be measured was cut into 6 cm × 6 cm, left in a drying oven at 80°C for 1 hour, and then returned to room temperature. The height of each of the four floating sides on a horizontal table was measured. When the total value was less than 10 mm, it was ○; when it was 10 mm or more and less than 20 mm, it was △; when it was 20 mm or more, it was ×. At this time, the curl of the substrate itself was 0 mm.

[0052] (Moisture and heat resistance) The coating film was left standing in a damp heat oven at 60°C and 90% RH for 200 hours, and then checked for any peeling, whitening, or cracking. Evaluation: No abnormality: ○ Presence of peeling or whitening: ×

[0053]

Table 2

[0054] From the results in Table 2 above, it can be seen that the polyamideimide (meth)acrylate resin (A) of the present invention and its composition are excellent in tackiness, hardness, curing shrinkage, and moisture and heat resistance. Therefore, they are suitably used as binder resins, crosslinking agents, and hard coat materials.

Claims

1. A polyamideimide (meth)acrylate resin (A) obtained by reacting a polyamideimide resin (a3) having terminal acid groups or acid anhydride groups, which is obtained by the reaction of an alicyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2), only with a (meth)acrylate compound (b) having an epoxy group in one molecule, wherein the molar ratio ((b) / (a2)) of the alicyclic tricarboxylic anhydride (a2) to the epoxy group-containing methacrylate compound (b) is 0.8 to 2.

0.

2. An active energy ray-curable resin composition containing the polyamideimide (meth)acrylate resin (A) according to Claim 1, a photopolymerization initiator (B), and an organic solvent (C).

3. The active energy ray-curable resin composition according to Claim 2, which contains a photopolymerizable monomer (D) other than the polyamideimide (meth)acrylate resin (A).

4. The active energy ray-curable resin composition according to Claim 2 or 3, which is an active energy ray-curable resin composition for a hard coat material.

5. A cured product of the active energy ray-curable resin composition according to any one of Claims 2 to 4.

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