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

Abstract

The purpose of this invention is to provide a polyamide imine (meth)acrylate resin with excellent adhesiveness, hardness, curing shrinkage, and resistance to damp heat. The present invention provides a polyamide imine (meth)acrylate resin (A), which is obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule with a polyamide resin (a3) ​​having an acid group or anhydride group at the end, obtained by reacting an alicyclic isocyanate type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2).

Description

Polyamide imine (meth)acrylate resin, active energy line curable resin composition using the same, and cured products thereof This invention relates to polyamide-imide (meth)acrylate resin and active energy line-curing resin compositions using the polyamide-imide (meth)acrylate resin. The polyamide-imide (meth)acrylate resin of this invention is suitable for use in adhesive resins, crosslinking agents, and hard coating materials. The use of irradiation with active energy beams such as ultraviolet light or electron beams to form cross-linked structures and harden compositions is of great importance. This technology is used in various applications such as composite material matrices, injection molding materials, inks, coatings, paints, and adhesives in residential construction, civil engineering and building, electrical and electronic and information technology, and transportation, making it extremely useful in industry. In this type of curable resin composition, by using compounds with multiple reactive functional groups, a cross-linked structure is formed after curing, increasing the glass transition point (Tg) and resulting in cured products with excellent heat resistance or solvent resistance. In the past, (meth)acrylate oligomers or (meth)acrylate monomers have been widely used as curing resins, especially for improving the softness or elastic modulus of the cured film. There has been active development of (meth)acrylate epoxy esters or aminocarbamate (meth)acrylates. For example, Patent Document 1 describes a curing resin using (meth)acrylate oligomers or (meth)acrylate monomers that exhibits excellent adhesion, transparency, and curability to the substrate. However, these curing resins suffer from significant curing shrinkage, leading to issues such as peeling from the substrate or deformation of the cured product. Patent Document 2 describes a curing resin using aminoformic acid (meth)acrylate, which is excellent in terms of flexibility and suppression of curing shrinkage; however, issues remain regarding hardness and resistance to damp heat. Patent Document 3 discloses a curing resin using amide-imid (meth)acrylate, which exhibits excellent solvent solubility and heat resistance; however, issues remain regarding resistance to damp heat. [Previous Technical Documents] [Patent Literature] [Patent Document 1] Japanese Patent Application Publication No. 2012-144641 [Patent Document 2] Japanese Patent No. 2964267 [Patent Document 3] Japanese Patent No. 6669311 In view of the above-mentioned situation, the present invention aims to provide a polyamide imine (meth)acrylate resin with excellent adhesiveness, hardness, curing shrinkage, and resistance to damp heat. Through careful investigation, the inventors discovered that a polyamide-imide (meth)acrylate resin (A) obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule with a polyamide resin (a3) ​​having an acid group or anhydride group at the end, obtained by reacting an alicyclic isocyanate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), can provide a curable composition with excellent adhesive properties after drying, which can be cured by irradiation with an active energy line, and has good hardness, curing shrinkage, and resistance to damp heat after curing. Thus, the present invention is completed. That is, the present invention relates to the following [1] to [5]. [1] A polyamide imine (meth)acrylate resin (A) is obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule with a polyamide imine resin (a3) ​​having an acid group or anhydride group at the end, obtained by reacting an alicyclic isocyanate type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2). [2] The polyamide imine (meth) acrylate resin (A) as described in [1], wherein the molar ratio ((b) / (a2)) of the aforementioned epoxy-containing methacrylate compound (b) to the aforementioned alicyclic tricarboxylic acid anhydride (a2) is 0.8 to 2.0. [3] An active energy line curing resin composition comprising: polyamide imine (meth) acrylate resin (A) as described in [1] or [2], a photopolymerization initiator (B) and an organic solvent (C). [4] The active energy line curing resin composition described in [3] contains photopolymerizable monomers (D) other than the aforementioned polyamide imine (meth) acrylate resin (A). [5] The active energy line curing resin composition as described in [3] or [4] is an active energy line curing resin composition for hard coating materials. [6] A hardener, which is a hardener of the active energy line hardening resin composition described in any one of [3] to [5]. According to the present invention, a polyamide imide (meth) acrylate resin with excellent hardness, low curing shrinkage and resistance to damp heat can be provided. The following is a detailed description of the embodiments used to implement the present invention (hereinafter referred to as "the embodiments"). The embodiments described below are illustrative of the invention and are not intended to limit the invention to these contents. The invention can be appropriately modified and implemented within the scope of this spirit. This invention relates to a polyamide imine (meth)acrylate resin (A), which is obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule with a polyamide imine resin (a3) ​​having an acid group or anhydride group at the end, obtained by reacting an alicyclic isocyanate type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2). The aforementioned alicyclic isocyanate-type polyisocyanate (a1) is obtained by isocyanating a diisocyanate compound containing an alicyclic diisocyanate compound in the presence or absence of a trimerizing catalyst. In this specification, the term "alicyclic" refers to compounds in the context of this invention, specifically compounds in which carbon atoms are arranged in a ring (as implied by the juxtaposition of the terms "alicyclic" and "cyclic"). Therefore, "alicyclic" is also synonymous with cyclic aliphatic compounds. Consequently, alicyclic compounds belong to the group of allocyclic compounds, which in this case includes cycloalkanes, cycloalkenes, and cycloalkynes. Aromatic compounds, heterocyclic compounds, and saturated examples of heterocyclic compounds are not considered alicyclic within the scope of this invention. Examples of the aforementioned diisocyanate compounds containing alicyclic diisocyanates include: isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate. The aforementioned trimerizing catalysts are not specifically designated, but examples include: 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-tris(dimethylaminomethyl)phenol. Amine compounds; alkali metal salts of carboxylic acids with 2 to 12 carbon atoms, such as potassium acetate, potassium 2-ethylhexanoate, and potassium octanoate; and fourth-order ammonium salts of carboxylic acids. Commercially available examples include: DABCO P15 (manufactured by Sankyo Film & Air Products), DABCO K15 (manufactured by Sankyo Film & Air Products), PELCAT 9540 (manufactured by Perlon), DABCO TMR (manufactured by Sankyo Film & Air Products), TOYOCAT TR20 (manufactured by Tosoh), and U-CAT 18X ​​(manufactured by Sun Apro). Examples of the aforementioned alicyclic isocyanate-type polyisocyanates (a1) include: alicyclic isocyanate-type triisocyanates (including polymers such as pentamers) synthesized from isophorone diisocyanate; alicyclic isocyanate-type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated toluene diisocyanate; alicyclic isocyanate-type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated xylene diisocyanate; isocyanate-type triisocyanates (including polymers such as pentamers) synthesized from norbornene diisocyanate; and alicyclic isocyanate-type triisocyanates (including polymers such as pentamers) synthesized from hydrogenated diphenylmethane diisocyanate. Among these, alicyclic isocyanate-type isocyanates synthesized from isophorone diisocyanate are preferred. By using the aforementioned alicyclic isocyanate-type polyisocyanate (a1), a polyamide imine (meth) acrylate resin (A) with excellent adhesiveness or curing shrinkage is obtained. Examples of the aforementioned alicyclic tricarboxylic anhydrides (a2) include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, and cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride. Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferred. By using the aforementioned alicyclic tricarboxylic anhydride (a2), a polyamide-imide (meth)acrylate resin (A) with excellent adhesive properties or curing shrinkage is obtained. In the reaction between the aforementioned alicyclic isocyanate-type polyisocyanate (a1) and the aforementioned alicyclic tricarboxylic acid anhydride (a2), the total amount of anhydride groups and carboxylic acid groups is preferably 1 mol or more, more preferably 1.2 mol or more, and even more preferably 1.4 mol or more, relative to 1 mol of isocyanate groups in the aforementioned alicyclic isocyanate-type polyisocyanate (a1). When using 1.4 mol or more, the polyamide-imide resin (a3) ​​with acid or anhydride groups at the ends exhibits excellent hardness or adhesiveness of the resulting cured product. This can be considered because when using 1.4 mol or more, since it essentially does not contain urethane bonds, the reaction is easier to control. The aforementioned (meth)acrylate compound (b) containing an epoxy group in one molecule is not particularly limited in its specific structure, as long as it contains both a (meth)acrylic group and an epoxy group in its molecular structure; various compounds can be used. Examples include: glycidyl (meth)acrylate monomers containing a glycidyl group, such as 4-hydroxybutyl (meth)acrylate glycidyl ether and epoxycyclohexyl methyl (meth)acrylate; and mono(meth)acrylate compounds containing dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, (meth)acrylate compounds with one epoxy group are preferred because the reaction is easier to control; and from the viewpoint of reactivity and curing properties, (meth)acrylate monomers containing a glycidyl group are preferred. In this invention, the reaction of the aforementioned alicyclic isocyanate-type polyisocyanate (a1) with alicyclic tricarboxylic anhydride (a2) to obtain the polyamide-imide resin (a3) ​​used in this invention (hereinafter also referred to as amide-imide reaction) is preferably solvent-free or uses organic solvents such as esters, ketones, or ethers without hydroxyl groups. Alcohol solvents with hydroxyl groups will react with isocyanates or anhydrides, and are therefore undesirable. Examples of ester solvents without hydroxyl groups include ethyl acetate, propyl acetate, and butyl acetate. Examples of ketone solvents without hydroxyl groups include acetone, butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Among them, ether solvents without hydroxyl groups include: ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and other ethylene glycol dialkyl ethers; 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, triethylene glycol dibutyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 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, triethylene glycol monobutyl ether acetate; and propylene glycol dialkyl ethers such as dimethyl ether, diethyl ether, and 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, and tripropylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 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, and tripropylene glycol monobutyl ether acetate; or dialkyl ethers of copolymerized polyether glycols such as low-molecular-weight ethylene-propylene copolymers, or monoacetate monoalkyl ethers of copolymerized polyether glycols; or alkyl esters of such polyether glycols; monoalkyl ester monoalkyl ethers of polyether glycols, etc. The aforementioned amide imide reaction is preferably carried out in a solvent or without solvent by mixing one or more of the aforementioned alicyclic isocyanate-type polyisocyanates (a1) and one or more of the aforementioned alicyclic tricarboxylic anhydrides (a2) while stirring and heating. The preferred reaction temperature for the aforementioned amide amide imidization reaction is in the range of 50°C to 250°C, and particularly preferably in the range of 70°C to 180°C. Setting the reaction temperature within this range results in an increased reaction rate. The reaction involves decarbonation while simultaneously allowing the anhydride group to form an amide group with the isocyanate group, and the carboxylic acid group to form an amide group with the isocyanate group. Antioxidants, leveling agents, defoamers, surfactants, etc., can be used during the reaction as needed. The aforementioned amide amide imidization reaction can be tracked using infrared spectroscopy, or analytical methods such as acid value analysis, gel permeation chromatography, liquid chromatography, gas chromatography, ¹H NMR, C NMR, and quantitative analysis of isocyanate groups. In infrared spectroscopy, the characteristic absorption of the isocyanate group is at 2250 cm⁻¹. -1 The amount decreases as the reaction proceeds, and reaches 1860 cm⁻¹. -1 With 850cm -1 The absorption of acid anhydride groups with characteristic absorption is reduced. On the other hand, the absorption of amide groups is at 1780 cm⁻¹. -1 With 1720cm -1 Increase. The reaction proceeds until the characteristic absorption as an isocyanate group reaches 2250 cm⁻¹. -1 Those that disappear completely are easier to control and are therefore better. The reaction of a (meth)acrylate compound (b) having an epoxy group in one molecule with the aforementioned polyamide imine resin (a3) ​​having an acid group or an anhydride group at the end is preferably carried out in the aforementioned organic solvent or in a solvent-free environment. To suppress the thermal polymerization reaction during the reaction, it is preferable to add a thermal polymerization inhibitor, which is 0.001 to 1 part by mass relative to 100 parts by mass of the reactants, namely, a (meth)acrylate compound (b) having an epoxy group in one molecule and a solvent, added to the polyamide-imide resin (a3). Examples of thermal polymerization inhibitors include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-bis(tert-butyl)-p-cresol. Furthermore, to promote the reaction, a catalyst is preferably used. The amount of catalyst is 0.001 to 1 part by mass relative to 100 parts by mass of the reactants (a molecule of an epoxy group-containing (meth)acrylate compound (b) and solvent added to the polyamide-imide resin (a3). The reaction temperature is 60 to 150°C, and the reaction time is preferably 3 to 60 hours. Examples of catalysts used in this reaction include: dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstirium hydrogen, methyltriphenylstirium hydrogen, chromium 2-ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethyl sulfide, diphenyl sulfide, etc. The reaction can be tracked using infrared spectroscopy, or analytical methods such as acid value, gel permeation chromatography, liquid chromatography, gas chromatography, ¹H NMR, C NMR, and quantitative analysis of epoxy groups. From a stability perspective, it is best to stop the reaction when the consumption of epoxy groups (converted from epoxy equivalents) reaches 95% or more. Furthermore, from the viewpoint of hardness or curability, a molar ratio ((b) / (a2)) of 0.8 to 2.0 between the aforementioned (meth)acrylate (b) having an epoxy group in one molecule and the aforementioned alicyclic tricarboxylic acid anhydride (a2) is preferred. A ratio of 0.9 to 1.80 is particularly preferred, and 1.0 to 1.5 is even more preferred. When ((b) / (a2)) is 0.8 to 2.0, a polyamide-imide (meth)acrylate resin (A) with excellent curability, hardness, and adhesiveness is obtained. On the other hand, when ((b) / (a2)) is less than 0.8, curability or hardness tends to decrease; when ((b) / (a2)) is greater than 2.0, hardness or adhesiveness tends to decrease. In the active energy line curing resin composition of the present invention, it is particularly preferable from the viewpoint of hardness or curability if the aforementioned polyamide imine (meth) acrylate resin (A) is 50 to 100 parts by mass relative to 100 parts by mass of solids in the composition excluding solvents, etc. In addition, a photopolymerization initiator (B) may be used as needed. The amount of photopolymerization initiator may be 0.01 to 10 parts by weight relative to 100 parts by weight of the total resin composition. Specific examples of photopolymerization initiators (B) include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and other benzoin derivatives; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, and other acetophenone derivatives; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone, and other anthraquinone derivatives; 2,4-diethylthioxanthone, 2,4-diethylthioxanthone, and other anthraquinone derivatives; and 2,4-diethylthioxanthone, 2-ethylthioxanthone, etc. Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and other thioxanthone derivatives; acetals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; diphenyl ketones such as benzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 4,4'-dimethylaminodiphenyl ketone; phosphine oxides such as 2,4,6-trimethylbenzyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, etc. In the active energy line curing resin composition of the present invention, organic solvents (C) may be used as needed. Specifically, in addition to ester solvents, ketone solvents, and ether solvents, the following may also be used: ethanol, isopropanol, alcohols or phenols such as phenols; alkoxyols such as 2-ethoxyethanol and 1-methoxy-2-propanol; diol oligomers such as diethylene glycol and tripropylene glycol; and water-soluble organic solvents such as alkoxyol esters such as 2-ethoxyethyl acetate. Furthermore, in the active energy line curing resin composition of the present invention, from the viewpoint of curability or plasticity and solvent compatibility, a photopolymerizable monomer (D) can be used. The photopolymerizable monomer (D) does not contain polyamide amide (meth)acrylate resin (A). The photopolymerizable monomer (D) can be used in 0 to 50 parts by weight relative to 100 parts by weight of solids in the composition excluding solvents, etc. The photopolymerizable monomers (D) other than the aforementioned polyamide imine (meth)acrylate resin (A) include monomers or oligomers that are cured by ultraviolet light or heat to form resins, and these can be used alone or in combination of two or more. Examples of the aforementioned photopolymerizable monomers (D) include monofunctional (meth)acrylates and polyfunctional (meth)acrylates. Examples of monofunctional (meth)acrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl methacrylate, biphenyl methacrylate, methoxyethyl methacrylate, etc. Ethoxyethyl acrylate, Butoxyethylene glycol (meth)acrylate, 2-Ethylhexyl ethylene glycol (meth)acrylate, Methoxypropylene glycol (meth)acrylate, Phenoxyethyl acrylate, Biphenoxyethyl acrylate, Dicyclopentenyl acrylate, Tricyclodecyl acrylate, Dicyclopentenyl acrylate, Tricyclodecyl acrylate, Nonylphenoxyethylene glycol (meth)acrylate, Nonylphenoxypropylene glycol (meth)acrylate, (meth)acrylate Benzyl acrylate, 2-hydroxyethyl methacrylate, and other methacrylates; methacrylamide (methacrylamide morpholine); methacrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-isobutyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-tert-octyl(meth)acrylamide, diacetone(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, etc. Monomers including (meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-triphenylmethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, etc.; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, acrylonitrile, etc.; and vinyl esters such as vinyl acetate. Examples of such multifunctional (meth)acrylates include: butanediol dimethacrylate, hexanediol dimethacrylate, neopentyl glycol dimethacrylate, nonanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. Acrylic esters, tri(meth)acrylic acid oxyethyl ester, polypropylene glycol di(meth)acrylate, di(meth)acrylate adipate epoxy ester, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of the ε-caprolactone adduct of neopentyl glycol hydroxytrimethylacetic acid, poly(meth)acrylate of the reaction product of dinepentylenetetrol and ε-caprolactone, poly(meth)acrylate dinepentylenetetrol ester, tri(meth)acrylate trimethylolpropane ester, tri(meth)acrylate triethylolpropane ester or its ethylene oxide adduct, tri(meth)acrylate neopentylenetetrol ester or its ethylene oxide adduct, tetra(meth)acrylate neopentylenetetrol ester or its ethylene oxide adduct, hexa(meth)acrylate dinepentylenetetrol ester or its ethylene oxide adduct, etc. Furthermore, various additives may be added as needed to improve the various properties of the composition, such as: fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, alumina, silicon dioxide, and clay; rheology modifiers such as nano-silica; plasticizers such as phthalic acid, adipic acid, succinic acid, phosphoric acid, and trimellitic acid; leveling agents, defoamers, or anti-static agents such as polysiloxane and fluorine compounds; conductive metal oxides selected from the group consisting of titanium, zinc, zirconium, antimony, indium, tin, silicon, and aluminum; colorants such as phthalocyanine blue, phthalocyanine green, carbon black, and titanium dioxide; and polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether. The cured product of this invention refers to the resin composition of this invention that is cured by irradiation with energy rays such as ultraviolet light or electron beams. Curing by irradiation with energy rays such as ultraviolet light can be carried out using common methods. For example, when irradiating with ultraviolet light, ultraviolet light generating devices such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and ultraviolet-emitting lasers (excimer lasers, etc.) can be used. Because the polyamide imide (meth)acrylate resin of this invention has excellent adhesive properties, hardness, curing shrinkage, and resistance to damp heat, it is suitable for use in adhesive resins, crosslinking agents, and hard coating materials. Applications of the cured products of this invention include automobiles, computers, monitors, and other household appliances, as well as portable devices such as mobile phones. [Example] The present invention will be described in more detail below by way of examples, but the present invention is not limited to the following examples. Manufacturing Example 1 In a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line, 287.2 g of methyl isobutyl ketone, 242.8 g of isocyanate modified isophorone diisocyanate (EVONIK "VESTANATT-1890 / 100", 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. Nitrogen was purged into the system while the temperature was raised to 116 °C, and the reaction was carried out at the same temperature for 30 hours. The characteristic absorbance at 2250 cm⁻¹ was confirmed by infrared spectroscopy. -1 The absorption has completely disappeared. Thus, a solution of amide-amide-imide resin intermediate (1) with a number average molecular weight of 1251, a weight average molecular weight of 3680, and a solid content acid value of 160 mg KOH / g, as determined by gel permeation chromatography using polystyrene as a standard, was obtained. After cooling to 60°C, 332.5 g of methyl isobutyl ketone, 184.6 g of glycidyl methacrylate (1.30 mol), 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-amide-imide (meth)acrylate resin (I) with a solid content acid value of 12 mg KOH / g, a number average molecular weight of 2027, and a weight average molecular weight of 5520, as determined by gel permeation chromatography. Manufacturing Example 2 In a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line, 411.1 g of methyl isobutyl ketone, 242.8 g of isocyanate modified isophorone diisocyanate (EVONIK "VESTANATT-1890 / 100", 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. Nitrogen was purged into the system while the temperature was raised to 116 °C, and the reaction was carried out at the same temperature for 30 hours. The characteristic absorbance at 2250 cm⁻¹ was confirmed by infrared spectroscopy. -1The absorption has completely disappeared. Thus, a solution of amide-amide-imide resin intermediate (1) with a number average molecular weight of 1420, a weight average molecular weight of 4120, and a solid content acid value of 120 mg KOH / g, as determined by gel permeation chromatography using polystyrene as a standard, was obtained. After cooling to 60°C, 188.8 g of methyl isobutyl ketone, 168.3 g of glycidyl methacrylate (0.95 mol), 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 14 hours to obtain a polyamide-amide-imide (meth)acrylate resin (II) with a solid content acid value of 35 mg KOH / g, a number average molecular weight of 2250, and a weight average molecular weight of 6840, as determined by gel permeation chromatography. Manufacturing Example 3 In a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line, 124.5 g of methyl isobutyl ketone, 65.6 g of isocyanate modified isophorone diisocyanate (EVONIK "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 58.8 g (0.3 mol) of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. Nitrogen was purged into the system while the temperature was raised to 116 °C, and the reaction was carried out at the same temperature for 24 hours. The characteristic absorbance at 2250 cm⁻¹ was confirmed by infrared spectroscopy. -1 The absorption has completely disappeared. Thus, a solution of amide-amide-imide resin intermediate (1) with a number average molecular weight of 1170, a weight average molecular weight of 3520, and a solid content acid value of 170 mg KOH / g, as determined by gel permeation chromatography using polystyrene as a standard, was obtained. After cooling to 60°C, 75.5 g of methyl isobutyl ketone, 74.2 g (0.4 mol) of 3,4-epoxycyclohexyl methacrylate, and 0.2 g of dibutylhydroxytoluene were added and stirred for a while. 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-amide-imide (meth)acrylate resin (III) with a solid content acid value of 20 mg KOH / g, a number average molecular weight of 1820, and a weight average molecular weight of 4440, as determined by gel permeation chromatography. Manufacturing Example 4 In the amide-imide resin intermediate (1) obtained in Manufacturing Example 1, 203.8 g of methyl isobutyl ketone, 56.8 g (0.4 mol) of glycidyl methacrylate, and 1.4 g of butylated hydroxytoluene were added and stirred for a period of time. 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 polyamide-imide (meth)acrylate resin (IV) with a solid content acid value of 142 mg KOH / g, a number average molecular weight of 1560 and a weight average molecular weight of 4050 as determined by gel permeation chromatography. Manufacturing Example 5 To the amide-imide resin intermediate obtained in Example 1, 179.1 g of methyl isobutyl ketone, 36 g (0.25 mol) of 4-hydroxybutyl acrylate, and 1.2 g of butylated hydroxytoluene were added and stirred for a period of time, then the temperature was raised to 100°C. The reaction was carried out at the same temperature for 5 hours to obtain polyamide-imide (meth)acrylate resin (V) with a solid content acid value of 175 mg KOH / g, a number average molecular weight of 1265 and a weight average molecular weight of 3750 as determined by gel permeation chromatography. Formulation of resin components and preparation of test membranes The polyamide imide (meth) acrylate resins obtained in Examples 1 to 5 were formulated with the compositions shown in Table 1 and constituted the Examples and Comparative Examples. [Table 1] KAYARAD DPHA: Dinepentylenetetraacrylate (manufactured by Nippon Kayaku Co., Ltd.) KAYARAD R-115: BisA type acrylate epoxy ester (manufactured by Nippon Kayaku Co., Ltd.) NOAA: Octyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) Light Acrylate SA: Stearyl acrylate (manufactured by Kyoei Chemical Co., Ltd.) Omnirad 184: α-Hydroxyalkylphenyl ketone (manufactured by IGMresins) BYK 307: Polyether-modified polydimethylsiloxane (manufactured by BYK Chemie Japan) MIBK: Methyl isobutyl ketone The following details each evaluation item. (Adhesive properties) Using a rod coater No. 16, a resin composition with a solids concentration of 20% was coated onto an easy-to-adhere polyester film (manufactured by Toyobo Co., Ltd.: A-4300, film thickness 100μm), and dried in an oven at 105°C for 2 minutes. The dried coating film was then touched with a finger and evaluated according to the following criteria. Assessment: No stickiness: ○ Resin adhering to fingers or causing deformation of the coating: × After drying, it is exposed to UV light at a rate of 300 mJ / cm using a conveyor belt UV exposure machine. 2 A coating film with a hardened film (5 μm) was obtained by irradiation. (Pencil hardness) Using a conveyor belt UV exposure machine, at 300mJ / cm 2 The dried coating was irradiated to obtain a hardened film (5 μm). Following JIS K 5400, the pencil hardness of the coating was determined using a pencil scratch tester. Specifically, a pencil with a 1 kg load was applied from above at a 45-degree angle to the polyester film with the hardened film to be tested, resulting in approximately 5 mm of scratches. The hardness of the pencil that did not cause damage was confirmed. (Hardening shrinkage) The polyester film with the measured hardened coating was cut into 6cm × 6cm pieces and placed in an 80°C drying oven for 1 hour before returning to room temperature. The height of each of the four sides floating on a horizontal platform was then measured. Values ​​totaling less than 10mm were marked ○, values ​​between 10mm and 20mm were marked △, and values ​​greater than 20mm were marked ×. At this point, the curl of the substrate itself was 0mm. (Resistance to damp heat) The coated film was placed in a humid heat oven at 60°C and 90% RH for 200 hours, and then it was confirmed whether peeling, whitening, or cracking occurred. Assessment: No abnormalities: ○ Peeling or whitening: × As can be seen from the results in Table 2 above, the polyamide imide (meth)acrylate resin (A) and its components of the present invention exhibit excellent adhesiveness, hardness, curing shrinkage, and resistance to damp heat. Therefore, it is suitable for use in adhesive resins, crosslinking agents, and hard coating materials.

Claims

1. A polyamide imine (meth)acrylate resin (A) is obtained by reacting a (meth)acrylate compound (b) having an epoxy group in only one molecule with a polyamide imine resin (a3) ​​having an acid group or anhydride group at the end, obtained by reacting an alicyclic isocyanate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), wherein the molar ratio ((b) / (a2)) of the aforementioned epoxy-containing (meth)acrylate compound (b) to the aforementioned alicyclic tricarboxylic acid anhydride (a2) is 0.8 to 2.

0.

2. An active energy line-curing resin composition comprising: the polyamide imine (meth)acrylate resin (A) described in claim 1, a photopolymerization initiator (B), and an organic solvent (C).

3. The active energy line curing resin composition as described in claim 2, which contains photopolymerizable monomers (D) other than the aforementioned polyamide imine (meth)acrylate resin (A).

4. The active energy line curing resin composition as described in claim 2 or 3, which is an active energy line curing resin composition for hard coating materials.

5. A cured compound, which is a cured compound of the active energy line curing resin composition described in any one of claims 2 to 4.