JP2023055304A - Polyamide-imide(meth)acrylate resin, active energy ray-curable resin composition using the same and cured product of the same - Google Patents

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 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 cross-linking agent, and a hard coat material.

It is important to construct a composition that forms a crosslinked structure and cures by irradiation with active energy rays such as ultraviolet rays and electron beams. , composite material matrices, casting materials, inks, coating agents, paints, adhesives, etc. in the transportation field, etc., and are industrially very useful. In such a curable resin composition, by using a compound having a plurality of reactive functional groups, a crosslinked structure is formed after curing, the glass transition point (Tg) is high, and heat resistance and solvent resistance are achieved. It is possible to obtain a cured product having excellent physical properties such as.

Conventionally, (meth)acrylate oligomers and (meth)acrylate monomers have been widely used as curable resins. In particular, epoxy (meth)acrylates and urethane (meth)acrylates have been widely used for the purpose of improving the flexibility and elastic modulus of cured films. ) acrylates have been actively developed.

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. The resin has a large curing shrinkage during curing, and there were problems such as 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 flexibility and suppression of cure shrinkage, but there are problems with hardness and moist heat 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 there is a problem with wet heat resistance.

JP 2012-144641 A Japanese Patent No. 2964267 Japanese Patent No. 6669311

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamideimide (meth)acrylate resin which is excellent in tackiness, hardness, curing shrinkage, and resistance to moist heat.

As a result of extensive research, the present inventors have found that the terminal acid group or acid anhydride group obtained by the reaction of the alicyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2) The polyamideimide resin (a3) having an epoxy group in one molecule (meth) acrylate compound (b) reacted with the polyamide imide (meth) acrylate resin (A) has excellent tackiness after drying, activity The inventors have found that it is possible to provide a curable composition that can be cured by irradiation with energy rays, and that can provide a curable composition having good hardness, curing shrinkage, and moist heat resistance after curing, and completed the present invention.

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

ADVANTAGE OF THE INVENTION According to this invention, the polyamide-imide (meth)acrylate resin which is excellent in hardness, low cure shrinkage, and heat-and-moisture resistance can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

The present invention relates to a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) and an alicyclic tricarboxylic acid anhydride (a2). , relates to a polyamideimide (meth)acrylate resin (A) reacted with a (meth)acrylate compound (b) having an epoxy group in one molecule.

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

Alicyclic as used herein, in the context of the present invention, means a compound in which the carbon atoms are arranged in a ring (the two terms "aliphatic" and "cyclic" being described together). (as already suggested by being identical). Cycloaliphatic is therefore also synonymous with cycloaliphatic. Consequently, cycloaliphatic compounds belong to the group of homocyclic compounds, which in this case include cycloalkanes, cycloalkenes and cycloalkynes. Aromatic and heterocyclic compounds, as well as saturated examples of heterocyclic compounds, are not considered to be cycloaliphatic within the meaning of the present invention.

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

The trimerization catalyst is not particularly specified. Examples thereof include amine compounds such as -S-triazine, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms such as potassium acetate, potassium 2-ethylhexanoate and 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 Perlon), DABCO TMR (manufactured by Sankyo Air Products), TOYOCAT TR20 (manufactured by Tosoh), U-CAT 18X ( San-Apro) and the like.

Examples of the alicyclic isocyanurate-type polyisocyanate (a1) include an alicyclic isocyanurate-type triisocyanate synthesized from isophorone diisocyanate (including polymers such as pentamers), and a hydrogenated tolylene diisocyanate synthesized from alicyclic isocyanurate-type triisocyanate (including polymers such as pentamers), alicyclic isocyanurate-type triisocyanates synthesized from hydrogenated xylene diisocyanate (including polymers such as pentamers), norbornane Isocyanurate-type triisocyanates synthesized from diisocyanates (including polymers such as pentamers), alicyclic isocyanurate-type triisocyanates synthesized from hydrogenated diphenylmethane diisocyanate (including polymers such as pentamers), etc. are mentioned. Among them, alicyclic isocyanurate-type isocyanates synthesized from isophorone diisocyanate are preferred. By using the alicyclic isocyanurate-type polyisocyanate (a1), a polyamideimide (meth)acrylate resin (A) having excellent tackiness and curing shrinkage can be obtained.

The alicyclic tricarboxylic anhydride (a2) includes 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 and the like. 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) having excellent tackiness and curing shrinkage can be obtained.

The reaction between the alicyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic acid anhydride (a2) is carried out by The total amount of the physical group and the carboxylic acid is preferably 1 mol or more, more preferably 1.2 mol or more, still more preferably 1.4 mol or more. By using 1.4 mol or more, the polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group has an effect that the obtained cured product is excellent in hardness and tackiness. This is probably because the use of 1.4 mol or more substantially does not contain urethane bonds, making it easier to control the reaction.

The (meth)acrylate (b) having epoxy in one molecule is not particularly limited as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure. A wide variety of compounds can be used. Examples thereof include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, glycidyl group-containing (meth)acrylate monomers such as epoxycyclohexylmethyl (meth)acrylate; Examples include mono(meth)acrylates of diglycidyl ether compounds such as naphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, a (meth)acrylate compound having one epoxy group is preferred because the reaction can be easily controlled, and a glycidyl group-containing (meth)acrylate monomer is preferred from the viewpoint of reactivity and curability.

In the present invention, the alicyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2) are reacted to obtain the polyamideimide resin (a3) used in the present invention (hereinafter referred to as amidimidation reaction), it is preferable to use organic solvents such as solvent-free or ester-based solvents having no hydroxyl groups, ketone-based solvents having no hydroxyl groups, ether-based solvents having no hydroxyl groups, and alcohol-based solvents having hydroxyl groups. Solvents are not preferred because they react with isocyanates or acid anhydrides. Ester-based solvents having no hydroxyl group include, for example, ethyl acetate, propyl acetate, and butyl acetate. Examples of ketone-based solvents having no hydroxyl group include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and the like. Of these, ether solvents having no hydroxyl group include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether; , triethylene glycol diethyl ether, triethylene glycol dibutyl ether and other polyethylene glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and other ethylene glycol monoalkyl ether acetates; diethylene glycol monomethyl Polyethylene glycol monoalkyl ether acetates such as 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; propylene glycol dimethyl ether, propylene Propylene glycol dialkyl ethers such as glycol diethyl ether and propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc. polypropylene glycol dialkyl ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, Polypropylene glycol monoalkyl ether acetates such as dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, and tripropylene glycol monobutyl ether acetate; or low molecular weight ethylene-propylene copolymers. Dialkyl ethers of copolymerized polyether glycols, monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of such polyether glycols; monoalkyl ester monoalkyl ethers of polyether glycols;

In the amidimidation reaction, one or more of the alicyclic isocyanurate-type polyisocyanates (a1) and one or more of the alicyclic tricarboxylic acid anhydrides (a2) are mixed in a solvent or in the absence of a solvent. It is preferable to raise the temperature while stirring.

The reaction temperature for the amidimidation reaction is preferably in the range of 50°C to 250°C, particularly preferably in the range of 70°C to 180°C. Setting the reaction temperature to such a temperature has the effect of increasing the reaction rate. The reaction, accompanied by decarboxylation, forms an imide group between an anhydride group and an isocyanate group, and an amide group between a carboxylic acid group and an isocyanate group. Antioxidants, leveling agents, antifoaming agents, surfactants and the like can be used as necessary during the reaction.

The progress of the amidimidation reaction can be monitored by analytical means such as infrared spectrum, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and isocyanate group quantification. can be done. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm ⁻¹ decreases with the reaction, and the acid anhydride group having characteristic absorptions at 1860 cm ⁻¹ and 850 cm ⁻¹ also decreases. On the other hand, the absorption of the imide group increases at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It is preferable to allow the reaction to proceed until 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappears, because the reaction can be easily controlled.

The polyamideimide resin (a3) having a terminal acid group or an acid anhydride group is reacted with a (meth)acrylate compound (b) having an epoxy group in one molecule in the organic solvent or in the absence of a solvent, preferably.

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

Further, it is preferable to use a catalyst during the reaction in order to promote the reaction. , 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the reactants to which the solvent is added. The reaction temperature at that time 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, triphenylstibine, methyltriphenylstibine, 2 -chromium ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethylsulfide, diphenylsulfide and the like.

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

Further, the molar ratio ((b)/(a2)) of the (meth)acrylate (b) having an epoxy group in one molecule and the alicyclic tricarboxylic acid anhydride (a2) is 0.8 to 2.0. is preferable from the viewpoint of hardness and curability. It is more preferably 0.9 to 1.80, even more preferably 1.0 to 1.5. When ((b)/(a2)) is 0.8 to 2.0, a polyamideimide (meth)acrylate resin (A) having excellent curability, hardness and tackiness can be obtained. On the other hand, when ((b)/(a2)) is less than 0.8, curability and hardness tend to decrease, and when ((b)/(a2)) is greater than 2.0, hardness and tackiness are decreased. prone to decline.

In the active energy ray-curable resin composition of the present invention, the polyamideimide (meth)acrylate resin (A) is 50 to 100 parts by mass with respect to 100 solids content in the composition excluding solvents etc. Hardness and more preferable from the viewpoint of curability.

Moreover, a photoinitiator (B) can be used as needed. The photopolymerization initiator can be used in an amount of 0.01 to 10 parts by mass per 100 parts of the total amount of the resin composition. Specific examples of the photopolymerization initiator (B) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2 ,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxychlorohexylphenylketone, 2-methyl-1- [4-(methylthio)phenyl]-2-morpholinopropan-1-one and other acetophenones; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone and other anthraquinones;2, Thioxanthones such as 4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4' -benzophenones such as bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

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

Moreover, in the active energy ray-curable resin composition of the present invention, a photopolymerizable monomer (D) can be used from the viewpoint of curability, plasticity, and solvent compatibility. The photopolymerizable monomer (D) does not contain the polyamideimide (meth)acrylate resin (A). The photopolymerizable monomer (D) can be used in an amount of 0 to 50 parts by mass per 100 solids in the composition excluding solvents and the like.

Photopolymerizable monomers (D) other than the polyamideimide (meth)acrylate resin (A) include monomers or oligomers that form resins by curing with ultraviolet rays, heat, or the like. More than one species can be mixed and used.

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

Examples of the monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and 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 ) 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 and other (meth)acrylic acid esters, (meth)acryloylmorpholine (morpholino (meth)acrylate), (meth)acrylamide, N-methyl (Meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, Nt-butyl (meth)acrylamide, Nt-octyl (meth)acrylamide, die Acetone (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-benzyl (meth)acrylamide, N- (Meth)acrylic acid amides such as triphenylmethyl (meth)acrylamide and N,N-dimethyl (meth)acrylamide; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; butadiene such as butadiene and isoprene; ethylene or substituted ethylene compounds such as substituted butadiene compounds, ethylene, propylene, vinyl chloride and acrylonitrile; and monomers such as vinyl esters such as vinyl acetate.

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, meth) acrylate, diethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, tris(meth) acryloyloxyethyl isocyanurate, polypropylene glycol di(meth) acrylate, adipate 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 neopentyl glycol hydroxybivalate, reaction product of dipentaerythritol and ε-caprolactone poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethylol propane tri (meth) acrylate or its ethylene oxide adduct, pentaerythritol tri (meth) acrylate or its ethylene oxide addition pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, and the like.

Further, if necessary, various additives such as fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica and clay, thixotropic imparting agents such as nanosilica,
Carboxylic acids such as phthalic acid, adipic acid, succinic acid, phosphoric acid, and trimellitic acid, plasticizers such as their esters, leveling agents such as silicone and fluorine, antifoaming agents and antistatic agents,
Colorants such as conductive metal oxides selected from the group consisting of titanium, zinc, zirconium, antimony, indium, tin, silicon, and aluminum, 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.

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

The polyamide-imide (meth)acrylate resin of the present invention is excellent in tackiness, hardness, curing shrinkage, and resistance to moist heat, and thus is suitably used as a binder resin, a cross-linking agent, and a hard coat material. Applications of the cured product of the present invention include automobiles, computers, household appliances such as displays, and mobile devices such as mobile phones.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Production example 1
287.2 g of methyl isobutyl ketone and an isocyanurate-modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate group content: 17.0 g) were placed in a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line. 3 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 in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin intermediate (1) having a number average molecular weight of 1251, a weight average molecular weight of 3680 and a solid content acid value of 160 mgKOH/g was obtained by gel osmotic pressure chromatography using polystyrene as a standard. 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 after stirring for a while, 1.7 g of triphenylphosphine was added and the temperature was raised to 116°C. bottom. The mixture was reacted at the same temperature for 10 hours to obtain a polyamideimide (meth)acrylate resin (I) having a solid content acid value of 12 mgKOH/g, a number average molecular weight of 2,027 and a weight average molecular weight of 5,520 as determined by gel osmotic pressure chromatography.

Production example 2
411.1 g of methyl isobutyl ketone and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate group content: 17.0 g) were placed in a four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen line. 3 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 in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin intermediate (1) having a number average molecular weight of 1420, a weight average molecular weight of 4120 and a solid content acid value of 120 mgKOH/g was obtained by gel osmotic pressure chromatography using polystyrene as a standard. 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 after stirring for a while, 1.7 g of triphenylphosphine was added and the temperature was raised to 116°C. bottom. The mixture was reacted at the same temperature for 14 hours to obtain a polyamideimide (meth)acrylate resin (II) having a solid content acid value of 35 mgKOH/g, a number average molecular weight of 2250 and a weight average molecular weight of 6840 as determined by gel osmotic pressure chromatography.

Production example 3
124.5 g of methyl isobutyl ketone and isocyanurate-modified isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate group content: 17.5 g) were placed in a four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen line. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin intermediate (1) having a number average molecular weight of 1170, a weight average molecular weight of 3520 and a solid content acid value of 170 mgKOH/g was obtained by gel osmotic pressure chromatography using polystyrene as a standard. 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, then 0.5 g of triphenylphosphine was added. 2 g was added and the temperature was raised to 116°C. The mixture was reacted at the same temperature for 14 hours to obtain polyamideimide (meth)acrylate resin (III) having a solid content acid value of 20 mgKOH/g, a number average molecular weight of 1820 and a weight average molecular weight of 4440 as determined by gel osmotic pressure chromatography.

Production example 4
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 after stirring for a while, triphenylphosphine 1 .4 g was added and the temperature was raised to 116°C. The mixture was reacted at the same temperature for 10 hours to obtain a polyamideimide (meth)acrylate resin (IV) having a solid content acid value of 142 mgKOH/g, a number average molecular weight of 1,560 and a weight average molecular weight of 4,050 as determined by gel osmotic pressure chromatography.

Production example 5
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 and then heated to 100°C. The mixture was reacted at the same temperature for 5 hours to obtain a polyamideimide (meth)acrylate resin (V) having a solid content acid value of 175 mgKOH/g, a number average molecular weight of 1265 and a weight average molecular weight of 3750 as determined by gel osmotic pressure chromatography.

Formulation of Resin Composition and Production of Test Film The polyamideimide (meth)acrylate resins obtained in Production Examples 1 to 5 were formulated in the composition shown in Table 1 to prepare Examples and Comparative Examples.

ＫＹＡＲＡＤ ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート日本化薬社製
ＫＡＵＡＲＡＤ Ｒ－１１５：ＢｉｓＡ型エポキシアクリレート（日本化薬社製）
ＮＯＡＡ：ｎ－オクチルアクリレート（大阪有機化学工業社製）
ライトアクリレートＳ－Ａ：ステアリルアクリレート（共栄社化学社製）
Ｏｍｎｉｒａｄ１８４：α－ヒドロキシアルキルフェノン（ＩＧＭｒｅｓｉｎｓ製）
ＢＹＫ３０７：ポリエーテル変性ポリジメチルシロキサン（ビックケミー・ジャパン社製）
ＭＩＢＫ：メチルイソブチルケトン

KYARAD DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. KAURAD R-115: BisA type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.)
NOAA: n-octyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Light acrylate SA: stearyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
Omnirad 184: α-hydroxyalkylphenone (manufactured by IGM resins)
BYK307: polyether-modified polydimethylsiloxane (manufactured by BYK-Chemie Japan)
MIBK: methyl isobutyl ketone

Each evaluation item is described in detail.
(tackiness)
A resin composition having a solid content concentration of 20% was coated on bar coater No. No. 16 was applied to an easy-adhesive polyester film (manufactured by Toyobo Co., Ltd.: A-4300, thickness 100 μm) and dried in an oven at 105° C. for 2 minutes. The coated film after drying was touched with a finger and evaluated according to the following criteria.
Evaluation: No tackiness: 〇 Resin adheres to fingers or deforms coating film: ×

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

(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 having a cured film (5 µm). The pencil hardness of the coating film was measured using a pencil scratch according to JIS K 5400. That is, the polyester film having the cured film to be measured was scratched with a pencil at an angle of 45 degrees and a load of 1 kg was applied from above to scratch about 5 mm to confirm the hardness of the pencil without scratching.

(curing shrinkage)
A polyester film having a cured film to be measured was cut into a size of 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 sides that floated on a horizontal table was measured. At this time, the curl of the substrate itself was 0 mm.

(Damp heat resistance)
The coating film was allowed to stand in a moist heat oven at 60° C. and 90 RH% for 200 hours, and then checked for peeling, whitening and cracking.
Evaluation: No abnormalities: 〇
With peeling or whitening: ×

From the results in Table 2 above, it can be seen that the polyamideimide (meth)acrylate resin (A) of the present invention and the composition thereof are excellent in tackiness, hardness, cure shrinkage, and moist heat resistance. Therefore, it is suitably used as a binder resin, a cross-linking agent, and a hard coat material.

Claims (6)

In a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group obtained by the reaction of an alicyclic isocyanurate-type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2), in one molecule A polyamideimide (meth)acrylate resin (A) obtained by reacting a (meth)acrylate compound (b) having an epoxy group with a polyamideimide (meth)acrylate resin (A). The molar ratio ((b)/(a2)) of the alicyclic tricarboxylic anhydride (a2) and the epoxy group-containing methacrylate compound (b) is 0.8 to 2.0 according to claim 1. Polyamideimide (meth)acrylate resin (A). An active energy ray-curable resin composition comprising the polyamideimide (meth)acrylate resin (A) according to claim 1 or 2, a photopolymerization initiator (B), and an organic solvent (C). The active energy ray-curable resin composition according to claim 3, further comprising a photopolymerizable monomer (D) other than the polyamideimide (meth)acrylate resin (A). 5. The active energy ray-curable resin composition according to claim 3, which is an active energy ray-curable resin composition for hard coat materials. A cured product of the active energy ray-curable resin composition according to any one of claims 3 to 5.