TW201037001A - Polyimide resin, curable resin composition and cured product - Google Patents

Abstract

Provided are a thermosetting resin composition and a polyimide resin. The thermosetting resin composition is soluble in general-purpose solvents and also can be made into a kind of cured product (cured coating film), that has high light permeability in the region of visible light to nearby 300 nm. The polyimide resin is suitable for use in preparing the thermosetting resin composition. Polyimide resin, which is synthesized from polyisocynate of isocyanurate type (a1), which is synthesized from isocynate having the structure of aliphatic series and tricarboxylic acid anhydride (a2), which has the structure of aliphatic series. Curable resin composition and its cured product, which comprise the polyimide resin.

Description

[Technical Field] The present invention relates to a polyilylimide resin, which comprises a curable resin composition of the polyimine resin and a cured product thereof. Specifically, the present invention can be suitably used in fields requiring heat resistance and transparency, such as fields for optical materials, solder resist materials for printed circuit boards, protective materials for household electrical appliances such as refrigerators and electronic pots, and insulating materials, liquid crystals. Display or liquid crystal display elements 'organic and inorganic electroluminescent displays or organic and inorganic electroluminescent elements, light-emitting diodes, electronic paper, solar cells, optical fibers or optical waveguides, protective materials, insulating materials, adhesives, or reflective A field of a material such as a material or a display device such as a liquid crystal alignment film or a protective film for a color filter; and a curable resin composition containing the polyimide resin and a cured product thereof. [Prior Art] Polyimine resin is excellent in heat resistance and mechanical properties, and can be used in various fields centering on the ❹Electronic motor industry. In recent years, in order to reduce the burden on the environment, it is necessary to dissolve in EDGA. The performance of general-purpose solvents such as (diethylene glycol monoethyl ether acetate). Further, the polyimide resin is expected to be used in the field of transparency of a cured product such as the above liquid crystal display, depending on the heat resistance or mechanical properties. In such fields, for example, from visible light to ultraviolet light (near 300 nm), light transmission is required. As for the polyimine resin dissolved in a general-purpose solvent, there is a literature revealing, for example, an isocyanate-type polyisocyanate 201037001 acid ester (a 1) having an aliphatic structure and a trimellitic anhydride reaction. The obtained polyimide resin (for example, refer to Patent Document 1). However, in the cured product obtained by using the polyimide resin disclosed in Patent Document 1, for example, in the measurement of the light transmittance, the light transmittance in the ultraviolet region (near 300 nm) is insufficient, and the transparency is insufficient. [Problem to be Solved by the Invention] [Problem to be Solved by the Invention] An object of the present invention is to provide a curable resin composition which is soluble in a general-purpose solvent and A cured product (hardened coating film) having high light transmittance from visible light to an ultraviolet region near 300 nm; and a polyimine resin which is suitable for use in the composition Modulation of matter. [Means for Solving the Problem] As a result of a review by the inventors of the present invention, it has been found that in the aforementioned Patent Document 1, a polyimine resin obtained by using a tricarboxylic anhydride having an aliphatic structure is used instead. A tricarboxylic acid anhydride having an aromatic structure such as trimellitic anhydride, a curable resin composition can be obtained, which is soluble in a general-purpose solvent, and a hardened coating film excellent in heat resistance and light transmittance can be obtained. The invention is completed. That is, the present invention provides a polyimine resin which makes isomeric cyanate type polyisocyanate 201037001 (a1) synthesized from an isocyanate having an aliphatic structure and a tricarboxylic anhydride (a2) having an aliphatic structure. ) obtained by reaction. Further, the present invention provides a curable resin composition characterized by comprising the above polyimine resin (A) and an epoxy resin (B) having two or more epoxy groups in a molecule. Further, the present invention provides a cured product obtained by curing the curable resin composition. [Effects of the Invention] 硬化 The curable resin composition obtained by using the polyimine resin of the present invention

The G substance is soluble in a general-purpose solvent, and a hardened coating film excellent in heat resistance and light transmittance can be obtained. It can be suitably used in the field where transparency of a hardened material is required. Further, it can be suitably used in fields where transparency of a cured product is not required, such as various heat-resistant coating materials or electrical insulating materials, such as interlayer insulating materials for printed circuit boards, reinforcing materials, passivation films for semiconductors, gate insulating films, and the like. , protective films and insulating materials, lithium-ion batteries and other batteries, conductive films, heat-resistant adhesives and other fields.实施 [Embodiment] The polyimine resin of the present invention is an isocyanurate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure and a tricarboxylic anhydride U2 having an aliphatic structure. The person who got the reaction and got it. The isomeric isocyanate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure may, for example, be an isomeric cyanate type synthesized from an isocyanate having a linear aliphatic structure. Polyisocyanate, isomeric isocyanate type poly 201037001 isocyanate synthesized from an isocyanate having a cyclic aliphatic structure. In the case of the isocyanurate type polyisocyanate synthesized from the isocyanate having a linear aliphatic structure, for example, HDI3N (isocyanuric acid type triisocyanate synthesized from hexamethylene diisocyanate) may be mentioned. A polymer such as a pentamer), HTMDI3N (a hetero-cyanate type triisocyanate (a polymer containing a pentamer) synthesized from trimethylhexamethylene diisocyanate), or the like. These systems can be used either singly or separately. For the isotrimeric oxime-type cyanate-type polyisocyanate synthesized from an isocyanate having a cyclic aliphatic structure, for example, IPDI3N (iso-isocyanate type III synthesized from isophorone monoisocyanate) may be mentioned. Isocyanate (polymer containing pentamer), HTDI3N (iso-isocyanate type triisocyanate synthesized from hydrogenated methyl benzene diisocyanate (polymer containing pentamer)), HXDI3N (from xylene hydrogenation) Isocyanurate type triisocyanate (polymer containing pentamer) synthesized by diisocyanate, NBDI3N (iso-isocyanate type triisocyanate synthesized from norbornane diisocyanate (containing quinone So-called polymer)), HMDI3N (iso-isocyanate-type triisocyanate (polymer containing pentamer) synthesized from hydrogenated diphenylmethane diisocyanate). The isocyanurate type polyisocyanate (a1) synthesized from the isocyanate having an aliphatic structure used in the present invention is particularly preferable from the viewpoint of obtaining a cured coating film having high Tg and excellent thermal properties. It is preferred to use a hetero-isocyanate-type polyisocyanate synthesized from an isocyanate having a cyclic aliphatic structure, which is a heterotrimeric 201037001 cyanate synthesized from isophorone diisofluoride. Type triisocyanate is preferred. Further, the isocyanurate type triisocyanate synthesized from isophorone diisocyanate may also contain a polymer such as a pentamer. The content of the isocyanurate type polyisocyanate synthesized from the isocyanate having a cyclic aliphatic structure in the isocyanurate type polyisocyanate (a1) synthesized from the isocyanate having an aliphatic structure, It is 50 to 80% by weight based on the weight of the compound (a1), and is suitable from the viewpoint of obtaining a cured coating film having a high Tg and excellent thermal properties, and is 80 to 100% by weight. Preferably, 100% by weight is optimal. Further, an adduct obtained by subjecting the above isocyanate compound to a urethane reaction of various polyols may be used insofar as the solvent solubility of the polyimine resin of the present invention is not impaired. The carboxyl group-containing quinone imine resin (A) used in the present invention directly forms an oximine bond from the above isocyanate compound (al) and a tricarboxylic anhydride U2 having an aliphatic structure, whereby the stability is not stabilized. A lysine intermediate which is problematic in terms of properties and the like, and a polyimine resin which is excellent in solubility and excellent in transparency can be synthesized with good reproducibility. In the present invention, by using a tricarboxylic anhydride U2) having an aliphatic structure as a raw material of the polyimine, the transparency of the obtained polyimide resin is enhanced. The tricarboxylic acid anhydride having an aliphatic structure may, for example, be a tricarboxylic anhydride having a linear aliphatic structure or a tricarboxylic anhydride having a cyclic aliphatic structure. As the tricarboxylic anhydride having a linear aliphatic structure, for example, propane tricarboxylic anhydride or the like can be listed. The tricarboxylic acid 201037001 anhydride having a cyclic aliphatic structure may, for example, be cyclohexanetricarboxylic anhydride, methylcyclohexanetricarboxylic anhydride, cyclohexenetricarboxylic anhydride or methylcyclohexenetricarboxylic anhydride. Among the tricarboxylic anhydrides U2) having an aliphatic structure used in the present invention, from the viewpoint of obtaining a cured coating film having high transparency and high Tg and excellent thermal properties, it is three having a cyclic aliphatic structure. Carboxylic anhydride is preferred. Examples of the tricarboxylic acid anhydride having a cyclic aliphatic structure include cyclohexane tricarboxylic anhydride and the like. These systems may be used alone or in combination of two or more. Further, 0 may also be used as a difunctional dicarboxylic acid compound such as adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, and the like. The cyclohexane tricarboxylic anhydride may, for example, be cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride or cyclohexane·l,3,5-tricarboxylic acid-3,5-anhydride. , cyclohexane-l, 2,3-tricarboxylic acid-2,3-anhydride, and the like. Among them, from the viewpoint of obtaining a polyimide film having excellent transparency and solvent solubility, and obtaining a cured coating film having high Tg and excellent thermal properties, cyclohexane-1,3,4-three is used. Preferably, formic acid-3,4-acetic acid is preferred. Here, the above-mentioned cyclohexane tricarboxylic anhydride is a substance represented by the structure of the following general formula (1), and may be mixed into a ring used as a raw material for production without damaging the range of curing of the present invention. Impurities such as hexane_1,2,3-tricarboxylic acid and cyclohexane-1,3,4-tricarboxylic acid are mixed, for example, in an amount of 1% by weight or less (preferably 5% by weight or less).

Ο (1) 201037001 If the carboxylic acid component of the above-mentioned tricarboxylic anhydride U2) reacts with the isocyanate component of the polyisocyanate (al), the quinone imine and the guanamine are formed. Amine amide resin. Further, when the polyisocyanate (al) is reacted with a tricarboxylic anhydride U2 having a fatty group structure, the tricarboxylic anhydride U2) and the polyisocyanate are allowed to be present in a ratio at which the carboxylic acid component of the tricarboxylic anhydride (a2) can remain ( a 1) When the reaction occurs, the obtained polyimine resin has a carboxyl group. This carboxyl group reacts with the epoxy group of the epoxy resin contained in the curable resin composition of the present invention to form a crosslinked structure of the cured product. Further, since the reaction rate of ruthenium imidization is fast, even in the reaction of a tricarboxylic acid with a triisocyanate, the tricarboxylic acid selectively forms quinone in the case of an acid anhydride. The polyisocyanate type polyisocyanate (al) synthesized from an isocyanate having an aliphatic structure is reacted with a tricarboxylic acid anhydride (a2) having an aliphatic structure to obtain a polyimine resin of the present invention (A) In the case of the reaction, it is preferred to carry out the reaction in a polar solvent containing no nitrogen atom or sulfur atom. 〇If a polar solvent containing a nitrogen atom or a sulfur atom is present, it is liable to cause environmental problems. In addition, in the reaction of the isocyanurate type polyisocyanate (a 1) and the tricarboxylic anhydride U2), the molecular Growth becomes easily hindered. When the related molecules are cut, the physical properties are liable to be lowered in the case of forming a composition, and even coating film defects such as "crawling" are likely to occur. In the present invention, a polar solvent containing no one of a nitrogen atom and a sulfur atom is preferably an aprotic solvent. For example, a cresol solvent is a phenolic solvent having a proton, and it is slightly inappropriate in consideration of an environmental level, and -10-201037001 easily reacts with an isocyanate compound to hinder molecular growth. Further, the cresol solvent reacts with the isocyanate group to easily become a blocking agent. Therefore, it reacts with other hardening components (for example, an epoxy resin) at the time of hardening, and it is difficult to obtain favorable physical properties. Furthermore, in the case where the agglomerating agent falls off, it is likely to cause contamination of the machine or other materials used. Further, since it is an alcohol solvent, it is not preferable because it reacts with an isocyanate or an acid anhydride. The aprotic solvent is, for example, an ether 0 system, an ester system or a ketone system which does not have a hydroxyl group, and particularly preferably an ether solvent having no hydroxyl group. In the present invention, a polar solvent containing no nitrogen atom or sulfur atom is preferred as the ether solvent. The ether solvent has a weak polarity, and is excellent in the reaction of the isocyanurate type polyisocyanate (a1) having the aliphatic structure of the isocyanate and the tricarboxylic acid anhydride (a2) having an aliphatic structure. Reaction site. As the related ether solvent, a well-known one can be used, for example, ethylene glycol dialkyl ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or ethylene glycol dibutyl ether; Polyethylene glycol such as glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether Dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, etc. ethylene glycol monoalkyl ether acetate; 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 Polyethylene glycol monoalkyl ether acetates such as ether acetate; propylene-11-201037001 diol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether and other propylene glycol dialkyl ethers; 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. Glycol dialkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc. propylene glycol monoalkyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Polypropylene glycol monoalkyl ether acetates such as acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate; or low a dialkyl ether of a polyether diol copolymerized with an ethylene-propylene copolymer of a molecule, or a monoacetate monoalkyl ether of a copolymerized polyether diol; or an alkyl ester of such a polyether diol; Monoalkyl ether monoalkyl ethers of polyether diols, and the like. Isocyanurate type polyisocyanate U1) synthesized from an isocyanate having an aliphatic structure and tricarboxylic anhydride U2) having an aliphatic structure, and isomeric cyanuric acid synthesized from the above-mentioned isocyanate having an aliphatic structure The total number of moles of the isocyanate group (N) of the ester type 聚 polyisocyanate U1) and the carboxyl group number (Ml) of the tricarboxylic anhydride (a2) having an aliphatic structure and the molar number of the acid anhydride group (M2) When the ratio of [(Ml)+(M2))/(N)] is 1.1 to 3, the reaction proceeds smoothly because the polarity in the reaction system becomes high, and the isocyanate group does not remain. The stability of the polyimine resin is good, and the residual amount of the tricarboxylic anhydride (a2) is also small, and the problem of separation such as recrystallization is unlikely to occur, which is suitable. Among them, 1.2 to 2 is preferred. Further, the acid anhydride group in the present invention means a -C0-0-C0- group obtained by dehydration condensation of two carboxylic acid molecules in the molecule -12 - 201037001. The hydrazine imidization reaction is preferably carried out by mixing one or more isocyanate compounds (a1) and one or more kinds of tricarboxylic anhydride (a2) in a solvent or without a solvent while raising the temperature while stirring. The reaction temperature is preferably from 50 ° C to 250 ° C, particularly preferably from 70 ° C to 180 ° C. By setting such a reaction temperature, it is possible to increase the reaction rate and to cause side effects or decomposition. This reaction proceeds with the decarbonation, and the acid anhydride group and the isocyanate group form a quinone imine group. The progress of the reaction can be traced by an infrared spectrum, or an analytical method such as an acid value or a hydrazine isocyanate group. In the infrared spectrum, 2270cnTl which is absorbed by the isocyanate group characteristic decreases as the reaction progresses, and further, the acid anhydride group having characteristic absorption at 1 860 cm·1 and 850 cm·1 is reduced. On the other hand, the absorption at the 1 7 80 cm·1 and 1720 cm·1 醯 imine groups increased. The reaction can also confirm the acid value, viscosity, molecular weight, etc. of the target while cooling down to complete the reaction. However, it is preferable to consider the stability from the level of stability over time so that the reaction proceeds to the disappearance of the isocyanate group. In addition, a catalyst, an antioxidant, a surfactant, another solvent, etc. may be added in the range of the reaction of the resin to be synthesized or after the reaction. The acid value of the polyimine resin of the present invention is preferably from 70 to 210 KOHmg/g, preferably from 90 to 190 KOH mg/g. As long as it is 70 to 210 KOHmg/g, it exhibits excellent performance in terms of cured physical properties. Further, the polyimine resin of the present invention is preferably a polyimine resin which is dissolved in a polar solvent containing no one of a nitrogen atom and a sulfur atom. Examples of such a polyimide resin include a branched polyimine resin having a branched structure of -13 to 201037001 and an acid value of the resin of 60 KOHmg/g or more. The number average molecular weight of the polyimine resin of the present invention is preferably from 1,000 to 20,000, and preferably from 2,000 to 8,000, from the viewpoint of good solubility in a solvent and a cured product excellent in mechanical strength. The molecular weight can be determined by gel permeation chromatography (GPC) or quantitative analysis of the amount of terminal functional groups. Λ In the present invention, the measurement of the number average molecular weight is determined by the following conditions using GPC. Measuring device: HTC-8120GPC manufactured by Tosoh Corporation, UV8020 Pipe column: TFKguardcolumnHXL-L, TFKgel (G1 000HXL, G2000HXL, G3000HXL, G4000HXL) manufactured by Tosoh Corporation. Detector: RI (differential refractometer) and UV (254nm)

Measurement conditions: column temperature 40 ° C Solvent THF ❹ Flow rate 1.0 m 1 / mi η Standard: Measured wire sample prepared from polystyrene standard sample: 0.1% by weight of THF solution in terms of resin solid content, The filter is obtained by filtration (injection amount: 200 μl). The carboxyl group-containing quinone imine resin (Α) used in the present invention may, for example, be an imine resin represented by the following formula (2). Wait. -14- 201037001

Rc

Rc (Formula 2) (n is a repeating unit of 0 to 30. Further, Rb is a structural unit represented by the following structural formula (Formula 3) or (Formula 4). 0 Ο II 0

A II —Nv N— , (/ Η (Formula 3)

II ο ο: ο

CMO N-H

% /" c C: / / 2 R

N ο V — / (S4 (R 2 is an aliphatic tricarboxylic acid residue having a substituent having 6 to 20 carbon atoms, for example) Rc is, for example, a structural unit represented by the following structural formula (Formula 5). 201037001 0 Η One NC — R II 0 II 0 Ο

X

Nf^R2 - COOH ¥ 〇 (R2 is, for example, the same as described above). Ο

Rd is, for example, a trivalent organic group represented by the following (Formula 6).

Ra_ no §

The Ra system represents, for example, a residue of a divalent aliphatic diisocyanate. The curable resin composition of the present invention contains the polyimide resin of the present invention (hereinafter referred to as polyimine resin (A)) and the curable resin (B). For example, a thermosetting resin composition containing an epoxide (B1) component having two or more epoxy groups in a molecule may be mentioned. As the (Bi) component, a conventionally known epoxy resin may be used, or two or more kinds may be used in combination. Further, examples of the other examples include melamine resin, isocyanate compound, decanoate, alkoxydecane compound, and (meth)acrylic resin, and heat resistance, dimensional stability, and mechanical properties are obtained. (Strong-16 - 201037001 Toughness, flexibility) It is preferable that an epoxy resin is preferable from the viewpoint of a cured product such as a hardened coating film. Further, the cured physical properties described in the above and below are the cured polyimine resin of the present invention and the cured product thereof; and the polyiminoimine resin of the present invention is included or not The other resin agent, inorganic material component, or the like which reacts with the polyimide resin is simply dried in a solvent to obtain a molded article or a molded article. Still further, the polyimine resin of the present invention is mixed with a hardener which reacts by heating or light, and/or an additive which does not react with the present hairpin resin itself is hardened by heat or light. The obtained cured product and its hardened properties are also included in the meaning of the epoxy resin, and examples thereof include bisphenol A type grease, bisphenol S type epoxy resin, bisphenol F type epoxy resin, and phenol ring. Oxygen resin, cresol novolac type epoxy resin, dicyclopentadiene and various dicyclopentadiene-modified phenol resins obtained by the respective reactions, epoxy oxime 2,2_,6,6'-tetramethylbiphenol Epoxide, anthracene phenolic resin derived from naphthalene skeleton, such as epoxide, 4,4-methylene biscresol), naphthol or binaphthol, or naphthoquinone or binaphthyl denature An aromatic epoxy resin such as an epoxy resin obtained by oxidation. In addition, an aliphatic epoxy resin such as neopentyl glycol diglycidyl ether or 1,6-diglycidyl ether; or hydrogenated bisphenol A resin, hydrogenated bisphenol F type epoxy resin, 3, 4 may also be used. - Epoxy cyclohexyl epoxicycline, bis-(3,4-epoxybicyclohexyl) adipic acid g, which is a meaning, and the composition also contains and adds a coating film and Polyepoxide occurs in the phenolic phenolic phenolic compound, (2,6-diphenol phenolic cyclohexanediol type epoxy-3,4-ί!, 2,2- -17- 201037001 double a cyclic aliphatic epoxy resin such as a 1,2-epoxy-4 (2-epoxyethyl)cyclohexane adduct of (hydroxymethyl)-1-butanol; such as polyethylene glycol condensate An epoxy resin containing a polyalkylene glycol chain in the main chain like a glyceryl ether or a polypropylene glycol diglycidyl ether; and a heterocyclic epoxy resin like triglycidyl isocyanurate. An epoxy group-containing polymer resin obtained by polymerization of an unsaturated group of an epoxy compound having a polymerizable unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and the like A copolymer of a monomer having a polymerizable unsaturated bond 。. A related compound having both a (meth) acryl fluorenyl group and an epoxy group may, for example, be a glycidyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate glycidyl ether, hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate Ester glycidyl ether, 5-hydroxy-3-methylpentyl (meth) acrylate glycidyl ether, (meth)acrylic acid-3,4-epoxycyclohexyl ester, lactone modified (methyl) fluorene acrylic acid -3,4-epoxycyclohexyl ester, vinylcyclohexene oxide, etc. In the present invention, an epoxy resin (B) having two or more epoxy groups in a molecule is a cyclic aliphatic system. The epoxy resin is particularly preferable. As long as it is a cyclic aliphatic epoxy resin, a cured coating film having high Tg and excellent thermal properties can be obtained, and a cured product having high light transmittance in an ultraviolet region (near 300 nm) can be obtained. Among the cyclic aliphatic epoxy resins, hydrogenated bisphenol A type epoxy trees 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol is preferred. -18- 201037001 The cyclic aliphatic epoxy resin is commercially available, and examples thereof include Denacol EX-252 (manufactured by Nagasechemtex Co., Ltd.), EHPE 3150, EHPE 3150CE (manufactured by Daicel Chemical Industry Co., Ltd.), and the like. The epoxy resin (B) having two or more epoxy groups can be heat-resistant in terms of the amount of use thereof in an amount of from 6 to 1,000,000 parts by weight based on 100 parts by weight of the polyimine resin (A). Preferably, the cured product is excellent in transparency and transparency, and is preferably 15 to 300 parts by weight. The polyimine resin (A) and the epoxy resin (B) having two or more epoxy groups in the molecule can be freely blended in accordance with physical properties of various targets, and thermal properties and mechanical properties such as Tg. Considering the balance of the transparency of the cured coating film, the carboxyl group number n (COOH) of the carboxyl group-containing quinone imine resin (A) and the epoxy resin (B) having two or more epoxy groups in the molecule The ratio of the epoxy group molar number n (EPOXY) [(EPOXY) / n (COOH)] is in the range of 0.3 to 4, and the polyimine resin (A) is blended with the epoxy resin (B). In the case of the cured product, it is easy to obtain a high Tg, and it is possible to obtain a cured product excellent in mechanical properties and the like, and it is suitable for further improving the transparency of the cured product. In the curable resin composition of the present invention, an epoxy-carboxylic acid-based curing catalyst or the like may be mixed. The related epoxy-carboxylic acid-based curing catalyst may, for example, be a first- to third-order amine or a fourth-order ammonium salt, a dicyandiamide or an imidazole compound for promoting the reaction. a phosphine-based compound such as a compound, TPP (triphenylphosphine), an alkyl-substituted trialkylphenylphosphine, or a derivative of -19-201037001, such a money salt, or a dialkyl urea or a carboxylic acid, A known epoxy hardening accelerator such as a phenol or a methylol group-containing compound can be used in a small amount. The curable resin composition of the present invention can be cured by heating after being applied to the object to be coated and subjected to casting or the like. The article thus obtained is a cured product containing the curable resin composition of the present invention. The hardening temperature is preferably from 80 ° C to 300 ° C, especially from 120 ° C to 250 ° C. In addition, it is also possible to carry out step curing at each temperature. Alternatively, the semi-hardened thin plate-like or film-like composition may be stored at a temperature of from about 50 ° C to about 170 ° C, and if necessary, treated at the above-mentioned hardening temperature. The hardening reaction of the carboxyl group-containing quinone imine resin (A) component with the epoxy resin (B) component having two or more epoxy groups in the molecule is basically a reaction of a carboxyl group with an epoxy group, and the related polyazide The amine resin (A) and the epoxy resin (B) having two or more epoxy groups in the molecule can be obtained by selecting a type, a blending ratio, a curing condition, etc., to obtain a curable resin composition having excellent physical properties and the like. . In the curable resin composition of the present invention, various solvents, various homogenizers, antifoaming agents, antioxidants, aging inhibitors, ultraviolet absorbers, sedimentation inhibitors, rheology control agents, etc. may be blended as necessary. Additives, or barium sulphate, strontium oxide, talc, clay, calcium carbonate, cerium oxide, colloidal cerium oxide, glass, etc., conventionally used additives, various metal powders, glass fibers or carbon fibers, ke vera fibers (ke A fibrous coloring agent such as vl ar fiber or the like, or a conventional pigment for coloring such as phthalocyanine blue, phthalocyanine, titanium oxide, carbon black or cerium oxide, and other adhesion imparting agents. In addition, -20-201037001 can be blended with polymers such as acrylic resin, cellulose resin, polyethylene resin, polyphenylene ether, and polyether oxime. [Examples] Next, the present invention will be further described in detail by way of examples. In the example, "parts" and "%" are based on weight unless otherwise specified. Synthesis Example 1 [Preparation of Polyimine Resin (A)] 烧瓶 In a flask equipped with a stirring device, a thermometer, and a condenser, EDGA (diethylene glycol monoethyl ether acetate) 462 8 g, IPDI 3N (from isophorone) was added. Iso-isocyanate type triisocyanate synthesized by diisocyanate: NCO% = 1 8.2) 2070 g (3 mol) and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 1 3 86 g (7 mol) , heat up to 140 ° C. The reaction system is carried out together with foaming. The reaction was allowed to proceed at this temperature for 8 hours. A pale yellow liquid was produced in the system, and the absorption of the characteristic was measured by infrared spectroscopy. 2270 cm_l of the isocyanate-based characteristic absorption completely disappeared, and the absorption of the quinone imine group was confirmed at 1 780 cm·1, 1720 cm·1. The acid value is 140 KOHmg/g in terms of solid content, and the molecular weight is, in terms of polystyrene, the number average molecular weight is 5,800. Further, the concentration of the resin component was 40% by weight. The solution of this resin was abbreviated as a solution of the quinone imine resin (A1). Synthesis Example 2 (ibid.) In a flask equipped with a stirring device, a thermometer, and a condenser, 0 elbow was added: &lt;: (propylene glycol monomethyl ether acetate) 4 94 2 £, 110131 (by hexamethylene diisocyanate) Synthetic isocyanurate type triisocyanate: NCO% = -21- 201037001 24.7) 2040 g (4 mol) and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 1 7 82 g (9 mol ), heat up to 140t. The reaction system is carried out together with foaming. The reaction was allowed to proceed at this temperature for 8 hours. A pale yellow liquid was produced in the system, and the absorption of the characteristic was measured by infrared spectroscopy. 2270 cm·1 of the isocyanate-based characteristic absorption completely disappeared, and the absorption of the quinone imine group was confirmed at 1 780 cm·1, 1720 cm·1. The acid value is 130 K 〇Hmg/g in terms of solid content; the molecular weight is in terms of polystyrene, and the number average molecular weight is 6,200. Further, the concentration of the resin component ^ was 40% by weight. The solution of this resin was abbreviated as a solution of the quinone imine resin (A2) 0 . Comparative Synthesis Example 1 In a flask equipped with a stirring device, a thermometer, and a condenser, EDG A (diethylene glycol monoethyl ether acetate) 45 00 g, IPDI 3N (isocyanuric acid synthesized from isophorone diisocyanate) was added. Ester-type triisocyanate: NCO% = 1 8.2) 2760 g (4 mol) and trimellitic anhydride 1 728 g (9 mol), and the temperature was raised to 140 °C. The reaction system is carried out together with foaming. At this temperature, it was allowed to react for 10 hours. A light brown transparent liquid was produced in the system, and the absorption of the characteristic was determined by infrared spectroscopy. The absorption of the isocyanate-based property completely disappeared, and the absorption of the quinone imine group was confirmed at 1 7 80 CHT1, 1 720 (^1^1). The component conversion is 95 KOHmg/g; the molecular weight is, in terms of polystyrene, the number average molecular weight is 4,300. The concentration of the resin component is 47% by weight. The solution of this resin is abbreviated as a solution of the quinone imine resin (a) Example 1 The curable resin group-22-201037001 of the present invention was prepared in the formulation disclosed in the first table. The appearance and heat of the cured coating film of the thermosetting resin composition 1 were carried out in accordance with the following method. Evaluation of film Tg and light transmittance of the curable resin composition 1. The evaluation results of the appearance of the cured film and the film Tg are shown in Table 2; the evaluation results of the light transmittance are shown in Table 3. Evaluation method&gt; The thermosetting resin composition 1 was applied onto a glass substrate so that the film thickness after hardening became 25 to 35; zm. Next, the coating was carried out by a drying machine at 50 °C. After drying the plate for 30 minutes, After drying at 100 ° C for 30 minutes, and finally hardening at 1 70 ° C for 1 hour, the appearance of the cured coating film was evaluated according to the following criteria: ◎: uniform and no foreign matter was observed. X : It was confirmed that there was shrinkage or Concavity and convexity, foreign matter, and cracking. <Method for evaluating Tg of film> Preparation of test piece for measurement The thermosetting resin composition 1 was coated so that the film thickness after hardening became 25 to 35/zm. On a tinplate substrate, the coated plate was dried in a dryer at 50 ° C for 30 minutes, dried at 100 ° C for 30 minutes, and finally cured at 1 70 ° C for 1 hour to prepare a cured coating film. After the room temperature, the hardened coating film was cut into a predetermined size and separated from the substrate to be used as a sample for measurement. The method for measuring the film Tg was measured for dynamic viscoelasticity, and Tan (5 maximum temperature of the obtained spectrum was determined as TG. In addition, the dynamic viscoelasticity was measured by the following conditions: -23- 201037001 Measuring machine: Rheovibron RSA-II (manufactured by Rheometric Co., Ltd.) Fixture: Stretching chuck spacing: 20 mm Measuring temperature: 25 ° C to 400 ° C Frequency·· 1 Η z Heating rate: 3°C /min &lt;Evaluation of light transmittance of film&gt; _ Preparation of test piece for measurement 热 Coating of thermosetting resin composition 1 on tinplate substrate so that film thickness after hardening becomes 25 to 35/zm Next, the coated plate was dried in a dryer at 50 ° C for 30 minutes, dried at 100 ° C for 30 minutes, and finally cured at 1 70 ° C for 1 hour to prepare a cured coating film. Thereafter, the cured coating film was cut into a predetermined size and separated from the substrate to serve as a sample for measurement. Method for measuring light transmittance of film ❹ The light transmittance was measured under the following conditions. The lanthanide light transmittance (%) was measured. Measurement apparatus: Spectrophotometer U-2800 (manufactured by Hitachi High-Technologies Co., Ltd.) Measurement wavelength range: 250 nm to 800 nm Example 2 and Comparative Examples 1 to 2 The thermosetting resin was prepared by the formulation shown in Table 1. The composition 2 and the comparative thermosetting resin compositions 1 to 2 were used. The evaluation was carried out in the same manner as in Example 1. The results are shown in the second table and the third table. • 24-201037001 [Table 1] Example Comparative Example Resin Composition 1 2 3 4 1 2 Solution of Polyanion Resin (A1) 184.7 184.8 175.7 Solution of Polyimine Resin (A2) 167.5 Polyimine Resin (al) Solution 156.2 156.4 Epoxy Resin (B) 1 EHPE3150 26.1 33.0 26.6 2 Epiclon N-680 26.1 26.5 3 Denacol EX-252 29.7 Catalyst (TPP) 1 1 1 1 1 1 Notes to Table 1

• EHPE3 150: 1,2-epoxy-4-(2-ring) of a cyclic aliphatic epoxy resin (2,2-bis(hydroxymethyl)-1-butanol) manufactured by Daicel Chemical Industry Co., Ltd. Oxyethyl)cyclohexane adduct). The epoxy equivalent is 177. The concentration of the resin component was 100% by weight. .Epiclon N-680: A 酣酣 酣酣 type epoxy resin manufactured by DIC Corporation. The epoxy equivalent was 211. The concentration of the resin component was 1% by weight. • Denacol EX-252: Cyclic aliphatic epoxy resin (hydrogenated bisphenol A epoxy resin) manufactured by Nagasechemtex Co., Ltd. The epoxy equivalent is 212. The concentration of the resin component was 100% by weight. .TPP : Triphenylphosphine-25 - 201037001 [Table 2] Solid Si 1 Comparative Example Resin Composition 1 2 3 4 1 2 Appearance of Hardened Coating Film ◎ ◎ ◎ ◎ X ◎ Film Tgfc) 310 260 211 210 308 260 [Table 3] Wavelength/nm 300 400 500 600 700 Example 1 81 89 90 90 91 2 63 85 88 89 90 3 72 85 88 89 89 4 80 89 90 90 90 Example 1 0 86 89 90 90 2 0 81 87 88 88

[Simple description of the diagram] Μ 〇 jw\ [Description of main component symbols] fiE 〇 -26-

Claims (1)

201037001 VII. Patent application scope: 1. A polyimine resin which is a hetero-cyanurate type polyisocyanate uu synthesized from an isocyanate having an aliphatic structure and a tricarboxylic anhydride U2 having an aliphatic structure) Obtained by reaction. 2. The polyimine resin according to claim 1, wherein the isotrimeric acid ester type polyisocyanate compound (al) is an isomeric cyanate synthesized from an isocyanate having a cyclic aliphatic structure. The polyisocyanate of the type; the tricarboxylic anhydride U2) having an aliphatic structure is a quinonetricarboxylic anhydride having a cyclic aliphatic structure. 3. The polyimine resin according to claim 2, wherein the isomeric isocyanate polyisocyanate compound having a cyclic aliphatic structure is isomeric cyanide synthesized from isophorone diisocyanate An acid ester type triisocyanate (containing a polymer such as a pentamer); a tricarboxylic acid anhydride having a cyclic aliphatic structure, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. 4. The polyimine resin according to claim 3, wherein the isocyanate-based polyisocyanate (al) synthesized from an isocyanate having a hydrazine aliphatic structure (N) has an isocyanate number (N) Ratio of the molar number of carboxyl groups (Ml) of the tricarboxylic anhydride U2 having an aliphatic structure and the number of moles of the anhydride group (M2) [(Ml) + (M2)) / (N)] Department 1.1~3. 5. The polyimine resin according to item 4 of the patent application, wherein the acid value is 70 to 2 1 OKOH mg/g 〇 6. The polyimine resin according to any one of claims 1 to 5 It is dissolved in a polar solvent containing no nitrogen atom or sulfur atom. -27-201037001, 7. A curable resin composition characterized by comprising the polyimide resin (A) and the curable resin (B) according to any one of claims 1 to 6. 8. The curable resin composition of claim 7, wherein the curable resin (B) is an epoxy compound (B1) having two or more epoxy groups in the molecule. 9. The curable resin composition of claim 8, wherein the epoxy resin (B) is an epoxy resin having a cyclic aliphatic structure. 10. The curable resin composition of claim 9, wherein the epoxy resin having a cyclic aliphatic structure is a 1,2-ring of 2,2-bis(hydroxymethyl)-1-butanol Oxy-4-(2-epoxyethyl)cyclohexane adduct. The curable resin composition of claim 8, wherein the epoxy resin (B1) content is from 6 to 1100 parts by weight based on 100 parts by weight of the polyimine resin (A). 12. A cured product characterized by curing a hardenable bismuth resin composition of claim 7 of the patent application. -28- 201037001 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 /INN Ο 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: