Imide group-containing resin

Abstract

Provided are: an imide-group-containing resin which is suitable for adhesive applications and coating applications while maintaining excellent heat resistance of the imide-group-containing resin, and which satisfies solvent solubility, flexibility, and adhesiveness; and an adhesive composition and a coating composition which contain the imide-group-containing resin. An imide group-containing resin containing, as constituent units, a dianhydride compound (A) having an ester group or an ether group and a long-chain aliphatic dicarboxylic acid (B). And a resin composition containing the imide group-containing resin and a curing agent (C). And an adhesive composition or a coating composition containing the imide group-containing resin or the resin composition.

Description

Technical Field

[0001] The present invention relates to an imide group-containing resin composition which is excellent in solvent solubility, flexibility and adhesion and is suitable for adhesive applications and coating applications. Background Art

[0002] The imide-containing resin represented by polyimide is widely used in the base film of flexible printed circuit boards, etc., because of the excellent heat resistance, mechanical strength and insulation embodied by the aromatic monomer and the imide group. On the other hand, due to its rigid molecular structure, the solvent solubility is poor. Therefore, it is necessary to dissolve the amic acid as an imide precursor in a solvent and then apply it, apply the solvent to dry and form the imide group by dehydration ring-closure reaction of the amic acid, but in order to fully react, it is necessary to heat at more than 200°C, more preferably more than 300°C, and the available uses are limited.

[0003] When imide group-containing resins are used in applications such as adhesives and coatings while maintaining their characteristic heat resistance and mechanical strength, they are required to be easily soluble in solvents, have excellent adhesion to substrates, and be flexible. As methods for improving solvent solubility for use in adhesives and coatings, methods of copolymerizing bulky monomers to improve solvent solubility, copolymerizing monomers with soft long-chain structures, and introducing amide groups to improve solvent solubility have been discussed.

[0004] Patent Document 1 proposes that a polyimide resin having excellent solvent solubility can be obtained by using a special bulky structural monomer.

[0005] Patent Document 2 proposes using a modified polyamideimide as a main agent of an adhesive, wherein a long-chain siloxane having a flexible amino group as a reactive functional group is introduced into the molecular chain terminal of a polyimide-based resin. Prior art literature Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-196630 Patent Document 2: Japanese Patent Application Laid-Open No. 2005-179513

[0007] However, bulky structural monomers such as those in patent document 1 are very expensive due to their special structures, so they are less economical, and are difficult to impart necessary flexibility and adhesion in the applications of adhesives, coatings, etc. In addition, when using monomers with long-chain siloxane structures as in patent document 2, although flexibility can be imparted, there is a worry that the heat resistance originally possessed by the resin will decrease. In addition, it is necessary to use very expensive starting materials with siloxane bonds, which are less economical. That is, relying on existing technology, it is not possible to obtain resins and resin compositions that are excellent in solvent solubility, flexibility, and adhesion and are suitable for adhesive applications and coating applications. Summary of the invention Problem that the invention aims to solve

[0008] The present invention is proposed to solve the problems of the above-mentioned prior art, and its purpose is to provide an imide-containing resin that maintains the excellent heat resistance of the imide-containing resin and is suitable for adhesive applications and coating applications, and at the same time satisfies solvent solubility, flexibility and adhesion, as well as an adhesive composition and a coating composition containing the same. Technical means of solving problems

[0009] As a result of in-depth research conducted by the present inventors to achieve the above-mentioned purpose, it was found that when a dianhydride compound having an ester group or an ether group and a long-chain aliphatic dicarboxylic acid are introduced into an imide-containing resin, and a component having an aromatic ring is further used as an amine or isocyanate component, the obtained imide-containing resin can simultaneously satisfy the requirements of solvent solubility, flexibility, and adhesion, thereby solving the above-mentioned problems and completing the present invention.

[0010] That is, the present invention is composed of the following structures [1] to

[11] . [1] An imide group-containing resin characterized by containing a dianhydride compound (A) having an ester group or an ether group and a long-chain aliphatic dicarboxylic acid (B) as structural units. [2] The imide group-containing resin according to [1], wherein the dianhydride compound (A) is alkylene glycol bis(trimellitic anhydride). [3] The imide group-containing resin according to [1], wherein the dianhydride compound (A) is 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride or oxydiphthalic anhydride. [4] The imide group-containing resin according to [1], wherein the long-chain aliphatic dicarboxylic acid (B) is a dimer acid. [5] The imide group-containing resin according to [1] is characterized in that the copolymerization amounts of the dianhydride compound (A) and the long-chain aliphatic dicarboxylic acid (B) are each in the range of 1 to 80 mol %, based on 100 mol % of the total polycarboxylic acid component constituting the imide group-containing resin. [6] The imide group-containing resin according to [1], characterized in that the copolymerization amount of the component having an aromatic ring among the amine component and the isocyanate component is 30 mol% or more, based on 100 mol% of the total amine component amount or the total isocyanate component amount constituting the imide group-containing resin. [7] An adhesive composition comprising the imide group-containing resin according to any one of [1] to [6]. [8] A coating composition comprising the imide group-containing resin according to any one of [1] to [6]. [9] A resin composition comprising the imide group-containing resin according to any one of [1] to [6] and a curing agent (C).

[10] An adhesive composition comprising the resin composition described in [9].

[11] A coating composition comprising the resin composition described in [9]. Effects of the Invention

[0011] The imide group-containing resin of the present invention can simultaneously exhibit excellent solvent solubility, flexibility, and adhesion. Therefore, the imide group-containing resin of the present invention can be preferably used as a raw material for an adhesive composition and a coating composition. DETAILED DESCRIPTION

[0012] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these.

[0013] The imide group-containing resin of the present invention is characterized by containing a dianhydride compound (A) having an ester group or an ether group (hereinafter referred to as the dianhydride compound (A) or simply referred to as the (A) component) and a long-chain aliphatic dicarboxylic acid (B) (hereinafter referred to as the (B) component) as structural units.

[0014] <Imido group-containing resin> The imide group-containing resin refers to a resin having an imide group as a repeating unit, that is, a so-called polyimide resin, but may have other groups such as an amide group, a urethane group, an ester group, an ether group, etc. as a repeating unit in addition to the imide group.

[0015] <Dianhydride compound (A)> When the imide-containing resin of gained is used as adhesive composition, the dianhydride compound (A) with ester group or ether group has the interaction that can promote adhesive and adherend surface because of its ester group or ether group polarity, and shows the effect of firmer bonding strength.In addition, the existence of ester group or ether group makes the distance between the anhydride groups in the monomer grow longer.As a result, it is also possible to expect the raising of solvent solubility brought by the amount reduction of the imide group in the resin of gained.

[0016] As the dianhydride compound (A) having an ester group, for example, ethylene glycol bis-trimellitic anhydride, propylene glycol bis-trimellitic anhydride, 1,4-butanediol bis-trimellitic anhydride, hexamethylene glycol bis-trimellitic anhydride, polyethylene glycol bis-trimellitic anhydride, polypropylene glycol bis-trimellitic anhydride and other alkylene glycol bis-trimellitic anhydride can be mentioned. In addition, as the dianhydride compound (A) having an ether group, for example, 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic anhydride, oxydiphthalic anhydride and the like can be mentioned. In addition, a compound hydrogenated from any one of these compounds can also be used. These can be used alone or in combination. Taking the total amount of polycarboxylic acid components constituting the imide group-containing resin as 100 mol%, the copolymerization amount of the (A) component is preferably 1 to 80 mol%, more preferably 10 to 60 mol%, and further preferably 15 to 50 mol%. If the copolymerization amount of the components is less than the above lower limit, there is a concern that the solvent solubility and adhesiveness may be poor. If it exceeds the above upper limit, the amount of the long-chain aliphatic carboxylic acid described later becomes relatively small, resulting in insufficient flexibility. In addition, the raw material price increases, which may be industrially disadvantageous.

[0017] <Long-chain aliphatic dicarboxylic acid (B)> Long-chain aliphatic dicarboxylic acid (B) refers to a compound having an alkyl chain with more than 10 carbon atoms and a structure of two carboxylic acids. A portion of the alkyl chain may have a branched chain, a cyclic structure, or a double bond. For example, compounds having carboxylic acids at the ends of both molecular chains of alkanes such as dodecanedioic acid, dimer acids, etc. may be cited. These may be used alone or in combination. Among these, dimer acids are preferred. If dimer acids are used, when the resulting resin composition is used for adhesive or coating applications, flexibility and solvent solubility are easily exhibited. Dimer acids are dicarboxylic acids with 36 carbon atoms generated by dimerization of unsaturated fatty acids with 18 carbon atoms. As dimer acids, dimer acids after hydrogenation of unsaturated bonds may also be used.

[0018] Since the imide-containing resin is mainly aromatic, it is generally poor in solvent solubility. However, since the imide-containing resin of the present invention introduces a long-chain aliphatic structure, the resin skeleton is soft and the solvent solubility is improved. In addition, the imide-containing resin usually lacks fluidity and flexibility in the deformation of the substrate after the adhesive bonding process and the coating / drying, and as a result, it is difficult to obtain sufficient bonding strength to the substrate. However, in the imide-containing resin of the present invention, as a structural unit, the long-chain aliphatic dicarboxylic acid (B) participates in copolymerization, so the aliphatic chain is used to give fluidity and flexibility, and the surface of the adherend can be filled during hot pressing. As a result, the adhesion can be improved. In addition, by giving flexibility, it can be deformed as the substrate is deformed after the coating / drying. Taking the total polycarboxylic acid component amount constituting the imide-containing resin as 100 mol%, the copolymerization amount of the long-chain aliphatic dicarboxylic acid (B) is preferably 1 to 80 mol%, more preferably 10 to 70 mol%, and further preferably 30 to 60 mol%. If the copolymerization amount of the long-chain aliphatic dicarboxylic acid (B) is less than the above lower limit, solvent solubility, adhesion and flexibility may be deteriorated. If it exceeds the above upper limit, the imide group-containing resin may not have good heat resistance.

[0019] The imide-containing resin may have a polycarboxylic acid component other than the above-mentioned (A) component and (B) component. As such a polycarboxylic acid component, from the viewpoint of improving the heat resistance of the obtained imide-containing resin and adhesive or coating composition, it is preferred to use a polycarboxylic acid component with an aromatic ring. As a polycarboxylic acid component with an aromatic ring, for example, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, (hexafluoroisopropylidene) diphthalic anhydride, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, etc. These can be used alone or in combination. From the balance of heat resistance, flexibility and adhesive strength, the copolymerization amount of the polycarboxylic acid component having an aromatic ring is preferably 20 to 90 mol%, more preferably 30 to 80 mol%, and further preferably 40 to 70 mol%, based on the total amount of the polycarboxylic acid component constituting the imide group-containing resin as 100 mol%. It should be noted that when the (A) component has an aromatic ring, it is included in the calculation.

[0020] In addition, as the polycarboxylic acid component, in addition to the polycarboxylic acid components having aromatic rings described above, the monoanhydride or dianhydride compound of the long-chain aliphatic or alicyclic polycarboxylic acid or polycarboxylic acid described above can also be used within the extent that the effect of the present invention is not impaired. For example, it can be mentioned: any one of the hydrides of the polycarboxylic acid components having aromatic rings, meso-butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane dicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 2-methylsuccinic acid. These can be used alone or in combination.

[0021] The imide group-containing resin can be obtained by polymerizing a polycarboxylic acid component as a main raw material with an amine component or an isocyanate component. In this case, as the amine component, a difunctional or higher amino group-containing compound can be used; as the isocyanate component, a difunctional or higher isocyanate group-containing compound can be used.

[0022] As the isocyanate component constituting the imide group-containing resin, from the viewpoint of improving the heat resistance of the adhesive composition, a component having an aromatic ring is preferred, for example, diphenylmethane-4,4'-diisocyanate and its isomers, dimethyldiphenylmethane diisocyanate, diethyldiphenylmethane diisocyanate, dimethoxydiphenylmethane diisocyanate, diphenylether diisocyanate, benzophenone diisocyanate, diphenylsulfone diisocyanate, toluene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4'-[2,2-bis(4-phenoxyphenyl)propane] diisocyanate, dimethylbiphenyl diisocyanate, diethylbiphenyl diisocyanate, dimethoxybiphenyl diisocyanate, diethoxybiphenyl diisocyanate and their isomers, etc. In addition, as the amine component, a component in which the isocyanate group of the above-mentioned isocyanate component is substituted with an amino group can be cited. These can be used alone or in combination. Among these amine components and isocyanate components, from the balance of heat resistance, flexibility and bonding strength, the copolymerization amount of the component with aromatic ring is preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 50 mol%. The upper limit is not particularly limited, but is usually 100 mol%.

[0023] In addition, as isocyanate components or amine components, in addition to the isocyanate components or amine components with aromatic rings that have been described, aliphatic or alicyclic isocyanate components or amine components can also be used within the extent that the effect of the present invention is not impaired. For example, it can be mentioned: any one of the hydrides of the above-mentioned isocyanate components or amine components with aromatic rings, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate, etc. As amine components, it can be mentioned: components in which the isocyanate groups of these isocyanate components are substituted with amino groups. These can be used alone or in combination of multiple types. From the viewpoint of heat resistance of a resin composition using the obtained imide group-containing resin, the copolymerization amount of these components is preferably 50 mol% or less, more preferably 20 mol% or less, based on 100 mol% of the total amount of the isocyanate component and the amine component.

[0024] In the imide-containing resin, in order to increase the reaction points with the curing agent and improve the heat resistance of the obtained resin composition, a compound having more than three functional groups can be copolymerized. For example, it can be cited: polyfunctional carboxylic acids such as trimesic acid, dicarboxylic acids with hydroxyl groups such as 5-hydroxyisophthalic acid, dicarboxylic acids with amino groups such as 5-aminoisophthalic acid, glycerol, polyglycerol and other compounds with more than three hydroxyl groups, tris (2-aminoethyl) amine and other compounds with more than three amino groups. When the total amount of the total polycarboxylic acid component or the total isocyanate component and the amine component is 100 mol%, the copolymerization amount is preferably less than 20 mol%. When it exceeds 20 mol%, there is a concern that gelation occurs during resin polymerization and insoluble matter is generated.

[0025] As a component that imparts flexibility to the obtained resin, polyester, polyether, polycarbonate, polysiloxane, etc. may be copolymerized with the imide group-containing resin to the extent that the effect of the present invention is not impaired. At this time, when the copolymerization amount of these components in the imide group-containing resin is large, there is a concern that heat resistance and economic efficiency may be impaired. Therefore, the copolymerization amount of these components is preferably 10 mol% or less, based on the total amount of the total polycarboxylic acid component amount or the total isocyanate component amount and the amine component amount as 100 mol%.

[0026] <Method for producing imide group-containing resin> For the imide group-containing resin, it can be manufactured by a method of making a polycarboxylic acid component react with an isocyanate component (isocyanate method), or a method of making a polycarboxylic acid component react with an amine component to generate an amic acid and then ring-closing it (direct method), or a method of making a compound having a carboxylic anhydride and a carboxylic acid chloride react with an amine component (acid chloride method). In industry, the isocyanate method is advantageous from the viewpoint that the carbon dioxide produced as a by-product is excluded from the system as a gas.

[0027] Hereinafter, the isocyanate method will be described as a representative method for producing the imide group-containing resin. However, the imide group-containing resin can also be produced in the same manner as the above-mentioned direct method or the acid chloride method by using the corresponding amine components and compounds having carboxylic acid chloride.

[0028] The polymerization reaction of the imide-containing resin can be carried out by stirring while heating the polycarboxylic acid component and the isocyanate component to 60°C to 200°C in a solvent. At this time, the molar ratio of the polycarboxylic acid component / isocyanate component is preferably in the range of 90 / 100 to 100 / 90. It should be noted that the content (copolymerization amount) of the polycarboxylic acid component and the isocyanate component in the imide-containing resin is usually the same as the ratio of each component during polymerization. In addition, in order to promote the reaction, alkali metals such as sodium fluoride, potassium fluoride, sodium methoxide, triethylenediamine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonene, and amines such as dibutyltin dilaurate can be used. When these catalysts are too little, the intended catalytic effect cannot be fully obtained; when they are too much, there is a possibility of causing side reactions. Therefore, based on 100 mol% of the larger of the polycarboxylic acid component or the isocyanate component, it is preferably used in an amount of 0.01 to 5 mol%, and more preferably 0.1 to 3 mol%.

[0029] As solvents that can be used for the polymerization reaction of the imide-containing resin, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, γ-butyrolactone, dimethylimidazolidinone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, cyclohexanone, cyclopentanone, etc. can be cited. Among them, from the solubility of the obtained imide-containing resin and the good degree of polymerization reaction efficiency, N-methyl-2-pyrrolidone or dimethylacetamide is preferred. In addition, after the polymerization reaction, the non-volatile component concentration and solution viscosity can be adjusted by diluting with the solvent used in the polymerization reaction or other low boiling point solvents. These can be used alone or in combination.

[0030] Examples of the low boiling point solvent for dilution include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane and octane, alcohol solvents such as methanol, ethanol, propanol, butanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, ether solvents such as diethyl ether and tetrahydrofuran, and ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate.

[0031] <Resin composition> The imide group-containing resin of the present invention can be used as an adhesive or coating resin composition alone or in combination with a curing agent (C) as needed. By using the imide group-containing resin and the curing agent in combination, the imide group-containing resin with excellent heat resistance can be reinforced to be fully adhered to the substrate by reaction with the curing agent, and excellent adhesion can be given to the resin, which is suitable as an adhesive and a coating.

[0032] <Curing Agent (C)> The curing agent (C) used in combination with the imide group-containing resin is not particularly limited, and examples thereof include epoxy resins, isocyanate curing agents, polycarbodiimide, etc. Among these, epoxy resins are preferred from the viewpoints of suitability of the reaction temperature and reaction time with the imide group-containing resin, heat resistance of the obtained reactant, and stability after mixing the imide group-containing resin and the curing agent.

[0033] Epoxy resins can be modified using silicone, polyurethane, polyimide, polyamide, etc., and can also contain sulfur atoms, nitrogen atoms, etc. in the molecular skeleton. Examples of epoxy resins include bisphenol-A epoxy resins, bisphenol-F epoxy resins, bisphenol-S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, etc., cycloaliphatic epoxy resins such as glycidyl hexahydrophthalate, hydrogenated products of the above-mentioned bisphenol-type epoxy resins, hydrogenated products of the above-mentioned novolac epoxy resins, and linear aliphatic epoxy resins such as glycidyl dimer acid, epoxidized polybutadiene, and epoxidized soybean oil. In terms of heat resistance of the reactant, stability after mixing the imide group-containing resin with the curing agent, and epoxy equivalent of the epoxy resin, it is preferably 100 to 300 g / eq, and more preferably 150 to 200 g / eq. The epoxy resin is preferably a resin having an aromatic ring, and more preferably a bisphenol-type epoxy resin or a novolac-type epoxy resin.

[0034] Commercially available products of epoxy resins include, for example, bisphenol A epoxy resins such as jER828 and 1001 manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A epoxy resins such as ST-2004 and 2007 manufactured by Nippon Steel Chemical & Materials Co., Ltd., EXA-9726 manufactured by DIC Corporation, bisphenol F epoxy resins such as YDF-170 and 2004 manufactured by Nippon Steel Chemical & Materials Co., Ltd., jER152 and 154 manufactured by Mitsubishi Chemical Corporation, and Dow Chemical Co., Ltd. Phenol novolac epoxy resins such as DEN-438, dicyclopentadiene epoxy resins such as HP7200 and HP7200H manufactured by DIC Corporation, YDCN-700 series manufactured by Nippon Steel Chemicals & Materials Co., Ltd., cresol novolac epoxy resins such as EOCN-125S, 103S, and 104S manufactured by Nippon Kayaku Co., Ltd., flexible epoxy resins such as YD-171 manufactured by Nippon Steel Chemicals & Materials Co., Ltd., Epon1031S manufactured by Mitsubishi Chemical Corporation, BASF Araldite 0163 manufactured by Japan Co., Ltd., Denacol EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321 and other multifunctional epoxy resins manufactured by Nagase ChemteX Co., Ltd., Epikote 604 manufactured by Mitsubishi Chemical Corporation, YH-434 manufactured by Nippon Steel Chemical & Materials Co., Ltd., Araldite PT810 manufactured by BASF Japan Co., Ltd., CELLOXIDE manufactured by Daicel Chemical Industries, Ltd. 2021, EHPE3150, ERL4234 and other alicyclic epoxy resins manufactured by UCC, bisphenol S-type epoxy resins such as EPICLONEXA-1514 manufactured by DIC Corporation, triglycidyl isocyanurate such as TEPIC manufactured by Nissan Chemical Co., Ltd., bisxylenol-type epoxy resins such as YX-4000 manufactured by Mitsubishi Chemical Corporation, bisphenol-type epoxy resins such as YL-6056 manufactured by Mitsubishi Chemical Corporation, TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., GAN manufactured by Nippon Kayaku Co., Ltd., and glycidylamine-type epoxy resins such as ELM-120 manufactured by Sumitomo Chemical Co., Ltd.

[0035] When the non-volatile components of the resin composition are 100% by mass as a whole, the content of the imide-containing resin in the resin composition of the present invention is preferably 30 to 99% by mass, and more preferably 60 to 95% by mass. When the content of the imide-containing resin is too little, the high molecular weight component in the resin composition decreases, so it becomes brittle, and there is a worry that it is difficult to operate. On the other hand, when the content of the imide-containing resin is too much, the proportion of the curing agent decreases, and the curing is insufficient, so there is a worry that the heat resistance decreases. In addition, when the non-volatile components of the resin composition are 100% by mass as a whole, the content of the curing agent (C) in the resin composition of the present invention is preferably 1 to 70% by mass, and more preferably 5 to 40% by mass. When the content of the curing agent is too little, sufficient thermosetting properties cannot be obtained, and as a result, there is a worry that the heat resistance of the adhesive composition deteriorates. When the content of the curing agent is too much, the flexibility of the resin composition is impaired, and there is a worry that the bonding strength decreases.

[0036] <Other ingredients> In the resin composition of the present invention, in particular, when the curing agent is an epoxy resin, a further curing agent for curing the epoxy resin and a curing catalyst for promoting the reaction between the epoxy resin and the imide group-containing resin may be added within a range that does not impair the properties. The curing agent is not particularly limited as long as it is a compound that reacts with the epoxy resin, and examples thereof include: amine curing agents, compounds having phenolic hydroxyl groups, compounds having carboxylic acids, compounds having acid anhydrides, and the like. These curing agents are used to adjust the functional group equivalents of the epoxy resin and the imide group-containing resin. The curing catalyst is not particularly limited as long as it promotes the reaction of the epoxy resin with the imide group-containing resin and the above-mentioned curing agent, and examples thereof include 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, Imidazole derivatives such as 2PHZ and 2P4BHZ, guanamines such as methylguanamine and benzoguanamine, diaminodiphenylmethane, m-phenylenediamine, m-phenylenediamine, diaminodiphenyl sulfone, dicyandiamide, urea, urea derivatives, melamine, polyhydrazides and other polyamines, organic acid salts and / or epoxy adducts thereof, amine complexes of boron trifluoride, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl) Tertiary amines such as DBU (1,8-diazabicyclo[5,4,0]-7-undecene) and DBN (1,5-diazabicyclo(4,3,0)-5-nonene), organic acid salts and / or tetraphenyl borate salts thereof, polyvinylphenol, polyvinylphenol bromide, organic phosphines such as tributylphosphine, triphenylphosphine and tri-2-cyanoethylphosphine, quaternary phosphonium salts such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide, hexadecyltributylphosphonium chloride and tetraphenylphosphonium tetraphenylborate, benzyltrimethylammonium chloride, phenyltributyl chloride Quaternary ammonium salts such as ammonium chloride, the above-mentioned polycarboxylic acid anhydride, diphenyl iodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyran hexafluorophosphate, Irgacure-261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Optoma-SP-170 (manufactured by ADEKA Co., Ltd.) and other photocationic polymerization catalysts, styrene-maleic anhydride resin, equimolar reactants of phenyl isocyanate and dimethylamine, equimolar reactants of organic polyisocyanates such as toluene diisocyanate and isophorone diisocyanate and dimethylamine, etc.These curing agents and curing catalysts may be used alone or in combination of two or more.

[0037] In the resin composition of the present invention, a silane coupling agent may be added for the purpose of improving adhesion to the substrate. Specific examples thereof include aminosilane, mercaptosilane, vinylsilane, epoxysilane, methacrylsilane, isocyanatesilane, ketiminesilane, or mixtures or reactants thereof, or compounds obtained by reacting these with polyisocyanates. Examples of such silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, tris(trimethoxysilylpropyl)amine, tris(triethoxysilylpropyl)amine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2- Aminosilanes such as (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylethyldiethoxysilane, and other mercaptosilanes; vinyl Vinyl silanes such as trimethoxysilane, vinyl triethoxysilane, tri-(2-methoxyethoxy)vinyl silane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl dimethylethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl methyldimethoxysilane, γ-glycidoxypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane Silane coupling agents include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, methacryloylsilane such as triethoxysilane, isocyanatepropylsilane such as triethoxysilane, ketone imide propyltrimethoxysilane, ketone imide propyltriethoxysilane and other ketone imine silanes. All of these can be used alone, or used in combination of two or more. Among these silane coupling agents, epoxy silane has a reactive epoxy group, so it can react with an imide-containing resin, and is preferred from the viewpoint of improving heat resistance and moisture resistance. When the non-volatile component of the resin composition is 100% by mass, the mixing amount of the silane coupling agent is preferably 0 to 3% by mass, and more preferably 0 to 2% by mass. When the amount exceeds the above range, the heat resistance tends to decrease.

[0038] In the resin composition of the present invention, organic fillers and inorganic fillers may be added for the purpose of improving heat resistance within the range that does not impair the effect of the present invention. Examples of organic fillers include powders of polyimide, polyamide-imide, and the like as heat-resistant resins. In addition, examples of inorganic fillers include silicon dioxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), silicon nitride (Si3N4), barium titanate (BaO·TiO2), barium carbonate (BaCO3), lead titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O3), mullite (3A l2 O3·2SiO2), cordierite (2MgO·2Al2O3·5SiO2), talc (3MgO·4SiO2·H2O), aluminum titanate (TiO2-Al2O3), yttria-containing zirconium oxide (Y2O3-ZrO2), barium silicate (BaO·8SiO2), boron nitride (BN), calcium carbonate (CaCO3), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), barium sulfate (BaSO4), organic bentonite, clay, mica, aluminum hydroxide, magnesium hydroxide, metal phosphite, etc. Among them, silicon dioxide is preferred from the perspective of the ease of dispersion and the effect of improving heat resistance. These can be used alone or in combination of two or more. In addition, the amount of these organic fillers and inorganic fillers added is preferably 1 to 30% by mass, and more preferably 3 to 15% by mass, relative to the non-volatile component of the resin composition. When the amount of the organic filler or inorganic filler added is too large, the coating film may become brittle, and when the amount of the organic filler or inorganic filler added is too small, a sufficient effect of improving heat resistance may not be obtained. Furthermore, various contents may be used for the purpose of coloring the coating resin composition.

[0039] In the resin composition of the present invention, a flame retardant can be added for the purpose of imparting flame retardancy within the scope of not damaging the effect of the present invention. There is no particular limitation on the flame retardant available, and conventional filler-based flame retardants and solvent-soluble flame retardants can be used, and these can be used alone or in combination of two or more.

[0040] <Adhesive Composition> The imide-containing resin of the present invention and the resin composition of the present invention are suitable for use as adhesive compositions containing these because of their excellent adhesion and flexibility to substrates. There is no restriction on the use when used as an adhesive, and in particular, because of their excellent adhesion to metals and heat-resistant films, they are suitable for laminating between metals, between heat-resistant films, or between metals and heat-resistant films. Since they still retain all the heat resistance and insulation of polyimide resins, they are more specifically suitable for the construction of components of electrical and electronic products. In addition, as laminating between metals or laminating between metals and engineering plastics, they can also be used for automotive structures, interior adhesives, and architectural adhesives.

[0041] <Coating composition> The imide group-containing resin and the resin composition of the present invention are suitable for use as a coating composition containing them because they have excellent adhesion to a substrate and flexibility. When used as a coating agent, the use is not particularly limited, but in particular, since they have excellent adhesion to metals and heat-resistant films or excellent flexibility, they are also suitable for applications requiring processing adaptability such as bending a substrate after coating and drying. Example

[0042] The effects of the present invention are demonstrated below by way of examples, but the present invention is not limited thereto. It should be noted that the property evaluations in the examples were performed according to the following methods.

[0043] (Evaluation method of solvent solubility) In the polymerization of the imide group-containing resin described below, the fluidity of the solution was observed at three time points: dilution, removal, and 1 hour after mixing with a curing agent to prepare an adhesive composition, and the solvent solubility was evaluated based on the following evaluation criteria. (Evaluation Criteria) A: Liquidity is maintained at any of the above time points B: The fluidity cannot be maintained at any of the above time points, and the substance becomes insoluble or solidified.

[0044] (As a method for evaluating the adhesiveness of an adhesive) The resin composition solution was applied to a polyimide film (Apical 12.5NPI manufactured by Kaneka) until the thickness after drying reached 20 μm, and dried at 140°C using a hot air dryer for 3 minutes to obtain a sample in a B-stage state. The resin composition-coated surface of the B-stage sample was overlapped with the glossy surface of a copper foil (BHY thickness 18 μm manufactured by JX Nippon Mining and Petrochemical Co., Ltd.), placed in an oven heated to 150°C, and thermally cured for 4 hours. For the thermally cured sample, a tensile tester (Automatic Drawing AG-X plus manufactured by Shimadzu) was used to pull the copper foil in a 180° direction at a speed of 50 mm / min in an atmosphere of 25°C to measure the bonding strength, and the bonding properties were evaluated according to the following evaluation criteria. (Evaluation Criteria) A: Adhesion strength is 0.5N / mm or more B: Adhesion strength is less than 0.5N / mm

[0045] (As a method for evaluating the adhesion of coatings) A resin composition mixed with a curing agent was applied to an aluminum plate having a thickness of 0.3 mm until the thickness after drying reached 5 μm. The plate was dried and cured at 100° C. for 5 minutes and at 230° C. for 10 minutes. Then, a grid-like cut of 10×10 grids, totaling 100 grids, was cut on the surface coated with the resin composition. A scotch tape (registered trademark) was affixed to the surface. The scotch tape was peeled off at an angle of 60°, and the peeling of the resin composition was observed. The adhesion was evaluated according to the following evaluation criteria. (Evaluation Criteria) A: Even one grid has not been peeled off B: There is more than one peeling

[0046] (As a method for evaluating the processing suitability of coatings) A resin composition mixed with a curing agent was applied to an aluminum plate having a thickness of 0.3 mm until the thickness after drying reached 5 μm. After drying and curing at 100°C for 5 minutes and at 230°C for 10 minutes, the coated surface of the resin composition was bent 180° outward to observe whether the bent portion of the resin composition had cracks or peeling, and the processing adaptability was evaluated according to the following evaluation criteria. (Evaluation Criteria) A: No cracks or peeling B: Cracks or peeling

[0047] (Production Example of Imide Group-Containing Resin (1)) In a four-necked separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer, 30 mol parts of trimellitic anhydride, 20 mol parts of BPADA, 50 mol parts of dimer acid, 100 mol parts of diphenylmethane diisocyanate and N-methyl-2-pyrrolidone as a polymerization solvent were added until the concentration of the decarboxylated resin component reached 40% by mass, and the temperature was raised to 100° C. under nitrogen to react for 2 hours, and further raised to 150° C. to react for 5 hours. Thereafter, cyclohexanone was added as a diluting solvent to dilute the mixture to a resin component concentration of 30% by mass, to prepare a solution of an imide group-containing resin (1).

[0048] (Production Example of Imido Group-Containing Resins (2) to (13)) Solutions of imide group-containing resins (2) to (13) were prepared in the same manner as in the imide group-containing resin 1 except that the types and amounts of the raw materials and the solvent were changed to the resin compositions shown in Table 1.

[0049] The details of the raw materials used in Table 1 are as follows. Dimer acid: Croda manufactured PRIPOL1013 Hydrogenated dimer acid: Croda manufactured PRIPOL1009 Dodecanedioic acid: Made by Fujifilm Wako Pure Chemical Industries, Ltd. BPADA: 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ODPA: Oxydiphthalic anhydride manufactured by Tokyo Chemical Industry TMEG: Ethylene glycol bis(trimellitic anhydride) manufactured by Shin Nippon Rika Co., Ltd. TMPG: Trylead Chemical manufactures propylene glycol bis(trimellitic anhydride) TMA: Trimellitic anhydride manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. PMDA: Tokyo Chemical Industry Co., Ltd. pyromellitic anhydride MDI: Methylene diphenyl diisocyanate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. TDI: Toluene diisocyanate manufactured by Tokyo Chemical Industry ToDI: Nippon Soda manufactures dimethyl biphenyl diisocyanate NMP: N-methyl-2-pyrrolidone manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. DMAc: N,N-dimethylacetamide manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0050] [Table 1]

[0051] <Example 1> A resin composition was prepared by mixing 85 parts by weight of a solution of an imide group-containing resin (1) in terms of solid content and 15 parts by weight of jER828 (epoxy resin (C) as a curing agent) in terms of solid content. It should be noted that a dimethylacetamide solution having a solid content of 30% by weight of jER828 was prepared in advance for use. The adhesive composition obtained was subjected to various evaluations of adhesion as an adhesive, adhesion as a coating, and processing adaptability. The results are shown in Table 2.

[0052] <Examples 2 to 13, Comparative Examples 1 to 3> The resin composition was prepared in the same manner as in Example 1 except that the type and amount of the imide-containing resin and the curing agent were changed to the adhesive composition mixture shown in Table 2. It should be noted that a dimethylacetamide solution with a solid content of 30% by mass was prepared in advance for the curing agent. The adhesive properties of the obtained adhesive composition were evaluated as an adhesive, the adhesion of the coating, and the processing adaptability. The results are shown in Table 2.

[0053] The details of the curing agents used in Table 2 are as follows. jER828: Epoxy resin manufactured by Mitsubishi Chemical (bisphenol type epoxy resin, epoxy equivalent 189 g / eq) jER152: Epoxy resin manufactured by Mitsubishi Chemical (phenol novolac type epoxy resin, epoxy equivalent 177 g / eq) jER1001: Epoxy resin manufactured by Mitsubishi Chemical (bisphenol type epoxy resin, epoxy equivalent 475 g / eq)

[0054] [Table 2]

[0055] As shown in Table 2, the resin compositions of Examples 1 to 11 that meet the necessary conditions of the present invention can simultaneously exhibit excellent solvent solubility, flexibility, and adhesion, and are suitable for adhesive and coating applications. In contrast, in Comparative Example 1, since the imide-containing resin does not have a long-chain aliphatic dicarboxylic acid (B) as a structural unit, although it exhibits adhesion to the substrate as a coating, in the evaluation of adhesive adhesion and coating processing adaptability accompanied by large deformation of the resin composition during the test, the flexibility is insufficient and good results cannot be obtained. In Comparative Example 2, since the imide-containing resin does not contain a dianhydride compound (A) having an ester group or an ether group as a structural unit, the adhesion to the substrate is poor, and as a result, the adhesive adhesion, coating adhesion, and coating processing adaptability are poor. In Comparative Example 3, since the imide group-containing resin does not contain the dianhydride compound (A) having an ester group or an ether group and the long-chain aliphatic dicarboxylic acid (B) as structural units, the solvent solubility is extremely poor, and the resin does not dissolve during the polymerization of the imide group-containing resin. Therefore, a resin composition cannot be obtained and cannot be evaluated as an adhesive and a coating. Industrial Applicability

[0056] Since the resin composition using the imide group-containing resin of the present invention is excellent in solvent solubility, flexibility, and adhesion, it is suitable for use in adhesives, coatings, etc. Therefore, the present invention is extremely useful industrially.

Claims

1. An imide group-containing resin, characterized in that: It contains a dianhydride compound (A) having an ester group or an ether group and a long-chain aliphatic dicarboxylic acid (B) as structural units.

2. The imide group-containing resin according to claim 1, characterized in that: The dianhydride compound (A) is alkylene glycol bis(trimellitic anhydride).

3. The imide group-containing resin according to claim 1, characterized in that: The dianhydride compound (A) is 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride or oxydiphthalic anhydride.

4. The imide group-containing resin according to claim 1, characterized in that: The long-chain aliphatic dicarboxylic acid (B) is a dimer acid.

5. The imide group-containing resin according to claim 1, characterized in that: The copolymerization amounts of the dianhydride compound (A) and the long-chain aliphatic dicarboxylic acid (B) are each in the range of 1 to 80 mol % based on 100 mol % of the total polycarboxylic acid component amount constituting the imide group-containing resin.

6. The imide group-containing resin according to claim 1, characterized in that: The copolymerization amount of the component having an aromatic ring among the amine components and the isocyanate components is 30 mol% or more, based on 100 mol% of the total amine component amount or the total isocyanate component amount constituting the imide group-containing resin.

7. An adhesive composition, characterized in that: The present invention comprises the imide group-containing resin according to any one of claims 1 to 6.

8. A coating composition, characterized in that The present invention comprises the imide group-containing resin according to any one of claims 1 to 6.

9. A resin composition, characterized in that The method comprises the imide group-containing resin according to any one of claims 1 to 6 and a curing agent (C).

10. An adhesive composition, characterized in that: A resin composition comprising the resin composition according to claim 9.

11. A coating composition, characterized in that: A resin composition comprising the resin composition according to claim 9.

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