Amide imide resin composition, curable resin composition, cured product and article

Abstract

To provide an amide imide resin composition that ensures excellent elongation and substrate adhesion in cured products, a curable resin composition containing the same, a cured product of the curable resin composition, and an article.SOLUTION: An amide imide resin composition contains an amide imide resin (A) with acid groups and / or acid anhydride groups and an epoxy compound (B) with two or more epoxy groups in each molecule. The amide imide resin (A) comprises a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) as essential reaction materials.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an amide-imide resin composition having excellent elongation and adhesion to a substrate in a cured product, a curable resin composition containing the same, a cured product of the curable resin composition, and an article. [Background technology]

[0002] Polyamide-imide resin is a material that has excellent heat resistance and mechanical properties and is used in various fields, primarily in the electrical and electronics industry.

[0003] For example, it is known to use a thermosetting resin composition that contains a carboxyl group-containing polyimide and a compound containing an oxirane ring as a polyamide-imide resin, and that the carboxyl group-containing polyimide has a structure in which a terminal acid anhydride group-containing imide prepolymer obtained by reacting an acid anhydride group in a tetracarboxylic dianhydride with an isocyanate group in a diisocyanate compound is chain-extended via a polyol compound (Patent Document 1). On the other hand, there is room for consideration in the selection of raw materials used for a resin composition having excellent elongation and substrate adhesion in a cured product. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2013-177548 A Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, an object of the present invention is to provide an amide-imide resin composition having excellent elongation and adhesion to a substrate in a cured product, a curable resin composition containing the same, a cured product of the curable resin composition, and an article. [Means for solving the problem]

[0006] As a result of intensive research conducted by the present inventors to solve the above-mentioned problems, they have found that an amide-imide resin composition containing an amide-imide resin having an acid group and / or an acid anhydride group obtained by reacting a polyisocyanate compound with a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof, and an epoxy compound having two or more epoxy groups in the molecule, has excellent elongation and adhesion to substrates in the cured product, which has led to the completion of the present invention.

[0007] That is, the present invention provides an amide-imide resin composition containing an amide-imide resin (A) having an acid group and / or an acid anhydride group, and an epoxy compound (B) having two or more epoxy groups in the molecule, The present invention relates to an amide-imide resin composition, characterized in that the amide-imide resin (A) contains, as essential reaction raw materials, a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2).

[0008] The present invention further relates to a curable resin composition containing the amide-imide resin composition.

[0009] The present invention further relates to a cured product of the curable resin composition.

[0010] The present invention further relates to an article having a coating film made of the above-mentioned cured product. Effect of the Invention

[0011] According to the present invention, it is possible to provide an amide-imide resin composition having excellent elongation and adhesion to a substrate in a cured product, a curable resin composition containing the same, a cured product of the curable resin composition, and an article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in detail below.

[0013] (Definition of terms) In the present specification, examples of the "substituent" include, but are not limited to, Hydroxyl group, aldehyde group, carboxyl group, alkoxy group, acyl group, acyloxy group, alkoxycarbonyl group, amino group, sulfo group, a linear or branched saturated aliphatic hydrocarbon group (for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms); A linear or branched unsaturated aliphatic hydrocarbon group (for example, a linear or branched alkenyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms); a group in which a methylene in the saturated aliphatic hydrocarbon group or unsaturated aliphatic hydrocarbon group is replaced with a "divalent group containing an oxygen atom, a nitrogen atom, and / or a sulfur atom" described below; A group in which a hydrogen atom in the saturated aliphatic hydrocarbon group or unsaturated aliphatic hydrocarbon group is substituted with a hydroxyl group, an aldehyde group, a carboxyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an amino group, a sulfo group, or the like. Examples include:

[0014] As used herein, the term "linker" refers to a divalent group or bond.

[0015] In the present specification, examples of the "divalent group" include, but are not limited to, a divalent group having an aliphatic hydrocarbon structure, a divalent group containing an oxygen atom, a nitrogen atom, and / or a sulfur atom, and A divalent group formed by linking two or more of these etc.

[0016] In the present specification, examples of the "divalent group having an aliphatic hydrocarbon structure" include, but are not limited to, a divalent group having a linear or branched saturated aliphatic hydrocarbon structure (e.g., a linear or branched alkylene group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms); a divalent group having a linear or branched unsaturated aliphatic hydrocarbon structure (e.g., a linear or branched alkenylene group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms); a divalent group in which a methylene in the divalent group having a saturated aliphatic hydrocarbon structure or the divalent group having an unsaturated aliphatic hydrocarbon structure is replaced with a divalent group containing an oxygen atom, a nitrogen atom, and / or a sulfur atom; A divalent group formed by linking two or more of these etc.

[0017] In the present specification, examples of the "divalent group containing an oxygen atom, a nitrogen atom, and / or a sulfur atom" include, but are not limited to, a carbonyl group (-C(=O)-), -O-, -S-, -SO 2 -, -N=N-, or [ka] [In formula (am-1), R am is a hydrogen atom or an arbitrary substituent selected from a hydroxyl group, an aldehyde group, a carboxyl group, an alkoxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an amino group, a sulfo group, a linear or branched saturated aliphatic hydrocarbon group, and a linear or branched unsaturated aliphatic hydrocarbon group. and the like.

[0018] In this specification, examples of the "halogen" in the terms "halogen atom" and "halide" include fluorine, chlorine, bromine, and iodine.

[0019] (Amide-imide resin composition) The amide-imide resin composition of the present invention is an amide-imide resin composition containing an amide-imide resin (A) having an acid group and / or an acid anhydride group, and an epoxy compound (B) having two or more epoxy groups in the molecule, The amide-imide resin (A) is characterized in that it contains, as essential reaction raw materials, a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2).

[0020] The amide-imide resin (A) having an acid group and / or an acid anhydride group may have only one of an acid group and an acid anhydride group, or may have both. Among them, from the viewpoint of obtaining an amide-imide resin composition having excellent elongation and substrate adhesion in a cured product, it is preferable that the resin has an acid anhydride group, and it is preferable that the resin has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin (A) is preferably in the range of 60 to 250 mgKOH / g measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 300 mgKOH / g measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0021] <Amide-imide resin (A) having an acid group and / or an acid anhydride group> The amide-imide resin (A) is characterized in that it contains a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) as essential reaction raw materials. The amide-imide resin (A) may contain any reaction raw materials other than the polyisocyanate compound (a1) and the trans-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) (hereinafter, sometimes referred to as "other reaction raw materials (a3)") as further optional reaction raw materials.

[0022] <Polyisocyanate compound (a1)> The polyisocyanate compound (a1) is a compound having two or more isocyanate groups (-NCO). The number of isocyanate groups in the polyisocyanate compound (a1) is two or more, for example, 2 to 15. In one embodiment, the polyisocyanate compound (a1) includes a compound having 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, 13 or more, or 14 or more isocyanate groups. In another embodiment, the polyisocyanate compound (a1) includes a compound having 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less isocyanate groups. In yet another embodiment, the polyisocyanate compound (a1) includes a compound having 2, 3, 4, or 5 isocyanate groups. Hereinafter, for convenience, the polyisocyanate compound (a1) may be collectively represented by the following structural formula (I). OCN-G-(NCO) n (I) (In the formula, G represents any chemical structure, and n represents an integer of 1 or more.)

[0023] The polyisocyanate compound (a1) is not particularly limited, and a known polyisocyanate compound can be used. Examples of the polyisocyanate compound (a1) include diisocyanate compounds, polymeric polyisocyanate compounds having a repeating structure with an isocyanate group (-NCO), polyisocyanate compounds having an isocyanurate structure in a part of the structure (also called "nurate modified body" or "nurate body"), polyisocyanate compounds having a biuret structure in a part of the structure (also called "biuret body"), and polyisocyanate compounds having an allophanate structure in a part of the structure (also called "allophanate body").

[0024] <Diisocyanate compounds> A diisocyanate compound is a compound that has two isocyanate groups (-NCO) and has the general formula: OCN-R ic -NCO [In the formula, R ic is a divalent group having a hydrocarbon structure, which may be substituted with a substituent and may contain an oxygen atom, a nitrogen atom, and / or a sulfur atom, and examples of such a divalent group include the following R ic1 , R ic2 , or R ic3 It may be defined as follows. In this case, G in structural formula (I) is R ic and n corresponds to 1. Examples of the diisocyanate compound include an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, and an aromatic diisocyanate compound.

[0025] <<Aliphatic diisocyanate compounds>> The term "aliphatic diisocyanate compound" refers to a compound that contains a linear or branched, saturated or unsaturated aliphatic hydrocarbon structure in its structure, does not contain an alicyclic structure or an aromatic ring, and the aliphatic hydrocarbon structure may be substituted with a substituent and may contain an oxygen atom, a nitrogen atom, and / or a sulfur atom. Examples of the aliphatic diisocyanate compound include compounds represented by the general formula: OCN-R ic1 -NCO [In the formula, R ic1 is the "divalent group having an aliphatic hydrocarbon structure" defined above. Examples of the compound include compounds represented by the following formula:

[0026] R ic1 Examples of the "divalent group having an aliphatic hydrocarbon structure" represented by the formula: The following structural formula (x-1): [ka] [In formula (x-1), "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO), R x1each independently represents a substituent, p1 represents an integer of 1 or more (for example, an integer from 1 to 20); Each q1 independently represents an integer of 0 or more (for example, an integer of 0 to 3). A divalent group represented by the formula: A divalent group in which the methylene in the divalent group represented by the above structural formula (x-1) is replaced with the above "divalent group containing an oxygen atom, a nitrogen atom, and / or a sulfur atom." etc.

[0027] R in structural formula (x-1) x1 Examples of the substituents represented by are as defined above.

[0028] R ic1 is represented by the above structural formula (x-1), specific examples of structural formula (x-1) include structures represented by the following structural formulae (x-1-1) to (x-1-8) and structures in which hydrogen atoms in the structures represented by the following structural formulae (x-1-1) to (x-1-8) are substituted with the substituents exemplified in the definition of "substituent" above. [ka] [ka] (In the formula, "*" indicates the point of attachment of the isocyanate group (-NCO) to the nitrogen atom.)

[0029] Specific examples of the aliphatic diisocyanate compound include monomethylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetratrimethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0030] <<Alicyclic diisocyanate compounds>> The term "alicyclic diisocyanate compound" refers to a compound that contains an alicyclic structure and two isocyanate groups in its structure and does not contain an aromatic ring. Examples of alicyclic diisocyanate compounds include those represented by the general formula: OCN-R ic2 -NCO [In the formula, R ic2 is a divalent group having an alicyclic hydrocarbon structure, the alicyclic hydrocarbon structure may be substituted with a substituent and may contain an oxygen atom, a nitrogen atom, and / or a sulfur atom. In the formula, R ic2 Examples of the alicyclic structure contained in include a cycloalkane ring having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms (e.g., cyclopropane, cyclobutane, cyclopentane, cyclohexane, etc.), a cycloalkene ring having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms (e.g., cyclohexene, cyclohexadiene, etc.), a condensed ring formed by combining two or more of these rings, a bridged ring (e.g., a bicyclo ring), a spiro ring, or a polycycle formed by combining these (e.g., norbornane, etc.), and a hydrogenated aromatic ring (e.g., a hydrogenated benzene ring, etc.). ic2 The "substituents" that may be possessed by R are as defined above. ic2 When has a "substituent", the number of the "substituents" may be, for example, 1 or more and 10 or less. The "substituents" may be the same or different. In the alicyclic diisocyanate compound, the isocyanate group (-NCO) may be bonded to either the ring structure portion or the substituent portion.

[0031] Alicyclic diisocyanate compounds have the general formula: OCN-R ic2 -NCO, R ic2 can be represented, for example, by the following structural formula (x-2) or (x-3). [ka] [ka] [In the formula (x-2) or (x-3), "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO), Ac a , Ac b , and Ac c each independently represents an alicyclic structure, R x2 , R x3 , and R x4 each independently represents a substituent, L x1 , L x2 , L x1’ , L x2’ , and L x3 each independently represents a linker, q2, q3, and q4 each independently represent an integer of 0 or more (for example, an integer of 0 to 3).

[0032] Ac in structural formula (x-2) or (x-3) a , Ac b , or Ac c Examples of the alicyclic structure represented by the formula (I) include cycloalkane monocyclic structures such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; cycloalkene monocyclic structures such as cyclopropene, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cyclooctene, cyclononene, and cyclodecene; condensed rings formed by combining two or more of these monocyclic structures (e.g., hydrindane, decahydronaphthalene, etc.), bridged rings (e.g., bicyclo rings such as norbornane, norbornene, and norbornadiene, cage molecules such as adamantane), spiro rings such as spirodecane, and polycyclic structures formed by combining these.

[0033] R in structural formula (x-2) or (x-3) x2 , R x3 , or R x4 The substituents represented by are as defined above.

[0034] L in structural formula (x-2) or (x-3)x1 , L x2 , L x1’ , L x2’ , and L x3 The linker represented by is as defined above.

[0035] R ic2 is represented by the above structural formula (x-2), specific examples of structural formula (x-2) include structures represented by any of the following structural formulae (x-2-1) to (x-2-8) and structures in which a hydrogen atom in the structure represented by the following structural formulae (x-2-1) to (x-2-8) is the above-mentioned "R x2 , R x3 , or R x4 Examples of the substituent include a structure substituted with a substituent exemplified as "the substituent represented by the formula: [ka] [ka] [ka] In the formula, "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO).

[0036] R ic2 When represented by the above structural formula (x-3), specific examples of structural formula (x-3) include those represented by any of the following structural formulas (x-3-1) to (x-3-3). [ka] In the formula, "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO).

[0037] Specific examples of the alicyclic diisocyanate compound include cyclohexane diisocyanate, cyclohexene diisocyanate, cyclohexane di(methylene isocyanate), isophorone diisocyanate, norbornane diisocyanate, norbornane di(methylene isocyanate), adamantane diisocyanate, pentylhexenylcyclohexeneoctamethylene isocyanatenonamethylene isocyanate, bicyclohexyl diisocyanate, methylene bis(cyclohexyl isocyanate), dimethylmethylene bis(cyclohexyl isocyanate), and the like.

[0038] <<Aromatic diisocyanate compounds>> The term "aromatic diisocyanate compound" refers to a compound containing an aromatic ring and two isocyanate groups in the structure. In this specification, the "aromatic ring" may be a condensed ring with an alicyclic structure. The "aromatic diisocyanate compound" may optionally further contain a hydrocarbon structure other than the aromatic ring in the structure (e.g., a linear or branched aliphatic hydrocarbon structure, an alicyclic hydrocarbon structure). Examples of aromatic diisocyanate compounds include those represented by the general formula: OCN-R ic3 -NCO [In the formula, R ic3 is a divalent group containing a structure containing an aromatic ring which may contain an oxygen atom, a nitrogen atom, and / or a sulfur atom, each of which may be substituted with a substituent. In the formula, R ic3 Examples of the ring structure constituting the "aromatic group" of the formula include a benzene ring and a naphthalene ring. ic3 Examples of the "substituents" that may be possessed by R include linear or branched aliphatic hydrocarbon groups (e.g., linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms), alicyclic hydrocarbon groups (e.g., cycloalkyl groups, cycloalkenyl groups, and groups having polycyclic structures such as condensed rings, bridged rings, and spiro rings, each having 3 to 30 carbon atoms). ic3When has a "substituent", the number of the "substituents" may be, for example, 1 or more and 10 or less. The "substituents" may be the same or different. In the aromatic diisocyanate compound, the isocyanate group (-NCO) may be bonded to either the ring structure portion or the substituent portion. Specific examples of aromatic diisocyanate compounds include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, diisocyanatodimethylbiphenyl, tolidine diisocyanate, etc.

[0039] The aromatic diisocyanate compound has the general formula: OCN-R ic3 -NCO, R ic3 can be represented by, for example, any of the following structural formulas (x-4) to (x-6). [ka] [ka] [ka] [In formulas (x-4) to (x-6), "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO), Ar a , Ar b , Ar c , and Ar d each independently represents an aromatic ring; Ac d represents an alicyclic structure, R x5 , R x6 , R x7 , R x8 , and R x9 each independently represents a substituent, L x4 , L x5 , L x6 , L x7 , L x8 , L x9 , Lx10 , and L x11 each independently represents a linker, q5, q6, q7, q8, and q9 each independently represent an integer of 0 or more (for example, an integer of 0 to 3).

[0040] Ar in structural formulas (x-4) to (x-6) a , Ar b , Ar c , and Ar d Examples of the aromatic ring represented by the formula (I) include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, an indane ring, an indene ring, a tetralin ring, a biphenylene ring, and a fluorene ring.

[0041] Ac in structural formula (x-6) d Examples of the alicyclic structure that can be represented by the formula (x-2) or (x-3) are a , Ac b , or Ac c This is the same as the example of "alicyclic structure represented by the formula:

[0042] R in structural formulas (x-4) to (x-6) x5 , R x6 , R x7 , R x8 , and R x9 Examples of the substituent represented by the formula (x-1) are R x1 These are the same as those exemplified as "the substituent represented by the formula:

[0043] L in structural formulas (x-4) to (x-6) x4 , L x5 , L x6 , L x7 , L x8 , L x9 , L x10 , and L x11 Examples of the linker represented by the formula (x-2) or (x-3) are x1 , L x2 , or L x3 The linker is the same as that exemplified above as the linker represented by the formula:

[0044] R ic3 is represented by the above structural formula (x-4), specific examples of structural formula (x-4) include structures represented by the following structural formulae (x-4-1) to (x-4-11) and structures in which a hydrogen atom in the structure represented by the following structural formulae (x-4-1) to (x-4-11) is the above-mentioned "R x5 , R x6 , R x7 , R x8 , and R x9 Examples of the substituent include a structure substituted with a substituent exemplified as "the substituent represented by the formula: [ka] [ka] [ka] [ka] In the formula, "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO).

[0045] R ic3 is represented by the above structural formula (x-5), specific examples of structural formula (x-5) include structures represented by the following structural formulae (x-5-1) to (x-5-11) and structures in which a hydrogen atom in the structure represented by the following structural formulae (x-5-1) to (x-5-11) is the above-mentioned "R x5 , R x6 , or R x7 Examples of the substituent include a structure substituted with a substituent exemplified as "the substituent represented by the formula: [ka] [ka] [ka] [ka] [ka] In the formula, "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO).

[0046] R ic3 is represented by the above structural formula (x-6), specific examples of structural formula (x-6) include structures represented by the following structural formulae (x-6-1) to (x-6-8) and structures in which a hydrogen atom in the structure represented by the following structural formulae (x-6-1) to (x-6-8) is not represented by the above "R x5 , R x6 , or R x7 Examples of the substituent include a structure substituted with a substituent exemplified as "the substituent represented by the formula: [ka] [ka] [ka] In the formula, "*" indicates the point of attachment to the nitrogen atom of the isocyanate group (-NCO).

[0047] Specific examples of the aromatic diisocyanate compound include: Phenol diisocyanate, phenol di(methylene isocyanate), phenol di(isopropyl isocyanate), naphthalene diisocyanate, Indane diisocyanate, indene diisocyanate, tetralin diisocyanate, Biphenyl diisocyanate, benzyl methylphenol diisocyanate, Phenylisopropyl(isopropyl)phenol diisocyanate, Phenylnaphthalene diisocyanate, Indanylbenzene diisocyanate, indenylbenzene diisocyanate, tetralinylbenzene diisocyanate, Cyclohexanylbenzene diisocyanate, cyclohexanedimethylenebenzene diisocyanate, isophoronylbenzene diisocyanate, Examples thereof include cyclohexenylbenzene diisocyanate, pentylhexenylcyclohexeneoctamethylene isocyanate, nonylenebenzene isocyanate, and the like.

[0048] <Polymer-type polyisocyanate compounds> Examples of polymeric polyisocyanate compounds having a repeating structure having an isocyanate group (-NCO) include polymethylene polyphenyl polyisocyanates having a repeating structure represented by structural formula (11) in JP 2021-102714 A.

[0049] [ka] [In the formula, R 1 R are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 2 are each independently either an alkyl group having 1 to 4 carbon atoms or a bonding point connecting the structural portion represented by structural formula (11) via a methylene group marked with an *, l is an integer of 0 to 5, and m is an integer of 2 to 15.

[0050] <Polyisocyanate compounds having an isocyanurate structure (nurate form)> Diisocyanate compounds (i.e., the above-mentioned general formula "OCN-R ic -NCO” [in the formula, R ic The definitions and examples are as described above.]) polyisocyanate compounds (hereinafter, sometimes referred to as "nurate compounds") are compounds having a structure represented by the following structural formula (NU-1), (NU-2) or (NU-3). [ka] [ka] [ka] [In formulas (NU-1) to (NU-3), R icThe definitions and examples are as described above.] Examples of the nurate form include a nurate form of an aliphatic diisocyanate compound, a nurate form of an alicyclic diisocyanate compound, and a nurate form of an aromatic diisocyanate compound.

[0051] <<Nurate form of aliphatic diisocyanate compound>> The nurate form of an aliphatic diisocyanate compound is a compound represented by the above structural formula (NU-1), (NU-2) or (NU-3), where R ic is the above R ic1 (R ic1 The definition and examples are as described above. Specific examples of the nurate form of the aliphatic diisocyanate compound include the nurate form derived from the above-mentioned aliphatic diisocyanate compound.

[0052] <<Nurate derivatives of alicyclic diisocyanate compounds>> The nurate form of the alicyclic diisocyanate compound is a compound represented by the formula (NU-1), (NU-2) or (NU-3) above, where R ic is the above R ic2 (R ic2 The definition and examples are as described above. Specific examples of the alicyclic diisocyanate compound include nurate derivatives derived from the above-mentioned diisocyanate compounds such as isophorone diisocyanate.

[0053] An example of the nurate of the alicyclic diisocyanate compound is the nurate of isophorone diisocyanate. The nurate of isophorone diisocyanate may have a wide variety of structures, and among these, the following structural formulas (IP-1), (IP-2) and (IP-3) are shown. [ka] [ka] [ka]

[0054] Examples of the nurate form of isophorone diisocyanate include nurate forms having three isocyanate groups as represented by the above structural formula (IP-1), (IP-2), or (IP-3), nurate forms having a total of four or five isocyanate groups, and mixtures thereof.

[0055] <<Nurate form of aromatic diisocyanate compound>> The nurate form of an aromatic diisocyanate compound is a compound represented by the above structural formula (NU-1), (NU-2) or (NU-3), in which R ic is the above R ic3 (R ic3 The definition and examples are as described above. Specific examples of the aromatic diisocyanate compound include nurate derivatives derived from the aromatic diisocyanate compounds described above.

[0056] <Polyisocyanate compounds having a biuret structure (biuret compounds)> The "biuret structure" in the polyisocyanate compound having a biuret structure (hereinafter, simply referred to as "biuret compound") is -N(CONH-) 2 The biuret form has the general formula (BU): OCN-R ic -N(CONH-R ic -NCO) 2 (BU) [In the formula, R ic The definitions and examples are as described above.] Examples of the biuret compound include a biuret compound of an aliphatic diisocyanate compound (i.e., a compound represented by the general formula (BU) above, represented by R ic is the R explained above. ic1 a biuret compound of an alicyclic diisocyanate compound (i.e., a compound represented by the general formula (BU) above, represented by R icis the R explained above. ic2 and a biuret compound of an aromatic diisocyanate compound (i.e., a compound represented by the general formula (BU) above, represented by R ic is the R explained above. ic3 Compounds in which

[0057] <Polyisocyanate compounds having an allophanate structure (allophanate compounds)> The "allophanate structure" in a polyisocyanate compound having an allophanate structure (hereinafter, sometimes simply referred to as an "allophanate body") refers to -OC(O)NC(O)-NH-. The allophanate body may be a compound represented by the general formula (AP): OCN-R ic -OC(O)NC(O)-NH-NCO (AP) [In the formula, R ic The definitions and examples are as described above.] The allophanate compound includes an allophanate compound of an aliphatic diisocyanate compound (i.e., a compound represented by the general formula (AP) above, ic is the R explained above. ic1 (i.e., a compound represented by the general formula (AP) above) and an allophanate compound of an alicyclic diisocyanate compound (i.e., a compound represented by the general formula (AP) above) ic is the R explained above. ic2 and an allophanate of an aromatic diisocyanate compound (i.e., a compound represented by the above general formula (AP) where R ic is the R explained above. ic3 Compounds in which

[0058] Examples of commercially available isocyanate compounds include, for example, the "VESTANAT (registered trademark)" series from EVONIK (IPDI, TMDI, H12MDI, T 1890 E, T 1890 L, T 1890 M, T 1890 / 100, etc.); the "Takenate (registered trademark)" series from Mitsui Chemicals (D-127N, etc.); and the "BURNOCK (registered trademark)" series from DIC Corporation (DN-901S, DN-902S, DN-980, DN-980S, DN-981, DN-992-S, etc.).

[0059] Among these, isocyanurate-modified products are preferred because they result in an amide-imide resin composition having excellent elongation and substrate adhesion in the cured product, and isocyanurate-modified products of aliphatic diisocyanate compounds or alicyclic diisocyanate compounds are more preferred. Further, the proportion of the isocyanurate-modified product relative to the total mass of the polyisocyanate compound (a1) is preferably 70% by mass or more, and preferably 90% by mass or more.

[0060] <trans-isomer-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2)> The "trans-isomer-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2)" (hereinafter also referred to as the "polycarboxylic acid compound (a2)") is an alicyclic polycarboxylic acid compound or its acid anhydride that contains a trans-isomer among them.

[0061] <Definition of terms related to carboxylic acids, etc.> In this specification, the "acid anhydride group" refers to a structure formed by dehydration condensation of two carboxyl groups (hereinafter referred to as "two adjacent carboxyl groups"), one carboxyl group bonded to one of two skeleton structure-forming carbon atoms adjacent to each other in a hydrocarbon-based skeleton structure (e.g., an alicyclic skeleton) and one carboxyl group bonded to the other carbon atom. In this specification, for convenience, the "number of carboxyl group substitutions" refers to [number of carboxyl groups] + 2 × [number of acid anhydride groups]. Similarly, the "molar number of carboxyl groups" refers to [molar number of carboxyl groups] + 2 × [molar number of acid anhydride groups].

[0062] <Characteristics of polycarboxylic acid compound (a2)> Although the detailed mechanism is unclear, the higher the trans content of the polycarboxylic acid compound (a2) used as the reaction raw material of the amide-imide resin (A), the higher the molar ratio of amide groups (the linking portion formed by linking the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) via an amide bond) / imide groups (the linking portion formed by linking the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) via an imide bond) in the resulting amide-imide resin (A), thereby making it possible to obtain an amide-imide resin composition having excellent elongation and substrate adhesion in the cured product. From this viewpoint, the higher the trans content of the polycarboxylic acid compound (a2) used as the reaction raw material of the amide-imide resin (A), the more preferable.

[0063] The term "alicyclic polycarboxylic acid compound" refers to a compound having two or more carboxyl groups in an alicyclic skeleton, and at least two of these carboxyl groups are bonded to adjacent ring carbon atoms.

[0064] The "acid anhydride of an alicyclic polycarboxylic acid compound" refers to a carboxylic acid anhydride having a structure (acid anhydride group) in which carboxyl groups bonded to two adjacent ring carbon atoms in the alicyclic polycarboxylic acid compound are intramolecularly dehydrated and condensed together.

[0065] The "trans isomer of an alicyclic polycarboxylic acid compound" refers to an alicyclic polycarboxylic acid compound in which the carboxyl groups bonded to the two ring-constituting carbon atoms in the alicyclic polycarboxylic acid compound are bonded to the ring-constituting carbon atoms in a trans orientation to each other, and is a compound having a structure represented by the following structural formula (PC-1). [ka] (In the formula, "*" indicates the positions of the two carbon atoms in the alicyclic skeleton to which the "two adjacent carboxyl groups" are bonded.)

[0066] The "trans isomer of an acid anhydride of an alicyclic polycarboxylic acid compound" refers to an acid anhydride of an alicyclic polycarboxylic acid compound in which the two carboxyl groups formed by dehydration condensation in the acid anhydride of the alicyclic polycarboxylic acid compound are bonded to ring-constituting carbon atoms in a trans orientation to each other, and is a compound having a structure represented by the following structural formula (PC-2). [ka]

[0067] In formulas (PC-1) and (PC-2), Ac is an alicyclic skeleton, and R pc are each independently any substituent other than a carboxyl group, and p 1 and q are each independently an integer of 0 or greater.

[0068] Examples of alicyclic skeletons include skeletons derived from saturated or unsaturated cyclic aliphatic hydrocarbons (e.g., 3- to 8-membered saturated or unsaturated cyclic aliphatic hydrocarbons) such as cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1,3-cyclohexadiene, cycloheptane, cycloheptene, cycloheptadiene (1,3-cycloheptadiene, 1,4-cycloheptadiene), cyclooctane, cyclooctene, cyclooctadiene (1,2-cyclooctadiene, 1,3-cyclooctadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene), and 1,3,5-cyclooctatriene, but are not limited to these.

[0069] The number of carboxyl groups in the trans form of alicyclic polycarboxylic acid compounds or their acid anhydrides (2+p 1 (corresponding to) may be 2 or more, for example, 2, 3, 4, 5, 6, 7, or 8 (however, it may not exceed the number of ring-constituting atoms of the alicyclic skeleton).

[0070] In formulas (PC-1) and (PC-2), R pc Examples of the optional substituent other than the carboxyl group represented by the formula (I) include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, a hydroxyl group, and an aldehyde group.

[0071] The number of optional substituents other than the carboxyl group that the trans isomer of the alicyclic polycarboxylic acid compound or its acid anhydride (corresponding to the above q) has is an integer of 0 or more, preferably 0 or 1, and more preferably 0.

[0072] Examples of the trans isomer of the alicyclic polycarboxylic acid compound include, but are not limited to, compounds having structures represented by the following structural formulas and compounds in which these are substituted with substituents. In the structural formulas below, bonds marked with dashed lines indicate single bonds or unsaturated bonds. [ka] [ka] [ka] [ka] [ka]

[0073] Examples of the trans isomer of the alicyclic polycarboxylic acid compound include: cyclopropane skeleton polycarboxylic acid trans compounds such as cyclopropane-r-1,trans-2-dicarboxylic acid, methylcyclopropane-r-2,trans-3-tricarboxylic acid, and cyclopropane-r-1,trans-2,trans-3-tricarboxylic acid; cyclobutane-based polycarboxylic acid trans compounds such as cyclobutane-r-1,trans-2-dicarboxylic acid, methylcyclobutane-r-2,trans-3-dicarboxylic acid, cyclobutane-r-1,trans-2,trans-4-tricarboxylic acid, and methylcyclobutane-r-2,trans-3,trans-4-tricarboxylic acid; cyclobutene-based polycarboxylic acid trans compounds such as cyclobutene-r-3,trans-4-dicarboxylic acid, cyclobutene-1,r-3,trans-4-tricarboxylic acid, and cyclobutene-2,r-3,trans-4-tricarboxylic acid; cyclopentane-based polycarboxylic acid trans compounds such as cyclopentane-r-1,trans-2-dicarboxylic acid, cyclopentene-r-3,trans-4-dicarboxylic acid, and cyclopentane-r-1,trans-2,trans-4-tricarboxylic acid; cyclopentene-based polycarboxylic acid trans compounds such as cyclopentene-r-3,trans-4-dicarboxylic acid and cyclopentene-1,r-3,trans-4-tricarboxylic acid; cyclohexane-based polycarboxylic acid trans compounds such as cyclohexane-r-1,trans-2-dicarboxylic acid, methylcyclohexane-r-3,trans-4-dicarboxylic acid, cyclohexane-r-1,trans-2,trans-4-tricarboxylic acid, and methylcyclohexane-r-3,trans-4,trans-6-tricarboxylic acid; cyclohexene-based polycarboxylic acid trans compounds such as cyclohexene-r-4,trans-5-dicarboxylic acid and cyclohexene-1,r-4,trans-5-tricarboxylic acid; 1,3-cyclohexadiene-r-5,trans-6-tricarboxylic acid, 1,3-cyclohexadiene-2,r-5,trans-6-tricarboxylic acid, and other trans-type polycarboxylic acid compounds having a cyclohexadiene skeleton; Cycloheptane-based polycarboxylic acid trans compounds such as cycloheptane-r-1,trans-2,trans-4-tricarboxylic acid; Cycloheptene-based polycarboxylic acid trans compounds such as cycloheptene-r-3,trans-4,trans-6-tricarboxylic acid; 1,3-cycloheptadiene-1,r-5,trans-6-tricarboxylic acid, 1,4-cycloheptadiene-2,r-6,trans-7-tricarboxylic acid, and other trans-isomers of polycarboxylic acids having a cycloheptadiene skeleton; Cyclooctane-r-1,trans-2,trans-4-tricarboxylic acid and other cyclooctane-based polycarboxylic acid trans compounds; Cyclooctene-based polycarboxylic acid trans compounds such as cyclooctene-r-3,trans-4,trans-6-tricarboxylic acid; cyclooctadiene-based polycarboxylic acid trans compounds such as 1,2-cyclooctadiene-r-4,trans-5,trans-7-tricarboxylic acid, 1,3-cyclooctadiene-r-5,trans-6,trans-8-tricarboxylic acid, 1,4-cyclooctadiene-1,r-6,trans-7-tricarboxylic acid, and 1,5-cyclooctadiene-2,r-7,trans-8-tricarboxylic acid; 1,3,5-cyclooctatriene-2,r-7,trans-8-tricarboxylic acid and other cyclooctatriene polycarboxylic acid trans compounds; These include, but are not limited to:

[0074] As the trans isomer of the alicyclic polycarboxylic acid compound, a trans isomer of an alicyclic polycarboxylic acid compound having a six-membered alicyclic skeleton is preferred, a trans isomer of an alicyclic polycarboxylic acid compound having a six-membered alicyclic skeleton and three carboxyl groups (hydrogenated trimellitic acid) is more preferred, and cyclohexane-r-1,trans-2,trans-4-tricarboxylic acid having the structure represented by the following structural formula is preferred. [ka]

[0075] The trans isomer of the acid anhydride of an alicyclic polycarboxylic acid compound is not particularly limited, but examples thereof include carboxylic acid anhydrides having a structure in which carboxyl groups bonded in the trans orientation to two adjacent ring carbon atoms in the compounds exemplified above as "trans isomers of alicyclic polycarboxylic acid compounds" are intramolecularly dehydrated and condensed together.

[0076] The trans isomer of the acid anhydride of an alicyclic polycarboxylic acid compound is preferably a trans isomer of an acid anhydride of an alicyclic polycarboxylic acid compound having a 6-membered alicyclic skeleton, more preferably a trans isomer of an acid anhydride of an alicyclic polycarboxylic acid compound having a 6-membered alicyclic skeleton and three carboxyl groups (e.g., hydrogenated trimellitic anhydride), and even more preferably cyclohexane-r-1,trans-2,trans-4-tricarboxylic acid-1,2-anhydride having the structure represented by the following structural formula. [ka]

[0077] As the trans isomer of the alicyclic polycarboxylic acid compound or its acid anhydride, a trans isomer of the acid anhydride of an alicyclic polycarboxylic acid compound is preferred, a trans isomer of the acid anhydride of an alicyclic polycarboxylic acid compound having a 6-membered alicyclic skeleton is more preferred, and cyclohexane-r-1,trans-2,trans-4-tricarboxylic acid-1,2-anhydride is even more preferred.

[0078] The trans-containing alicyclic polycarboxylic acid compound or its anhydride (a2) may be a mixture of the trans and cis isomers of the corresponding alicyclic polycarboxylic acid compound or its anhydride. For example, the trans-containing alicyclic polycarboxylic acid compound or its anhydride (a2) may be a mixture of cyclohexane-r-1,trans-2,trans-4-tricarboxylic acid-1,2-anhydride, which is a trans isomer, and (1R,3R,4S)-cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, which is a cis isomer. For the reasons mentioned above, the trans content ratio (the ratio of the trans isomer to the total of the trans and cis isomers) in the trans-containing alicyclic polycarboxylic acid compound or its anhydride (a2) is preferably as high as possible from the viewpoint of obtaining an amide-imide resin composition having excellent elongation and substrate adhesion in the cured product. The trans isomer content in the trans isomer-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, and even more preferably 55 mol% or more.

[0079] In order to fully exert the effects of the present invention, the ratio of the total mass of the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) to the total mass of the reaction raw materials of the amide-imide resin (A) is preferably 90 mass% or more, and more preferably 95 mass% or more.

[0080] <Other reaction raw materials (a3)> The reaction raw materials of the amide-imide resin (A) may optionally contain, in addition to the essential reaction raw materials, the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2), other reaction raw materials (hereinafter referred to as "other reaction raw materials (a3)") in combination depending on the desired resin performance, etc. Examples of the other reaction raw materials (a3) ​​include polycarboxylic acid compounds other than the polycarboxylic acid compound (a2) or their acid anhydrides.

[0081] Examples of the other reaction raw material (a3) ​​include hydroxyl group-containing compounds, aliphatic polybasic acids, alicyclic polybasic acids, aromatic polybasic acids, their polybasic acid anhydrides, and acid halides of these polybasic acids or polybasic acid anhydrides.

[0082] Examples of the hydroxyl group-containing compound include hydroxyl group-containing non-acrylate compounds. Examples of the hydroxyl group-containing non-acrylate compounds include alcohol compounds such as methanol, ethanol, propanol, butanol, and the like; phenolic hydroxyl group-containing compounds such as phenol and naphthol; and the like. When an acid anhydride group and a carboxyl group may remain in the reaction product of the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2), if a hydroxyl group-containing compound is used as the other reaction raw material (a3), the hydroxyl group of the hydroxyl group-containing compound reacts preferentially with the acid anhydride group rather than the carboxyl group, and is converted into a carboxyl ester-containing group and one carboxyl group derived from one of the hydroxyl group-containing compounds.

[0083] Examples of the aliphatic polybasic acids, aliphatic polybasic acid anhydrides, and acid halides of these aliphatic polybasic acids or aliphatic polybasic acid anhydrides include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, these polybasic acid anhydrides, and acid halides of these polybasic acids or polybasic acid anhydrides, etc. The aliphatic hydrocarbon groups in these compounds may be either linear or branched, and may have an unsaturated bond in the structure.

[0084] Examples of the alicyclic polybasic acids, alicyclic polybasic acid anhydrides, and acid halides of these alicyclic polybasic acids or alicyclic polybasic acid anhydrides include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, polybasic acid anhydrides thereof, and acid halides of these polybasic acids or polybasic acid anhydrides.

[0085] Examples of the aromatic polybasic acids, aromatic polybasic acid anhydrides, and acid halides of these aromatic polybasic acids or aromatic polybasic acid anhydrides include phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, polybasic acid anhydrides thereof, and acid halides of these polybasic acids or polybasic acid anhydrides.

[0086] The other reaction raw materials (a3) ​​can be used alone or in combination of two or more kinds.

[0087] In order to fully exert the effects of the present invention, the ratio of the total mass of the polyisocyanate compound (a1), the polycarboxylic acid compound (a2) and the other reaction raw materials (a3) ​​to the total mass of the reaction raw materials of the amide-imide resin (A) is preferably 90 mass% or more, and more preferably 95 mass% or more.

[0088] <Reaction conditions, etc.> The method for producing the amide-imide resin (A) using the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) as essential reaction raw materials is not particularly limited, and any method may be used. For example, it can be produced by the same method as that for general amide-imide resins. Specifically, the method includes using 0.6 to 3 moles of the polycarboxylic acid compound (a2) per mole of isocyanate group of the polyisocyanate compound (a1), stirring and mixing under a temperature condition of preferably 50°C to 250°C, particularly preferably about 70 to 180°C, to cause the reaction. The reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours. The reaction is preferably carried out under an inert gas (e.g., nitrogen; rare gases such as helium, neon, argon, krypton, and xenon, etc.) atmosphere.

[0089] In the case of the method for producing the amide-imide resin (A) using polyisocyanate compound (a1), polycarboxylic acid compound (a2) and other reaction raw materials (a3) ​​as reaction raw materials, the ratio of these reaction raw materials may be 0.6 to 3 moles of the polycarboxylic acid compound (a2) per mole of isocyanate group of the polyisocyanate compound (a1). The reaction of these reaction raw materials may be carried out by stirring and mixing at a temperature condition preferably in the range of 50°C to 250°C, particularly preferably about 70 to 180°C. The reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours.

[0090] The polyisocyanate (a1) and the polycarboxylic acid compound (a2) are reacted so that the ratio (M / N) of the number of moles (N) of the isocyanate groups of the polyisocyanate (a1) to the number of moles (M) of the polycarboxylic acid compound (a2) converted into carboxyl groups (i.e., [the number of moles of carboxy groups] + 2 × [the number of moles of acid anhydride groups]) is 0.7 to 4.5, more preferably 1 to 3.5, so that the amide-imide resin composition obtained by the reaction with an epoxy compound (B) having two or more epoxy groups in the molecule described below can be an amide-imide resin composition having excellent elongation and substrate adhesion in the cured product. Among them, (M / N) is more preferably 2 to 3.2.

[0091] The polyisocyanate compound (a1) reacts with the polycarboxylic acid compound (a2) to form an amide group or an imide group, thereby forming the amide-imide resin (A) described below. Hereinafter, this reaction is referred to as the "amide / imidization reaction". The amide / imidization reaction is preferably carried out by mixing one or more of the polyisocyanate compounds (a1) and one or more of the polycarboxylic acid compounds (a2) in a solvent or without a solvent, and raising the temperature while stirring. In this case, when a polyamide-imide resin with a narrow molecular weight distribution is to be obtained, it is preferable to add the polyisocyanate (a1) to the polycarboxylic acid compound (a2) at least twice, more preferably 3 to 5 times. The amide / imidization reaction is a reaction in which, when the polycarboxylic acid compound (a2) has an acid anhydride group, an imide group is formed from the isocyanate group in the polyisocyanate (a1) and the acid anhydride group in the polycarboxylic acid compound (a2), and, when the polycarboxylic acid compound (a2) has a carboxyl group, an amide group is formed from the isocyanate group in the polyisocyanate (a1) and the carboxyl group in the polycarboxylic acid compound (a2). Specific structural formulas of the amide group and the imide group in the reaction product will be described later.

[0092] The progress of the amide / imidization reaction can be monitored by analytical means such as infrared spectroscopy, acid value, and quantification of the isocyanate group or modified portion of the isocyanate group. In the infrared spectrum, the characteristic absorption of the isocyanate group or modified portion of the isocyanate group (e.g., isocyanurate portion, biuret portion, allophanate portion) is observed in the range of 1690 to 1720 cm. -1 and 1406~1428cm -1 decreases with the reaction and further increases to 1860cm -1 and 850cm -1 The acid anhydride group, which has a characteristic absorption at 1780cm, is decreased. -1 and 1720cm -1 The absorption of the imide group increases with increasing temperature. It is preferable to allow the amide / imidization reaction to proceed until the isocyanate group disappears. In addition, during or after the amide / imidization reaction, a basic catalyst, a polymerization inhibitor, an antioxidant, other solvents, etc. may be added within a range that does not impair the properties of the acid group- and polymerizable unsaturated group-containing resin and the cured product obtained from the acid group- and polymerizable unsaturated group-containing resin.

[0093] <<Basic catalyst>> Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, dimethylpropylamine, diethylpropylamine, dipropylmethylamine, and the like. ammine, dipropylethylamine, tripropylamine, dimethylbutylamine, diethylbutylamine, dibutylmethylamine, dibutylethylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4 -Amine compounds such as diethylimidazole, 2-ethyl-4-methylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride;Examples of the basic catalyst include organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. These basic catalysts can be used alone or in combination of two or more. When used, these basic catalysts can be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.

[0094] From the viewpoint of obtaining an amide-imide resin composition having excellent elongation and adhesion to substrates in a cured product, the amount of the basic catalyst used is preferably in the range of 0.01 to 1 part by mass, and more preferably in the range of 0.05 to 0.8, per 100 parts by mass of the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) in total.

[0095] <<Polymerization inhibitor>> Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, hindered phenol compounds (e.g., dibutylhydroxytoluene), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxyphenylbenzene, 1,2-dimethyl ... phenolic compounds such as 2,2,4-trimethyl-1,2-dihydroquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone, and other quinone compounds, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,2-dimethyl-2,4-phenylenediamine), and phenylenediamine.amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite and other phosphite compounds, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, diethyldithiocarbamate , zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination of two or more.

[0096] <<Antioxidants>> As the antioxidant, the same compounds as those exemplified above as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0097] In addition, examples of commercially available antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0098] <<Solvent>> The amide / imidization reaction may be carried out in an organic solvent as necessary. The organic solvent to be used may be appropriately selected depending on the solubility of the reaction raw materials and the product, that is, the amide-imide resin composition, reaction temperature conditions, and the like.

[0099] Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, isopropanol, butanol (n-butanol, isobutanol, secondary butanol, tertiary butanol), and cyclohexanol. Examples of the organic solvent include alcohol solvents such as propylene glycol monomethyl ether, propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and the like; ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether acetate, and the like; lactone solvents such as α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and the like; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; methoxypropanol, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. These organic solvents can be used alone or in combination of two or more.

[0100] In addition, commercially available products can also be used as the organic solvent. Examples of commercially available products include "No. 1 Spindle Oil", "No. 3 Solvent", "No. 4 Solvent", "No. 5 Solvent", "No. 6 Solvent", "Naphthesol H", "Alkene 56NT", "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", and "AF Solvent No. 7" manufactured by ENEOS Corporation, "Diadol 13" and "Dialen 168" manufactured by Mitsubishi Chemical Corporation, "Supersol LA35" and "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd., and "Exxol D80", "Exxol D110", "Exxol D120", "Exxol D130", "Exxol D160", "Exxol D100K", "Exxol D120K", "Exxol D130K", "Exxol D280", "Exxol D300", and "Exxol D320" manufactured by ExxonMobil Chemical Co., Ltd. The amount of the organic solvent used is preferably within the range of about 0.1 to 5 times the total mass of the reaction raw materials, since this improves the reaction efficiency.

[0101] <Structure of amide-imide resin (A)> The amide-imide resin (A) is a polymer in which a polyisocyanate compound (a1) and a polycarboxylic acid compound (a2) are linked by an amide / imidization reaction. In the amide-imide resin (A), the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) are linked by an amide bond or an imide bond.

[0102] Hereinafter, the polymerization unit structure of the amide-imide resin (A) will be described using as an example a case where the polycarboxylic acid compound (a2) contains two carboxyl groups (hereinafter, for convenience, referred to as "adjacent carboxyl groups") bonded to adjacent ring carbon atoms in the alicyclic skeleton or one acid anhydride group and one carboxyl group (hereinafter, for convenience, referred to as "isolated carboxyl group") bonded to another ring carbon atom. In this case, the equivalent number of carboxyl groups in the polycarboxylic acid compound (a2) is 3. Even when the equivalent number of carboxyl groups in the polycarboxylic acid compound (a2) is other than 3, the polymerization unit structure of the amide-imide resin (A) can be represented by a structural formula according to the following explanation.

[0103] Assumed states after the reaction between adjacent carboxyl groups or acid anhydride groups in the polycarboxylic acid compound (a2) and isocyanate groups in the polyisocyanate compound (a1), there are four cases (i-1) to (i-4) below. For convenience, in the explanation of the reaction formula below, the polyisocyanate compound (a1) is collectively represented by the following structural formula (I). OCN-G-(NCO) n (I) (In the formula, G represents any chemical structure, and n represents an integer of 1 or more.)

[0104] (i-1) Two adjacent carboxyl groups or acid anhydride groups do not react with an isocyanate group and remain as two carboxyl groups or one acid anhydride group.

[0105] (i-2) One of two adjacent carboxyl groups reacts with an isocyanate group to form an amide group, and the other does not react with the isocyanate group and remains as a carboxyl group. [ka] [ka] Alternatively, an acid anhydride group reacts with one isocyanate group to form one amide group and one carboxyl group. [ka] [ka]

[0106] (i-3) Each of the two adjacent carboxyl groups reacts with an isocyanate group to form a total of two amide groups. [ka] Alternatively, an anhydride group can react with two isocyanate groups to form a total of two amide groups. [ka]

[0107] (i-4) An acid anhydride group reacts with one isocyanate group to form one imide group. [ka]

[0108] The above reaction formula shows the portion of the linking reaction between the polycarboxylic acid compound (a2) and the polyisocyanate compound (a1) that is related to the linking reaction between one isocyanate group in the polyisocyanate compound (a1) (the portion represented by "OCN-" in structural formula (I)) and the polycarboxylic acid compound (a2). In the structural formula of the reaction product, "···" indicates that an isocyanate group other than the one isocyanate group in the polyisocyanate compound (a1) (the portion represented by "-(NCO)" in structural formula (I)) is a carboxyl group. n" represents a portion of the polycarboxylic acid compound (a2) that is an isolated carboxyl group and an isolated carboxyl group that is an isocyanate group to form an amide group. In the above reaction formula, "*" in Ac represents the positions of two carbon atoms in the alicyclic skeleton to which adjacent carboxyl groups or acid anhydride groups in the polycarboxylic acid compound (a2) are bonded, and the positions of the corresponding two carbon atoms in the reaction product. For simplicity, the above reaction formula shows only the case in which an isolated carboxyl group does not react with an isocyanate group. However, in reality, as described below, there are cases in which an isolated carboxyl group does not react with an isocyanate group and cases in which an isolated carboxyl group reacts with an isocyanate group to form an amide group.

[0109] Assumed states after the reaction between an isolated carboxyl group in the polycarboxylic acid compound (a2) and an isocyanate group in the polyisocyanate compound (a1), there are two cases, (ii-1) and (ii-2), as follows. (ii-1) The isolated carboxyl group does not react with the isocyanate group and remains as a carboxyl group. (ii-2) An isolated carboxyl group reacts with an isocyanate group to form an amide group.

[0110] As described above, the higher the trans content of the polycarboxylic acid compound (a2), the higher the molar ratio of amide groups / imide groups in the resulting amide-imide resin (A), and thus an amide-imide resin composition having excellent elongation and substrate adhesion in the cured product can be obtained. From this viewpoint, the higher the trans content of the polycarboxylic acid compound (a2) used as the reaction raw material for the amide-imide resin (A), the more preferable it is. The preferred range of the trans content is as described above.

[0111] In addition, when the number of moles (N) of isocyanate groups in the polyisocyanate (a1) used in the reaction for forming the amide-imide resin (A) is almost the same as the number of moles (M) of the polycarboxylic acid compound (a2) converted into carboxyl groups (i.e., [the number of moles of carboxyl groups] + 2 × [the number of moles of acid anhydride groups]), the higher the molar ratio of amide groups / imide groups in the amide-imide resin (A) as an index, the greater the number of carboxyl groups converted into carboxyl groups in the amide-imide resin (A), and the greater the amount of bonds between the amide-imide resin (A) and the epoxy compound (B). Therefore, the thermosetting property of the curable resin composition used for thermosetting is improved, and it is preferable to obtain an amide-imide resin composition having excellent elongation and substrate adhesion in the cured product. The molar ratio of amide groups / imide groups in the amide-imide resin (A) is preferably 1.2 or more, more preferably 1.5 or more.

[0112] Examples of the linking mode between the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) include terminal structures (X1-1) to (X1-3) (number of branches = 1), linear structures (X2-1) to (X2-3) (number of branches = 2), and a branched structure (X3-1) (number of branches = 3) in Table 1 below.

[0113] [Table 1]

[0114] Here, for convenience, the polyisocyanate compound (a1) is represented by the following structural formula (I): OCN-G-(NCO) n (I) (In the formula, G represents any chemical structure, and n represents an integer of 1 or more.) When the linking modes (X1-1) to (X1-3), (X2-1) to (X2-3), and (X3-1) of the polycarboxylic acid compound (a2) with the polyisocyanate compound (a1) can be comprehensively represented by the following structural formulas (X1-1a) to (X1-3), (X2-1a) to (X2-3), and (X3-1), respectively.

[0115] Linkage type (X1-1): Terminal structure type (number of branches = 1) [ka] [ka]

[0116] Linkage type (X1-2): Terminal structure type (number of branches = 1) [ka] [ka]

[0117] Linkage type (X1-3): Terminal structure type (number of branches = 1) [ka]

[0118] Linkage type (X2-1): Linear structure type (number of branches = 2) [ka] [ka]

[0119] Linkage type (X2-2): Linear structure type (number of branches = 2) [ka]

[0120] Linkage type (X2-3): Linear structure (number of branches = 2) [ka]

[0121] Linkage style (X3-1): Branched structure type (number of branches = 3) [ka]

[0122] In the formulae (X1-1a) to (X1-3), (X2-1a) to (X2-3), and (X3-1), "G" is a structure corresponding to the portion of the polyisocyanate compound (a1) defined above. "*" indicates the positions of two carbon atoms in the alicyclic skeleton to which "two adjacent carboxyl groups" or "acid anhydride groups" are bonded in the polycarboxylic acid compound (a2) before the reaction. Ac, R pc and q are as described for the polycarboxylic acid compound (a2).

[0123] In addition, in the above structural formula, the parts surrounded by dashed lines are collectively represented as [PCN1], [PCN2], and [PCN3]. [PCN1], [PCN2], and [PCN3] conveniently represent the central structures of the linkage patterns of the terminal structure type (number of branches = 1), the linear structure type (number of branches = 2), and the branched structure type (number of branches = 3), respectively. In this way, the structure of the linkage pattern of the terminal structure type (number of branches = 1) can be expressed as ···G-[PCN1] and The structure of the linear structure (number of branches = 2) ···G-[PCN2]-G··· and The structure of the branched structure (number of branches = 3) [ka] It can be expressed comprehensively as:

[0124] That is, [PCN1] represents a portion (central structure) excluding one "···G-" in any of the above structural formulas (X1-1a) to (X1-3) representing the linking patterns (X1-1) to (X1-3) of the terminal structure type (number of branches = 1). [PCN2] represents the portion (central structure) excluding two "···G-"s in any of the above structural formulas (X2-1a) to (X2-3) representing the linking patterns (X2-1) to (X2-3) of a linear structure type (number of branches = 2). [PCN3] represents the portion (core structure) excluding the three "···G-"s in the above structural formula (X3-1) which represents the linking pattern (X3-1) of a branched structure type (number of branches=3).

[0125] Here, the polyisocyanate compound (a1) has the following structural formula (DI-1): OCN-R ic -NCO (DI-1) The linking mode between the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) will be explained using as an example a diisocyanate compound having a structure represented by the following formulas (DX1-1) to (DX3-3).

[0126] [ka]

[0127] In each formula, "..." indicates the linking site to the [PCN1], [PCN2], and [PCN3] structures of adjacent repeating units. ic , [PCN1], [PCN2], and [PCN3] are as described above.

[0128] For example, the polyisocyanate compound (a1) may be represented by the following structural formula (NU-1): [ka] In the case of an isocyanurate compound having a structure represented by the following formulas (NUX1-1-1) to (NUX3-3-3), examples of the linking mode between the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) include structures represented by the following formulas (NUX1-1-1) to (NUX3-3-3).

[0129] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0130] In each formula, "..." indicates the linking site to the [PCN1], [PCN2], and [PCN3] structures of adjacent repeating units. ic , [PCN1], [PCN2], and [PCN3] are as described above.

[0131] The polyisocyanate compound (a1) is represented by the following structural formula (NU-2) or (NU-3): [ka] [ka] In the case of an isocyanurate compound having a structure represented by the above structural formula (NU-1), the amide-imide resin (A) has a structure similar to that described for the isocyanurate compound having a structure represented by the above structural formula (NU-1).

[0132] For example, the polyisocyanate compound (a1) may be represented by the following structural formula (IP-1): [ka] In the case of a nurate of isophorone diisocyanate having a structure represented by the formula: ...

[0133] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0134] In each formula, "..." indicates the linking site to the adjacent repeating units, [PCN1], [PCN2], and [PCN3] structures, where [PCN1], [PCN2], and [PCN3] are as described above.

[0135] In addition, since the nurate form of isophorone diisocyanate having the structure represented by the above structural formula (IP-1) has three isocyanate groups (-NCO) in asymmetric positions, there are linkage modes between the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) other than the structures represented by the above structural formulas (IPX1-1-1) to (IPX3-3-3) as examples. However, except for the positions of the three isocyanate groups in the central structure of the nurate form of isophorone diisocyanate, the linkage mode is similar to the structures represented by the above structural formulas (IPX1-1-1) to (IPX3-3-3).

[0136] In addition, for example, the polyisocyanate compound (a1) may be represented by the following structural formula (IP-2) or (IP-3): [ka] [ka] In the case of a nurate of isophorone diisocyanate having a structure represented by the above structural formula (IP-1), the amide-imide resin (A) has a structure similar to that described for the nurate of isophorone diisocyanate having a structure represented by the above structural formula (IP-1).

[0137] When the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) have structures other than those described above, it may be considered that the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) form amide groups and / or imide groups to produce the amide-imide resin (A), as in the above examples.

[0138] <Epoxy compound (B) having two or more epoxy groups in the molecule> The epoxy compound (B) having two or more epoxy groups in the molecule (hereinafter, also referred to as "epoxy compound (B)") is a component that can form a cured product by reacting with the amide-imide resin (A). The mechanism by which the amide-imide resin (A) and the epoxy compound (B) react to form a cured product is as follows. When the curable resin composition containing the amide-imide resin (A) and the epoxy compound (B) is heated to thermally cure, the epoxy group in the epoxy compound (B) bonds with the (anhydrous) carboxyl group in the amide-imide resin (A), and the curable resin composition cures to form a cured product. The epoxy compound (B) is not particularly limited, and a wide variety of compounds can be used, such as low molecular epoxy compounds having two or more epoxy groups in the molecule, epoxy group-containing polymers other than epoxy resins, and epoxy resins. The epoxy compounds (B) may be used alone or in combination of two or more. From the viewpoint of obtaining an amide-imide resin composition having excellent elongation and adhesion to substrates in the cured product, the epoxy compound (B) is preferably an epoxy resin, more preferably a novolac type epoxy resin, and even more preferably a cresol novolac type epoxy resin.

[0139] <<Low molecular weight epoxy compound with two or more epoxy groups in the molecule>> The low molecular weight epoxy compound having two or more epoxy groups in the molecule is not particularly limited, and examples thereof include: butanediol diglycidyl ether, pentanediol diglycidyl ether, hexanediol diglycidyl ether, heptanediol diglycidyl ether, octanediol diglycidyl ether, nonanediol diglycidyl ether, decanediol diglycidyl ether, undecanediol diglycidyl ether, dodecanediol diglycidyl ether, tridecanediol diglycidyl ether, tetradecanediol diglycidyl ether, pentadecanediol diglycidyl ether, hexadecanediol diglycidyl ether, Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, pentamethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, heptamethylene glycol diglycidyl ether, Bisphenol A diglycidyl ether, Trimethylolpropane Triglycidyl Ether etc.

[0140] <<Epoxy group-containing polymer>> The epoxy group-containing polymer other than the epoxy resin is not particularly limited, and examples thereof include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, and polyheptamethylene glycol diglycidyl ether.

[0141] <<Epoxy resin>> As the epoxy resin, for example, the epoxy resin described in JP 2022-098702 A can be used, and examples thereof include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more.

[0142] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0143] Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0144] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin.

[0145] Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0146] <<Epoxy compound (B) content>> The mixing ratio of the amide-imide resin (A) and the epoxy compound (B) is preferably such that the number of epoxy groups in the epoxy compound (B) is in the range of 0.9 to 10 mol, and particularly preferably in the range of 0.9 to 2 mol, relative to the total of the acid groups and acid anhydride groups in the amide-imide resin (A).

[0147] <Other Components That May Be Contained in the Amide-imide Resin Composition> The amide-imide resin composition may contain components other than the amide-imide resin (A) and the epoxy compound (B) (hereinafter, also referred to as "other components"). Examples of the other components include a solvent, a polymerization inhibitor, and an antioxidant. The solvent, polymerization inhibitor, and / or antioxidant may be the same as those used in the production of the amide-imide resin (A) having an acid group and / or an acid anhydride group, or may be newly added.

[0148] <<Solvent>> Examples of the solvent are as described above in the section "amide-imide resin (A) having an acid group and / or an acid anhydride group". The amount of the solvent used is preferably in the range of about 0.1 to 5 times the total mass of the non-volatile components, since this provides good solubility and uniformity.

[0149] <Polymerization inhibitor> As the polymerization inhibitor, the compounds exemplified as the "polymerization inhibitor" in the above section "Amide-imide resin (A) having an acid group and / or an acid anhydride group" can be used.

[0150] <Antioxidants> As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0151] In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0152] <Other resin components> The amide-imide resin composition of the present invention may contain a resin component that does not fall under either the amide-imide resin (A) or the epoxy resin (hereinafter also referred to as "other resin components"). The other resin components may be, for example, those described in JP-A-2022-098702.

[0153] <(Meth)acrylate Monomer> The curable resin composition of the present invention may contain various (meth)acrylate monomers other than hydroxy (meth)acrylate compounds (compounds having a hydroxyl group and a (meth)acryloyl group in the molecular structure). These (meth)acrylate monomers can be, for example, those described in JP-A-2022-098702.

[0154] The content of the (meth)acrylate monomer in the non-volatile matter of the amide-imide resin composition of the present invention is preferably 90% by mass or less.

[0155] (Method of producing amide-imide resin composition) The amide-imide resin composition of the present invention can be produced by the following steps: (i) reacting a polyisocyanate compound (a1) with a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) to produce an amide-imide resin (A) having an acid group and / or an acid anhydride group; and (ii) a step of mixing the amide-imide resin (A) obtained in the step (i) with an epoxy compound having two or more epoxy groups in the molecule to produce an amide-imide resin composition containing the amide-imide resin (A) and the epoxy compound (B). The amide-imide resin composition can be produced by a method for producing the amide-imide resin composition, comprising the steps of:

[0156] The reaction in step (i) can be carried out under the reaction conditions explained above in the section "Amide-imide resin (A) having an acid group and / or an acid anhydride group."

[0157] The conditions for mixing in step (ii) are not particularly limited, but from the viewpoint of improving the uniformity of mixing, it is preferable to carry out in a solvent. As for the solvent, the solvent in which the amide-imide resin (A) obtained in step (i) is dissolved may be used continuously, or a solvent may be added. In order to suppress the deterioration of the amide-imide resin (A) and the epoxy compound (B) during the mixing operation or storage, and the polymerization of the amide-imide resin (A) and the epoxy compound (B), the mixing in step (ii) may be carried out in the presence of a polymerization inhibitor or an antioxidant. The mixing in step (ii) may be carried out by stirring, but it is preferable to carry out by stirring under mild conditions in order to suppress the cutting of the resin component due to shear force. The temperature of mixing in step (ii) is preferably as low as possible from the viewpoint of suppressing thermal curing during mixing, and is preferably in the range of, for example, 0 to 100°C.

[0158] (Curable resin composition) The curable resin composition of the present invention contains the above-mentioned amide-imide resin composition and optionally additional components. The curable resin composition of the present invention can be used to form a cured product by curing (particularly, thermal curing). Examples of the optional additional components include a curing accelerator, a polymerization inhibitor, an antioxidant, a solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, a storage stabilizer, and the like. Among these, when a polymerization inhibitor, an antioxidant, or a solvent is used, those described in the above section "Other components that may be contained in the amide-imide resin composition" may be used.

[0159] <Curing accelerator> The curing accelerator is one that accelerates the curing reaction, and examples thereof include the compounds exemplified as "basic catalysts" in the above section "amide-imide resin (A) having an acid group and / or an acid anhydride group", Lewis acids, etc. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.05 to 5 parts by mass, based on 100 parts by mass of the total of the amide-imide resin (A) and the epoxy compound (B), from the viewpoint of improving the elongation and substrate adhesion of the cured product obtained by curing (particularly, thermal curing) the curable resin composition.

[0160] <Inorganic filler> Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0161] <Pigments> As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0162] Examples of the inorganic pigment include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds.

[0163] Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide.

[0164] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more kinds.

[0165] <Flame retardants> Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oils, silicone rubbers, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, the amount is preferably in the range of 0.1 to 20 mass% in the total resin composition.

[0166] (Method for producing curable resin composition) The curable resin composition of the present invention can be prepared by the following steps: (i) reacting a polyisocyanate compound (a1) with a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) to produce an amide-imide resin (A) having an acid group and / or an acid anhydride group; and (ii) a step of mixing the amide-imide resin (A) obtained in the step (i) with an epoxy compound having two or more epoxy groups in the molecule to produce a curable resin composition containing the amide-imide resin (A) and the epoxy compound (B). The curable resin composition can be produced by a method for producing a curable resin composition comprising the steps of:

[0167] In addition, when the curable resin composition of the present invention contains an optional additional component such as a catalyst, the optional additional component may be mixed together with the amide-imide resin (A) and the epoxy compound (B) when they are mixed, or the optional additional component may be mixed with the curable resin composition after a curable resin composition, which is a mixture of the amide-imide resin (A) and the epoxy compound (B), is produced in advance.

[0168] That is, when the curable resin composition of the present invention contains an optional additional component such as a catalyst, in step (ii), the amide-imide resin (A) obtained in step (i), an epoxy compound having two or more epoxy groups in the molecule, and further optional additional components such as a catalyst may be mixed to produce a curable resin composition containing the amide-imide resin (A), the epoxy compound (B), and further optional additional components. Alternatively, the method for producing a curable resin composition may include the following step (iii): (iii) The method may further include a step of mixing the curable resin composition obtained in step (ii) with an optional additional component such as a catalyst to produce a curable resin composition containing the amide-imide resin (A), the epoxy compound (B), and further optional additional components.

[0169] The conditions for carrying out steps (i) and (ii) in the method for producing a curable resin composition may be the same as those described for steps (i) and (ii) in the method for producing an amide-imide resin composition, respectively. The conditions for carrying out step (iii) in the method for producing a curable resin composition may be the same as the conditions for carrying out step (ii) in the same method.

[0170] (cured product) The cured product of the present invention is a cured product obtained by curing (particularly, thermal curing) the above-mentioned curable resin composition. Thermal curing can be performed, for example, by applying the curable resin composition to a substrate, partially or completely removing the solvent and the like from the curable resin composition (for example, volatilization drying), and thermal curing by heating. The thickness of the coating is preferably in the range of 0.5 to 500 μm. The temperature of the volatilization drying is preferably in the range of 60 to 100° C., for example. The time of the volatilization drying is preferably in the range of 10 to 60 min, for example. The temperature of the thermal curing is preferably in the range of 140 to 250° C., for example. The time of the thermal curing is preferably in the range of 0.5 to 10 h, for example.

[0171] (Applications of the curable resin composition and the cured product) The curable resin composition of the present invention produces a cured product having excellent elongation and substrate adhesion, and therefore can be used universally as a material for forming various articles, and can be suitably used, for example, as an insulating material. The curable resin composition of the present invention can be suitably used, for example, as a resin material used in package adhesive layers such as solder resist, interlayer insulating material, packaging material, underfill material, and circuit elements in semiconductor device applications, and adhesive layers between integrated circuit elements and circuit boards. The cured product of the present invention has excellent elongation and substrate adhesion, and therefore can be used universally as various articles, and can be suitably used, for example, as package adhesive layers such as solder resist, interlayer insulating material, packaging material, underfill material, and circuit elements in semiconductor device applications, and adhesive layers between integrated circuit elements and circuit boards. The curable resin composition of the present invention can be suitably used in thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, and the like in thin-film display applications such as LCDs and OELDs. Among these, it can be particularly suitably used for solder resist applications.

[0172] The cured product of the present invention can be used for an article having a coating film made of the cured product. Examples of substrates to which the coating film can be applied include metal-clad laminates such as copper and aluminum, glass, and various resins. EXAMPLES

[0173] The present invention will be described in more detail below with reference to examples and comparative examples. The unit of blend amounts in the tables is parts by mass unless otherwise specified.

[0174] In the present examples, the acid value of the amide-imide resin composition was measured by the neutralization titration method of JIS K 0070 (1992).

[0175] In the present examples, the cis / trans ratio and the amide group / imide group molar ratio of the amide-imide resin composition were measured by NMR under the following conditions.

[0176] Measuring device: JNM-ECA500 (JEOL Ltd.) Magnetic field strength: 11.7 T (500MHz) Probe: SuperCOOL open type probe (5mmΦ) Measurement solvent: DMSO-d6 (Kanto Chemical Co., Ltd.) Measurement conditions: 13 C-NMR, DEPT135 Sample concentration: 1 H-NMR 3% (w / v), 13 C-NMR 30% (w / v) 13 The sample for C-NMR measurement is used as a relaxation reagent. Chromium (III) acetylacetonate (Tokyo Chemical Industry Co., Ltd.) was added and the measurement was performed in nne mode. Number of times: 13 C-NMR 4,000 times

[0177] Example 1: Synthesis of amide-imide resin (A-1) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 579.8 parts by mass of diethylene glycol monoethyl ether acetate was placed, and 244.3 parts by mass of an isocyanurate-modified isophorone diisocyanate (EVONIK's "VESTANAT T-1890 / 100", NCO%=17.2%) and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (Mitsubishi Gas Chemical Company, Inc.'s "H-TMAn", cis / trans=42 / 58 (mol%), cis / trans ratio was 13 C NMR) was added to dissolve 207.9 parts by mass of dibutylhydroxytoluene. The mixture was reacted at 140° C. for 4 hours in a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less, to obtain an amide-imide resin (A-1). 13 The molar ratio of amide groups / imide groups in the amide-imide resin (A-1) calculated by C NMR was 1.52 (mol / mol). The nonvolatile content of the resin (A-1) was 38 mass%, and the acid value of the solid content was 188 mg KOH / g.

[0178] (Example 2): Synthesis of amide-imide resin (A-2) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 515 parts by mass of γ-butyrolactone, 178.7 parts by mass of a nurate-modified hexamethylene diisocyanate (DIC Corporation's "Burnoc DN901S", isocyanate group content 23.5% by mass) and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (Mitsubishi Gas Chemical Company, Inc.'s "H-TMAn", cis / trans = 42 / 58 (mol%), cis / trans ratio 13 207.9 parts by mass of toluene (calculated by C NMR) was dissolved, and 0.3 parts by mass of dibutylhydroxytoluene was added. The mixture was reacted at 140°C for 6 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less, to obtain an amide-imide resin (A-2). The non-volatile content of the resin (A-2) was 38% by mass, and the solid acid value was 215 mgKOH / g.

[0179] (Example 3): Synthesis of amide-imide resin (A-3) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 680 parts by mass of γ-butyrolactone, 304 parts by mass of an isocyanurate-modified product of hydrogenated xylylene diisocyanate (Takenate D-127N, manufactured by Mitsui Chemicals, Inc., NCO%=13.8, non-volatile content 75.5% by mass) and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (manufactured by Mitsubishi Gas Chemical Company, Inc., "H-TMAn", cis / trans=42 / 58 (mol%), cis / trans ratio was 13 207.9 parts by mass of toluene (calculated by C NMR) was dissolved, and 0.4 parts by mass of dibutylhydroxytoluene was added. The mixture was reacted at 140°C for 5 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less, to obtain an amide-imide resin (A-3). The non-volatile content of the resin (A-3) was 38% by mass, and the solid acid value was 179 mgKOH / g.

[0180] Comparative Example 1: Synthesis of amide-imide resin (C-1) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 579.8 parts by mass of diethylene glycol monoethyl ether acetate was placed, and 244.3 parts by mass of isocyanurate modified isophorone diisocyanate (EVONIK's "VESTANAT T-1890 / 100", NCO%=17.2%) and 207.9 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (Mitsubishi Gas Chemical Company, Inc.'s "H-TMAn-S", cis-only) were dissolved, and 0.4 parts by mass of dibutylhydroxytoluene was added. The mixture was reacted at 140°C for 4 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less, to obtain an amide-imide resin (C-1). 13 The molar ratio of amide groups / imide groups in the amide-imide resin (C-1) calculated by C NMR was 1.08 (mol%). The non-volatile content of the resin (C-1) was 38 mass%, and the acid value of the solid content was 180 mg KOH / g.

[0181] (Comparative Example 2): Synthesis of amide-imide resin (C-2) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 515 parts by mass of γ-butyrolactone was placed, and 178.7 parts by mass of nurate-modified hexamethylene diisocyanate (DIC Corporation's "Burnoc DN901S", isocyanate group content 23.5% by mass) and 207.9 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (Mitsubishi Gas Chemical Company, Inc.'s "H-TMAn-S", cis-isomer only) were dissolved, and 0.3 parts by mass of dibutylhydroxytoluene was added. The mixture was reacted at 140°C for 6 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less, to obtain an amide-imide resin (C-2). The non-volatile content of the resin (C-2) was 38% by mass, and the solid acid value was 209 mgKOH / g.

[0182] (Comparative Example 3): Synthesis of amide-imide resin (C-3) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 680 parts by mass of γ-butyrolactone was placed, 304 parts by mass of isocyanurate modified product of hydrogenated xylylene diisocyanate (Takenate D-127N, manufactured by Mitsui Chemicals, Inc., NCO%=13.8, non-volatile content 75.5% by mass) and 207.9 parts by mass of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., "H-TMAn-S", cis-only) were dissolved, and 0.4 parts by mass of dibutylhydroxytoluene was added. The mixture was reacted at 140°C for 5 hours under a nitrogen atmosphere, and it was confirmed that the NCO% was 0.1 or less, to obtain an amide-imide resin (C-3). The non-volatile content of the resin (C-3) was 38% by mass, and the solid acid value was 174 mgKOH / g.

[0183] (Examples 4 to 6 and Comparative Examples 4 to 6) <Preparation of Curable Resin Compositions (1) to (3) and (C1) to (C3)> Curable resin compositions (1) to (3) and (C1) to (C3) were obtained by mixing the components in the amounts shown in Table 2. A cresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214 g / equivalent) was used as the epoxy compound (curing agent) having two or more epoxy groups in the molecule, and triphenylphosphine was used as the basic catalyst.

[0184] Unless otherwise specified, the curing conditions (thermal curing) when curing the curable resin composition are as follows. Apply with a 50μm applicator Pre-dry at 80℃ for 30 minutes Cured at 175℃ for 5 hours

[0185] In each test, copper foil was used as the substrate.

[0186] [Method of evaluating adhesion] The adhesion was evaluated by measuring the peel strength. Specifically, the curable resin compositions obtained in the examples and comparative examples were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha, Ltd.) with a 50 μm applicator, and 10 kJ / m was applied using a metal halide lamp. 2 After irradiating with ultraviolet light of 1000 u / s, the sample was heated at 160°C for 1 hour. The cured product was peeled off from the copper foil to obtain test piece 1 (cured product). This test piece 1 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength (N / cm) was measured using a peel tester (A&D Tensilon, manufactured by A&D Co., Ltd., peel speed 50 mm / min). A higher value indicates better adhesion.

[0187] [Method of measuring elongation] The elongation was measured based on a tensile test. Specifically, the same test piece 1 (cured product) as above was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine "AG-IS" manufactured by Shimadzu Corporation. The elongation (%) until the test piece broke was measured. Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between supports 20mm, tensile speed 10mm / min

[0188] [Table 2]

[0189] "Curing agent (N-680)" in Table 2 refers to a cresol novolac type epoxy resin ("EPICLON N-680" manufactured by DIC Corporation). The numerical values ​​of the blending amounts indicate parts by mass of non-volatile content.

[0190] From the comparisons between Example 4 and Comparative Example 4, Example 5 and Comparative Example 5, and Example 6 and Comparative Example 6 shown in Table 2, it was confirmed that the cured products of the curable resin compositions of the Examples had superior elongation and adhesion to substrates compared to the Comparative Examples.

Claims

1. An amide-imide resin composition comprising (A) an amide-imide resin having an acid group and / or an acid anhydride group, and (B) an epoxy compound having two or more epoxy groups in the molecule, 1. An amide-imide resin composition, comprising the amide-imide resin (A) containing, as essential reaction raw materials, a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2).

2. 2. The amide-imide resin composition according to claim 1, wherein the trans-isomer content in the trans-isomer-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) is 30 mol % or more.

3. The amide-imide resin composition according to claim 1 , wherein the polyisocyanate compound (a1) is a nurate compound.

4. A curable resin composition comprising the amide-imide resin composition according to any one of claims 1 to 3.

5. The curable resin composition according to claim 4, further comprising a catalyst.

6. A cured product of the curable resin composition according to claim 4.

7. An article having a coating film comprising the cured product according to claim 6.

8. The following steps: (i) reacting a polyisocyanate compound (a1) with a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) to produce an amide-imide resin (A) having an acid group and / or an acid anhydride group; and (ii) a step of mixing the amide-imide resin (A) obtained in the step (i) with an epoxy compound having two or more epoxy groups in the molecule to produce an amide-imide resin composition containing the amide-imide resin (A) and the epoxy compound (B). A method for producing an amide-imide resin composition comprising the steps of:

9. 9. The method for producing an amide-imide resin composition according to claim 8, wherein the trans-isomer content in the trans-isomer-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) is 30 mol % or more.

10. The method for producing an amide-imide resin composition according to claim 8, wherein the polyisocyanate compound (a1) is a nurate compound.

11. The following steps: (i) reacting a polyisocyanate compound (a1) with a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) to produce an amide-imide resin (A) having an acid group and / or an acid anhydride group; and (ii) A step of mixing the amide-imide resin (A) obtained in the step (i) with an epoxy compound having two or more epoxy groups in the molecule to produce a curable resin composition containing the amide-imide resin (A) and the epoxy compound (B). A method for producing a curable resin composition comprising the steps of:

12. In step (ii), the amide-imide resin (A) obtained in step (i), an epoxy compound having two or more epoxy groups in the molecule, and a catalyst are mixed to produce a curable resin composition containing the amide-imide resin (A), the epoxy compound (B), and a catalyst; or Step (iii): mixing the curable resin composition obtained in step (ii) with a catalyst to produce a curable resin composition containing the amide-imide resin (A), the epoxy compound (B), and a catalyst; A method for producing the curable resin composition according to claim 11.

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