Resin containing acid groups and polymerizable unsaturated groups, curable resin composition, cured product, insulating material, resin material for solder resist and resist member

Abstract

To provide a resin containing acid groups and polymerizable unsaturated groups that ensures high heat resistance in cured products, while also offering excellent sensitivity and developability, a curable resin composition containing the same, and an insulating material, a resin material for solder resist and a resist member composed of the curable resin composition.SOLUTION: A resin containing acid groups and polymerizable unsaturated groups comprises an amide imide resin (A) with acid groups and / or acid anhydride groups and a hydroxy (meth)acrylate compound (B) as essential reaction materials. 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 acid group- and polymerizable unsaturated group-containing resin which has high heat resistance in a cured product and is also excellent in sensitivity and developability, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material made of the curable resin composition, a solder resist resin material made of the curable resin composition, and a resist member made using the solder resist resin material. [Background technology]

[0002] When mounting and soldering electronic components on a printed wiring board, solder resist is widely used as a material to prevent solder from adhering to areas other than the mounted area and to form a coating that semi-permanently prevents oxidation and corrosion of wiring. As a technique for forming such solder resist patterns, the photoresist method, which can accurately form fine patterns, is the mainstream, and in particular, due to environmental considerations, the alkaline development type liquid photoresist method is the most popular.

[0003] In addition, printed wiring boards are becoming finer, more multi-layered, and more one-board in order to achieve higher density, and the mounting method is also shifting to surface mount technology (SMT).As a result, there is an increasing demand for solder resist films that are finer, have higher T mass, have higher resolution, higher precision, and are more reliable.

[0004] Conventionally known resin materials for solder masks include a photosensitive resin composition comprising (a) a carboxyl group-containing radical polymerizable compound, (b) a polyimide resin, (c) an epoxy compound, (d) a photopolymerization initiator, and (e) a reactive diluent, the polyimide resin (b) having polymerization units containing an isocyanurate ring, a cyclic aliphatic structure, and an imide ring (Patent Document 1); a photosensitive polyamide resin having a carboxyl group obtained by reacting a carboxyl group-terminated polyamide resin (a1) with an epoxy resin (b) at a molar ratio of epoxy group / carboxyl group greater than 1 to obtain an epoxy group-containing polyamide resin (c1), which is reacted with an ethylenically unsaturated monocarboxylic acid (d) and then further reacted with a polybasic acid anhydride (e); and a photosensitive polyamide resin having a carboxyl group obtained by reacting a carboxyl group-terminated polyamideimide resin (a2) with an epoxy resin (b) at a molar ratio of epoxy group / carboxyl group greater than 1 to obtain an epoxy group-containing polyamideimide resin (c2), which is reacted with an ethylenically unsaturated monocarboxylic acid (d) and then further reacted with a polybasic acid anhydride (e). A photosensitive resin composition (Patent Document 2) is characterized by comprising, as essential components, at least one photosensitive resin selected from photosensitive polyamideimide resins having carboxyl groups obtained by reacting an ethylenically unsaturated monocarboxylic acid (d) with a photosensitive resin having carboxyl groups, the photosensitive resin having at least one polymer unit selected from a polyalkylene oxide unit and a polycarbonate unit in its molecular structure; an epoxy resin (B) having a photosensitive group; and a photopolymerization initiator (C). Another photosensitive resin composition (Patent Document 3) is known, which contains a photosensitive resin (A) having carboxyl groups obtained by reacting an ester of an epoxy compound (a) with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride, at least one photosensitive resin (B) selected from photosensitive polyamide resins having carboxyl groups and photosensitive polyamideimide resins having carboxyl groups, an epoxy curing agent (C), a photopolymerization initiator (D), and a flame retardant (E). The photosensitive resin compositions described in Patent Documents 1 to 3 do not fully satisfy the performance requirements for a resin material for a solder resist, that is, excellent heat resistance, sensitivity, and developability in a cured product all at the same time. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5621595 [Patent Document 2] Patent No. 3931370 [Patent Document 3] Japanese Patent Application Publication No. 11-288090 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide an acid group- and polymerizable unsaturated group-containing resin which has high heat resistance in a cured product and is also excellent in sensitivity and developability, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material comprising the curable resin composition, a solder resist resin material comprising the curable resin composition, and a resist member using the solder resist resin material. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted extensive research to solve the above problems and have found that an acid group- and polymerizable unsaturated group-containing resin using a trans isomer of a compound having an acid anhydride group and a carboxyl group in an alicyclic skeleton as a polycarboxylic acid raw material has excellent heat resistance, sensitivity, and developability in the cured product, thereby completing the present invention.

[0008] That is, the present invention provides an acid group- and polymerizable unsaturated group-containing resin, which comprises an amide-imide resin (A) having an acid group and / or an acid anhydride group and a hydroxy(meth)acrylate compound (B) as essential reaction raw materials, The present invention relates to an acid group- and polymerizable unsaturated group-containing resin, characterized in that the amide-imide resin (A) is produced using a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) as essential reaction raw materials.

[0009] The present invention further relates to a curable resin composition containing the acid group- and polymerizable unsaturated group-containing resin and a photopolymerization initiator.

[0010] The present invention further relates to a cured product of the curable resin composition.

[0011] The present invention further relates to an insulating material comprising the curable resin composition.

[0012] The present invention further relates to a resin material for a solder resist comprising the above curable resin composition.

[0013] The present invention further relates to a resist member made of the above-mentioned resin material for a solder resist. Effect of the Invention

[0014] According to the present invention, there are provided an acid group- and polymerizable unsaturated group-containing resin which has high heat resistance in a cured product and is also excellent in sensitivity and developability, a curable resin composition containing the same, a cured product of the curable resin composition, an insulating material made of the curable resin composition, a solder resist resin material made of the curable resin composition, and a resist member made using the solder resist resin material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below.

[0016] (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:

[0017] As used herein, the term "linker" refers to a divalent group or bond.

[0018] 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.

[0019] 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.

[0020] 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-, -SO2-, -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.

[0021] In this specification, examples of the "halogen" in the terms "halogen atom" and "halide" include fluorine, chlorine, bromine, and iodine.

[0022] (Resin containing acid groups and polymerizable unsaturated groups) The acid group- and polymerizable unsaturated group-containing resin of the present invention is an acid group- and polymerizable unsaturated group-containing resin comprising an amide-imide resin (A) having an acid group and / or an acid anhydride group and a hydroxy(meth)acrylate compound (B) as essential reaction raw materials, characterized in that the amide-imide resin (A) comprises a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) as essential reaction raw materials.

[0023] 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 reactivity with the hydroxy (meth)acrylate compound (B) and reaction control, 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 mg KOH / g measured under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 300 mg KOH / g measured under conditions in which the acid anhydride group is ring-opened, such as in the presence of water.

[0024] <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.

[0025] <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.)

[0026] 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").

[0027] <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.

[0028] <<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-Ric1 -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:

[0029] 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 x1 each 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.

[0030] R in structural formula (x-1) x1 Examples of the substituents represented by are as defined above.

[0031] 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.)

[0032] 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.

[0033] <<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. ic2When 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.

[0034] Alicyclic diisocyanate compounds have the general formula: OCN-R ic2 When the structure is represented by -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).

[0035] Ac in structural formula (x-2) or (x-3) a , Ac b , or Ac cExamples 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.

[0036] R in structural formula (x-2) or (x-3) x2 , R x3 , or R x4 The substituents represented by are as defined above.

[0037] 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.

[0038] 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).

[0039] 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).

[0040] 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.

[0041] <<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, Ric3 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). ic3 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 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.

[0042] The aromatic diisocyanate compound has the general formula: OCN-R ic3 When the structure is represented by -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 , L x10 , 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).

[0043] 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.

[0044] 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:

[0045] 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:

[0046] L in structural formulas (x-4) to (x-6) x4 , Lx5 , 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:

[0047] 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).

[0048] 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).

[0049] 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).

[0050] 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.

[0051] <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.

[0052] [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.

[0053] <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 icThe 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 ic The 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.

[0054] <<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.

[0055] <<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.

[0056] 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]

[0057] 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.

[0058] <<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.

[0059] <Polyisocyanate compounds having a biuret structure (biuret compounds)> The "biuret structure" in a polyisocyanate compound having a biuret structure (hereinafter, simply referred to as a "biuret compound") refers to -N(CONH-)2. The biuret compound 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 ic is 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

[0060] <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 Ric is the R described above ic3 and compounds thereof).

[0061] Examples of commercially available isocyanate compounds include, for example, the "VESTANAT (registered trademark)" series (IPDI, TMDI, H12MDI, T 1890 E, T 1890 L, T 1890 M, T 1890 / 100, etc.) of EVONIK; the "TAKENATE (registered trademark)" series (D-127N, etc.) of Mitsui Chemicals; and the "BURNOCK (registered trademark)" series (DN-901S, DN-902S, DN-980, DN-980S, DN-981, DN-992-S, etc.) of DIC Corporation.

[0062] Among these, isocyanurate-modified products are preferred because they provide an acid group- and polymerizable unsaturated group-containing resin that is excellent in the balance between sensitivity and developability and heat resistance 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 with respect to the total mass of the polyisocyanate compound (a1) is preferably 70% by mass or more, and more preferably 90% by mass or more.

[0063] <trans-form-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2)> The "trans-form-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 form.

[0064] <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 "adjacent two 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. For the sake of convenience, in this specification, the "number of converted carboxyl groups" 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].

[0065] <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 the amide group (the linking portion formed by linking the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) through an amide bond) / imide group (the linking portion formed by linking the polyisocyanate compound (a1) and the polycarboxylic acid compound (a2) through an imide bond) in the resulting amide-imide resin (A), thereby obtaining an acid group- and polymerizable unsaturated group-containing resin having high heat resistance in the cured product and excellent sensitivity and developability. 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.

[0066] 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.

[0067] 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.

[0068] 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.)

[0069] 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]

[0070] In formulas (PC-1) and (PC-2), Ac is an alicyclic skeleton, and R pc each independently represents any substituent other than a carboxyl group, and p1 and q each independently represent an integer of 0 or more.

[0071] 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.

[0072] The number of carboxyl groups (corresponding to 2+p1) in the trans isomer of the alicyclic polycarboxylic acid compound or its acid anhydride is 2 or more, and may be, 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).

[0073] 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.

[0074] 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.

[0075] 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]

[0076] 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-based polycarboxylic acid trans compounds such as cyclooctane-r-1,trans-2,trans-4-tricarboxylic acid; 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-based polycarboxylic acid trans compounds; These include, but are not limited to:

[0077] 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]

[0078] 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.

[0079] 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]

[0080] 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.

[0081] The trans-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) may be a mixture of the trans and cis isomers of the corresponding alicyclic polycarboxylic acid compound or its acid anhydride. For example, the trans-containing alicyclic polycarboxylic acid compound or its acid 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 isomer and the cis isomer) in the trans-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) is preferably as high as possible from the viewpoint of obtaining an acid group- and polymerizable unsaturated group-containing resin having high heat resistance in the cured product and excellent sensitivity and developability. 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.

[0082] 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.

[0083] <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.

[0084] Examples of the other reaction raw material (a3) ​​include aliphatic polybasic acids, alicyclic polybasic acids, aromatic polybasic acids, their polybasic acid anhydrides, and acid halides of these polybasic acids or polybasic acid anhydrides.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] The other reaction raw materials (a3) ​​can be used alone or in combination of two or more kinds.

[0089] <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.

[0090] The polyisocyanate (a1) and the polycarboxylic acid compound (a2) are reacted so that the ratio (M / N) of the molar number (N) of the isocyanate group of the polyisocyanate (a1) to the molar number (M) of the polycarboxylic acid compound (a2) converted into carboxyl groups (i.e., [molar number of carboxyl groups] + 2 × [molar number of acid anhydride groups]) is 0.7 to 4.5, more preferably 1 to 3.5, so that the acid group- and polymerizable unsaturated group-containing resin obtained by the reaction with a hydroxy (meth)acrylate compound (B) described later can be made into an acid group- and polymerizable unsaturated group-containing resin having high heat resistance in the cured product, and excellent sensitivity and developability. 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] 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, from the viewpoint of obtaining an acid group- and polymerizable unsaturated group-containing resin having high heat resistance in a cured product and excellent sensitivity and developability.

[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 acid group- and polymerizable unsaturated group-containing resin, reaction temperature conditions, etc.

[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 group / imide group in the resulting amide-imide resin (A), and thus the acid group and polymerizable unsaturated group-containing resin having high heat resistance in the cured product and excellent sensitivity and developability 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) and the number of moles (M) of carboxyl groups in the polycarboxylic acid compound (a2) (i.e., [the number of moles of carboxyl groups] + 2 × [the number of moles of acid anhydride groups]) are almost the same, the higher the molar ratio of amide groups / imide groups in the amide-imide resin (A) as an index, the higher the number of carboxyl groups in the amide-imide resin (A), and the amount of hydroxy (meth) acrylate compound (B) introduced into the amide-imide resin (A) increases, which improves the UV curability of the obtained acid group- and polymerizable unsaturated group-containing resin, and the heat resistance of the cured product is high, and it is possible to obtain an acid group- and polymerizable unsaturated group-containing resin that is also excellent in sensitivity and developability, which is preferable. 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] <Hydroxy (meth)acrylate compound (B)> The hydroxy(meth)acrylate compound (B) is not particularly limited in structure as long as it has a hydroxyl group and a (meth)acryloyl group in its molecular structure, and a wide variety of compounds can be used. The hydroxy(meth)acrylate compound (B) may be used alone or in combination of two or more kinds. Among them, monohydroxy(meth)acrylate compounds are preferred because they facilitate reaction control. Examples of such compounds include hydroxy(meth)acrylate compounds such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the various hydroxy(meth)acrylate compounds; and lactone modified compounds in which a (poly)lactone structure is introduced into the molecular structure of the various hydroxy(meth)acrylate compounds. These compounds may be used alone or in combination of two or more. Among them, those having a molecular weight of 1,000 or less are preferred because they provide an acid group- and polymerizable unsaturated group-containing resin with an excellent balance between heat resistance and elongation in the cured product. When the hydroxy(meth)acrylate compound (B) is an oxyalkylene-modified compound or a lactone-modified compound, it is preferable that the weight average molecular weight (Mw) is 1,000 or less.

[0139] In addition, the hydroxy(meth)acrylate compound (B) may be used in the form of a mixture with a component other than the hydroxy(meth)acrylate compound (B) that does not affect the reaction between the amide-imide resin (A) and the hydroxy(meth)acrylate compound (B). Examples of such components other than the hydroxy(meth)acrylate compound (B) include compounds in which the hydroxyl group of the monohydroxy(meth)acrylate compound is esterified with (meth)acrylic acid. Examples of such mixtures include a mixture of pentaerythritol tri(meth)acrylate and pentaerythritol tetraacrylate (e.g., "Aronix M-306" manufactured by Toa Gosei Co., Ltd.).

[0140] In the acid group- and polymerizable unsaturated group-containing resin of the present invention, in addition to the amide-imide resin (A) having an acid group and / or an acid anhydride group and the hydroxy(meth)acrylate compound (B), any further reaction raw material (C) (e.g., a (meth)acrylate compound (C1) having an epoxy group, a polybasic acid anhydride (C2), etc., described below) may be used in combination depending on the desired resin performance, etc. In this case, the ratio of the total mass of the components (A) and (B) to the total mass of the reaction raw materials of the acid group- and polymerizable unsaturated group-containing resin is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more, in order to fully exert the effects of the present invention.

[0141] <Additional Optional Reactant (C)> The acid group- and polymerizable unsaturated group-containing resin of the present invention may be used in combination with an optional further reaction raw material (C). Examples of the optional further reaction raw material (C) include an epoxy group-containing (meth)acrylate compound (C1) and a polybasic acid anhydride (C2).

[0142] Examples of the (meth)acrylate compound (C1) having an epoxy group include (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds, such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Of these, (meth)acrylate monomers having a glycidyl group (e.g., glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate) are preferred, and glycidyl (meth)acrylate and epoxycyclohexylmethyl (meth)acrylate are more preferred.

[0143] Examples of the polybasic acid anhydride (C2) include polybasic acid anhydrides and acid halides of polybasic acid anhydrides among the compounds explained above as "other reaction raw materials (a3)".

[0144] The further optional reactants (C) can be used alone or in combination of two or more.

[0145] <Method of producing acid group and polymerizable unsaturated group-containing resin> The method for producing the acid group- and polymerizable unsaturated group-containing resin includes the steps of: (i) reacting a polyisocyanate compound (a1) with a polycarboxylic acid compound (a2) to produce an amide-imide resin (A) having an acid group and / or an acid anhydride group; and (ii) A step of reacting the amide-imide resin (A) obtained in the step (i) with a hydroxy(meth)acrylate compound (B) to produce a resin containing an acid group and a polymerizable unsaturated group. may also include

[0146] In another embodiment, the method for producing the acid group- and polymerizable unsaturated group-containing resin comprises the following steps (iii): (iii) A step of reacting the reaction product obtained in the step (ii) with a (meth)acrylate compound (C) having an epoxy group to produce a resin containing an acid group and a polymerizable unsaturated group. It may further include.

[0147] The 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".

[0148] The conditions for reacting the amide-imide resin (A) with the hydroxy(meth)acrylate compound (B) in the step (ii) are not particularly limited, but can be, for example, the following conditions.

[0149] The reaction ratio between the amide-imide resin (A) and the hydroxy(meth)acrylate compound (B) is preferably in the range of 0.9 to 10 mol of the hydroxy(meth)acrylate compound (B) relative to the total of the acid groups and acid anhydride groups in the amide-imide resin (A). In particular, it is preferable to use the hydroxy(meth)acrylate compound (B) in the range of 0.9 to 1.1 mol relative to the total of the acid anhydride groups in the amide-imide resin (A).

[0150] In the step (ii), the reaction liquid used for producing the amide-imide resin (A) may be used continuously, and the hydroxy(meth)acrylate compound (B) and other components may be added as necessary. Examples of the other components include a polymerization inhibitor (which also serves as an antioxidant), a catalyst (basic catalyst), and a solvent (organic solvent). Specific examples of these other components will be described later. The reaction temperature is preferably 50°C to 160°C, and more preferably 70 to 150°C. The reaction time is preferably 1 to 24 hours, and more preferably 1 to 10 hours. The reaction is preferably carried out while blowing in an oxygen (O2)-containing gas (e.g., oxygen (O2) gas, air, etc.).

[0151] The content of acid anhydride groups in the amide-imide resin (A) can be calculated from the difference between the two measured acid values ​​mentioned above, i.e., the difference between the acid value under conditions in which the acid anhydride groups are ring-opened and the acid value under conditions in which the acid anhydride groups are not ring-opened. More specifically, it can be determined by the following method.

[0152] That is, the number of moles of the acid anhydride group in the polyamideimide resin (A) can be calculated by the following (1) to (3) since the polycarboxylic acid or its acid anhydride (a2) is consumed in the reaction with the polyisocyanate (a1). (1) Polyamide-imide resin (A) is diluted with water, a solvent, etc., and the acid value (a) is determined by titration with an aqueous KOH solution. (2) The polyamide-imide resin (A) is diluted with a non-alcoholic solvent, and the acid anhydride group is reacted with an excess amount of n-butanol. The acid value (b) is then determined by titration with an aqueous KOH solution. In (2), the reaction between the acid anhydride group and n-butanol is carried out at 117°C. The disappearance of the acid anhydride is confirmed by the disappearance of the characteristic absorption peak of the acid anhydride group at 1860cm in the infrared spectrum. -1 This is confirmed by checking that the has completely disappeared. (3) The concentration of acid anhydride groups in the polyamide-imide resin (A) used in the present invention is calculated from the difference between the acid value (a) and the acid value (b) and converted into the number of moles.

[0153] The polyamideimide resin (A) used as the raw material may be one produced by the above-mentioned method, but it is preferable to use one in which the isocyanate groups have completely disappeared (which can be confirmed, for example, by infrared spectroscopy) in order to suppress the urethane reaction during the reaction with the hydroxy(meth)acrylate compound (B).

[0154] In addition, when the method for producing the acid group- and polymerizable unsaturated group-containing resin includes the step (iii), the ratio of the total mass of the components (A) and (B) to the total mass of the reaction raw materials for the acid group- and polymerizable unsaturated group-containing resin (i.e., the total mass of the components (A), (B) and (C)) is preferably 80 mass% or more, and more preferably 90 mass% or more.

[0155] The organic solvent is as described above. These organic solvents can be used alone or in combination of two or more kinds. The amount of the organic solvent used is preferably about 0.1 to 5 times the total mass of the reaction raw materials, since this improves the reaction efficiency. The reaction may be carried out with stirring. The reaction may be carried out, for example, under a temperature condition of about 80 to 140°C.

[0156] The basic catalyst is as described above. In particular, alkali metal hydroxides are preferred because they have excellent catalytic activity in the epoxy resin synthesis reaction, and for example, sodium hydroxide and potassium hydroxide are more preferred.

[0157] <Acid value of solid content of acid group- and polymerizable unsaturated group-containing resin> The acid value of the solid content of the acid group- and polymerizable unsaturated group-containing resin of the present invention is preferably in the range of 60 to 200 mgKOH / g, since the acid group- and polymerizable unsaturated group-containing resin has excellent heat resistance and elongation in the cured product as well as excellent developability, etc. The acid value of the solid content of the acid group- and polymerizable unsaturated group-containing resin can be a value measured by the neutralization titration method of JIS K 0070 (1992).

[0158] <(Meth)acryloyl group equivalent of acid group- and polymerizable unsaturated group-containing resin> The (meth)acryloyl group equivalent of the acid group- and polymerizable unsaturated group-containing resin of the present invention is preferably in the range of 200 to 1,500 g / equivalent. The (meth)acryloyl group equivalent [g / equivalent] of the acid group- and polymerizable unsaturated group-containing resin can be a theoretical value calculated using the following formula based on the amount of raw materials charged. (Meth)acryloyl group equivalent [g / equivalent] = (total mass [g] of solid content of acid group- and polymerizable unsaturated group-containing resin) / {(number of moles [mol] of compound having (meth)acryloyl group in raw material) × (average number of (meth)acryloyl groups in compound having (meth)acryloyl group in raw material)}

[0159] <Weight average molecular weight (Mw) of resin containing acid group and polymerizable unsaturated group> The weight average molecular weight (Mw) of the acid group- and polymerizable unsaturated group-containing resin is preferably in the range of 500 to 10,000, and more preferably in the range of 500 to 6,000. The weight average molecular weight (Mw) of the acid group- and polymerizable unsaturated group-containing resin can be a value published by the manufacturer or a value obtained by measurement using gel permeation chromatography (GPC).

[0160] (Curable resin composition) The acid group- and polymerizable unsaturated group-containing resin of the present invention has a polymerizable (meth)acryloyl group in its molecular structure, and therefore can be used as a curable resin composition containing the acid group- and polymerizable unsaturated group-containing resin and a photopolymerization initiator.

[0161] <Photopolymerization initiator> A photopolymerization initiator is a compound that initiates a polymerization reaction by irradiation with light (e.g., ultraviolet light having a wavelength of 250 to 400 nm). Examples of photopolymerization initiators include photoradical initiators. The photopolymerization initiator may be appropriately selected depending on the type of active energy rays to be irradiated. In addition, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound. Specific examples of the photopolymerization initiator include, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone. Examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators such as ethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photopolymerization initiators such as diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds. These may be used alone or in combination of two or more.

[0162] Commercially available products of the photopolymerization initiator include, for example, "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", "Omnirad 81" (manufactured by IGM), "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure 10", "Vicure Examples of such polymers include "55" (manufactured by Stauffer Chemical Co.), "Trigonal P1" (manufactured by AKZO Corporation), "Sandoray 1000" (manufactured by SANDOZ Corporation), "Deep" (manufactured by Upjohn Corporation), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop Corporation), and "Runtecure (registered trademark) 1104" (manufactured by Runtec Corporation).

[0163] The amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15 mass %, and more preferably in the range of 0.1 to 10 mass %, based on the total of the components other than the solvent in the curable resin composition.

[0164] <Other resin components> The curable resin composition of the present invention may contain a resin component other than the acid group- and polymerizable unsaturated group-containing resin of the present invention (hereinafter also referred to as "other resin components"). As the other resin component, for example, those described in JP-A-2022-098702 can be used.

[0165] <(Meth)acrylate Monomer> The curable resin composition of the present invention may contain various (meth)acrylate monomers. These (meth)acrylate monomers can be, for example, those described in JP-A-2022-098702.

[0166] The content of the (meth)acrylate monomer is preferably 90 mass % or less in the non-volatile matter of the curable resin composition of the present invention.

[0167] <Optional addition ingredients> Furthermore, the curable resin composition of the present invention may contain various additives, such as a curing agent, a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

[0168] <Hardening agent> Examples of the curing agent include epoxy resins, polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins.

[0169] Examples of the epoxy resin include those described above.

[0170] The epoxy resins may be used alone or in combination of two or more kinds.

[0171] Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo[2.2.1]heptacarboxylic acid. Examples of the polybasic acid include 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, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. In addition, examples of the polybasic acid include a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule. These polybasic acids can be used alone or in combination of two or more.

[0172] As the unsaturated monobasic acid, the same as those exemplified as the unsaturated monocarboxylic acid described above can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more kinds.

[0173] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more kinds.

[0174] Examples of the amide-based compound include dicyandiamide, a polyamide resin synthesized from a dimer of linoleic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more kinds.

[0175] Examples of the azo compound include azobisisobutyronitrile.

[0176] Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxydicarbonates, alkyl peroxycarbonates, etc. These organic peroxides can be used alone or in combination of two or more kinds.

[0177] Examples of the polyol compound include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; mixtures of the above polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. polyester polyols obtained by co-condensation with dicarboxylic acids such as carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation reaction of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and polyether polyols obtained by ring-opening polymerization of the above polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more.

[0178] As the epoxy resin, the same ones as those exemplified above as the epoxy resin can be used, and the epoxy resins can be used alone or in combination of two or more kinds.

[0179] <Curing accelerator> The curing accelerator is one that accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably within a range of 0.01 to 10 mass % based on the solid content of the curable resin composition.

[0180] <Ultraviolet absorbing agent> Examples of the ultraviolet absorbent include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbents can be used alone or in combination of two or more.

[0181] <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.

[0182] <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.

[0183] 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.

[0184] <Organic solvent> As the organic solvent, for example, the solvents described above can be used.

[0185] <Inorganic filler> Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0186] <Pigments> As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] <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.

[0191] (cured product) The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere in order to efficiently carry out a curing reaction by ultraviolet rays.

[0192] As a source of ultraviolet light, ultraviolet lamps are generally used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

[0193] The cumulative amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions.

[0194] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0195] (Uses of the curable resin composition) The curable resin composition of the present invention has excellent alkaline developability and produces a cured product having excellent heat resistance and elasticity, and therefore can be suitably used, for example, as an insulating material. In addition, the curable resin composition of the present invention can be suitably used, for example, as a resin material used in a package adhesive layer such as a solder resist, an interlayer insulating material, a packaging material, an underfill material, a circuit element, or an adhesive layer between an integrated circuit element and a circuit board in semiconductor device applications. In addition, the cured product of the present invention has excellent alkaline developability and excellent heat resistance and elasticity, and therefore can be suitably used, for example, as a package adhesive layer such as a solder resist, an interlayer insulating material, a packaging material, an underfill material, a circuit element, or an adhesive layer between an integrated circuit element and a circuit board in semiconductor device applications. In addition, the curable resin composition of the present invention can be suitably used for thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, resists for black matrices, spacers, etc. in thin display applications such as LCDs and OELDs. Among these, the composition can be particularly suitably used for solder resist applications.

[0196] The solder resist resin material can be suitably used for a resist member. The resist member of the present invention can be obtained, for example, by applying the solder resist resin material onto a substrate, evaporating and drying the organic solvent at a temperature range of about 60 to 100°C, exposing the substrate to active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing the substrate at a temperature range of about 140 to 200°C.

[0197] Examples of the substrate include a metal-clad laminate of copper, aluminum, or the like. EXAMPLES

[0198] 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.

[0199] In the present examples, the acid values ​​of the acid group- and polymerizable unsaturated group-containing resins were measured by the neutralization titration method of JIS K 0070 (1992).

[0200] In the present examples, the cis / trans ratio and the amide / imide molar ratio of the acid group- and polymerizable unsaturated group-containing resin were measured by NMR under the following conditions.

[0201] 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

[0202] Example 1: Synthesis of Resin (A-1) Having Acid Group and Polymerizable Unsaturated Group 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 allowed to react 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 (a1). 13 The molar ratio of amide group / imide group of the amide-imide resin (a1) calculated by C NMR was 1.52 (mol / mol). Next, 0.2 parts by mass of methoquinone (p-methoxyphenol) was added, followed by adding 140.5 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toa Gosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) and 1.6 parts by mass of triphenylphosphine, and reacting for 5 hours at 110°C while blowing in air to obtain a resin (A-1) having an acid group and a polymerizable unsaturated group. The non-volatile content of the resin (A-1) was 45% by mass, and the solid content acid value was 120 mg KOH / g.

[0203] (Example 2): Synthesis of Resin (A-2) Having Acid Group and Polymerizable Unsaturated Group 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 DN-901S", 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 was 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 (a2). Next, 0.2 parts by mass of methoquinone was added, and then 117.9 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toa Gosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) and 1.4 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 5 hours while blowing in air, to obtain a resin (A-2) having an acid group and a polymerizable unsaturated group. The non-volatile content of the resin (A-2) was 45% by mass, and the solid acid value was 135 mg KOH / g.

[0204] (Example 3): Synthesis of Resin (A-3) Having Acid Group and Polymerizable Unsaturated Group 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 13207.9 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 (a3). Next, 0.3 parts by mass of methoquinone was added, and then 135.4 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toa Gosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) and 1.6 parts by mass of triphenylphosphine were added, and the mixture was reacted at 110°C for 5 hours while blowing in air, to obtain a resin (A-3) having an acid group and a polymerizable unsaturated group. The non-volatile content of the resin (A-3) was 45% by mass, and the solid acid value was 110 mg KOH / g.

[0205] Comparative Example 1: Synthesis of Resin (C-1) Having Acid Groups and Polymerizable Unsaturated Groups 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 (c1). 13 The molar ratio of amide group / imide group of the amide-imide resin (c1) calculated by C NMR was 1.08 (mol%). Next, 0.2 parts by mass of methoquinone was added, followed by 140.5 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toa Gosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) and 1.6 parts by mass of triphenylphosphine, and the reaction was carried out at 110°C for 5 hours while blowing in air, to obtain a resin (C-1) having an acid group and a polymerizable unsaturated group. The non-volatile content of the resin (C-1) was 45% by mass, and the solid content acid value was 117 mg KOH / g.

[0206] Comparative Example 2: Synthesis of Resin (C-2) Having Acid Groups and Polymerizable Unsaturated Groups 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 (c2). Next, 0.2 parts by mass of methoquinone was added, followed by 117.9 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) and 1.4 parts by mass of triphenylphosphine, and the reaction was carried out at 110°C for 5 hours while blowing in air, to obtain a resin (C-2) having acid groups and polymerizable unsaturated groups. The non-volatile content of the resin (C-2) was 45% by mass, and the solid content acid value was 132 mg KOH / g.

[0207] Comparative Example 3: Synthesis of Resin (C-3) Having Acid Groups and Polymerizable Unsaturated Groups 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 Company, Inc., "H-TMAn-S", cis-isomer 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 (c3). Next, 0.3 parts by mass of methoquinone was added, followed by 135.4 parts by mass of a pentaerythritol polyacrylate mixture ("Aronix M-306" manufactured by Toagosei Co., Ltd., hydroxyl value: 159.7 mg KOH / g) and 1.6 parts by mass of triphenylphosphine, and the reaction was carried out at 110°C for 5 hours while blowing in air, to obtain a resin (C-3) having acid groups and polymerizable unsaturated groups. The non-volatile content of the resin (C-3) was 45% by mass, and the solid content acid value was 106 mg KOH / g.

[0208] (Examples 4 to 6 and Comparative Examples 4 to 6): Evaluation of photosensitivity and alkaline developability The evaluation tests for photosensitivity and alkaline developability were carried out as follows. The amounts of each component of the curable resin composition and the evaluation results are shown in Table 2.

[0209] Preparation of curable resin composition The components were mixed in the amounts shown in Table 2 to obtain curable resin compositions (1) to (3) and (C1) to (C3). Hardener: DIC Corporation's "EPICLON N-680" (cresol novolac epoxy resin) Organic solvent: Diethylene glycol monoethyl ether acetate Photoinitiator: Omnirad 907

[0210] Light sensitivity evaluation The curable resin composition was applied onto a glass substrate using a 50 μm applicator and dried at 80° C. for 30 minutes. Then, the composition was exposed to light at 10 kJ / m using a metal halide lamp through a Kodak Step Tablet No. 2. 2 This was developed for 180 seconds in a 5% aqueous sodium carbonate solution, and the number of remaining steps was used for evaluation. The more remaining steps, the higher the photosensitivity.

[0211] Evaluation of alkaline developability (drying control range) The curable resin composition was applied onto a glass substrate using a 50 μm applicator, and samples with different drying times at 80°C were prepared in 10-minute increments, from 30 minutes to 100 minutes. These were developed for 180 seconds with a 5% by mass aqueous solution of sodium carbonate, and the drying time at 80°C of the sample that left no residue was evaluated as the drying control range. The longer the drying control range, the better the alkaline developability.

[0212] [Table 2]

[0213] (Examples 7 to 9 and Comparative Examples 7 to 9): Heat resistance evaluation The heat resistance evaluation test was carried out as follows. The amounts of each component of the curable resin composition and the evaluation results are shown in Table 3.

[0214] Preparation of curable resin composition The components were mixed in the amounts shown in Table 3 to obtain curable resin compositions (4) to (6) and (C4) to (C6). Hardener: DIC Corporation's "EPICLON EXA-850CRP" (bisphenol A type epoxy resin) Organic solvent: Diethylene glycol monoethyl ether acetate Photoinitiator: Omnirad 907

[0215] Heat resistance evaluation The curable resin composition was applied onto glass using a 50 μm applicator and dried at 80° C. for 30 minutes. A metal halide lamp was used for irradiation at 10 kJ / m2 After irradiating with ultraviolet light, the film was heated at 160° C. for 1 hour.

[0216] The cured product was peeled off from the glass and a 6mm x 40mm test piece was cut out. Using a viscoelasticity measuring device (DMA: Rheometrics' solid viscoelasticity measuring device "RSAII", tensile method: frequency 1Hz, heating rate 3℃ / min), the temperature at which the change in elastic modulus was maximum (the rate of change in tan δ was the largest) was evaluated as the glass transition temperature (Tg). A higher glass transition temperature indicates better heat resistance.

[0217] [Table 3]

Claims

1. An acid group- and polymerizable unsaturated group-containing resin, comprising an amide-imide resin (A) having an acid group and / or an acid anhydride group and a hydroxy(meth)acrylate compound (B) as essential reaction raw materials, The amide-imide resin (A) is a resin containing an acid group and a polymerizable unsaturated group, which is prepared by reacting a polyisocyanate compound (a1) with a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) as essential reaction raw materials.

2. 2. The acid group- and polymerizable unsaturated group-containing resin 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. 2. The acid group- and polymerizable unsaturated group-containing resin according to claim 1, wherein the polyisocyanate compound (a1) is a nurate compound.

4. 4. A curable resin composition comprising the acid group- and polymerizable unsaturated group-containing resin according to claim 1 and a photopolymerization initiator.

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

6. An insulating material comprising the curable resin composition according to claim 4.

7. A resin material for a solder resist comprising the curable resin composition according to claim 4.

8. A resist member made by using the solder resist resin material according to claim 7.

9. A method for producing a resin containing an acid group and a polymerizable unsaturated group, comprising a step of mixing an amide-imide resin (A) having an acid group and / or an acid anhydride group with a hydroxy(meth)acrylate compound (B) as essential reaction raw materials, wherein the amide-imide resin (A) is produced by mixing a polyisocyanate compound (a1) and a trans-containing alicyclic polycarboxylic acid compound or an acid anhydride thereof (a2) as essential reaction raw materials.

10. 10. The method for producing a resin containing an acid group and a polymerizable unsaturated group according to claim 9, wherein the trans-isomer content in the trans-isomer-containing alicyclic polycarboxylic acid compound or its acid anhydride (a2) is 30 mol % or more.

11. The method for producing a resin containing an acid group and a polymerizable unsaturated group according to claim 9, wherein the polyisocyanate compound (a1) is a nurate compound.

12. A method for producing a curable resin composition, comprising a step of mixing the acid group- and polymerizable unsaturated group-containing resin obtained by the method for producing a curable resin composition according to any one of claims 9 to 11 with a photopolymerization initiator.

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