Curable resin composition, resin film, cured product, and laminate

Abstract

A curable resin composition contains a block polymer in which a polyimide unit is linked to a polymer unit of an ethylenically unsaturated monomer via a chain transfer agent residue, and a crosslinking agent, the polymer unit containing a structural unit derived from an ethylenically unsaturated monomer having one or more crosslinking groups in the molecule. A curable resin composition, a resin film, a cured product, and a laminate are provided which have high adhesion strength and softness, and exhibit excellent heat resistance even in a high-temperature environment.

Description

TECHNICAL FIELD

[0001] The present application relates to a curable resin composition, a resin film, a cured product of these, and a laminate including a layer containing the cured product, which are excellent in adhesion strength and flexibility, have sufficient heat resistance even in a high-temperature environment, and are effectively used as a bonding material in the fields of power elements, automobiles, building materials, ships, aircraft, and the like. BACKGROUND

[0002] In recent years, in the fields of automobile body structures or power elements and the like, adhesion has been attracting attention from the viewpoint of efficiency, miniaturization, and weight reduction, and in these fields, further improvement in heat resistance is required because of the large thermal load in the use environment.

[0003] In order to solve this problem, for example, in Patent Literature 1, an epoxy-based adhesive is described as an adhesive excellent in heat resistance. However, the epoxy-based adhesive is excellent in heat resistance but lacks flexibility, and further, becomes hard and brittle when exposed for a long time in a high-temperature environment, so in the case of use in applications in which the temperature environment changes significantly, there is a problem that the adhesive layer is cracked due to internal stress caused by differences in linear expansion coefficients between substrates or with the substrate, and the adhesion strength is reduced.

[0004] In addition, for example, in Patent Literature 2, a silicone-based adhesive is described as a resin high in heat resistance and flexibility. However, such a silicone-based adhesive is excellent in adhesion strength for a long time by relaxing the internal stress generated, but has a problem that the adhesion strength is insufficient compared to the epoxy-based adhesive, and the applications that can be used are limited.

[0005] Therefore, it is desired to develop an adhesive that has high adhesion strength and flexibility, and also satisfies heat resistance, and is effectively used as a bonding material.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Application Laid-Open No. 2003-292568

[0009] Patent Literature 2: Japanese Patent Application Laid-Open No. 2005-320461 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] The present application relates to a curable resin composition, a resin film, a cured product of these, and a laminate including a layer containing the cured product, which are excellent in adhesion strength and flexibility, have sufficient heat resistance even in a high-temperature environment, and are effectively used as a bonding material in the fields of power elements, automobiles, building materials, ships, aircraft, and the like.

[0012] TECHNICAL MEANS FOR SOLVING THE PROBLEM

[0013] As a result of intensive studies to solve the problems, it has been found that the problems can be solved by the embodiments described below, and the present application has been completed.

[0014] An embodiment of the present application relates to a hardening resin composition containing a block polymer (C) in which a polyimide unit (A) and a polymer unit (B) of an ethylenically unsaturated monomer are linked by a chain transfer agent residue, and a crosslinking agent (D), in the hardening resin composition, the polymer unit (B) contains a structural unit derived from an ethylenically unsaturated monomer (b1) having one or more crosslinking groups in the molecule.

[0015] Another embodiment of the present application relates to the hardening resin composition, wherein the ethylenically unsaturated monomer (b1) includes an ethylenically unsaturated monomer having a carboxyl group.

[0016] Another embodiment of the present application relates to the hardening resin composition, wherein the crosslinking agent (D) includes a compound having two or more epoxy groups in the molecule.

[0017] Another embodiment of the present application relates to the hardening resin composition, wherein the chain transfer agent residue is a group derived from a chain transfer agent having an amino group.

[0018] Another embodiment of the present application relates to the hardening resin composition, wherein the block polymer (C) contains the polymer unit (B) in an amount of 10 to 50% by mass, based on the total mass of the block polymer (C).

[0019] Another embodiment of the present application relates to the hardening resin composition, wherein the ethylenically unsaturated monomer constituting the polymer unit (B) contains the ethylenically unsaturated monomer (b1) in an amount of 5 to 50% by mass, based on the total mass of the ethylenically unsaturated monomer.

[0020] Another embodiment of the present application relates to the hardening resin composition, wherein the diamine constituting the polyimide unit (A) is any one selected from the group consisting of a combination of a dimer diamine and a diamine having an aromatic ring, and a combination of a diamino polysiloxane and a diamine having an aromatic ring.

[0021] Another embodiment of the present application relates to a hardened product obtained by hardening the hardening resin composition.

[0022] Another embodiment of the present application relates to a resin film including a polyimide unit (A) and a polymer unit (B) of an ethylenically unsaturated monomer, wherein the content of the polymer unit (B) is in the range of 10 to 50 mass% based on the total mass of the polyimide unit (A) and the polymer unit (B), and the haze value is not more than 50.

[0023] Another embodiment of the present application relates to a hardened product obtained by hardening the resin film.

[0024] Another embodiment of the present application relates to a laminate having a layer including the hardened product on a substrate.

[0025] Effects of the Invention

[0026] According to the embodiments of the present application, a curable resin composition, a resin film, a hardened product of each of them, and a laminate including a layer including the hardened product, which have high adhesion strength and softness, and exhibit excellent heat resistance even in a high-temperature environment, can be provided. DETAILED DESCRIPTION

[0027] Curable resin composition, resin film

[0028] The curable resin composition of the embodiments of the present application contains a block polymer (C) in which a polyimide unit (A) and a polymer unit (B) of an ethylenically unsaturated monomer are linked via a chain transfer agent residue, and a crosslinking agent (D), and the polymer unit (B) contains a structural unit derived from an ethylenically unsaturated monomer (b1) having one or more crosslinkable groups in the molecule. By including the soft polyimide unit (A) and the polymer unit (B) of the ethylenically unsaturated monomer having a crosslinkable group and excellent heat resistance in the block polymer (C), the obtained curable resin composition can achieve not only high adhesion strength and softness but also heat resistance.

[0029] In addition, by having a structure in which a polyimide unit (A) and a polymer unit (B) of an ethylenically unsaturated monomer are linked, a resin film having excellent compatibility between the units and high transparency can be obtained compared to the case where each is mixed separately. A hardened product obtained by hardening such a resin film can achieve excellent adhesion strength, softness, and heat resistance.

[0030] The embodiments of the present application are described in detail below.

[0031] (Block polymer (C))

[0032] The block polymer (C) can be formed by linking polyimide units (A) and polymer units (B) of vinyl unsaturated monomers through chain transfer agent residues. There are no restrictions on its manufacturing method, but it is preferred to be manufactured by the following method.

[0033] First, diamine is reacted with excess acid dianhydride in a solvent to form polyamic acid, which is then heated to a high temperature for dehydration and cyclization to imidize it, forming a polyimide unit (A) with acid anhydride at both ends (step 1).

[0034] Subsequently, a chain transfer agent is added to synthesize a prepolymer with chain transfer agent residues at both ends of the polyimide unit (A) (step 2).

[0035] Subsequently, using the chain transfer agent residues present in the obtained prepolymer, the ethylene unsaturated monomer (b1), which contains an ethylene unsaturated monomer (b1) having one or more crosslinking groups within the molecule, undergoes chain transfer polymerization in the presence of a polymerization initiator, thereby forming a polymer unit (B) of the ethylene unsaturated monomer (step 3).

[0036] Thus, a block polymer (C) can be obtained by linking a polyimide unit (A) with a polymer unit (B) of an ethylene unsaturated monomer through chain transfer agent residues, wherein the polymer unit (B) of the ethylene unsaturated monomer contains a structural unit derived from an ethylene unsaturated monomer (b1) having one or more crosslinking groups in the molecule.

[0037] [Polyimide unit (A)]

[0038] The block polymer (C) has a structure in which a polyimide unit (A) is linked to a polymeric unit (B) of an ethylene unsaturated monomer via chain transfer agent residues. The polyimide unit (A) can be formed by reacting a diamine with an excess of acid dianhydride in a solvent to form polyamic acid, and then heating it to a high temperature for dehydration cyclization to imidize it.

[0039] [Diamine]

[0040] Examples of diamines that constitute the polyimide unit (A) include:

[0041] Diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6 Decane, 1,3-diaminomethylcyclohexane, isophorone diamine and other alicyclic diamines;

[0042] As an example of the diamine having an aromatic ring

[0043] 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and the like bisaminophenoxyphenylpropane;

[0044] 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and the like diaminodiphenyl ether;

[0045] p-phenylenediamine, m-phenylenediamine, and the like phenylenediamine;

[0046] 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, and the like diaminodiphenyl sulfide;

[0047] 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, and the like diaminodiphenyl sulfone;

[0048] 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, and the like diaminobenzophenone;

[0049] 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, and the like diaminodiphenylmethane;

[0050] 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, and the like diaminophenylpropane;

[0051] 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, and the like diaminophenylhexafluoropropane;

[0052] 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane, and the like diaminophenylphenylethane;

[0053] 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, and the like bisaminophenoxybenzene;

[0054] 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene and other bisaminobenzoylbenzene derivatives;

[0055] 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene and other bisamino-dimethylbenzylbenzene derivatives;

[0056] 1,3-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-di-trifluoromethylbenzyl)benzene and other bisamino-di-trifluoromethylbenzylbenzene derivatives;

[0057] 2,6-bis(3-aminophenoxy)benzyl nitrile, 2,6-bis(3-aminophenoxy)pyridine, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl and other aminophenoxybiphenyl derivatives;

[0058] Bis[4-(3-aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl]one, and other aminophenoxyphenyl ketones;

[0059] Bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, and other aminophenoxyphenyl sulfides;

[0060] Bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, and other aminophenoxyphenyl sulfones;

[0061] Bis[4-(3-aminophenoxy)phenyl] ether, bis[4-(4-aminophenoxy)phenyl] ether, and other aminophenoxyphenyl ethers;

[0062] 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and other aminophenoxyphenyl propane derivatives.

[0063] In addition, other diamines (including diamines with aromatic rings) include: 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-( [4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl sulfone, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-diphenyloxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-diphenyloxybenzophenone Phenoxybenzophenone, 6,6'-bis(3-aminophenoxy)3,3,3,'3,'-tetramethyl-1,1'-spirodiindane, 6,6'-bis(4-aminophenoxy)3,3,3,'3,'-tetramethyl-1,1'-spirodiindane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, bis(aminomethyl) ether, bis(2-aminoethyl) ether, bis(3-aminopropyl) ether, bis[(2-aminomethoxy)ethyl] ether, bis[2-(2-aminoethoxy)ethyl] ether, bis[2-(3-aminopropoxy)ethyl] ether, 1,2-bis(aminomethyl) 1,2-Bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane.

[0064] Alternatively, the diamine can be a dimer derived from dimers of unsaturated fatty acids such as oleic acid, i.e., dimer acids. Commercially available examples of dimer diamines include Versamine 551 (manufactured by BASF Japan), Versamine 552 (manufactured by Cognis Japan; a hydride of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (manufactured by Croda Japan).

[0065] Alternatively, the diamine can be any diaminopolysiloxane, such as α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl]polydimethylsiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 1,3-bis(4-aminobutyl)tetramethyldisiloxane. Commercially available diaminopolysiloxanes include, for example, KF-8010, X-22-161A, and X-22-161B (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0066] Alternatively, polyoxypropylene diamine can be used as the diamine. Commercially available polyoxypropylene diamines include, for example, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, and Jeffamine D-4000 (all manufactured by Huntsman).

[0067] These diamines can be used alone or in combination of two or more. Preferably, the diamine is selected from at least one of the group consisting of dimer diamines, diamines having an aromatic ring, and diaminopolysiloxanes, more preferably from any one of the group consisting of a combination of dimer diamines and diamines having an aromatic ring, and a combination of diaminopolysiloxanes and diamines having an aromatic ring, and even more preferably from a combination of diaminopolysiloxanes and diamines having an aromatic ring.

[0068] Examples of combinations of dimer diamines with diamines having aromatic rings include PRIAMINE 1075 with 2,2-bis[4-(4-aminophenoxy)phenyl]propane and PRIAMINE 1075 with bis[4-(4-aminophenoxy)phenyl]sulfone.

[0069] Examples of combinations of diaminopolysiloxanes and diamines with aromatic rings include KF-8010 with 2,2-bis[4-(4-aminophenoxy)phenyl]propane and KF-8010 with bis[4-(4-aminophenoxy)phenyl]sulfone.

[0070] [Acid dianhydride]

[0071] There are no particular limitations on its use as an acid dianhydride; for example, the following can be listed:

[0072] Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride, and 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride.

[0073] Alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and 3,5,6-tricarboxy-2-norborneneacetic dianhydride.

[0074] Aliphatic tetracarboxylic dianhydrides, such as 1,2,3,4-butanetetracarboxylic dianhydride.

[0075] These acid dianhydrides can be used alone or in combination of two or more. Preferably, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride and 4,4'-(4,4'-isopropylidene diphenoxy) phthalic anhydride are preferred, and more preferably 4,4'-(4,4'-isopropylidene diphenoxy) phthalic anhydride are preferred.

[0076] Polyamic acid can be readily formed by mixing the diamine and the acid dianhydride at any temperature between -20°C and 150°C, preferably between -5°C and 100°C.

[0077] As a method for imidizing polyamic acid by dehydration and cyclization, existing thermal imidization and chemical imidization methods can be used. In thermal imidization, imidization can be easily carried out, for example, by heating while dehydrating at a high temperature of 150°C to 250°C. In chemical imidization, for example, imidization can be carried out by adding 2 to 10 molar equivalents of a base such as pyridine or triethylamine to acetic anhydride relative to the diamine used as a raw material, and then carrying out a cyclization reaction at 0°C to 50°C.

[0078] [[Number-average molecular weight of polyimide units (A)]]

[0079] The average molecular weight of the polyimide units (A) is preferably in the range of 20,000 to 200,000. If it is 20,000 or more, the fracture strength of the obtained cured material is excellent, and if it is 200,000 or less, the viscosity is easy to adjust, so it is preferred.

[0080] [Chain transfer agent]

[0081] By reacting the anhydride groups at both ends of the polyimide unit (A) with a chain transfer agent, a prepolymer having chain transfer agent residues at both ends can be obtained. The chain transfer agent is not particularly limited, but is preferably a chain transfer agent having functional groups that can react with the anhydride groups and sulfanyl groups. When the chain transfer agent is used, the terminal anhydride groups in the polyimide unit (A) and the functional groups in the chain transfer agent that can react with the anhydride groups react to form a prepolymer having sulfanyl groups at both ends. The reaction between the polyimide unit (A) and the chain transfer agent is readily carried out by mixing at any temperature from 20°C to 120°C. Existing chain transfer agents can be used alone or in combination of two or more.

[0082] As functional groups that can react with acid anhydrides, examples include amino or hydroxyl groups, where the hydrogen atom of the amino group can be substituted by organic residues such as alkyl or aryl groups. Substituted amino groups (also called substituted amino groups) include, for example, monosubstituted amino groups such as N-alkylamino and N-arylamino. Hydroxyl groups include primary hydroxyl, secondary hydroxyl, and tertiary hydroxyl groups.

[0083] Regarding its good reactivity with acid anhydride groups, the functional group that can react with acid anhydride groups is preferably an amino group. That is, the chain transfer agent residue is preferably derived from a chain transfer agent having an amino group. By using a chain transfer agent having both an amino and a thiol group, a thiol group can be efficiently introduced to the end of the prepolymer, which is therefore preferred.

[0084] Examples of chain transfer agents containing one amino group and one thiol group within the molecule include: aminoalkyl thiols such as 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, and 4-amino-1-butanethiol; and aminophenylthiols such as 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Among these, aminoalkyl thiols are preferred, and 2-aminoethanethiol is more preferred.

[0085] [Polymer unit of vinyl unsaturated monomer (B)]

[0086] The polymer unit (B) of the vinyl unsaturated monomer contains a structural unit derived from an vinyl unsaturated monomer (b1) having one or more crosslinking groups in the molecule, and is a structure obtained by polymerizing an vinyl unsaturated monomer containing an vinyl unsaturated monomer (b1) having one or more crosslinking groups in the molecule in the presence of a polymerization initiator.

[0087] Specifically, by polymerizing the prepolymer obtained in step 2, which has chain transfer agent residues at both ends, with an ethylene unsaturated monomer (b1) containing an ethylene unsaturated monomer having one or more crosslinking groups within the molecule, in the presence of a polymerization initiator, a block polymer (C) can be obtained by linking polyimide units (A) and polymer units (B) of ethylene unsaturated monomers through chain transfer agent residues.

[0088] (Ethylene unsaturated monomers with more than one crosslinking group in the molecule (b1))

[0089] Crosslinking groups included in an ethylene unsaturated monomer (b1) having one or more crosslinking groups within the molecule can be, for example, hydroxyl, carboxyl, epoxy, isocyanate groups and their end caps, and can be used alone or in combination of two or more.

[0090] Examples of vinyl unsaturated monomers with carboxyl groups include: (meth)acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, α-(hydroxymethyl)(meth)acrylic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylic acid, ethylene oxide modified succinic acid (meth)acrylate, ω-carboxylated polycaprolactone (meth)acrylate, and p-vinylbenzoic acid.

[0091] Examples of vinyl unsaturated monomers having hydroxyl groups include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate or caprolactone adducts of these monomers (addition molar number of 1 to 5), polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, and glycerol mono(meth)acrylate.

[0092] Examples of epoxy-containing vinyl unsaturated monomers include: glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 3-ethyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxyhexyl (meth)acrylate, α-ethyl glycidyl acrylate, allyl glycidyl ether, crotonyl glycidyl ether, (iso)crotonic glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, N-(3,5-dimethyl-4-glycidyl)acrylate, etc. (Alkyl) benzylacrylamide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyloxymethylstyrene.

[0093] Examples of vinyl unsaturated monomers having an isocyanate group include: (meth)acryloyl isocyanate, ethyl (meth)acrylate, 2-(meth)acryloyloxyethoxyethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, m-(meth)acryloylphenyl isocyanate, and α,α-dimethyl-4-isopropenylbenzyl isocyanate.

[0094] Among them, the vinyl unsaturated monomer (b1) having one or more crosslinking groups in the molecule is preferably a vinyl unsaturated monomer having a carboxyl group. If a vinyl unsaturated monomer having a carboxyl group is used, a cured product with better heat resistance and flexibility can be obtained when reacting with the crosslinking agent (D) described later, and therefore it is preferred.

[0095] The content of the vinyl unsaturated monomer (b1) having one or more crosslinking groups within the molecule is preferably 5% to 50% by mass, more preferably 5% to 30% by mass, based on the total mass of the vinyl unsaturated monomers constituting the polymer unit (B) of the vinyl unsaturated monomer. If it is in the range of 5% to 50% by mass, the heat resistance and flexibility are excellent, and therefore it is preferred.

[0096] (Other vinyl unsaturated monomers)

[0097] In addition to ethylene unsaturated monomers (b1) that have one or more crosslinking groups in the molecule, the ethylene unsaturated monomers constituting the polymer unit (B) of the ethylene unsaturated monomer may also include other ethylene unsaturated monomers.

[0098] There are no particular limitations on other vinyl unsaturated monomers, such as: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, cetyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, isomyristyl methacrylate, stearyl methacrylate. (Meth)acrylate isostearate and other (meth)acrylate linear or branched alkyl esters; (meth)acrylate cyclohexyl acrylate, (meth)acrylate tert-butylcyclohexyl acrylate, (meth)acrylate dicyclopentane acrylate, (meth)acrylate dicyclopentoxyethyl acrylate, (meth)acrylate dicyclopentenyl acrylate, (meth)acrylate dicyclopentenoxyethyl acrylate, (meth)acrylate isobornyl acrylate and other (meth)acrylate cyclic alkyl esters; (meth)acrylate trifluoroethyl acrylate, (meth)acrylate octafluoropentyl acrylate, (meth)acrylate perfluorooctyl ethyl acrylate, (meth)acrylate tetrafluoropropyl acrylate and other (meth)acrylate fluoroalkyl esters; (meth)acrylate tetrahydrofurfuryl acrylate, (meth)acrylate 3-methyl- 3-Oxycyclic butyl ester and other heterocyclic (meth)acrylates; benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, p-cumylphenoxy polyethylene glycol (meth)acrylate, or nonylphenoxy polyethylene glycol (meth)acrylate and other aromatic ring (meth)acrylates; methoxy polyethylene glycol mono(meth)acrylate, octyloxy polyethylene glycol polypropylene glycol mono(meth)acrylate, lauryloxy polyethylene glycol mono(meth)acrylate, stearyloxy polyethylene glycol mono(meth)acrylate, phenoxy polyethylene glycol mono(meth)acrylate, benzyl... Oxygenated polyethylene glycol polypropylene glycol mono(meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, lauryloxy polyethylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, phenoxy polyethylene glycol mono(meth)acrylate, methoxy polyethylene glycol (meth)acrylate, n-butoxyethyl (meth)acrylate, n-butoxydiethylene glycol (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, etc. (meth)acrylates containing alkyl ether groups;(Methyl)acrylamide, N-methyl(methyl)acrylamide, N-butylacrylamide, diacetone acrylamide, N-methoxymethyl-(methyl)acrylamide, N-ethoxymethyl-(methyl)acrylamide, N-propoxymethyl-(methyl)acrylamide, N-butoxymethyl-(methyl)acrylamide, N-pentoxymethyl-(methyl)acrylamide, N,N-dimethylacrylamide, N,N-dibenzylacrylamide, formamide methacrylate, N-methylN-vinylacetamide, N-vinylpyrrolidone, N,N-di(methoxymethyl)acrylamide, N-ethoxymethyl-N-methoxymethylmethylacrylamide, N,N-di(ethoxymethyl)acrylamide, N- Ethoxymethyl-N-propoxymethylmethacrylamide, N,N-di(propoxymethyl)acrylamide, N-butoxymethyl-N-(propoxymethyl)methacrylamide, N,N-di(butoxymethyl)acrylamide, N-butoxymethyl-N-(methoxymethyl)methacrylamide, N,N-di(pentoxymethyl)acrylamide, N-methoxymethyl-N-(pentoxymethyl)methacrylamide, cinnamic acid amide, and other vinyl unsaturated monomers containing amide groups; vinyl groups such as styrene, α-methylstyrene, and vinyl acetate; and vinyl ethers containing ether groups such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether.

[0099] These can be used individually or in combination.

[0100] The content of the polymeric unit (B) of the vinyl unsaturated monomer, based on the total mass of the block polymer (C), is preferably in the range of 10% to 50% by mass, more preferably in the range of 20% to 40% by mass. A range of 10% to 50% by mass results in excellent heat resistance and flexibility, and is therefore preferred.

[0101] (Polymerization initiator)

[0102] Existing azo compounds and organic peroxides can be used as polymerization initiators. These can be used alone or in combination of two or more.

[0103] There are no particular limitations on the azo compounds, for example: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carboxylonitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypentanitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), dimethyl 1,1'-azobis(1-cyclohexanecarboxylate), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentaic acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0104] There are no particular limitations on organic peroxides, for example: benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanate, tert-butyl peroxytrimethylacetate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0105] The amount of polymerization initiator is based on the total amount of ethylene unsaturated monomers, and is preferably 0.001% to 15% by mass. If it is in the range of 0.001% to 15% by mass, chain transfer polymerization will proceed effectively, and therefore is preferred.

[0106] [[Number-average molecular weight of polymer units (B) of vinyl unsaturated monomers]]

[0107] The average molecular weight of the polymer units (B) of the ethylene unsaturated monomer is preferably in the range of 2,000 to 200,000. If it is above 2,000, the obtained hardened material has excellent fracture strength, and if it is below 200,000, the viscosity is easy to adjust, so it is preferred.

[0108] (Number-average molecular weight of block polymers (C))

[0109] The number average molecular weight of the block polymer (C) is preferably in the range of 5,000 to 300,000. If it is above 5,000, the obtained hardened material has excellent fracture strength, and if it is below 300,000, the viscosity is easy to adjust, so it is preferred.

[0110] <<Haze value of resin film>>

[0111] The haze value of the resin film is preferably less than 50, more preferably less than 30. If it is less than 50, the hardened product obtained by curing the resin film has excellent adhesion strength, flexibility, and heat resistance.

[0112] [Solvent]

[0113] Solvents that can be used in the manufacture of block polymers (C) include, for example: acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, toluene, xylene, anisole, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, and γ-valerol. These solvents can be used alone or in combination of two or more.

[0114] The solvent that can be used in the synthesis of the polyimide unit (A) is preferably a high-boiling-point solvent that does not react with chain transfer agents having amino and thiol groups. Examples of such solvents include xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, m-cresol, γ-butyrolactone, and γ-valerolactone.

[0115] (Crosslinking agent (D))

[0116] The curable resin composition of embodiments of the present invention further comprises a crosslinking agent (D). By reacting the crosslinking groups of the block polymer (C) derived from the vinyl unsaturated monomer (b1) with the crosslinking agent (D) and then curing, a cured product with excellent heat resistance, flexibility, and adhesion can be obtained. Therefore, the crosslinking agent (D) is preferably a crosslinking agent having two or more functional groups that can react with the crosslinking groups derived from the vinyl unsaturated monomer (b1), such as compounds having epoxy, acid anhydride, phenolic, isocyanate, carboxyl, amino, or hydroxyl groups.

[0117] Crosslinking agent (D) can be used alone or in combination of two or more.

[0118] Examples of crosslinking agents with epoxy groups include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidylaminophenylmethane, and triglycidyl isocyanate.

[0119] As a crosslinking agent containing anhydrides, in addition to using the dianhydrides that constitute the polyimide unit (A), existing compounds such as phthalic anhydride, trimellitic anhydride, and maleic anhydride can also be used.

[0120] Crosslinking agents containing phenol groups can be monomeric compounds or polymeric compounds. As polymeric compounds, crosslinking agents containing phenol groups can be polymers of a single monomer (homopolymers) or copolymers of multiple monomers (polymers). Furthermore, crosslinking agents containing phenol groups can be any of random copolymers, block copolymers, or graft copolymers.

[0121] Examples of crosslinking agents containing phenol groups include: bisphenol A, bisphenol F, bisphenol S, resorcinol, catechol, hydroquinone, fluorenebisphenol, 4,4'-biphenol, 4,4',4”-trihydroxytriphenylmethane, naphthol, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, calixarene, phenolic varnish-type phenolic resins (e.g., polyphenolic varnish resins synthesized from polyhydroxy compounds represented by phenolic varnish resins, cresol varnish resins, bisphenol A varnish resins, bisphenol S varnish resins, and resorcinol varnish resins with formaldehyde), naphthol-phenol cocondensed phenolic varnish resins, naphthol-cresol cocondensed phenolic varnish resins, naphthol varnish resins, and alkoxy-containing aromatic ring-modified resins. Phenolic varnish resins (polyphenolic compounds that utilize formaldehyde to link a phenol core and an aromatic ring containing an alkoxy group), aralkyl phenolic resins (e.g., xylokresin and other phenol aralkyl resins and naphthol aralkyl resins), aromatic hydrocarbon formaldehyde resin modified phenolic resins, dicyclopentadienylphenol addition-type resins, trimethylolpropane resins, tetraphenylol ethane resins, biphenyl-modified phenolic resins (polyphenolic compounds that utilize dimethylene to link a phenol core), biphenyl-modified naphthol resins (polyphenolic compounds that utilize dimethylene to link a phenol core), and aminotriazine-modified phenolic resins (polyphenolic compounds that utilize melamine, benzoguanamine, etc., to link a phenol core).

[0122] Specific examples of phenolic resins for varnishes include "Phenolite TD-2131" and "Phenolite TD-2090" (trade names) manufactured by DIC Co., Ltd. Specific examples of aralkyl phenolic resins include GPH-65 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0123] Examples of crosslinking agents having isocyanate groups include compounds having two or more isocyanate groups in the molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate, as well as biuret bodies, ureates, adducts, and other condensates thereof.

[0124] Examples of biuret compounds include hexamethylene diisocyanate biuret compounds (product name "sumidur N-75", manufactured by Sumika Bayer Urethane Co., Ltd.; product name "Duranate 24A-100", manufactured by Asahi Kasei Chemical Co., Ltd.).

[0125] Examples of urea esters include hexamethylene diisocyanate urea ester (product name "sumidur N-3300", manufactured by Sumika Bayer Urethane), isophorone diisocyanate urea ester (product name "Desmodur Z-4370", manufactured by Sumika Bayer Urethane), and toluene diisocyanate urea ester (product name "Coronate 2030", manufactured by Japan Polyurethane).

[0126] Examples of adducts include the hexamethylene diisocyanate adduct of trimethylolpropane (product name "Takenate D-160N", manufactured by Mitsui Chemicals), the isophorone diisocyanate adduct of trimethylolpropane (product name "Takenate D-140N", manufactured by Mitsui Chemicals), and the toluene diisocyanate adduct (product name "Desmodur L75", manufactured by Sumika Covestro Urethane).

[0127] Other condensates include: multifunctional compounds containing isocyanate groups, carbodiimide-modified compounds, biuret-modified compounds, and urea-formate-modified compounds, such as: polymethylene polyphenyl polyisocyanate (product name "PAPI27", manufactured by Dow Chemical Company), biuret of hexamethylene diisocyanate (product name "Takenate D-165N", manufactured by Mitsui Chemicals Company), and carbodiimide-modified diphenylmethane diisocyanate (product name "Isonate 143L", manufactured by Dow Chemical Company).

[0128] Examples of crosslinking agents with carboxyl groups include: succinic acid, adipic acid, sebacic acid, maleic acid, phthalic acid, naphthalene dicarboxylic acid, methyl phthalic acid, cyclohexane dicarboxylic acid, methyl cyclohexane dicarboxylic acid, methyl norbornene dicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, pyromellitic tetracarboxylic acid, and naphthalene tetracarboxylic acid.

[0129] Examples of crosslinking agents containing amino groups include: ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, p-phenylenediamine, and other diamines; 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropyldiamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropyldiamine, di-2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and other hydroxyl groups. Diamines; including diethylenetriamine, iminodipropylamine, triethylenetetramine, N-(3-aminopropyl)butane-1,4-diamine, 6,6-iminodihexylamine, 3,7-diazanonane-1,9-diamine, N,N'-bis(3-aminopropyl)ethylenediamine, and polyfunctional amines with trifunctional or higher functions such as JEFFAMINE D-230, D-400, D-2000, T-403, and T-3000 (all manufactured by Huntsman).

[0130] Examples of crosslinking agents containing hydroxyl groups include: ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butanediol, polytetramethylene glycol, methylpropylene glycol, pentanediol, methylpentanediol, hexanediol, nonanediol, neopentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanediol, tricyclodecanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl hydroxypentanoate, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolethane, trimethylolpropane, trimethylolbutane, glycerol, and pentaerythritol.

[0131] The crosslinking agent (D) is preferably a compound having at least two functional groups selected from the group consisting of epoxy groups and acid anhydrides within the molecule, and more preferably a compound having two or more epoxy groups within the molecule. In particular, if the vinyl unsaturated monomer (b1) having one or more crosslinking groups within the molecule includes a vinyl unsaturated monomer having one or more carboxyl groups, and the crosslinking agent (D) includes a compound having two or more epoxy groups within the molecule, a cured material with particularly excellent heat resistance and flexibility can be obtained, and is therefore preferred.

[0132] The molar ratio of the functional groups in the crosslinking agent (D) to the crosslinking groups in the block polymer (C) (moles of functional groups in the crosslinking agent (D) / moles of crosslinking groups in the block polymer (C)) is preferably 0.2 to 5.0, more preferably 0.5 to 3.0. A ratio of 0.2 to 5.0 results in excellent heat resistance and flexibility, and is therefore preferred. Furthermore, from the viewpoint of adhesion, a range of 0.2 to 20.0 is preferred, more preferably 0.5 to 16.0.

[0133] <Other Ingredients>

[0134] The curable resin composition may also include existing additives such as silane coupling agents, fillers, propellants, plasticizers, superplasticizers, wetting agents, flame retardants, viscosity modifiers, preservatives, stabilizers, and colorants. These additives may be used alone or in combination of two or more.

[0135] Examples of silane coupling agents include: vinyltrimethoxysilane, vinyltriethoxysilane, and other vinyl-containing trialkoxysilanes; 3-aminopropyltriethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, and other amino-containing trialkoxysilanes; 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and other glycidyl groups; 3-isocyanate-propyltriethoxysilane, and other isocyanate groups; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and other mercapto groups.

[0136] The amount of silane coupling agent prepared is based on the mass of the block polymer (C) in the curable resin composition, and is preferably 0.05% to 10% by mass.

[0137] [Hardened material, laminate]

[0138] The cured product of the embodiments of the present invention is a cured product obtained by curing the aforementioned curable resin composition or resin film, and is effectively used in the fields of adhesives, adhesive sheets, coating agents, film substrates, elastomers, medical materials, and optical materials. From the viewpoint of having high adhesive strength and flexibility, and excellent heat resistance, it is preferably used as an adhesive sheet.

[0139] There are no particular limitations on the method of forming the hardened material. For example, it can be obtained by coating a hardening resin composition with a viscosity adjusted to be suitable for the coating method using a solvent or the like onto a substrate, heating it to a temperature of, for example, 50°C to 200°C and removing the solvent, and then hardening it at a temperature of 20°C to 200°C.

[0140] The laminate of the present invention is a laminate comprising a layer containing the cured material on a substrate. The manufacturing method of the laminate is not particularly limited, and for example, it can be manufactured by: coating a curable resin composition onto a first substrate, drying volatile components such as solvents in an oven to form an uncured resin layer, overlapping a second substrate on the resin layer, and performing heat pressing or other methods as needed to soften and seal the resin layer while simultaneously curing it. Alternatively, the laminate can also be manufactured, for example, by sandwiching an uncured resin layer, pre-formed into a sheet and dried from a curable resin composition, between two substrates, and then curing it by heat pressing or other methods to soften and seal it while simultaneously curing it. The thickness of the cured layer is preferably 0.1 μm to 300 mm.

[0141] There are no particular limitations on the substrate. For example, in addition to metals such as aluminum and copper, thermoplastic polymers such as polyethylene, polypropylene, polyurethane, polyester, polyacrylate, polycarbonate and copolymers thereof, thermosetting polymers such as epoxy resin, melamine resin, vulcanized rubber, polyamide, polyimide, polyamide-imide, polymethacrylamide, polyphenylene sulfide, polyarylate, liquid crystal polymer (LCP), polysulfone, polyethersulfone and other heat-resistant polymers, carbon fiber reinforced plastics, glass fiber reinforced plastics and other fiber reinforced plastics, glass and wood can also be listed.

[0142] There are no particular restrictions on the shape of these substrates; suitable materials include porous materials such as structures, metal foils, films, sheets, foams, and nonwoven fabrics, as well as composites thereof.

[0143] When a laminate includes two or more substrates, the substrates may be the same or different.

[0144] The laminates of the embodiments of the present invention have excellent adhesion, flexibility and heat resistance, and are effectively used as structural components in the fields of power devices, automobiles, building materials, ships, and aircraft.

[0145] This invention is related to the subject matter of Japanese Patent Application No. 2020-073976 filed on April 17, 2020 and Japanese Patent Application No. 2020-212798 filed on December 22, 2020, the entire disclosure of which is incorporated herein by reference.

[0146] Example

[0147] The present invention will be described in more detail below through embodiments, but the following embodiments do not limit the scope of the invention in any way. In addition, unless otherwise specified, "parts" and "%" in the embodiments refer to "parts by mass" and "% by mass", respectively.

[0148] [Solid component concentration]

[0149] The concentration of the solid components of the resin was determined according to Japanese Industrial Standards (JIS) K5601-1-2, and was the residual component after heating at a temperature of 150°C and a heating time of 20 minutes.

[0150] [Number average molecular weight (Mn), weight average molecular weight (Mw)]

[0151] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were calculated using converted values ​​obtained from polystyrene with known molecular weights, determined by gel permeation chromatography (GPC). The determination was performed using a GPC-8020 (manufactured by Tosoh Corporation) as the GPC apparatus, tetrahydrofuran as the eluent, and three TSK gelSuper HM-M (manufactured by Tosoh Corporation) gels connected in series as a column, at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 °C.

[0152] [Acid Value]

[0153] The acid value was determined according to the following procedure. First, 1 g of resin solution was dissolved in 40 mL of toluene, followed by the addition of 20 mL of methanol and 1 mL of deionized water to prepare a sample for acid value determination. Then, using an automatic titration apparatus "AT-510" manufactured by Kyoto Electronics Industry Co., Ltd., connected to an "APB-510-20B" burette manufactured by the same company as the titrating reagent, a 0.02 mol / L ethanolic potassium hydroxide solution was used for potentiometric titration. The mg of KOH relative to 1 g of solid resin was calculated based on the concentration of the solid component of the resin.

[0154] The following are abbreviations used in this specification.

[0155] BPADA: 4,4'-(4,4'-isopropylidene diphenoxy)phthalic anhydride

[0156] DSDA: 3,3',4,4'-Diphenylsulfone tetracarboxylic dianhydride

[0157] BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane

[0158] BAPS: bis[4-(4-aminophenoxy)phenyl]sulfone

[0159] PRIAMINE 1075: A hydrogenated dimerized diamine, manufactured by Croda Japan.

[0160] KF-8010: Diaminopolysiloxane, product name "KF-8010", manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0161] DMF: N,N-dimethylformamide

[0162] AIBN: 2,2'-azobisisobutyronitrile

[0163] MMA: Methyl methacrylate

[0164] St: Styrene

[0165] MAA: Methacrylic acid

[0166] AA: Acrylic acid

[0167] GMA: Glycidyl methacrylate

[0168] HEMA: 2-Hydroxyethyl methacrylate

[0169] TETRAD-X: N,N,N',N'-Tetraglycidyl-m-xylenediamine, manufactured by Mitsubishi Gas Chemical Company.

[0170] Desmodur L75: Toluene diisocyanate (TDI) adduct, manufactured by Sumika Covestro Urethane.

[0171] jER828: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation.

[0172] <Manufacturing of Block Polymers>

[0173] (Manufacturing Example 1) Block Polymer (C-1) Solution

[0174] 100 parts of BPADA, 17.4 parts of BAPP, 78.5 parts of PRIAMINE 1075 (manufactured by Croda Japan), and 457 parts of DMF were charged into a reaction vessel including a gas inlet pipe, thermometer, condenser, and stirrer, and nitrogen was used for purging. The reaction vessel was heated to 150°C while stirring, and the reaction was continued until the acid value was less than 2 mg KOH / g, thereby obtaining polyimide units.

[0175] Then, after cooling to 80°C, 0.89 parts of 2-aminoethanethiol were added, and the mixture was reacted at 80°C for 5 hours to obtain the polyimide prepolymer.

[0176] Subsequently, 75.9 parts MMA, 8.4 parts MAA, and 199 parts DMF were added to the polyimide prepolymer, which had been restored to room temperature. After uniform stirring, the mixture was heated to 75°C under a nitrogen environment. 0.1 parts AIBN, acting as a polymerization initiator, were added in 13 portions every 30 minutes. After adding the polymerization initiator, the reaction was continued for 2 hours to form polymer units of ethylene unsaturated monomers. DMF was added to bring the solids concentration to 30%, thereby obtaining a block polymer (C-1) solution. The number-average molecular weight (Mn) of the block polymer (C-1) was 49,000, and the weight-average molecular weight (Mw) was 97,000.

[0177] (Manufacturing Examples 2 to 42) Block Polymer (C-2) Solution to Block Polymer (C-42) Solution

[0178] The formulation was changed to the one shown in Table 1 or Table 2, and the same operation as in Manufacturing Example 1 was performed to obtain block polymer (C-2) solution to block polymer (C-42) solution.

[0179] (Comparative Manufacturing Example 1) Comparative Resin (H-1) Solution

[0180] A reaction vessel, including a gas inlet tube, thermometer, condenser, and stirrer, was loaded with 100 parts BPADA, 17.4 parts BAPP, 78.5 parts PRIAMINE 1075, and 457 parts DMF, and purged with nitrogen. The reaction vessel was heated to 150°C while stirring, and the reaction continued until the acid value was less than 2 mg KOH / g. DMF was added to bring the solids concentration to 30%, thus obtaining a comparative resin (H-1) solution.

[0181] (Comparative Manufacturing Example 2) Comparative Resin (H-2) Solution

[0182] The formulation was changed to the one shown in Table 3, and the same operation as in Comparative Manufacturing Example 1 was performed to obtain a comparative resin (H-2) solution.

[0183] (Comparative Manufacturing Example 3) Comparative Resin (H-3) Solution

[0184] 90 parts MMA, 10 parts MAA, and 233 parts DMF were added to a reaction vessel including a gas inlet pipe, thermometer, condenser, and stirrer. After uniform stirring, the mixture was heated to 75°C under nitrogen. 0.1 parts AIBN, acting as a polymerization initiator, were added in 13 portions every 30 minutes, and the reaction was continued for 2 hours after the addition of the polymerization initiator. DMF was then added to bring the solids concentration to 30%, thus obtaining a comparative resin (H-3) solution.

[0185] (Comparative Manufacturing Examples 4 and 5) Comparative resin (H-4) solution ~ Comparative resin (H-5) solution

[0186] The formulation was changed to the one shown in Table 3, and the same operation as in Comparative Manufacturing Example 3 was performed to obtain the comparative resin (H-4) solution and the comparative resin (H-5) solution.

[0187] (Comparative Manufacturing Example 6) Comparative use of block polymer (H-6) solution

[0188] A reaction vessel, including a gas inlet tube, thermometer, condenser, and stirrer, was loaded with 100 parts BPADA, 17.4 parts BAPP, 78.5 parts PRIAMINE 1075, and 457 parts DMF, and purged with nitrogen. The reaction vessel was heated to 150°C while stirring, and the 1850 cm⁻¹ region was confirmed to originate from the acid anhydride by infrared absorption spectroscopy. -1 The disappearance of absorption, and the 1780cm from the imide group -1 The absorption of the substance occurred, and the reaction ended. Next, the mixture was cooled to 80°C, and 0.89 parts of 2-aminoethanethiol were added. The mixture was then reacted at 80°C for 5 hours to obtain the polyimide prepolymer.

[0189] Subsequently, 84.3 parts of MMA and 199 parts of DMF were added to the polyimide prepolymer, which had been restored to room temperature, and the mixture was stirred uniformly. The temperature was then raised to 75°C under a nitrogen environment. 0.1 parts of AIBN, acting as a polymerization initiator, were added in 13 portions every 30 minutes. After adding the polymerization initiator, the reaction was carried out for 2 hours to form polymer units of ethylene unsaturated monomers, thereby obtaining a comparative block polymer (H-6) solution.

[0190] (Comparative Manufacturing Example 7) Comparative Block Polymer (H-7) Solution

[0191] The formulation was changed to the one shown in Table 3, and the same operation as in Comparative Manufacturing Example 6 was performed to obtain a comparative block polymer (H-7) solution.

[0192] Details of the obtained block polymers and comparative resins are shown in Tables 1 to 3.

[0193] [Table 1]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] <Preparation of Curable Resin Compositions>

[0200] [Example 1]

[0201] 30 parts of block polymer (C-1) and 0.37 parts of TETRAD-X as crosslinking agent (D) were added and mixed by stirring at room temperature to obtain a curable resin composition.

[0202] [Examples 2-42, Examples 85-94, Comparative Examples 1-10]

[0203] The formulation was changed to the composition shown in Tables 4 to 7, and the same operation as in Example 1 was performed to obtain the curable resin compositions of Examples 2 to 42, Examples 85 to 94, and Comparative Examples 1 to 10.

[0204] [Evaluation of Curable Resin Compositions]

[0205] The obtained curable resin composition was used and evaluated as follows. The results are shown in Tables 4 to 7.

[0206] [Break stress, elongation at break]

[0207] The curable resin composition was placed into a silicone mold to achieve a cured thickness of 2 mm. After the solvent dried, it was cured under the following curing conditions corresponding to the crosslinking agent. Subsequently, the cured film was punched using a dumbbell-shaped mold to produce a dumbbell-shaped cured film. The obtained cured film was stretched using a tensile testing machine at a tensile speed of 50 mm / min at a temperature of 23°C and a relative humidity of 50%. The breaking stress (MPa) and elongation at break (%) were measured and judged according to the following criteria. Higher values ​​for breaking stress and elongation at break are considered superior, with a practical level of B or higher.

[0208] Hardening conditions

[0209] • When the crosslinking agent is TETRAD-X: 3 hours at 150°C

[0210] • When the crosslinking agent is BPADA: After standing at 100°C for 10 minutes, it is then placed at 220°C for 1 hour.

[0211] • When the crosslinking agent is Desmodur L75: 3 hours at 100°C

[0212] (Evaluation criteria for fracture stress)

[0213] SS: Fracture stress above 30 MPa

[0214] S: Fracture stress is above 25MPa but less than 30MPa

[0215] A: The fracture stress is above 20 MPa but less than 25 MPa.

[0216] B: Fracture stress is 15MPa or higher but less than 20MPa

[0217] C: Fracture stress less than 15MPa (unusable)

[0218] (Elongation at break evaluation criteria)

[0219] SS: Elongation at break is 200% or more

[0220] S: Elongation at break is 150% or more but less than 200%.

[0221] A: Elongation at break is 100% or more but less than 150%.

[0222] B: Elongation at break is 50% or more but less than 100%.

[0223] C: Elongation at break is less than 50% (unusable)

[0224] [Next intensity]

[0225] A curable resin composition was applied to a release film (PET-38GS, manufactured by Lintec) using a scraper to achieve a dried thickness of 50 μm. The film was dried under reduced pressure at 100°C, and the release film was then peeled off to obtain an adhesive sheet. The adhesive sheet was cut into 12.5 mm × 25.0 mm pieces, and sandwiched between two copper substrates (2.0 mm × 25 mm × 100 mm). Bonding was performed using a press at the following pressing temperature conditions for 1 hour. The bonded test piece was then subjected to tensile testing using a tensile testing machine at 23°C and 50% relative humidity, and the shear adhesion strength (MPa) was measured. The following criteria were used for evaluation: a higher shear adhesion strength value indicates better performance, with a practical level of B or higher.

[0226] Pressing Temperature Conditions

[0227] • When the crosslinking agent is TETRAD-X: 160℃

[0228] • When the crosslinking agent is BPADA: 230℃

[0229] • When the crosslinking agent is Desmodur L75: 160℃

[0230] (Following the strength evaluation criteria)

[0231] SS: Shear adhesion strength above 12.5 MPa

[0232] S: Shear adhesion strength is 10.0 MPa or higher but less than 12.5 MPa

[0233] A: Shear adhesion strength is 7.5 MPa or higher but less than 10.0 MPa.

[0234] B: Shear adhesion strength is 5.0 MPa or higher but less than 7.5 MPa

[0235] C: Shear adhesion force is less than 5.0 MPa (unusable)

[0236] [Heat resistance]

[0237] A hardened film with a thickness of approximately 50 μm was prepared using the same method as that used for the adhesion strength test. The hardened film was cut into 5 mm wide strips and used as test pieces, which were then left to stand in an oven at 150°C for 1000 hours. Dynamic viscoelasticity was measured using a DVA-200 / L2 (IT Measurement & Control Co., Ltd.) for the test pieces before and after the 1000-hour heat resistance test at 150°C. The rate of change Z was calculated using the stored elastic coefficient at 200°C using the following formula, and evaluated according to the following criteria. A smaller rate of change is better, with a practical level of B or higher.

[0238] Conditions for the Determination of Dynamic Viscoelasticity

[0239] Measurement mode: Tensile mode

[0240] Frequency: 10Hz

[0241] Temperature range: -80℃ to the measurement limit

[0242] Heating conditions: 10℃ / min

[0243] Rate of change of storage elasticity coefficient

[0244] When the storage elasticity coefficient at 200℃ before the heat resistance test is set as X (Pa) and the storage elasticity coefficient at 200℃ after the heat resistance test is set as Y (Pa), the rate of change Z of the storage elasticity coefficient is expressed by the following formula.

[0245] When X ≥ Y: Z = X / Y

[0246] When Y > X: Z = Y / X

[0247] (Evaluation criteria for heat resistance)

[0248] S: Rate of change Z is less than 5

[0249] A: The rate of change Z is greater than 5 but less than 10.

[0250] B: The rate of change Z is greater than 10 but less than 100.

[0251] C: Rate of change Z is above 100 (unusable)

[0252] [Table 4]

[0253]

[0254]

[0255]

[0256]

[0257] <Manufacturing of Resin Films>

[0258] [Examples 43-84, Comparative Examples 11-20]

[0259] With a dried thickness of 50 μm, the block polymer solution, comparative resin solution, and mixture of comparative resin used in Examples 1 to 42, Comparative Examples 1 to 10 (as shown in Table 8) were coated onto a release film (PET-38GS, manufactured by Lintec Corporation). After drying under reduced pressure at 100°C, the release film was peeled off to obtain a resin film.

[0260] <Evaluation of Resin Membranes>

[0261] The obtained resin film was evaluated as follows, and the results are shown in Table 8.

[0262] [Haze Value]

[0263] The obtained resin film was tested for haze using a haze meter (NDH-5000 manufactured by Nippon Denshoku Co., Ltd.), and judged according to the following criteria. The lower the haze value, the better, with a practical level of B or above.

[0264] (Evaluation criteria for haze value)

[0265] A: Haze level is below 30

[0266] B: Haze value is 30 or higher but less than 50.

[0267] C: Haze value above 50 but below 80 (cannot be used)

[0268] D: Haze value above 80 (Poor)

[0269] [Table 8]

[0270]

[0271] According to the evaluation results in Tables 4 to 7, the cured products of the curable resin compositions of the embodiments of the present invention exhibit good fracture stress, elongation at break, adhesion strength, and heat resistance. In particular, when the polymeric unit (B) contains ethylene unsaturated monomers in a range of 20% to 40% by mass based on the total mass of the block polymer (C), and when the polymeric unit (B) contains ethylene unsaturated monomers having one or more crosslinking groups within the molecule in a range of 5% to 30% by mass based on the total mass of the ethylene unsaturated monomers constituting the polymeric unit (B), the fracture stress, elongation at break, adhesion strength, and heat resistance are excellent.

[0272] Furthermore, according to the evaluation results in Table 8, the resin film of the embodiment of the present invention has a low haze value and excellent transparency.

Claims

1. A curable resin composition comprising a block polymer formed by linking polyimide units and vinyl unsaturated monomer polymer units through chain transfer agent residues containing an amino group and a thiol group within the molecule, and a crosslinking agent, wherein the curable resin composition, The polymer unit comprises structural units derived from a first vinyl unsaturated monomer having one or more crosslinking groups selected from hydroxyl, carboxyl, epoxy, isocyanate groups and their end-capped forms within the molecule, as well as structural units derived from other vinyl unsaturated monomers besides the structural units of the first vinyl unsaturated monomer. The block polymer contains Polyamide units derived from the reaction of terminal anhydride groups in the polyimide units and amino groups in the chain transfer agent to form prepolymers with thiol groups at both ends, and Polymer units are formed by chain transfer polymerization of an ethylene-unsaturated monomer containing the first ethylene-unsaturated monomer in the presence of a polymerization initiator, using the chain transfer agent residues present in the prepolymer. The diamine constituting the polyimide unit is selected from at least one of the group consisting of dimer diamines, diamines having an aromatic ring, and diaminopolysiloxanes. The other vinyl unsaturated monomers contain methyl methacrylate or styrene. The crosslinking agent has two or more functional groups within its molecule that can react with the crosslinking groups of the first vinyl unsaturated monomer, wherein the functional groups contain at least one functional group selected from the group consisting of epoxy groups, isocyanate groups, and phenol groups. The block polymer comprises, based on the total mass of the block polymer, 10% to 50% by mass of the polymeric units. The vinyl unsaturated monomers constituting the polymer unit contain a first vinyl unsaturated monomer in an amount of 5% to 50% by mass, based on the total mass of the vinyl unsaturated monomers. The molar ratio of the functional groups contained in the crosslinking agent to the crosslinking groups contained in the block polymer satisfies the condition that the molar number of functional groups contained in the crosslinking agent / the molar number of crosslinking groups contained in the block polymer = 0.2 to 20.

0.

2. The curable resin composition according to claim 1, wherein the first vinyl unsaturated monomer comprises an vinyl unsaturated monomer having a carboxyl group.

3. The curable resin composition according to claim 1 or 2, wherein the crosslinking agent comprises a compound having two or more epoxy groups within the molecule.

4. The curable resin composition according to claim 1, wherein the block polymer comprises 20% to 40% by mass of the polymeric units based on the total mass of the block polymer.

5. The curable resin composition according to claim 2, wherein the block polymer comprises 20% to 40% by mass of the polymeric units based on the total mass of the block polymer.

6. The curable resin composition according to claim 3, wherein the block polymer comprises 20% to 40% by mass of the polymeric units based on the total mass of the block polymer.

7. The curable resin composition according to claim 1, wherein the first vinyl unsaturated monomer comprises an vinyl unsaturated monomer having a carboxyl group. The crosslinking agent comprises a compound having two or more epoxy groups within its molecule. The block polymer comprises 20% to 40% by mass of the polymeric units based on the total mass of the block polymer.

8. The curable resin composition according to claim 1, wherein the chain transfer agent residue is one or more residues selected from the group consisting of 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, 4-amino-1-butanethiol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol.

9. The curable resin composition according to claim 2, wherein the chain transfer agent residue is an aminoalkane thiol residue.

10. The curable resin composition according to claim 3, wherein the chain transfer agent residue is a residue of 2-aminoethanethiol.

11. The curable resin composition according to claim 4, wherein the vinyl unsaturated monomer constituting the polymer unit comprises a first vinyl unsaturated monomer in an amount of 5% to 30% by mass based on the total mass of the vinyl unsaturated monomer.

12. The curable resin composition according to claim 1, wherein the first vinyl unsaturated monomer comprises an vinyl unsaturated monomer having a carboxyl group. The crosslinking agent comprises a compound having two or more epoxy groups within its molecule. The block polymer comprises, based on the total mass of the block polymer, 20% to 40% by mass of the polymeric units. The vinyl unsaturated monomer constituting the polymer unit contains a first vinyl unsaturated monomer in an amount of 5% to 30% by mass, based on the total mass of the vinyl unsaturated monomer.

13. The curable resin composition according to claim 1, wherein the diamine constituting the polyimide unit is selected from any one of the group consisting of a combination of a dimer diamine and a diamine having an aromatic ring, and a combination of a diaminopolysiloxane and a diamine having an aromatic ring.

14. The curable resin composition according to claim 2, wherein the diamine constituting the polyimide unit is selected from any one of the group consisting of a combination of a dimer diamine and a diamine having an aromatic ring, and a combination of a diaminopolysiloxane and a diamine having an aromatic ring.

15. The curable resin composition according to claim 3, wherein the diamine constituting the polyimide unit is selected from any one of the group consisting of a combination of a dimer diamine and a diamine having an aromatic ring, and a combination of a diaminopolysiloxane and a diamine having an aromatic ring.

16. The curable resin composition according to claim 4, wherein the diamine constituting the polyimide unit is selected from any one of the group consisting of a combination of a dimer diamine and a diamine having an aromatic ring, and a combination of a diaminopolysiloxane and a diamine having an aromatic ring.

17. The curable resin composition according to claim 5, wherein the diamine constituting the polyimide unit is selected from any one of the group consisting of a combination of a dimer diamine and a diamine having an aromatic ring, and a combination of a diaminopolysiloxane and a diamine having an aromatic ring.

18. The curable resin composition according to claim 1, wherein the first vinyl unsaturated monomer comprises an vinyl unsaturated monomer having a carboxyl group. The crosslinking agent comprises a compound having two or more epoxy groups within its molecule. The block polymer comprises, based on the total mass of the block polymer, 20% to 40% by mass of the polymeric units. The vinyl unsaturated monomers constituting the polymer unit contain a first vinyl unsaturated monomer in an amount of 5% to 30% by mass, based on the total mass of the vinyl unsaturated monomers. The diamine constituting the polyimide unit is a diaminopolysiloxane or a diamine having an aromatic ring.

19. A hardened material, formed by hardening a hardening resin composition as described in any one of claims 1 to 18.

20. A resin film using a curable resin composition as described in any one of claims 1 to 18, said resin film comprising a block polymer of polyimide units and vinyl unsaturated monomers linked by chain transfer agent residues containing an amino group and a thiol group within the molecule, wherein the resin film, The content of the polymer unit is in the range of 10% to 50% by mass, based on the total mass of the polyimide unit and the polymer unit, and the haze value is less than 50.

21. A hardened material formed by hardening the resin film as described in claim 20.

22. A laminate having a layer comprising the hardened material as described in claim 19 or 21 on a substrate.

Images