CN115397877A

CN115397877A - Curable resin composition, resin film, cured product, and laminate

Info

Publication number: CN115397877A
Application number: CN202180027582.0A
Authority: CN
Inventors: 方田大遥; 大宅彻
Original assignee: Toyo Ink SC Holdings Co Ltd; Toyochem Co Ltd
Current assignee: Toyochem Co Ltd; Artience Co Ltd
Priority date: 2020-04-17
Filing date: 2021-04-15
Publication date: 2022-11-25
Also published as: WO2021210625A1; JP2021172809A; KR20230008082A; JP6897856B1

Abstract

A curable resin composition comprising a block polymer wherein a polyimide unit and a polymer unit of an ethylenically unsaturated monomer are linked to each other via a chain transfer agent residue, and a crosslinking agent, wherein the polymer unit contains a structural unit derived from the ethylenically unsaturated monomer having one or more crosslinking groups in the molecule.

Description

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

Technical Field

The present invention relates to a curable resin composition and a resin film 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 devices, automobiles, building materials, ships, airplanes, and the like, cured products of these, and a laminate including a layer containing the cured products.

Background

In recent years, in the field of semiconductors such as automobile body structures and power elements, attention has been paid to joining in terms of efficiency, size reduction, and weight reduction, and in these fields, further improvement in heat resistance is required because of a large thermal load in the use environment.

To solve such a problem, for example, patent document 1 describes an epoxy adhesive as an adhesive having excellent heat resistance. However, epoxy adhesives have excellent heat resistance but lack flexibility, and further deteriorate when exposed to a high-temperature environment for a long period of time, and therefore, when used in applications where changes in the temperature environment are significant, there are problems as follows: the adhesive layer is cracked due to internal stress caused by the difference in linear expansion coefficient between the base material and the base material, and the adhesion is reduced.

Further, for example, patent document 2 describes a silicone adhesive as a resin having high heat resistance and flexibility. However, although such a silicone adhesive is excellent in long-term adhesion by relaxing the generated internal stress, there is a problem that the adhesive strength is insufficient compared with an epoxy adhesive and the usable application is limited.

Therefore, it is desired to develop an adhesive which has high adhesive strength and flexibility, satisfies heat resistance, and is effectively used as a bonding material.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 2003-292568

Patent document 2: japanese patent laid-open publication No. 2005-320461

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a curable resin composition, a resin film, a cured product of these, and a laminate comprising a layer containing the cured product, which have high adhesive strength and flexibility and exhibit excellent heat resistance even in a high-temperature environment.

Means for solving the problems

As a result of repeated research to solve the above problems, the following embodiments have found that the above problems can be solved, and the present invention has been completed.

An embodiment of the present invention relates to a curable 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 to each other by a chain transfer agent residue, and a crosslinking agent (D), wherein the polymer unit (B) contains a structural unit derived from an ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule.

Another embodiment of the present invention relates to the curable resin composition, wherein the ethylenically unsaturated monomer (b 1) comprises an ethylenically unsaturated monomer having a carboxyl group.

Another embodiment of the present invention relates to the curable resin composition, wherein the crosslinking agent (D) contains a compound having two or more epoxy groups in a molecule.

Another embodiment of the present invention relates to the curable resin composition, wherein the chain transfer agent residue is a group derived from a chain transfer agent having an amino group.

Another embodiment of the present invention relates to the curable 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).

Another embodiment of the present invention relates to the curable 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.

Another embodiment of the present invention relates to the curable resin composition, wherein the diamine constituting the polyimide unit (a) is any one selected from the group consisting of a combination of dimer diamine and diamine having an aromatic ring, and a combination of diaminopolysiloxanes and diamine having an aromatic ring.

Another embodiment of the present invention relates to a cured product obtained by curing the curable resin composition.

Another embodiment of the present invention relates to a resin film comprising a polyimide unit (a) and a polymer unit (B) of an ethylenically unsaturated monomer, wherein the content of the polymer unit (B) in the resin film is in a range of 10 to 50% by mass based on the total mass of the polyimide unit (a) and the polymer unit (B), and the haze value is less than 50.

Another embodiment of the present invention relates to a cured product obtained by curing the resin film.

Another embodiment of the present invention relates to a laminate having a layer containing the cured product on a substrate.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the embodiments of the present invention, a curable resin composition, a resin film, a cured product of the curable resin composition and the resin film, and a laminate including a layer including the cured product, which have high adhesive strength and flexibility and exhibit excellent heat resistance even in a high-temperature environment, can be provided.

Detailed Description

< curable resin composition, resin film >

The curable resin composition according to an embodiment of the present invention is characterized in that: the polyimide resin composition contains a block polymer (C) in which a polyimide unit (A) and a polymer unit (B) of an ethylenically unsaturated monomer are linked to each other by a chain transfer agent residue, and a crosslinking agent (D), wherein the polymer unit (B) contains a structural unit derived from an ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule. The block polymer (C) comprises a flexible polyimide unit (A) and a polymer unit (B) of an ethylenically unsaturated monomer having a crosslinking group and excellent heat resistance, and the obtained curable resin composition can achieve not only high adhesion strength and flexibility but also heat resistance.

Further, by having a structure in which the polyimide units (a) and the ethylenically unsaturated monomer polymer units (B) are linked, a resin film having excellent compatibility between the units and high transparency can be obtained as compared with the case where the units are mixed individually. A cured product obtained by curing such a resin film can achieve excellent adhesive strength, flexibility, and heat resistance.

The embodiments of the present invention will be described in detail below.

(Block Polymer (C))

The block polymer (C) is not limited as long as it has a structure in which the polyimide unit (a) and the ethylenically unsaturated monomer polymer unit (B) are linked by a chain transfer agent residue, and can be produced preferably by the following method.

First, a diamine and an excess amount of acid dianhydride are reacted in a solvent to form a polyamic acid, which is further heated to a high temperature to undergo cyclodehydration and imidization, thereby forming a polyimide unit (a) having acid anhydrides at both ends (step 1).

Then, a chain transfer agent is added to synthesize a prepolymer having chain transfer agent residues at both ends of the polyimide unit (a) (step 2).

Then, the ethylenically unsaturated monomer (B1) containing one or more crosslinking groups in the molecule is subjected to chain transfer polymerization in the presence of a polymerization initiator using the chain transfer agent residue of the obtained prepolymer, thereby forming a polymer unit (B) of the ethylenically unsaturated monomer (step 3).

Thus, a block polymer (C) can be obtained in which the polyimide units (A) and the polymer units (B) of ethylenically unsaturated monomers containing a structural unit derived from an ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule are linked by a chain transfer agent residue.

[ polyimide Unit (A) ]

The block polymer (C) has a structure in which the polyimide unit (a) and the polymer unit (B) of the ethylenically unsaturated monomer are linked by a chain transfer agent residue, and the polyimide unit (a) can be formed by: diamine is reacted with an excessive amount of acid dianhydride in a solvent to form polyamic acid, which is heated to a high temperature to dehydrate and cyclize to imidize it.

[ diamine ]

Examples of the diamine constituting the polyimide unit (a) include:

alicyclic diamines such as 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 [5.2.1.02,6] decane, 1, 3-bisaminomethylcyclohexane, and isophoronediamine;

as an example of the diamine having an aromatic ring

Bisaminophenoxyphenylpropanes such as 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane;

diaminodiphenyl ethers such as 3,3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether and 4,4' -diaminodiphenyl ether;

phenylenediamines such as p-phenylenediamine and m-phenylenediamine;

diaminodiphenyl sulfides such as 3,3' -diaminodiphenyl sulfide, 3,4' -diaminodiphenyl sulfide and 4,4' -diaminodiphenyl sulfide;

diaminodiphenyl sulfones such as 3,3' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone and 4,4' -diaminodiphenyl sulfone;

diaminobenzophenones such as 3,3' -diaminobenzophenone, 4' -diaminobenzophenone, and 3,4' -diaminobenzophenone;

diaminodiphenylmethane such as 3,3' -diaminodiphenylmethane, 4' -diaminodiphenylmethane, and 3,4' -diaminodiphenylmethane;

diaminophenylpropanes such as 2, 2-bis (3-aminophenyl) propane, 2-bis (4-aminophenyl) propane and 2- (3-aminophenyl) -2- (4-aminophenyl) propane;

2, 2-bis (3-aminophenyl) -1, 3-hexafluoropropane 2, 2-bis (4-aminophenyl) -1, 3-hexafluoropropane diaminophenylhexafluoropropanes such as 2- (3-aminophenyl) -2- (4-aminophenyl) -1, 3-hexafluoropropane;

diaminophenylethanes such as 1, 1-bis (3-aminophenyl) -1-phenylethane, 1-bis (4-aminophenyl) -1-phenylethane and 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane;

bisaminophenoxybenzenes such as 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene;

bis-aminobenzoylbenzenes such as 1, 3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1, 4-bis (3-aminobenzoyl) benzene, 1, 4-bis (4-aminobenzoyl) benzene, etc.;

bisaminodimethylbenzenes such as 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, and 1, 4-bis (4-amino- α, α -dimethylbenzyl) benzene;

bisaminobistrifluoromethylbenzyl benzenes such as 1, 3-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 3-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 4-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, and 1, 4-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene;

aminophenoxy biphenyls such as 2, 6-bis (3-aminophenoxy) benzonitrile, 2, 6-bis (3-aminophenoxy) pyridine, 4 '-bis (3-aminophenoxy) biphenyl, and 4,4' -bis (4-aminophenoxy) biphenyl;

aminophenoxyphenyl ketones such as bis [4- (3-aminophenoxy) phenyl ] ketone and bis [4- (4-aminophenoxy) phenyl ] ketone;

aminophenoxyphenyl sulfides such as bis [4- (3-aminophenoxy) phenyl ] sulfide and bis [4- (4-aminophenoxy) phenyl ] sulfide;

aminophenoxy phenyl sulfones such as bis [4- (3-aminophenoxy) phenyl ] sulfone and bis [4- (4-aminophenoxy) phenyl ] sulfone;

aminophenoxyphenyl ethers such as bis [4- (3-aminophenoxy) phenyl ] ether and bis [4- (4-aminophenoxy) phenyl ] ether;

2, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [3- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane aminophenoxyphenylpropanes such as 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane.

Examples of the other diamines (including diamines having an aromatic ring) 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, alpha-dimethylbenzyl ] benzene, 4 '-bis [4- (4-aminophenoxy) benzoyl ] diphenyl ether, 4' -bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] benzophenone, 4 '-bis [4- (4-amino-alpha, alpha-dimethylbenzyl) phenoxy ] diphenylsulfone, 4' -bis [4- (4-aminophenoxy) phenoxy ] diphenylsulfone, 3 '-diamino-4, 4' -diphenoxybenzophenone, 3 '-diamino-4, 4' -diphenoxybenzophenone, alpha-dimethylbenzyl) phenoxy ] diphenylsulfone, alpha-dimethylbenzyl-phenyl, 3,3 '-diamino-4-phenoxybenzophenone, 3' -diamino-4-diphenoxybenzophenone, 6 '-bis (3-aminophenoxy) 3,3', 3, '-tetramethyl-1, 1' -spirobiindan, 6 '-bis (4-aminophenoxy) 3,3', 3, '-tetramethyl-1, 1' -spirobiindan, 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 (aminomethoxy) ethane, 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, 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.

As the diamine, dimer diamine derived from dimer acid which is a dimer of unsaturated fatty acid such as oleic acid can be used. Examples of commercially available dimer diamines include Barsaman (Versamine) 551 (manufactured by BASF Japan), barsaman (Versamine) 552 (manufactured by Cognis Japan; hydrogenated product of Barsaman (Versamine) 551), polycosamine (PRIAMINE) 1075, and Polycosamine (PRIAMINE) 1074 (manufactured by Croda Japan).

In addition, as the diamine, there can be used a 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 products of diaminopolysiloxane include, for example, KF-8010, X-22-161A and X-22-161B (manufactured by shin-Etsu chemical Co., ltd.).

As the diamine, polyoxypropylene diamine can be used. Commercially available products of polyoxypropylene diamine include, for example: jeffamine (Jeffamine) D-230, jeffamine (Jeffamine) D-400, jeffamine (Jeffamine) D-2000, jeffamine (Jeffamine) D-4000 (all manufactured by Huntsman (HUNTSMAN)).

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

Examples of the combination of dimer diamine and diamine having an aromatic ring include a combination of Policosane (PRIAMINE) 1075 and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, and a combination of Policosane (PRIAMINE) 1075 and bis [4- (4-aminophenoxy) phenyl ] sulfone.

Examples of the combination of the diaminopolysiloxane and the diamine having an aromatic ring include a combination of KF-8010 and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, and a combination of KF-8010 and bis [4- (4-aminophenoxy) phenyl ] sulfone.

[ acid dianhydride ]

The acid dianhydride is not particularly limited, and examples thereof include:

pyromellitic dianhydride, 3', 4' -biphenyltetracarboxylic dianhydride, 3', 4' -benzophenonetetracarboxylic dianhydride, 3',4,4' -diphenylethertetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 3', aromatic tetracarboxylic dianhydrides such as 4,4' -diphenylsulfone tetracarboxylic dianhydride, 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride and 9,9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride;

alicyclic tetracarboxylic dianhydrides such as 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-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalenecarboxylic dianhydride, 2,3, 5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride, 3,5, 6-tricarboxy-2-norbornaneacetic acid dianhydride and the like;

aliphatic tetracarboxylic dianhydrides such as 1,2,3, 4-butanetetracarboxylic dianhydride and the like.

These acid dianhydrides may be used singly or in combination of two or more kinds. The acid dianhydride is preferably 3,3', 4' -diphenylsulfone tetracarboxylic dianhydride or 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and more preferably 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride.

The polyamic acid can be easily formed by mixing the diamine and the acid dianhydride at an arbitrary temperature of-20 to 150 ℃, preferably-5 to 100 ℃.

As a method for imidizing a polyamic acid by dehydrating and cyclizing it, a conventional thermal imidization method and a conventional chemical imidization method can be used. In the thermal imidization method, imidization can be easily performed by, for example, performing a heat treatment at a high temperature of 150 to 250 ℃ while dehydrating. In the chemical imidization method, imidization can be performed by, for example, adding 2 to 10 molar equivalents of a base such as pyridine or triethylamine and acetic anhydride to a diamine as a raw material, and performing a cyclization reaction at 0 to 50 ℃.

[ [ number average molecular weight of polyimide units (A) ]

The number average molecular weight of the polyimide unit (a) is preferably in the range of 20,000 to 200,000. When the content is 20,000 or more, the obtained cured product has excellent fracture strength, and when the content is 200,000 or less, the viscosity is easily adjusted, which is preferable.

[ chain transfer agent ]

By reacting the acid 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, and is preferably a chain transfer agent having a functional group reactive with an acid anhydride group and a mercapto group (mercapto group). When the chain transfer agent is used, the terminal acid anhydride group in the polyimide unit (a) and the functional group reactive with the acid anhydride group in the chain transfer agent react to form a prepolymer having a mercapto group at both terminals. The reaction of the polyimide unit (a) with the chain transfer agent is easily performed by mixing at an arbitrary temperature of 20 to 120 ℃. The chain transfer agent may be used alone or in combination of two or more.

Examples of the functional group reactive with an acid anhydride group include an amino group, a hydroxyl group and the like, and a hydrogen atom of the amino group may be substituted with an organic residue such as an alkyl group or an aryl group. Examples of the substituted amino group (also referred to as a substituted amino group) include monosubstituted amino groups such as an N-alkylamino group and an N-arylamino group. Examples of the hydroxyl group include a primary hydroxyl group, a secondary hydroxyl group, and a tertiary hydroxyl group.

The functional group reactive with an acid anhydride group is preferably an amino group in terms of good reactivity with an acid anhydride group. That is, the chain transfer agent residue is preferably a group derived from a chain transfer agent having an amino group. The use of a chain transfer agent having an amino group and a mercapto group is preferable because the mercapto group can be efficiently introduced into the terminal of the prepolymer.

Examples of such a chain transfer agent containing one amino group and one mercapto group in a molecule include: aminoalkane thiols such as 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol and 4-amino-1-butanethiol; and aminobenzenethiols such as 2-aminothiophenol, 3-aminothiophenol and 4-aminothiophenol. Among these, aminoalkane thiols are preferable, and 2-aminoethanethiol is more preferable.

[ Polymer units (B) of ethylenically unsaturated monomers ]

The polymer unit (B) of the ethylenically unsaturated monomer is a structure which contains a structural unit derived from the ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule and is obtained by polymerizing the ethylenically unsaturated monomer containing the ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule in the presence of a polymerization initiator.

Specifically, the block polymer (C) in which the polyimide unit (a) and the polymer unit (B) of the ethylenically unsaturated monomer are linked by the chain transfer agent residue can be obtained by polymerizing the prepolymer having the chain transfer agent residue at both ends obtained in the step 2 and the ethylenically unsaturated monomer containing the ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule in the presence of a polymerization initiator.

(ethylenically unsaturated monomer (b 1) having one or more crosslinking groups in the molecule)

Examples of the crosslinking group contained in the ethylenically unsaturated monomer (b 1) having one or more crosslinking groups in the molecule include: the hydroxyl group, carboxyl group, epoxy group, isocyanate group and block thereof may be used singly or in combination of two or more.

Examples of the ethylenically unsaturated monomer having a carboxyl group 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) acryloyloxypropylhexahydrophthalate, β -carboxyethyl (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, ω -carboxy polycaprolactone (meth) acrylate, p-vinylbenzoic acid.

Examples of the ethylenically unsaturated monomer having a hydroxyl group 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 adduct of these monomers (the number of addition moles is 1 to 5), polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, glycerol mono (meth) acrylate.

Examples of the ethylenically unsaturated monomer having an epoxy group include: <xnotran> () , () , () 4- , () 3,4- , () 3- -3,4- , () 3- -3,4- , () 4- -4,5- , () 5- -5,6- , α - , , , () , () (3,4- ) , N- (3,5- -4- ) , , , , α - - , α - - , α - - ,2,3- ,2,4- ,2,5- ,2,6- ,2,3,4- , </xnotran> 2,3, 5-triglycidyloxymethylstyrene, 2,3, 6-triglycidyloxymethylstyrene, 3,4, 5-triglycidyloxymethylstyrene and 2,4, 6-triglycidyloxymethylstyrene.

Examples of the ethylenically unsaturated monomer having an isocyanate group include: (meth) acryloyl isocyanate, 2-isocyanatoethyl (meth) acrylate, 2- (meth) acryloyloxyethoxyethyl isocyanate, 1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, m- (meth) acryloylphenyl isocyanate, α -dimethyl-4-isopropenylbenzyl isocyanate.

Among these, the ethylenically unsaturated monomer (b 1) having one or more crosslinking groups in the molecule is preferably an ethylenically unsaturated monomer having a carboxyl group. When an ethylenically unsaturated monomer having a carboxyl group is used, a cured product having more excellent heat resistance and flexibility can be obtained when reacting with a crosslinking agent (D) described later, and therefore, it is preferable.

The content of the ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the ethylenically unsaturated monomers constituting the polymer unit (B) of the ethylenically unsaturated monomer. A range of 5 to 50% by mass is preferable because heat resistance and flexibility are excellent.

(other ethylenically unsaturated monomer)

The ethylenically unsaturated monomer constituting the polymer unit (B) of the ethylenically unsaturated monomer may contain other ethylenically unsaturated monomer in addition to the ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule.

The other ethylenically unsaturated monomer is not particularly limited, and examples thereof include: linear or branched alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate; cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like; fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate; (meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate; (meth) acrylates having an aromatic ring such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, p-cumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate; (meth) acrylates having an alkyl ether group such as 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 polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, lauryloxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, n-butoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-butylacrylamide, diacetoneacrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, n-dimethylacrylamide, N-dibenzylacrylamide, formamide methacrylate, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, amide group-containing ethylenically unsaturated monomers such as N-bis (pentyloxymethyl) acrylamide, N-methoxymethyl-N- (pentyloxymethyl) methacrylamide and cinnamamide; vinyl groups such as styrene, α -methylstyrene and vinyl acetate; vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether.

These may be used alone or in combination of two or more.

The content of the polymer unit (B) of the ethylenically unsaturated monomer is preferably within a range of 10 to 50% by mass, more preferably within a range of 20 to 40% by mass, based on the total mass of the block polymer (C). A range of 10 to 50 mass% is preferable because heat resistance and flexibility are excellent.

(polymerization initiator)

As the polymerization initiator, conventional azo compounds and organic peroxides can be used. These may be used alone or in combination of two or more.

The azo compound is not particularly limited, and examples thereof include: 2,2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane 1-carbonitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile) dimethyl 1,1' -azobis (1-cyclohexanecarboxylate), dimethyl 2,2' -azobis (2-methylpropionate), 4' -azobis (4-cyanovaleric acid), 2' -azobis (2-hydroxymethylpropionitrile), or 2,2' -azobis [2- (2-imidazolin-2-yl) propane ].

The organic peroxide is not particularly limited, and examples thereof include: benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3, 5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide.

The amount of the polymerization initiator to be blended is preferably 0.001 to 15% by mass based on the total amount of the ethylenically unsaturated monomers. A range of 0.001 to 15% by mass is preferable because chain transfer polymerization effectively proceeds.

[ [ number average molecular weight of Polymer units (B) of ethylenically unsaturated monomer ] ]

The number average molecular weight of the polymer unit (B) of the ethylenically unsaturated monomer is preferably in the range of 2,000 to 200,000. When the content is 2,000 or more, the obtained cured product has excellent fracture strength, and when the content is 200,000 or less, the viscosity is easily adjusted, which is preferable.

((number average molecular weight of Block Polymer (C))

The number average molecular weight of the block polymer (C) is preferably in the range of 5,000 to 300,000. When the content is 5,000 or more, the obtained cured product has excellent fracture strength, and when the content is 300,000 or less, the viscosity is easily adjusted, which is preferable.

< haze value of resin film >

The haze value of the resin film is preferably less than 50, more preferably less than 30. If the content is less than 50, a cured product obtained by curing the resin film is excellent in adhesive strength, flexibility, and heat resistance.

[ solvent ]

Examples of the solvent that can be used in the production of the block polymer (C) include: acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, toluene, xylene, anisole, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, m-cresol, γ -butyrolactone, γ -valerolactone. These solvents may be used alone or in combination of two or more.

The solvent that can be used for the synthesis of the polyimide unit (a) is preferably a high boiling point solvent that does not react with a chain transfer agent having an amino group and a mercapto group. Examples of such solvents include: xylene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, m-cresol, gamma-butyrolactone and gamma-valerolactone.

(crosslinking agent (D))

The curable resin composition according to the embodiment of the present invention further contains a crosslinking agent (D). By reacting the crosslinking group derived from the ethylenically unsaturated monomer (b 1) contained in the block polymer (C) with the crosslinking agent (D) and curing the reaction product, a cured product excellent in heat resistance, flexibility and adhesion can be obtained. Therefore, the crosslinking agent (D) is preferably a crosslinking agent having two or more functional groups reactive with the crosslinking group derived from the ethylenically unsaturated monomer (b 1), and examples thereof include compounds having an epoxy group, an acid anhydride, a phenol group, an isocyanate group, a carboxyl group, an amino group, and a hydroxyl group.

The crosslinking agent (D) may be used alone or in combination of two or more.

Examples of the crosslinking agent having an epoxy group include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N ' -diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidylaminophenylmethane, triglycidyl isocyanurate.

As the crosslinking agent having an acid anhydride, in addition to the acid dianhydride constituting the polyimide unit (a), a conventional compound such as phthalic anhydride, trimellitic anhydride, or maleic anhydride can be used.

The crosslinking agent having a phenol group may be a monomer compound or a polymer compound. The crosslinking agent having a phenol group as the polymer compound may be a polymer (homopolymer) of a single monomer or a copolymer (copolymer) of a plurality of monomers. In addition, the crosslinking agent having a phenol group may be any of a random copolymer, a block copolymer, or a graft copolymer.

Examples of the crosslinking agent having a phenol group include: examples of the phenol-based resin include bisphenol a, bisphenol F, bisphenol S, resorcinol, catechol, hydroquinone, fluorene bisphenol, 4 '-biphenol, 4',4 ″ -trihydroxy triphenylmethane, naphthalenediol, 1, 2-tetrakis (4-hydroxyphenyl) ethane, calixarene, novolak-type phenol resins (for example, polyphenol novolak resins synthesized from formaldehyde and polyhydric hydroxyl compounds represented by phenol novolak resins, cresol novolak resins, bisphenol a novolak resins, bisphenol S novolak resins, and resorcinol novolak resins, naphthol-phenol copolycondensate resins, naphthol-cresol copolycondensate resins, naphthol novolak resins, and alkoxy-containing aromatic ring-modified novolak resins (polyhydric phenol compounds in which a phenol core and an alkoxy-containing aromatic ring are linked by formaldehyde)), aralkyl-type phenol resins (for example, phenol aralkyl resins and naphthol aralkyl resins such as a neophenol resin (xylok in), aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol adduct resin, trimethylolmethane resins, tetraphenol (phenol) ethane resins, biphenyl-modified phenol resins (bisphenol-linked with a polyphenol compound), and polyvalent phenol compounds such as a polyphenol amine-linked with a phenol core, and a polyphenol compound (cresol-linked with a polyphenol compound).

Specific examples of the novolak-type phenol resin include "phenolite (TD-2131)" and "phenolite (TD-2090" (trade name) "manufactured by Diegon (DIC) Co., ltd. Specific examples of the aralkyl type phenol resin include GPH-65 (trade name) manufactured by Nippon chemical Co., ltd.

Examples of the crosslinking agent having an isocyanate group include: compounds having two or more isocyanate groups in a molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate, and biuret, urate, adduct, and other condensate thereof.

Examples of the biuret compound include a biuret compound of hexamethylene diisocyanate (product name "Sumidur N-75", manufactured by Sumika Bayer Urethane (Sumika Bayer Urethane) Co., ltd.; product name "Polydande (Duranate) 24A-100", manufactured by Asahi Kasei Chemicals Co., ltd.).

Examples of the urea acid ester include a urea acid ester of hexamethylene diisocyanate (product name "Sumidur N-3300", manufactured by Sumika Bayer Urethane), a urea acid ester of isophorone diisocyanate (product name "Desmodur Z-4370", manufactured by Sumika Bayer Urethane), a urea acid ester of toluene diisocyanate (product name "Crosstate 2030", manufactured by Japan polyurethane).

Examples of the adduct include a hexamethylene diisocyanate adduct of trimethylolpropane (product name "Takeite (Takenate) D-160N", manufactured by Mitsui chemical Co., ltd.), an isophorone diisocyanate adduct of trimethylolpropane (product name "Takeite (Takenate) D-140N", manufactured by Mitsui chemical Co., ltd.), and an adduct of toluene diisocyanate (product name "Desmodur (Desmodur) L75", manufactured by Sumika covstrono Urethane Co., ltd.).

Examples of other condensation products include: polyfunctional compounds, carbodiimide-modified compounds, biuret-modified compounds and allophanate-modified compounds containing an isocyanate group include, for example: polymethylene polyphenyl polyisocyanate (product name "PAPI27", manufactured by DOW corporation), biuret product of hexamethylene diisocyanate (product name "Takenate D-165N", manufactured by mitsui chemical corporation), carbodiimide-modified diphenylmethane diisocyanate (product name "Isonate 143L", manufactured by DOW corporation).

Examples of the crosslinking agent having a carboxyl group include: succinic acid, adipic acid, sebacic acid, maleic acid, phthalic acid, naphthalenedicarboxylic acid, methylphthalic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, methylnorbornene dicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid.

Examples of the crosslinking agent having an amino group include: diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine, isophoronediamine, dicyclohexylmethane-4, 4' -diamine, and p-phenylenediamine; diamines having a hydroxyl group such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylpropylenediamine, and di-2-hydroxypropylethylenediamine; polyfunctional amines having three or more functional groups such as diethylenetriamine, iminodipropylamine, triethylenetetramine, N- (3-aminopropyl) butane-1, 4-diamine, 6-iminodihexylamine, 3, 7-diazananane-1, 9-diamine, N' -bis (3-aminopropyl) ethylenediamine, jeffamine (JEFFAMINE) D-230, D-400, D-2000, T-403 and T-3000 (the aforementioned compounds are produced by HunSMAN).

Examples of the crosslinking agent having a hydroxyl group include: ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butanediol, polytetramethylene glycol, methylpropanediol, pentanediol, methylpentanediol, hexanediol, nonanediol, neopentyl glycol, 2-butyl-2-ethyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, hydroxypivalic acid-neopentyl glycol ester, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolethane, trimethylolpropane, trimethylolbutane, glycerol, pentaerythritol.

Among them, the crosslinking agent (D) is preferably a compound having two or more functional groups selected from the group consisting of epoxy groups and acid anhydrides in the molecule, and more preferably a compound having two or more epoxy groups in the molecule. In particular, it is preferable that the ethylenically unsaturated monomer having one or more crosslinking groups in the molecule (b 1) comprises an ethylenically unsaturated monomer having one or more carboxyl groups, and the crosslinking agent (D) comprises a compound having two or more epoxy groups in the molecule, because a cured product having particularly excellent heat resistance and flexibility can be obtained.

The molar ratio of the functional group in the crosslinking agent (D) to the crosslinking group in the block polymer (C) (the number of moles of the functional group in the crosslinking agent (D)/the number of moles of the crosslinking group in the block polymer (C)) is preferably 0.2 to 5.0, more preferably 0.5 to 3.0. The content of 0.2 to 5.0 is preferable because it is excellent in heat resistance and flexibility. From the viewpoint of adhesion, the range of 0.2 to 20.0 is preferable, and the range of 0.5 to 16.0 is more preferable.

< other ingredients >

The curable resin composition may further contain conventional additives such as a silane coupling agent, a filler, a propellant, a plasticizer, a superplasticizer, a wetting agent, a flame retardant, a viscosity modifier, a preservative, a stabilizer, and a colorant. These additives may be used singly or in combination of two or more kinds.

Examples of the silane coupling agent include: trialkoxysilanes having an amino group such as trialkoxysilanes having a vinyl group, e.g., vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane; trialkoxysilanes having a glycidyl group such as 3-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane; trialkoxysilanes having an isocyanate group such as 3-isocyanatopropyltriethoxysilane; trialkoxysilanes having a mercapto group such as 3-mercapto (mercapto) propylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

The amount of the silane coupling agent to be blended is preferably 0.05 to 10% by mass based on the mass of the block polymer (C) in the curable resin composition.

[ cured product, laminate ]

The cured product according to the embodiment of the present invention is obtained by curing the curable resin composition or the resin film, and is effectively used in the fields of adhesives, adhesive sheets, coating agents, film substrates, elastomers, medical materials, optical materials, and the like. Among them, from the viewpoint of having high adhesive strength and flexibility and being excellent in heat resistance, it is preferably used as an adhesive sheet.

The method of forming the cured product is not particularly limited, and can be obtained, for example, by: after a curable resin composition adjusted to a viscosity suitable for a coating method using a solvent or the like is applied to a substrate, the substrate is heated to a temperature of, for example, 50 to 200 ℃ to remove the solvent, and then cured at a temperature of 20 to 200 ℃.

The laminate according to the embodiment of the present invention is a laminate including a layer containing the cured product on a substrate. The method for producing the laminate is not particularly limited, and can be produced, for example, by: after a curable resin composition is applied to a first substrate, a volatile component such as a solvent is dried in an oven to form an uncured resin layer, and a second substrate is stacked on the resin layer and, if necessary, heat-pressed to be bonded, and the resin layer is cured while being softened and adhered. The laminate may be produced, for example, by: an uncured resin layer obtained by drying a curable resin composition, which has been molded into a sheet in advance, is sandwiched between two substrates, and is cured while being softened and adhered to each other by thermocompression bonding or the like. The thickness of the cured layer is preferably 0.1 μm to 300mm.

The substrate is not particularly limited, and examples thereof include metals such as aluminum and copper, thermoplastic polymers such as polyethylene, polypropylene, polyurethane, polyester, polyacrylate, polycarbonate and copolymers thereof, thermosetting polymers such as epoxy resins, melamine resins and vulcanized rubbers, polyamides, polyimides, polyamideimides, polymethacrylimides, polyphenylene sulfides, polyarylates, liquid Crystal Polymers (LCP), heat-resistant polymers such as polysulfone and polyether sulfone, carbon fiber-reinforced plastics, glass fiber-reinforced plastics and other fiber-reinforced plastics, and glass and wood.

The shape of the substrate is not particularly limited, and a structure, a porous body such as a metal foil, a film, a sheet, a foam, a nonwoven fabric, or a composite thereof can be appropriately selected and used.

When the laminate includes two or more substrates, the substrates may be the same or different.

The laminate according to the embodiment of the present invention has excellent adhesion, flexibility, and heat resistance, and is effectively used as a structural member in the fields of power devices, automobiles, building materials, ships, airplanes, and the like.

The present invention is related to the subject matter of japanese patent application No. 2020-073976, filed on day 4/2020 and to the subject matter of japanese patent application No. 2020-212798, filed on day 22/2020, the entire disclosures of which are incorporated herein by reference.

Examples

The present invention will be described more specifically with reference to the following examples, which are not intended to limit the scope of the present invention. In the examples, "part" and "%" represent "part by mass" and "% by mass", respectively, unless otherwise specified.

[ solid content concentration ]

As the solid content concentration of the resin, the heating residue content was measured at a heating temperature of 150 ℃ for 20 minutes in accordance with Japanese Industrial Standards (JIS) K5601-1-2.

[ number average molecular weight (Mn), weight average molecular weight (Mw) ]

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin are calculated from polystyrene having a known molecular weight, as measured by Gel Permeation Chromatography (GPC). The measurement was carried out at a flow rate of 0.6ml/min, an injection amount of 10. Mu.l and a column temperature of 40 ℃ by using GPC-8020 (manufactured by Toso Co., ltd.) as a GPC apparatus, tetrahydrofuran as an eluent and three TSK gel Supo (gelSuper) HM-M (manufactured by Toso Co., ltd.) connected in series as a column.

[ acid value ]

The acid value was measured according to the following procedure. First, 1g of a resin solution was dissolved in 40mL of toluene, and 20mL of methanol and 1mL of ion-exchanged water were added to prepare a sample for measuring an acid value. Subsequently, an automatic titration apparatus "AT-510" manufactured by Kyoto electronics industries, to which "APB-510-20B" manufactured by the above company was connected as a burette was used, and a 0.02mol/L ethanolic potassium hydroxide solution was used as a titration reagent to perform potential difference titration, and the number of mg of KOH per 1g of solid resin was calculated from the solid content concentration of the resin.

The abbreviations in this specification are as follows.

BPADA:4,4'- (4,4' -isopropylidenediphenoxy) diphthalic anhydride DSDA:3,3',4,4' -Diphenylsulphonetetracarboxylic dianhydride

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

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

Policosanamine (praiamine) 1075: hydrogenated dimer diamine, product name "Polycosamine (PRIAMINE) 1075", manufactured by Croda Japan

KF-8010: diaminopolysiloxanes having the product name "KF-8010" manufactured by shin-Etsu chemical industries, ltd

DMF: n, N-dimethylformamide

AIBN:2,2' -azobisisobutyronitrile

MMA: methacrylic acid methyl ester

St: styrene (meth) acrylic acid ester

MAA: methacrylic acid

AA: acrylic acid

GMA-glycidyl methacrylate

HEMA: methacrylic acid 2-hydroxyethyl ester

Terard (TETRAD) -X: n, N, N ', N' -tetraglycidyl-m-xylylenediamine manufactured by Mitsubishi gas chemical corporation

Desmodur (Desmodur) L75: tolylene Diisocyanate (TDI) adduct, manufactured by Sumika Covestro Urethane

jER828: bisphenol A epoxy resin manufactured by Mitsubishi chemical corporation

< production of Block Polymer >

Production example 1 Block Polymer (C-1) solution

A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer was charged with 100 parts of BPADA, 17.4 parts of BAPP, 78.5 parts of Prilamine (PRIAMINE) 1075 (manufactured by Croda Japan) and 457 parts of DMF, and the mixture was replaced with nitrogen. The reaction vessel was heated to 150 ℃ with stirring, and the reaction was carried out until the acid value was less than 2mgKOH/g, thereby obtaining a polyimide unit.

Then, the mixture was cooled to 80 ℃ and 0.89 part of 2-aminoethanethiol was added thereto to carry out a reaction at 80 ℃ for 5 hours, thereby obtaining a polyimide prepolymer.

Then, to the polyimide prepolymer recovered to room temperature were added 75.9 parts of MMA, 8.4 parts of MAA, and 199 parts of DMF, and after uniformly stirring, the temperature was raised to 75 ℃ under a nitrogen atmosphere. 0.1 part of AIBN as a polymerization initiator was added thereto in 13 portions every 30 minutes, and after the addition of the polymerization initiator, the mixture was reacted for 2 hours to form a polymer unit of an ethylenically unsaturated monomer, and DMF was added so that the solid content concentration became 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.

Production example 2 to production example 42 Block Polymer (C-2) solution to Block Polymer (C-42) solution

The same operations as in production example 1 were carried out except that the formulation compositions shown in Table 1 or Table 2 were changed to obtain block polymer (C-2) solution to block polymer (C-42) solution.

Comparative production example 1 comparative resin (H-1) solution

A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer was charged with 100 parts of BPADA, 17.4 parts of BAPP, 78.5 parts of Prilamine (PRIAMINE) 1075 and 457 parts of DMF, and the mixture was replaced with nitrogen. The reaction vessel was heated to 150 ℃ with stirring, and the reaction was carried out until the acid value was less than 2 mgKOH/g. DMF was added so that the solid content concentration became 30%, thereby obtaining a solution of the comparative resin (H-1).

Comparative production example 2 comparative resin (H-2) solution

A comparative resin (H-2) solution was obtained in the same manner as in comparative production example 1, except that the formulation composition shown in Table 3 was changed.

Comparative production example 3 comparative resin (H-3) solution

To a reaction vessel including a gas inlet tube, a thermometer, a condenser, and a stirrer, 90 parts of MMA, 10 parts of MAA, and 233 parts of DMF were added and uniformly stirred, and then, the temperature was raised to 75 ℃ in a nitrogen atmosphere. 0.1 part of AIBN as a polymerization initiator was added thereto in 13 portions every 30 minutes, and the reaction was continued for 2 hours after the addition of the polymerization initiator. DMF was added so that the solid content concentration became 30%, thereby obtaining a solution of comparative resin (H-3).

Comparative production example 4 and comparative production example 5 comparative resin (H-4) solution to comparative resin (H-5) solution

A comparative resin (H-4) solution and a comparative resin (H-5) solution were obtained in the same manner as in comparative production example 3 except that the formulation compositions shown in Table 3 were changed.

Comparative production example 6 solution of comparative Block Polymer (H-6)

A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer was charged with 100 parts of BPADA, 17.4 parts of BAPP, 78.5 parts of Prilamine (PRIAMINE) 1075 and 457 parts of DMF, and the mixture was replaced with nitrogen. The reaction vessel was heated to 150 ℃ with stirring, and 1850cm of acid anhydride-derived crystals were confirmed by infrared absorption spectrometry ^-1 Disappearance of absorption and 1780cm from imide group ^-1 And the reaction is terminated. Next, it was cooled to 80 ℃ and 0.89 part of 2-aminoethanethiol was added thereto to conduct a reaction at 80 ℃ for 5 hours, thereby obtaining a polyimide prepolymer.

Then, 84.3 parts of MMA and 199 parts of DMF were added to the polyimide prepolymer returned to room temperature, and after uniformly stirring, the temperature was raised to 75 ℃ in a nitrogen atmosphere. 0.1 part of AIBN as a polymerization initiator was added thereto in 13 portions every 30 minutes, and reacted for 2 hours after the addition of the polymerization initiator to form polymer units of ethylenically unsaturated monomers, thereby obtaining a solution of a block polymer (H-6) for comparison.

Comparative production example 7 solution of block Polymer for comparison (H-7)

A block polymer (H-7) solution for comparison was obtained in the same manner as in comparative production example 6, except that the composition was changed to the blending composition shown in Table 3.

Details of the obtained block polymer and comparative resin are shown in tables 1 to 3.

[ Table 1]

< production of curable resin composition >

[ example 1]

A curable resin composition was obtained by adding 30 parts of block polymer (C-1) and 0.37 part of Terard (TETRAD) -X as a crosslinking agent (D) and mixing them at room temperature with stirring.

Examples 2 to 42, examples 85 to 94, and comparative examples 1 to 10

Curable resin compositions of examples 2 to 42, 85 to 94, and comparative examples 1 to 10 were obtained in the same manner as in example 1 except that the formulation compositions shown in tables 4 to 7 were changed.

[ evaluation of curable resin composition ]

The obtained curable resin composition was used, and the following evaluations were performed. The results are shown in tables 4 to 7.

[ breaking stress and elongation at Break ]

The curable resin composition was put into a silicone mold so that the cured thickness became 2mm, and after drying the solvent, the cured resin composition was cured under the following curing conditions according to the crosslinking agent. Then, the hardened film is punched out by the dumbbell-shaped die frame, thereby producing a dumbbell-shaped hardened film. The obtained cured film was stretched at a stretching speed of 50mm/min under conditions of a temperature of 23 ℃ and a relative humidity of 50%, and the stress at break (MPa) and elongation at break (%) were measured and evaluated according to the following criteria. The larger the numerical values of the breaking stress and the breaking elongation are, the more excellent the values are, the practical level is B or more.

Conditions for hardening

In the case where the crosslinking agent is terrad (tetra) -X: at 150 ℃ for 3 hours

In the case where the cross-linking agent is BPADA: standing at 100 deg.C for 10 min, and standing at 220 deg.C for 1 hr

In the case of a crosslinker of desmordu (Desmodur) L75: 3 hours at 100 DEG C

(evaluation criteria for breaking stress)

And SS: a breaking stress of 30MPa or more

S: a breaking stress of 25MPa or more and less than 30MPa

A: the breaking stress is more than 20MPa and less than 25MPa

B: the breaking stress is more than 15MPa and less than 20MPa

C: breaking stress less than 15MPa (unusable)

(evaluation criteria for elongation at Break)

And SS: elongation at break of 200% or more

S: the elongation at break is more than 150% and less than 200%

A: the elongation at break is more than 100 percent and less than 150 percent

B: the elongation at break is more than 50% and less than 100%

C: elongation at break less than 50% (unusable)

[ adhesive Strength ]

The curable resin composition was applied to a release film (PET-38 GS, lintec, inc.) using a squeegee so that the thickness after drying became 50 μm, and dried under reduced pressure at 100 ℃ to peel the release film, thereby obtaining an adhesive sheet. The adhesive sheet was cut into a size of 12.5mm × 25.0mm, and the cut adhesive sheet was sandwiched between two copper substrates (size: 2.0mm × 25mm × 100 mm), and was pressed for 1 hour under the following pressing temperature conditions using a press. The test piece after the bonding was stretched by a tensile tester at a temperature of 23 ℃ and a relative humidity of 50%, and the shear adhesion (MPa) was measured and determined according to the following criteria. The larger the value of the shear adhesion force, the more excellent it is, and the practical level is B or more.

Condition of pressing temperature

In the case where the crosslinking agent is Terard (TETRAD) -X: 160 deg.C

In the case where the cross-linking agent is BPADA: 230 deg.C

In the case of a crosslinker of desmordu (Desmodur) L75: 160 deg.C

(evaluation criteria for adhesion Strength)

And SS: the shear adhesion force is more than 12.5MPa

S: the shear adhesion is more than 10.0MPa and less than 12.5MPa

A: the shear adhesion is more than 7.5MPa and less than 10.0MPa

B: the shear adhesion is more than 5.0MPa and less than 7.5MPa

C: shear adhesion force less than 5.0MPa (unusable)

[ Heat resistance ]

A cured film having a thickness of about 50 μm was prepared in the same manner as in the preparation of the adhesion strength test sample. The cured film was cut into a 5 mm-wide strip and used as a test piece, and the test piece was left to stand in an oven at 150 ℃ for 1000 hours. Dynamic viscoelasticity was measured using DVA-200/L2 (IT measurement control Co., ltd.) on test pieces before and after the heat resistance test at 150 ℃ for 1000 hours. The change rate Z was calculated from the following equation using the value of the storage modulus of elasticity at 200 ℃ and evaluated according to the following criteria. The smaller the numerical value of the rate of change, the more excellent the rate of change, and the practical level is B or more.

Conditions for measuring dynamic viscoelasticity

Measurement mode: stretching mode

Frequency: 10Hz

Temperature range: -80 ℃ to the limit of determination

Temperature rising conditions are as follows: 10 ℃/min

Storage modulus of elasticity change

When the storage elastic modulus at 200 ℃ before the heat resistance test is represented by X (Pa) and the storage elastic modulus at 200 ℃ after the heat resistance test is represented by Y (Pa), the change rate Z of the storage elastic modulus is represented by the following formula.

When X is more than or equal to Y: z = X/Y

In the case of Y > X: z = Y/X

(evaluation criteria for Heat resistance)

S: rate of change Z less than 5

A: the rate of change Z is 5 or more and less than 10

B: the rate of change Z is 10 or more and less than 100

C: rate of change Z is 100 or more (unusable)

[ Table 4]

< production of resin film >

Examples 43 to 84 and comparative examples 11 to 20

The block polymer solutions, comparative resin solutions, and comparative resin mixture solutions used in examples 1 to 42 and comparative examples 1 to 10 shown in table 8 were applied to a release film (PET-38 GS, lindecco (linetec)) using a squeegee so that the thickness after drying became 50 μm, and after drying at 100 ℃, the release film was peeled to obtain a resin film.

< evaluation of resin film >

The resin film obtained was evaluated as follows, and the results are shown in table 8.

[ haze value ]

The obtained resin film was evaluated for haze value using a haze meter ("NDH-5000" manufactured by japan electrochrome corporation) according to the following criteria. The smaller the haze value, the more excellent the haze value, and the practical level is B or more.

(evaluation criterion of haze value)

A: haze value less than 30

B: a haze value of 30 or more and less than 50

C: haze value of 50 or more and less than 80 (unusable)

D: haze value of 80 or more (bad)

[ Table 8]

From the evaluation results in tables 4 to 7, the cured product of the curable resin composition of the embodiment of the present invention exhibits good stress at break, elongation at break, adhesive strength and heat resistance. In particular, when the ethylenically unsaturated monomer (B) is contained in the range of 20 to 40% by mass based on the total mass of the block polymer (C) and the ethylenically unsaturated monomer (B1) having one or more crosslinking groups in the molecule is contained in the range of 5 to 30% by mass based on the total mass of the ethylenically unsaturated monomers constituting the ethylenically unsaturated monomer polymer unit (B), the block polymer (C) is excellent in stress at break, elongation at break, adhesive strength and heat resistance.

In addition, 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 in which a polyimide unit and a polymer unit of an ethylenically unsaturated monomer are linked to each other through a chain transfer agent residue, and a crosslinking agent,

the polymer unit contains a structural unit derived from a first ethylenically unsaturated monomer having one or more crosslinking groups in the molecule.

2. The curable resin composition according to claim 1, wherein the first ethylenically unsaturated monomer comprises an ethylenically 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 in a molecule.

4. The curable resin composition according to any one of claims 1 to 3, wherein the chain transfer agent residue is a group derived from a chain transfer agent having an amino group.

5. The curable resin composition according to any one of claims 1 to 4, wherein the block polymer contains the polymer unit in an amount of 10 to 50% by mass based on the total mass of the block polymer.

6. The curable resin composition according to any one of claims 1 to 5, wherein the ethylenically unsaturated monomer constituting the polymer unit contains a first ethylenically unsaturated monomer in an amount of 5 to 50% by mass based on the total mass of the ethylenically unsaturated monomer.

7. The curable resin composition according to any one of claims 1 to 6, wherein the diamine constituting the polyimide unit is any one selected from the group consisting of a combination of dimer diamine and diamine having an aromatic ring, and a combination of diaminopolysiloxanes and diamine having an aromatic ring.

8. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 7.

9. A resin film comprising a polymer unit of a polyimide unit and an ethylenically unsaturated monomer, wherein,

the content of the polymer unit 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 less than 50.

10. A cured product obtained by curing the resin film according to claim 9.

11. A laminate having a layer comprising the cured product according to claim 8 or 10 on a substrate.