Polymers, adhesive resin cured products, and adhesive resin sheets

Abstract

The object of the present invention is to provide a resin composition containing a polymer having dynamic covalent bonding units within the molecule, high adhesive strength, flexibility, easy peeling by an external trigger utilizing dynamic covalent bonding, and viscosity that can be used by a simple method such as mixing two components in a solvent-free or high-solid state. [Solution] The polymer of the present invention is characterized by having a dynamic covalent bond, having two or more structures of formula (I) within the molecule, and having a skeleton derived from a compound having two or more amino groups in the structure, and / or a skeleton derived from a bifunctional or higher polyol, and having a weight-average molecular weight Mw of 500 or more.

Description

[Technical Field]

[0001] This invention relates to polymers, adhesive resin cured products, and adhesive resin sheets. [Background technology]

[0002] The demand for adhesives is growing as structural adhesives for joining structural members, often used as a substitute for or in combination with rivets, and as adhesives for improving noise reduction. There is a need for adhesives with higher bonding strength and greater durability, and development is currently underway to achieve even higher performance. On the other hand, in recent years, from the perspective of resource recycling and environmental issues, there has been a growing demand for the development of adhesives that can disassemble bonded structural members after their service life using external stimuli such as light, heat, and electricity, in order to reuse the bonded structural members. However, strong adhesion and easy dismantling after use are conflicting properties, making product development difficult, and there have been no publicly commercialized examples of high-strength structural adhesives. Recently, studies on peelable adhesives utilizing dynamic covalent bonding for these applications have begun to be reported in papers and other publications. However, these are still at the research stage, and products using adhesive compositions that have high adhesive strength, flexibility (elongation of 10% or more), are easily peeled off by an external trigger utilizing dynamic covalent bonding, and are solvent-free or high-solids are not yet available on the market. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2020 / 051506 [Non-patent literature]

[0004] [Non-Patent Document 1] Science, Damien Montarnal, Mathieu Capelot, Franois Tournilhac, Ludwik Leibler, 2011, Vol334, pages 965-968 [Non-Patent Document 2] Chem.Sci., Wim Denissen, Johan M. Winne, Filip E. Du Prez, 2016, Vol7, pages 30-38 [Overview of the project] [Problems that the invention aims to solve]

[0005] Thermoplastic adhesives, whose constituent resin is a thermoplastic resin, soften when heated, making it relatively easy to dismantle structural members by physically peeling them off the adherend. However, they often struggle to achieve sufficient adhesive strength and high durability as adhesives. Another challenge is that they often soften gradually rather than undergoing a rapid change in elastic modulus at a certain temperature. On the other hand, thermosetting adhesives, whose constituent resins are thermosetting resins, have sufficient adhesive strength and durability as adhesives, but in principle, it is difficult to break the molecular bonds, requiring a great deal of energy to break the bonds and potentially destroying structural members. Therefore, in many cases, dismantling structural members is impossible. For this reason, there is a need for an adhesive that can achieve both strong adhesion and ease of dismantling structural members. One possible way to achieve both is to introduce cleavable functional groups into the thermosetting resin. As such resins, for example, vitrimer is known (see, for example, Non-Patent Document 1), and those having vinyllogous urethane bonds as cleavable weak bonds (see, for example, Non-Patent Document 2) or imine bonds (see, for example, Patent Document 1) have been reported. However, this document does not describe the evaluation of adhesive properties, and therefore cannot be said to achieve both strong adhesion and easy disassembly. There is much room for improvement in developing an adhesive that can maintain adhesive performance while also achieving easy disassembly (the ability of the bonded objects to be easily disassembled).

[0006] From such a background, there is a problem of providing a resin composition containing a polymer that has a dynamic covalent bond unit in the molecule, has high adhesive strength, has flexibility (elongation rate of 10% or more), is easily peeled off by an external trigger using a dynamic covalent bond, and has a viscosity that can be used by a simple method such as solventless or mixing two liquids in a high solid state.

Means for Solving the Problems

[0007] That is, the present invention is as follows. [1] A polymer having a dynamic covalent bond, having two or more of the structures of (I) in the molecule, and having a skeleton derived from a compound having two or more amino groups in the structure and / or a skeleton derived from a polyol having two or more functional groups, and having a weight average molecular weight Mw of 500 or more.

Chemical formula

[10] An adhesive resin cured product of any of [7] to [9], wherein the elongation of the film made of the adhesive resin cured product in a tensile test at 23°C is 10% or more.

[11] An adhesive resin cured product of any of [7] to

[10] , wherein the tanδ peak temperature in dynamic viscoelasticity measurement is -20°C or higher.

[12] The storage modulus E' at 23°C in dynamic viscoelasticity measurements is 1.0 × 10⁻⁶. 6 An adhesive resin cured product of any of [7] to

[11] , having a Pa of or greater.

[13] An adhesive resin cured product of any of [7] to

[12] wherein the maximum stress of the film made of the adhesive resin cured product in a tensile test at 23°C is 1 MPa or more.

[14] A cured adhesive resin product of any of the following [7] to

[13] , having a bonding exchange temperature Tv of 50°C or higher.

[15] A cured adhesive resin product of any of the following [7] to

[14] , having a shear adhesive strength of 1 MPa or more.

[16] A cured adhesive resin product of any of the following types [7] to

[15] , having a gel fraction of 40% or more and 100% or less.

[17] An adhesive resin sheet containing any of the cured adhesive resin products [7] to

[16] .

[18] An adhesive resin sheet of

[17] having a thickness of 1 μm or more and 3000 μm or less.

[19] An adhesive resin cured product according to any one of [7] to

[16] , wherein the shear adhesive strength measured using a metal as the adherend is 1 MPa or more.

[20] An adhesive resin cured product according to any of [7] to

[16] or

[19] , wherein the shear adhesive strength measured using plastic as the adherend is 1 MPa or more. [twenty one] An adhesive resin cured product according to any of [7] to

[16] ,

[19] , or

[20] , wherein the shear adhesive strength when dismantled by an external stimulus is 10% or less of the shear adhesive strength at 23°C and 50RH before the application of the external stimulus. [twenty two] A polymer solution containing the polymer and solvent described in any of [1] to [6]. [Effects of the Invention]

[0008] The polymer of the present invention has high adhesive strength, is flexible, has Tv, is easily peelable, and is solvent-free or high-solid. [Modes for carrying out the invention]

[0009] The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following description and can be implemented in various modifications within the scope of its essence.

[0010] [polymer] The polymer of this embodiment has dynamic covalent bonds, possesses two or more of the structure of (I) within the molecule, and has a skeleton derived from a compound having two or more amino groups in its structure, and / or a skeleton derived from a bifunctional or more polyol, and has a weight-average molecular weight Mw of 500 or more. [ka] (In formula (I), R1 is a C1-C20 hydrocarbon group which may contain a heteroatom, R2 is H or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, R3 is a hydrocarbon group which may contain a heteroatom, and X is N, O, or S.) In this specification, a "skeleton derived from a compound having two or more amino groups in its structure" may be referred to as an "amino skeleton." Similarly, a "skeleton derived from a polyol with two or more functions" may be referred to as a "polyol skeleton." Furthermore, the functional group represented by the following formula included in formula (I) may be referred to as "functional group Y." [ka] (In the formula, R1 is a hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom. R1 in the formula may be the same as R1 in formula (I) above.)

[0011] (dynamic covalent bond) The above-mentioned dynamic covalent bond can be at least one selected from the group consisting of vinylogous urethane type, imine type, cyclic acetal type, urethane type, carbonate type, diketoenamine type, silyl ether type, and disulfide type, with vinylogous urethane type being preferred.

[0012] Examples of the vinylogas urethane type mentioned above include a structure having a bond formed by dehydration condensation between an acetoacetate ester compound having one or more (preferably two or more) acetoacetate ester groups in the molecule and an amine compound having two or more amino groups (preferably primary amino groups) in the molecule.

[0013] The above vinylogas urethane type (which may be referred to as "vinylogas urethane bond" in this specification) may have a structure represented by the following formula (1). [ka] In equation (1), the zigzag lines represent bonds and indicate bonding with any chemical structure.

[0014] The number of dynamic covalent bonds in the polymer may be one or more, or multiple, but it is preferable that there be two. In particular, it is preferable that the dynamic covalent bond includes at least one type of vinylogousurethane bond. The number of vinylogousurethane bonds may be one or more, or multiple, but it is preferable that there are two.

[0015] The acetoacetate ester compound used when forming the vinylogous urethane bond may be an acetoacetate ester compound having one acetoacetate group in its molecule, an acetoacetate ester compound having two acetoacetate groups in its molecule (bisacetoacetate ester compound), or an acetoacetate ester compound having three or more acetoacetate groups in its molecule. Among these, an acetoacetate ester compound having two acetoacetate groups in its molecule (bisacetoacetate ester compound) is preferred. The above-mentioned acetoacetate ester compounds may be used individually or in combination of two or more.

[0016] Acetoacetate ester compounds having one acetoacetate ester group in the molecule are not particularly limited, but examples include esters of alcohols such as monoalcohols, diols, and triols with one acetylacetic acid. From the viewpoint of the viscosity of the resulting oligomer or polymer and the adhesive strength as an adhesive, among these, esters of a polyhydric alcohol such as ethylene glycol-modified monoacetoacetate, propylene glycol-modified monoacetoacetate, butylene glycol-modified monoacetoacetate, pentamethylene glycol-modified monoacetoacetate, hexamethylene glycol-modified monoacetoacetate, polyethylene glycol-modified monoacetoacetate, and polypropylene glycol-modified monoacetoacetate with one acetylacetic acid are particularly preferred.

[0017] Examples of bisacetoacetate ester compounds include esters of polyols such as diols and triols with two acetylacetic acids. Examples of bisacetoacetate compounds are not particularly limited, but include ethylene glycol-1,2-bisacetoacetate, propanediol-1,3-bisacetoacetate, propanediol-1,2-bisacetoacetate, butanediol-1,4-bisacetoacetate, pentanediol-1,5-bisacetoacetate, hexanediol-1,6-bisacetoacetate, heptanediol-1,7-bisacetoacetate, octanediol-1,8-bisacetoacetate, decanediol-1,10-bisacetoacetate and other alkanediol bisacetoacetates, diethylene glycol bisacetoacetate, triethylene glycol bisacetoacetate, polyethylene glycol bisacetoacetate, polypropylene glycol bisacetoacetate and other oxyalkylenediol bisacetoacetate, and 1,4-cyclohexanedimethanol bisacetoacetate. From the viewpoint of the strength of the resulting oligomer or polymer and the adhesive strength as an adhesive, among these, ethylene glycol-1,2-bisacetoacetate, butanediol-1,4-bisacetoacetate, polyethylene glycol bisacetoacetate, polypropylene glycol bisacetoacetate, and 1,4-cyclohexanedimethanol bisacetoacetate are particularly preferred, and ethylene glycol-1,2-bisacetoacetate and butanediol-1,4-bisacetoacetate are more preferred. The above-mentioned bisacetoacetate compounds may be used individually or in combination of two or more.

[0018] Examples of monomers having three or more acetoacetic acid ester groups include esters of polyols such as triols with three or more acetylacetic acids. Examples of acetoacetic acid ester compounds having three or more acetoacetic acid ester groups in the molecule include esters of polyols such as triols with three or more acetoacetic acid groups. Acetoacetate ester compounds having three or more acetoacetate groups in their molecule are not particularly limited, but examples include polyacetoacetates such as trisacetoacetate and tetrakisacetoacetate. Examples of trisacetoacetate esters are not particularly limited, but include trimethylolpropane trisacetoacetate, trisacetoacetate-1,2,3-propanetriol, trisacetoacetate-1,2,4-butanetriol, and trisacetoacetate-1,2,6-hexanetriol. Other polyacetoacetates are not particularly limited, but include pentaerythritol tetrakisacetoacetate and those that can be obtained by the method described in Japanese Patent Publication No. 2017-533088. From the viewpoint of the strength of the resulting oligomer or polymer and the adhesive strength as an adhesive, trimethylolpropane trisacetoacetate and trisacetoacetate-1,2,3-propanetriol are particularly preferred among these.

[0019] When the acetoacetate compound contains a monoacetoacetate compound, the monomer units derived from the monoacetoacetate compound are preferably greater than 0 parts by mass and 25 parts by mass or less, more preferably greater than 0 parts by mass and 20 parts by mass or less, even more preferably greater than 0 parts by mass and 15 parts by mass or less, and most preferably greater than 0 parts by mass and 10 parts by mass or less, based on 100 parts by mass of the total polymer. When the content of monomer units derived from the monoacetoacetate compound is within the above range, the three-dimensional crosslinks formed by the condensation reaction between the acetoacetate group of monomer units derived from a polyfunctional acetoacetate compound having two or more acetoacetate groups and the primary amino group of the amine compound are appropriately controlled, and high adhesive strength, good viscosity, and film strength tend to be obtained. When the acetoacetate compound contains a bisacetoacetate compound, the content is preferably 20 to 100 parts by mass, more preferably 30 to 100 parts by mass, more preferably 40 to 100 parts by mass, even more preferably 80 to 100 parts by mass, even more preferably 85 to 100 parts by mass, and even more preferably 90 to 100 parts by mass. When the content of monomer units derived from the bisacetoacetate compound is within the above range, the three-dimensional crosslinks formed by the condensation reaction between the acetoacetate group of the bisacetoacetate compound and the primary or secondary amino group of the amine compound are appropriately controlled, and high mechanical properties and strong adhesive strength tend to be obtained. When the acetoacetate ester compound contains an acetoacetate ester compound having three or more acetoacetate groups in its molecule, the monomer units derived from the acetoacetate ester compound having three or more acetoacetate groups in its molecule are preferably greater than 0 parts by mass and 60 parts by mass or less, more preferably greater than 0 parts by mass and 50 parts by mass or less, more preferably greater than 0 parts by mass and 40 parts by mass or less, more preferably greater than 0 parts by mass and 30 parts by mass or less, and more preferably greater than 0 parts by mass and 20 parts by mass or less, based on 100 parts by mass of the total amount of the oligomer or polymer. When the content of monomer units derived from the acetoacetate ester compound having three or more acetoacetate groups in its molecule is within the above range, the three-dimensional crosslinks formed by the condensation reaction between the acetoacetate group of the acetoacetate ester compound having three or more acetoacetate groups in its molecule and the primary or secondary amino group of the amine compound are appropriately adjusted, and high mechanical properties and good adhesive strength tend to be obtained.

[0020] The amine compound used when forming the vinylogous urethane bond contains two or more amino groups (preferably -NH) within the molecule. 2 It may be a compound having a group. The above amine compound may be a diamine, triamine, or polyamine, and may be an aromatic amine, an aliphatic amine, or a compound having both an aliphatic amino group and an aromatic amino group. The above amine compounds may be used individually or in combination of two or more.

[0021] Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene Benzene, 1,4-bis(4-aminophenoxy)benzene, 3,5-bis(4-aminophenoxy)benzoic acid, 4,4'-bis(4-aminophenoxy)bibenzyl, 2,2-bis[(4-aminophenoxy)methyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 1,1-bis(4-aminophenyl)cyclohex Sun, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-Bis(4-aminophenyl)tetramethyldisiloxane, benzidine, 2,2'-dimethylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)nonane, 1,1 0-Bis(4-aminophenyl)decane, 1,3-Bis(4-aminophenoxy)propane, 1,4-Bis(4-aminophenoxy)butane, 1,5-Bis(4-aminophenoxy)pentane, 1,6-Bis(4-aminophenoxy)hexane, 1,7-Bis(4-aminophenoxy)heptane, 1,8-Bis(4-aminophenoxy)octane, 1,9-Bis(4-aminophenoxy)nonane, 1,10-Bis(4-aminophenoxy)decane, Di(4-aminophenyl)propane-1,3-GioA To, di(4-aminophenyl)butane-1,4-dioate, di(4-aminophenyl)pentane-1,5-dioate, di(4-aminophenyl)hexane-1,6-dioate, di(4-aminophenyl)heptane-1,7-dioate, di(4-aminophenyl)octane-1,8-dioate, di(4-aminophenyl)nonane-1,9-dioate, di(4-aminophenyl)decane-1,10-dioate, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4- Examples include bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy)phenoxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]nonane, and 1,10-bis[4-(4-aminophenoxy)phenoxy]decane.

[0022] Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4- Examples include minobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, and 3-(6-aminonaphthyl)ethylamine.

[0023] Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, and 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole.

[0024] Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diaminododecane, 1,18-diaminooctadecane, and 1,2-bis(3-aminopropoxy)ethane.

[0025] Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophorone diamines.

[0026] From the viewpoint of improving reactivity, among these aliphatic diamines, those in which the amino group is located at the end of the molecular chain are preferred.

[0027] From the viewpoint of high adhesive strength, good handling viscosity, and flexibility, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane are preferred among these. Furthermore, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and 1,8-diaminooctane are preferred, with 1,5-diaminopentane and 1,6-diaminohexane being the most preferred.

[0028] Specific examples of aromatic triamines include 1,3,5-triaminobenzene, tris(3-aminophenyl)amine, tris(4-aminophenyl)amine, tris(3-aminophenyl)benzene, tris(4-aminophenyl)benzene, 1,3,5-tris(3-aminophenoxy)benzene, 1,3,5-tris(4-aminophenoxy)benzene [TAPOB], 1,3,5-tris(aminophenyl)benzene [TAPB], or 1,3,5-tris(4-aminophenoxy)triazine.

[0029] Furthermore, it is also possible to use aromatic triamines having a predetermined asymmetric structure represented by the following general formula (1). [ka] (In the formula, -Z- is -O-, -CO-, -S-, -SO2-, -CH2-, -C(CH3)2-, -C(CF3)2-, or a single bond. Ra and Rb are independently a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group. m is an integer from 0 to 3, and n is an integer from 0 to 4.)

[0030] Specific examples of aromatic triamines having a predetermined asymmetric structure represented by the above general formula (1) include 2,3',4-triaminobiphenyl, 2,4,4'-triaminobiphenyl, 3,3',4-triaminobiphenyl, 3,3',5-triaminobiphenyl, 3,4,4'-triaminobiphenyl, 3,4',5-triaminobiphenyl, 2,3',4-triaminodiphenyl ether, 2,4,4'-triaminodiphenyl ether, 3,3',4-triaminodiphenyl ether, 3,3',5-triaminodiphenyl ether, and 3,4,4'-triaminodiphenyl ether. Triaminodiphenyl ether, 3,4',5-triaminodiphenyl ether, 2,3',4-triaminobenzophenone, 2,4,4'-triaminobenzophenone, 3,3',4-triaminobenzophenone, 3,3',5-triaminobenzophenone, 3,4,4'-triaminobenzophenone, 3,4',5-triaminobenzophenone, 2,3',4-triaminodiphenyl sulfide, 2,4,4'-triaminodiphenyl sulfide, 3,3',4-triaminodiphenyl sulfide, 3,3',5-triaminodiphenyl sulfide 3,4,4'-triaminodiphenyl sulfide, 3,4',5-triaminodiphenyl sulfide, 2,3',4-triaminodiphenyl sulfone, 2,4,4'-triaminodiphenyl sulfone, 3,3',4-triaminodiphenyl sulfone, 3,3',5-triaminodiphenyl sulfone, 3,4,4'-triaminodiphenyl sulfone, 3,4',5-triaminodiphenyl sulfone, 2,3',4-triaminodiphenylmethane, 2,4,4'-triaminodiphenylmethane, 3,3',4-triaminodiphenyl Tan, 3,3',5-triaminodiphenylmethane, 3,4,4'-triaminodiphenylmethane, 3,4',5-triaminodiphenylmethane, 2-(2,4-diaminophenyl)-2-(3-aminophenyl)propane, 2-(2,4-diaminophenyl)-2-(4-aminophenyl)propane, 2-(3,4-diaminophenyl)-2-(3-aminophenyl)propane, 2-(3,5-diaminophenyl)-2-(3-aminophenyl)propane, 2-(3,Examples include 5-diaminophenyl)-2-(4-aminophenyl)propane, 2-(2,4-diaminophenyl)-2-(3-aminophenyl)hexafluoropropane, 2-(2,4-diaminophenyl)-2-(4-aminophenyl)hexafluoropropane, 2-(3,4-diaminophenyl)-2-(3-aminophenyl)hexafluoropropane, 2-(3,5-diaminophenyl)-2-(3-aminophenyl)hexafluoropropane, 2-(3,4-diaminophenyl)-2-(4-aminophenyl)hexafluoropropane, and 2-(3,5-diaminophenyl)-2-(4-aminophenyl)hexafluoropropane.

[0031] Among the aromatic triamines mentioned above, those having two or more primary amines are preferred. More preferably, those having three or more primary amines are preferred.

[0032] Aliphatic triamines are not particularly limited, but examples include 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane, tris(2-aminoethyl)amine, and 4-aminomethyl-1,8-octanediamine.

[0033] Specific examples of amine compounds having both aliphatic and aromatic amino groups include 5-(2-aminoethyl)benzene-1,3-diamine and 2-((4-aminophenoxy)methyl)propane-1,3-diamine.

[0034] As amine compounds having three or more primary amino groups in the molecule, commercially available products can also be used. Examples include JEFFAMINE T-403, JEFFAMINE T-3000, and JEFFAMINE T-5000 from Huntsman, as well as Polyment NK-350 from Nippon Shokubai Co., Ltd. and Hexatran 110 from Ascend. Furthermore, amine compounds having three or more primary amino groups in their molecule include amino group-modified polysiloxanes. For example, X-22-3939A manufactured by Shin-Etsu Silicone Co., Ltd. is one such example.

[0035] Amine compounds having two or more primary amino groups in their molecule may also contain a secondary amino group.

[0036] From the viewpoint of high mechanical properties and thermal stability, among these, amines having three primary amino groups in the molecule (trifunctional) are particularly preferred, and it is even more preferable that they do not contain heteroatoms other than the three amino groups. The amine compounds having three or more primary amino groups in the molecule may be used individually or in combination of two or more types.

[0037] The amine compounds used when forming the vinylogous urethane bond described above are preferably 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane. More preferably, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and 1,8-diaminooctane are used, and examples include 1,5-diaminopentane and 1,6-diaminohexane.

[0038] In the reaction in which the vinylogous urethane bond is formed, the diamine compound (amine or amino ion (-NH3) formed by the isocyanate compound and moisture in the air or water in the system) is used to form 100 mol% of the functional group represented by the following formula in the acetoacetic acid ester compound. + The molar proportion of the amino group (which may also be used) is preferably 30 to 95 mol%, more preferably 40 to 90 mol%, even more preferably 40 to 85 mol%, and particularly preferably 40 to 80 mol%. [ka] The above reaction produces a polymer having a skeleton derived from a compound that possesses dynamic covalent bonds, has two or more of structure (I) within the molecule, and has two or more amino groups within the structure. Furthermore, this polymer is primarily composed of uncrosslinked polymers and is a polymer that is liquid at room temperature, or can be melted by heating even if it is solid.

[0039] When adding an amine having two or more primary or secondary amino groups to the above polymer to form an adhesive resin cured product having a three-dimensional crosslinked network, the amount of amine added is preferably such that the molar ratio of amino groups in the amine is 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, even more preferably 15 mol% to 60 mol%, and particularly preferably 20 mol% to 60 mol%, relative to 100 mol% of the functional groups represented by the following formula in the acetoacetate ester used as the raw material for the polymer. It is more preferable that the molar ratio of amino groups in the amine added to the polymer during the preparation of the adhesive resin cured product to the functional group represented by the following formula in the structure represented by formula (I) in the polymer is 1 or less. This allows for appropriate control of three-dimensional crosslinking, which tends to result in high adhesive strength and good decomposition properties.

[0040] (Structure of (I)) The polymer of this embodiment has at least two structures represented by the above formula (I). Preferably, the polymer of this embodiment has two structures represented by the above formula (I). In the above formula (I), R1 is preferably an alkyl group having 1 to 20 carbon atoms, which may contain a heteroatom; more preferably an alkyl group having 1 to 10 carbon atoms, which may contain a heteroatom; and even more preferably an alkyl group having 1 to 5 carbon atoms, which may contain a heteroatom. Furthermore, R1 does not have to contain a heteroatom; it may be an alkyl group having 1 to 20 carbon atoms that does not contain a heteroatom; it may be an alkyl group having 1 to 10 carbon atoms that does not contain a heteroatom; or it may be an alkyl group having 1 to 5 carbon atoms that does not contain a heteroatom. In the above formula (I), R2 is preferably an alkyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom or a heteroatom; more preferably an alkyl group having 1 to 18 carbon atoms, which may contain a heteroatom; even more preferably an alkyl group having 1 to 15 carbon atoms, which may contain a hydrogen atom or a heteroatom; and even more preferably a hydrogen atom. In the above formula (I), R3 is preferably an alkylene group having 1 to 20 carbon atoms, which may contain a heteroatom, and more preferably an alkylene group having 1 to 18 carbon atoms, which may contain a heteroatom. Furthermore, R3 does not have to contain a heteroatom, and may be an alkylene group having 1 to 20 carbon atoms that does not contain a heteroatom, an alkylene group having 1 to 15 carbon atoms that does not contain a heteroatom, or an alkylene group having 1 to 12 carbon atoms that does not contain a heteroatom. In the above formula (I), X is preferably O. The two or more structures represented by formula (I) in the polymer of this embodiment may be the same or may be different from each other.

[0041] (Amino skeleton and / or polyol skeleton) The polymer of this embodiment has an amino skeleton and / or a polyol skeleton. The polymer of this embodiment may have only one of the amino skeleton and / or the polyol skeleton, or it may have both the amino skeleton and the polyol skeleton. The total number of amino and polyol skeletons contained in the polymer of this embodiment may be one or more. In particular, it is preferable that the number of structures represented by formula (I) be the same. In this embodiment, it is preferable that the polymer has only a polyol skeleton among the amino skeleton and the polyol skeleton.

[0042] The compound having two or more amino groups in the above amino skeleton preferably contains a hydrocarbon group having 1 to 18 carbon atoms (preferably an alkyl group), preferably a hydrocarbon group having 2 to 16 carbon atoms (preferably an alkyl group), preferably a hydrocarbon group having 4 to 12 carbon atoms (preferably an alkyl group), preferably a hydrocarbon group having 4 to 8 carbon atoms (preferably an alkyl group), and preferably a hydrocarbon group having 5 to 7 carbon atoms (preferably an alkyl group). As compounds having two or more amino groups, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane are preferred. Furthermore, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and 1,8-diaminooctane are preferred, with 1,5-diaminopentane and 1,6-diaminohexane being the most preferred.

[0043] The polyols with two or more functions in the polyol skeleton described above are preferably polyols selected from the group consisting of polyester polyols, polyether polyols with 4 or more carbon atoms in the repeating units, polycarbonate polyols, polyolefin polyols, polyamide polyols, polyamide polyester polyols, silicone polyols, acrylic polyols, and polyurethane polyols. Polyolefin polyols such as ethylene glycol, propylene glycol, butylene glycol, pentamethylene glycol, and hexamethylene glycol are preferred, and ethylene glycol, propylene glycol, and butylene glycol are more preferred.

[0044] The above-mentioned polyester polyol is preferably a polycaprolactone polyol. The above-mentioned bifunctional or more polyols are preferably polycaprolactone polyols and / or polycarbonate polyols.

[0045] The number-average molecular weight (Mn) of the above-mentioned bifunctional or more functional polyols is preferably 200 or more, more preferably 220 to 12000, and even more preferably 230 to 10000, from the viewpoint of viscosity, adhesive strength, and ease of disassembly. The above number-average molecular weight Mn can be measured by GPC measurement. (Measurement conditions) Equipment: HLC-802A, manufactured by Tosoh Corporation Column: Tosoh Corporation, G1000HXL x 1 G2000HXL x 1 G3000HXL x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

[0046] In this embodiment, it is preferable that the polymer has a structure represented by formula (I) and the amino backbone and / or polyol backbone in close proximity. Preferably, it has the following structure. [ka] The NH portion of the vinylogas urethane bond is preferably derived from a compound having two or more amino groups in its structure. Note that R1 and R2 do not necessarily have the same structure in each respective part.

[0047] In this embodiment, X in formula (I) is preferably O, and in that case, R3 is preferably the structure of the portion derived from the polyol excluding the hydroxyl group. When the above polyol skeleton is present, it is preferable that X in formula (I) is O and R3 is a structure derived from an alcohol used in the synthesis of acetoacetate ester compounds. In particular, from the viewpoint of even better adhesive strength, flexibility, and ease of disassembly, it is preferable that X in formula (I) is O, R1 is a methyl group, R2 is H, and R3 is an ethylene group, a propylene group, or a butylene group. It is more preferable that R3 is an ethylene group or a butylene group, and even more preferable that it is a butylene group. R2 may also be replaced by other structures by reaction.

[0048] (Weight average molecular weight) The weight-average molecular weight Mw of the polymer in this embodiment is 500 or more, preferably 550 to 500,000, more preferably 600 to 400,000, even more preferably 650 to 300,000, even more preferably 700 to 200,000, even more preferably 750 to 100,000, even more preferably 800 to 9,000, even more preferably 850 to 8,000, and particularly preferably 880 to 7,000. The above weight-average molecular weight can be measured by GPC measurement.

[0049] (Method of manufacturing polymers) Examples of methods for producing the polymer in this embodiment include a method in which a compound having one or more acetoacetate groups is reacted with an alcohol to obtain an acetoacetate compound, and then the modified acetoacetate is dehydrated and condensed with an amine compound having two or more amino groups (preferably primary amino groups) in its molecule.

[0050] [Adhesive resin cured product] The adhesive resin cured product of this embodiment is a cured product obtained by curing the polymer of this embodiment described above with a compound having a bifunctional or higher primary or secondary amino group and / or polyisocyanate.

[0051] Examples of compounds having two or more primary or secondary amino groups include 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane, tris(2-aminoethyl)amine, and 4-aminomethyl-1,8-octanediamine. Of these, 4-aminomethyl-1,8-octanediamine is preferred from the viewpoint of stability, and Hexatran 110 (Ascend Co., Ltd.) is preferred.

[0052] The ratio of "the number of moles of the functional group Y in the polymer before condensation reaction with any amine in the structure of (I) above" to "the total number of moles of the amino groups of the amine having two or more primary or secondary amino groups and the total number of moles of the amino groups and / or polyisocyanates in the compound having two or more primary or secondary amino groups and / or polyisocyanates" is preferably 1 or less, more preferably 0.75 to 1.00, and even more preferably 0.77 to 0.99.

[0053] When curing as described above, the molar ratio of the amine having two or more primary or secondary amino groups (referred to as the curing agent) relative to 100 mol% of the polymer is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, more preferably 15 mol% to 60 mol%, and most preferably 20 mol% to 60 mol%.

[0054] (characteristic) The properties of the adhesive resin cured product of this embodiment will now be described.

[0055] The elongation of the film made of the above-mentioned adhesive resin cured product in a tensile test at 23°C is preferably 10% or more, more preferably 20% to 1000%, even more preferably 30% to 900%, even more preferably 40% to 800%, even more preferably 45% to 700%, even more preferably 50% to 600%, even more preferably 55% to 500%, even more preferably 60% to 400%, even more preferably 65% ​​to 300%, and even more preferably 70% to 300%. The above elongation rate can be measured by the method described in the examples below.

[0056] The tanδ peak temperature in the dynamic viscoelasticity measurement of the above-mentioned cured adhesive resin is preferably -20°C or higher, more preferably -15°C or higher and 130°C or lower, and even more preferably -10°C or higher and 120°C or lower. The tanδ peak temperature can be adjusted by the molecular weight of the polymer, the ratio of diamine to trifunctional amine, etc. The above-mentioned tanδ peak temperature can be measured by the method described in the examples below.

[0057] The storage elastic modulus E’ at 23°C in the dynamic viscoelasticity measurement of the above-mentioned cured adhesive resin is preferably 1.0×10 6 Pa or more, more preferably 1.0×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 1.0×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 1.2×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 1.4×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 1.6×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 1.8×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 2.0×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 2.2×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 2.5×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 3.0×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 3.5×10 6 Pa or more and 1.0×10 10 Pa or less, more preferably 3.8×10 6 Pa or more and 9.0×10 9 Pa or less, more preferably 4.0×10 6 Pa or more and 9.0×109 Pa or less, more preferably 5.0 × 10 6 Pa or more 8.0×10 9 Pa or less, more preferably 7.0 × 10 6 Pa or more 7.0×10 9 Pa or less, more preferably 9.0 × 10 6 Pa or more 6.0×10 9 Pa or less, more preferably 1.0 × 10 7 Pa or more 5.0×10 9 Pa or less, more preferably 1.2 × 10 7 Pa or more 3.0×10 9 Pa or less, more preferably 1.3 × 10 7 Pa or more 2.0×10 9 Pa or less, more preferably 1.4 × 10 7 Pa or more 1.0×10 9 Pa or less, more preferably 1.6 × 10 7 Pa or more 9.0×10 8 It is less than or equal to Pa. The storage modulus E' can be adjusted by the gel fraction, the molecular weight of the polymer, the ratio of diamine to trifunctional amine, etc. The above storage modulus E' can be measured by the method described in the examples below.

[0058] The maximum stress of the film made of the above-mentioned adhesive resin cured product in a tensile test at 23°C is preferably 1 MPa or more, preferably 2 MPa or more, more preferably 2.2 MPa or more and 100 MPa or less, and even more preferably 2.5 MPa or more and 100 MPa or less. The fracture strength described above can be measured by the method described in the examples below.

[0059] The bonding exchange temperature Tv of the above-mentioned adhesive resin cured product is preferably 50°C or higher, more preferably 55°C to 150°C, even more preferably 60°C to 140°C, and even more preferably 65°C to 130°C from the viewpoint of easy disassembly. The above Tv can be measured by the method described in the examples below.

[0060] The shear adhesive strength of the above-mentioned adhesive resin cured product is preferably 1 MPa or more, and from the viewpoint of firmly bonding the members, it is more preferably 1.5 to 60.0 MPa, even more preferably 2.0 to 50.0 MPa, even more preferably 2.5 to 40.0 MPa, even more preferably 3.0 to 35.0 MPa, and even more preferably 3.5 to 32.0 MPa. The above shear adhesive strength can be measured by the method described in the examples below. Preferably, the adherend used for measuring the shear adhesive strength is a metal such as aluminum, steel plate, SUS, or electrodeposited plate (with paint on the surface), or a plastic such as PET, PC (polycarbonate), ABS, PMMA, polyamide, FRP, or PP. It is preferable that the shear adhesive strength measured using the above metal as the adherend satisfies the above range. It is preferable that the shear adhesive strength measured using the above metal as the adherend satisfies the above range. It is preferable that the shear adhesive strength measured using the above plastic as the adherend satisfies the above range.

[0061] In this embodiment, the cured adhesive resin product preferably has a shear adhesive strength of 10% or less, more preferably 7.0% or less, and more preferably 5.0% or less, when disassembled by external stimuli. The above values ​​can be measured by the method described in the examples below. The external stimuli mentioned above include heating (for example, heating at the bond exchange temperature Tv + 20°C for 10 minutes).

[0062] The gel fraction of the above-mentioned adhesive resin cured product is preferably 40% to 100%, more preferably 60-100% from the viewpoint of adhesive strength and durability, more preferably 65-100%, more preferably 70-100%, more preferably 75-100%, even more preferably 80-100%, even more preferably 83-100%, and even more preferably 87-100%. The above gel fraction can be adjusted by the polymer molecular weight, the amount of bifunctional or more amines, etc. The gel fraction described above can be measured by the method described in the examples below.

[0063] [Adhesive resin sheet] The adhesive resin sheet of this embodiment preferably includes the cured adhesive resin of this embodiment described above, and more preferably consists solely of the cured adhesive resin of this embodiment described above.

[0064] The thickness of the adhesive resin sheet is preferably 1 μm to 3000 μm, more preferably 5 μm to 2500 μm, even more preferably 10 μm to 2000 μm, even more preferably 20 μm to 1500 μm, even more preferably 30 μm to 1200 μm, and even more preferably 40 μm to 1100 μm.

[0065] The above-mentioned adhesive resin sheet can be manufactured, for example, by applying a cured adhesive resin to a substrate (e.g., a release-treated PET substrate) to a specific thickness and then drying it.

[0066] [Polymer solution] The polymer solution of this embodiment comprises the polymer of this embodiment described above and a solvent. Examples of the solvent include ethyl acetate, butyl acetate, toluene, MEK, etc. The mass percentage of the polymer in the solution is preferably 50 to 99.9% by mass or more, more preferably 60 to 99.9% by mass, and even more preferably 65 to 99.9% by mass. [Examples]

[0067] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0068] [Synthesis Example 1] Synthesis of polymer raw material R1 In a 2L two-necked flask, 100g of a bifunctional alcohol (ethylene glycol) and 765g of tert-butyl acetoacetate (3 equivalents relative to the OH groups of the alcohol) were mixed and nitrogen purged. The mixture was heated at 130°C for 4 hours while stirring with a stirring blade, and tBuOH was removed by distillation via transesterification. The mixture was heated to 140°C and distilled under reduced pressure for 5 hours to remove unreacted tert-butyl acetoacetate, and then allowed to cool to room temperature to obtain ethylene glycol-modified acetoacetate ester R1 (EAA).

[0069] [Synthesis Example 2] Synthesis of polymer P1 In a 300 mL two-necked flask, 50 mol% hexamethylenediamine, dissolved by heating in 100 mol% ethylene glycol-modified acetoacetate ester R1 (EAA) obtained in Synthesis Example 1, was added dropwise over 30 minutes. After stirring at room temperature for another 30 minutes, the temperature was raised to 50°C. Subsequently, the temperature was gradually increased to 80°C under reduced pressure, and the mixture was further heated under reduced pressure at 80°C for 10 hours to remove the generated water, thereby obtaining polymer P1 having vinylogous urethane groups as dynamic covalent bonds.

[0070] [Synthesis Example 3] Synthesis of polymer P2 In a 300 mL two-necked flask, 60 mol% hexamethylenediamine, dissolved by heating in 100 mol% ethylene glycol-modified acetoacetate ester R1(EAA) obtained in Synthesis Example 1, was added dropwise over 40 minutes. After stirring at room temperature for 30 minutes, the temperature was raised to 50°C. Subsequently, the temperature was gradually increased to 80°C under reduced pressure, and the mixture was further heated under reduced pressure at 80°C for 12 hours to remove the generated water, thereby obtaining polymer P2 having vinylogous urethane groups as dynamic covalent bonds.

[0071] [Synthesis Example 4] Synthesis of polymer P3 In a 300 mL two-necked flask, 70 mol% hexamethylenediamine, dissolved by heating in 100 mol% ethylene glycol-modified acetoacetate ester R1 (EAA) obtained in Synthesis Example 1, was added dropwise over 40 minutes. The mixture was then stirred at room temperature for 30 minutes, and the temperature was raised to 50°C. Subsequently, the temperature was gradually increased to 80°C under reduced pressure, and the mixture was further heated under reduced pressure at 80°C for 12 hours, followed by heating at 100°C for 2 hours to remove the generated water, thereby obtaining polymer P3 having vinylogous urethane groups as dynamic covalent bonds.

[0072] [Synthesis Example 6] Synthesis of polymer raw material R2 In a 2L two-necked flask, 100g of a bifunctional alcohol (1,4-butanediol) and 527g of tert-butyl acetoacetate (3 equivalents relative to the OH groups of the alcohol) were combined and the mixture was purged with nitrogen. The mixture was heated at 130°C for 4 hours while stirring with a stirring blade, and tBuOH was removed by distillation via transesterification. The mixture was then heated to 140°C and distilled under reduced pressure for 6 hours to remove unreacted tert-butyl acetoacetate, and the mixture was allowed to cool to room temperature to obtain butylene glycol-modified acetoacetate ester R2 (BAA).

[0073] [Synthesis Example 7] In a 300 mL two-necked flask, 60 mol% hexamethylenediamine, dissolved by heating in 100 mol% butylene glycol-modified acetoacetate R2(BAA) obtained in Synthesis Example 6, was added dropwise over 20 minutes. After stirring at room temperature for 30 minutes, the temperature was raised to 50°C. Subsequently, the temperature was gradually increased to 80°C under reduced pressure, and the mixture was further heated under reduced pressure at 80°C for 12 hours to remove the generated water, thereby obtaining polymer P5 having vinylogous urethane groups as dynamic covalent bonds.

[0074] [Synthesis Example 8] In a 300 mL two-necked flask, 70 mol% hexamethylenediamine, dissolved by heating in 100 mol% butylene glycol-modified acetoacetate R2(BAA) obtained in Synthesis Example 6, was added dropwise over 20 minutes. The mixture was then stirred at room temperature for 30 minutes, and the temperature was raised to 50°C. Subsequently, the temperature was gradually increased to 80°C under reduced pressure, and the mixture was further heated at 80°C under reduced pressure for 12 hours to remove the generated water, thereby obtaining polymer P6 having vinylogous urethane groups as dynamic covalent bonds.

[0075] [Synthesis Example 9] In a 300 mL two-necked flask, 90 mol% hexamethylenediamine, dissolved by heating in 100 mol% butylene glycol-modified acetoacetate R2(BAA) obtained in Synthesis Example 6, was added dropwise over 20 minutes. The mixture was then stirred at room temperature for 30 minutes, and the temperature was raised to 50°C. Subsequently, the temperature was gradually increased to 80°C under reduced pressure, and the mixture was further heated under reduced pressure at 80°C for 12 hours to remove the generated water, thereby obtaining polymer P7 having vinylogous urethane groups as dynamic covalent bonds.

[0076] (Example 1) [Preparation of Adhesive Resin Cured Product 1] To the polymer P1 obtained in Synthesis Example 2, hexatran (a trifunctional amine) was added as a crosslinking agent in an amount such that the ratio of NH2 in hexatran to functional groups Y before condensation reaction with any amine in polymer P1 was 45 mol% / 100 mol% (total functional group ratio NH2 / functional group Y = 95 mol% / 100 mol%), and the mixture was stirred to obtain a resin composition. The resin composition was then dried at 180°C for 30 minutes and cured at 23°C for 168 hours to produce adhesive resin cured product 1. [Preparation of adhesive resin sheet AH1] To the polymer P1 obtained in Synthesis Example 2, hexatran (a trifunctional amine) was added as a crosslinking agent in an amount such that the ratio of NH2 in hexatran to functional groups Y before condensation reaction with any amine in polymer P1 was 45 mol% / 100 mol% (total functional group ratio NH2 / functional group Y = 95 mol% / 100 mol%). The mixture was stirred and coated onto a PP plate to a thickness of 200 μm. After drying at 120°C for 30 minutes and curing at 23°C for 168 hours, an adhesive resin sheet AH1 with dynamic covalent bonds was obtained.

[0077] Examples 2-10 and Comparative Examples 1-2 were prepared and evaluated in the same manner as Example 1, except that modifications were made from Example 1 according to Table 1, and the evaluation results are also shown.

[0078] [evaluation] The polymers, cured adhesive resins, and adhesive resin sheets obtained in the examples and comparative examples were subjected to the following measurements.

[0079] (Shear adhesion strength) To the obtained polymers P1-P3 and P5-7, hexatran (a trifunctional amine) was added as a crosslinking agent in an amount such that the ratio of NH2 in hexatran to functional group Y in polymers was 45 mol% / 100 mol%, the mixture was stirred, and bubbles were removed. The liquid resin composition was then applied to electrodeposited coated plates (steel plates with paint coating on the surface) with an area of ​​12.5 mm x 25 mm, by bonding two electrodeposited plates together using a 50 μm thick spacer. After drying at 180°C for 30 minutes, the plates were cured at 23°C for 168 hours to obtain test specimens. At 23°C and 50 RH%, the obtained test specimens were pulled in the shear direction at a speed of 5 mm / min, and the force (N) at which they broke was divided by the bonding area to obtain the shear bonding strength (MPa). In Examples 2-10 and Comparative Examples 1-2, test specimens were prepared by changing the NH2 / functional group Y to the values ​​listed in Table 1.

[0080] (Shear adhesion strength to aluminum and steel plates) To the obtained polymers P1-P3 and P5-7, hexatran (a trifunctional amine) was added as a crosslinking agent in an amount such that the ratio of NH2 in hexatran to functional group Y in polymers was 45 mol% / 100 mol%, the mixture was stirred, and bubbles were removed. The liquid resin composition was then bonded to two sandblasted aluminum plates and two steel plates (untreated SPCC-SD, with the surface wiped with alcohol) using a 50 μm thick spacer to create a 12.5 mm x 25 mm area. After drying at 180°C for 30 minutes, the plates were cured at 23°C for 168 hours to obtain two test specimens with different substrates. At 23°C and 50 RH%, the obtained test specimens were pulled in the shear direction at a speed of 5 mm / min, and the force (N) at which they broke was divided by the bonding area to obtain the shear bonding strength (MPa). In Examples 2-10 and Comparative Examples 1-2, test specimens were prepared by changing the NH2 / functional group Y to the values ​​listed in Table 1.

[0081] (Shear adhesion strength to plastic substrates) To the obtained polymers P1-P3 and P5-7, hexatran (a trifunctional amine) was added as a crosslinking agent in an amount such that the ratio of NH2 in hexatran to functional group Y in polymers was 45 mol% / 100 mol%, the mixture was stirred, and the foam was removed. The liquid resin composition was then bonded to two polycarbonate (PC), polyethylene terephthalate (PET), and polymethyl methacrylate (PMMA) plates using a 50 μm thick spacer to create a 12.5 mm x 25 mm area. Each plate was wiped with alcohol before bonding. The plates were cured at 23°C for 168 hours to obtain three test specimens with different substrates. At 23°C and 50 RH%, the obtained test specimens were pulled in the shear direction at a speed of 5 mm / min, and the force (N) at which they broke was divided by the bonding area to determine the shear adhesive strength (MPa). In Examples 2-10 and Comparative Examples 1-2, test specimens were prepared by changing the NH2 / functional group Y to the values ​​listed in Table 1.

[0082] (Solubility in solvents) The obtained polymer was weighed into a 50 ml glass sample bottle, and various solvents (ethyl acetate, butyl acetate, toluene, and MEK) were added to prepare a 10 g solution with a polymer ratio of 70 wt%. The solution was stirred with a stirring rod for 1 minute, and then allowed to stand for 10 minutes at 23°C to observe and evaluate its solubility. Samples without separation or turbidity were rated ◎ (Excellent), samples with no separation but slight turbidity (where the sample on the opposite side of the sample bottle could be visually confirmed) were rated ○ (Good), and samples with separation, significant turbidity (where the sample on the opposite side of the sample bottle could not be visually confirmed) or precipitation were rated × (Poor).

[0083] (Tensile strength (maximum stress), elongation) A 60 μm thick adhesive sheet was prepared using the same method as for adhesive resin sheet AH1. The test specimens were cut to a width of 10 mm and a length of 40 mm. The specimens were set on a tensile testing machine with a grip distance of 20 mm, and measurements were taken at a temperature of 23°C and a speed of 20 mm / min to obtain the values ​​of maximum stress (i.e., maximum point strength, MPa) and elongation (%). In Examples 2-10 and Comparative Examples 1-2, test specimens were prepared by changing the NH2 / functional group Y to the values ​​listed in Table 1.

[0084] (Dynamic viscoelasticity) Except for using the polymers listed in Table 1 and changing the NH2 / functional group Y to the values ​​listed in Table 1, the resin composition was coated onto a PP board to a thickness of 200 μm in the same manner as for adhesive resin sheet AH1. After drying at 120°C for 30 minutes, it was cured at room temperature for 168 hours to obtain an adhesive resin sheet with dynamic covalent bonding. The test specimens were cut to a width of 10 mm and a length of 40 mm, set in a DMA measuring device, and measured at a variable temperature from -50°C to 150°C under conditions of frequency of 1 Hz and strain of 0.2% to obtain the storage modulus E' (Pa), Tg (temperature at the peak of tanδ) (°C), and Tv (°C) at room temperature (23°C).

[0085] (Gel fraction) Approximately 0.1 to 0.2 g of the obtained adhesive resin curing material was taken, wrapped in a mesh sheet, immersed in a butyl acetate / ethanol mixture (80 wt% / 20 wt%) for 24 hours, and then dried at 120°C for 2 hours. The gel fraction was calculated as follows: Gel fraction = 100 × (weight of sample after drying) / (weight of sample before solvent addition).

[0086] (Easy disassembly) Test samples similar to those used for shear adhesion strength tests were prepared. For each sample with an electrodeposited board as the substrate, the sample was heated at Tv+20°C for 10 minutes, and the shear adhesion strength was measured at that temperature. Samples that were 1 / 15 or less of the shear adhesion strength value at 23°C were rated ◎ (Excellent), samples that were 1 / 10 or less but greater than 1 / 15 of the shear adhesion strength value at 23°C were rated ○ (Good), samples that were 1 / 2 or less but greater than 1 / 10 of the shear adhesion strength value at 23°C were rated △ (Poor), and samples that were greater than 1 / 2 of the shear adhesion strength value at 23°C and could not be peeled off by hand were rated × (Inferior).

[0087] [Table 1]

Claims

1. A polymer having a dynamic covalent bond, possessing two or more of structure (I) within the molecule, and having a skeleton derived from a compound having two or more amino groups in its structure, and / or a skeleton derived from a bifunctional or more polyol, with a weight-average molecular weight Mw of 500 or more. 【Chemistry 1】 (In formula (I), R １ R is a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms. ２ R is a hydrocarbon group having 1 to 20 carbon atoms, which may contain H or a heteroatom. ３ (where X is a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms, and X is N, O, or S)

2. The polymer according to claim 1, wherein the number-average molecular weight of the bifunctional or more polyols is 200 or more.

3. The polymer according to claim 1, wherein the bifunctional or more polyol is a polyol selected from the group consisting of polyester polyols, polyether polyols having 4 or more carbon atoms in the repeating unit, polycarbonate polyols, polyolefin polyols, polyamide polyols, polyamide polyester polyols, silicone polyols, acrylic polyols, and polyurethane polyols.

4. The polymer according to claim 1, wherein the compound having two or more amino groups in the structure contains a hydrocarbon group having 1 to 18 carbon atoms.

5. The polymer according to claim 1, wherein the dynamic covalent bond is at least one selected from the group consisting of vinylogous urethane type, imine type, cyclic acetal type, urethane type, carbonate type, diketoenamine type, silyl ether type, and disulfide type.

6. The polymer according to claim 3, wherein the polyester polyol is a polycaprolactone polyol.

7. An adhesive resin cured product obtained by curing the polymer according to claim 1 with a compound having a bifunctional primary or secondary amino group and / or polyisocyanate.

8. The adhesive resin cured product according to claim 7, wherein the ratio of the number of moles of the amino group and / or the polyisocyanate in the compound having two or more primary or secondary amino groups and / or polyisocyanates to the number of moles of the functional group represented by the following formula in the structure of the polymer (I) is 1 or less. 【Chemistry 2】 (In the formula, R １ (This refers to a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms.)

9. The adhesive resin cured product according to claim 7, wherein the polyol is a polycaprolactone polyol and / or a polycarbonate polyol.

10. The adhesive resin cured product according to claim 7, wherein the elongation of the film made of the adhesive resin cured product in a tensile test at 23°C is 10% or more.

11. The adhesive resin cured product according to claim 7, wherein the tanδ peak temperature in dynamic viscoelasticity measurement is -20°C or higher.

12. The storage modulus E' at 23°C in dynamic viscoelasticity measurements is 1.0 × 10⁻⁶. ６ The adhesive resin cured product according to claim 7, wherein the pressure is Pa or higher.

13. The adhesive resin cured product according to claim 7, wherein the maximum stress of the film made of the adhesive resin cured product in a tensile test at 23°C is 1 MPa or more.

14. The adhesive resin cured product according to claim 7, wherein the bonding exchange temperature Tv is 50°C or higher.

15. The adhesive resin cured product according to claim 7, wherein the shear adhesive strength is 1 MPa or more.

16. The adhesive resin cured product according to claim 7, wherein the gel fraction is 40% or more and 100% or less.

17. An adhesive resin sheet comprising the adhesive resin cured product described in claim 7.

18. The adhesive resin sheet according to claim 17, wherein the thickness is 1 μm or more and 3000 μm or less.

19. The adhesive resin cured product according to claim 7, wherein the shear adhesive strength measured using a metal as the adherend is 1 MPa or more.

20. The adhesive resin cured product according to claim 7, wherein the shear adhesive strength measured using plastic as the adherend is 1 MPa or more.

21. The adhesive resin cured product according to claim 7, wherein the shear adhesive strength when dismantled by an external stimulus is 10% or less of the shear adhesive strength at 23°C and 50 RH before the application of the external stimulus.

22. A polymer solution containing the polymer and solvent described in claim 1.

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