Resin, resin composition, structure, method for bonding, method for separating, and method for identifying the same

Abstract

The purpose of this invention is to provide resin usable as an adhesive, exhibiting fluidity and excellent in adhesive strength, and resin exhibiting fluidity, excellent in adhesive strength, while also exhibiting dismantling property. The resin is characterized by having a dynamic covalent bond and having a crosslinking density of 180 mol / m3 to 800 mol / m3 and a glass transition temperature of -20°C to 120°C.

Description

Resin, resin composition, structure, bonding method, separation method and identification method

[0001] The present invention relates to a resin, and also describes a resin composition containing the resin, a structure containing the resin composition, a method for bonding using the resin composition, a method for separating the structure, and a method for identifying crosslinked organic structures using solid-state NMR techniques for resins containing dynamic covalent bonds.

[0002] In recent years, as a measure against global warming, there has been a demand for a shift to a resource recycling society and a carbon neutral society. For example, by using multi-materials in transportation vehicles such as automobiles, trains, and airplanes, the weight can be reduced, which results in fuel savings and CO ２ The aim is to reduce emissions. Multi-material materials specifically refer to materials made by bonding and joining together similar (or dissimilar) materials, such as resin, metal, fiber-reinforced plastic (FRP), and fiber-reinforced thermoplastic resin (FRTP), among other materials (i.e., multi-materialization). For example, while the materials that make up automobile bodies (i.e., structural components) have traditionally been metal, multi-material materials composed of bonding and joining dissimilar materials, such as metal-aluminum and metal-CFRP, are increasingly being adopted. The adhesives used to bond these materials must be high-strength enough to provide the strength required for structural components. Meanwhile, with the aim of resource circulation, including the separation and recycling of metals and CFRP, automobile structural components must also be easily dismantled. However, in the past, multi-material materials with high-strength adhesives were difficult to dismantle.

[0003] International Publication No. 2016-097169

[0004] In recent years, Vitrimer, a resin three-dimensionally crosslinked by dynamic covalent bonds, has been attracting attention. In Vitrimer, the dissociation and formation of dynamic covalent bonds occur simultaneously, so the connectivity of the polymer chains forming the three-dimensional crosslinked structure is not lost, and crosslink density is maintained to a certain extent. Therefore, when heated, Vitrimer does not flow rapidly or soften excessively like thermoplastic resins, but it exhibits fluidity and processability, and at the same time, due to its three-dimensional network, it is expected to exhibit excellent mechanical properties like thermosetting resins.

[0005] Patent Document 1 discloses a vinylogous urethane type Vitrimer, its properties, and the possibility of material recycling and chemical recycling. On the other hand, it discloses an adhesive as one possibility for industrial use, but makes no mention of specific compositions, bonding methods, adhesive strength, or dismantling properties.

[0006] An object of the present invention is to provide a resin that can be used as an adhesive, has fluidity and excellent adhesive strength, and also has dismantling properties.

[0007] That is, the present invention is as follows: [1] A polymer having a dynamic covalent bond and a crosslink density of 180 mol / m ３ More than 800mol / m ３ [2] The resin according to [1], wherein the gel fraction with respect to tetrahydrofuran is 95% or less. [3] The resin 1m ３ The bond density, which is the molar ratio of the dynamic covalent bonds in ３ More than 7000mol / m ３The resin according to [1] or [2], which is the following: [4] The resin according to any one of [1] to [3], wherein the dynamic covalent bond is at least one selected from the group consisting of a vinylogous urethane bond, an ester bond, and a disulfide bond. [5] The resin according to [4], wherein the dynamic covalent bond comprises a vinylogous urethane bond, and the molar ratio of primary amino groups present in the resin to 100 mol % of the molar number of vinylogous urethane bonds in the resin is 0 to 30 mol %. [6] A resin composition comprising the resin according to any one of [1] to [5]. [7] The resin composition according to [6], which is an adhesive. [8] A structure having a structure in which the resin composition according to [6] or [7] is applied to at least a portion of the surface of a member. [9] A method for bonding two members using the resin composition according to [7], comprising the steps of applying the resin composition between the two members or disposing a sheet of the resin composition between the two members.

[10] The method according to [9], wherein the member is made of a metal, a thermoplastic resin, a thermosetting resin, a ceramic, a glass, a fiber-reinforced composite material, a resin composition, or a combination thereof.

[11] A method for separating the member and the resin composition from the structure according to [8], comprising the steps of contacting the structure with an amine solution or an acid solution to depolymerize the resin composition to form a liquid, and separating the liquid from the member.

[12] A method for separating the member and the resin composition from the structure according to [8], comprising the steps of heating the structure to separate the member and the resin composition.

[13] A method for identifying a crosslinked organic structure in a resin containing dynamic covalent bonds using solid-state NMR.

[14] The method according to

[13] , wherein the resin is immersed in a measurement organic solvent for 3 hours or more, and identification is performed within 48 hours from the start of immersion.

[15] The method according to

[14] , wherein the measurement organic solvent is an aprotic solvent.

[0008] According to the present invention, it is possible to provide a resin that can be used as an adhesive and has fluidity and excellent adhesive strength, or a resin that has fluidity, excellent adhesiveness, and dismantling properties, and also to provide a method for identifying the crosslinked structure of the resin.

[0009] Hereinafter, the embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following description and can be practiced in various modifications within the scope of the gist thereof.

[0010] [Resin] The resin of this embodiment has a dynamic covalent bond and a crosslink density of 180 mol / m ３ More than 800mol / m ３ The glass transition temperature is -20°C or higher and 120°C or lower.

[0011] <Dynamic Covalent Bond> The resin has a dynamic covalent bond. The resin is cross-linked by the dynamic covalent bond, and therefore has high strength. Furthermore, the dynamic covalent bond can be cleaved by an acid or a base, making it recyclable. Furthermore, the dynamic covalent bond rearranges when heated, making it fluid and deformable. The resin may have the dynamic covalent bond in its main chain or in its side chain. That is, the reactive group or bond that forms the dynamic covalent bond may be located in the main chain of the polymer, or may be located as a substituent or the like in the side chain of the polymer.

[0012] Examples of the dynamic covalent bond include a vinylogous urethane bond, an ester bond (for example, an ester bond that undergoes a reversible bond exchange reaction between an ester and a hydroxyl group), a disulfide bond (for example, a disulfide bond that undergoes a reversible bond exchange reaction between disulfides), an imine bond (for example, an imine bond that undergoes a reversible bond exchange reaction between an imine and an amine), a carbonate bond, a cyclic acetal bond, a quaternary ammonium salt bond, an oxazoline bond, a spiroorthoester bond, a borate ester bond, a diketoenamine bond, etc. Among these, from the viewpoint of achieving even better adhesive strength and dismantling properties, at least one bond selected from the group consisting of a vinylogous urethane bond, an ester bond, a disulfide bond, and a diketoenamine bond is preferred, at least one bond selected from the group consisting of a vinylogous urethane bond, an ester bond, and a disulfide bond is more preferred, and a vinylogous urethane bond is even more preferred.

[0013] (Vinylogous Urethane Bond) Examples of the vinylogous urethane bond include: (i) a bond formed by dehydration condensation between an acetoacetate compound having one or more (preferably two or more) acetoacetate groups in the molecule and an amine compound having two or more primary amino groups in the molecule; and (ii) a bond formed by addition of an amine compound having two or more primary amino groups in the molecule to a propargylic acid ester derivative. An example of the reactions (i) and (ii) is shown below. In this specification, an acetoacetate compound having one or more (preferably two or more) acetoacetate groups in the molecule may be referred to as an "(A) acetoacetate compound," and a monomer unit derived from an (A) acetoacetate compound may be referred to as an "A monomer unit." Furthermore, an amine compound having two or more primary amino groups in the molecule may be referred to as a "(B) amine compound," and a monomer unit derived from an (B) amine compound may be referred to as a "B monomer unit." Furthermore, the monomer unit derived from the (C) propargylic acid ester derivative may be referred to as a “C monomer unit.” The A monomer unit and the C monomer unit may have the same structure.

[0014] The vinylogous urethane bond may be a structure represented by the following formula (1): An example of the structure represented by formula (1) is a structure represented by formula (2). In formula (1), the zigzag line represents a bond and indicates a bond to an arbitrary chemical structure. １ represents a functional group bonded to the ester group in the (A) acetoacetic acid ester compound or the (C) propargylic acid ester derivative, R in the adjacent vinylogous urethane bond ２ or R ３ and the like. １ is preferably a structure obtained when synthesized using an acetoacetic acid ester compound or a propargylic acid ester derivative described below. For example, R may be a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group having 1 to 15 carbon atoms, an optionally substituted cycloalkyl group having 1 to 15 carbon atoms, an optionally substituted aryl group having 1 to 15 carbon atoms, an optionally substituted (poly)alkylene glycol group, an optionally substituted alkoxy group having 1 to 15 carbon atoms, or a combination thereof. ２ and R ３ may each independently be a corresponding structure in the amine compound (B). ２ and R ３ is preferably a structure obtained when synthesized using the amine compound described below. For example, it may be a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group having 1 to 15 carbon atoms, an optionally substituted cycloalkyl group having 1 to 15 carbon atoms, an optionally substituted aryl group having 1 to 15 carbon atoms, an optionally substituted (poly)alkylene glycol group, an optionally substituted alkoxy group having 1 to 15 carbon atoms, or a combination thereof. Examples of the substituent include an alkyl group having 1 to 15 carbon atoms, a halogen atom, a hydroxyl group, and an ester group.

[0015] The number of vinylogous urethane bonds contained in the resin may be one or more, or may be plural. In particular, from the viewpoint of resin strength in a high-temperature environment (e.g., 80°C or higher) and / or adhesive strength, it is preferable to use a vinylogous urethane bond containing one or more vinylogous urethane bonds per 1 m of resin. ３The bond density, which is the molar ratio of dynamic covalent bonds in ３ More than 7000mol / m ３ It is preferably 3000 mol / m or less, and more preferably 3000 mol / m ３ More than 6000mol / m ３ From the viewpoint of resin strength, it is more preferable that the bond density is 3000 mol / m or less. ３ More than 5800mol / m ３ Particularly preferably, from the viewpoint of adhesive strength, the bond density is 4500 mol / m or less. ３ More than 5800mol / m ３ or less. Furthermore, by being within the above range, the hydrogen bonding sites derived from the vinylogous urethane bonds strongly interact with the adherend, mainly the metal surface, thereby achieving high adhesive strength. There are no particular limitations on the metal member, but aluminum, steel plate, etc. are strongly adhered. The presence or absence of the vinylogous urethane bonds and their number can be analyzed by solid-state NMR analysis. The resin preferably contains A monomer units and / or C monomer units and B monomer units, and more preferably contains A monomer units and B monomer units. Furthermore, it is preferable that the resin is composed only of A monomer units and / or C monomer units and B monomer units, and more preferably consists only of A monomer units and B monomer units.

[0016] The resin preferably contains, in its molecule, an A monomer unit derived from an acetoacetic ester compound (A). The A monomer unit contained in the resin may be of one type or of multiple types.

[0017] The (A) acetoacetic acid ester compound may be an acetoacetic acid ester compound having one acetoacetic acid ester group in the molecule, an acetoacetic acid ester compound having two acetoacetic acid ester groups in the molecule (bisacetoacetic acid ester compound), or an acetoacetic acid ester compound having three or more acetoacetic acid ester groups in the molecule.

[0018] The acetoacetate compound having one acetoacetate group in the molecule is not particularly limited, and examples thereof include esters of one acetylacetate with an alcohol such as a monoalcohol, diol, or triol. From the viewpoints of the fluidity of the resulting resin and the adhesive strength as an adhesive, particularly preferred among these are esters of one acetylacetate with a polyhydric alcohol such as ethylene glycol monoacetoacetate, propylene glycol monoacetoacetate, polyethylene glycol monoacetoacetate, or polypropylene glycol monoacetoacetate.

[0019] Examples of bisacetoacetate compounds include esters of two acetylacetic acids with a polyol such as a diol or triol. Examples of bisacetoacetate compounds include, but are not limited to, alkanediol bisacetoacetates such as ethylene glycol-1,2-bisacetoacetate, propanediol-1,3-bisacetoacetate, propanediol-1,2-bisacetoacetate, butanediol-1,4-bisacetoacetate, hexanediol-1,6-bisacetoacetate, and decanediol-1,10-bisacetoacetate; oxyalkylenediol bisacetoacetates such as diethylene glycol bisacetoacetate, triethylene glycol bisacetoacetate, polyethylene glycol bisacetoacetate, and polypropylene glycol bisacetoacetate; and 1,4-cyclohexanedimethanol bisacetoacetate. From the viewpoints of the strength of the resulting resin and the adhesive strength as an adhesive, ethylene glycol-1,2-bisacetoacetate, polyethylene glycol bisacetoacetate, polypropylene glycol bisacetoacetate, and 1,4-cyclohexanedimethanol bisacetoacetate are particularly preferred. The above bisacetoacetic acid ester compounds may be used alone or in combination of two or more.

[0020] Examples of monomers having three or more acetoacetate groups include esters of polyols such as triols with three or more acetylacetates. Examples of acetoacetate compounds having three or more acetoacetate groups in the molecule include esters of polyols such as triols with three or more acetoacetates. Examples of acetoacetate compounds having three or more acetoacetate groups in the molecule include, but are not limited to, polyacetoacetates such as trisacetoacetate and tetrakisacetoacetate. Examples of trisacetoacetates include, but are not limited to, trimethylolpropane acetoacetate, 1,2,3-propanetriol trisacetoacetate, 1,2,4-butanetriol trisacetoacetate, and 1,2,6-hexanetriol trisacetoacetate. Examples of other polyacetoacetates include, but are not limited to, pentaerythritol tetrakisacetoacetate, as well as those obtainable by the method described in JP-A-2017-533088. Of these, trimethylolpropane trisacetoacetate and 1,2,3-propanetriol trisacetoacetate are particularly preferred from the viewpoints of the strength of the resulting resin, the adhesive strength as an adhesive, and the resin strength.

[0021] When the acetoacetic acid ester compound contains a monoacetoacetic acid ester compound, the amount of the monomer units derived from the monoacetoacetic acid ester compound is preferably more than 0 parts by mass and not more than 25 parts by mass, more preferably more than 0 parts by mass and not more than 20 parts by mass, even more preferably more than 0 parts by mass and not more than 15 parts by mass, and most preferably more than 0 parts by mass and not more than 10 parts by mass, based on 100 parts by mass of the total amount of the resin. When the content of the monomer units derived from the monoacetoacetic acid ester compound is within the above range, the density of the three-dimensional crosslinked structure formed by the condensation reaction between the acetoacetic acid ester groups of the monomer units derived from the polyfunctional acetoacetic acid ester compound having two or more acetoacetic acid ester groups and the primary amino groups of the amine compound is appropriately adjusted, tending to result in high mechanical properties and good flowability. When the acetoacetic acid ester compound contains a bisacetoacetic acid ester compound, the amount of the monomer units derived from the bisacetoacetic acid ester compound is preferably 20 to 80 parts by mass, more preferably 40 to 75 parts by mass, and even more preferably 45 to 70 parts by mass, based on 100 parts by mass of the total amount of the resin. When the content of the monomer units derived from the bisacetoacetic acid ester compound is within the above range, the density of the three-dimensional crosslinked structure formed by the condensation reaction between the acetoacetic acid ester groups of the bisacetoacetic acid ester compound and the primary amino groups of the amine compound is appropriately adjusted, tending to provide high mechanical properties and good fluidity. When the acetoacetic acid ester compound includes an acetoacetic acid ester compound having three or more acetoacetic acid ester groups in the molecule, the monomer units derived from the acetoacetic acid ester compound having three or more acetoacetic acid ester groups in the molecule are preferably more than 0 parts by mass and not more than 40 parts by mass, more preferably more than 0 parts by mass and not more than 20 parts by mass, based on 100 parts by mass of the total amount of the resin. When the content of the monomer units derived from the acetoacetic acid ester compound having three or more acetoacetic acid ester groups in the molecule is within the above range, the density of the three-dimensional crosslinked structure formed by the condensation reaction between the acetoacetic acid ester groups of the acetoacetic acid ester compound having three or more acetoacetic acid ester groups in the molecule and the primary amino groups of the amine compound is appropriately adjusted, tending to provide high mechanical properties and good fluidity.

[0022] The resin preferably contains a monomer unit derived from (B) an amine compound having two or more primary amino groups in the molecule. (B) An amine compound having two or more primary amino groups in the molecule is an amine compound having two or more -NH ２ It is a compound having a group.

[0023] The (B) amine compound having two or more primary amino groups in the molecule may be a diamine, triamine, or polyamine, or may be an aromatic amine, an aliphatic amine, or a compound having both an aliphatic amino group and an aromatic amino group. The (B) amine compound having two or more primary amino groups in the molecule may be used alone or in combination of two or more.

[0024] 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)cyclohexyl San, 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-diene 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 of such an alkyl ester 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.

[0025] 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-aminopropyl)aniline, 4 ...

[0033] Examples of the aminonaphthyl methylamine include 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.

[0026] 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.

[0027] 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.

[0028] Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophoronediamine.

[0029] Among these aliphatic diamines, those in which the amino group is located at the end of the molecular chain are preferred from the viewpoint of improving reactivity.

[0030] Among these, 1,6-diaminohexane is particularly preferred from the viewpoint of high mechanical properties and good fluidity. The above diamine compounds may be used alone or in combination of two or more.

[0031] 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], and 1,3,5-tris(4-aminophenoxy)triazine.

[0032] It is also possible to use an aromatic triamine having a predetermined asymmetric structure represented by the following general formula (1). (Wherein, -Z- represents -O-, -CO-, -S-, -SO ２ -, -CH ２ -, -C(CH ３ ) ２ -, -C(CF ３ ) ２ - or a single bond. Ra and Rb each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group. m represents an integer of 0 to 3, and n represents an integer of 0 to 4.

[0033] 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, 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 amide, 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-triaminodiphenyl methane, 2,4,4'-triaminodiphenyl methane, 3,3',4-triaminodiphenyl methane ethane, 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-(3,4-diaminophenyl)-2-(4-aminophenyl)propane, 2-(3,2-(3,5-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, 2-(3,5-diaminophenyl)-2-(4-aminophenyl)hexafluoropropane, and the like can be mentioned.

[0034] Among the above aromatic triamines, those having a symmetrical molecular structure are preferred.

[0035] The aliphatic triamine is not particularly limited, but examples thereof include 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane, and tris(2-aminoethyl)amine.

[0036] Specific examples of the amine compound having both an aliphatic amino group and an aromatic amino group include 5-(2-aminoethyl)benzene-1,3-diamine and 2-((4-aminophenoxy)methyl)propane-1,3-diamine.

[0037] Commercially available amine compounds having three or more primary amino groups in the molecule can also be used. Examples include JEFFAMINE T-403, JEFFAMINE T-3000, and JEFFAMINE T-5000 manufactured by Huntsman, Polyment NK-350 manufactured by Nippon Shokubai Co., Ltd., and Hexatran 110 manufactured by Ascend. Other examples of amine compounds having three or more primary amino groups in the molecule include amino-modified polysiloxanes. Examples include X-22-3939A manufactured by Shin-Etsu Silicones Co., Ltd.

[0038] The amine compound having two or more primary amino groups in the molecule preferably does not contain a secondary amino group or a tertiary amino group in the molecule.

[0039] Among these, Hexatran 110 manufactured by Ascend Corp. is particularly preferred from the viewpoint of high mechanical properties and thermal stability. The amine compound having three or more primary amino groups in the molecule may be used alone or in combination of two or more.

[0040] The molar proportion of primary amino groups in the monomer units derived from the (B) amine compound is preferably 100 to 130 mol%, more preferably 100 to 110 mol%, and even more preferably 100 to 105 mol%, when the total of acetoacetate groups in the monomer units derived from acetoacetate compounds having one or more acetoacetate groups in the molecule is taken as 100 mol%. When the amount of primary amino groups is within the above range, the density and bond exchange rate of the three-dimensional crosslinked structure formed by the condensation reaction between the acetoacetate groups of the acetoacetate ester compound and the primary amino groups of the amine compound are appropriately adjusted, and high mechanical properties and good fluidity tend to be obtained.

[0041] When the acetoacetic ester compound includes a bisacetoacetic ester compound, the amount of the monomer units derived from the amine compound is preferably 20 to 70 parts by mass, more preferably 30 to 55 parts by mass, and even more preferably 35 to 50 parts by mass, relative to 100 parts by mass of the total amount of the resin. When the content of the monomer units derived from the amine compound is within the above range, the density of the three-dimensional crosslinked structure formed by the condensation reaction between the acetoacetic ester group of the acetoacetic ester compound and the primary amino group of the amine compound is appropriately adjusted, tending to result in high mechanical properties and good flowability. When the acetoacetic ester compound includes an acetoacetic ester compound having three or more acetoacetic ester groups in the molecule, the amount of the monomer units derived from the amine compound is preferably more than 0 parts by mass and not more than 30 parts by mass, more preferably more than 0 parts by mass and not more than 20 parts by mass, and even more preferably 5 to 15 parts by mass, relative to 100 parts by mass of the total amount of the resin. When the content of the monomer units derived from the amine compound is within the above range, the density of the three-dimensional crosslinked structure formed by the condensation reaction between the acetoacetic ester group of the acetoacetic ester compound and the primary amino group of the amine compound is appropriately adjusted, and high mechanical properties and good flowability tend to be obtained.

[0042] The resin of this embodiment contains, as an essential constituent unit, (B) a monomer unit derived from an amine compound having two or more primary amino groups in the molecule, but may also contain a monomer unit derived from a monoamine within the scope of the invention. Examples of monoamines include n-butylamine and benzylamine.

[0043] The (C) propargylic acid ester derivative may be a propargylic acid ester derivative having one propargylic acid ester group in the molecule, a propargylic acid ester derivative having two propargylic acid ester groups in the molecule, or a propargylic acid ester derivative having three or more propargylic acid ester groups in the molecule.

[0044] The propargylic acid ester derivative having one propargylic acid ester group in the molecule is not particularly limited, and examples thereof include esters of propargylic acid with alcohols such as monoalcohols, diols, and triols. Among these, from the viewpoint of adhesive strength, esters of one propargylic acid with a polyhydric alcohol such as ethylene glycol monopropargylic acid ester and polypropylene glycol monopropargylic acid ester are particularly preferred.

[0045] Examples of bispropargyl acid ester derivatives include esters of two propargyl acids with a polyol such as a diol or triol. Examples of bispropargyl acid ester derivatives include, but are not limited to, alkanediol bispropargyl acid esters such as ethylene glycol-1,2-bispropargyl acid ester, propanediol-1,3-bispropargyl acid ester, propanediol-1,2-bispropargyl acid ester, butanediol-1,4-bispropargyl acid ester, hexanediol-1,6-bispropargyl acid ester, and decanediol-1,10-bispropargyl acid ester; oxyalkylenediol bispropargyl acid esters such as diethylene glycol bispropargyl acid ester, triethylene glycol bispropargyl acid ester, polyethylene glycol bispropargyl acid ester, and polypropylene glycol bispropargyl acid ester; and 1,4-cyclohexanedimethanol bispropargyl acid ester. From the viewpoint of adhesive strength, ethylene glycol-1,2-bispropargyl acid ester, polyethylene glycol bispropargyl acid ester, polypropylene glycol bispropargyl acid ester, and 1,4-cyclohexanedimethanol bispropargyl acid ester are particularly preferred. The above bispropargyl acid ester derivatives may be used alone or in combination of two or more.

[0046] Examples of propargylic acid ester derivatives having three or more propargylic acid ester groups in the molecule include esters of three or more propargylic acids with polyols such as triols. Examples of propargylic acid ester compounds having three or more propargylic acid ester groups in the molecule include, but are not limited to, polypropargylic acid esters such as trispropargylic acid esters and tetrakispropargylic acid esters. Examples of trispropargylic acid esters include, but are not limited to, trimethylolpropane trispropargylate, 1,2,3-propanetriol trispropargylate, 1,2,4-butanetriol trispropargylate, and 1,2,6-hexanetriol trispropargylate.

[0047] The resin of this embodiment is preferably three-dimensionally crosslinked by (i) a condensation reaction between an acetoacetate group of an (A) acetoacetate ester compound and a primary amino group of an (B) amine compound to form a vinylogous urethane bond, or (ii) a condensation reaction between a propargylic acid ester group of a (C) propargylic acid ester compound and a primary amino group of an (B) amine compound to form a vinylogous urethane bond. The vinylogous urethane bond is a dynamic covalent bond that can be reversibly dissociated and bonded in response to external stimuli such as heat (temperature), light, or a catalyst. Among resins having dynamic covalent bonds, resins having vinylogous urethane bonds are preferred from the viewpoints of high mechanical strength (e.g., bending strength) as a resin and short decomposition time. Furthermore, since the recycling reaction proceeds even without a catalyst, there is no need to worry about catalyst bleed-out over time, which is more preferred.

[0048] As shown below, the vinylogous urethane reaction includes the formation of vinylogous urethane bonds, as well as amine exchange and hydrolysis. Reversible dissociation and bonding are possible through the formation of vinylogous urethane bonds, amine exchange reaction, and hydrolysis reaction. In the following reaction formula, R １ , R ２ , R ３ each independently represents an arbitrary chemical structure.

[0049] The three-dimensional crosslinked structure (polymer network structure) formed by vinylogous urethane bonds is a strong structure, so resins containing vinylogous urethane bonds have good mechanical strength and excellent heat resistance and chemical resistance. Furthermore, because the polymer network structure can be returned to a monomer or a linear low-molecular-weight derivative by hydrolysis of the vinylogous urethane or an amine exchange reaction with a monofunctional primary amine, resins containing vinylogous urethane bonds have excellent recyclability.

[0050] The resin having the vinylogous urethane bond as the dynamic covalent bond may be used in the form of a film. The film can be prepared by the following pressing method, coating method, or the like. (I) Pressing Method: i) An amine compound having two or more primary amino groups in the molecule (e.g., a mixture of a trifunctional amine and a difunctional amine) is mixed with an acetoacetate compound having one or more (preferably two or more) acetoacetate groups in the molecule, and the mixture is stirred to cause condensation polymerization. ii) The resulting resin is dried in a vacuum dryer (drying temperature: 80 to 150°C) and then pulverized. iii) The resulting pulverized pieces are pressed in a heat press to form a sheet (e.g., dimensions: 60 mm x 60 mm, thickness: 0.2 mm, etc.). The heat press may be, for example, a press (e.g., "SA-301" manufactured by Tester Sangyo Co., Ltd.). (II) Coating Film Production Method i) An amine compound having two or more primary amino groups in the molecule (e.g., a mixture of a trifunctional amine and a difunctional amine) is mixed with an acetoacetic acid ester compound having one or more (preferably two or more) acetoacetic acid ester groups in the molecule and stirred. ii) Before solidification, the mixture is applied to a glass plate or a polypropylene plate using a bar coater and allowed to stand. iii) After solidification, the film is peeled off from the glass plate or the like and dried in a vacuum dryer (e.g., drying at 80°C for 2 hours or 150°C for 4 hours).

[0051] The resin having the vinylogous urethane bond as the dynamic covalent bond may be applied to a member to be used as an adhesive. Examples of the method for bonding by application include the method of applying the monomer mixed solution (a mixture of an amine compound and an acetoacetic ester compound) described above (II) to a member before solidification.

[0052] (Ester bond) The ester bond may be a Vitrimer that utilizes a reversible bond exchange reaction between an ester and a hydroxyl group. The ester bond is, for example, a bond obtained by curing a monomer that forms an ester bond upon curing with any other monomer to produce a resin, and is capable of reversible dissociation and bonding depending on reaction conditions such as a catalyst, acid / base, and temperature, an ester exchange reaction, or the like. A resin having an ester bond as a dynamic covalent bond can be synthesized with reference to, for example, the method described in ACS Macro Lett. 1, 789-792 (2012).

[0053] Resins having an ester bond as a dynamic covalent bond tend to have high mechanical strength. An example of a reversible reaction of an ester bond is the transesterification reaction shown below. In the following reaction formula, R ４ , R ５ , R ６ each independently represents an arbitrary chemical structure. Resins having ester bonds as dynamic covalent bonds can be recycled because the polymer network structure can be returned to monomers or chain-like low-molecular-weight derivatives by dissociating the bonds through a transesterification reaction.

[0054] Examples of resins having an ester bond as a dynamic covalent bond include resins obtained by reacting a resin precursor having a hydroxyl group and / or an epoxy group, a curing agent, and another compound (e.g., a compound having an associative group on one side and a functional group that enables grafting on the other side) in the presence of a transesterification catalyst, and epoxy resins obtained by reacting a polyfunctional epoxy compound, optionally other monomers within the scope of the object of the invention, and a curing agent.

[0055] Examples of resin precursors having hydroxyl groups and / or epoxy groups include acrylic or methacrylic resins containing epoxy groups. Examples of the resin precursor include epoxy resins, more specifically glycidyl epoxy resins (e.g., resins prepared by the condensation reaction of a diacid or diamine with epichlorohydrin and an appropriate dihydroxy compound), non-glycidyl epoxy resins (e.g., resins prepared by peroxidation of the olefin double bonds of a polymer or polyunsaturated molecule), and the like. Among these, examples of the epoxy resins include novolac epoxy resins, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetraglycidylmethylenedianiline, pentaerythritol tetraglycidyl ether, tetrabromobisphenol A diglycidyl ether, hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like. Examples of suitable resin precursors include bisphenol A diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, terephthalic acid diglycidyl ester, epoxidized polyunsaturated fatty acid, epoxidized vegetable oil, epoxidized fish oil, and epoxidized limonene. Among these, bisphenol A diglycidyl ether is preferred from the viewpoint of adhesive strength. The resin precursors having hydroxyl groups or epoxy groups may be used alone or in combination.

[0056] Examples of polyfunctional epoxy compounds that can be used include glycidyl ether-type epoxy compounds, glycidyl ester-type epoxy compounds, glycidyl amine-type epoxy compounds, alicyclic epoxy compounds, and prepolymers obtained by polymerizing these compounds. Examples of prepolymers that can be used include glycidyl ether-type epoxy resins, glycidyl ester-type epoxy resins, glycidyl amine-type epoxy resins, alicyclic epoxy resins, and the like, with an appropriate degree of polymerization. One type of polyfunctional epoxy compound may be used alone, or two or more types may be used in combination.

[0057] Examples of the glycidyl ether type epoxy compound include bisphenol A diglycidyl ether, bisphenol AD ​​diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, biphenol diglycidyl ether, hexahydrobisphenol A diglycidyl ether, hexahydrobisphenol AD ​​diglycidyl ether, hexahydrobisphenol F diglycidyl ether, hexahydrobisphenol S diglycidyl ether, propanediol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and cyclohexanediol diglycidyl ether. Examples of the glycidyl ether include bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, biphenyl diglycidyl ether, dihydroxynaphthalene diglycidyl ether, cresol novolac glycidyl ether, xylylene novolac glycidyl ether, bisphenol A novolac glycidyl ether, bisphenol F novolac diglycidyl ether, bisphenol S novolac diglycidyl ether, triphenylmethane novolac glycidyl ether, biphenyl novolac glycidyl ether, terpene phenol novolac glycidyl ether, and derivatives thereof.

[0058] Examples of the glycidyl ester type epoxy compound include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, benzenetricarboxylic acid triglycidyl ester, benzenetetracarboxylic acid tetraglycidyl ester, trimellitic acid glycidyl ester, pyromellitic acid glycidyl ester, and derivatives thereof, such as acid anhydrides.

[0059] Examples of the glycidylamine type epoxy compound include triglycidyl isocyanurate, tetraglycidyldiaminodiphenylmethane, tetraglycidylbenzenedimethaneamine, tetraglycidyldiaminodiphenyl ether, triglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylphenoxyaniline, diglycidylpiperazine, diglycidyltoluidine, diglycidylaminophenol, triglycidylaminophenol, diglycidylaminocresol, triglycidylaminocresol, and derivatives thereof.

[0060] Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3',4'-epoxy-6-methyl-cyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, ethyleneoxy-3,4-epoxycyclohexane, dicyclopentadiene diepoxide, cyclohexadiene diepoxide, cyclooctadiene diepoxide, and derivatives thereof.

[0061] Examples of the curing agent include acid anhydrides and carboxylic acids, and carboxylic acid anhydrides and polycarboxylic acids are preferred. One type of curing agent may be used alone, or two or more types may be used in combination.

[0062] Examples of carboxylic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, 3-dodecenylsuccinic anhydride, octenylsuccinic anhydride, dodecylsuccinic anhydride, maleic anhydride, methylnadic anhydride, chlorendic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis(anhydrotrimate), methylcyclohexene tetracarboxylic anhydride, polyazelaic anhydride, polysebacic anhydride, and ethylene glycol bisanhydrotrimellitate.

[0063] Examples of polyvalent carboxylic acids include 1,2,3,4-butanetetracarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, malonic acid, maleic acid, succinic acid, fumaric acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, and polyvalent fatty acids such as adipic acid, azelaic acid, sebacic acid, dimer acid, and trimer acid.

[0064] The compounding ratio of the curing agent to the epoxy resin is preferably 0.4 mol or more and less than 1.0 mol, more preferably 0.5 mol or more and 0.9 mol or less, and even more preferably 0.5 mol or more and 0.8 mol or less, per 1 mol of epoxy groups in the epoxy resin. When the compounding ratio of the curing agent is within the above range, hydroxyl groups are present after polymerization, which tends to enable efficient reorganization of the polymer structure by dynamic covalent bonds.

[0065] The resin having an ester bond as a dynamic covalent bond can be produced, for example, by heating, mixing, and stirring the above-mentioned polyfunctional epoxy compound, optionally other monomers within the scope of the object of the invention, and the above-mentioned curing agent.

[0066] The resin having the ester bond as the dynamic covalent bond may be used in the form of a film. The film can be prepared by the following method: i) The polyfunctional epoxy compound and the curing agent are heated, mixed, and stirred. ii) The obtained resin is dried in a vacuum dryer (drying temperature: 80 to 150°C) and pulverized. iii) The obtained pulverized pieces are pressed in a heat press to form a sheet (e.g., dimensions: 60 mm x 60 mm, thickness: 0.2 mm, etc.). In the above method, i) may be replaced by i') below: i') The resin precursor having a hydroxyl group and / or an epoxy group and the curing agent are heated, mixed, and stirred.

[0067] In resins having an ester bond as a dynamic covalent bond, examples of catalysts that promote the transesterification reaction include zinc acetate (II), zinc (II) acetylacetonate, zinc naphthenate (II), iron acetylacetonate (III), cobalt acetylacetonate (II), aluminum isopropoxide, titanium isopropoxide, methoxide (triphenylphosphine) copper (I) complex, ethoxide (triphenylphosphine) copper (I) complex, propoxide (triphenylphosphine) copper (I) complex, and isopropoxide (triphenylphosphine) copper (I) complex. Examples of suitable catalysts include methyl methacrylate, methoxidebis(triphenylphosphine)copper(II) complex, ethoxidebis(triphenylphosphine)copper(II) complex, propoxidebis(triphenylphosphine)copper(II) complex, isopropoxidebis(triphenylphosphine)copper(II) complex, tris(2,4-pentanedionato)cobalt(III), tin(II) diacetate, tin(II) di(2-ethylhexanoate), N,N-dimethyl-4-aminopyridine, diazabicycloundecene, diazabicyclononene, triazabicyclodecene, and triphenylphosphine. The amount of the catalyst added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total amount of the resin having an ester bond.

[0068] (Imine bond) The imine bond may be a Vitrimer that utilizes a reversible bond exchange reaction between imine and amine. The imine bond is, for example, a bond obtained by a condensation reaction between a carbonyl group of an aldehyde compound or a ketone compound and a primary amino group of an amine compound, and is capable of reversible dissociation and bonding by an imine-amine exchange reaction or the like. A resin having an imine bond as a dynamic covalent bond can be synthesized with reference to, for example, the method described in Polym. Chem. 7, 7052-7056 (2016).

[0069] Resins having imine bonds as dynamic covalent bonds tend to have a short decomposition time. An example of a reversible reaction of an imine bond is the imine-amine exchange reaction shown below. In the following reaction formula, R ７ , R ８ , R ９ each independently represents an arbitrary chemical structure. By dissociating the bond through the imine-amine exchange reaction, the polymer network structure can be returned to a monomer or a chain-like low-molecular-weight derivative. Therefore, it is possible to separate the components and the resin composition from a structure in which two components are bonded together with a resin composition containing a resin having an imine bond as a dynamic covalent bond, and also to recycle the resin.

[0070] A resin having an imine bond as a dynamic covalent bond can be obtained, for example, by a condensation reaction of an aldehyde compound or ketone compound having two or more carbonyl groups in the molecule, an amine compound having two or more primary amino groups in the molecule, and optionally other monomers within the scope of the invention, or by reacting an imine-bonded oligomer with a crosslinking agent.

[0071] Examples of amine compounds having two or more primary amino groups in the molecule include those listed as raw materials for synthesizing the resin having a vinylogous urethane bond. The amine compounds having two or more primary amino groups in the molecule may be used alone or in combination of two or more.

[0072] Examples of the aldehyde compound having two or more carbonyl groups in the molecule include terephthalaldehyde, isophthalaldehyde, 2,5-diformylfuran, 3,4-diformylthiophene, 2,4-diformylimidazole, 3,4-dicarboxaldehydepyrrole, etc. The aldehyde compound having two or more carbonyl groups in the molecule may be used alone or in combination of two or more.

[0073] The amount of primary amino groups in a monomer unit derived from an amine compound having two or more primary amino groups in the molecule is preferably 1.0 to 1.3 equivalents, more preferably 1.0 to 1.1 equivalents, and even more preferably 1.0 to 1.05 equivalents, relative to the amount of carbonyl groups in a monomer unit derived from an aldehyde compound or ketone compound. When the amount of primary amino groups is within the above range, the density of the three-dimensional crosslinked structure formed by the condensation reaction between the carbonyl groups of the aldehyde compound or ketone compound and the primary amino groups of the amine compound is appropriately adjusted, and high mechanical properties and good flowability tend to be obtained.

[0074] A resin having an imine bond as a dynamic covalent bond can be produced, for example, by dissolving the above-mentioned aldehyde compound or ketone compound, the above-mentioned amine compound, and optionally other monomers within the scope of the object of the invention in an organic solvent (e.g., methanol, ethanol, etc.), and then mixing and stirring the resulting mixture.

[0075] The imine-linked oligomer may be an oligomer containing at least one non-terminal imine moiety within the oligomer backbone. The imine-linked oligomer may be linear or branched. Preferably, the imine-linked oligomer contains at least one secondary amine within the oligomer backbone. The imine-linked oligomer may be prepared from a monofunctional or polyfunctional amine and a monofunctional or polyfunctional aldehyde or carbonyl. For example, the polyfunctional aldehyde or carbonyl may be terephthalaldehyde, 2,5-diformylfuran, diformylthiophene, diformylpyrrole, diformylimidazole, or a combination thereof. The polyfunctional carbonyl may be an aldehyde, ketone, carboxylic acid ester, amide, enone, acid anhydride, imide, or a combination thereof. The polyfunctional aldehyde or carbonyl may be derived from a renewable biological source.

[0076] The crosslinking agent may be a compound that chemically reacts with and covalently bonds to the oligomer and / or polymer. Examples of the crosslinking agent include compounds containing reactive moieties selected from the group consisting of epoxy, isocyanate, bismaleimide, sulfide, polyurethane, acid anhydride, polyester, and combinations thereof. Examples include novolac resins, bisphenols (e.g., bisphenol A (BPA)), monoglycidyl, diglycidyl, or triglycidyl molecules, N-containing triglycidyl molecules, cresol or SU-8 photoresists containing epoxy, isocyanate, bismaleimide, sulfide, polyurethane, acid anhydride, and / or polyester functional groups.

[0077] The resin having the imine bond as a dynamic covalent bond may be used in the form of a film. The film can be prepared by the following method: i) Mix and stir the aldehyde compound or ketone compound having two or more carbonyl groups in the molecule with an amine compound having two or more primary amino groups in the molecule. ii) Dry the resulting resin in a vacuum dryer (drying temperature: 80 to 150°C) and then pulverize it. iii) Press the resulting pulverized pieces in a heat press to form a sheet (e.g., dimensions: 60 mm x 60 mm, thickness: 0.2 mm, etc.). In the above method, i) may be replaced by i') below: i') Mix and stir the imine-bonded oligomer and a crosslinking agent (e.g., epoxy, isocyanate, bismaleimide, etc.).

[0078] In resins having imine bonds as dynamic covalent bonds, examples of catalysts that promote the imine-amine exchange reaction include sulfuric acid, paratoluenesulfonic acid, paratoluenesulfonic acid monohydrate, ethylphosphinic acid, phenylphosphinic acid, ethylphosphonic acid, phenylphosphonic acid, zinc(II) chloride, zinc(II) acetate, iron(II) chloride, iron(III) chloride, diethylamine, diisopropylamine, triethylamine, tributylamine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]non-5-yne, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, ammonium chloride, ammonium acetate, and ammonium carbamate. The amount of the catalyst added is preferably 0 to 6 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the resin having imine bonds.

[0079] (Disulfide bond) The disulfide bond may be a Vitrimer that utilizes a reversible bond exchange reaction between disulfides. The disulfide bond can be reversibly dissociated and bonded, for example, depending on the conditions of an oxidation-reduction reaction with a thiol. A resin having a disulfide bond as a dynamic covalent bond can be synthesized, for example, with reference to the method described in ACS Macro Lett. 8, 255-260 (2019).

[0080] Examples of the reversible reaction of disulfide bonds include the reaction shown below. In the following reaction formula, R １０ , R １１ , R １２ , R １３ each independently represents an arbitrary chemical structure.

[0081] A resin having a disulfide bond as a dynamic covalent bond can be obtained, for example, by thermally curing a resin such as epoxy or urethane using a curing agent containing a disulfide unit.

[0082] Examples of the resin include MDS-EPO, which is obtained by thermally curing an isosorbide-based epoxy resin (IS-EPO) obtained by reacting isosorbide (1,4:3,6-dianhydro-d-glucitol) with epichlorohydrin in the presence of a concentrated aqueous solution of NaOH, using 4,4'-disulfanediyldianiline (MDS) as a curing agent.

[0083] The resin having the disulfide bond as the dynamic covalent bond may be used in the form of a film. The film can be prepared by the following method: i) A resin such as epoxy or urethane is thermally cured using a curing agent containing a disulfide unit. ii) The resulting resin is dried in a vacuum dryer (drying temperature: 80 to 150°C) and then pulverized. iii) The resulting pulverized pieces are pressed in a heat press to form a sheet (e.g., dimensions: 60 mm x 60 mm, thickness: 0.2 mm, etc.).

[0084] (Diketoenamine bond) A diketoenamine bond is a bond obtained, for example, by condensing a triketone compound with an amine compound, and is capable of reversible dissociation and bonding by an exchange reaction with an amino group. A resin having a diketoenamine bond as a dynamic covalent bond can be synthesized with reference to, for example, the method described in Nature Chemistry 11, 442-448 (2019). Specifically, an example of a reversible reaction of a diketoenamine bond is the diketoenamine-amine exchange reaction shown below. In the reaction formula below, R １４ ~R １６ each independently represents an arbitrary chemical structure.

[0085] The carbonate bond is a bond obtained, for example, by producing a resin by ring-opening polymerization of a biscyclic carbonate compound in the presence of a polyol and, optionally, other monomers, and is capable of reversible dissociation and bonding by a carbonate exchange reaction or the like.

[0086] A cyclic acetal bond is a bond obtained, for example, between a carbonyl group and a diol compound. Reversible dissociation and recombination are possible depending on reaction conditions such as acid catalyst conditions and temperature.

[0087] A quaternary ammonium salt bond is a bond obtained by crosslinking tertiary amines together by alkylation, and allows for reversible dissociation and bonding depending on the thermal equilibrium relationship of the crosslink.

[0088] The oxazoline bond is a bond obtained by crosslinking, for example, 4,4-dimethyl-2-oxazolin-5-one with bisphenol, and is capable of reversible dissociation and bonding depending on the thermal equilibrium relationship of the crosslink.

[0089] A spiroorthoester bond is a bond obtained by crosslinking, for example, spiroorthoesters with each other, and is capable of reversible dissociation and bonding depending on reaction conditions such as solvent and temperature.

[0090] A borate ester bond is a bond obtained by crosslinking, for example, phenylboronic acid with a diol, and is capable of reversible dissociation and bonding depending on reaction conditions such as pH, acid / base, and temperature.

[0091] <Characteristics> The characteristics of the resin of this embodiment will be described.

[0092] The crosslinking density of the resin of this embodiment is 180 to 800 mol / m ３ and preferably 200 to 800 mol / m ３ , more preferably 200 to 500 mol / m ３ , more preferably 250 to 400 mol / m ３ , particularly preferably 250 to 350 mol / m ３ When the crosslink density is within the above range, the adhesive strength and fluidity during heating are excellent. The crosslink density refers to the density of crosslinking points in the resin, and is expressed as the density of crosslinking points per volume (m ３ The molar ratio of the polyfunctional monomer to the total molecular weight of the copolymer (polymer) can be measured by the method described in the Examples below. The polyfunctional monomer in the present invention refers to a monomer having three or more functional groups capable of forming a dynamic covalent bond.

[0093] The glass transition temperature (Tg) of the resin of this embodiment is -20 to 120°C, preferably 0 to 120°C, more preferably 0 to 100°C, even more preferably 20 to 80°C, and particularly preferably 20 to 60°C. When the glass transition temperature is in the above range, the adhesive strength and fluidity during heating are excellent. The glass transition temperature can be measured by the method described in the examples below.

[0094] The resin of this embodiment has a crosslink density of 180 to 800 mol / m ３ Furthermore, the glass transition temperature is −20 to 120° C., which increases the fluidity during bonding and allows the resin to sufficiently contact and spread on the surface of the adherend, thereby achieving high adhesive strength.

[0095] The resin of this embodiment preferably has a gel fraction relative to tetrahydrofuran of 95% or less, more preferably 90% or less. When the gel fraction is within the above range, the adhesive strength and fluidity upon heating are excellent. The lower limit of the gel fraction is preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, and particularly preferably 65% ​​or more. When the gel fraction is below the above range, the adhesive strength is insufficient, the adhesive strength retention period is shortened, and other adhesive performance problems occur. The gel fraction can be measured by the method described in the Examples below.

[0096] The resin of this embodiment is resin 1 m ３ The bond density, which is the molar ratio of the dynamic covalent bonds in the ３ is preferable, and more preferably 4000 to 7000 mol / m ３ , more preferably 5000 to 7000 mol / m ３ When the bond density is within the above range, the adhesive strength is excellent. The bond density refers to the density of dynamic covalent bonds (i.e., Vitrimer bonds) in the resin, and is expressed as the density of the dynamic covalent bonds (i.e., Vitrimer bonds) in the resin volume (m ３ It can be measured by the method described in the Examples below. For example, when a plurality of types of dynamic covalent bonds are contained, it is calculated from the total number of dynamic covalent bonds of all types, and when the dynamic covalent bonds are only vinylogous urethane bonds, it is calculated from the number of vinylogous urethane bonds.

[0097] In the resin of this embodiment, the dynamic covalent bonds include vinylogous urethane bonds (preferably, the dynamic covalent bonds are exclusively vinylogous urethane bonds), and the molar ratio of primary amino groups present in the resin relative to 100 mol % of the vinylogous urethane bonds in the resin is preferably 0 to 30 mol %, more preferably 0 to 10 mol %, and even more preferably 0 to 5 mol %. The presence of free amino groups in the resin facilitates bond exchange (i.e., exchange of bond combinations between acetoacetate ester groups and amino groups), resulting in higher fluidity. When the molar ratio is within the above range, the fluidity is further increased, resulting in higher adhesive strength. The molar ratio can be measured by the method described in the Examples below. Here, the primary amino groups present in the resin may refer to free primary amino groups not incorporated into vinylogous urethane bonds.

[0098] The resin of this embodiment preferably has a relaxation time at 180°C of 300 to 2000 seconds, more preferably 400 to 1500 seconds, and even more preferably 500 to 1000 seconds. A relaxation time within this range provides excellent adhesive strength and fluidity during heating. The relaxation time (seconds) can be determined by analyzing the results of measurements taken using a rheometer (TA Instruments' "ARES-G2") at a temperature range of 150 to 200°C and a strain range of 1 to 5%.

[0099] [Resin Composition] The resin composition of this embodiment contains the resin of this embodiment described above. The resin composition may contain only the resin of this embodiment described above, or may further contain other components. The resin component contained in the resin composition is preferably only the resin of this embodiment described above. The mass proportion of the resin of this embodiment described above relative to 100 mass% of the resin composition is preferably more than 50 mass%, more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 95 mass% or more.

[0100] (Other Components) Examples of the other components include resins other than the resin of the present embodiment described above (sometimes referred to as "other resins" in this specification), curing accelerators, fillers, coupling agents, additives, etc.

[0101] Other Resins Examples of the other resins include thermoplastic resins. Examples of the thermoplastic resins include phenoxy resins, acrylic resins, methacrylic resins, polyvinyl acetal resins, thermoplastic polyimide resins, polyamide resins, polyamideimide resins, polyphenylene oxide resins, polyethersulfone resins, polyester resins, polyethylene resins, polystyrene resins, polysulfone resins, polybutadiene resins, ABS resins, and coumarone resins. One type of the thermoplastic resin may be used alone, or two or more types having different weight-average molecular weights may be used in combination, or one or more types may be used in combination with their prepolymers. Among these, it is preferable to use one or more types selected from the group consisting of polyimide resins, polyamide resins, phenoxy resins, and coumarone resins.

[0102] The phenoxy resin is not particularly limited, and examples thereof include phenoxy resins having a bisphenol skeleton such as phenoxy resins having a bisphenol A skeleton, phenoxy resins having a bisphenol F skeleton, phenoxy resins having a bisphenol S skeleton, phenoxy resins having a bisphenol M (4,4'-(1,3-phenylenediisopridiene)bisphenol) skeleton, phenoxy resins having a bisphenol P (4,4'-(1,4)-phenylenediisopridiene)bisphenol) skeleton, and phenoxy resins having a bisphenol Z (4,4'-cyclohexydienebisphenol) skeleton, phenoxy resins having a novolac skeleton, phenoxy resins having an anthracene skeleton, phenoxy resins having a fluorene skeleton, phenoxy resins having a dicyclopentadiene skeleton, phenoxy resins having a norbornene skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton, and phenoxy resins having an adamantane skeleton. The phenoxy resin may have a structure having multiple types of the above skeletons, or may have different ratios of the skeletons. Furthermore, multiple types of phenoxy resins with different skeletons may be used, or multiple types of phenoxy resins with different weight-average molecular weights may be used, or prepolymers of these may be used in combination.

[0103] The lower limit of the weight-average molecular weight (Mw) of the phenoxy resin is, for example, 10,000 or more, preferably 15,000 or more, and more preferably 20,000 or more. When the lower limit of the weight-average molecular weight (Mw) is within the above range, compatibility with other resins and solubility in solvents can be improved. On the other hand, the upper limit of the weight-average molecular weight (Mw) of the phenoxy resin is, for example, 60,000 or less, preferably 55,000 or less, and more preferably 50,000 or less.

[0104] From the viewpoint of recyclability, the mass proportion of the other resins in the resin composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and even more preferably 15 to 30 mass%, with the resin composition (total solids content when the resin composition is in a varnish state) being 100 mass%.

[0105] -Curing Accelerator- The resin composition of this embodiment can improve the curability of the resin composition by including a curing accelerator (curing catalyst). The mass proportion of the curing accelerator in the resin composition is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, and even more preferably 1 to 3 mass%, relative to 100 mass% of the resin composition (total solids content when the resin composition is in varnish form).

[0106] Filler: The filler is preferably an inorganic filler. Examples of the inorganic filler include silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; and titanates such as strontium titanate and barium titanate. Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferred, and silica is particularly preferred. As the inorganic filler, one of these may be used alone, or two or more may be used in combination.

[0107] The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but may be, for example, 0.01 μm or more, or 0.05 μm or more. When the lower limit of the average particle diameter is within the above range, the viscosity of the resin composition can be prevented from becoming too high. Furthermore, the upper limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably, for example, 5.0 μm or less, more preferably 2.0 μm or less, and even more preferably 1.0 μm or less. When the upper limit of the average particle diameter is within the above range, phenomena such as sedimentation of the inorganic filler in the resin composition can be suppressed, and a uniform resin composition can be obtained. In this embodiment, the average particle diameter of the inorganic filler can be determined, for example, by measuring the particle size distribution of the particles on a volume basis using a laser diffraction particle size distribution analyzer (LA-500, manufactured by HORIBA), and the median diameter (D50) can be used as the average particle diameter.

[0108] The inorganic filler is not particularly limited, but may be an inorganic filler having a monodisperse average particle size, or an inorganic filler having a polydisperse average particle size. Furthermore, one or more types of inorganic fillers having monodisperse and / or polydisperse average particle sizes may be used in combination.

[0109] The lower limit of the mass proportion of the inorganic filler in the resin composition is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on 100% by mass of the resin composition (total solids when the resin composition is in varnish form). When the lower limit of the mass proportion is within the above range, the resin composition can have particularly low thermal expansion and low water absorption. On the other hand, the upper limit of the mass proportion of the inorganic filler is not particularly limited, but may be, for example, 85% by mass or less, 80% by mass or less, or 75% by mass or less, based on 100% by mass of the resin composition. This improves handleability.

[0110] - Coupling Agent - The coupling agent may be added directly during preparation of the resin composition, or may be added to the inorganic filler in advance. The use of a coupling agent can improve the wettability of the interface between the inorganic filler and each resin. Therefore, it is preferable to use a coupling agent, especially when an inorganic filler is contained, and it can improve the heat resistance of the resin composition.

[0111] Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and amino silane coupling agents, titanate coupling agents, and silicone oil coupling agents. The coupling agents may be used alone or in combination of two or more. The coupling agent may contain a silane coupling agent. This can enhance the wettability of the interface between the inorganic filler and each resin.

[0112] Various types of silane coupling agents can be used, including, for example, epoxy silane, amino silane, alkyl silane, ureido silane, mercapto silane, vinyl silane, etc. Specific examples include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-6-(aminohexyl)3-aminopropyltrimethoxysilane, N-(3-(trimethoxysilylpropyl)-1,3-benzenedimethanane, γ-glycidoxypropyltriethoxysilane, Examples of suitable silanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane (also known as 3-mercaptopropyltrimethoxysilane), methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and vinyltriethoxysilane. These silanes may be used singly or in combination of two or more. Of these, epoxysilanes, mercaptosilanes, and aminosilanes are preferred, and primary aminosilanes or anilinosilanes are more preferred as aminosilanes.

[0113] The mass proportion of the coupling agent in the resin composition can be appropriately adjusted based on the specific surface area of ​​the inorganic filler. The lower limit of the mass proportion of such a coupling agent may be, for example, 0.01 mass% or more, preferably 0.05 mass% or more, based on 100 mass% of the resin composition (total solids when the resin composition is in varnish form). When the mass proportion of the coupling agent is equal to or greater than the lower limit, the inorganic filler can be sufficiently coated, thereby improving the heat resistance of the resin composition. On the other hand, the upper limit of the mass proportion of the coupling agent may be, for example, 3 mass% or less, preferably 1.5 mass% or less, based on 100 mass% of the resin composition. When the mass proportion of the coupling agent is equal to or less than the upper limit, the reaction can be prevented from being affected, and a decrease in the bending strength of the resin composition can be suppressed.

[0114] -Additives- The additives may include colorants containing one or more selected from the group consisting of dyes such as green, red, blue, yellow, and black, pigments such as black pigments, and dyes, as well as additives other than those listed above, such as stress reducers, antifoaming agents, leveling agents, UV absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, rubber components, light stabilizers, dispersants, lubricants, plasticizers, and antistatic agents. These may be used alone or in combination of two or more. The mass proportion of the additives in the resin composition is preferably 0.1 to 25 mass%, more preferably 0.2 to 20 mass%, and even more preferably 0.5 to 15 mass%, based on 100 mass% of the resin composition (total solids content if the resin composition is in varnish form). The mass proportion of the additives can be confirmed not only from the charge ratio, but also by extracting the additives from the resulting resin composition using a solvent or the like, or by decomposing the resin composition using a decomposition solution containing a low-molecular-weight amine or alcohol, extracting the additives, and quantifying them using an analytical device such as liquid chromatography.

[0115] Examples of the pigment include inorganic pigments such as kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, and synthetic ultramarine blue; polycyclic pigments such as phthalocyanine; and azo pigments.

[0116] Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, and azomethine.

[0117] The rubber component may include, for example, one or more selected from the group consisting of butadiene rubber, acrylic rubber, and silicone rubber. The rubber component may be contained in the form of particles. Examples of such rubber particles include core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, acrylic rubber particles, and silicone particles.

[0118] When the resin composition is in the form of a varnish, the resin composition may contain a solvent. Examples of the solvent include organic solvents such as methanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve-based solvents, carbitol-based solvents, anisole, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0119] When the resin composition is in the form of a varnish, the mass proportion of the solid content in the resin composition may be, for example, 30 to 80 mass%, more preferably 40 to 70 mass%. When the mass proportion of the solid content of the resin composition is in the above range, a resin composition with excellent workability and film-forming properties can be obtained.

[0120] The resin composition of this embodiment can be produced by mixing and stirring the resin of this embodiment described above and, if necessary, the other components described above. In the case of a varnish-like resin composition, the components described above can be dissolved in a solvent, mixed, and stirred using various mixers such as those used in ultrasonic dispersion, high-pressure collision dispersion, high-speed rotation dispersion, bead mill dispersion, high-speed shear dispersion, and rotation-revolution dispersion.

[0121] The resin composition of the present embodiment can be used as an adhesive.

[0122] [Structure] The structure of this embodiment has at least a structure in which the resin composition of this embodiment described above is applied to at least a portion of the surface of a component. In the structure, the resin composition may be applied to a portion of the surface of a component, or the resin composition may be applied to the entire surface of a component. In the structure, the resin composition may be applied to one surface of a component, or the resin composition may be applied to both surfaces of a component. The structure may be a structure in which the resin composition is applied to at least a portion of the surface of one component, a structure in which two components are bonded using the resin composition, or a structure in which three or more components are bonded. In the case of a structure in which three or more components are bonded, it is sufficient that the resin composition is used on at least a portion of the bonding surfaces, and it may be used in combination with other adhesives.

[0123] The components may be metals, thermoplastic resins, thermosetting resins, ceramics, glass, fiber-reinforced composite materials, resin compositions, or combinations thereof. When two or more components are used, the components may be the same or different.

[0124] [Bonding Method] The bonding method of this embodiment is a method of bonding two members using the resin composition of this embodiment described above. The bonding method includes a step of applying the resin composition between the two members, or a step of placing a sheet of the resin composition between the two members. An example of a method including the application step is a method of applying a raw material monomer mixed solution of the resin before curing to a member and then curing it. An example of a method including a step of placing the sheet-like resin composition is a method of placing a film of the resin of this embodiment described above between two members and applying pressure (preferably heat and pressure) to bond them.

[0125] The materials used in the bonding method include metal, thermoplastic resin, thermosetting resin, ceramic, glass, fiber-reinforced composite material, resin composition, and combinations thereof. The two materials may be the same or different.

[0126] [Method for Separating the Structure] The method for separating the structure of this embodiment is a method for separating the resin composition and the member from the structure of this embodiment described above.

[0127] The method for separating the structure is preferably a method (sometimes referred to herein as "separation method I") that includes the steps of contacting the structure with an amine solution or an acid solution to depolymerize the resin composition into a liquid, and separating the liquid from the member. In separation method I, the resin contained in the resin composition is preferably a resin whose dynamic covalent bonds include vinylogous urethane bonds (preferably, whose dynamic covalent bonds are exclusively vinylogous urethane bonds). In separation method I, when the structure is contacted with an acid solution, the dynamic covalent bonds such as vinylogous urethane bonds are cleaved by hydrolysis, returning to the raw materials, acetoacetate ester and amine compound, and the resin contained in the resin composition is depolymerized to a liquid. Furthermore, when the structure is contacted with an amine solution, the proportion of free amino groups increases, and the combination of bonds between acetoacetate ester groups and amino groups is rearranged, improving fluidity and enabling separation of the structure. Furthermore, the resin in the resin composition can be depolymerized to a liquid.

[0128] In Separation Method I, only an acid solution or an amine solution may be used, or both an acid solution and an amine solution may be used. Examples of the acid solution include a hydrochloric acid solution. Examples of the amine solution include a solution containing a low-molecular-weight amine compound such as ethylenediamine or benzylamine. The low-molecular-weight amine compound may be dissolved in a solvent such as N-methylpyrrolidone (NMP).

[0129] In separation method I, the acid solution or amine solution may be heated (for example, heated to 25 to 100° C.) during contact in order to promote depolymerization of the resin.

[0130] In the separation method I, the contact may be immersing the structure in an acid solution or an amine solution, spraying the structure with an acid solution or an amine solution, etc. During the immersion, the structure may be stirred or left to stand.

[0131] The method for separating the structure is preferably a method including a step of heating the structure to separate the resin composition from the member (sometimes referred to herein as "separation method II"). Heating the structure improves fluidity by rearranging the bond combinations of the dynamic covalent bonds constituting the resin contained in the resin composition, specifically, in the case of vinylogous urethane bonds, the bond combinations between acetoacetate ester groups and amino groups. As a result, the structure can be separated. Furthermore, the dynamic covalent bonds of the resin in the resin composition can be depolymerized to form a liquid. As a result, the structure can be separated.

[0132] In Separation Method II, examples of the heating method include a method of simply heating the structure, an electromagnetic induction method, a laser method, etc. The heating temperature for separation is 50 to 200°C, for example. The heating time for separation is 5 seconds to 2 hours, for example.

[0133] The component and resin composition after the separation can be separated into the resin composition and / or decomposition products of the resin composition and the component (with no remaining resin composition on the surface of the component) by filtering using filter paper or the like and recovering the component.

[0134] [Method for Identifying Crosslinked Organic Structures Using Solid-State NMR] A method for identifying a crosslinked organic structure using solid-state NMR for a resin containing a dynamic covalent bond will be described. The method for identifying a crosslinked organic structure (e.g., free functional groups) of this embodiment is a method for identifying a crosslinked organic structure (e.g., the amount of free functional groups) using solid-state NMR for a resin containing a dynamic covalent bond. The resin containing a dynamic covalent bond may be the resin of this embodiment described above. Examples of the crosslinked organic structure to be identified include structures having vinylogous urethane, ester, imine, disulfide, and diketoenamine. In the above identification method, it is preferable to further quantify the amount of free functional groups constituting the dynamic covalent bond. Examples of the free functional groups include functional groups that are not incorporated into the Vitrimer bond described below and are in a free state. In the above identification method, it is preferable to immerse the resin in a measurement organic solvent for at least 3 hours, and to perform the identification within 48 hours from the start of immersion. The measurement organic solvent is preferably an aprotic solvent.

[0135] (Method for Quantifying the Amount of Functional Groups in a Free State without Being Incorporated into Vitrimer Bonds) The resin is preferably a Vitrimer having a structure that is three-dimensionally crosslinked by dynamic covalent bonds. In order for a Vitrimer to exhibit Vitrimer properties, the amounts of functional groups that make up the pair of dynamic covalent bonds (for example, in the case of vinylogous urethane bonds, the total amount of acetoacetic acid groups (Aa: mol) and the total amount of amine groups (Am: mol)) must be different, and it is known that |Aa - Am| = D > 0. The greater the difference (D), the more likely bond recombination occurs.

[0136] Using a Vitrimer consisting of vinylogous urethane bonds as an example, the method for determining the different degrees (D) will be explained below. Methods for quantifying free amino groups (i.e., unreacted functional groups not incorporated into vinylogous urethane bonds) include: i) decomposing the Vitrimerized resin and then quantifying using various measurement methods (chromatography, amine value measurement method), and ii) directly quantifying without decomposition (IR, NMR, etc.). However, decomposing a Vitrimerized resin increases the amount of free amino groups, which differs from the amount of free amino groups in the resin that was originally intended to be quantified. Therefore, a measurement method that can directly measure without decomposing the resin is preferred. Furthermore, because of its high quantitative accuracy, a measurement method that can directly measure the amount of free amino groups in the resin without decomposing the resin is preferred. １ A quantitative method using H-NMR is more preferred.

[0137] solid １ In the H-NMR measurement method, it is preferable to measure after immersing the resin to be measured in a solvent. This is because the resin swells in the solvent, improving the mobility of the main chain and improving the accuracy of peak separation. The immersion time is preferably 3 hours or more and 48 hours or less. If it is shorter than 3 hours, the resin will not fully swell, making accurate measurement impossible. If it is longer than 48 hours, the solvent used may volatilize, making accurate measurement impossible.

[0138] It is preferable to use an aprotic solvent as the solvent for immersing the resin. If a protic solvent is used, a side reaction may occur due to nucleophilic attack on the vinylogous urethane bonds in the resin, which may result in bond decomposition. This may change the amount of free amino groups before immersion in the solvent and the amount of free amino groups present. Preferred aprotic solvents include deuterated chloroform, deuterated methylene chloride, deuterated benzene, deuterated toluene, and deuterated acetone.

[0139] In addition, the above solid １ The H-NMR measurement method can be applied as a method for quantifying crosslinked organic structures (e.g., free functional groups) in a resin having a dynamic covalent bond, and can be applied to resins having dynamic covalent bonds such as ester bonds, disulfide bonds, imine bonds, and diketoenamine bonds.

[0140] (Method for quantifying free primary amines in a resin having a vinylogous urethane bond) Approximately 10 mg of a resin having a vinylogous urethane bond was cut into a size of 5 mm square or less, and the organic structure was analyzed under the above measurement conditions to identify the peak positions of the vinylogous urethane structure and the free amino group. The quantification of the free amino group was calculated as mol% of the functional group from the area ratio of the peak a derived from the vinylogous urethane structure of the bond species in the NMR spectrum. The proton a used in the calculation

[0141] (Method for quantifying free hydroxyl groups in a resin having an ester bond) Approximately 10 mg of a resin having an ester bond was cut into a size of 5 mm square or less, and the organic structure was analyzed under the above measurement conditions to identify the peak positions of the ester structure and the free hydroxyl group. The quantification of the free hydroxyl group was calculated as mol% of the functional group from the area ratio of the peak b derived from the following ester structure of the bond species in the NMR spectrum. The proton b used in the calculation

[0142] (Method for quantification of free amino groups in resin having imine bonds) Approximately 10 mg of resin having imine bonds was cut into a size of 5 mm square or less, and the organic structure was analyzed under the above measurement conditions to identify the peak positions of the imine structure and free amino groups. The quantification of free amino groups was calculated as mol% of functional groups from the area ratio of peak c derived from the following imine structure of the bonded species in the NMR spectrum. The proton c used in the calculation

[0143] (Method for quantifying free thiol groups in a resin having disulfide bonds) Approximately 10 mg of a resin having disulfide bonds was cut into a size of 5 mm square or less, and the organic structure was analyzed under the above measurement conditions to identify the peak positions of the disulfide structure and free thiol groups. The quantification of free thiol groups was calculated as mol% of functional groups from the area ratio of peak d derived from the following disulfide group of the bond species in the NMR spectrum. The proton d used in the calculation

[0144] (Method for quantifying free primary amino groups in a resin having a diketoenamine bond) Approximately 10 mg of a resin having a diketoenamine bond was cut into a size of 5 mm or less, and the organic structure was analyzed under the above measurement conditions to identify the peak positions of the diketoenamine structure and the free amino group. The free primary amino group was quantified as mol% of the functional group from the area ratio of the peak e derived from the diketoenamine structure of the bond species in the NMR spectrum. The proton e used in the calculation

[0145] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0146] [Evaluation] The resins obtained in the examples and comparative examples were subjected to the following measurements.

[0147] (Crosslink density) The crosslink density (mol / m ３ ) was calculated as follows: c = n × d / W (where c is the crosslink density [mol / m ３ ], n is the number of moles of the polyfunctional monomer [mol], d is the density of the resin [1 × 10 ６ g / m ３ ], and W is the total mass [g] of the monomers.) The number of moles of the polyfunctional monomer was measured by hydrolyzing the resin obtained in the Examples or Comparative Examples and quantifying the resulting monomer.

[0148] (Method for calculating crosslink density from resin decomposition and component analysis) Resin containing vinylogous urethane bonds The resin was immersed in a 1M aqueous hydrochloric acid solution and subjected to an acid hydrolysis reaction at 60°C. The resulting decomposition solution was separated with ethyl acetate, and the organic and aqueous layers were recovered. The organic solvent was distilled off from the organic layer, and it was confirmed by IR and NMR that it was the raw material acetoacetic acid compound. Meanwhile, the aqueous layer was neutralized with an aqueous sodium bicarbonate solution and then distilled (or distilled under reduced pressure) to obtain the raw material amine compound. It was confirmed by IR and NMR that it was the raw material amine compound. After the resin was subjected to a hydrolysis reaction using an acid and a base, the compound species were identified from the separated and recovered decomposition products by infrared absorption spectroscopy, mass spectroscopy, and nuclear magnetic resonance spectroscopy. Next, the molar ratio of each compound was calculated using a calibration curve method by gas chromatography mass spectrometry, and the molar ratio was then calculated by introducing it into the following formula: c = n × d / W (where c is the crosslink density [mol / m ３ ], n is the number of moles of the polyfunctional monomer [mol], d is the density of the resin [1 × 10 ６ g / m ３ ], W is the total mass of the monomers [g].

[0149] Resins containing imine bonds or diketoenamine bonds are hydrolyzed in an acidic or basic aqueous solution in the same manner as resins containing vinylogous urethane bonds. Monomer components are separated, recovered, and identified from the resulting hydrolysis solution. i) In the case of a resin containing an imine bond, the aforementioned acetoacetic ester group is replaced with an aldehyde group, and ii) in the case of a resin containing a diketoenamine bond, the aforementioned acetoacetic ester group is replaced with a triketone group, and the crosslink density can be determined by carrying out the same quantitative operation.

[0150] Resins containing ester bonds: Similar to resins containing vinylogous urethane bonds, these resins are hydrolyzed in an acidic or basic aqueous solution. Subsequently, various decomposition products are separated, recovered, and identified as monomer components from the resulting hydrolysis solution. Specifically, (multifunctional) epoxy ring-opening compounds (containing -OH groups) or (multifunctional) carboxylic acid compounds (containing -COOH groups) are identified and quantified. Crosslink density c [mol / m ３] is the ratio of the confirmed amount of polyfunctional component n [mol] to the amount of resin w [g] used in this quantitative operation and the resin density d [1 × 10 ６ g / m ３ ] can be calculated from the following formula: c = n × d / w

[0151] Resins containing disulfide bonds: Similar to resins containing vinylogous urethane bonds, these resins are hydrolyzed in an acidic or basic aqueous solution. Subsequently, various decomposition products are separated, recovered, and identified as monomer components from the resulting hydrolysis solution. The monomer components identified and quantified at this time may include (multifunctional) epoxy ring-opening compounds (containing -OH groups) and (multifunctional) carboxylic acid compounds (containing -COOH groups). Crosslink density c [mol / m ３ ] is the ratio of the confirmed amount of polyfunctional component n [mol] to the amount of resin w [g] used in this quantitative operation and the resin density d [1 × 10 ６ g / m ３ ] can be calculated from the following formula: c = n × d / w

[0152] (Bond Density) The bond density (mol / m ３ Vc = Vn × Vd / VW (where Vc is the bond density [mol / m ３ ], Vn is the number of moles of dynamic covalent bonds [mol], Vd is the density of the resin [1 × 10 ６ g / m ３ ], VW is the total mass [g] of the monomers.) The number of moles of dynamic covalent bonds was measured by hydrolyzing the resin obtained in the Examples or Comparative Examples and quantifying the resulting monomers. Note that, for example, in the case of an excess amount of amine groups, n may be the functional group amount [mol] of acetoacetic ester groups.

[0153] (Glass Transition Temperature) The glass transition temperature Tg (°C) of the resin obtained in the Examples or Comparative Examples was measured by differential scanning calorimetry. Specifically, using a differential scanning calorimeter (DSC) (Perkin-Elmer "Pyris-1"), the resin was heated from -30°C to 250°C at a heating rate of 20°C / min under a nitrogen atmosphere, then cooled to -30°C at 20°C / min, and then heated at a heating rate of 20°C / min to measure the glass transition temperature Tg (°C).

[0154] (Method for Confirming Dynamic Covalent Bonds) The resins obtained in the Examples and Comparative Examples were identified using an infrared spectrophotometer (IR) ("Fourier Transform Infrared Spectrophotometer FT / IR-4100" manufactured by JASCO Corporation), and analyzed to determine whether the resins contained dynamic covalent bonds such as vinylogous urethane bonds, imine bonds, ester bonds, disulfide bonds, and diketoenamine bonds.

[0155] (Gel Fraction) The resins obtained in the Examples and Comparative Examples were precisely weighed, then wrapped in a 120 mesh (opening 0.132 mm) wire netting and precisely weighed. The wire netting-wrapped sample was immersed in a vial containing tetrahydrofuran (THF) solvent and allowed to stand for 24 hours. The wire netting-wrapped sample was removed from the vial and dried in a vacuum dryer at 60°C for 4 hours. The wire netting-wrapped sample was precisely weighed, and the gel fraction was calculated using the following formula: Gel Fraction (%) = M2 / M1 x 100 M1: Mass of the sample before immersion in tetrahydrofuran M2: Mass of the sample after immersion in tetrahydrofuran and drying

[0156] (solid １ Amount of free functional groups determined by H-NMR) The resins having dynamic covalent bonds obtained in the Examples and Comparative Examples (sample amount: approximately 10 mg) were cut into pieces of approximately 5 mm square or less using scissors or the like, placed in NMR sample tubes, and immersed in deuterated chloroform, an aprotic solvent, for 3 hours or more. The measurement conditions were as follows, and measurements were taken within 48 hours from the start of swelling. The quantitative values ​​were calculated as the amount of free functional groups corresponding to each bond type (in the case of vinylogous urethane, imine, and diketoenamine, the molar ratio of free primary amino groups to each bond type; in the case of esters, the molar ratio of free hydroxyl groups to ester groups; and in the case of disulfide bonds, the molar ratio of free thiol groups to disulfide groups). Measurement temperature: 25°C Apparatus: Bruker Biospin Avance500 Frequency: 500.1 MHz Measurement method: Single pulse method Waiting time: 5 seconds MAS rotation speed: 8 kHz NMR sample tube: 4 mmφ Number of accumulations: 128 Chemical shift reference: TMS (0.0 ppm). The free functional groups in the table are values ​​calculated from the weight of raw materials charged, and the solid １The amount of free functional groups determined by H-NMR is a value measured by the method described above.

[0157] (Adhesive Strength) When using a film, a sample was prepared using the following method. The resins obtained in the Examples and Comparative Examples were dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours. The resulting resin was crushed, pressed in a heat press (temperature setting: 160°C, pressure setting: 3 MPa) for 25 minutes, and cut out to obtain a film measuring 60 mm x 60 mm x 0.2 mm thick. The film was sandwiched between two adherends (electrodeposition-coated metal plates, product name "SPCC-SD 1.6*25*100 φ5-1 Laser Cationic Electrodeposition Coating (Black)", manufactured by Standard Test Piece Co., Ltd.) and secured with double clips. When coating was used, a sample was prepared using the following method. The mixed solution of monomer raw materials used in synthesizing the resins in the examples and comparative examples was applied at 200 g / m onto an adherend (electrodeposition-coated metal plate, product name "SPCC-SD 1.6*25*100 φ5-1 laser cation electrodeposition coating (black)" manufactured by Standard Test Piece Co., Ltd.). ２ The adhesive was applied at a ratio of 0.05 to 0.05 mm. Then, to make the thickness uniform when using the above-mentioned film, a Teflon (registered trademark) spacer (dimensions: 25 mm x 5 mm x thickness 0.05 mm, product name "Skived Tape 0.05t x 300w x 10m", manufactured by Chukoh Chemical Industry Co., Ltd.) was placed on top of the film, and the same adherend was placed on top and secured with double clips. The film or coated sample was heated in a vacuum dryer at 190°C for 1.5 hours to prepare a measurement sample. Then, in accordance with JIS K6850, the adhesive strength (MPa) was measured using an Instron material testing machine 5967. Note that the adhesive position is shifted due to the Teflon (registered trademark) spacer sandwiched between the two to make the thickness uniform, which differs from JIS. The adhesive strength was evaluated according to the following criteria. A (Excellent): 25 MPa or more B (Good): 15 MPa or more and less than 25 MPa C (Practical): 10 MPa or more and less than 15 MPa D (Not practical): Less than 10 MPa

[0158] (Adhesive Strength, Measurement Method II) A sample prepared by film or coating was heated in a vacuum dryer at 190°C for 0.5 hours, and then stored in an environment of 23°C and 50% RH to prepare a measurement sample. Then, in accordance with JIS K6850, adhesive strength (MPa) was measured using an Instron 5967 material testing machine. Note that this method differs from JIS in that a Teflon (registered trademark) spacer was inserted to make the thickness uniform, resulting in misalignment of the adhesive position. A steel plate (SPCC-SD) was used as the adherend, and the surface was polished with sandpaper, and 200 g / m ２ The adhesive strength and dismantling property of the resin of Example 1 were evaluated for the steel plate using the resin of Example 1, and this was used to evaluate the adhesive strength and dismantling property of the resin of Example 17. The evaluations for Example 18 and subsequent examples were performed according to the compositions in the table. A (Excellent): 15 MPa or more B (Good): 9 MPa or more and less than 15 MPa C (Practical): 5 MPa or more and less than 9 MPa D (Not Practical): Less than 5 MPa

[0159] (Dismantling Ease) Measurement samples were prepared in the same manner as for the adhesive strength described above. The measurement samples were clamped in a tabletop press heated to 150°C and heated for 5 minutes. Then, dismantling ease was evaluated according to the way the test pieces peeled off, using the following criteria: A (Excellent): The adherend and resin separated as soon as the measurement sample was lifted from the press. B (Good): The adherend and resin separated with only slight force applied by hand. C (Practical): The adherend and resin separated when strong force was applied by hand. D (Not practical): They did not peel off even when force was applied.

[0160] The methods for preparing the resins of the examples and comparative examples will be described below.

[0161] (Example 1) (Production of Resin Composition) Ethylene glycol (18.6 g) and tert-butyl acetoacetate (100 g) were placed in a 300 mL four-neck flask, and N ２The mixture was stirred with a stirring blade under a flow. The temperature was then raised to an external temperature of 130°C in an oil bath, and the pressure inside the system was gradually reduced to 68 hPa. After heating and reducing the pressure for 4 hours, the external temperature was set to 130°C and the reduced pressure was set to 3 hPa in order to distill off unreacted tert-butyl acetoacetate. After heating and reducing the pressure for 2 hours, the mixture was allowed to cool to room temperature, and the bis(ethylene glycol) acetoacetate (EGAA) in the flask was recovered (66.3 g). TREN (0.64 g) and HMDA (4.36 g) were dissolved in ethanol (8.4 mL). The EGAA (10.0 g) obtained above was added to this solution and stirred. Before solidification, the mixture was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like, and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The resulting resin composition was identified by IR, and it was confirmed that it contained a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) The resulting resin composition was pulverized and pressed in a press ("SA-301" manufactured by Tester Sangyo Co., Ltd.) at a temperature of 160°C and a pressure of 3 MPa for 10 minutes to prepare a sheet (60 mm x 60 mm x 1.0 mm thick), which was then punched out to obtain a sample piece. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0162] (Example 2) (Production of Resin Composition) EGAA was obtained in the same manner as in Example 1. TREN (1.21 g) and HMDA (3.85 g) were dissolved in ethanol (8.0 mL). The EGAA (10.0 g) obtained above was added to this solution and stirred to allow a reaction. The mixture was then dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The resulting resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Production of Film) The resulting resin composition was pulverized and pressed in a press ("SA-301" manufactured by Tester Sangyo Co., Ltd.) at a temperature of 160°C and a pressure of 3 MPa for 10 minutes to produce a film (60 mm x 60 mm x 0.25 mm thick). (Production of Sample for Stress Relaxation Measurement) Sample pieces were prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0163] Example 3 (Production of Resin Composition) EGAA was obtained in the same manner as in Example 1. TREN (0.32 g) and trimethylhexamethylenediamine (2,2,4-,2,4,4-mixture) (TMHMDA, 3.09 g) were dissolved in ethanol (7 mL). EGAA (5.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was characterized by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0164] (Example 4) (Production of Resin Composition) EGAA was obtained in the same manner as in Example 1. JEFFAMINE T-403 (manufactured by Huntsman) (1.72 g) and MXDA (4.79 g) were dissolved in ethanol (5.8 mL). The EGAA (9.0 g) obtained above was added to this solution and stirred to allow a reaction. The mixture was then dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR, and it was confirmed to contain a crosslinked resin having a VU bond. (Production of Film) A film (60 mm x 60 mm x 0.25 mm thick) was produced in the same manner as in Example 2. (Production of Sample for Stress Relaxation Measurement) A sample piece was produced in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0165] (Example 5) (Production of Resin Composition) Trimethylolpropane (65 g) and tert-butyl acetoacetate (268 g) were placed in a 300 mL four-neck flask, and N ２The mixture was stirred with a stirring blade under a flow. Thereafter, the temperature was raised to an external temperature of 140°C in an oil bath, and the pressure inside the system was gradually reduced to 68 hPa. After heating and reducing the pressure for 4 hours, the external temperature was set to 130°C and the reduced pressure was set to 3 hPa in order to distill off unreacted tert-butyl acetoacetate. After heating and reducing the pressure for 2 hours, the mixture was allowed to cool to room temperature, and tris(trimethylolpropane acetoacetate) (TMPAA) (182 g) was recovered from the flask. 1,4-cyclohexanedimethanol (48.5 g) and tert-butyl acetoacetate (160 g) were placed in a 300 mL four-neck flask, and N ２ The mixture was stirred with a stirring blade under a flow. Thereafter, the temperature was raised to an external temperature of 140°C in an oil bath, and the pressure inside the system was gradually reduced to 68 hPa. After heating and reducing the pressure for 4 hours, the external temperature was set to 130°C and the reduced pressure was set to 3 hPa in order to distill off unreacted tert-butyl acetoacetate. After heating and reducing the pressure for 2 hours, the flask was allowed to cool to room temperature and 1,4-cyclohexanedimethanol bisacetoacetate (CHDMAA) (107 g) was recovered from the flask. 1,4-Cyclohexanedimethanol bisacetoacetate (CHDMAA) (7.27 g) and TMPAA (1.0 g) were dissolved in ethanol (16 mL). 4,4'-methylenebis(cyclohexylamine) (MBCA; 6.0 g) was added to this solution and stirred to cause a reaction. The mixture was then dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and was confirmed to contain a crosslinked resin having a VU bond. (Preparation of film) A film (60 mm x 60 mm x 0.25 mm thick) was prepared in the same manner as in Example 2. (Preparation of sample for stress relaxation measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0166] (Example 6) (Production of Resin Composition) EGAA was obtained in the same manner as in Example 1. TREN (0.32 g) and MXDA (2.66 g) were dissolved in ethanol (8.0 mL). EGAA (5.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0167] (Example 7) (Production of Resin Composition) Propanediol (50 g) and tert-butyl acetoacetate (311 g) were placed in a 300 mL four-neck flask, and N ２ The mixture was stirred with a stirring blade under flow. The temperature was then raised to 140°C in an oil bath, and the pressure in the system was gradually reduced to 68 hPa. After heating and reducing the pressure for 4 hours, the system was heated to 130°C and reduced pressure was set to 3 hPa to distill off unreacted tert-butyl acetoacetate. After heating and reducing the pressure for 2 hours, the system was allowed to cool to room temperature, and trisacetoacetic acid propanediol ester (PGAA) (152 g) was recovered from the flask. TREN (0.16 g) and 4,4'-methylenebis(cyclohexylamine) (MBCA, 2.09 g) were dissolved in ethanol (5.0 mL). PGAA (3.0 g) was added to this solution and stirred, allowing it to react. Before solidification, the mixture was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of sample for stress relaxation measurement) Sample pieces were prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0168] Example 8 EGAA was obtained in the same manner as in Example 1. TREN (0.24 g) and 4,4'-methylenebis(cyclohexylamine) (MBCA, 1.39 g) were dissolved in ethanol (4.0 mL). EGAA (2.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was characterized by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0169] (Example 9) (Production of resin composition and preparation of adhesive specimen) EGAA was obtained in the same manner as in Example 1. The EGAA (10.0 g) obtained above was added to a mixed solution of TREN (0.64 g) and HMDA (4.36 g), and the mixture was stirred to cause a reaction. Before the reaction solution solidified, it was applied to an adherend, which was then clipped and heated at 190°C for 1.5 hours to prepare a measurement specimen. The measurement and evaluation results are shown in Tables 1 to 4.

[0170] Example 10 EGAA was obtained in the same manner as in Example 1. TREN (0.64 g) and HMDA (3.57 g) were dissolved in ethanol (10.6 mL). EGAA (8.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0171] (Example 11) EGAA was obtained in the same manner as in Example 1. TREN (0.25 g) and TMHMDA (1.06 g) were dissolved in ethanol (4.0 mL). EGAA (2.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0172] Example 12 EGAA was obtained in the same manner as in Example 1. TREN (1.41 g) and HMDA (2.64 g) were dissolved in ethanol (23.6 mL). EGAA (8.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0173] Example 13: Ester: A 100 mL round-bottom flask was charged with Pripol 1040 (16.63 g) and 10 mol % zinc acetate dihydrate (Zn(Ac)) based on COOH groups. ２ ・2H ２0) was added, and the temperature was gradually increased from 100°C to 180°C under vacuum. The mixture was left at 180°C under vacuum for approximately 3 hours until gas generation ceased, yielding a mixed solution. The resulting mixed solution, DGEBA (9.25 g), and butyl acetate (20 mL) were added to a PTFE beaker, and reacted by heating to 100°C and stirring until phase miscibility occurred. The mixture was then dried in a vacuum dryer at 80°C for 2 hours and at 150°C for 4 hours to yield a resin composition. (Film Production) A film (60 mm x 60 mm x 0.25 mm thick) was produced in the same manner as in Example 2. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0174] (Example 14: Imine) A mixed solution of terephthalaldehyde (6.70 g; 49.97 mmol), ethyl acetate (2.0 mL), and ethanol (10.0 mL) was prepared, and a solution prepared by dissolving diethylenetriamine (3.92 g; 38.00 mmol) and TREN (1.32 g; 9.0 mmol) in ethanol (10.0 mL) was added dropwise thereto and allowed to react. The mixture was then dried in a vacuum dryer at 75°C for 1 hour, 85°C for 2 hours, and 105°C for 2 hours to obtain a resin composition. (Film Preparation) A film (60 mm x 60 mm x 0.25 mm thick) was prepared in the same manner as in Example 2. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0175] (Example 15: Disulfide) DGEBA (8.51 g) and bis(3-carboxypropyl) disulfide (DTDA; 6.28 g) were placed in a PTFE beaker and stirred at 100°C until homogenous. The resulting solution was poured into a 100 mm x 100 mm mold and cured at 180°C for 4 hours to obtain a sheet-shaped sample. The resulting resin composition was identified by IR, and it was confirmed to contain a crosslinked resin having a disulfide bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results for each physical property are shown in Tables 1 to 4.

[0176] Example 16: Synthesis of triketone (TK) compound. Dimedone (74 g, 0.53 mol), adipic acid (37 g, 0.25 mol), and DMAP (92 g, 0.75 mol) were dissolved in methylene chloride (250 mL), and a solution of DCC (124 g, 0.60 mol) dissolved in methylene chloride (600 mL) was added. The reaction was carried out at room temperature for 4 hours. The precipitated white solid was removed by filtration, and a 3 wt% aqueous hydrochloric acid solution was added to separate the layers. The organic layer was recovered by removing the solvent from the resulting organic layer, yielding a pale yellow solid. Recrystallization was carried out using a mixed solvent of ethyl acetate and hexane to obtain a white solid (87.9 g, 90% yield). TREN (0.41 g) and HMDA (2.96 g) were dissolved in ethanol (8.4 mL). The TK (10.54 g) obtained above was added to this solution and stirred. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a diketoenamine bond. (Preparation of Sample for Stress Relaxation Measurement) Sample pieces were prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0177] (Comparative Example 1) EGAA was obtained in the same manner as in Example 1. TREN (0.10 g) and 4,4'-methylenebis(cyclohexylamine) (MBCA; 1.84 g) were dissolved in ethanol (4.0 mL). EGAA (2.2 g) was added to this solution and stirred to allow a reaction. The mixture was then dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Film Preparation) A film (60 mm x 60 mm x 0.25 mm thick) was prepared in the same manner as in Example 2. (Sample Preparation for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results for each physical property are shown in Tables 1 to 4.

[0178] (Comparative Example 2) (Production of Resin Composition) EGAA was obtained in the same manner as in Example 1. TREN (0.53 g) and TMHMDA (0.58 g) were dissolved in ethanol (3.0 mL). EGAA (2.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0179] (Comparative Example 3) (Production of Resin Composition) EGAA was obtained in the same manner as in Example 1. JEFFAMINE T-403 (manufactured by Huntsman) (1.18 g) and MXDA (4.85 g) were dissolved in ethanol (5.8 mL). EGAA (9.0 g) was added to this solution and stirred to allow a reaction. Before solidification, the solution was applied to a polypropylene plate using a bar coater and allowed to stand. After solidification, the film was peeled off from the glass plate or the like and dried in a vacuum dryer at 80°C for 2 hours and at 160°C for 4 hours to obtain a resin composition. The obtained resin composition was identified by IR and confirmed to contain a crosslinked resin having a VU bond. (Preparation of Sample for Stress Relaxation Measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0180] Comparative Example 4 Propylene glycol 400 (120 g) and tert-butyl acetoacetate (100 g) were placed in a 300 mL four-neck flask, and N ２The mixture was stirred with a stirring blade under flow. Thereafter, the temperature was raised to an external temperature of 130 ° C. in an oil bath, and the pressure inside the system was gradually reduced to 68 hPa. After heating and reducing the pressure for 4 hours, the external temperature was set to 130 ° C. and the reduced pressure was set to 3 hPa in order to distill off unreacted tert-butyl acetoacetate. After heating and reducing the pressure for 2 hours, the mixture was allowed to cool to room temperature and the bis(propylene glycol) acetoacetate (PPG (400) AA) in the flask was recovered (164 g). PPG (400) AA (2.0 g) was added to 2.0 mL of methanol and heated to 65 ° C. to dissolve. TREN (0.35 g) was added to this solution and stirred to allow the reaction. The mixture was then dried in a vacuum dryer at 80 ° C. for 2 hours and at 150 ° C. for 4 hours to obtain a resin composition. The resulting resin composition was identified by IR, and it was confirmed that it contained a crosslinked resin having a VU bond. (Preparation of film) A film (60 mm x 60 mm x 0.25 mm thick) was prepared in the same manner as in Example 2. (Preparation of sample for stress relaxation measurement) A sample piece was prepared in the same manner as in Example 1. The measurement and evaluation results of each physical property are shown in Tables 1 to 4.

[0181]

[0182]

[0183]

[0184] Regarding thermal dismantling, Tables 1 to 4 show that the Examples with high adhesive strength exhibited dismantling properties despite their high adhesive strength. On the other hand, the Comparative Examples, which had low adhesive strength to begin with, were easily dismantled due to their low adhesive strength, and it is clear that there is a clear difference between the two.

[0185] The resin of the present invention has flowability, excellent adhesive strength, and also has dismantling properties, and therefore can be used as an adhesive or the like.

[0186] Invention (II) will be described below. The matters described in Invention (II) may be incorporated into the above-mentioned invention.

[0187] Invention (II) relates to a mixture containing at least one of a compound, an oligomer thereof, and a polymer thereof, a method for producing the same, and a dynamic covalent network polymer synthesized from the compound, the oligomer thereof, and / or the polymer thereof.

[0188] Conventionally, adhesives, including adhesives for structural members, have been required to have stronger adhesive strength, better durability, and heat resistance, and tolerant to temperature fluctuations, and development has been progressing accordingly. However, in recent years, from the viewpoints of resource reuse and environmental issues, there has been a demand for the development of adhesives that allow bonded structural members to be disassembled by some kind of treatment after use, in order to reuse the bonded structural members.

[0189] Thermoplastic adhesives, whose constituent resins are thermoplastic resins, soften when heated, making it relatively easy to dismantle structural components by physically peeling the adherends, but it is difficult to achieve sufficient adhesive strength as an adhesive. On the other hand, thermosetting adhesives, whose constituent resins are thermosetting resins, have sufficient adhesive strength as an adhesive, but in principle, it is difficult to sever molecular bonds, which requires a great deal of energy to sever bonds and can destroy structural components, making it impossible to dismantle structural components in many cases. Therefore, there is a demand for adhesives that combine adhesive strength with the ease of dismantling structural components. One possible way to achieve both is to introduce cleavable functional groups into the thermosetting resin. As such a resin, for example, vitrimer is known (see, for example, Science 2011, 334, 965-968), and resins having a vinylogous urethane bond as a cleavable weak bond (see, for example, Chem. Sci. 2016, 7, 30-38.) or an imine bond have been reported (see, for example, WO 2020 / 051506).

[0190] However, there is much room for improvement in the development of adhesives that maintain adhesiveness while also having dismantling properties (the ability to easily dismantle adherends joined with the adhesive).

[0191] In view of the state of the prior art, the problem to be solved by the present invention is to provide a dynamic covalent bond network polymer having sufficient adhesiveness and dismantling properties, a novel compound capable of synthesizing the dynamic covalent bond network polymer, an oligomer thereof, and a mixture containing at least one of the polymers, and a method for producing the same.

[0192] That is, invention (II) is as follows: [1] A mixture comprising at least one of a compound (1) having two or more partial skeletons (1-1) represented by the following general formula (1-1), an oligomer thereof, and a polymer thereof, wherein the partial skeletons (1-1) may be the same or different from each other. (In the general formula (1-1), A is an oxygen atom, a sulfur atom, a nitrogen atom, or a carbon atom; X is a hydrocarbon group which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group; Y is —N(R ２ ) ２ , —OH, —COOH, an epoxy group, an isocyanate group, or —SH, and R ２ are each independently a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, １represents a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, and the wavy line represents a bonding point to the portion of the compound (1) other than the partial skeleton (1-1). [2] The mixture according to [1], wherein the X is a hydrocarbon group having 2 to 18 carbon atoms which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group. [3] The mixture according to [1], wherein the portion of the compound (1) other than the partial skeleton (1-1) is a hydrocarbon group having a number average molecular weight of 30 to 10,000 which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group. [4] The mixture according to [1], wherein the A is an oxygen atom. [5] The mixture according to [1], wherein X is a hydrocarbon group having 2 to 18 carbon atoms which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group, and the portion of the compound (1) other than the partial skeleton (1-1) is a hydrocarbon group having a number average molecular weight of 30 to 10,000 which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group, and A is an oxygen atom. [6] The mixture according to [1], wherein Y is -N(R ２ ) ２ , —OH, —COOH, an isocyanate group, or —SH. [7] A dynamic covalent network polymer comprising a structural unit derived from the compound, its oligomer, or its polymer contained in the mixture according to any one of [1] to [6], and a structural unit derived from an independent crosslinking agent containing a reactive moiety selected from the group consisting of epoxy, urea, (poly)urethane, isocyanate, bismaleimide, sulfide, anhydride, (poly)ol, and combinations thereof. [8] A molded article comprising the dynamic covalent network polymer according to [7]. [9] A method for producing a mixture comprising at least one of compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), its oligomer, and its polymer, comprising a step of reacting compound (2) having two or more partial skeletons (2-1) represented by general formula (2-1) with compound (3) represented by general formula (3): (In the general formulae (1-1), (2-1), and (3), A represents an oxygen atom, a sulfur atom, a nitrogen atom, or a carbon atom; * represents a bonding point to a portion of the compound (2) other than the partial skeleton (2-1); X represents a hydrocarbon group which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group; Y represents -N(R ２ ) ２ , —OH, —COOH, an epoxy group, an isocyanate group, or —SH, and R ２ are each independently a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, １ represents a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, and the wavy line represents a bonding point to a portion of the compound (1) other than the partial skeleton (1-1).

[0193] According to invention (II), it is possible to provide a dynamic covalent bond network polymer having sufficient adhesiveness and dismantling properties, a novel compound capable of synthesizing the dynamic covalent bond network polymer, an oligomer thereof, and a mixture containing at least one of the polymers, and a method for producing the same.

[0194] Hereinafter, a mode for carrying out the invention (II) (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content.

[0195] <Mixture> The mixture of this embodiment is characterized in that it contains at least one of a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), an oligomer of the compound, and a polymer of the compound, wherein the partial skeletons (1-1) may be the same or different from one another. The mixture of this embodiment may contain only a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), only an oligomer of the compound (1), or only a polymer of the compound (1), or may contain two or all three of these. Note that when the compound (1) is a compound that is prone to oligomerization and polymerization over time, two or more of the compound (1), its oligomer, and its polymer are often present in a mixed state.

[0196] (In the general formula (1-1), A is an oxygen atom, a sulfur atom, a nitrogen atom, or a carbon atom; X is a hydrocarbon group which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group; Y is —N(R ２ ) ２ , —OH, —COOH, an epoxy group, an isocyanate group, or —SH, and R ２ are each independently a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, １ represents a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, and the wavy line represents a bonding point to a portion of compound (1) other than the partial skeleton (1-1).

[0197] In the above general formula (1-1), A is an oxygen atom, a sulfur atom, a nitrogen atom, or a carbon atom, and is preferably an oxygen atom.

[0198] In the general formula (1-1), X represents a hydrocarbon group, preferably an aliphatic group, which may be linear or branched, saturated or unsaturated. X may also contain a heteroatom, an alicyclic group, or an aromatic ring group. Examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, chlorine, iodine, and bromine atoms. The alicyclic group is preferably an alicyclic group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The aromatic ring group is preferably an aromatic ring group having 6 to 20 carbon atoms, such as a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, a fused ring group such as a naphthalene ring group, and an anthracene ring group, and an aromatic heterocyclic group such as a pyridine ring group. X preferably has 1 to 18 carbon atoms, more preferably 2 to 16 carbon atoms, and even more preferably 2 to 14 carbon atoms.

[0199] In the general formula (1-1), Y is —N(R ２ ) ２ , —OH, —COOH, an epoxy group, an isocyanate group, or —SH, and preferably —N(R ２ ) ２ , —OH, —COOH, an isocyanate group, or —SH, and particularly preferably —N(R ２ ) ２ It is. ２ are each independently a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group. ２ When R is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 8 carbon atoms, and even more preferably a linear alkyl group having 1 to 4 carbon atoms. ２ When R is an alicyclic group, it is preferably an alicyclic group having 3 to 20 carbon atoms, more preferably an alicyclic group having 4 to 20 carbon atoms, and even more preferably an alicyclic group having 5 to 18 carbon atoms. ２ When R is an aromatic ring group, it is preferably an aromatic ring group having 6 to 20 carbon atoms, more preferably an aromatic ring group having 6 to 18 carbon atoms, and even more preferably an aromatic ring group having 6 to 16 carbon atoms. ２It is particularly preferred that both of Y and Y are hydrogen atoms. In particular, when Y is —OH, bond exchange reactions over time are unlikely to occur between compounds (1) having two or more partial skeletons (1-1) represented by general formula (1-1), and therefore oligomerization or polymerization is unlikely to proceed, and compounds (1) having two or more partial skeletons (1-1) represented by general formula (1-1) tend to have excellent storage stability.

[0200] In the above general formula (1-1), R １ is a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group. １ When R is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 8 carbon atoms, and even more preferably a linear alkyl group having 1 to 4 carbon atoms. １ When R is an alicyclic group, it is preferably an alicyclic group having 3 to 20 carbon atoms, more preferably an alicyclic group having 3 to 18 carbon atoms, and even more preferably an alicyclic group having 3 to 16 carbon atoms. １ When R is an aromatic ring group, it is preferably an aromatic ring group having 6 to 20 carbon atoms, more preferably an aromatic ring group having 6 to 18 carbon atoms, and even more preferably an aromatic ring group having 6 to 16 carbon atoms. １ is particularly preferably a hydrogen atom.

[0201] The methyl group in the above general formula (1-1) may be other alkyl groups such as an ethyl group, a propyl group, an isopropyl group, or a butyl group.

[0202] The number of partial skeletons (1-1) is 2 or more, preferably 2 to 4, and more preferably 2 to 3. The partial skeletons (1-1) may be the same or different from one another. That is, they may all have the same structure, or they may all have different structures, or only some of them may have the same structure.

[0203] The partial skeleton (1-1) is bonded to a portion of the compound (1) other than the partial skeleton (1-1) via the wavy line in the general formula (1-1) above, which serves as the bonding point. The portion other than the partial skeleton (1-1) refers to the portion of the compound (1) excluding all of the partial skeletons (1-1). In the portion other than the partial skeleton (1-1), the bonding point to the partial skeleton (1-1) is not particularly limited, and the partial skeleton (1-1) may be bonded to any atom. For example, the partial skeleton (1-1) may be bonded to any carbon atom in the portion other than the partial skeleton (1-1), and may include a case in which all of the partial skeletons (1-1) are bonded to one carbon atom, a case in which a plurality of partial skeletons (1-1) are bonded to each of a plurality of carbon atoms, or a case in which one partial skeleton (1-1) is bonded to each of a plurality of carbon atoms.

[0204] The portion other than the partial skeleton (1-1) is preferably an optionally substituted hydrocarbon group. The hydrocarbon group is more preferably an aliphatic group, and may be either linear or branched, and may be either saturated or unsaturated. Furthermore, when the portion other than the partial skeleton (1-1) is a partially substituted hydrocarbon group, it may partially contain, for example, a heteroatom, an alicyclic group, or an aromatic ring group. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, chlorine atoms, iodine atoms, and bromine atoms. Examples of the alicyclic group include an alicyclic group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aromatic ring group include an aromatic ring group having 6 to 20 carbon atoms, such as a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, a fused ring group such as a naphthalene ring group, and an anthracene ring group, and an aromatic heterocyclic group such as a pyridine ring group. The number average molecular weight (Mn) of the portion of compound (1) other than the partial skeleton (1-1) is preferably 30 to 10,000, more preferably 30 to 9000, and even more preferably 30 to 8000. The number average molecular weight of Z can be measured using gel permeation chromatography (GPC).

[0205] When a compound (1), an oligomer, or a polymer thereof having two or more partial skeletons (1-1) represented by general formula (1-1) is heated, a bond exchange reaction occurs between the compound, the oligomer, and the polymer. Therefore, a dynamic covalent network polymer containing structural units derived from the compound, the oligomer, or the polymer exhibits excellent fluidity and self-repairing properties under certain temperature conditions.

[0206] Furthermore, when a monofunctional low molecular weight compound is added to a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), its oligomers, and polymers, a bond exchange reaction occurs in the partial skeletons (1-1) and the compound disintegrates. Therefore, a dynamic covalent network polymer containing structural units derived from the compound, its oligomer, or its polymer exhibits excellent disintegration properties. Examples of the bond exchange reaction include amine exchange and hydrolysis, as shown below.

[0207] <Method for Producing Mixture> The method for producing the mixture of the present embodiment is not particularly limited, but includes, for example, a step of reacting a compound (2) having two or more partial skeletons (2-1) represented by the following general formula (2-1) with a compound (3) represented by general formula (3). (In the general formulae (1-1), (2-1), and (3), A represents an oxygen atom, a sulfur atom, a nitrogen atom, or a carbon atom; * represents a bonding point to a portion of the compound (2) other than the partial skeleton (2-1); X represents a hydrocarbon group which may partially contain a heteroatom, an alicyclic group, or an aromatic ring group; Y represents —N(R ２ ) ２ , —OH, —COOH, an epoxy group, an isocyanate group, or —SH, and R ２ are each independently a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, １ represents a hydrogen atom, an alkyl group, an alicyclic group, or an aromatic ring group, and the wavy line represents a bonding point to a portion of the compound (1) other than the partial skeleton (1-1). １Suitable examples of the portion of compound (1) other than the partial skeleton (1-1) are as described above. Furthermore, the methyl group in the general formulas (1-1) and (2-1) may be other alkyl groups such as an ethyl group, a propyl group, an isopropyl group, or a butyl group. Furthermore, the portion of compound (2) other than the partial skeleton (2-1) refers to the portion to which each partial skeleton (2-1) is bonded via * in general formula (2-1) as the bonding point, i.e., the portion of compound (2) excluding all partial skeletons (2-1). The portion of compound (2) other than the partial skeleton (2-1) corresponds to the portion of compound (1) other than the partial skeleton (1-1), and suitable examples thereof are the same as the suitable examples of the portion of compound (1) other than the partial skeleton (1-1) described above. One type of compound (2) may be used alone, or two or more types may be used in combination. One type of compound (3) may be used alone, or two or more types may be used in combination.

[0208] A compound (2) having two or more partial skeletons (2-1) represented by general formula (2-1) and a compound (3) represented by general formula (3) are mixed and stirred at 23 to 250°C without a solvent or in an organic solvent (e.g., ethanol, etc.), whereby a mixture containing at least one of a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), an oligomer thereof, and a polymer thereof can be produced.

[0209] Hereinafter, a method for producing the compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), an oligomer thereof, and a polymer thereof will be specifically described using a case where A is an oxygen atom and there are two partial skeletons (1-1) as an example of a mixture containing at least one of the compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1). Compound (1a) represented by the following general formula (1a), in which A is an oxygen atom and there are two partial skeletons (1-1), can be produced, for example, by a production method including a step of reacting acetoacetic acid diester (2a) represented by the following general formula (2a) with compound (3) represented by general formula (3). Furthermore, when a bond exchange reaction occurs between compounds (1a) represented by general formula (1a), an oligomer and / or polymer of compound (1a) represented by general formula (1a) is produced. (In general formulas (1a), (2a), and (3), X, Y, and R １ is as defined in the above general formulas (1-1), (2-1), and (3). Z is a portion of compound (1a) other than the two partial skeletons, and a portion of acetoacetic acid diester (2a) other than the two acetoacetic acid ester groups. Suitable examples of Z are the same as the suitable examples of the portion of compound (1) other than the partial skeleton (1-1).

[0210] Compound (1a) represented by general formula (1a) is produced by mixing and stirring acetoacetic acid diester (2a) represented by general formula (2a) and compound (3) represented by general formula (3) at 25 to 250°C, whereby the acetoacetic acid ester group of acetoacetic acid diester (2a) represented by general formula (2a) and the amino group of compound (3) represented by general formula (3) undergo a condensation reaction to form the following vinylogous urethane bond:

[0211] <Dynamic Covalent Network Polymer> The dynamic covalent network polymer of this embodiment includes a structural unit derived from a compound (1), an oligomer thereof, or a polymer thereof, having two or more partial skeletons (1-1) represented by the general formula (1-1) of this embodiment described above, and a structural unit derived from an independent crosslinking agent containing a reactive moiety. The structural unit derived from a compound (1), an oligomer thereof, or a polymer thereof having two or more partial skeletons (1-1) represented by the general formula (1-1), and the structural unit derived from an independent crosslinking agent containing a reactive moiety may each be a single type or a combination of multiple types. That is, the dynamic covalent network polymer of this embodiment may include only one type of structural unit derived from a compound (1) having two or more partial skeletons (1-1) represented by the general formula (1-1), a structural unit derived from an oligomer of the compound (1), or a structural unit derived from a polymer of the compound (1), or may include two or more types of structural units. The dynamic covalent network polymer of the present embodiment contains a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), an oligomer thereof, or a structural unit derived from the polymer thereof. Therefore, the dynamic covalent network polymer has excellent fluidity and self-repairing properties under heating (under certain temperature conditions), and further, by adding a monofunctional small molecule, adherends bonded with an adhesive containing the dynamic covalent network polymer can be easily disassembled.

[0212] Examples of independent crosslinkers containing reactive moieties include novolac resins, bisphenols (e.g., bisphenol A (BPA)), monoglycidyl, diglycidyl, or triglycidyl molecules, N-containing triglycidyl molecules, epoxies, epoxy-containing cresol or SU-8 photoresists, isocyanates, bismaleimides, sulfides, (poly)urethanes, ureas, anhydrides, polyesters, polyols, (poly)amines, and (poly)carboxylic acids. These may be used alone or in combination. Among these, preferred crosslinkers are those selected from the group consisting of epoxies, ureas, (poly)urethanes, isocyanates, bismaleimides, anhydrides, sulfides, polyols, (poly)amines, (poly)carboxylic acids, and combinations thereof. More preferred are those selected from the group consisting of epoxies, ureas, (poly)urethanes, isocyanates, bismaleimides, sulfides, anhydrides, (poly)ols, and combinations thereof. Isocyanates, epoxies, and (poly)ols are even more preferred. In this specification, the term "independent crosslinking agent" refers to a crosslinking agent other than the compound (1) having two or more partial skeletons (1-1) represented by the general formula (1-1), its oligomer, and its polymer.

[0213] Dynamic covalent network polymers are polymers that include vitrimers and / or thermosetting polymers. Dynamic covalent network polymers are capable of undergoing dynamic bond exchange reactions even in the cured state.

[0214] In the dynamic covalent network polymer, when the amount of functional groups derived from an independent crosslinking agent containing a reactive moiety is A (mol), and the amount of functional groups derived from a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), an oligomer thereof, or a polymer thereof is B (mol), the ratio A / B is preferably 0.1 to 10, more preferably 0.2 to 8, even more preferably 0.3 to 5, and most preferably 0.6 to 1.5. When A / B is in the above range, moldability tends to be improved.

[0215] The dynamic covalent network polymer of this embodiment essentially comprises structural units derived from a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), an oligomer thereof, or a polymer thereof, and a structural unit derived from an independent crosslinking agent containing a reactive moiety, but may also contain other structural units within the scope of the invention. Examples of other structural units include monomer units derived from trisacetoacetate esters, monomer units derived from polyacetoacetate esters, and structural units derived from amines.

[0216] The dynamic covalent network polymer can be produced by, for example, mixing a mixture containing at least one of a compound (1) having two or more partial skeletons (1-1) represented by general formula (1-1), an oligomer thereof, and a polymer thereof with an independent crosslinking agent containing a reactive moiety, and then crosslinking the mixture. Examples of the mixing method include mechanical stirring, reactive extrusion, reactive injection molding, slot die coating, shear mixing, and combinations thereof.

[0217] <Resin Composition> The resin composition of this embodiment contains the dynamic covalent network polymer of this embodiment. From the viewpoint of dismantling property, the content of the dynamic covalent network polymer in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the resin composition (total solids content when the resin composition is in a varnish state).

[0218] The resin composition of this embodiment may also contain additives such as catalysts, curing accelerators, inorganic fillers, coupling agents, thermoplastic resins, colorants including one or more selected from the group consisting of dyes (e.g., green, red, blue, yellow, and black), pigments (e.g., black pigments), colorants, stress reducers, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, and rubber components, as long as the effects of the present invention are not impaired. These may be used alone or in combination of two or more. In the resin composition of this embodiment, the amount of additive added is preferably 0.1 to 200 parts by mass per 100 parts by mass of the dynamic covalent network polymer.

[0219] The resin composition of this embodiment may contain a catalyst for purposes such as promoting the bond exchange reaction, reducing resin viscosity, and enhancing self-healing properties. Examples of catalysts include sulfuric acid, paratoluenesulfonic acid, paratoluenesulfonic acid monohydrate, ethylphosphinic acid, phenylphosphinic acid, ethylphosphonic acid, phenylphosphonic acid, zinc(II) chloride, zinc(II) acetate, iron(II) chloride, iron(III) chloride, diethylamine, diisopropylamine, triethylamine, tributylamine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]non-5-yne, 1,5,7-triazabicyclo[4.4.0]dec-5-yne, ammonium chloride, ammonium acetate, and ammonium carbamate. In the resin composition of this embodiment, the amount of catalyst added is preferably 0.01 to 10 parts by mass per 100 parts by mass of the dynamic covalent network polymer. When the amount of catalyst added is within the above range, the bond exchange reaction is appropriately adjusted, and high mechanical properties and good self-repairing properties tend to be obtained.

[0220] The resin composition of this embodiment may contain a curing accelerator (curing catalyst). This can improve the curability of the resin composition. Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts, cycloamidine compounds, and phosphines. Specific examples of the curing accelerator include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, and 2-phenyl-4-methylimidazole. Imidazoles such as ethyl imidazoline, 2-ethyl imidazoline, 2-isopropyl imidazoline, 2,4-dimethyl imidazoline, and 2-phenyl-4-methyl imidazoline; imidazoles masked with acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate as a masking agent for the imino group of imidazole; triethanolamine, dimethylamino Examples of the organic phosphines include tertiary amines such as ethanol and tris(dimethylaminomethyl)phenol; cycloamidine compounds such as diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 and 1,8-diazabicyclo[5.4.0]undecene-7, and derivatives thereof; and organic phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphines, dialkylarylphosphines, and alkyldiarylphosphines, as well as complexes of these organic phosphines with organic borons.In the resin composition of the present embodiment, the amount of the curing accelerator added is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 7 parts by mass, and even more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the dynamic covalent network polymer.

[0221] Examples of the inorganic filler include silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; titanates such as strontium titanate and barium titanate, and graphene. Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferred, and silica is particularly preferred. As the inorganic filler, one of these may be used alone, or two or more may be used in combination.

[0222] The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but may be, for example, 0.01 μm or more, or 0.05 μm or more. When the lower limit of the average particle diameter is within the above range, an increase in the viscosity of the varnish-like resin composition described below can be suppressed, improving workability during the preparation of the composite reinforced material. The upper limit of the average particle diameter of the inorganic filler is also not particularly limited, but is preferably, for example, 5.0 μm or less, more preferably 2.0 μm or less, and even more preferably 1.0 μm or less. When the upper limit of the average particle diameter is within the above range, phenomena such as sedimentation of the inorganic filler in the varnish-like resin composition described below can be suppressed, allowing a uniform resin composition to be obtained. In this embodiment, the average particle diameter of the inorganic filler can be determined by, for example, measuring the particle size distribution of the particles on a volume basis using a laser diffraction particle size distribution analyzer (LA-500, manufactured by HORIBA), and using the median diameter (D50) as the average particle diameter.

[0223] The inorganic filler is not particularly limited, but may be an inorganic filler having a monodisperse average particle size, or an inorganic filler having a polydisperse average particle size. Furthermore, one or more types of inorganic fillers having monodisperse and / or polydisperse average particle sizes may be used in combination.

[0224] The lower limit of the amount of inorganic filler added is not particularly limited, but is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, based on 100 parts by mass of the dynamic covalent network polymer. When the lower limit of the amount added is within the above range, the resin composition can have particularly low thermal expansion and low water absorption. On the other hand, the upper limit of the amount of inorganic filler added is not particularly limited, but may be, for example, 180 parts by mass or less, 160 parts by mass or less, or 140% by mass or less, based on 100 parts by mass of the dynamic covalent network polymer. This improves handling during the preparation of the composite reinforced material.

[0225] The resin composition of this embodiment may contain a coupling agent. The coupling agent may be added directly during preparation of the resin composition, or may be added to the inorganic filler in advance. The use of a coupling agent can improve the wettability of the interface between the inorganic filler and each resin. Therefore, it is preferable to use a coupling agent, especially when an inorganic filler is added, as this can improve the heat resistance of the resin composition.

[0226] Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and amino silane coupling agents, titanate coupling agents, and silicone oil coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination. In this embodiment, the coupling agent may contain a silane coupling agent. This can increase the wettability of the interface between the inorganic filler and each resin.

[0227] Various types of silane coupling agents can be used, including, for example, epoxy silane, amino silane, alkyl silane, ureido silane, mercapto silane, and vinyl silane. Specific examples include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-6-(aminohexyl)3-aminopropyltrimethoxysilane, N-(3-(trimethoxysilylpropyl)-1,3-benzenedimethanane, γ-glycidoxypropyl Examples of suitable silanes include vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and vinyltriethoxysilane. These silanes may be used singly or in combination of two or more. Of these, epoxysilanes, mercaptosilanes, and aminosilanes are preferred, and primary aminosilanes or anilinosilanes are more preferred as aminosilanes.

[0228] The amount of the coupling agent added can be appropriately adjusted based on the specific surface area of ​​the inorganic filler. The lower limit of the amount of the coupling agent added may be, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, based on 100 parts by mass of the dynamic covalent network polymer. When the amount of the coupling agent added is equal to or greater than the lower limit, the inorganic filler can be sufficiently coated, and the heat resistance of the resin composition can be improved. On the other hand, the upper limit of the amount of the coupling agent added may be, for example, 5 parts by mass or less, preferably 3 parts by mass or less, based on 100 parts by mass of the dynamic covalent network polymer. When the amount of the coupling agent added is equal to or less than the upper limit, the reaction can be prevented from being affected, and a decrease in the bending strength of the resin composition can be prevented.

[0229] Examples of the thermoplastic resin include phenoxy resins, acrylic resins, methacrylic resins, polyvinyl acetal resins, thermoplastic polyimide resins, polyamide resins, polyamideimide resins, polyphenylene oxide resins, polyethersulfone resins, polyester resins, polyethylene resins, polystyrene resins, polysulfone resins, polybutadiene resins, ABS resins, coumarone resins, etc. One type of the thermoplastic resin may be used alone, or two or more types having different weight average molecular weights may be used in combination, or one or more types may be used in combination with their prepolymers.

[0230] The phenoxy resin is not particularly limited, and examples thereof include phenoxy resins having a bisphenol skeleton such as phenoxy resins having a bisphenol A skeleton, phenoxy resins having a bisphenol F skeleton, phenoxy resins having a bisphenol S skeleton, phenoxy resins having a bisphenol M (4,4'-(1,3-phenylenediisopridiene)bisphenol) skeleton, phenoxy resins having a bisphenol P (4,4'-(1,4)-phenylenediisopridiene)bisphenol) skeleton, and phenoxy resins having a bisphenol Z (4,4'-cyclohexydienebisphenol) skeleton, phenoxy resins having a novolac skeleton, phenoxy resins having an anthracene skeleton, phenoxy resins having a fluorene skeleton, phenoxy resins having a dicyclopentadiene skeleton, phenoxy resins having a norbornene skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton, and phenoxy resins having an adamantane skeleton. The phenoxy resin may have a structure having multiple types of the above skeletons, or may have different ratios of the skeletons. Furthermore, multiple types of phenoxy resins with different skeletons may be used, or multiple types of phenoxy resins with different weight-average molecular weights may be used, or prepolymers of these may be used in combination.

[0231] The lower limit of the weight-average molecular weight (Mw) of the phenoxy resin is, for example, 3,000 or more, preferably 5,000 or more, and more preferably 10,000 or more. When the lower limit of the weight-average molecular weight (Mw) is within the above range, compatibility with other resins and solubility in solvents can be improved. On the other hand, the upper limit of the weight-average molecular weight (Mw) of the phenoxy resin is, for example, 100,000 or less, preferably 70,000 or less, and more preferably 50,000 or less.

[0232] In the resin composition of the present embodiment, the amount of the thermoplastic resin added is preferably 5 to 200 parts by mass, more preferably 10 to 180 parts by mass, and even more preferably 15 to 160 parts by mass, based on 100 parts by mass of the dynamic covalent network polymer, from the viewpoint of recyclability.

[0233] Examples of the pigment include inorganic pigments such as kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, and synthetic ultramarine blue; polycyclic pigments such as phthalocyanine; and azo pigments.

[0234] Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, and azomethine.

[0235] The rubber component may include, for example, one or more selected from the group consisting of butadiene rubber, acrylic rubber, and silicone rubber. The rubber component may be contained in the form of particles. Examples of such rubber particles include core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, acrylic rubber particles, and silicone particles.

[0236] In this embodiment, when the resin composition is in the form of a varnish, the resin composition may contain a solvent. Examples of the solvent include organic solvents such as methanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve-based solvents, carbitol-based solvents, anisole, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0237] When the resin composition is in the form of a varnish, the solid content of the resin composition may be, for example, 30 to 99 mass %, more preferably 40 to 99 mass %. When the solid content of the resin composition is in the above range, a resin composition with excellent workability and film-forming properties can be obtained.

[0238] The resin composition of this embodiment can be produced by mixing and stirring the dynamic covalent network polymer of this embodiment and, if necessary, additives. In the case of a varnish-like resin composition, the components described above can be dissolved in a solvent, mixed, and stirred using a mixer such as an ultrasonic dispersion system, a high-pressure collision dispersion system, a high-speed rotation dispersion system, a bead mill system, a high-speed shear dispersion system, or a rotation-revolution dispersion system.

[0239] <Adhesive> The adhesive of this embodiment includes a resin composition containing the dynamic covalent network polymer of this embodiment described above. The adhesive is cured to bond adherends to each other. As described above, the adhesive of this embodiment includes a dynamic covalent network polymer that has excellent dismantling properties, fluidity under heat (under certain temperature conditions), and self-repairing properties, thereby realizing a long life for the adhesive and enabling adherends bonded with the adhesive to be easily dismantled.

[0240] <Molded Article> The molded article of this embodiment includes a resin composition containing the dynamic covalent network polymer of this embodiment. As described above, the molded article of this embodiment is preferable in terms of recyclability because it contains the dynamic covalent network polymer of this embodiment, which has excellent dismantling properties, fluidity under heat (under certain temperature conditions), and self-repairing properties.

[0241] The molded article of this embodiment can be produced, for example, by curing a resin composition containing the dynamic covalent network polymer of this embodiment in a molding die. The curing method is not particularly limited, and examples include heating, UV treatment, IR treatment, microwave treatment, the addition of a catalyst, an accelerator, or a radical initiator, or a combination thereof. Furthermore, molded articles containing dynamic covalent network polymers obtained using polyisocyanate as an independent crosslinking agent containing a reactive moiety are particularly suitable for structural component applications because their curing conditions are milder than those of epoxy resins and the like.

[0242] Hereinafter, the invention (II) will be specifically explained using examples, but it goes without saying that the invention (II) is not limited to these examples and can be practiced with various modifications within the scope of the gist of the invention (II).

[0243] The evaluation methods used in the examples and comparative examples are as follows.

[0244] [Adhesion] A mixture of the compound synthesized in each Example and Comparative Example (a diol in Comparative Example 1, and an amine compound in Comparative Example 2) and a crosslinker containing a reactive moiety was applied to the edge (25 mm wide x 12.5 mm long) of a 25 mm wide x 100 mm long metal plate (hereinafter referred to as the "electrodeposition-coated plate") with an electrodeposition-coated surface. Another electrodeposition-coated plate was then placed on top of the coated portion, overlapping only the edge (25 mm wide x 12.5 mm long). A 0.2 mm thick steel plate was used as a spacer to adjust the thickness of the bonded area to 0.2 mm. The pair of electrodeposition-coated plates was heated at 80°C for 5 hours in a heating device to cure the resin, and the electrodeposition-coated plates were bonded together to obtain an adhesion test sample. The shear adhesive strength (MPa) of this sample was measured by gripping both ends with the chucks of a tensile tester (Instron "Universal Testing Machine") and pulling. The measurement conditions were a measurement temperature of 23° C. and a pulling speed of 5 mm / min. Here, the magnitude of the shear adhesive strength corresponds to the magnitude of the adhesive strength, so a shear adhesive strength of 5 MPa or more was evaluated as "A (excellent)," a shear adhesive strength of 2 MPa or more but less than 5 MPa was evaluated as "B (good)," and a shear adhesive strength of less than 2 MPa was evaluated as "C (poor)."

[0245] [Dismantling property] Dynamic covalent bond network polymer (500 mg) was heated in a mixed solution of primary amine and N,N-dimethylformamide (amine concentration 1.0 N, 5 mL) in a pressure vessel at 100°C for 4 hours. It was confirmed whether the polymer had been dismantled or not, and the dismantling property was evaluated according to the following evaluation criteria. (Evaluation criteria) A (Excellent): The polymer was completely dissolved to form a homogeneous solution. B (Good): A small amount of polymer fragments remained in the solution. C (Possible): Only a small amount of the polymer surface was dissolved. D (Unacceptable): No change at all.

[0246] Example 1 Ethylene glycol (15.0 g, 0.24 mol) as a diol and tert-butyl acetoacetate (114.6 g, 0.72 mol) were charged into a 300 mL two-neck flask and stirred with a stirring blade under Ar flow. The temperature was then raised to an external temperature of 125°C in an oil bath, and the pressure inside the system was gradually reduced to 68 hPa. After heating and reducing pressure for 4 hours, the external temperature was adjusted to 130°C and the reduced pressure to 3 hPa in order to distill off unreacted tert-butyl acetoacetate. After heating and reducing pressure for 2 hours, the flask was allowed to cool to room temperature, and ethylene glycol-1,2-bisacetoacetate was recovered from the flask (recovery amount: 55.4 g, yield 99.5%). Hexamethylenediamine (10.1 g, 0.086 mol) was placed in a 300 mL flask, and the obtained ethylene glycol-1,2-bisacetoacetate (10.0 g, 0.043 mol) was added dropwise to the mixture while stirring at 65° C. This caused a condensation reaction between ethylene glycol-1,2-bisacetoacetate and hexamethylenediamine, yielding a compound represented by the following formula (I). To the resulting chloroform solution of the compound represented by formula (I) (2.3 g), a chloroform solution of polyisocyanate (Duranate (trademark) (TPA-100) manufactured by Asahi Kasei Corporation, 3.0 g) was added as a crosslinking agent (molar ratio of functional groups (NCO / NH ２ ) = 0.77). After thoroughly stirring the reaction mixture, it was poured into a silicone mold and air-dried for 24 hours, followed by oven curing at 80°C for 5.5 hours to obtain a dynamic covalent network polymer. Tables 5 and 6 show the evaluation results.

[0247] [Examples 2 to 13] Dynamic covalent network polymers were obtained in the same manner as in Example 1, except that the ethylene glycol, hexamethylenediamine, and polyisocyanate used in Example 1 were changed to the diol, amine compound, and crosslinking agent shown in Tables 5 and 6, respectively. Tables 5 and 6 show the evaluation results.

[0248] Comparative Example 1 To 20 g of the diol shown in Tables 5 and 6, 3.0 g of polyisocyanate (Duranate™ (TPA-100) manufactured by Asahi Kasei Corporation) was added as a monomer, and after thorough stirring, the mixture was poured into a silicone mold and oven-cured at 80°C for 4 hours to obtain a polymer. Tables 5 and 6 show the evaluation results.

[0249] Comparative Example 2 Epoxy (5.0 g of "Lubeac 812" manufactured by Nacalai Tesque, Inc.) was added as a monomer to 3.0 g of an amine compound shown in Tables 5 and 6, and after thorough stirring, the mixture was poured into a silicone mold and oven-cured at 180° C. for 2 hours to obtain a polymer. Tables 5 and 6 show the evaluation results.

[0250]

[0251]

[0252] The dynamic covalent network polymer synthesized from a mixture containing at least one of the compound of invention (II), its oligomer, and its polymer has sufficient adhesive properties and allows adherends bonded with an adhesive containing the dynamic covalent network polymer to be easily disassembled, and therefore has industrial applicability.

Claims

1. It has dynamic covalent bonds and a crosslink density of 180 mol / m ３ More than 800mol / m ３ or less, and having a glass transition temperature of -20°C or more and 120°C or less.

2. The resin according to claim 1, which has a gel fraction of 95% or less with respect to tetrahydrofuran.

3. 1 m of the resin ３ The bond density, which is the molar ratio of the dynamic covalent bonds in ３ More than 7000mol / m ３ 3. The resin of claim 1 or 2, wherein:

4. The resin according to claim 1 or 2, wherein the dynamic covalent bond is at least one selected from the group consisting of a vinylogous urethane bond, an ester bond, and a disulfide bond.

5. The resin according to claim 4, wherein the dynamic covalent bond contains a vinylogous urethane bond, and the molar ratio of primary amino groups present in the resin to the number of moles of vinylogous urethane bonds in the resin (100 mol %) is 0 to 30 mol %.

6. A resin composition comprising the resin according to claim 1 or 2.

7. The resin composition according to claim 6, which is an adhesive.

8. A structure having a structure in which the resin composition according to claim 6 is applied to at least a portion of the surface of a member.

9. A method for bonding two members using the resin composition according to claim 7, comprising the steps of applying the resin composition between the two members, or placing a sheet of the resin composition between the two members.

10. The method of claim 9, wherein the component is made of metal, thermoplastic resin, thermosetting resin, ceramic, glass, fiber reinforced composite material, resin composition, or a combination thereof.

11. A method for separating the member and the resin composition from the structure according to claim 8, comprising the steps of: contacting the structure with an amine solution or an acid solution to depolymerize the resin composition into a liquid; and separating the liquid from the member.

12. A method for separating the member and the resin composition from the structure according to claim 8, comprising the step of heating the structure to separate the member and the resin composition.

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