Cured product, self-healing member, adhesive, method for manufacturing a cured product, method for repairing a cured product, method for decomposing a cured product, and monomer

Abstract

Provided is a cured product obtained by curing a composition containing: a monomer A having an ethylenically unsaturated group and a host group in a molecule thereof, wherein the host group is a monovalent group obtained by removing one hydrogen atom or hydroxy group from cyclodextrin or a cyclodextrin derivative; a monomer B having a dynamic covalent bond in a molecule thereof; and a monomer C that may have the abovementioned dynamic covalent bond. In the cured product, at least one monomer selected from the group consisting of the monomer B and the monomer C can penetrate through the host group in a skewered manner, the monomer B and the monomer C each have, in a molecule thereof, at least two curable groups, which could react with the other type of curable group, and at least one set of the curable groups in the monomer B are coupled via the dynamic covalent bond. Thus, said cured product could exhibit excellent toughness and / or excellent strength.

Description

[Technical Field]

[0001] This disclosure relates to cured products, self-healing material components, adhesives, methods for manufacturing cured products, methods for repairing cured products, methods for decomposing cured products, and monomers. [Background technology]

[0002] Thermosetting resins such as epoxy resins are widely used as paints and adhesives due to their high water resistance and / or high adhesiveness. On the other hand, they have lower toughness compared to other resins, and durability is a challenge. To address these challenges, composite and modification using elastomers (rubber) and thermoplastic resins have been considered. Non-patent document 1 describes such a technology, specifically the modification of epoxy resin with a thermoplastic resin. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Journal of the Japan Society for Circuit Implementation, 1996, Vol. 11, No. 1, pp. 53-58. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Conventional modification methods described in Non-Patent Document 1 have limitations, such as restrictions on the types of resins that can be used due to compatibility issues between resins, and limitations on the amount of modifier that can be added, which can make it difficult to obtain the desired function and can lead to complicated manufacturing processes. This disclosure presents a solution to the problems of the prior art through a different approach, and provides a cured product that may have at least one of excellent toughness and excellent strength. Furthermore, this disclosure may also provide self-healing materials, adhesives, methods for manufacturing cured products, methods for repairing cured products, methods for decomposing cured products, and monomers. [Means for solving the problem]

[0005] One embodiment of the cured product in this disclosure is a cured product obtained by curing a composition comprising: monomer A, which has an ethylenically unsaturated group and a host group in its molecule, wherein the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from cyclodextrin or a cyclodextrin derivative; monomer B, which has at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a diterlide bond in its molecule; and monomer C, which may have the dynamic covalent bond, wherein at least one selected from the group consisting of monomer B and monomer C can pierce the host group in a skewer-like manner; monomer B and monomer C each have at least two of the curable groups that can react with each other in their respective molecules; and at least one pair of the curable groups in monomer B is linked via the dynamic covalent bond.

[0006] One embodiment of the adhesive in this disclosure is an adhesive comprising a first agent containing monomer B or monomer C and monomer A, and a second agent containing the other monomer B or monomer C, wherein monomer A has an ethylenically unsaturated group and a host group in its molecule, the host group being a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from cyclodextrin or a cyclodextrin derivative, and monomer B has a disulfide bond, a diselenide bond and a diterlide in its molecule The adhesive has at least one dynamic covalent bond selected from the group consisting of bonds, monomer C may also have the dynamic covalent bond, at least one selected from the group consisting of monomer B and monomer C can pierce the host group in a skewer-like manner, monomer B and monomer C each have at least two of the curable groups that can react with each other within their respective molecules, and at least one pair of the curable groups in monomer B is linked via the dynamic covalent bond.

[0007] One embodiment of the adhesive in this disclosure is an adhesive comprising a first agent containing a polymer having a substructure represented by formula (5) described later, a second agent containing monomer B, and a third agent containing monomer C, wherein monomer B has a disulfide bond as a dynamic covalent bond within its molecule, monomer C may also have the disulfide bond, at least one selected from the group consisting of monomer B and monomer C is capable of piercing a host group which is a monovalent group from which one hydrogen atom or a hydroxyl group has been removed from cyclodextrin or a cyclodextrin derivative, monomer B and monomer C each have at least two of one of the curable groups that can react with each other within their respective molecules, and at least one pair of the curable groups in monomer B is linked via the dynamic covalent bond.

[0008] One embodiment of the monomer in this disclosure is a monomer represented by formula (6), which will be described later. [Effects of the Invention]

[0009] This disclosure provides a cured product that may have at least one of excellent toughness and excellent strength. It also provides a self-healing material, an adhesive, a method for manufacturing the cured product, a method for repairing the cured product, a method for decomposing the cured product, and monomers. [Brief explanation of the drawing]

[0010] [Figure 1A] This figure shows an example of the structure of the compound represented by formula (3). [Figure 1B] This figure shows structural examples of compounds that do not fall under formula (3). [Figure 2] This is a flowchart of one embodiment of a method for manufacturing a cured product. [Figure 3] This is an example of a reaction scheme representing a series of steps: curing a composition containing monomers A, B, and C to obtain a polymer, and then decomposing the disulfide bonds in this polymer using the method described above to obtain new monomers as decomposition products. [Figure 4]This is an example of a reaction scheme representing a series of steps: curing a composition containing monomers A, B, and C to obtain a polymer, and then decomposing the disulfide bonds in this polymer using the method described above to obtain new monomers as decomposition products. [Figure 5] This is an example of a reaction scheme representing a series of steps: curing a composition containing monomers A, B, and C to obtain a polymer, and then decomposing the disulfide bonds in this polymer using the method described above to obtain new monomers as decomposition products. [Figure 6A] This figure shows the toughness of a cured product cured at 160°C, as determined from the stress-strain curve, with respect to the host group content. [Figure 6B] This figure shows the Young's modulus as a function of host group content, calculated from the stress-strain curve of a cured product cured at 160°C. [Figure 7A] This is a comparison of the stress-strain curves of the cured product from Example 2 and the cured product from the comparative example. [Figure 7B] This figure shows the changes in Young's modulus and toughness when the curing temperature of the cured product of Example 2 and the cured product of the Comparative Example is changed. [Modes for carrying out the invention]

[0011] The first embodiment of the cured product in this disclosure is a cured product obtained by curing a composition comprising: monomer A, which has an ethylenically unsaturated group and a host group in its molecule, wherein the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from cyclodextrin or a cyclodextrin derivative; monomer B, which has at least one dynamic covalent bond selected from the group consisting of a disulfide bond, a diselenide bond, and a diterlide bond in its molecule; and monomer C, which may have the dynamic covalent bond, wherein at least one selected from the group consisting of monomer B and monomer C can pierce the host group in a skewer-like manner; monomer B and monomer C each have at least two of the curable groups that can react with each other in their respective molecules; and at least one pair of the curable groups in monomer B is linked via the dynamic covalent bond.

[0012] The cured product described above contains a polymer formed by the polymerization of the aforementioned monomers. (The cured product may also contain components other than polymers.) The polymer has both a "mobile crosslink" structure and a "reversible crosslink" structure within its molecule. The mobile crosslink maintains high mobility of the polymer chain. Furthermore, the reversible crosslinks coexisting within the molecule allow for rearrangement through the dissociation and recombination of crosslinking points, further expanding the range of motion of the crosslinking points of the mobile crosslinks. The synergistic effect of these two crosslinking structures enables a wide range of relaxation behavior beyond the range of motion of conventional mobile crosslinks, resulting in a cured product that achieves both excellent toughness and excellent strength. Further details on the "movable crosslinking" structure and the "reversible crosslinking" structure will be explained later.

[0013] The second embodiment of the cured product in this disclosure is a cured product of the first embodiment in which the composition contains an inclusion complex in which either monomer B or monomer C penetrates the host group in a skewer-like manner.

[0014] When either monomer B or monomer C penetrates the host group in a skewer-like manner, mobile crosslinking is more likely to occur when the polymer is formed. In other words, the cured product of the second embodiment is more likely to contain mobile crosslinking sites within the polymer molecules contained in the resulting cured product. As a result, the cured product has better toughness and / or better strength.

[0015] A third embodiment of the cured product in this disclosure is a cured product of the first embodiment in which the composition comprises an inclusion complex in which monomer B penetrates the host group in a skewer-like manner, and an inclusion complex in which monomer C penetrates the host group in a skewer-like manner.

[0016] The cured product of the third embodiment, obtained by curing a composition containing both an inclusion complex in which monomer B is impaled and a inclusion complex in which monomer C is impaled, has superior toughness and / or superior strength because the crosslinking points of movable crosslinks are more easily formed uniformly within the molecular chains of the polymer contained in the cured product.

[0017] The fourth embodiment of the cured product in this disclosure is a cured product of the first to third embodiments that includes a polymer having a substructure represented by the following formula (5). [ka] In equation (5), * represents the bond position, R 1 R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. H represents the host group, L 1 This represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group which may have a linear, branched, or cyclic heteroatom having 1 to 20 carbon atoms, and divalent groups formed by combinations thereof.

[0018] The above substructure is formed when an ethylenically unsaturated group of monomer A reacts with a disulfide bond, which is a dynamic covalent bond, of monomer B (and possibly monomer C). A polymer having the above substructure may be included in a cured product obtained by curing a composition containing monomer A, monomer B having a disulfide bond as a dynamic covalent bond, and monomer C (which may also have a disulfide bond).

[0019] The above polymer exhibits stronger interactions with metals. Therefore, the cured product has excellent adhesion to the substrate (especially metals). Furthermore, the above polymer contains disulfide bonds within its molecule, derived from monomer B. Disulfide bonds have a bond dissociation energy that is weaker than carbon-carbon bonds and stronger than oxygen-oxygen bonds. Therefore, exchange reactions can be induced in a practically preferable lower temperature range (in one form, room temperature to 160°C). This means that the function of reversible crosslinking can be exhibited more easily, and as a result, the cured product has better toughness and / or better strength.

[0020] The fifth embodiment of the cured product in this disclosure is a cured product that contains monomer A as described above in the cured products of the first to fourth embodiments.

[0021] Monomer A possesses ethylenically unsaturated bonds. Therefore, it can react with radicals generated by the dynamic dissociation of covalent bonds in the polymer. Consequently, the range of possible bond rearrangements (within the molecule) due to the dissociation and recombination of dynamic covalent bonds is broader, and the cured product has superior toughness and / or superior strength.

[0022] The sixth embodiment of the cured product in this disclosure is a cured product of the first to fifth embodiments in which the content ratio of the total molar content of the host group to the total molar content of the dynamic covalent bond in the composition is 0.01 or more and 0.1 or less.

[0023] When the host group / dynamic covalent bond content ratio is within the above range, the cured product achieves both superior toughness and superior strength (rigidity).

[0024] The seventh embodiment of the cured product in this disclosure is a cured product of the first to sixth embodiments in which monomer A contains a compound represented by the following formula (1). [ka] In formula (1), R 1represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, and R H represents the host group, and L 1 represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group that may have a linear, branched, or cyclic heteroatom having 1 to 20 carbon atoms, and a divalent group formed by combining these.

[0025] In the polymer contained in the cured product obtained by curing the composition containing the above monomer A, the main chain is formed by the reaction of ethylenically unsaturated groups (typically, the reaction with radicals generated by the dissociation of dynamic covalent bonds, etc.), and it is likely to have a form containing the host group as a side group. Therefore, the effect of mobile crosslinking is more easily obtained, and as a result, the cured product has more excellent toughness and / or more excellent strength.

[0026] In the eighth embodiment of the cured product in the present disclosure, in the cured products of the first to seventh embodiments, the cured product is such that the above monomer B contains a compound represented by the following formula (3).

Chemical formula

[0027] In monomer B described above, groups having at least two curable groups are linked via groups containing dynamic covalent bonds. In other words, groups containing dynamic covalent bonds are sandwiched between a pair of groups having curable groups. Polymers contained in cured products obtained by curing compositions containing such monomer B tend to have a structure in their main chain that includes dynamic covalent bonds. Therefore, they are more susceptible to greater stereochemical changes in the molecular chain due to the dissociation and recombination of dynamic covalent bonds (by reversible crosslinking). As a result, the cured product has superior toughness and / or superior strength.

[0028] The ninth embodiment of the cured product in this disclosure is a cured product of the first to eighth embodiments in which monomer B and monomer C have a disulfide bond as the dynamic covalent bond, and at least one set of curable groups in monomer C is linked via the disulfide bond.

[0029] A cured product obtained by curing a composition containing monomer B and monomer C having disulfide bonds may contain a polymer having disulfide bonds in its main chain. This polymer has a stronger interaction with metals. Therefore, the cured product has excellent adhesion to the substrate (especially metals). Furthermore, disulfide bonds have a bond dissociation energy that is weaker than carbon-carbon bonds and stronger than oxygen-oxygen bonds. Therefore, the exchange reaction can be carried out in a practically more preferable low temperature range (in one form, room temperature to 160°C). This means that the function of reversible crosslinking can be exhibited more easily, and as a result, the cured product has better toughness and / or better strength.

[0030] The first embodiment of the self-healing material in this disclosure is a self-healing material that includes the cured products of the first to ninth embodiments.

[0031] The cured product described above contains a polymer having dynamic covalent bonds. Furthermore, the polymer contains movable crosslinks. The structural characteristics of such polymers can contribute to significant relaxation of residual stress in the cured product and repair of cracks by flattening the surface of the cured product. Therefore, self-healing materials containing the cured product described above possess excellent self-healing properties.

[0032] The first embodiment of the adhesive in this disclosure is an adhesive comprising a first agent containing monomer B or monomer C and monomer A, and a second agent containing the other monomer B or monomer C, wherein monomer A has an ethylenically unsaturated group and a host group in its molecule, the host group being a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from cyclodextrin or a cyclodextrin derivative, and monomer B has a disulfide bond, a diselenide bond and a diterlide in its molecule The adhesive has at least one dynamic covalent bond selected from the group consisting of bonds, monomer C may also have the dynamic covalent bond, at least one selected from the group consisting of monomer B and monomer C can pierce the host group in a skewer-like manner, monomer B and monomer C each have at least two of the curable groups that can react with each other within their respective molecules, and at least one pair of the curable groups in monomer B is linked via the dynamic covalent bond.

[0033] The above adhesive is a two-part type, which is mixed at the application site to allow the curing reaction to proceed and form a cured product that can bond the objects to be bonded. As the cured product obtained by curing the above adhesive is as described above, the adhesive of the first embodiment has excellent toughness and / or superior adhesive strength. Furthermore, since curing mainly occurs when monomer B and monomer C are mixed (and heated as needed), the curing reaction of the aforementioned two-component adhesive is easy to control.

[0034] The second embodiment of the adhesive in this disclosure is an adhesive in which the first agent contains an inclusion complex in which one of the host groups is pierced in a skewer-like manner, as in the adhesive of the first embodiment.

[0035] When either monomer B or monomer C penetrates the host group in a skewer-like manner, mobile crosslinking is more likely to occur when the polymer is formed. In other words, the adhesive of the second embodiment is more likely to contain mobile crosslinking sites within the polymer molecules contained in the resulting cured product. As a result, the adhesive of the second embodiment has better toughness and / or better adhesive strength.

[0036] A third embodiment of the adhesive in this disclosure is an adhesive comprising a first agent containing a polymer having a substructure represented by the following formula (5), a second agent containing monomer B, and a third agent containing monomer C, wherein monomer B has a disulfide bond as a dynamic covalent bond within its molecule, monomer C may also have the disulfide bond, at least one selected from the group consisting of monomer B and monomer C is capable of piercing a host group which is a monovalent group from which one hydrogen atom or a hydroxyl group has been removed from cyclodextrin or a cyclodextrin derivative, monomer B and monomer C each have at least two of one of the curable groups that can react with each other within their respective molecules, and at least one pair of the curable groups in monomer B is linked via the dynamic covalent bond. [ka] In equation (5), * represents the bond position, R 1 R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. H The above represents the host group, L 1 This represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group which may have a linear, branched, or cyclic heteroatom having 1 to 20 carbon atoms, and divalent groups formed by combinations thereof.

[0037] The above substructure is formed when an ethylenically unsaturated group of monomer A reacts with a disulfide bond, which is a dynamic covalent bond, of monomer B (and possibly monomer C). A polymer having the above substructure may be included in a cured product obtained by curing an adhesive containing monomer A, monomer B having a disulfide bond as a dynamic covalent bond, and monomer C (which may also have a disulfide bond).

[0038] The above polymer exhibits stronger interactions with metals. Therefore, the cured product has excellent adhesion to the substrate (especially metals). Furthermore, the above polymer contains disulfide bonds within its molecule, derived from monomer B. Disulfide bonds have a bond dissociation energy that is weaker than carbon-carbon bonds and stronger than oxygen-oxygen bonds. Therefore, exchange reactions can be induced in a practically more favorable low-temperature range (in one form, room temperature to 160°C). This means that the function of reversible crosslinking can be exhibited more easily, resulting in adhesives with better toughness and / or better strength.

[0039] Furthermore, the cured product of the adhesive contains a polymer having dynamic covalent bonds. The polymer also contains movable crosslinks. The structural characteristics of such polymers can contribute to significant relaxation of residual stress in the cured product and repair of cracks by flattening the surface of the cured product. Therefore, the above adhesive contains a self-healing material.

[0040] Furthermore, since monomer A is separated from the other components (monomers B and C), the amount of monomer A-derived units in the polymer of the cured adhesive and the amount of unreacted monomer A in the cured product can be easily adjusted. As a result, the adhesive has superior toughness and / or superior adhesive strength, and the structure of the polymer in the cured product can be arbitrarily controlled by the mixing ratio of the three components (especially the first component). Consequently, toughness and adhesive strength can be adjusted according to the application.

[0041] The first embodiment of the method for producing a cured product in this disclosure is a method for producing a cured product according to the first to ninth embodiments, which includes imparting energy to the composition to obtain a cured product. In other words, the first embodiment of the method for producing a cured product is a method for producing a cured product, which includes imparting energy to the composition to obtain a cured product according to the first to ninth embodiments.

[0042] A second embodiment of the method for producing a cured product in this disclosure is a method for producing a cured product in which, in the method for producing a cured product of the first embodiment, before applying the energy, one of monomers B or C penetrates the host group of monomer A in a skewer-like manner to form an inclusion complex.

[0043] According to the method for producing the cured product of the second embodiment, an inclusion complex is formed in advance. In the inclusion complex, the state in which one of monomer B or monomer C penetrates the host group in a skewer-like manner is a portion that can become a mobile crosslink when the cured product (and the polymer contained therein) is formed. Therefore, the cured product obtained by the above method for producing the cured product is more likely to contain crosslinking points for mobile crosslinks within the polymer molecules contained in the resulting cured product, and as a result has better toughness and / or better strength.

[0044] The first embodiment of the method for decomposing a cured product in this disclosure is a method for decomposing a cured product by contacting the cured product of the ninth embodiment with a two-phase solution comprising an organic phase containing an organic solvent, a water-soluble compound containing at least one mercapto group in its molecule, and water, and decomposing the cured product.

[0045] The cured products of the ninth embodiment are obtained by curing a composition containing monomers B and C, which have disulfide bonds in their molecules. Therefore, when a water-soluble compound containing a mercapto group is brought into contact with the cured product, the disulfide bonds in the polymer are cleaved, and the polymer can be decomposed. Since the main component of the cured product is the above polymer, the cured product can be decomposed in this manner. Furthermore, these decomposition products can be recovered into the organic phase. According to the decomposition method of the cured product of this embodiment, in addition to the cured product being easily decomposed, reusable decomposition products can be easily recovered.

[0046] The first embodiment of the monomer in this disclosure is a monomer represented by the following formula (6). The monomer may also be referred to as a "compound." [ka] In formula (6), R 1 R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. H L represents a host group which is a monovalent group from which one hydrogen atom or a hydroxyl group has been removed from a cyclodextrin or a cyclodextrin derivative. 1 L represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group which may have a linear, branched, or cyclic heteroatom having 1 to 20 carbon atoms, and divalent groups which are combinations thereof. 6 This represents a divalent group that does not contain a disulfide bond and can penetrate the host group in a skewer-like manner, or a single bond, L 5 L represents a base with a+1 valency, where a is an integer greater than or equal to 1, and there are multiple L 5 , and L 6 These may be the same or different.

[0047] The above monomers can be cured by heating and / or light irradiation. The polymer obtained by curing the above monomers may contain a reversible crosslinked structure by disulfide bonds, and therefore the resulting cured product has excellent toughness and / or excellent strength. Note that "cured product" in the context of "cured monomer" is synonymous with the monomer polymer.

[0048] The tenth embodiment of the cured product in this disclosure is a cured product obtained by curing the monomer of the first embodiment (described immediately above). In this context, "cured product" refers to a polymer, and the above can be rephrased as "a polymer obtained by curing a monomer (compound)."

[0049] The above cured product (polymer) contains disulfide bonds in its main chain. Therefore, the polymer has a stronger interaction with metals and exhibits excellent adhesion to the substrate (especially metals). Furthermore, disulfide bonds have a bond dissociation energy that is weaker than carbon-carbon bonds and stronger than oxygen-oxygen bonds. Therefore, the exchange reaction can be induced in a practically more favorable low temperature range (in one form, room temperature to 160°C). This means that the function of reversible crosslinking can be exhibited more easily, and as a result of this effect, the above cured product (polymer) has excellent toughness and / or excellent strength.

[0050] The following description is based on non-limiting embodiments. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. Furthermore, the term (meth)acryloyl refers to at least one of methacryloyl and acryloyl, and the term (meth)acrylic refers to at least one of methacrylic and acrylic.

[0051] Furthermore, in this specification, when there are multiple substituents or linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by a specific symbol, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. may be identical or different from the others. The same applies to the specification of the number of substituents, etc. Furthermore, unless otherwise specified, when multiple substituents are in close proximity (especially adjacent), they may be linked to each other or fused to form a ring. Furthermore, substituents that are not specified as substituted or unsubstituted in this specification may have additional substituents on their base, to the extent that they do not impair the intended effect. The same applies to compounds that are not specified as substituted or unsubstituted. [Cured product] One embodiment of the cured product (hereinafter also referred to as "the cured product") is a cured product obtained by curing a composition comprising monomer A having an ethylenically unsaturated group and a host group in its molecule, monomer B having a dynamic covalent bond, and monomer C which may have a dynamic covalent bond, wherein at least one selected from the group consisting of monomer B and monomer C can pierce the host group in a skewer-like manner, monomer B and monomer C each have at least two of the curable groups that can react with each other in their respective molecules, and at least one pair of curable groups in monomer B is linked via a dynamic covalent bond.

[0052] The mechanism by which this cured material solves the problem is not entirely clear, but we will explain one possible mechanism. Please note that the following explanation is speculative and does not necessarily describe the specific mechanism by which this cured material solves the problem.

[0053] The main component of this cured product is a polymer (copolymer) obtained by the curing reaction of monomers A, B, and C. The polymer backbone (main chain) is obtained by a chain reaction of the pairs of curable groups that monomers B and C each possess. Furthermore, at least monomer B has a dynamic covalent bond within its molecule. Moreover, this dynamic covalent bond is bonded to at least one pair of curable groups, as described later, in such a way that each curable group is separated from the others. Therefore, the main chain of the cured product obtained by curing the composition containing monomer B will contain dynamic covalent bonds.

[0054] When energy (heat, light, etc.) is applied to a dynamic covalent bond, it dissociates and generates radicals. Specifically, if the dynamic covalent bond is a disulfide bond, heating and / or UV irradiation will cause it to dissociate and generate thiyl radicals.

[0055] On the other hand, monomer A contains an ethylenically unsaturated group and a host group. Because monomer A has an ethylenically unsaturated group, it undergoes an addition reaction with the dynamic covalent bond present in monomer B. As a result, the host group of monomer A is introduced into the main chain of the polymer, which is the main component of the cured product, as part of the side branches (side groups or side chains). Furthermore, at least one selected from the group consisting of monomer B and monomer C can pierce the host group of monomer A in a skewer-like manner. In other words, monomer A can form an inclusion complex with monomer B and / or monomer C.

[0056] Therefore, when energy is applied to a composition containing monomers A, B, and C and cured, the formation of inclusion complexes and polymers proceeds sequentially or simultaneously. The polymer thus obtained has a structure in which at least some of the host groups, which are the side branches of the polymer, are pierced by some of the polymer's molecular chains. This structure acts like a crosslinking point, but is also mobile within a certain range when subjected to stress, functioning as a so-called "mobile crosslink," and is presumed to contribute to the manifestation of the unique mechanical properties of this cured product.

[0057] Furthermore, because the polymers described above incorporate dynamic covalent bonds in their main chains, this dissociation and recombination can easily occur due to external stimuli (thermal, mechanical, and / or optical stimuli). In other words, it is presumed that the reconnection of the crosslinking points that constitute the molecular chain network of the polymer can easily occur due to external stimuli (reversible crosslinking). The range of motion of a mobile crosslink may be limited by other crosslinking points (chemical crosslinking, physical crosslinking). However, in the polymer described above, it is hypothesized that the host group may be able to move beyond this range of motion through the dissociation / recombination of the reversible crosslink, thus enabling a broader range of relaxation behavior than that of the mobile crosslink itself.

[0058] As described above, the polymer contained as the main component of this cured product possesses both "mobile crosslinking" and "reversible crosslinking." Therefore, it is presumed that, through the synergistic effect of the organic linkage between these functions, not only are the individual properties of mobile and reversible crosslinking achieved, but the resulting material exhibits both superior toughness and strength that were not possible with conventional thermosetting resins. The following will provide a detailed description of this cured product, but first, we will explain the components and other details of the composition used in its manufacture.

[0059] <Composition> The cured product is obtained by curing a composition containing monomer A, monomer B, and monomer C. The main component of the cured product is a polymer obtained from monomers A, B, and C. In this specification, the main component means a component with a content of 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. In one embodiment, the cured product may consist only of polymer, or the cured product may consist only of polymer and impurities that are unintentionally mixed in.

[0060] (Monomer A) Monomer A is a compound that has an ethylenically unsaturated group and a host group within its molecule. The content of monomer A in the composition is not particularly limited, but from the viewpoint of obtaining a monomer with a better effect, when the total content of monomers A, B, and C is set to 100 mol%, it is preferably 0.1 mol% or more, preferably 1.0 mol% or more, more preferably 1.8 mol% or more, even more preferably 2.0 mol% or more, particularly preferably 2.5 mol% or more, and most preferably 3.0 mol% or more. On the other hand, from the viewpoint of obtaining a cured product with superior toughness while maintaining excellent rigidity, the content of monomer A is preferably 50 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, particularly preferably 5.0 mol% or less, and most preferably less than 5.0 mol%, when the total content of monomers A, B, and C is 100 mol%.

[0061] The content of monomer A in the composition is preferably 0.1 to 50 mol%, 1.0 to 20 mol%, 1.8 to 10 mol%, 2.0 to 10 mol%, 2.5 to 10 mol%, 3.0 to 10 mol% or less, 1.0 to 5.0 mol%, 1.8 to 5.0 mol%, 2.0 to 5.0 mol%, 2.5 to 5.0 mol%, or 3.0 to 5.0 mol% or less, when the total content of monomers A, B, and C is set to 100 mol%. Furthermore, concentrations of 1.0 mol% or more and less than 5.0 mol%; 1.8 mol% or more and less than 5.0 mol%; 2.0 mol% or more and less than 5.0 mol%; 2.5 mol% or more and less than 5.0 mol%; or 3.0 mol% or more and less than 5.0 mol% are preferred.

[0062] Furthermore, the ratio of the molar (amount of substance) content of host groups derived from monomer A to the molar (total) content of dynamic covalent bonds (typically derived from monomer B) contained in the composition (host group / dynamic covalent bond, hereinafter also referred to as the "H / D" ratio) is preferably 0.01 or higher, more preferably 0.02 or higher, even more preferably 0.04 or higher, particularly preferably greater than 0.04, and most preferably greater than 0.06, from the viewpoint of obtaining a cured product that achieves both superior toughness and superior strength (rigidity). On the other hand, the H / D ratio is preferably less than 0.5, more preferably less than 0.2, even more preferably 0.1 or lower, and particularly preferably less than 0.1. The H / D ratio should be determined to one significant figure.

[0063] The HD ratio is preferably 0.01 or more and less than 0.5; 0.01 or more and less than 0.2; 0.01 to 0.1; 0.01 or more and less than 0.1; 0.02 or more and less than 0.2; 0.04 or more and less than 0.2; 0.04 to 0.1; 0.04 or more and less than 0.1; greater than 0.04 and less than 0.5; greater than 0.04 and less than 0.2; greater than 0.04 and 0.1 or less; greater than 0.04 and less than 0.1; greater than 0.06 and less than 0.5; greater than 0.06 and less than 0.2; greater than 0.06 and 0.1 or less; or greater than 0.06 and less than 0.1.

[0064] Monomer A may be used alone or in combination of two or more types. When two or more types of monomer A are used in combination, it is preferable that their total content be within the above range.

[0065] Furthermore, if monomer C, in addition to monomer B, also possesses a dynamic covalent bond, then in the calculation of the H / D ratio, "D" shall be the total content of dynamic covalent bonds in the composition. The same applies when the composition contains a cured precursor (inclusion complex) as described later, in which case "D" shall be the total content of dynamic covalent bonds in the composition. Furthermore, if the composition contains an inclusion complex as described later, "H" is calculated as the total content of host groups derived from monomer A and host groups derived from the inclusion complex.

[0066] The number of ethylenically unsaturated groups in monomer A is not particularly limited, but in order to obtain a cured product with better effects, it is preferable to have one or more, four or fewer, and more preferably two or fewer, and in one embodiment, it may be one. Monomer A may contain one type of ethylenically unsaturated group, or two or more types. If monomer A contains two or more types of ethylenically unsaturated groups, it is preferable that the total number of such groups be 2 to 4.

[0067] In this specification, an ethylenically unsaturated group means a functional group containing a carbon-carbon double bond that can undergo addition reactions by radicals. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyl groups. Ethylene-unsaturated groups form bonds through addition reactions with dynamic covalent bonds, as described later, and have the function of fixing host groups as side branches to the main chain of the polymer.

[0068] The host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin or a cyclodextrin derivative (hereinafter collectively referred to as "cyclodextrin derivatives, etc."). Furthermore, the host group can pierce monomer B and / or monomer C through host-guest interactions. That is, monomer A can form an inclusion complex with monomer B and / or monomer C.

[0069] A cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives. In this specification, "cyclodextrin derivative" refers to a molecule having a structure in which a cyclodextrin molecule is substituted with another organic group. Furthermore, in this specification, "cyclodextrin" means at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0070] The hydrogen atoms and hydroxyl groups removed from the cyclodextrin derivative may be attached to any site on the cyclodextrin derivative. From the viewpoint of easy host group formation, the host group is preferably a monovalent group from which one hydroxyl group has been removed from the cyclodextrin derivative.

[0071] The cyclodextrin derivative for forming the host group is one in which at least one hydroxyl group (preferably a hydrogen atom of the hydroxyl group) of the cyclodextrin is a hydrocarbon group, an acyl group, and -CONHR A (R A It is preferable that the cyclodextrin derivative has a structure substituted with at least one group selected from the group consisting of a methyl group or an ethyl group. When the cyclodextrin derivative has the above structure, monomer A exhibits a higher affinity for monomers B and C, for example, regardless of whether they are hydrophilic or hydrophobic. This makes the composition more homogeneous, and as a result the resulting cured product has better uniformity. In this specification, "hydrocarbon group, acyl group, and -CONHR" refers to a hydrocarbon group, an acyl group, and -CONHR A For convenience, "at least one group selected from the group consisting of these elements" is sometimes referred to as a "CD modifying group."

[0072] Here, if we let N be the total number of hydroxyl groups in one cyclodextrin molecule, then α-cyclodextrin has N=18, β-cyclodextrin has N=21, and γ-cyclodextrin has N=24.

[0073] If the host group is a monovalent group obtained by removing one "hydroxyl group" from a cyclodextrin derivative, then up to N-1 hydrogen atoms of hydroxyl groups per molecule of the cyclodextrin derivative can be substituted with CD modifying groups. On the other hand, if the host group is a monovalent group obtained by removing one "hydrogen atom" from a cyclodextrin derivative, then up to N hydrogen atoms of hydroxyl groups per molecule of the cyclodextrin derivative can be substituted with CD modifying groups.

[0074] It is preferable that the host group has a structure in which 70% or more of the hydrogen atoms of the hydroxyl groups present in one molecule of the cyclodextrin derivative are substituted with CD modifying groups. In this case, monomer A exhibits a higher affinity for other hydrophobic monomers. It is more preferable that, of the total number of hydroxyl groups present in one molecule of the cyclodextrin derivative, 80% or more of the hydrogen atoms of the hydroxyl groups are substituted with CD modifying groups, and even more preferable that 90% or more of the hydrogen atoms of the hydroxyl groups are substituted with CD modifying groups. The upper limit is 100% or less, and it is preferable that 70-100%, 80-100%, or 90-100% of the hydrogen atoms of the hydroxyl groups are substituted with CD modifying groups.

[0075] It is preferable that the host group has a structure in which 13 or more hydrogen atoms of hydroxyl groups (18 or 72%) of the total hydroxyl groups present in one molecule of the α-cyclodextrin derivative are substituted with CD modifying groups. In this case, monomer A exhibits a higher affinity for other hydrophobic monomers. It is more preferable that 15 or more hydrogen atoms of hydroxyl groups (21 or 71%) of the total hydroxyl groups present in one molecule of the α-cyclodextrin derivative are substituted with CD modifying groups, and even more preferable that 17 or more hydrogen atoms of hydroxyl groups (24 or 70%) of the total hydroxyl groups are substituted with CD modifying groups. That is, it is preferable that 13 to 18, 15 to 17, or 17 to 18 hydrogen atoms of the total hydroxyl groups are substituted with CD modifying groups.

[0076] It is preferable that the host group has a structure in which 13 or more hydrogen atoms of the hydroxyl groups present in one molecule of the β-cyclodextrin derivative are substituted with CD modifying groups. In this case, monomer A exhibits a higher affinity for other hydrophobic monomers. It is more preferable that 17 or more hydrogen atoms of the hydroxyl groups present in one molecule of the β-cyclodextrin derivative are substituted with CD modifying groups, and even more preferable that 19 or more hydrogen atoms of the hydroxyl groups are substituted with CD modifying groups. That is, it is preferable that 13 to 21, 17 to 21, or 19 to 21 hydrogen atoms of the hydroxyl groups are substituted with CD modifying groups.

[0077] It is preferable that the host group has a structure in which 17 or more hydrogen atoms of the hydroxyl groups present in one molecule of the γ-cyclodextrin derivative are substituted with CD modifying groups or the like. In this case, monomer A exhibits a higher affinity for other hydrophobic monomers. It is more preferable that 19 or more hydrogen atoms of the hydroxyl groups present in one molecule of the γ-cyclodextrin derivative are substituted with CD modifying groups, and even more preferable that 22 or more hydrogen atoms of the hydroxyl groups are substituted with CD modifying groups. That is, it is preferable that 17 to 24, 17 to 24, or 19 to 24 hydrogen atoms of the hydroxyl groups are substituted with CD modifying groups.

[0078] The type of hydrocarbon group among the CD modifying groups is not particularly limited. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. Furthermore, the number of carbon atoms in the hydrocarbon group is not particularly limited. From the viewpoint of monomer A showing a higher affinity to other hydrophilic or hydrophobic monomers and facilitating host-guest interactions, the number of carbon atoms in the hydrocarbon group is preferably 1 to 4. Examples of hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups. When the hydrocarbon group is a propyl or butyl group, it may be linear or branched. Furthermore, the hydrocarbon group may have substituents, as long as they do not inhibit the effect.

[0079] Examples of acyl groups among the CD modifying groups include acetyl groups, propionyl groups, and formyl groups. The acyl group may further have substituents. From the viewpoint of obtaining a cured product in which monomer A shows a higher affinity to other hydrophilic or hydrophobic monomers, host-guest interactions are more easily performed, and superior toughness and / or strength, the acyl group is preferably an acetyl group.

[0080] Among the CD modifiers, -CONhub A This is a methylcarbamate group or an ethylcarbamate group. From the viewpoint of monomer A showing higher affinity to other hydrophilic or hydrophobic monomers and host-guest interactions being more efficient, -CONHR A An ethylcarbamate group is preferred.

[0081] In terms of obtaining a cured product with superior effects, monomer A is preferably a compound represented by the following formula (1).

[0082] [ka]

[0083] In formula (1), R 1 R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. H represents the host group, L 1The group is at least one selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a linear, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, which may have heteroatoms, and divalent groups formed by combining these. Note L 1 Preferably, it does not have dynamic covalent bonds.

[0084] In terms of obtaining a cured product with superior effects, R 1 The atom is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably at least one selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group, and even more preferably a hydrogen atom or a methyl group.

[0085] Also, L 1 As for the divalent group, at least one group selected from the group consisting of the group represented by formula (2-1), the group represented by formula (2-2), and the group represented by formula (2-3) is preferred, in that a cured product with superior effects can be obtained. Formula (2-1)*-L 21 -CH2-O-** Formula (2-2)*-L 21 -** Formula (2-3)*-L 21 -(CH2) n -N(Rb)-C(=O)-O-**

[0086] Note that in equations (2-1), (2-2), and (2-3), the right-hand side is "** " is the host base R H This indicates the bonding position with the other side, and the "*" on the left indicates the bonding position with the other side (the ethylenically unsaturated group side).

[0087] In the above formula, L 21The group does not contain dynamic covalent bonds and represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a linear, branched, or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, which may have heteroatoms, and divalent groups formed by combining these. Preferably, the group is a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of a hydroxyl group, a mercapto group, an alkoxy group which may have one or more substituents, a thioalkoxy group which may have one or more substituents, an alkyl group which may have one substituent, an amino group which may have one substituent, an amide group which may have one substituent, a formyl group, and a carboxyl group.

[0088] In formula (2-3), n represents an integer from 1 to 20, preferably from 1 to 10, and more preferably from 1 to 5. Rb represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms).

[0089] L 21 The "substituents" that the compound possesses are not particularly limited, but examples include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, halogen atoms, carboxyl groups, carbonyl groups, sulfonyl groups, sulfone groups, cyano groups, and groups that combine these.

[0090] L 21 If it is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, then the nitrogen atom of the amino group becomes the bonding position with the ethylenically unsaturated group (it becomes the bonding position with the carbon atom of the C=C double bond). L 21 If the group is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, then the carbon atom of the amide group becomes the bonding position with the ethylenically unsaturated group.

[0091] L 21If it is a divalent group formed by removing one hydrogen atom from a formyl group, then the carbon atom of the formyl group becomes the bonding position with the ethylenically unsaturated group.

[0092] Monomer A, represented by equations (2-1) to (2-3), is, for example, (meth)acrylic. L acid ester derivatives (i.e., L 21 (-C(=O)O-), (meth)acrylamide derivative (i.e., L 21 It is preferable that is -C(=O)NH- or -C(=O)NR-, where R is synonymous with the above substituent. For example, R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0093] Specific examples of monomer A represented by formula (2-1) include the compounds represented by formulas (2-1-1) to (2-1-6) below. [ka]

[0094] The compounds represented by formulas (2-1-1), (2-1-2), and (2-1-3) are, in formula (2-1), L 21The compound is -CON(CH3)-, and each has a host group in which one hydrogen atom has been removed from the single hydroxyl group present in the α-cyclodextrin derivative, β-cyclodextrin derivative, and γ-cyclodextrin derivative. Furthermore, in all of these compounds, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivative are replaced with methyl groups. In addition, in the compounds represented by formulas (2-1-1), (2-1-2), and (2-1-3), the nitrogen atom of the amide moiety in each compound can be methylated by the same reaction as the methylation of the hydrogen atoms of the hydroxyl groups in the cyclodextrin derivative. In other words, methylation of the cyclodextrin moiety and methylation of the amide moiety can be performed in a single reaction, and the compounds represented by formulas (2-1-1), (2-1-2), and (2-1-3) can be easily obtained.

[0095] The compounds represented by formulas (2-1-4), (2-1-5), and (2-1-6) are, in formula (2-1), L 21 The group is -CONH-, and each has a host group in which one hydrogen atom has been removed from one hydroxyl group, as is the case with α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives. In addition, in all cases, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivatives are substituted with methyl groups.

[0096] Furthermore, specific examples of monomer A represented by formula (2-1) include the compounds represented by formulas (2-1-7) to (2-1-9) below. [ka]

[0097] The compounds represented by formulas (2-1-7), (2-1-8), and (2-1-9) are L in formula (2-1). 21The group is -CONH-, and each has a host group in which one hydrogen atom has been removed from one hydroxyl group, as is the case with α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives. In addition, in all of these, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivatives are replaced with acetyl groups (indicated as "Ac" in each formula).

[0098] Furthermore, as a concrete example of monomer A represented by equation (2-1), see the following equation (2- Examples of compounds represented in 1-10) are shown. [ka]

[0099] In equation (2-1-10), at least one Y 1 is a hydrogen atom, and also at least one Y 1 The group is -CONH(C2H5) (ethyl carbamate group). n is 5, 6, or 7.

[0100] The compound represented by formula (2-1-10) is L in formula (2-1). 21 The host group is -CONH- and has a host group from which a hydrogen atom has been removed from one hydroxyl group in the cyclodextrin derivative. Also, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivative are Y 1 It has been replaced with.

[0101] As a specific example of monomer A represented by equation (2-2), see equation (2-2-1) below... Examples of compounds represented by formula (2-2-9) include those shown below.

[0102] [ka]

[0103] The compounds represented by formulas (2-2-1), (2-2-2), and (2-2-3) are L in formula (2-2). 21The group is -CONR- (R = methyl group), and each has a host group obtained by removing one hydroxyl group from an α-cyclodextrin derivative (wherein the formula, the number of repeats indicated by the subscript is 5, and so on), a β-cyclodextrin derivative (number of repeats is 6, and so on), and a γ-cyclodextrin derivative (number of repeats is 7, and so on). In addition, in all cases, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivative are substituted with methyl groups.

[0104] The compounds represented by formulas (2-2-4), (2-2-5), and (2-2-6) are L in formula (2-2). 21 The host group is -CONH-, and each has a host group obtained by removing one hydroxyl group from the α-cyclodextrin derivative, β-cyclodextrin derivative, and γ-cyclodextrin derivative, respectively. In addition, in all cases, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivative are substituted with methyl groups.

[0105] The compounds represented by formulas (2-2-7), (2-2-8), and (2-2-9) are L in formula (2-2). 21 The group is -COO-, and each has a host group obtained by removing one hydroxyl group from the α-cyclodextrin derivative, β-cyclodextrin derivative, and γ-cyclodextrin derivative, respectively. In addition, in all cases, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivative are substituted with methyl groups.

[0106] As a specific example of monomer A represented by equation (2-3), see equation (2-3-1) below... Compounds represented by formula (2-3-3) are also examples.

[0107] [ka]

[0108] The compounds represented by formulas (2-3-1), (2-3-2), and (2-3-3) are L in formula (2-3). 21The formulas are -COO-, n=2, and Rb is a hydrogen atom, and each has a host group in which a hydrogen atom has been removed from one hydroxyl group, as is the case with α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives. In all of these, the hydrogen atoms of the N-1 hydroxyl groups in the cyclodextrin derivative are substituted with acetyl groups (Ac). In formulas (2-3-1), (2-3-2), and (2-3-3), the hydrogen atom at the Rb position may be substituted with a methyl group.

[0109] Although monomer A, represented by formulas (2-1-1) to (2-1-9), (2-2-1) to (2-2-9), and (2-3-1) to (2-3-3) above, is an acrylic system, it may also be a methacrylic system in which the hydrogen at the meta position is replaced by a methyl group. The method for producing monomer A is not particularly limited and can be synthesized by known methods; for example, refer to the description in International Publication No. 2018 / 159791.

[0110] (Monomer B) Monomer B is a compound that has at least one dynamic covalent bond selected from the group consisting of disulfide bonds, diselenide bonds, and diterlide bonds within its molecule, and has at least two of the curable groups that can react with monomer C (described later), and at least one pair of curable groups is linked via a dynamic covalent bond. Monomer B reacts with monomer C to form the main chain of the polymer, which is the main component of the cured product. Furthermore, because it possesses dynamic covalent bonds at specific locations within the molecule, dynamic covalent bonds are incorporated into the polymer's main chain. This serves as a reversible crosslink.

[0111] The amount of monomer B in the composition is not particularly limited, but can be appropriately selected based on the equivalent (molar equivalent) ratio with monomer C. When the equivalent amount of monomer B in the reaction with monomer C is set to 1.0, the amount of monomer B in the composition is preferably 0.5 to 2.0, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1.

[0112] Furthermore, while the content of monomer B in the composition is not particularly limited, from the viewpoint of obtaining a cured product with superior effects, when the total content of monomers A, B, and C is set to 100 mol%, it is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. When the total content of monomers A, B, and C is 100 mol%, the content of monomer B is preferably 10-80 mol%, 20-70 mol%, or 30-60 mol%. Furthermore, it is preferable that the content of monomer B in the composition be adjusted to satisfy the H / D ratio already described. Monomer B may be used alone or in combination of two or more types. When two or more types of monomer B are used in combination, it is preferable that their total content be adjusted to fall within the above range.

[0113] The curable groups of monomer B and monomer C are in a relationship where they can react with each other. In other words, the curable groups of monomer B and monomer C are a pair of curable groups that can react with each other.

[0114] Here, "curable groups that can react with each other" refers to, for example, curable group X. 1 and curable group X 2 If and can react, this X 1 and X 2 It means a combination with. For example, (X 1 , X 2 Among the curable groups of ), monomer B is at least one of (X 1 If it has the other curable group (X 2 It has ) and there are at least two of each in each molecule.

[0115] The combination of paired curable groups is not particularly limited, but for example, X 1If X is an epoxy group, a glycidyl group, or a glycidyl ether group (hereinafter also referred to as "epoxy group, etc."), 2 This may be an amino group (primary or secondary), an acid anhydride group, a hydroxyl group, a carboxyl group, and a mercapto group, etc. Also, X 1 If X is a hydroxyl group, 2 This may be a carboxyl group, an acid anhydride group, etc. Also, X 1 If is an isocyanate group or a blocked isocyanate group, X 2 X may be an amino group, a hydroxyl group, etc. Also, X 1 If it is an amino group, X 2 X may be a carboxyl group, etc. Also, X 1 When it is a hydroxyl group, X 2 A monomer having this structure may also be a compound having an acetal structure.

[0116] Furthermore, the curable group may be an active ester group. In this specification, "active ester" means a carboxylic acid derivative that can react with an amino group, and includes active esters and active thioesters having such properties. Examples of active esters include N-hydroxysuccinimide (ONSu) groups, methyl thioesters, aryl thioesters, and aralkyl thioesters.

[0117] The above-mentioned curable group (X 1 , X 2 Of the combinations of ), the curable group possessed by monomer B is X 1 , or X 2 Either of the following may be used. For example, if monomer B has two or more epoxy groups, etc., in its molecule, monomer C, described later, is X 2 The molecule only needs to have two or more curable groups selected from the group consisting of amino groups, acid anhydride groups, hydroxyl groups, carboxyl groups, and mercapto groups. Conversely, if monomer C has an epoxy group or the like, monomer B only needs to have two or more curable groups selected from the group consisting of amino groups, acid anhydride groups, hydroxyl groups, carboxyl groups, and mercapto groups within its molecule.

[0118] The structure of monomer B is not particularly limited, but it is preferable that it can pierce the host group of monomer A in a skewer-like manner. Note that "piercing the host group in a skewer-like manner" means that at least a portion of the monomer can pierce the host group in a skewer-like manner, and it is preferable that the entire monomer can pierce the host group in a skewer-like manner. If monomer B can penetrate monomer A in a skewer-like manner, an inclusion complex between monomer A and monomer B is more likely to form during the curing process of the composition, resulting in a cured product with superior effects.

[0119] Examples of guest groups that can pierce the host group include linear, branched, or cyclic hydrocarbon groups having 3 to 30 carbon atoms, which may have heteroatoms, and linear, branched, or cyclic hydrocarbon groups having 4 to 18 carbon atoms. In particular, monomer B is preferred when it has a (poly)oxyalkylene group (preferably with a repeating number n of 0 to 20), as this makes it easier for monomer A and monomer B to form an inclusion complex.

[0120] Preferred form of monomer B In terms of obtaining a cured product with superior effects, monomer B is preferably a compound represented by the following formula (3). [ka]

[0121] In formula (3), Z 3 R is a group having a curable group, 3 is a hydrogen atom or a monovalent organic group, L 3 Z is a p+q valence base containing a dynamic covalent bond, where p represents a non-negative integer and q represents a non-negative integer. 3At least one set of elements represented by are connected via a dynamic common bond.

[0122] Note that in equation (3), there are multiple Z 3 They may be the same or different, but it is preferable that they be the same. In equation (3), p is an integer greater than or equal to 0, preferably 10 or less, more preferably 8 or less, even more preferably 6 or less, particularly preferably 4 or less, and most preferably 2 or less. p is preferably between 0 and 10, 0 and 8, 0 and 6, 0 and 4, or 0 and 2, with p being 0 being the most preferred.

[0123] In equation (3), q is an integer greater than or equal to 2, preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, particularly preferably 3 or less, and most preferably 2. Q is preferably between 2 and 8, 2 and 6, 2 and 4, or 2 and 3, with q being 2 being the most preferred.

[0124] In formula (3), R 3 R is a hydrogen atom or a monovalent organic group. The monovalent organic group is a group different from any of the curable groups, and more specifically, a cyclic or chain-like alkyl group, an aryl group, or a combination thereof is preferred, and among these, an alkyl group having 1 to 4 carbon atoms is preferred. 3 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Note that there are multiple R 3 These elements may be identical or different, and they may be joined together to form a ring.

[0125] In formula (3), L 3 L is a p+q valence group containing a dynamic covalent bond. 3 If the group is divalent, it has at least one dynamic covalent bond (-SS-, -Se-Se-, and -Te-Te-) selected from the group consisting of disulfide bonds, diselenide bonds, and diterlide bonds, and furthermore, -C(O)-, -C(O)O-, -OC(O)-, -O-, -NR 20 -(R 20represents a hydrogen atom or a monovalent organic group), an alkylene group (preferably having 1 to 20 carbon atoms, including cyclic and linear), an alkenylene group (preferably having 2 to 20 carbon atoms, including cyclic and linear), an arylene group, a heteroarylene group, a (poly)oxyalkylene group (preferably having a repetition number of 0 to 20), and combinations thereof may be included. In addition, the rings of the cyclic alkylene group, the cyclic alkenylene group, the arylene group, and the heteroarylene group may each form a condensed ring.

[0126] Among these, examples of the arylene group include a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, a 1,8-naphthylene group, a 1,2-anthrylene group, a 2,3-anthrylene group, a 1,2-phenanthrylene group, a 3,4-phenanthrylene group, and a 9,10-phenanthrylene group, etc., and any of them may have a substituent.

[0127] Examples of the heteroarylene group include a group obtained by removing any two hydrogen atoms from thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline, etc.

[0128] Among them, in terms of obtaining a composition having a more excellent effect, L 3 As the divalent group of, a dynamic covalent bond (among which, -S-S- is preferable) itself, or in addition to the dynamic covalent bond, a group having -O-, a linear or cyclic alkylene group, an arylene group, or a (poly)oxyalkylene group (preferably having a repetition number n of 0 to 20) is preferable. When the divalent group is the above group, the monomer B is more likely to form an inclusion complex with the monomer A.

[0129] Also, when L 3 is a trivalent or higher-valent group, there is no particular limitation, and examples thereof include groups represented by the following (3a) to (3d). In the following formulas, "*" represents the bonding position.

[0130] [Chemical formula]

[0131] In formula (3a), Q 3 represents a trivalent group. T 3 represents a single bond or a divalent group, and the three Ts 3 may be the same as or different from each other. Note that at least one of the Ts 3 is a divalent group. Examples of Q 3 include a tertiary amino group, a trivalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.), or a trivalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a hetero atom (for example, -O-). Specific examples of Q 3 include a glycerin residue, a trimethylolpropane residue, a phloroglucinol residue, a cyanuric acid residue, a xanthine residue, and a cyclohexanetriol residue, etc.

[0132] Note that the divalent group of T 3 may be the same group as the divalent group of L 3 already described. Among the plurality of Ts 3 , at least one is a divalent group having a dynamic covalent bond, and all may be groups having a dynamic covalent bond. When T 3 has a dynamic covalent bond, T 3 may be the dynamic covalent bond (such as a disulfide bond) itself, or a combination with another divalent group. In that case, a combination with an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferable. When T 3 is a group having no dynamic covalent bond, T 3An alkylene group having 1 to 5 carbon atoms which may have a substituent is preferable.

[0133] In formula (3b), Q 4 represents a tetravalent group. T 4 represents a single bond or a divalent group, and the four Ts 4 may be the same as or different from each other. Incidentally, at least one or more of the Ts 4 are divalent groups. Incidentally, as Q 4 , there may be mentioned a tetravalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), a tetravalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a hetero atom (for example, -O-). Specific examples of Q 4 include a pentaerythritol residue, a glycoluril residue, a ditrimethylolpropane residue, and the like.

[0134] Incidentally, the divalent group of T 4 may be the same group as the divalent group of L 3 already described, and the preferred forms are also the same. However, among the plurality of Ts 4 , at least one is a divalent group having a dynamic covalent bond, and all of them may be groups having a dynamic covalent bond. When T 4 has a dynamic covalent bond, T 4 may be the dynamic covalent bond (such as a disulfide group) itself, or a combination with another divalent group. In that case, a combination with an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferable. When T 4 is a group having no dynamic covalent bond, T 4 is preferably an alkylene group having 1 to 5 carbon atoms which may have a substituent.

[0135] In formula (3c), Q 5 represents a pentavalent group. T 5 represents a single bond or a divalent group, and the five Ts 5 may be the same as or different from each other. Incidentally, T 5At least one of them is a divalent group. Q 5 Examples include pentavalent hydrocarbon groups (preferably with 2 to 10 carbon atoms; the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or pentavalent heterocyclic groups (preferably heterocyclic groups with 5 to 7 members). The hydrocarbon group may also contain a heteroatom (e.g., -O-). Q 5 Specific examples include arabinitol residues, phloroglucidol residues, and cyclohexanepentaol residues.

[0136] Note T 5 The divalent group of L has already been explained. 3 The group may be similar to the divalent group of the same group, and the preferred form is also the same. However, if there are multiple T 5 Of these, at least one is a divalent group having a dynamic covalent bond, and all may be groups having a dynamic covalent bond. 5 If T has a dynamic covalent bond, 5 This may be a dynamic covalent bond (such as a disulfide group) itself, or it may be a combination with other divalent groups, in which case a combination with an alkylene group having 1 to 5 carbon atoms, which may have substituents, is preferred. T 5 If the group does not have a dynamic covalent bond, T 5 Preferably, it is an alkylene group having 1 to 5 carbon atoms, which may have substituents.

[0137] In formula (3d), Q 6 represents a hexavalent group. 6 represents a single bond or a divalent group, and 6 T 6 They may be the same or different from each other. 6 At least one of them is a divalent group. Q 6 Examples include hexavalent hydrocarbon groups (preferably with 2 to 10 carbon atoms; the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or hexavalent heterocyclic groups (preferably heterocyclic groups with 6 to 7 members), and the hydrocarbon group may contain a heteroatom (e.g., -O-). Q6 Specific examples include mannitol residues, sorbitol residues, dipentaerythritol residues, hexahydroxybenzene, and hexahydroxycyclohexane residues.

[0138] Note T 6 The divalent group of L has already been explained. 3 The group may be similar to the divalent group of the same group, and the preferred form is also the same. However, if there are multiple T 6 Of these, at least one is a divalent group having a dynamic covalent bond, and all may be groups having a dynamic covalent bond. 6 If T has a dynamic covalent bond, 6 This may be a dynamic covalent bond (such as a disulfide group) itself, or it may be a combination with other divalent groups, in which case a combination with an alkylene group having 1 to 5 carbon atoms, which may have substituents, is preferred. T 6 If the group does not have a dynamic covalent bond, T 6 Preferably, it is an alkylene group having 1 to 5 carbon atoms, which may have substituents.

[0139] Note L 3 If the group has a valency of 7 or higher, the group can be a combination of the groups represented by formulas (3a) to (3d).

[0140] Furthermore, in monomer B, Z 3 At least one set of groups represented by Z is connected via a dynamic common bond. 3 This means that at least one pair of groups represented by are separated by a dynamic covalent bond. Figures 1A and 1B show Z in the compound represented by formula (3). 3 This is an explanatory diagram of the arrangement of the elements represented by .

[0141] Figure 1A shows an example of the structure of a compound represented by formula (3). In other words, it shows an example of the structure of a compound that "corresponds" to formula (3). [II-A] is L 3 is a divalent group, L 3It is composed of a dynamic covalent bond 11 and other parts 10 (divalent groups). In [II-A], Z 3 A group having a curable group represented by (Z 31 , Z 32 ) are connected via a dynamic covalent bond 11. In other words, Z is connected via a dynamic covalent bond 11. 31 and Z 32 They are separated. Furthermore, the other part 10 does not have a dynamic covalent bond, and the same applies in the following explanation.

[0142] Next, [III-A1] is L 3 It is a trivalent group, L 3 It is composed of a dynamic covalent bond 11 and other parts 10 (trivalent groups). In [III-A1], Z 3 A group having a curable group represented by (Z 31 , Z 32 ) are connected via dynamic covalent bonds 11. 32 and R 3 This means that they are not separated by a dynamic covalent bond 11, but the above does not affect the applicability to equation (3).

[0143] Next, [III-A2] is L 3 It is a trivalent group, L 3 It is composed of a dynamic covalent bond 11 and other parts 10 (trivalent groups). In [III-A2], Z 3 A group having a curable group represented by (Z 31 , Z 32 , Z 33 ) of Z 31 -Z 32 , Z 31 -Z 33 , Z 32 -Z 33 These three pairs are connected via dynamic covalent bonds 11.

[0144] Next, [IV-A1] is L 3 It is a tetravalent group, L 3 It is composed of a dynamic covalent bond 11 and the other part 10 (a tetravalent group). In [IV-A1], Z3 A group having a curable group represented by (Z 31 , Z 32 , Z 33 ) of Z 31 -Z 33 , Z 32 -Z 33 The two sets are connected via a dynamic covalent bond 11. 31 -Z 32 Although one pair is not separated by the dynamic covalent bond 11, the other pair is separated by the dynamic covalent bond 11, and therefore corresponds to equation (3).

[0145] Next, [IV-A2] is L 3 It is a tetravalent group, L 3 It is composed of a dynamic covalent bond 11 and the other part 10 (a tetravalent group). In [IV-A2], Z 3 A group having a curable group represented by (Z 31 , Z 33 Since the two are connected via dynamic covalent bond 11, this corresponds to equation (3). Note, Z 31 (Z 33 )-R 3 , R 3 -R 3 Although they are separated by a dynamic covalent bond 11, the above does not affect the applicability of equation (3).

[0146] On the other hand, Figure 1B shows examples of structures of compounds that "do not fall under" formula (3). [II-B] is L 3 is a divalent group, L 3 It does not have a dynamic covalent bond 11 and is composed of other parts 10 (divalent groups). Therefore, Z 3 A group having a curable group represented by (Z 31 , Z 32 ) are bonded without the use of dynamic covalent bonds 11. Therefore, the compound represented by [II-B] does not correspond to formula (3).

[0147] Next, [III-B1] is L 3 It is a trivalent group, L 3It is composed of a dynamic covalent bond 11 and other parts 10 (trivalent groups). In [III-B1], Z 3 A group having a curable group represented by (Z 31 , Z 32 ) is bonded without a dynamic covalent bond 11. Therefore, the compound represented by [III-B1] does not correspond to formula (3). Note that R 3 -Z 31 (Z 32 ) are separated by a dynamic covalent bond 11, but [III-B1] does not correspond to equation (3).

[0148] Next, [III-B2] is L 3 It is a trivalent group, L 3 It does not have a dynamic covalent bond 11 and is composed of other parts 10 (trivalent groups). Therefore, Z 3 A group having a curable group represented by (Z 31 , Z 32 , Z 33 All of these are bonded without the use of dynamic covalent bonds 11. Therefore, the compound represented by [III-B2] does not correspond to formula (3).

[0149] Next, [IV-B1] is L 3 It is a tetravalent group, L 3 It does not have a dynamic covalent bond 11 and is composed of other parts 10 (tetravalent groups). Therefore, Z 3 A group having a curable group represented by (Z 31 , Z 32 , Z 33 All of these are bonded without the use of dynamic covalent bonds 11. Therefore, the compound represented by [IV-B2] does not correspond to formula (3).

[0150] Next, [IV-B2] is L 3 It is a tetravalent group, L 3 It is composed of a dynamic covalent bond 11 and the other part 10 (a tetravalent group). In [IV-B2], Z 3 A group having a curable group represented by (Z 31 , Z 33) is bonded without passing through the dynamic covalent bond 11. Note that Z 31 (Z 33 )-R 3 、R 3 -R 3 is separated by the dynamic covalent bond 11, but since none of the groups represented by Z 3 are bonded through the dynamic covalent bond 11, the compound represented by [IV - B2] does not correspond to formula (3).

[0151] Returning to formula (3), when L 3 is a divalent group (p = 2 and q = 0), for example, groups represented by the following formulae can be mentioned. In the following formulae, * represents the bonding position with a group having a curable group represented by Z 3 .

[0152]

Chemical formula

[0153] As the monomer B, from the viewpoint of more easily forming an inclusion complex with the host group of the monomer A formula (3 - 1): Z 3 -L 31 -Z 3 The compound represented by is preferred. In formula (3 - 1), L 31 represents a divalent group, which is synonymous with the divalent group of L 3 and the preferred forms are also the same. Also, Z 3 is synonymous with Z 3 in formula (3), and the preferred forms are also the same. The plurality of Z 3 may be the same or different, but it is preferably the same. When the monomer B is a compound represented by formula (3 - 1), it is easier to form an inclusion complex with the host group, and the whole is more likely to be able to penetrate the host group.

[0154] In formula (3 - 1), the group having a curable group of Z 3 is not particularly limited, but a group represented by the following formula (11) is preferred.

[0155] [ka]

[0156] In formula (11), L 11 represents a single bond or a divalent group, X 3 L represents a curable group. 11 The divalent group is not particularly restricted, but L has already been explained 3 Examples of divalent groups include those similar to those in L. 11 It may have dynamic covalent bonds, but it is preferable that it does not. In particular, L 11 The divalent groups are preferably -O-, -C(=O)-, alkylene groups having 1 to 5 carbon atoms, (poly)oxyalkylene groups, and groups formed by combining these, with the presence of -O- being more preferable.

[0157] Also, L 11 If the group is divalent and has hydrogen atoms, one or more of them may be substituted with monovalent substituents. Substituents can be used to adjust the reactivity of the curable group and include, for example, electron-withdrawing groups such as halogen groups, nitro groups, trifluoromethyl groups, and nitrile groups; electron-donating groups such as alkoxy groups and alkyl groups; bulky substituents such as t-butyl groups and isopropyl groups; and long-chain alkyl groups for adjusting hydrophobicity.

[0158] X 3The curable group is not particularly limited in type as long as it is capable of curing in relation to monomer C, but it is preferable that it can penetrate the host group. Examples of such curable groups include epoxy groups, glycidyl groups, glycidyl ether groups, amino groups, hydroxyl groups, carboxyl groups, acid anhydride groups, isocyanate groups, blocked isocyanate groups, and mercapto groups, with epoxy groups, glycidyl groups, glycidyl ether groups, amino groups, hydroxyl groups, carboxyl groups, acid anhydride groups, mercapto groups, and isocyanate groups being preferred, and epoxy groups, glycidyl groups, glycidyl ether groups, amino groups, hydroxyl groups, carboxyl groups, and mercapto groups being more preferred. Furthermore, a carboxylic acid anhydride group is preferred as the acid anhydride group. A carboxylic acid anhydride group is a group obtained by removing one arbitrary hydrogen atom from a carboxylic acid anhydride group, and more preferably a group obtained by removing one arbitrary hydrogen atom from at least one selected from the group consisting of acetic acid anhydride, succinic acid anhydride, phthalic acid anhydride, and maleic acid anhydride.

[0159] Monomer B can be synthesized by known methods or used as a commercially available product. Examples of commercially available products include 4,4′-dithiodianiline, cystamine (dihydrochloride), 2,2′-dithiodianiline, 3,3′-dithiodipropionic acid, 2,2′-dithiodipropionic acid, 6,6′-dithiodinicotinic acid, dithiodiglycolic acid, 2,2′-dithiodibenzoic acid, 5,5′-dithiobis(2-nitrobenzoic acid), 4,4′-dihydroxydiphenyl disulfide, 6,6′-dihydroxy-2,2′-dinaphthyl disulfide, bis(2-hydroxyethyl) disulfide, bis(2-hydroxyethyl) disulfide, and 4,4′-dithiodibutyric acid (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0160] In addition to the above, other suitable compounds can be used, such as Trans-4,5-dihydroxy-1,2-dithiane, Dithiodiglycolic acid, 2,2′-Dithiodipropionic acid, 3,3′-Dithiobisbenzoic acid, and "HG-4045" (all manufactured by Combi-Blocks); "ACID-PEG2-SS-PEG2-ACID", "ACID-PEG3-SS-PEG3-ACID", "ACID-PEG4-SS-PEG4-ACID", and "ACID-PEG6-SS-PEG6-ACID" (all manufactured by Apollo Scientific); and Hydroxy-PEG3-SS-PEG3-alcohol (manufactured by Broad Pharma).

[0161] Furthermore, if the curable group represented by formula (11) is a glycidyl ether group, i.e., *-O-CH2-(C2H3O) (* represents the bond position), then compounds described in paragraph 0025 of U.S. Patent Application Publication No. 2017 / 0038687 and compounds described in Chinese Patent Application Publication No. 108641065, etc., can be used. Furthermore, monomer B may be synthesized and used by methods such as those described in Mat.Res.Soc.Symp.Proc.Vol.304.p.49-54(1993) and Chinese Patent Application Publication No. 108641065. One specific embodiment involves reacting an epichlorohydrin with a precursor compound having a dynamic covalent bond and a hydroxyl group in the presence of NaOH to produce a glycidyl ether group.

[0162] The molecular weight of monomer B is not particularly limited, but as one form, it is preferably 100 or more, more preferably 120 or more, even more preferably 130 or more, preferably 3000 or less, and more preferably 2000 or less. The molecular weight of monomer B is preferably 100-3000, 120-3000, 130-3000, 100-2000, 120-2000, or 130-2000.

[0163] (Monomer C) Monomer C is a compound having at least two of the curable groups that can react with monomer B within its molecule. Monomer C reacts with monomer B to form the main chain of the polymer, which is the main component of the cured product. In this specification, monomer B and monomer C refer to different compounds, typically differing in at least the type of curable group.

[0164] The content of monomer C in the composition is not particularly limited and can be appropriately selected based on the equivalent (chemical equivalent) ratio with monomer B. However, when the equivalent amount of monomer C in the reaction with monomer B is set to 1.0, the content of monomer C in the composition is preferably 0.5 to 2.0, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1.

[0165] Furthermore, while the content of monomer C in the composition is not particularly limited, from the viewpoint of obtaining a cured product with superior effects, when the total content of monomers A, B, and C is set to 100 mol%, then 10 mol% or more is preferred, more preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. When the total content of monomers A, B, and C is set to 100 mol%, then 10 to 80 mol%, 20 to 70 mol%, or 30 to 60 mol% is preferred.

[0166] Furthermore, if monomer C has a dynamic covalent bond, it is preferable that the amount of monomer C in the composition be adjusted to satisfy the H / D ratio already described. Monomer C may be used alone or in combination of two or more types. When two or more types of monomer C are used in combination, it is preferable that their total content be adjusted to fall within the above range.

[0167] Monomer C may have dynamic covalent bonds. If monomer C has dynamic covalent bonds, it is preferable that it has the same dynamic covalent bonds as monomer B. Furthermore, it is preferable that at least one set of curable groups are linked via dynamic covalent bonds.

[0168] When monomer C has dynamic covalent bonds, it is preferable because the decomposition of the hardened product by the decomposition method described later becomes easier. When dynamic covalent bonding is present, monomer C can be a compound represented by formula (3), and the preferred form is the same. In this case, Z 3 The curable group in the "group having a curable group" represented by is a different group from the curable group in monomer B, and should be selected to be reactive with each other.

[0169] On the other hand, if monomer C does not have a dynamic covalent bond, monomer C is preferably a compound represented by the following formula (4).

[0170] [ka]

[0171] In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, Z 4 represents a group having a curable group, L 4 The symbol represents a single bond or a base with j+k valencies, where j is a non-negative integer and k is a non-negative integer.

[0172] R 4 The monovalent organic group is not particularly limited, but R in formula (3) 3 Examples of groups similar to the monovalent organic group can be cited, and the preferred form is also similar.

[0173] Z 4 As for the group having a curable group, Z in formula (3) 3 Examples of groups similar to the curable group of the above, and the preferred form is also the same. However, Z 3 The curable group that Z 4 The curable groups possessed by the compound are pairs of groups that can react with each other, and are selected from the combinations already described.

[0174] In formula (4), L 4The base of the j+k valence is not particularly restricted, except that it does not have a dynamic covalent bond, and the L in equation (3) 3 Similar groups can be cited, and the preferred form is also the same. Note that L in formula (3) 3 The group represented by and L in formula (4) 4 Having identical portions of the groups represented by is preferable because it increases the compatibility of each component in the composition, allowing for the preparation of a more uniform cured product. In particular, L 4 The group is preferably a divalent group (with k = 2 and j = 0) having an -O-, linear or cyclic alkylene group, an arylene group, or a (poly)oxyalkylene group (preferably with n = 0 to 20 repetitions). In this specification, "(poly)oxyalkylene group" refers to a poly(oxyalkylene) group and an oxyalkylene group.

[0175] In equation (4), j is an integer greater than or equal to 0, preferably an integer less than or equal to 10, more preferably an integer less than or equal to 8, even more preferably an integer less than or equal to 6, particularly preferably an integer less than or equal to 4, and most preferably an integer less than or equal to 2. Of these, 0 is preferred. j is preferably 0-10, 0-8, 0-6, 0-4, or 0-2, with 0 being more preferable.

[0176] In equation (4), k is an integer greater than or equal to 2, preferably an integer less than or equal to 10, more preferably an integer less than or equal to 8, even more preferably an integer less than or equal to 6, and particularly preferably an integer less than or equal to 4. Of these, 2 is preferred. k is preferably 2-10, 2-8, 2-6, or 2-4, with 2 being more preferred.

[0177] As monomer C that does not have a dynamic covalent bond, the compound represented by the following formula (4-1) is preferred. Formula (4-1):Z 4 -L 41 -Z 4 In formula (4-1), L 41 This represents a divalent group. 41The divalent groups are -C(O)-, -C(O)O-, -OC(O)-, -O-, and -NR 20 -(R 20 Examples include (where represents a hydrogen atom or a monovalent organic group), alkylene groups (preferably with 1 to 20 carbon atoms, including cyclic and linear structures), alkenylene groups (preferably with 2 to 20 carbon atoms, including cyclic and linear structures), arylene groups, heteroarylene groups, (poly)oxyalkylene groups (preferably with n=0 to 20 repeats), and groups formed by combining these. Furthermore, the rings of the cyclic alkylene group, the cyclic alkenylene group, the arylene group, and the heteroarylene group may each form a fused ring.

[0178] Examples of arylene groups include 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,8-naphthylene group, 1,2-antrylene group, 2,3-antrylene group, 1,2-phenanthrylene group, 3,4-phenanthrylene group, and 9,10-phenanthrylene group, all of which may have substituents.

[0179] Examples of heteroarylene groups include those obtained by removing two arbitrary hydrogen atoms from thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzothiophene, indole, isoindole, indidine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline, etc.

[0180] In particular, L 41Preferred divalent groups include -O-, linear or cyclic alkylene groups, arylene groups, (poly)oxyalkylene groups (preferably with n=0 to 20 repetitions), and combinations thereof. When the divalent group is one of the above groups, monomer C is more likely to form an inclusion complex with monomer A (or its host group), and the entire complex is more likely to penetrate the host group.

[0181] (Other ingredients) The composition may further contain components other than those listed above. Examples of these other components include coloring pigments, extender pigments, dyes, ultraviolet absorbers, various fillers, and solvents.

[0182] ·solvent The solvent is not particularly limited, and known organic solvents can be used. Specifically, it is preferable to use alcohols with 1 to 6 carbon atoms and aprotic polar solvents such as tetrahydrofuran. If the composition contains a solvent, the solvent content in the composition is not particularly limited, but when the total mass of the composition is taken as 100% by mass, it is preferably 0.001 to 99% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.02 to 10% by mass, particularly preferably 0.03 to 5% by mass, and most preferably 0.03 to 3% by mass. Note that one solvent may be used alone, or two or more solvents may be used in combination. When two or more solvents are used in combination, it is preferable that their total content is within the above range.

[0183] • Inclusion complex Furthermore, in order to obtain a cured product with superior effects, the composition may also contain an inclusion complex in which either monomer B or monomer C pierces the host group of monomer A in a skewer-like manner. When the composition contains an inclusion complex, the movable crosslinks formed by the host group are more easily incorporated into the polymer network, which is the main component of the cured product, resulting in a cured product with superior effects.

[0184] The content of the inclusion complex in the composition is not particularly limited, but it is preferable to adjust it to satisfy the above H / D ratio in order to obtain a cured product with better effects. When the composition contains an inclusion complex in addition to monomer A, it is preferable that the ratio of the molar content of host groups derived from the inclusion complex to the total molar content (based on amount of substance) of host groups in the composition is 0.01 to 0.99. Furthermore, one type of inclusion complex may be used alone, or two or more types may be used in combination. When two or more types of inclusion complexes are used in combination, it is preferable that their total content be within the above range.

[0185] The method for producing the inclusion complex is not particularly limited, but one method involves mixing monomer A and monomer B (or monomer C) to prepare a mixture, adding a solvent as needed, and heating the mixture. The heating temperature is not particularly limited, but is generally preferably 20 to 100°C, and more preferably 50 to 80°C. The heating time is also not particularly limited, but is preferably 1 minute to 12 hours, and more preferably 15 minutes to 1 hour. The heating means is also not particularly limited; for example, a hot stirrer may be used, or a constant temperature bath may be used. In addition, the mixture may be irradiated with ultrasound along with or instead of heating.

[0186] Whether or not an inclusion complex has been formed can be determined, for example, by visually inspecting the state of the mixture of monomer A and monomer B (or monomer C). Typically, if the mixture is in a suspended state or in a state where it separates phases upon standing before the formation of an inclusion complex, the mixture may become viscous, such as a gel or cream, once the inclusion complex is formed. Furthermore, the mixture may become transparent once the inclusion complex is formed.

[0187] In addition to the above, the composition may also contain oligomers produced by curing monomer B and monomer C (which may further contain monomer A). When the composition contains oligomers, the amount is not particularly limited, but it is preferable that the amount is such that the composition maintains its fluidity.

[0188] <Method for manufacturing hardened products> The method for producing the cured product is not particularly limited. The composition may be coated onto a support to form layers, injected into a mold, or formed into a mass by cell casting, and the formed composition may then be heated. In addition, the composition may be irradiated with light in conjunction with or before heating to react the ethylenically unsaturated groups of monomer A with the dynamic covalent bonds.

[0189] Methods for forming the composition include, for example, coating it onto a support using a known method. If the composition contains a solvent, it may be dried as necessary (in which case the drying may be done under reduced pressure). The materials for the support and mold are not particularly limited, but include glass, metal, and resins (fluororesins and silicone resins).

[0190] The thickness of the composition is not particularly limited and can be appropriately selected depending on the intended use of the cured product. In one form, when the obtained cured product is used as a sheet, the thickness of the molded body is preferably 0.1 to 5000 μm in the cured state.

[0191] The heating temperature is not particularly limited and can be arbitrarily selected depending on the type of curable group, etc., and in one embodiment, 20 to 250°C is preferred, 50 to 200°C is more preferred, 80 to 170°C is even more preferred, and 100 to 160°C is particularly preferred. The heating time is not particularly limited, but 1 minute to 24 hours is preferred, and 5 minutes to 12 hours is more preferred.

[0192] When irradiating a composition with light, the irradiated light may be one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, as well as active energy rays such as active electron beams. Among these, ultraviolet light is preferred from the viewpoint of obtaining a more superior effect.

[0193] Furthermore, the temperature of the composition may be adjusted during light irradiation. For example, the composition may be cooled depending on the heat resistance of each monomer and the cured product (especially the polymer). Alternatively, the composition may be heated to allow the reaction between the radicals generated by the cleavage of the dynamic covalent bonds and the ethylenically unsaturated groups to proceed more uniformly. When heating the composition, the heating temperature is not particularly limited, but it should be lower than the temperature at which the curing reaction by the reaction of the curable groups of monomer B and monomer C is likely to occur, specifically 100°C or lower, and more preferably 80°C or lower.

[0194] Light irradiation may be performed in a patterned manner. By irradiating with light in a patterned manner, the bonding state of monomer A within the cured material can be controlled. The method of irradiating with light in a patterned manner is not particularly limited, but examples include irradiating the composition with light via a photomask, and using an electron beam lithography apparatus.

[0195] There are no particular limitations on the light source, but examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, and excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

[0196] The light irradiation intensity is not particularly limited, but one form is 10 to 3,000 mW / cm². 2 This is preferable. The irradiation time is preferably 0.1 seconds to 60 minutes, more preferably 1 second to 30 minutes, and even more preferably 10 seconds to 20 minutes. The integrated light intensity is 10 to 9,000 mJ / cm². 2 It is preferable.

[0197] In terms of obtaining a cured product with superior effects, a preferred method for producing a cured product includes imparting energy to a prepared composition to obtain a cured product precursor, and further imparting energy to the obtained cured product precursor to obtain a cured product.

[0198] Figure 2 is a flow chart of one embodiment of a method for manufacturing a cured product. First, in step S1, the composition is prepared. The method for preparing the composition is not particularly limited, and the components already described may be mixed by known methods. If at least one selected from the group consisting of monomer A, monomer B, and monomer C is liquid at the temperature in which the preparation is carried out (preferably liquid at the application temperature of the composition and / or the molding temperature), the other monomers may be dissolved or dispersed in the liquid monomer. Alternatively, each monomer may be dissolved or dispersed sequentially in a solvent. When dissolving or dispersing one monomer into another without using a solvent, solvent removal becomes unnecessary, making it easier to obtain a cured product.

[0199] In the flowchart of Figure 2, the method for manufacturing the cured product includes the preparation of the composition (step S1), but other embodiments of the method for manufacturing the cured product do not necessarily include step S1. In this case, a pre-prepared composition may be used.

[0200] Next, in step S2, energy is imparted to the composition to produce a cured product precursor. The cured product precursor is a mixture containing an inclusion complex of monomer B and / or monomer C and monomer A (or its host group). Preferably, the cured product precursor contains, in addition to the inclusion complex, at least one monomer selected from the group consisting of monomer A, monomer B, and monomer C, and more preferably monomer A, monomer B, and monomer C.

[0201] This step can also be described as the step of forming an inclusion complex with monomers contained in the composition. Therefore, it is preferable that the energy imparted is sufficient to form an inclusion complex, and also sufficient to prevent the reaction of the curable group from proceeding. For example, if the energy to be supplied is thermal energy, the composition can be heated. The heating temperature is not particularly limited, but is generally preferably 20 to 100°C, and more preferably 50 to 80°C. The heating time is also not particularly limited, but is preferably 1 minute to 12 hours, and more preferably 15 minutes to 1 hour. The heating means is also not particularly limited; for example, a hot stirrer may be used, or a constant temperature bath may be used. In addition to heating, or instead of heating, the composition may be irradiated with ultrasound.

[0202] When the method for producing the cured product includes this step, the curing reaction is more likely to proceed with monomer B or monomer C penetrating the host group. Therefore, the host group is more likely to function as a mobile crosslink. In addition to the formation of the inclusion complex, this step may also involve a reaction between the ethylenically unsaturated bond of monomer A and a dynamic covalent bond.

[0203] Next, in step S3, energy is applied to the curing precursor to produce a cured product. The applied energy is preferably thermal energy. One method of applying thermal energy is to heat the curing precursor.

[0204] The heating temperature is not particularly limited and can be arbitrarily selected depending on the type of curable group, etc., and in one embodiment, 70 to 250°C is preferred, 100 to 200°C is more preferred, 85 to 170°C is even more preferred, and 105 to 160°C is particularly preferred. The heating time is not particularly limited, but 1 minute to 24 hours is preferred, and 5 minutes to 12 hours is more preferred.

[0205] In this step, the curing reaction proceeds, and a network of polymer molecular chains, which is the main component of the cured product, is formed. The method for producing this cured product is characterized by the fact that, by applying appropriate energy to the composition in two stages, divided into steps S2 and S3, the host groups are incorporated into the network more efficiently, and a cured product with superior effects is obtained.

[0206] <Cured product> The cured product according to this embodiment mainly consists of a polymer formed by the reaction of two or more curable groups in monomer B and monomer C within their molecules, and a host group derived from monomer A is attached to the main chain of this polymer as a side branch. The host group is attached by the reaction between the dynamic covalent bonds of monomer B (and monomer C) and the ethylenically unsaturated bonds of monomer A.

[0207] The cured product of this embodiment is typically formed by a curing reaction of the composition, or a curing reaction of a composition containing a cured product precursor. In this process, at least one selected from the group consisting of monomer B and monomer C penetrates the host group in a skewer-like manner, and the host group fixed to the polymer functions as a movable crosslink (point).

[0208] The host group is fixed to the main chain of the polymer by the reaction between the dynamic covalent bond of monomer B (and monomer C) and the ethylenically unsaturated group of monomer A. Therefore, the rate of introduction of host groups in the polymer is expressed as H = (molar basis) of the host group content in the polymer. P The content of dynamic common bonds in polymers (on a molar basis) is D P Therefore, the adoption rate = H P / (H P +D P It can be expressed as ). The rate of host group introduction in the polymer is not particularly limited, but in order to obtain a cured product with better effects, it is preferably 0.01 or more, more preferably 0.02 or more, even more preferably 0.04 or more, particularly preferably greater than 0.04, and most preferably greater than 0.06. On the other hand, H P / (H P +D P The ratio is preferably less than 0.5, more preferably less than 0.2, even more preferably 0.1 or less, and particularly preferably less than 0.1. P / (H P +D P The answer should be given to one significant figure.

[0209] H P / (H P +D P) is preferably 0.01 or more and less than 0.5; 0.01 or more and less than 0.2; 0.01 to 0.1; 0.01 or more and less than 0.1; 0.02 or more and less than 0.2; 0.04 or more and less than 0.2; 0.04 to 0.1; 0.04 or more and less than 0.1; greater than 0.04 and less than 0.5; greater than 0.04 and less than 0.2; greater than 0.04 and 0.1 or less; greater than 0.04 and less than 0.1; greater than 0.06 and less than 0.5; greater than 0.06 and less than 0.2; greater than 0.06 and 0.1 or less; or greater than 0.06 and less than 0.1.

[0210] When monomer A has one ethylenically unsaturated group in its molecule, and monomer B (and monomer C) has one dynamic covalent bond in its molecule, in the cured product obtained by sufficiently curing the composition, the H / D ratio of the composition and the H ratio of the polymer are P / (H P +D P ) are presumed to be equal. In other words, in this case, D P This can also be described as the residual amount of dynamic covalent bonds.

[0211] In terms of obtaining a cured product with superior effects, it is preferable that the polymer has a substructure represented by the following formula (5).

[0212] [ka]

[0213] In equation (5), * represents the bond position, R 1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, with a hydrogen atom or a methyl group being preferred. L 1 represents a divalent group, and L in formula (1) 1 Examples of groups similar to the divalent group of the above include the same group, and the preferred form is also the same. H represents the host group, and R in formula (1) H Similar groups can be cited, and the preferred forms are also similar.

[0214] The above substructure is formed when an ethylenically unsaturated group of monomer A reacts with a disulfide bond, which is a dynamic covalent bond, of monomer B (and possibly monomer C). In other words, a polymer having the above substructure is obtained by curing a composition containing monomer A, monomer B having a disulfide bond as a dynamic covalent bond, and monomer C (which may also have a disulfide bond).

[0215] The cured product may contain other components as long as it contains the above polymer as its main component. Examples of such components include coloring pigments, extender pigments, dyes, ultraviolet absorbers, various fillers, and solvents. The above components are the same as those contained in the composition, and the preferred form is also the same.

[0216] In terms of having superior toughness, the cured product preferably contains monomer A. The method for producing the cured product containing monomer A is not particularly limited, and examples include leaving a portion of monomer A in the composition unreacted or adding monomer A to the cured product, and it is preferable that at least a portion of monomer A in the composition remains unreacted. The unreacted state means a state in which no bond has been formed between the ethylenically unsaturated group and the dynamic covalent bond, and the polymer main chain may pierce the host group in a skewer-like manner.

[0217] The method for leaving at least a portion of monomer A unreacted is not particularly limited, but if the composition is heated to cure, the heating temperature can be adjusted to be lower.

[0218] This cured product possesses both excellent toughness and rigidity, and as described below, it has self-healing properties, making it suitable for a wide range of applications. For example, it can be used in automobiles, electronic components, building materials, food containers, and transport containers. The composition can also be used as a coating agent and paint. In this case, the cured product is used as a coating film and paint film. Furthermore, the composition can be used as an adhesive.

[0219] The shape of the cured product is not particularly limited and can be adjusted as appropriate depending on the application. It may be in the form of a film, sheet, particulate, plate, block, pellet, lump, or powder. It may also be a three-dimensional shape with curved surfaces.

[0220] Furthermore, if one of the curing groups is an epoxy group, it is possible to maintain the rigidity, which is one of the advantages of conventional epoxy resins, while significantly improving the brittleness, which was one of its disadvantages. Therefore, it can be an excellent alternative material in fields where epoxy resins have been used.

[0221] Furthermore, this cured material possesses excellent self-healing properties. Therefore, this cured material can also be used as a self-healing component. In this specification, self-healing means the property that stress relaxation and / or repair of cracks, etc., can occur, either by external stimulation (energy application) or independently of external stimulation. Typically, it means the property that when the cut surfaces of a cut member are brought together, the cut surfaces disappear or decrease, restoring the member to its original state.

[0222] Because the main polymer chain of this cured product has dynamic covalent bonds, the application of thermal energy (heating) or light energy (light irradiation) causes the dynamic covalent bonds to dissociate and recombine, resulting in a rearrangement of crosslinking points (reversible crosslinks). This significantly relieves residual stress in the cured product and flattens the surface, thereby repairing cracks.

[0223] In the case of light irradiation, the light to be irradiated can be, for example, one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, as well as active energy rays such as active electron beams. Among these, ultraviolet light is preferred from the viewpoint of obtaining a more superior effect.

[0224] When heating a self-healing member as a self-healing method (repair method) in response to external stimuli, the heating temperature is not particularly limited, but 100 to 140°C is preferred, 105 to 135°C is more preferred, and 110 to 130°C is even more preferred. The heating time is not particularly limited, but 0.5 to 24 hours is preferred, and 0.5 to 4 hours is more preferred.

[0225] When irradiating a self-healing material with light, it is sufficient to irradiate it with one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, as well as active energy rays such as active electron beams.

[0226] The light irradiation intensity can be selected as appropriate, but one possible configuration is 10 to 3,000 mW / cm². 2 This is preferable. The irradiation time is preferably 0.1 seconds to 60 minutes, more preferably 1 second to 30 minutes, and even more preferably 10 seconds to 20 minutes. The integrated light intensity is 10 to 9,000 mJ / cm². 2 This is preferable. Heating and light irradiation may be used in combination.

[0227] <Adhesive> One preferred use of the cured product is as an adhesive. When using this cured product as an adhesive, it is preferable to allow the curing reaction to proceed at the application site to form a cured product. In this regard, a preferred form of adhesive comprises a first agent containing monomer B or monomer C and monomer A, and a second agent containing the other of monomer B or monomer C.

[0228] The first agent contains monomer B or monomer C and monomer A. The content of each monomer in the first agent is not particularly limited, but when the total content of monomer A and monomer B(C) in the first agent and monomer C(B) in the second agent is 100 mol%, the content of monomer A is preferably 0.1 mol% or more, preferably 1.0 mol% or more, more preferably 1.8 mol% or more, even more preferably 2.0 mol% or more, particularly preferably 2.5 mol% or more, and most preferably 3.0 mol% or more. Furthermore, it is preferably 50 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, particularly preferably 5.0 mol% or less, and most preferably less than 5.0 mol%.

[0229] When the total content of monomer A and monomer B(C) in the first agent and monomer C(B) in the second agent is set to 100 mol%, the content of monomer A is preferably 0.1 to 50 mol%, 1.0 to 20 mol%, 1.8 to 10 mol%, 2.0 to 10 mol%, 2.5 to 10 mol%, 3.0 to 10 mol% or less, 1.0 to 5.0 mol%, 1.8 to 5.0 mol%, 2.0 to 5.0 mol%, 2.5 to 5.0 mol%, or 3.0 to 5.0 mol% or less. Furthermore, concentrations of 1.0 mol% or more and less than 5.0 mol%; 1.8 mol% or more and less than 5.0 mol%; 2.0 mol% or more and less than 5.0 mol%; 2.5 mol% or more and less than 5.0 mol%; or 3.0 mol% or more and less than 5.0 mol% are preferred.

[0230] Furthermore, the content of monomer B or monomer C in the first agent may be appropriately selected based on the equivalent ratio of the monomer contained in the second agent with the other monomer. When the equivalent amount of the monomer contained in the second agent in the reaction with the other monomer is set to 1.0, the content of monomer B or C in the first agent is preferably 0.5 to 2.0, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1. Furthermore, regarding the content, when the total content of monomers A, B, and C is taken as 100 mol%, it is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less.

[0231] The content of monomer B or monomer C in the first agent is preferably 10-80 mol%, 20-70 mol%, or 30-60 mol%, when the total content of monomers A, B, and C is set to 100 mol%.

[0232] The first agent may contain other components besides those mentioned above. Examples of other components include solvents and inclusion complexes. If the first component contains a solvent, its type and amount are the same as the type and amount of solvent that may be contained in the composition described above, and the preferred form is also the same.

[0233] Furthermore, the first agent may contain an inclusion complex. Preferably, the inclusion complex is one in which monomer B or monomer C penetrates the host group of monomer A in a skewer-like manner, and it is preferable that the inclusion complex is between monomer A and monomer A, which is the same monomer as the monomer (B or C) contained in the first agent. When the first agent contains an inclusion complex, the movable crosslinks formed by the host group in the polymer, which is the main component of the cured product, are more easily incorporated into the polymer network, resulting in a cured product with superior effects.

[0234] The content of the inclusion complex in the first agent is not particularly limited, but should be adjusted to satisfy the H / D ratio already described. One type of inclusion complex may be used alone, or two or more may be used in combination. When two or more inclusion complexes are used in combination, it is preferable that their total content be within the above range.

[0235] The second agent contains monomer B or the other monomer C. The content of monomer B or monomer C in the second agent is not particularly limited, but when the equivalent amount in the reaction with one of the monomers contained in the first agent is taken as 1.0, the content of monomer B or C in the second agent is preferably 0.5 to 2.0, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1.

[0236] The second agent may further contain monomer A, a solvent, and an inclusion complex in addition to the above. If the second agent contains monomer A and an inclusion complex, their content should be adjusted in the same way as the content of monomer A and the inclusion complex in the first agent. Specifically, it is preferable that their total content be adjusted to within the above numerical range.

[0237] The method of using the above-mentioned two-component adhesive is not particularly limited, but one method is to mix the first and second components at the time of use to prepare a mixture, apply this mixture to the application site, and then apply energy to cure it. The energy to be supplied is preferably thermal energy. A method for supplying thermal energy is, for example, heating a mixture.

[0238] The heating temperature is not particularly limited and can be arbitrarily selected depending on the type of curable group, etc., and in one embodiment, 70 to 250°C is preferred, 100 to 200°C is more preferred, 85 to 170°C is even more preferred, and 105 to 160°C is particularly preferred. The heating time is not particularly limited, but 1 minute to 24 hours is preferred, and 5 minutes to 12 hours is more preferred.

[0239] This adhesive exhibits excellent adhesive strength because the cured product possesses both superior toughness and rigidity after reaction. Furthermore, its self-healing properties allow it to repair microcracks and other damage through external stimuli (heat and light), making it suitable for a wide range of applications.

[0240] Although the above describes a two-part adhesive, the adhesive is not limited to the above and may consist of three or more components. For example, a three-part adhesive may contain monomers A, B, and C, respectively. Alternatively, a composition containing monomers A, B, and C may be cured to form an oligomer that maintains fluidity, and the three-part adhesive may consist of a first component containing this oligomer, a second component containing monomer B, and a third component containing monomer C.

[0241] <Method for decomposing hardened material> The polymer, which is the main component of this cured product, has dynamic covalent bonds in its main chain. Therefore, by dissociating these bonds through heating and / or light irradiation, it can be softened and reshaped.

[0242] The heating temperature is not particularly limited, but in one embodiment, 70 to 250°C is preferred, 100 to 200°C is more preferred, 85 to 170°C is even more preferred, and 105 to 160°C is particularly preferred. The heating time is not particularly limited, but 1 minute to 24 hours is preferred, and 5 minutes to 12 hours is more preferred.

[0243] In the case of light irradiation, the light to be irradiated can be, for example, one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, as well as active energy rays such as active electron beams. Among these, ultraviolet light is preferred from the viewpoint of obtaining a more superior effect.

[0244] The light irradiation intensity can be selected as appropriate, but one possible configuration is 10 to 3,000 mW / cm². 2 This is preferable. The irradiation time is preferably 0.1 seconds to 60 minutes, more preferably 1 second to 30 minutes, and even more preferably 10 seconds to 20 minutes. The integrated light intensity is 10 to 9,000 mJ / cm². 2 It is preferable.

[0245] Furthermore, if the polymer has disulfide bonds as dynamic covalent bonds, these disulfide bonds can be dissociated and monomers can be recovered. A method for decomposing this cured product will now be described.

[0246] One embodiment of the method for decomposing a cured product involves contacting the cured product with a two-phase solution comprising an organic phase (oil phase) containing an organic solvent, an aqueous phase containing a water-soluble compound having at least one mercapto group in its molecule, and water.

[0247] The cured products used in this decomposition method are all obtained by curing compositions containing monomer B and monomer C, which have disulfide bonds in their molecules, and are cured products (hereinafter also referred to as "specific cured products") in which at least one set of curable groups in monomer C are linked via disulfide bonds. By contacting a specific cured product with a water-soluble compound having a mercapto group (hereinafter also referred to as "specific water-soluble compound"), disulfide bonds can be cleaved, and the molecular chain network of the polymer can be broken. The decomposition products generated by this decomposition method contain new monomers that have at least two mercapto groups at their terminal ends, and can therefore be repolymerized to form polymers by heating or other means.

[0248] Furthermore, by carrying out this reaction in a two-phase solution of organic / aqueous phases (especially at the interface), the decomposition products are distributed into the organic and aqueous phases, respectively. As a result, the monomers produced by the cleavage of the polymer network are distributed into the organic phase, while the specific water-soluble compound and its reaction products (also referred to as "specific water-soluble compound, etc.") are distributed into the aqueous phase. This allows the new monomers to be easily recovered from the organic phase without being mixed with the specific water-soluble compound, etc.

[0249] The organic solvent included in the organic phase is not particularly limited, but can be aromatic hydrocarbons such as benzene, tert-butylbenzene, and chlorobenzene; aliphatic hydrocarbons such as cyclohexane, n-hexane, n-pentane, and n-octane; or chlorinated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, dichloromethyl, and dichloroethane.

[0250] Water-soluble compounds having a mercapto group are preferably compounds having a mercapto group and a hydrophilic group such as a hydroxyl group. Examples of water-soluble compounds having a mercapto group include glutathione, thioredoxin, peroxiredoxin, and dithiothreitol (DTT), with glutathione being the most preferred.

[0251] In a two-phase solution of organic and aqueous phases, when a specific water-soluble compound is brought into contact with a specific cured product, a thiol-disulfide exchange reaction occurs, cleaving the disulfide bonds in the cured product and exchanging them with the SH bonds of the specific water-soluble compound. This allows the decomposed products (monomers) to be dissolved in the organic phase. On the other hand, for example, the specific water-soluble compound can be dissolved in the aqueous phase.

[0252] For detailed information on the decomposition conditions, please refer to SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS (2021), VOL.22, NO.1, pp. 532-542. The above conditions can also be used in this decomposition method.

[0253] The specific cured products to which this decomposition method can be applied are similar to monomers B and C described above, except that both monomer B and monomer C have disulfide bonds within their molecules, and these disulfide bonds separate one or more sets of curable groups. The preferred form is also the same. In particular, monomer B and monomer C are preferably compounds represented by formula (32).

[0254] [ka]

[0255] In formula (32), Z 3 represents a group having a curable group, and Z in formula (3) 3 This is synonymous with the base represented by , and the preferred form is also the same. In formula (32), L 32 L in formula (3) is a divalent group containing a disulfide bond that can pierce the host group in a skewer-like manner. 3 This is synonymous with the divalent group, and the preferred form is also the same.

[0256] The decomposition products obtained by the above decomposition method have at least two mercapto groups formed by the decomposition of disulfide bonds at their terminal ends, and can be polymerized by reforming the disulfide bonds through energy application (heat and / or light). In other words, the decomposition products obtained by the above decomposition method can be used as new monomers. The monomer obtained as a decomposition product is preferably a compound represented by the following formula (6).

[0257] [ka]

[0258] In formula (6), R 1 L represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. 1 represents a divalent group, R H R represents a host group. 1 , L 1 , and R H The group represented by is a bond introduced into the polymer network through the reaction between monomer A and a disulfide bond. In other words, R 1 , L 1 , and R H This group originates from monomer A.

[0259] L 1 The divalent group is not particularly restricted, but L in formula (1) 1 Examples of groups similar to the divalent group of the above include the same group, and the preferred form is also the same. H A host group represented by R 1 The bases represented by are also R in equation (1), respectively. H A host group represented by R 1 Examples of groups similar to the group represented by can be cited, and the preferred form is also similar.

[0260] In formula (6), L 6 This represents a divalent group that does not contain a disulfide bond and can penetrate the host group in a skewer-like manner, or a single bond. 6 The divalent group represented by is typically L 32It is preferable that the residue is formed by the addition of monomer A, represented by formula (1), to the disulfide bond of the divalent group represented by . That is, *-L 6 -SSL 6 -* represents the group L 32 It is preferable that this is synonymous with the group represented by L. 6 They may be the same or different from each other.

[0261] L 6 The divalent groups are -C(O)-, -C(O)O-, -OC(O)-, -O-, and -NR 20 -(R 20 Examples include groups such as (where represents a hydrogen atom or a monovalent organic group), -N=, alkylene groups (preferably with 1 to 20 carbon atoms, including cyclic and linear structures), alkenylene groups (preferably with 2 to 20 carbon atoms, including cyclic and linear structures), arylene groups, heteroarylene groups, (poly)oxyalkylene groups (preferably with n=0 to 20 repeats), and groups formed by combining these.

[0262] In formula (6), L 5 L is a base with a+1 valency, where a is an integer greater than or equal to 1, preferably 9 or less, more preferably 7 or less, even more preferably 5 or less, and particularly preferably 3 or less. 5 As the a+1 valent base, L is in equation (4). 4 Groups similar to those represented by can be cited. Among them, L 5 The a+1 valent group is preferably a linking group formed by the reaction of the curable groups present in monomer B and monomer C, respectively. L 5 The group represented by is not particularly limited, but examples include the group represented by the following formula. In the formula, "*" represents the bond position. In the formula, R represents a hydrogen atom or a monovalent organic group (excluding curable groups and disulfide bonds).

[0263] [ka]

[0264] Figures 3 to 5 are examples of reaction schemes representing a series of steps: [1] curing a composition containing monomers A, B, and C; [2] obtaining a polymer; [3] decomposing the disulfide bonds in this polymer using the method described above; and [4] obtaining new monomers as decomposition products. In the formula, L 61 , L 62 , L 63 , and L 64 L represents a divalent group that does not have a disulfide bond, or a single bond. 6 This is synonymous with the group represented by L, and the preferred form is the same. 61 and L 62 L may be the same or different, 63 , and L 64 They may be the same or different.

[0265] According to the decomposition method of the cured product of this embodiment, decomposition products that can be used as new monomers can be easily obtained. Furthermore, since the obtained monomers can be molded into any shape and cured again, this method can also be used as a recycling method for cured products.

[0266] Furthermore, it is known that polymers containing disulfide bonds undergo reductive cleavage of the disulfide bonds under reducing conditions (low oxidation-reduction potential). The decomposition products may be metabolized into inorganic compounds by marine microorganisms, and the cured product of this embodiment is expected to also possess the function of a biodegradable plastic. [Examples]

[0267] (Preparation of composition and production of cured product) TAcγCD, Polyethylene Glycol Diglycidyl Ether (PEO, M nbis(4-aminophenyl) disulfide (AMDS, manufactured by Tokyo Chemical Industry Co., Ltd.) (500 ml, manufactured by Sigma-Aldrich) was dissolved in methanol and poured into a polytetrafluoroethylene mold. The mixture was then heated in a 50°C windy oven for 2 hours to dry the solvent. When heated in a 130°C or 160°C windy oven for 4 hours, a rubbery target product was obtained.

[0268] TAcγCD was synthesized referring to Preparation Example 6 in paragraph 0250 of International Publication No. 2018 / 159791. TAcγCD is a compound represented by formula (2-1-9), in which 100% of the hydroxyl groups present in one molecule of the cyclodextrin derivative are replaced with acetyl groups. The reaction scheme is as follows:

[0269] [ka]

[0270] Tables 1 and 2 show the composition of the compositions used to prepare the cured product. Each column in Table 1 shows the content of each component. For example, in Example 1, the composition contained 0.1 g (0.04 mmol) of TAcγCD, 0.50 g (1.01 mmol) of PEO, and 0.25 g (1.01 mmol) of AMDS, and the amount of methanol (MeOH) used was 0.70 mg. The same applies to the other examples.

[0271] Table 2 shows the calculation results, such as the content ratio of each component. For example, in Example 1, it contains 0.04 mmol of TAcγCD, which corresponds to 1.9 mol% when the total content of TAcγCD, PEO, and AMDS is set to 100 mol%, and is 0.10 g by mass, which corresponds to 6.5 mass% when the total mass of the composition is set to 100 mass%. Similarly, the content of PEO and AMDS is also described. Furthermore, for MeOH (methanol), the content in the composition (mg) and the content when the total mass of the product is taken as 100% by mass (mass%) are described.

[0272] Furthermore, regarding the H / D ratio, AMDS has one SS bond per molecule, TAcγCD has one host group per molecule, and PEO does not have SS bonds. Therefore, the H / D ratio (host group / dynamic covalent bond) for each composition was calculated as shown in Table 2.

[0273] [Table 1]

[0274] [Table 2]

[0275] (Evaluation of mechanical properties) The mechanical properties of the cured products of the comparative example and Examples 1-3 were evaluated. Dumbbell specimens of the obtained cured products were prepared and tensile tests were performed at room temperature (tensile speed 1 mm / s). From the obtained stress-strain curves, the area under the curve was determined and defined as Toughness, and Young's modulus was calculated from the slope at initial strains of 1-5%.

[0276] Figure 6A shows the toughness (Toughness / KJm) as a function of host group (CD group) content (mol%), determined from the stress-strain curve of a cured product cured at 160°C. -3 Figure 6B is a diagram showing the Young's modulus (Young's modulus / MPa) relative to the host group content (mol%) obtained from the stress-strain curve for a cured product cured at 160°C. In each figure, the plots "E1," "E2," and "E3" correspond to the cured products of Examples 1-3, respectively, and "C1" corresponds to the cured product of the comparative example.

[0277] The results in Figure 6B show that the cured product obtained by curing the composition containing TAcγCD had superior toughness compared to the cured product of the comparative example. Furthermore, the results in Figure 6B also show that the cured product obtained by curing the composition containing TAcγCD had a superior Young's modulus compared to the cured product of the comparative example.

[0278] In cured products primarily composed of polymers, there is often a trade-off between Young's modulus, one of the indicators of stiffness, and toughness. However, the cured products of Examples 1-3 exhibited both excellent toughness and excellent Young's modulus (stiffness) compared to the cured products of the comparative examples. Furthermore, the cured product of Example 2, with an H / D ratio exceeding 0.04, exhibited superior toughness and a superior Young's modulus compared to the cured product of Example 1. Additionally, the cured product of Example 3, with an H / D ratio exceeding 0.06, exhibited superior toughness compared to the cured product of Example 2, despite maintaining a similar Young's modulus.

[0279] Figure 7A compares the stress-strain curves of the cured product of Example 2 (labeled "E2" in the figure) and the cured product of the comparative example (labeled "C1" in the figure). Both cured products were cured at 130°C. Figure 7B shows the changes in Young's modulus and toughness when the curing temperature of the cured product of Example 2 (labeled "E2" in the figure) and the cured product of the comparative example (labeled "C1" in the figure) is varied. The triangular markers labeled T=130 all represent cured products cured at 130°C, and the circular markers labeled T=160 all represent cured products cured at 160°C. Specifically, the data for the cured product of the comparative example cured at 130°C is plotted as "C1, T=130", the data for the cured product of the comparative example cured at 160°C is plotted as "C1, T=160", the data for the cured product of Example 2 cured at 130°C is plotted as "E2, T=130", and the data for the cured product of Example 2 cured at 160°C is plotted as "E2, T=160".

[0280] The results in Figure 7B show that when curing at a temperature of 130°C, the cured product exhibits superior toughness compared to when curing at 160°C. Furthermore, in a comparison with the case cured at 160°C, the difference in toughness between the comparative example's cured product and the comparative example's cured product was 150 kJ·m. -3 In contrast to the above, the cured product of Example 2 showed 200 kJ·m -3 As mentioned above, a larger difference was found.

[0281] The same monomers forming the main chain were used in both the cured product of Example 2 and the cured product of the Comparative Example, and their quantitative ratio and absolute amounts were also the same. Therefore, the above difference suggests that unreacted monomer A remains in the cured product of Example 2 cured at 130°C. In other words, it was found that when cured at 130°C, the content of unreacted monomer A in the cured product was higher compared to when cured at 160°C.

[0282] The cured product of Example 2 (T=130), which has these characteristics, was found to have excellent toughness while maintaining excellent rigidity because it contains unreacted monomer A. In other words, it was found that cured products containing monomer A have excellent toughness while maintaining excellent rigidity.

Claims

1. Monomer A has an ethylenically unsaturated group and a host group within the molecule, wherein the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin or a cyclodextrin derivative, Monomer B having at least one dynamic covalent bond selected from the group consisting of disulfide bonds, diselenide bonds, and diterlide bonds within the molecule, A cured product obtained by curing a composition comprising monomer C which may have the aforementioned dynamic covalent bond, At least one selected from the group consisting of monomer B and monomer C is capable of piercing the host group in a skewer-like manner. Monomer B and monomer C each have at least two of one of the curable groups that can react with each other within their respective molecules. At least one set of the curable groups in monomer B is linked via the dynamic covalent bond, The monomer A comprises a compound represented by the following formula (1), (In formula (1), R1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; RH represents the host group; and L1 represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a linear, branched, or cyclic heteroatom, and divalent groups formed by combinations thereof.) The monomer B comprises a compound represented by the following formula (3), (In formula (3), Z3 is a group having a curable group, R3 is a hydrogen atom or a monovalent organic group, L3 is a p+q valent group containing the dynamic covalent bond, p represents an integer of 0 or more, q represents an integer of 2 or more, and at least one set of the groups represented by Z3 is linked via the dynamic covalent bond.) A cured product wherein the monomer C contains a compound represented by the following formula (4). (In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, Z 4 represents a group having a curable group, L 4 represents a single bond or a j+k valent group, j represents an integer of 0 or more, and k represents an integer of 2 or more.)

2. The cured product according to claim 1, comprising a polymer having a substructure represented by the following formula (5). (In equation (5), * represents the bonding position, R １ R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. Ｈ represents the host group, L １ (This represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group which may have a linear, branched, or cyclic heteroatom having 1 to 20 carbon atoms, and divalent groups formed by combinations thereof.)

3. The cured product according to claim 2, wherein the composition comprises an inclusion complex in which either monomer B or monomer C penetrates the host group in a skewer-like manner.

4. The host group is in an inclusion complex in which the monomer B is pierced through in a skewer-like manner, The cured product according to claim 3, wherein the composition comprises an inclusion complex in which the monomer C penetrates the host group in a skewer-like manner.

5. The cured product according to claim 1, comprising the unreacted monomer A.

6. The cured product according to claim 1, wherein the ratio of the total molar content of the host group to the total molar content of the dynamic covalent bond in the composition is 0.01 or more and 0.1 or less.

7. The cured product according to claim 1, wherein monomer B and monomer C have disulfide bonds as the dynamic covalent bonds, and at least one set of curable groups in monomer C are linked via the disulfide bonds.

8. A self-healing member comprising a cured product according to any one of claims 1 to 7.

9. A first agent containing either monomer B or monomer C, and monomer A, An adhesive comprising a second agent containing monomer B or the other of monomer C, The monomer A has an ethylenically unsaturated group and a host group within its molecule, and the host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin or a cyclodextrin derivative. The monomer B has at least one dynamic covalent bond selected from the group consisting of disulfide bonds, diselenide bonds, and diterlide bonds within its molecule. The monomer C may have the dynamic covalent bond, At least one selected from the group consisting of monomer B and monomer C is capable of piercing the host group in a skewer-like manner. Monomer B and monomer C each have at least two of one of the curable groups that can react with each other within their respective molecules. At least one set of the curable groups in monomer B is linked via the dynamic covalent bond, The monomer A comprises a compound represented by the following formula (1), (In formula (1), R1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; RH represents the host group; and L1 represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a linear, branched, or cyclic heteroatom, and divalent groups formed by combinations thereof.) The monomer B comprises a compound represented by the following formula (3), (In formula (3), Z3 is a group having a curable group, R3 is a hydrogen atom or a monovalent organic group, L3 is a p+q valent group containing the dynamic covalent bond, p represents an integer of 0 or more, q represents an integer of 2 or more, and at least one set of the groups represented by Z3 is linked via the dynamic covalent bond.) An adhesive wherein monomer C contains a compound represented by the following formula (4). (In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, Z 4 represents a group having a curable group, L 4 represents a single bond or a j+k valent group, j represents an integer of 0 or more, and k represents an integer of 2 or more.)

10. The adhesive according to claim 9, wherein the first agent contains an inclusion complex in which one of the aforementioned components penetrates the host group in a skewer-like manner.

11. A polymer obtained by curing a composition comprising monomer A, monomer B, and monomer C, comprising a first agent containing a polymer having a substructure represented by the following formula (5), The second agent contains monomer B, An adhesive comprising a third agent containing monomer C, The monomer B has a disulfide bond as a dynamic covalent bond within the molecule. The monomer C may have the disulfide bond, At least one selected from the group consisting of monomer B and monomer C is capable of piercing a host group, which is a monovalent group from which one hydrogen atom or a hydroxyl group has been removed from a cyclodextrin or cyclodextrin derivative, in a skewer-like manner. Monomer B and monomer C each have at least two of one of the curable groups that can react with each other within their respective molecules. At least one set of the curable groups in monomer B is linked via the dynamic covalent bond, (In formula (5), * represents a bond position, R1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms, RH represents the host group, and L1 represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a linear, branched, or cyclic heteroatom, and divalent groups which are combinations thereof.) The monomer A comprises a compound represented by the following formula (1), (In formula (1), R1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms; RH represents the host group; and L1 represents at least one group selected from the group consisting of -O-, -NR- (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -S-, a carbonyl group, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a linear, branched, or cyclic heteroatom, and divalent groups formed by combinations thereof.) The monomer B comprises a compound represented by the following formula (3), (In formula (3), Z3 is a group having a curable group, R3 is a hydrogen atom or a monovalent organic group, L3 is a p+q valent group containing the dynamic covalent bond, p represents an integer of 0 or more, q represents an integer of 2 or more, and at least one set of the groups represented by Z3 is linked via the dynamic covalent bond.) An adhesive wherein monomer C contains a compound represented by the following formula (4). (In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, Z 4 represents a group having a curable group, L 4 represents a single bond or a j+k valent group, j represents an integer of 0 or more, and k represents an integer of 2 or more.)

12. A method for producing a cured product according to any one of claims 1 to 7, comprising applying energy to the composition to obtain a cured product.

13. The method for producing a cured product according to claim 12, further comprising, before imparting the aforementioned energy, forming an inclusion complex in which either monomer B or monomer C penetrates the host group of monomer A in a skewer-like manner.

14. A method for decomposing a cured product, comprising contacting the cured product according to claim 7 with a two-phase solution comprising an organic phase containing an organic solvent, a water-soluble compound containing at least one mercapto group in its molecule, and water, to decompose the cured product.

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