Epoxy resin composition, epoxy resin cured product, prepreg, fiber-reinforced composite material, repair method of epoxy resin cured product, repair method of fiber-reinforced composite material, re-molding method of epoxy resin cured product, re-molding method of fiber-reinforced composite material, decomposition method of epoxy resin cured product, and reinforcement fiber recovery method of fiber-reinforced composite material

Abstract

To provide an epoxy resin composition which is excellent in re-moldability and self-repair property in a cured product, in use of a compound containing a dynamic covalent bond equal to or less than a theoretical equivalent to an epoxy resin, an epoxy resin cured product obtained by curing the epoxy resin composition, a prepreg, a fiber-reinforced composite material, a repair method, a re-molding method and a decomposition method of an epoxy resin cured product, and a repair method, a re-molding method and a reinforcement fiber recovery method of a fiber-reinforced composite material.SOLUTION: An epoxy resin composition contains at least an epoxy resin [A] and a curing agent [B], wherein an average epoxy equivalent of the epoxy resin [A] is within a range of 320 g / eq or more and 5,000 g / eq or less, the curing agent [B] contains at least a curing agent [B1] containing a dynamic covalent bond Y, the curing agent [B1] contains active hydrogen, and a ratio (b1) / (a) of a molar quantity (b1) of the active hydrogen to a molar quantity (a) of an epoxy group in the epoxy resin [A] is within a range of 0.25 or more and 2.0 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an epoxy resin composition, a cured epoxy resin product, a prepreg, a fiber-reinforced composite material, a method for repairing a cured epoxy resin product, a method for repairing a fiber-reinforced composite material, a method for remolding a cured epoxy resin product, a method for remolding a fiber-reinforced composite material, a method for decomposing a cured epoxy resin product, and a method for recovering reinforcing fibers from a fiber-reinforced composite material. [Background technology]

[0002] Fiber-reinforced composite materials, obtained by combining reinforcing fiber materials such as carbon fiber, glass fiber, and aramid fiber with various matrix resins, are widely used in a variety of fields and applications. Traditionally, in the aerospace and industrial fields, where high mechanical properties and heat resistance are required, thermosetting resins such as unsaturated polyester resin, epoxy resin, and polyimide resin have been mainly used as the matrix resin.

[0003] However, these thermosetting resins, once cured, do not retain fluidity even when heated, and therefore cannot be molded or deformed again, resulting in the disposal of leftover cured products and defective molded products generated during the manufacturing process. Although various improvements have been made to the manufacturing process in order to reduce the amount of discarded cured products, it has been difficult to reduce the amount of discarded cured products by improving the manufacturing process alone.

[0004] Therefore, in light of the above-mentioned background, improvements in resin compositions have been investigated. Among these, a method that has attracted attention is to reuse cured offcuts and defective molded products by introducing exchangeable and / or recombinable chemical bond sites (also called dynamic covalent bond sites) into the resin composition. In this method, the exchangeable and / or recombinable chemical bond sites are cleaved by heating, thereby dissolving the internal network structure of the cured product and allowing the resin to regain fluidity and be molded again. For example, Patent Document 1 discloses an epoxy resin composition that uses, as a curing agent, a compound that contains a disulfide bond as an exchangeable and / or recombinable chemical bonding site. As another example, Non-Patent Document 1 discloses an epoxy resin composition using, as a curing agent, a compound containing a silyl ether bond as an exchangeable and / or recombinable chemical bonding site. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2015 / 181054 [Non-patent literature]

[0006] [Non-Patent Document 1] J. Am. Chem. Soc. 2022, 144, 12280-12289 Summary of the Invention [Problem to be solved by the invention]

[0007] However, in the epoxy resin compositions described in Patent Document 1 and Non-Patent Document 1, in order to obtain sufficient fluidity in the cured product, excessive amounts of expensive compounds, such as compounds containing disulfide bonds or silyl ether bonds, were required. This is thought to be due to the fact that the activation energy of the bond exchange reaction at the molecular level is higher than the binding energy of the rigid molecular network formed, and that the low amount of dynamic covalent bonding moieties introduced and the low frequency of collisions between them result in poor bond exchange activity. On the other hand, using a curing agent in excess of the theoretical equivalent of the epoxy resin significantly impairs the heat resistance and mechanical properties of the cured product. In particular, disulfide bonds increase the degree of freedom of intramolecular rotation, which can easily impair the resin fracture toughness of the cured product. Furthermore, many compounds containing silyl ether bonds contain flexible alkyl chains, which reduces the rigidity of the molecular chains in the cured product and can easily impair mechanical heat resistance.

[0008] The present disclosure has been made in view of the above, and an object of the present disclosure is to provide an epoxy resin composition which uses a compound containing dynamic covalent bonding moieties in an amount equal to or less than the theoretical equivalent relative to the epoxy resin, yet which has excellent remoldability and self-repairing properties in the cured product; an epoxy resin cured product obtained by curing the epoxy resin composition, a prepreg, a fiber-reinforced composite material; a method for repairing an epoxy resin cured product, a method for repairing a fiber-reinforced composite material, a method for remolding an epoxy resin cured product, a method for remolding a fiber-reinforced composite material, a method for decomposing an epoxy resin cured product, and a method for recovering reinforcing fibers from a fiber-reinforced composite material. [Means for solving the problem]

[0009] Specific means for solving the above problems include the following aspects. <1> Contains at least an epoxy resin [A] and a curing agent [B], the average epoxy equivalent of the epoxy resin [A] is in the range of 320 g / eq or more and 5000 g / eq or less, the curing agent [B] includes at least a curing agent [B1] containing a dynamic covalent bonding moiety Y; The curing agent [B1] contains active hydrogen, and the ratio (b1) / (a) of the molar amount (b1) of the active hydrogen to the molar amount (a) of the epoxy groups in the epoxy resin [A] is in the range of 0.25 or more and 2.0 or less. <2> After the composition has been cured to a degree of cure of 90% or more to form a cured product, an external force is applied to the cured product at a temperature 40°C higher than the glass transition temperature of the cured product, and the resulting stress is measured. The stress relaxation rate is 80% or more one hour after the start of application of the external force. <1> The epoxy resin composition according to claim 1. <3> the concentration of the dynamic covalent bonding moiety Y relative to the total mass of the epoxy resin [A] and the curing agent [B] is in the range of 0.05 mmol / g or more and 0.65 mmol / g or less; <1> or <2> The epoxy resin composition according to claim 1. <4> the dynamic covalent bonding moiety Y undergoes concerted bond exchange without cleavage; <1> ~ <3> 1. The epoxy resin composition according to claim 1 . <5> The curing agent [B1] contains an amine-based curing agent represented by the following formula (2): <1> ~ <4> 1. The epoxy resin composition according to claim 1 .

[0010] [ka]

[0011] In formula (2), R1 and R2 each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an ether group, or a divalent group formed by combining two or more groups selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an ether group, and Y represents a dynamic covalent bond moiety.

[0012] <6> the dynamic covalent bonding site Y comprises a disulfide bond; <1> ~ <5> 1. The epoxy resin composition according to claim 1 . <7> The curing agent [B1] contains an amine-based curing agent represented by the following formula (3): <1> ~ <6> 1. The epoxy resin composition according to claim 1 .

[0013] [ka]

[0014] <8> <1> ~ <7> 1. A cured epoxy resin product obtained by curing the epoxy resin composition according to any one of 1 to 8. <9> When the cured epoxy resin is brought into contact with a decomposing agent containing a reducing agent and heated at 100°C for 48 hours, 80% by mass or more of the cured epoxy resin dissolves. <8> The epoxy resin cured product according to claim 1. <10> <1> ~ <7> a prepreg obtained by impregnating a fiber-reinforced substrate having reinforcing fibers with the epoxy resin composition according to any one of the above items, A prepreg in which the content of the reinforcing fibers is in the range of 25% by volume or more and 75% by volume or less relative to the total volume of the prepreg. <11> <8> or <9> and a fiber-reinforced substrate having reinforcing fibers, A fiber-reinforced composite material in which the content of the reinforcing fibers is in the range of 25% by volume or more and 75% by volume or less relative to the total volume of the fiber-reinforced composite material. <12> Has a void inside <8> or <9> 10. A method for repairing a cured epoxy resin material, comprising heating the cured epoxy resin material described in claim 1 at a temperature equal to or higher than the glass transition temperature of the cured epoxy resin material, thereby repairing the voids. <13> Has a void inside <11> 10. A method for repairing a fiber-reinforced composite material, comprising heating the fiber-reinforced composite material described in claim 1 to a temperature equal to or higher than the glass transition temperature of the fiber-reinforced composite material, thereby repairing the voids. <14> <8> or <9> 1. A method for remolding a cured epoxy resin product, comprising heating and pressurizing the cured epoxy resin product described in claim 1 at a temperature equal to or higher than the glass transition temperature of the cured epoxy resin product. <15> <11> 1. A method for remolding a fiber-reinforced composite material, comprising heating and pressurizing the fiber-reinforced composite material described in 1. above at a temperature equal to or higher than the glass transition temperature of the fiber-reinforced composite material. <16> <8> or <9> 1. A method for decomposing a cured epoxy resin material, comprising contacting the cured epoxy resin material according to claim 1 with a decomposition agent containing a reducing agent. <17> <11> A method for recovering reinforcing fibers from a fiber-reinforced composite material, comprising contacting the fiber-reinforced composite material according to claim 1 with a decomposition agent containing a reducing agent. [Effects of the Invention]

[0015] According to the present disclosure, there are provided an epoxy resin composition which uses a compound containing dynamic covalent bonding moieties in an amount equal to or less than the theoretical equivalent relative to the epoxy resin, yet which exhibits excellent remoldability and self-repairability in the cured product; an epoxy resin cured product obtained by curing the epoxy resin composition; a prepreg; a fiber-reinforced composite material; a method for repairing an epoxy resin cured product; a method for repairing a fiber-reinforced composite material; a method for remolding an epoxy resin cured product; a method for remolding a fiber-reinforced composite material; a method for decomposing an epoxy resin cured product; and a method for recovering reinforcing fibers from a fiber-reinforced composite material. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a graph showing the results of stress relaxation measurements. [Figure 2] FIG. 2 is a graph showing the results of the stress relaxation mode separation analysis. DETAILED DESCRIPTION OF THE INVENTION

[0017] An embodiment of the present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiment. In the following disclosure, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0018] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the lower and upper limits, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. In the present disclosure, when a composition contains multiple substances corresponding to each component, the content of each component in the composition means the total content of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, when multiple elements are listed using "or" or "or," unless otherwise expressly stated, it does not exclude the selection of a combination of the multiple elements unless a technical contradiction arises. In the present disclosure, even if an element is referred to in the singular, unless expressly stated otherwise, it does not exclude the presence of a plurality insofar as it does not create a technical contradiction. In the present disclosure, multiple exemplary aspects described separately may be combined with each other to form a new aspect, unless they contradict each other.

[0019] <Epoxy resin composition> The epoxy resin composition of the present disclosure comprises at least an epoxy resin [A] and a curing agent [B], wherein the average epoxy equivalent of the epoxy resin [A] is in the range of 320 g / eq or more and 5000 g / eq or less, the curing agent [B] comprises at least a curing agent [B1] containing a dynamic covalent bonding site Y, and the curing agent [B1] contains active hydrogen, and the ratio (b1) / (a) of the molar amount (b1) of the active hydrogen to the molar amount (a) of the epoxy groups in the epoxy resin [A] is in the range of 0.25 or more and 2.0 or less.

[0020] The epoxy resin composition of the present disclosure uses a compound having dynamic covalent bonding sites in an amount equal to or less than the theoretical equivalent of the epoxy resin, yet exhibits excellent remoldability and self-repairability in the cured product. In this disclosure, "remoldability" refers to the state in which multiple cured products adhere to each other and no grain boundaries are visible on the surface, and "self-repairability" refers to the state in which cracks in the cured product disappear or shrink. Although the action of the epoxy resin composition of the present disclosure is not clear, it is presumed as follows.

[0021] The epoxy resin composition of the present disclosure comprises an epoxy resin [A] having an average epoxy equivalent ranging from 320 g / eq to 5000 g / eq, and a curing agent [B] containing at least a curing agent [B1] containing a dynamic covalent bonding moiety Y. In the present disclosure, a dynamic covalent bonding moiety refers to a covalent bonding moiety that can be exchanged and / or recombined. More specifically, a dynamic covalent bonding moiety is a bonding moiety that can reversibly exchange the bonding partners in two pairs of covalent bonds cleaved by heating, thereby forming a new combination of two covalent bonds. Alternatively, a dynamic covalent bond site is a bond site in which, upon heating, a pair of covalent bonds can reversibly recombine with another cleaved covalent bond, thereby causing recombination. That is, in the cured epoxy resin material obtained by curing the epoxy resin composition of the present disclosure, the dynamic covalent bond sites are reversibly cleaved and exchanged and / or recombined upon heating, thereby continuously changing the molecular network inside the cured epoxy resin material, and therefore the cured epoxy resin material has excellent fluidity, remoldability, and self-repairing properties.

[0022] Furthermore, in the epoxy resin composition of the present disclosure, the curing agent [B1] contains active hydrogen, and the ratio (b1) / (a) of the molar amount (b1) of the active hydrogen to the molar amount (a) of the epoxy groups in the epoxy resin [A] is in the range of 0.25 or more and 2.0 or less. When the ratio (b1) / (a) is 0.25 or more, the dynamic covalent bond moieties in the curing agent [B1] are fully utilized, improving remoldability and self-repairing properties. Furthermore, when the ratio (b1) / (a) is 2.0 or less, the molar balance between the epoxy groups in the epoxy resin [A] and the active hydrogen in the curing agent [B1] is appropriate, resulting in a cured epoxy resin with a sufficiently high crosslink density, which tends to improve the mechanical properties of the cured epoxy resin, such as heat resistance, elastic modulus, and fracture toughness.

[0023] As explained above, the epoxy resin composition of the present disclosure, by the mechanism described above, provides an epoxy resin composition that exhibits excellent remoldability and self-repairing properties in the cured product, even though it uses a compound having dynamic covalent bonding sites in an amount equal to or less than the theoretical equivalent relative to the epoxy resin. It should be noted that the present disclosure is in no way limited to the above-mentioned presumed mechanism.

[0024] <Epoxy resin [A]> The epoxy resin composition of the present disclosure contains an epoxy resin [A]. The epoxy resin [A] contained in the epoxy resin composition of the present disclosure has an average epoxy equivalent in the range of 320 g / eq or more and 5000 g / eq or less. The epoxy resin [A] may be a known epoxy resin. The epoxy resin [A] may be monofunctional, difunctional, or polyfunctional, and may be a glycidyl ether compound or a glycidyl amine compound. The epoxy resin [A] may be a single epoxy resin or a mixture of a high molecular weight epoxy resin and a low molecular weight epoxy resin.

[0025] Examples of the epoxy resin [A] include difunctional glycidylamine type epoxy resins, tetrafunctional glycidylamine type epoxy resins, difunctional glycidyl ether type epoxy resins, polyfunctional glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, and trifunctional epoxy resins. Specific examples of bifunctional glycidylamine epoxy resins include diglycidyl aniline, diglycidyl aniline derivatives such as diglycidyl-o-toluidine, diglycidyl-m-toluidine, diglycidyl-p-toluidine, diglycidyl-xylidine, diglycidyl-mesidine, diglycidyl-anisidine, diglycidyl-phenoxyaniline, and diglycidyl-naphthylamine, and derivatives thereof. Specific examples of tetrafunctional glycidylamine epoxy resins include tetraglycidyl-4,4'-diaminodiphenylmethane, tetraglycidyl-4,4'-diaminodiphenyl sulfone, tetraglycidyl-3,3'-diaminodiphenyl sulfone, tetraglycidyl-4,4'-diaminodiphenyl ether, tetraglycidyl-3,4'-diaminodiphenyl ether, and tetraglycidyl-4,4'-didithiodianiline, as well as derivatives thereof. Specific examples of bifunctional glycidyl ether epoxy resins include bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, bisphenol S-diglycidyl ether, resorcinol diglycidyl ether, 1,6-naphthalenediol diglycidyl ether, and 4,4′-dithiodiphenol diglycidyl ether, as well as derivatives thereof. Specific examples of polyfunctional glycidyl ether type epoxy resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, and derivatives thereof. Specific examples of the glycidyl ester type epoxy resin include phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, and derivatives thereof. Specific examples of trifunctional epoxy resins include triglycidyl-m-aminophenol, triglycidyl-p-aminophenol, triglycidyl isocyanurate, and derivatives thereof.

[0026] Among these epoxy resins, difunctional glycidyl ether epoxy resins are particularly preferred because of the ease of handling of the epoxy resin composition and the remoldability of the epoxy resin cured product. As the difunctional glycidyl ether epoxy resin, at least one selected from bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether is preferred. The epoxy resin [A] is not limited to the above-mentioned epoxy resins, and may be, for example, an aliphatic epoxy resin such as polyethylene glycol diglycidyl ether.

[0027] The epoxy resin [A] is composed of one or more types of epoxy resin, and its average epoxy equivalent is in the range of 320 g / eq to 5000 g / eq, preferably in the range of 320 g / eq to 2000 g / eq, more preferably in the range of 320 g / eq to 1000 g / eq, even more preferably in the range of 380 g / eq to 1000 g / eq, and particularly preferably in the range of 430 g / eq to 1000 g / eq. When the average epoxy equivalent of the epoxy resin [A] is 320 g / eq or more, the fluidity of the cured product increases, and the remoldability of the cured product tends to improve. When the average epoxy equivalent of the epoxy resin [A] is 5000 g / eq or less, the viscosity of the epoxy resin composition does not become excessively high, which reduces the likelihood of unimpregnated areas in the prepreg and impairs the moldability of the prepreg. As a result, the formation of voids in the cured product and the deterioration of dimensional stability are suppressed.

[0028] In the present disclosure, the "average epoxy equivalent weight of the epoxy resin [A]" means the weighted average epoxy equivalent weight of all the epoxy resins [A] contained in the epoxy resin composition of the present disclosure. The epoxy equivalent of the epoxy resin [A] is a value measured by a method in accordance with JIS K 7236:2009.

[0029] The epoxy resin [A] may be a synthetic product or a commercially available product. Commercially available examples of the epoxy resin [A] include bisphenol A diglycidyl ethers manufactured by Mitsubishi Chemical Corporation, such as "jER1001" having an average epoxy equivalent of 475 g / eq, "jER1002" having an average epoxy equivalent of 650 g / eq, "jER1003" having an average epoxy equivalent of 700 g / eq, "jER1004" having an average epoxy equivalent of 950 g / eq, and "jER1007" having an average epoxy equivalent of 2000 g / eq, as well as bisphenol F diglycidyl ethers manufactured by Mitsubishi Chemical Corporation, such as "jER4005" having an average epoxy equivalent of 1050 g / eq, "jER4007" having an average epoxy equivalent of 2200 g / eq, and "jER4010" having an average epoxy equivalent of 4000 g / eq.

[0030] The epoxy resin composition of the present disclosure may contain only one type of epoxy resin [A], or may contain two or more types.

[0031] [Method for synthesizing epoxy resin [A]] When synthesizing the epoxy resin [A], the method for synthesizing the epoxy resin [A] is not particularly limited. The epoxy resin [A] may be synthesized by any method, for example, by reacting raw materials, such as an aromatic amine, aminophenol, or diphenol, with an epihalohydrin such as epichlorohydrin to obtain a halohydrin compound, and then subjecting the obtained halohydrin compound to a cyclization reaction using an alkaline compound.

[0032] <Hardening agent [B]> The epoxy resin composition of the present disclosure contains a curing agent [B]. The curing agent [B] contained in the epoxy resin composition of the present disclosure includes at least a curing agent [B1] containing a dynamic covalent bond moiety Y.

[0033] <Hardening agent [B1]> The curing agent [B1] is not particularly limited as long as it contains a dynamic covalent bond moiety Y. The curing agent [B1] may be an amine-based curing agent, an acid anhydride curing agent, a phenol-based curing agent, or a polyamide-based curing agent. Examples of the amine-based curing agent include an aliphatic amine-based curing agent and an aromatic amine-based curing agent. Phenol-based curing agents are preferred because they tend to produce cured products with low curing activity at room temperature, excellent latency, and high heat resistance. Aliphatic amine-based curing agents are more preferred because they can be synthesized and obtained inexpensively and tend to be economically superior. Acid anhydride curing agents are even more preferred because they tend to produce cured products with long storage stability and a relatively good balance of electrical properties, chemical properties, and mechanical properties. Aromatic amine-based curing agents are particularly preferred because they tend to produce cured products with excellent heat resistance, mechanical properties, electrical properties, and chemical resistance.

[0034] The curing agent [B1] contains a dynamic covalent bonding site Y. The dynamic covalent bonding site Y is not particularly limited. The dynamic covalent bonding moiety Y is preferably a group containing at least one bond selected from the group consisting of an ester bond, an imine bond, a urethane bond, a carbonate bond, a vinylogous urethane bond, a boronic acid ester bond, a silyl ether bond, and a disulfide bond. From the viewpoint of not requiring a catalyst to promote the exchange and / or recombination, a group containing at least one bond selected from the group consisting of an imine bond, a silyl ether bond, and a disulfide bond is more preferred as the dynamic covalent bonding moiety Y. Furthermore, from the viewpoint of extremely fast exchange and / or recombination speed, a group containing a disulfide bond is preferred as the dynamic covalent bonding moiety Y, and a disulfide bond is more preferred.

[0035] In addition, when two pairs of covalent bonds of a urethane bond, a carbonate bond, a vinylogous urethane bond, a boronate ester bond, a silyl ether bond, and a disulfide bond are cleaved by heating, the binding partners of each pair are exchanged to form a new combination of two pairs of covalent bonds, that is, the two pairs of covalent bonds can be reversibly dissociated once and then recombine. On the other hand, with regard to ester bonds and imine bonds, heating can reversibly cause one pair of covalent bonds to recombine with another cleaved covalent bond, resulting in recombination; that is, the two pairs of covalent bonds do not all dissociate at the same time, and cleavage and recombination occur simultaneously.

[0036] Preferably, the dynamic covalent bonding moiety Y undergoes concerted bond exchange without cleavage. Examples of the dynamic covalent bond moiety Y that undergoes concerted bond exchange without cleavage include disulfide bonds, ester bonds, boronic acid ester bonds, imine bonds, and vinylogous urethane bonds.

[0037] The ester bond is represented by the following formula (Y-1), the imine bond is represented by the following formula (Y-2), the urethane bond is represented by the following formula (Y-3), the carbonate bond is represented by the following formula (Y-4), the vinylogous urethane bond is represented by the following formula (Y-5), the boronic acid ester bond is represented by the following formula (Y-6) or (Y-7), the silyl ether bond is represented by the following formula (Y-8), and the disulfide bond is represented by the following formula (Y-9).

[0038] [ka]

[0039] In formulae (Y-1) to (Y-9), * represents a bond. R in formula (Y-5) Y1 is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 4 carbon atoms, and further preferably a methyl group, an ethyl group, or a phenyl group. In formula (Y-7), k and l each independently represent preferably an integer of 0 to 10, more preferably an integer of 0 to 5, and further preferably an integer of 0 to 2. R in formula (Y-8) Y2 and R Y3 are each independently preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group, more preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 4 carbon atoms, and further preferably a methyl group, an ethyl group, or a phenyl group.

[0040] The concentration of the dynamic covalent bonding moiety Y relative to the total mass of the epoxy resin [A] and the curing agent [B] (so-called molar concentration) is not particularly limited, but is preferably in the range of 0.05 mmol / g or more and 2.0 mmol / g or less, more preferably in the range of 0.1 mmol / g or more and 1.5 mmol / g or less, and even more preferably in the range of 0.2 mmol / g or more and 1.2 mmol / g or less. When the concentration of the dynamic covalent bond moiety Y relative to the total mass of the epoxy resin [A] and the curing agent [B] is 0.05 mmol / g or more, the remoldability and self-repairability tend to be better exhibited. When the concentration of the dynamic covalent bond moiety Y relative to the total mass of the epoxy resin [A] and the curing agent [B] is 2.0 mmol / g or less, the mechanical properties tend to be less likely to be impaired.

[0041] The curing agent [B1] preferably contains a compound represented by the following formula (2) (a so-called amine-based curing agent), and more preferably is a compound represented by the following formula (2).

[0042] [ka]

[0043] In formula (2), R1 and R2 each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an ether group, or a divalent group formed by combining two or more groups selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an ether group, and Y represents a dynamic covalent bond moiety. The compound represented by formula (2) is an amine-based curing agent in which the dynamic covalent bond site Y is bonded to two amino groups via R1 and R2.

[0044] The aliphatic hydrocarbon group has 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. Specific examples of the aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group, and unsaturated aliphatic hydrocarbon groups such as an allyl group and a vinyl group.

[0045] The alicyclic hydrocarbon group preferably has 4 to 18 carbon atoms, and more preferably has 5 to 10 carbon atoms. Specific examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group.

[0046] The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 12 carbon atoms. Specific examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group and a naphthyl group.

[0047] Specific examples of divalent groups formed by combining two or more groups selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and ether groups, each having 1 to 20 carbon atoms, include -(CH2-CH2-O)3-, -C6H4-O-C6H4-, and -C6H4-O-C2H4-.

[0048] In formula (2), R1 and R2 are each preferably independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably an ethyl group, an n-propyl group, or a phenyl group. In formula (2), Y is preferably an imine bond, a disulfide bond, or a silyl ether bond, more preferably a disulfide bond or a silyl ether bond, and even more preferably a disulfide bond.

[0049] The curing agent [B1] is preferably a compound containing an Ar-SS-Ar structure, and specific examples thereof include compounds represented by the following formula (3) (so-called amine-based curing agents) in which the dynamic covalent bonding site Y is a disulfide bond (Y-9) and compounds represented by the following formula (4) (so-called phenol-based curing agents). From the viewpoint of the heat resistance of the resulting cured product, the curing agent [B1] preferably contains a compound represented by the following formula (3), and more preferably is a compound represented by the following formula (3).

[0050] [ka]

[0051] Among the compounds represented by formula (3), the compound represented by the following formula (3-1) is preferred as the curing agent [B1] from the viewpoint of the heat resistance of the resulting cured product. Among the compounds represented by formula (4), the compound represented by the following formula (4-1) is preferred as the curing agent [B1] from the viewpoint of the heat resistance of the resulting cured product.

[0052] [ka]

[0053] Other examples of the curing agent [B1] include a compound represented by the following formula (5) in which the dynamic covalent bonding moiety Y is a silyl ether bond (Y-8) and a compound represented by the following formula (6).

[0054] [ka]

[0055] In formula (5), R1, R2, R3, and R4 each independently represent an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, or a monovalent group formed by combining two or more groups selected from the group consisting of an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and alkoxy group, all of which have 1 to 20 carbon atoms, and n represents an integer of 1 to 20.

[0056] The aliphatic hydrocarbon group has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms. Specific examples of the aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group, and unsaturated aliphatic hydrocarbon groups such as an allyl group and a vinyl group.

[0057] The alicyclic hydrocarbon group preferably has 4 to 18 carbon atoms, and more preferably has 5 to 10 carbon atoms. Specific examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group.

[0058] The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 15 carbon atoms, further preferably 6 to 12 carbon atoms, and particularly preferably 6 to 10 carbon atoms. Specific examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group and a naphthyl group.

[0059] The alkoxy group may be linear, branched, or cyclic. The alkoxy group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, an n-pentyloxy group, and an n-hexyloxy group.

[0060] Specific examples of the monovalent group formed by combining two or more groups selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and alkoxy groups having 1 to 20 carbon atoms include -CH2-Ph, -CH2-O-Ph, and -CH2-O-CH 12 In this disclosure, "Ph" represents phenyl.

[0061] In formula (5), R1, R2, R3, and R4 are each independently preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a methyl group, an ethyl group, or a phenyl group. In formula (5), n preferably represents an integer of 1 to 12, more preferably an integer of 2 to 8, and even more preferably an integer of 2 to 6. In formula (5), the two n's may be the same or different.

[0062] In formula (6), R5 and R6 each independently represent a hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group having 1 to 20 carbon atoms; n represents an integer of 1 to 20. In formula (6), R5 and R6 are each independently preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 1 to 10 carbon atoms, and further preferably a methyl group, an ethyl group, or a phenyl group. In formula (6), n preferably represents an integer of 1 to 12, more preferably an integer of 2 to 8, and even more preferably an integer of 2 to 6. In formula (6), the two n's may be the same or different.

[0063] Among the compounds represented by formula (5), the compound (5-1) is preferred as the curing agent [B1] from the viewpoint of the remoldability and self-repairing properties of the resulting cured product.

[0064] [ka]

[0065] The molecular weight of the curing agent [B1] is not particularly limited, but is preferably in the range of 100 or more and 1,000 or less, more preferably in the range of 100 or more and 500 or less, and even more preferably in the range of 100 or more and 300 or less. In the present disclosure, the molecular weight of the curing agent [B1] is a value determined by mass spectrometry.

[0066] The curing agent [B1] contains active hydrogen. The active hydrogen equivalent of the curing agent [B1] is not particularly limited, but is preferably in the range of 25 g / eq or more and 250 g / eq or less, more preferably in the range of 25 g / eq or more and 150 g / eq or less, and even more preferably in the range of 25 g / eq or more and 100 g / eq or less. In the present disclosure, the active hydrogen equivalent of the curing agent [B1] is a value calculated from the amount of active hydrogen groups (so-called active hydrogen value) contained in the curing agent [B1] using the following formula: [Active hydrogen equivalent] = 56.1 x 1000 ÷ [Active hydrogen number] The active hydrogen number is the amine number determined by a method conforming to JIS K 7237:1995 in the case of an amine-based curing agent, and is the hydroxyl number determined by a method conforming to JIS K 0070:1992 in the case of a phenol-based curing agent.

[0067] The remoldability and self-repairing properties of the cured epoxy resin product obtained by curing the epoxy resin composition of the present disclosure are presumed to be due to the dynamic covalent bonding moiety Y contained in the curing agent [B1]. The high heat resistance, elastic modulus, and strength of the cured epoxy resin product obtained by curing the epoxy resin composition of the present disclosure are presumed to be brought about by the rigid aromatic ring contained in the above formula (3) or formula (4).

[0068] The proportion of the curing agent [B1] contained in the curing agent [B] is not particularly limited and is adjusted appropriately depending on the type of curing agent [B1], the desired properties of the cured product, and the like.

[0069] (ratio (b1) / (b)) The ratio (b1) / (b) of the molar amount (b1) of active hydrogen in the curing agent [B1] to the molar amount (b) of active hydrogen in the curing agent [B] is not particularly limited, but is, for example, preferably in the range of 0.1 or more and 1.0 or less, more preferably in the range of 0.4 or more and 1.0 or less, even more preferably in the range of 0.7 or more and 1.0 or less, particularly preferably in the range of 0.9 or more and 1.0 or less, and most preferably 1.0. When the ratio (b1) / (b) is 0.1 or more, the performance provided by the dynamic covalent bond moiety Y in the cured epoxy resin material is more satisfactorily exhibited, and the remoldability and self-repairability of the cured epoxy resin material tend to be further improved.

[0070] In the present disclosure, the "molar amount (b) of active hydrogen in curing agent [B]" means the total molar amount of active hydrogen derived from curing agent [B] (hereinafter also referred to as "total molar amount of active hydrogen in curing agent [B]"). The molar amount of all active hydrogen in the curing agent [B] is calculated from the sum of the molar amount of active hydrogen derived from the curing agent [B1] and the molar amount of active hydrogen derived from curing agents other than the curing agent [B1], both of which are contained in the epoxy resin composition. The "molar amount of active hydrogen derived from curing agent [B1]" can be calculated by dividing the molar amount of curing agent [B1] contained in the epoxy resin composition by the number of active hydrogens contained in one molecule of the compound that is curing agent [B1]. The "molar amount of active hydrogen derived from a curing agent other than curing agent [B1]" can be calculated by dividing the molar amount of a curing agent other than curing agent [B1] contained in the epoxy resin composition by the number of active hydrogens contained in one molecule of the compound that is a curing agent other than curing agent [B1].

[0071] <Curing agents other than curing agent [B1]> The curing agent [B] may contain, in addition to the curing agent [B1], a known curing agent that cures epoxy resins. The curing agent other than the curing agent [B1] is not particularly limited as long as it is a curing agent that can cure epoxy resins, and may be appropriately selected depending on the intended use, etc.

[0072] Specifically, examples of curing agents other than the curing agent [B1] include dicyandiamide, phenolic curing agents that do not contain the dynamic covalent bond moiety Y and various isomers thereof, aromatic amine curing agents that do not contain the dynamic covalent bond moiety Y and various isomers thereof, and aminobenzoic acid ester compounds. Dicyandiamide is preferred because it provides excellent storage stability to the prepreg described below. Among aromatic amine-based curing agents that do not contain a dynamic covalent bond moiety Y, aromatic diamine compounds such as 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenylmethane, as well as derivatives thereof having a non-reactive substituent, are preferred because they can give cured products with high heat resistance, and among aromatic diamine compounds, 3,3'-diaminodiphenyl sulfone is the most preferred because it can give cured products with high heat resistance and elastic modulus. Examples of non-reactive substituents include alkyl groups such as methyl, ethyl, and isopropyl groups, aromatic groups such as phenyl groups, and halogen groups such as alkoxyl groups, aralkyl groups, and chlorine and bromine groups.

[0073] (Total amount of hardener [B]) The total amount of the curing agent [B] contained in the epoxy resin composition of the present disclosure is not particularly limited as long as it is an amount suitable for curing all of the epoxy resins [A] contained in the epoxy resin composition, and is adjusted appropriately depending on the types of the epoxy resins [A] or the curing agent [B].

[0074] (Total amount of epoxy resin [A] and hardener [B]) The total amount of the epoxy resin [A] and the curing agent [B] contained in the epoxy resin composition of the present disclosure is not particularly limited, but is, for example, preferably in the range of 50% by mass or more and less than 100% by mass, more preferably in the range of 70% by mass or more and less than 100% by mass, and even more preferably in the range of 90% by mass or more and less than 100% by mass, relative to the total mass of the epoxy resin composition.

[0075] (ratio (b) / (a)) The ratio (b) / (a) of the molar amount (b) of active hydrogen in the curing agent [B] to the molar amount (a) of epoxy groups in the epoxy resin [A] is not particularly limited, but is preferably, for example, in the range of 0.5 or more and 2.0 or less, more preferably in the range of 0.75 or more and 1.5 or less, even more preferably in the range of 0.9 or more and 1.2 or less, and particularly preferably 1.0. When the ratio (b) / (a) is within the above range, the molar balance between the epoxy groups in the epoxy resin [A] and the active hydrogen in the curing agent [B] is good, so that a cured epoxy resin product having sufficient crosslink density can be obtained, and the mechanical properties such as heat resistance, elastic modulus, and fracture toughness of the cured epoxy resin product tend to be further improved.

[0076] In the present disclosure, the "molar amount (a) of epoxy groups in the epoxy resin [A]" means the total molar amount of epoxy groups in the epoxy resin [A] (hereinafter also referred to as "the molar amount of all epoxy groups in the epoxy resin [A]"). The molar amount of all epoxy groups in the epoxy resin [A] is determined from the sum of the molar amounts of epoxy groups obtained by dividing the mass of each epoxy resin [A] contained in the epoxy resin composition by the respective epoxy equivalents.

[0077] (ratio (b1) / (a)) The ratio (b1) / (a) of the molar amount (b1) of active hydrogen in the curing agent [B1] to the molar amount (a) of epoxy groups in the epoxy resin [A] is in the range of 0.25 or more and 2.0 or less, preferably in the range of 0.6 or more and 1.5 or less, more preferably in the range of 0.8 or more and 1.2 or less, even more preferably in the range of 0.9 or more and 1.1 or less, and particularly preferably 1.0. When the ratio (b1) / (a) is 0.25 or more, the performance provided by the dynamic covalent bond moiety Y is well exhibited, and the remoldability and self-repairability of the cured product tend to be improved. Furthermore, when the ratio (b1) / (a) is 2.0 or less, the molar balance between the epoxy groups in the epoxy resin [A] and the active hydrogen in the curing agent [B1] becomes appropriate, and a cured epoxy resin product having a sufficiently high crosslink density is obtained, and the mechanical properties such as heat resistance, elastic modulus, and fracture toughness of the cured epoxy resin product tend to be improved.

[0078] The ratio (b1) / (a) is the epoxy resin composition 1 The obtained 1 This can be confirmed by the integrated area ratio of the peak derived from the epoxy group to the peak derived from the active hydrogen in the H-NMR spectrum.

[0079] In the present disclosure, using a theoretically equivalent amount of the compound containing dynamic covalent bonding moieties relative to the epoxy resin means using the compound containing dynamic covalent bonding moieties in an amount such that the molar amount of active hydrogen in the compound containing dynamic covalent bonding moieties is 1 relative to the molar amount of epoxy groups in the epoxy resin of 1, and in this case, the ratio (b1) / (a) is 1.0. In the present disclosure, using a compound containing dynamic covalent bonding sites in an amount equal to or less than the theoretical equivalent relative to the epoxy resin means that the ratio (b1) / (a) is 1.0 or less.

[0080] <Curing accelerator> The epoxy resin composition of the present disclosure may contain a curing accelerator in addition to the epoxy resin [A] and curing agent [B] described above. The curing accelerator accelerates the curing reaction of the epoxy resin composition and the prepreg impregnated therewith, thereby forming a cured product having high elastic modulus and strength in a short production time. The curing accelerator is not particularly limited as long as it accelerates the curing reaction between the epoxy resin [A] and the curing agent [B], and examples thereof include nitrogen-containing heterocyclic compounds such as imidazole compounds and tertiary amine compounds, as well as onium salts thereof, phosphine compounds, and phosphonium salts thereof.

[0081] Specific examples of the curing accelerator include imidazole compounds such as 2-ethyl-4-methylimidazole and 1-(2-cyanoethyl)-2-phenylimidazole, and salts thereof; tertiary amine compounds such as diazabicycloundecene, diazabicyclononene, and tris(dimethylaminomethyl)phenol, and salts thereof; phosphine compounds such as triphenylphosphine and tri(orthotolyl)phosphine; and phosphonium salts such as tetraphenylphosphonium tetraphenylborate.

[0082] When the epoxy resin composition of the present disclosure contains a curing accelerator, the content of the curing accelerator is not particularly limited and is set appropriately as needed.

[0083] <Other ingredients> The epoxy resin composition of the present disclosure may contain components other than the essential components, the epoxy resin [A] and the curing agent [B], and the optional curing accelerator (so-called other components). The other components include, for example, a thermoplastic resin, conductive particles, a flame retardant, an inorganic filler, and an internal mold release agent.

[0084] The thermoplastic resin improves the fracture toughness and impact resistance of the resulting fiber reinforced composite material. Examples of the thermoplastic resin include epoxy resin-soluble thermoplastic resins and epoxy resin-insoluble thermoplastic resins.

[0085] The epoxy resin-soluble thermoplastic resin adjusts the viscosity of the epoxy resin composition and further improves the impact resistance of the resulting fiber-reinforced composite material. Examples of epoxy resin-soluble thermoplastic resins include polyethersulfone, polysulfone, polyetherimide, and polycarbonate. The epoxy resin-soluble thermoplastic resin preferably contains at least one selected from polyethersulfone and polysulfone, and more preferably is at least one selected from polyethersulfone and polysulfone. When the epoxy resin composition of the present disclosure contains an epoxy resin-soluble thermoplastic resin as the thermoplastic resin, it may contain only one type of the epoxy resin-soluble thermoplastic resin, or may contain two or more types of the epoxy resin-soluble thermoplastic resin.

[0086] The epoxy resin-soluble thermoplastic resin preferably has a weight average molecular weight (Mw) in the range of 8,000 or more and 100,000 or less as measured by gel permeation chromatography. When the weight-average molecular weight (Mw) of the epoxy resin-soluble thermoplastic resin is 8000 or more, the impact resistance of the obtained fiber-reinforced composite material tends to be further improved. Also, when the weight-average molecular weight (Mw) of the epoxy resin-soluble thermoplastic resin is 100000 or less, the viscosity of the epoxy resin composition does not become too high, and therefore the handling property is good. The epoxy resin-soluble thermoplastic resin preferably has a narrow molecular weight distribution as measured by gel permeation chromatography. The polydispersity (Mw / Mn), which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), is preferably in the range of 1-10, and more preferably in the range of 1.1-5.

[0087] The epoxy resin-soluble thermoplastic resin preferably has a reactive group reactive with the epoxy resin or a functional group capable of forming a hydrogen bond. Such an epoxy resin-soluble thermoplastic resin can improve the solubility stability of the epoxy resin during the curing process. Furthermore, such an epoxy resin-soluble thermoplastic resin can impart toughness, chemical resistance, heat resistance, and moist heat resistance to the fiber-reinforced composite material obtained after curing.

[0088] The reactive group reactive with the epoxy resin is not particularly limited, but is preferably, for example, a hydroxyl group, a carboxylic acid group, an imino group, or an amino group. The epoxy resin-soluble thermoplastic resin is preferably a hydroxyl-terminated polyethersulfone. When the epoxy resin composition of the present disclosure contains a hydroxyl-terminated polyethersulfone as the epoxy resin-soluble thermoplastic resin, the impact resistance, fracture toughness, and solvent resistance of the resulting fiber-reinforced composite material tend to be further improved.

[0089] A part of the epoxy resin-insoluble thermoplastic resin or epoxy resin-soluble thermoplastic resin (i.e., the epoxy resin-soluble thermoplastic resin that remains undissolved in the matrix resin after curing) is in a state where its particles are dispersed in the matrix resin of the fiber-reinforced composite material. These dispersed particles suppress the propagation of impacts received by the fiber-reinforced composite material, thereby improving the impact resistance of the resulting fiber-reinforced composite material.

[0090] Examples of epoxy resin-insoluble thermoplastic resins include polyamide, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyester, polyamideimide, polyimide, polyether ketone, polyether ether ketone, polyethylene naphthalate, polyether nitrile, and polybenzimidazole. Among these, polyamide, polyamideimide, and polyimide are preferred due to their high toughness and heat resistance, and polyamide and polyimide are particularly effective in improving the toughness of fiber-reinforced composite materials. When the epoxy resin composition of the present disclosure contains an epoxy resin-insoluble thermoplastic resin as a thermoplastic resin, it may contain only one type of the epoxy resin-insoluble thermoplastic resin, or may contain two or more types of the epoxy resin-insoluble thermoplastic resin, or may contain a copolymer of two or more types of the epoxy resin-insoluble thermoplastic resin.

[0091] In particular, polyamides such as amorphous polyimide, Nylon 6 (registered trademark) (a polyamide obtained by a ring-opening polycondensation reaction of caprolactam), Nylon 11 (a polyamide obtained by a ring-opening polycondensation reaction of undecane lactam), Nylon 12 (a polyamide obtained by a ring-opening polycondensation reaction of lauryllactam), Nylon 1010 (a polyamide obtained by a copolymerization reaction of sebacic acid and 1,10-decanediamine), and amorphous nylon (also known as transparent nylon, which does not crystallize or whose polymer crystallization rate is extremely slow) can significantly improve the heat resistance of the resulting fiber-reinforced composite material.

[0092] Examples of conductive particles include conductive polymer particles such as polyacetylene particles, polyaniline particles, polypyrrole particles, polythiophene particles, polyisothianaphthene particles, and polyethylenedioxythiophene particles; carbon particles; carbon fiber particles; metal particles; and particles in which a core material made of an inorganic or organic material is coated with a conductive substance.

[0093] Examples of the flame retardant include phosphorus-based flame retardants. The phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom in the molecule. Examples of phosphorus-based flame retardants include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, phosphazene compounds, and polyphosphates, as well as red phosphorus.

[0094] Examples of inorganic fillers include aluminum borate, calcium carbonate, silicon carbonate, silicon nitride, potassium titanate, basic magnesium sulfate, zinc oxide, graphite, calcium sulfate, magnesium borate, magnesium oxide, and silicate minerals. As the inorganic filler, silicate minerals are preferred. A specific example of the silicate mineral is THIXOTROPIC AGENT DT 5039 (manufactured by Huntsman Japan Co., Ltd.).

[0095] Examples of internal release agents include metal soaps, vegetable waxes such as polyethylene wax and carnauba wax, fatty acid ester-based release agents, silicone oils, animal waxes, and fluorine-based nonionic surfactants. When the epoxy resin composition of the present disclosure contains an internal mold release agent, the content of the internal mold release agent is not particularly limited, but is, for example, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass, per 100 parts by mass of the epoxy resin [A]. When the content of the internal mold release agent in the epoxy resin composition of the present disclosure is within the above range relative to 100 parts by mass of the epoxy resin [A], the mold release effect from the mold is excellent.

[0096] Examples of commercially available internal mold release agents include MOLD WIZ (registered trademark) INT1846 (manufactured by AXEL PLASTICS RESEARCH LABORATORIES INC.), Licowax S, Licowax P, Licowax OP, Licowax PE190, and Licowax PED (all manufactured by Clariant Japan K.K.), and Rikemal (registered trademark) SL-900A (manufactured by Riken Vitamin Co., Ltd.).

[0097] [Stress relaxation rate] The epoxy resin composition of the present disclosure is cured to a degree of cure of 90% or more to form a cured product, and then an external force is applied to the cured product at a temperature 40°C higher than the glass transition temperature of the cured product. When the stress generated is measured, the stress relaxation rate one hour after the start of application of the external force is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. When the stress relaxation rate is 80% or more, the remoldability of the epoxy resin cured product and the fiber reinforced composite material described below tends not to be impaired, and the strength and elastic modulus tend not to decrease.

[0098] The stress relaxation rate is a value calculated by the following formula for the change in modulus G over time for 3600 seconds (1 hour) that occurs in the measurement of stress relaxation. The modulus is the value of stress that occurs when an external force is applied to cause distortion. [1-((G(min)) / (G(0)))]×100 G(0) is the modulus value at the start of application of the external force (ie, 0 seconds after the start of application of the external force). G(min) is the minimum modulus value at 3600 seconds after the start of application of external force, in other words, the minimum modulus value up to 3600 seconds after the start of application of external force.If the modulus value reaches the lower limit of measurement by the device within 3600 seconds after the start of application of external force, this is the numerical value.If the modulus value does not reach the lower limit of measurement by the device within 3600 seconds after the start of application of external force, this is the modulus value at 3600 seconds after the start of application of external force.

[0099] A stress relaxation rate of 80% or more one hour after the start of application of an external force means that the stress, which was 100% at the start of application of the external force, relaxes with the application of the external force and the passage of time, decreasing to less than 20% one hour after the start of application of the external force, and the cured product becomes fluid. By becoming fluid, the cured product can have remoldability and self-repairing properties.

[0100] [Stress relaxation mode separation analysis] The stress relaxation mode separation analysis is described in detail. The stress relaxation behavior of the cured product of the epoxy resin composition of the present disclosure when stress is applied can be approximated by a generalized Maxwell model. This generalized Maxwell model is a model in which multiple types of two-element models, so-called Maxwell elements, consisting of a dashpot and a spring arranged in series, are arranged in parallel. In this generalized Maxwell model, each constituent Maxwell element corresponds to one relaxation mode. In other words, the stress relaxation behavior of the generalized Maxwell model when stress is applied can be described as a linear sum of the behavior of each constituent Maxwell element (each relaxation mode). Then, by separating the stress relaxation measurement results according to the linear sum equation of the generalized Maxwell model and evaluating the relaxation time for each relaxation mode, it becomes possible to quantitatively evaluate the bond exchange performance within the cured product of the epoxy resin composition of the present disclosure.

[0101] The modulus value G(t) over 3600 seconds resulting from stress relaxation measurements is approximated by the following formula with a correlation square coefficient R2 > 0.999:

[0102]

number

[0103] In the above formula, t is time (unit: seconds), and G0 is the modulus value G(0) at t = 0 seconds. i is Σμ i = 1, and is a variable that indicates the contribution (unit: %) of each term (so-called each relaxation mode) in this multi-dimensional linear equation. τ i is the relaxation time (seconds) in each relaxation mode that is arbitrarily set, and is set to include a relaxation mode having a relaxation time that is sufficiently large relative to the measurement time. Furthermore, each relaxation mode is set so that its relaxation time is uniform across the same logarithmic range and uniform within the same logarithmic range. The number and range of relaxation modes to be set are not particularly limited, but it is preferable to have as many as possible in terms of, for example, calculation load.

[0104] For example, when performing stress relaxation mode separation analysis in the range of 0 seconds to 3600 seconds on the cured epoxy resin material of the present disclosure, it is preferable to analyze using the following 25 types of relaxation modes (that is, values ​​of τi). τi=1,2.5,4,5.5,7,8.5,10,25,40,55,70,85,100,250,400,550,700,850,1000,2500,4000,5500,7000,8500,10000 In this case, τ is set to include the measurement time of 3600 seconds. i The maximum value of τ i = 10,000 (seconds). Furthermore, each relaxation mode is set so that its relaxation time is uniform across the same logarithmic range, such as 1, 4, 7, 10, 40, etc. The cured product of the epoxy resin composition of the present disclosure is then approximated by a linear sum of relaxation modes with 25 different relaxation times, and the stress relaxation behavior is measured.

[0105] Next, for each measured relaxation mode, the logarithm of the relaxation time is plotted on the horizontal axis and the logarithm of the stress is plotted on the vertical axis, and an approximate formula is obtained using the above formula. i and μ i On the horizontal axis, τ i Plot the logarithm of μ on the vertical axis. i τ, which has a peak in the distribution when plotted i is the relaxation time of the separated relaxation modes. Furthermore, the τ that constitutes each peak i μ in the group i τ that constitutes any peak for the sum of i μ in i The value of is the contribution (%) of the isolated relaxation mode.

[0106] The stress relaxation can be measured using a conventionally known device and method. In measuring stress relaxation, it is sufficient to be able to track and record the change in stress over time after applying an external force instantaneously under isothermal conditions using a thermostatic device. Specific examples of stress relaxation measurements include measurements in shear mode using a rheometer equipped with parallel plates and measurements in bending or tension mode using dynamic mechanical analysis (DMA). Measurements are preferably performed in an inert gas atmosphere and in a humidity-controlled environment. Although not particularly limited, stress relaxation measurements are preferably performed in a room with a low humidity atmosphere of 50% RH or less, with nitrogen flowing through the measurement device at a flow rate of 10 L / min or more.

[0107] After the epoxy resin composition of the present disclosure is cured to a degree of cure of 90% or more to form a cured product, an external force is applied to the cured product at a temperature 40°C higher than the glass transition temperature of the cured product. The stress relaxation behavior when the stress is measured is shown in the stress relaxation mode separation analysis. i Plot the logarithm of μ on the vertical axis. i In the graph where the above equations are plotted, it is preferable to have two or more relaxation mode groups with distributions. In the graph, it is preferable that the contribution of the relaxation mode group with a relaxation time of more than 1000 seconds is 40% or less, more preferably that the contribution of the relaxation mode group with a relaxation time of more than 1000 seconds is 25% or less, and even more preferably that the contribution of the relaxation mode group with a relaxation time of more than 1000 seconds is 25% or less, the contribution of the relaxation mode group with a relaxation time of 200 to 1000 seconds is 50% or less, and the contribution of the relaxation mode group with a relaxation time of less than 200 seconds is 50% or more. An epoxy resin composition that, when cured, gives a graph having two or more relaxation mode groups tends to be less likely to impair the creep properties of the epoxy resin cured product or fiber-reinforced composite material under high temperature conditions. Furthermore, when the cured product is obtained, a graph having two or more relaxation mode groups is obtained, and the contribution rate of the relaxation mode group having a relaxation time of more than 1000 seconds is 40% or less, the remoldability and self-repairability of the cured epoxy resin product or fiber-reinforced composite material tend to be less likely to be impaired.

[0108] <Method of producing epoxy resin composition> The method for producing the epoxy resin composition of the present disclosure is not particularly limited. The epoxy resin composition of the present disclosure may be produced by any conventionally known method. The epoxy resin composition of the present disclosure can be produced, for example, by mixing an epoxy resin [A], a curing agent [B], and, if necessary, a curing accelerator and other components. The order of mixing these components does not matter. The mixing temperature is not particularly limited, and may be, for example, 40°C to 120°C. When the mixing temperature is 40°C or higher, the viscosity of the epoxy resin composition does not become too high, and mixing tends to be good. If the mixing temperature is 120°C or lower, the curing reaction will proceed partially, which will tend to reduce the impregnation into the fiber-reinforced base material layer and the storage stability of the resulting epoxy resin composition and the prepreg produced using it. The mixing temperature is preferably 50 to 100°C, and more preferably 50 to 90°C.

[0109] The mixing means is not particularly limited. The mixing means may be a conventionally known mixing device. Examples of the mixing device include a roll mill, a planetary mixer, a kneader, an extruder, a Banbury mixer, a mixing vessel equipped with stirring blades, and a horizontal mixing tank. The components can be mixed in the air or in an inert gas atmosphere. When mixing is carried out in air, a temperature and humidity controlled atmosphere is preferred. Although not particularly limited, it is preferable that the components are mixed at a constant temperature of, for example, 30° C. or less, in a low humidity atmosphere with a relative humidity of 50% RH or less.

[0110] <Epoxy resin cured product> The epoxy resin cured product of the present disclosure includes aspects of the epoxy resin cured product of the first embodiment and the second embodiment shown below. <Epoxy Resin Cured Product of First Embodiment> The cured epoxy resin product of the first embodiment is obtained by curing the epoxy resin composition of the present disclosure. The method for curing the epoxy resin composition of the present disclosure to obtain the cured epoxy resin product of the first embodiment is not particularly limited, and curing may be performed by a known method. The cured epoxy resin product of the first embodiment can be obtained, for example, by degassing the epoxy resin composition of the present disclosure in a vacuum and then curing it at a temperature of 120°C to 200°C for 15 minutes to 24 hours, preferably at a temperature of 120°C to 180°C for 1 hour to 12 hours, and more preferably at a temperature of 150°C to 180°C for 1 hour to 6 hours. Specifically, for example, the epoxy resin composition of the present disclosure can be degassed in a vacuum and then cured at a temperature of 120°C for 2 hours, at a temperature of 150°C for 2 hours, and at a temperature of 180°C for 2 hours to obtain the cured epoxy resin product of the first embodiment.

[0111] When the cured epoxy resin material of the first embodiment is brought into contact with a decomposer containing a reducing agent and heated at 100°C for 48 hours, preferably 80% by mass or more of the cured epoxy resin material dissolves, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, i.e., the entire cured epoxy resin material dissolves. The explanation for the fact that 80 mass % or more of the cured product dissolves when it is brought into contact with a decomposing agent containing a reducing agent and heated at 100°C for 48 hours is the same as that in the <Cured epoxy resin product of the second embodiment> described later.

[0112] In the present disclosure, the dissolution rate (unit: mass %) of a cured epoxy resin material is measured by filtering a solution in which the cured epoxy resin material is dissolved and dividing the mass of the residue obtained by filtering the solution by the mass of the cured epoxy resin material before dissolution.

[0113] <Epoxy Resin Cured Product of Second Embodiment> The cured epoxy resin material of the second embodiment is obtained by curing the epoxy resin composition of the present disclosure, and when the cured epoxy resin material is brought into contact with a decomposing agent containing a reducing agent and heated at 100°C for 48 hours, 80 mass% or more of the cured epoxy resin material dissolves. The cured epoxy resin material of the second embodiment has excellent solubility, and can be dissolved in a low molecular weight compound by contacting the cured epoxy resin material with a decomposing agent.

[0114] The method for curing the epoxy resin composition of the present disclosure to obtain the cured epoxy resin product of the second embodiment is the same as the method for curing the epoxy resin composition of the present disclosure to obtain the cured epoxy resin product of the first embodiment, and therefore, description thereof will be omitted here.

[0115] The reducing agent is not particularly limited as long as it dissolves the cured epoxy resin material, and can be appropriately selected depending on the type of bond contained in the cured epoxy resin material. Reducing agents include, for example, dithiothreitol, 2-mercaptoethanol, 1-thioglycerol, glutathione, 2-mercaptoethylamine hydrochloride, cystine hydrochloride, and tris(2-carboxyethyl)phosphine hydrochloride. The reducing agent is preferably one that reduces disulfide bonds. The reducing agent may be used alone or in combination.

[0116] The reducing agent may be used without a solvent or may be used as a decomposition agent solution by diluting it with a solvent. The cured epoxy resin material of the second embodiment may be dissolved by immersing it in a decomposition agent solution containing a reducing agent. The amount of the decomposing agent solution used is not particularly limited and is determined depending on the shape of the cured epoxy resin material, dissolution conditions, etc. The amount of the decomposer contained in the decomposer solution is, for example, preferably 0.5 to 1000 times, more preferably 0.5 to 100 times, and even more preferably 0.5 to 10 times, the amount of the epoxy resin cured product, on a mass basis.

[0117] The concentration of the reducing agent in the decomposition agent solution is not particularly limited, but is preferably 0.1% by mass to 99.9% by mass, more preferably 1% by mass to 80% by mass, and even more preferably 5% by mass to 50% by mass, for example.

[0118] The solvent used for dilution is not particularly limited as long as it can dissolve the reducing agent and the cured epoxy resin, and may be water or an organic solvent. Examples of organic solvents used for dilution include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,4-dioxane, tetrahydrofuran, methanol, and ethanol. In particular, polar organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide are preferred because they can completely dissolve the cured epoxy resin material.

[0119] The decomposer may contain, in addition to the reducing agent, an additive that promotes dissolution of the cured epoxy resin material. In particular, nitrogen-containing bases such as triethylamine, DBU (1,8-diazabicycloundecene), and ammonia are preferred because their addition has a high effect of promoting dissolution of the cured epoxy resin material.

[0120] In the cured epoxy resin material of the second embodiment, upon contact with a decomposing agent containing a reducing agent and heating, preferably 80 mass % or more of the cured epoxy resin material is dissolved, more preferably 90 mass % or more is dissolved, even more preferably 95 mass % or more is dissolved, and particularly preferably 100 mass % is dissolved, i.e., the entire cured epoxy resin material is dissolved.

[0121] <Physical properties of cured epoxy resin> The glass transition temperature (Tg) of the epoxy resin cured product of the present disclosure is not particularly limited, but is preferably from 80°C to 300°C, and more preferably from 100°C to 200°C, for example. When the glass transition temperature is 80° C. or higher, the heat resistance of the cured epoxy resin is further improved, and as a result, the formation of voids and the like tends to be more unlikely in the resulting fiber-reinforced composite material. If the glass transition temperature is 300°C or lower, the temperature conditions in the remolding and self-repairing processes are mild, and the mechanical properties tend not to be impaired due to resin deterioration. In the present disclosure, the glass transition temperature of a cured epoxy resin material is measured using a differential scanning calorimeter. Specifically, the temperature of the cured epoxy resin material is raised from 30°C to 350°C at a rate of 10°C / min, and the inflection point in the transition process of the obtained curve is taken as the glass transition temperature of the cured epoxy resin material.

[0122] The compressive strength (CS) of the epoxy resin cured product of the present disclosure is not particularly limited, but is preferably, for example, 200 MPa or more, more preferably 230 MPa to 400 MPa, and even more preferably 250 MPa to 350 MPa. When the compressive strength is 200 MPa or more, the properties of the resulting fiber reinforced composite material tend not to deteriorate. In the present disclosure, the compressive strength of a cured epoxy resin product is measured by a method in accordance with JIS K7171:2016.

[0123] The degree of cure of the epoxy resin cured product of the present disclosure is not particularly limited, but is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. If the degree of cure is insufficient, poor toughness is likely to occur. In the present disclosure, the degree of cure of the epoxy resin cured product is measured by a method in accordance with JIS K 7148-1:2015.

[0124] Even if the cured epoxy resin material of the present disclosure has voids inside due to cracks, peeling, or the like, the voids can be repaired by subjecting the material to a process that includes heating.

[0125] <Prepreg> The prepreg of the present disclosure is a prepreg obtained by impregnating a fiber-reinforced substrate having reinforcing fibers with the epoxy resin composition of the present disclosure, and the content of the reinforcing fibers is 25% by volume to 75% by volume relative to the total volume of the prepreg.

[0126] The prepreg of the present disclosure is a prepreg in which a fiber-reinforced substrate is partially or entirely impregnated with the epoxy resin composition of the present disclosure. When the content of reinforcing fibers in the prepreg of the present disclosure is 25% by volume or more, the reinforcing effect of the reinforcing fibers is sufficiently obtained, and the mechanical properties relative to the mass tend to be substantially higher. When the content of reinforcing fibers in the prepreg of the present disclosure is 75% by volume or less, voids and the like are less likely to occur in the resulting fiber-reinforced composite material, and deterioration of mechanical properties tends to be less likely to occur. The content of reinforcing fibers in the prepreg of the present disclosure is preferably 45 to 70% by volume, and more preferably 50 to 65% by volume, relative to the total volume of the prepreg.

[0127] The prepreg of the present disclosure may be in the form of a tow prepreg in which the reinforcing fibers are formed in the form of strands, an SMC (Sheet Molding Compound) in which the reinforcing fibers are formed of short fibers with a fiber length of 5 mm to 100 mm, or a woven fabric prepreg in which the reinforcing fibers are formed of a woven fabric or a multi-layered woven fabric. A tow prepreg is a narrow intermediate substrate obtained by impregnating a reinforcing fiber bundle, in which several thousand to several tens of thousands of reinforcing fiber filaments are aligned in one direction, with a matrix resin composition and then winding the impregnated fiber bundle around a bobbin such as a paper tube. In the present disclosure, the material wound around a bobbin or the material unwound after being wound is referred to as a "tow prepreg."

[0128] <Fiber reinforced substrate> The type of fiber-reinforced substrate is not particularly limited. Examples of fiber-reinforced substrates include carbon fibers, glass fibers, aramid fibers, silicon carbide fibers, polyester fibers, ceramic fibers, alumina fibers, boron fibers, metal fibers, mineral fibers, rock fibers, and slag fibers. Among these, carbon fiber, glass fiber, or aramid fiber is preferred as the fiber-reinforced substrate, with carbon fiber being more preferred because it has good specific strength and specific modulus and can provide a lightweight, high-strength fiber-reinforced composite material.Among carbon fibers, polyacrylonitrile (PAN)-based carbon fiber is particularly preferred as the fiber-reinforced substrate because of its excellent tensile strength.

[0129] When PAN-based carbon fibers are used as the fiber-reinforced substrate, the tensile modulus is preferably 100 GPa to 600 GPa, more preferably 200 GPa to 500 GPa, and even more preferably 230 GPa to 450 GPa, and the tensile strength is preferably 2000 MPa to 10000 MPa, and more preferably 3000 MPa to 8000 MPa.

[0130] When carbon fibers are used as the fiber-reinforced substrate, the diameter thereof is preferably 4 μm to 20 μm, and more preferably 5 μm to 10 μm. By using such carbon fibers, the mechanical properties of the resulting fiber-reinforced composite material can be improved.

[0131] The fiber-reinforced substrate is preferably formed into a sheet before use. Examples of reinforcing fiber sheets include sheets in which a large number of reinforcing fibers are aligned in one direction, bidirectional fabrics such as plain weave or twill weave, multiaxial fabrics, nonwoven fabrics, mats, knits, braids, and paper made from a fiber-reinforced substrate. Among these, it is preferable to use a unidirectionally aligned sheet, a bidirectional woven fabric, or a multiaxial woven fabric substrate in which the fiber-reinforced substrate is formed into a sheet shape using continuous fibers, as this will result in a fiber-reinforced composite material with better mechanical properties. The thickness of the sheet-like fiber-reinforced substrate is preferably 0.01 mm to 3 mm, and more preferably 0.1 mm to 1.5 mm.

[0132] <Prepreg manufacturing method> The method for producing the prepreg of the present disclosure is not particularly limited. The prepreg of the present disclosure may be produced by any conventionally known method. The hot melt method or solvent method can be suitably employed as the method for producing the prepreg of the present disclosure.

[0133] The hot melt method is a method in which an epoxy resin composition is applied in the form of a thin film onto release paper to form an epoxy resin composition film, and the epoxy resin composition film is laminated onto a fiber-reinforced substrate and heated under pressure, thereby impregnating the fiber-reinforced substrate layer with the epoxy resin composition.

[0134] The method for forming the epoxy resin composition into an epoxy resin composition film is not particularly limited, and any conventionally known method can be applied. Specifically, a resin composition film can be obtained by casting the epoxy resin composition onto a support such as release paper or film using die extrusion, an applicator, a reverse roll coater, a comma coater, or the like. The resin temperature during film production is determined appropriately depending on the composition or viscosity of the epoxy resin composition. Specifically, the same temperature conditions as the mixing temperature in the above-mentioned method for producing the epoxy resin composition are preferably used. The epoxy resin composition may be impregnated into the fiber-reinforced substrate layer in one step or in multiple steps.

[0135] The solvent method is a method in which an epoxy resin composition is made into a varnish using an appropriate solvent, and the varnish is impregnated into the fiber-reinforced substrate layer.

[0136] Among conventional methods, the hot melt method, which does not use a solvent, is suitable as a method for producing the prepreg of the present disclosure.

[0137] When the epoxy resin composition film is impregnated into the fiber reinforced base material layer by the hot melt method, the impregnation temperature is preferably 50°C to 120°C. When the impregnation temperature is 50°C or higher, the viscosity of the epoxy resin composition does not become too high, and the epoxy resin composition tends to be sufficiently impregnated into the fiber-reinforced base material layer. If the impregnation temperature is 120°C or lower, the curing reaction of the epoxy resin composition will not proceed easily, and the deterioration of the storage stability and drapeability of the obtained prepreg will tend to be suppressed. The impregnation temperature is more preferably 60°C to 110°C, and particularly preferably 70°C to 100°C.

[0138] The impregnation pressure when the epoxy resin composition film is impregnated into the fiber reinforced substrate layer by the hot melt method is appropriately determined taking into consideration the viscosity, resin flow, etc. of the epoxy resin composition. The impregnation pressure is preferably 0.01 N / cm to 250 N / cm, and more preferably 0.1 N / cm to 200 N / cm.

[0139] <Fiber-reinforced composite materials> The fiber-reinforced composite material of the present disclosure is a fiber-reinforced composite material comprising a cured epoxy resin product (i.e., the cured epoxy resin product of the present disclosure) obtained by curing the epoxy resin composition of the present disclosure, and a fiber-reinforced substrate having reinforcing fibers, and the content of the reinforcing fibers is 25% by volume to 75% by volume of the total volume of the fiber-reinforced composite material. The fiber-reinforced composite material of the present disclosure preferably comprises a cured epoxy resin product obtained by curing the epoxy resin composition of the present disclosure (i.e., the cured epoxy resin product of the present disclosure) and a fiber-reinforced substrate having reinforcing fibers. The content of reinforcing fibers in the fiber reinforced composite material of the present disclosure is preferably 45 to 70% by volume, and more preferably 50 to 65% by volume, relative to the total volume of the fiber reinforced composite material.

[0140] The epoxy resin composition of the present disclosure has high impregnation ability and handleability for a fiber-reinforced substrate, and can be used to produce a fiber-reinforced composite material with excellent properties. Furthermore, even if the fiber-reinforced composite material of the present disclosure has voids due to cracks, delamination, or the like, the voids can be repaired by subjecting the fiber-reinforced composite material to a process that includes heating.

[0141] <Method of manufacturing fiber-reinforced composite materials> The fiber-reinforced composite material of the present disclosure can be obtained by combining a fiber-reinforced substrate having reinforcing fibers with the epoxy resin composition of the present disclosure, and curing the resulting composite. The fiber-reinforced composite material of the present disclosure can also be obtained by curing the prepreg of the present disclosure by heating and pressurizing it under specific conditions. Methods for producing a fiber-reinforced composite material using the prepreg of the present disclosure include known molding methods such as autoclave molding and press molding.

[0142] [Autoclave molding method] An autoclave molding method is preferably used as a method for producing the fiber-reinforced composite material of the present disclosure. The autoclave molding method involves sequentially placing a prepreg and a film bag in the lower mold of a metal mold, sealing the prepreg between the lower mold and the film bag, evacuating the space formed by the lower mold and the film bag, and then applying heat and pressure in an autoclave molding machine. The molding conditions are preferably a temperature rise rate of 1°C / min to 50°C / min, a pressure of 0.2 MPa to 0.7 MPa, and heating and pressure at 130°C to 180°C for 1 hour to 12 hours.

[0143] [Press molding method] A press molding method is preferably used as a method for producing the fiber-reinforced composite material of the present disclosure. The fiber-reinforced composite material is produced by the press molding method by heating and pressurizing the prepreg of the present disclosure or a preform formed by laminating the prepregs of the present disclosure using a mold. The mold is preferably preheated to a curing temperature.

[0144] The temperature of the mold during press molding is preferably 150°C to 210°C. When the molding temperature is 150°C or higher, the curing reaction can be sufficiently induced, and the fiber-reinforced composite material tends to be obtained with high productivity. When the molding temperature is 210°C or lower, the viscosity of the epoxy resin composition does not become too low, and excessive flow of the epoxy resin composition in the mold can be suppressed, which in turn can suppress outflow of the epoxy resin composition from the mold and meandering of the fibers, tending to produce a high-quality fiber-reinforced composite material.

[0145] The pressure during molding is preferably 0.05 MPa to 2 MPa, and more preferably 0.2 MPa to 2 MPa. When the pressure is 0.05 MPa or more, the epoxy resin composition tends to flow appropriately, preventing poor appearance and the occurrence of voids, and the prepreg tends to adhere well to the mold, resulting in a fiber-reinforced composite material with good appearance. When the pressure is 2 MPa or less, the epoxy resin composition is not made to flow more than necessary, so that the resulting fiber-reinforced composite material tends to be less likely to have poor appearance, and since more load than necessary is not applied to the mold, deformation of the mold tends to be less likely to occur. The molding time is preferably 1 hour to 8 hours.

[0146] <Examples of fiber-reinforced composite materials> Examples of fiber reinforced composite materials include fiber reinforced plastics (FRP) and carbon fiber reinforced plastics (CFRP).

[0147] <Method for repairing cured epoxy resin> The method for repairing a cured epoxy resin material according to the present disclosure includes heating a cured epoxy resin material having voids therein at a temperature equal to or higher than the glass transition temperature of the cured epoxy resin material, thereby repairing the voids. The cured epoxy resin material of the present disclosure has excellent self-repairing properties and is capable of repairing voids that occur inside the material during molding or in the environment in which it is used. Specific examples of voids include cracks and delaminations.

[0148] The heating temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of the cured epoxy resin. The heating temperature is preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The heating method can be any conventionally known method, and the heating time can be set arbitrarily. A specific example of the method for repairing a cured epoxy resin material according to the present disclosure is a method in which a cured epoxy resin material having voids therein is heated at 200° C. for 1 hour using an autoclave or a blower dryer. Furthermore, the method for repairing a cured epoxy resin material according to the present disclosure may include applying pressure in addition to the heating. The pressure may be applied using a mold or a support frame. The pressure during pressurization is preferably 0.05 MPa to 2 MPa, more preferably 0.2 MPa to 2 MPa, and these pressures may be applied stepwise.

[0149] <Repair method for fiber-reinforced composite materials> The method for repairing a fiber-reinforced composite material disclosed herein includes heating a fiber-reinforced composite material having voids therein at a temperature equal to or higher than the glass transition temperature of the fiber-reinforced composite material, thereby repairing the voids. The fiber-reinforced composite material of the present disclosure has excellent self-repairing properties and is capable of repairing voids that occur inside the material during molding or in the environment in which it is used. Specific examples of voids include cracks and delaminations.

[0150] The heating temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of the fiber-reinforced composite material. The heating temperature is preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The heating method can be any conventionally known method, and the heating time can be set arbitrarily. A specific example of the repair method for a fiber-reinforced composite material of the present disclosure is a method in which a fiber-reinforced composite material having voids therein is heated at 200° C. for 1 hour using an autoclave or a blower dryer. Furthermore, the method for repairing a fiber-reinforced composite material of the present disclosure may include applying pressure in addition to the heating. The pressure may be applied using a mold or a support frame. The pressure during pressurization is preferably 0.05 MPa to 2 MPa, more preferably 0.2 MPa to 2 MPa, and these pressures may be applied stepwise.

[0151] <Method for remolding cured epoxy resin> The method for remolding a cured epoxy resin material of the present disclosure includes heating and pressurizing the cured epoxy resin material of the present disclosure at a temperature equal to or higher than the glass transition temperature of the cured epoxy resin material. The cured epoxy resin material of the present disclosure has excellent remoldability and can be molded again after molding.

[0152] The heating temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of the cured epoxy resin. The heating temperature is preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The heating method can be any conventionally known method, and the heating time can be set arbitrarily. Examples of the heating means include an autoclave and a blower dryer. The heating conditions include, for example, heating at 200° C. for 1 hour. The pressure may be applied using a mold or a support frame. The pressure during pressurization is preferably 0.05 MPa to 2 MPa, more preferably 0.2 MPa to 2 MPa, and these pressures may be applied stepwise.

[0153] <Method for remolding fiber-reinforced composite material> The method for reshaping the fiber-reinforced composite material of the present disclosure includes heating and pressurizing the fiber-reinforced composite material of the present disclosure at a temperature equal to or higher than the glass transition temperature of the fiber-reinforced composite material. The fiber-reinforced composite material of the present disclosure has excellent remoldability and can be molded again after molding.

[0154] The heating temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of the fiber-reinforced composite material. The heating temperature is preferably 160°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. The heating method can be any conventionally known method, and the heating time can be set arbitrarily. Examples of the heating means include an autoclave and a blower dryer. The heating conditions include, for example, heating at 200° C. for 1 hour. The pressure may be applied using a mold or a support frame. The pressure during pressurization is preferably 0.05 MPa to 2 MPa, more preferably 0.2 MPa to 2 MPa, and these pressures may be applied stepwise.

[0155] <Method for decomposing cured epoxy resin> The method for decomposing a cured epoxy resin material according to the present disclosure includes contacting the cured epoxy resin material according to the present disclosure with a decomposition agent containing a reducing agent. The cured epoxy resin material of the present disclosure has excellent resin decomposition properties, and can be decomposed into low molecular weight compounds.

[0156] The reducing agent is not particularly limited as long as it decomposes the epoxy resin cured product, and can be appropriately selected depending on the type of bond contained in the epoxy resin cured product. Reducing agents include, for example, dithiothreitol, 2-mercaptoethanol, 1-thioglycerol, glutathione, 2-mercaptoethylamine hydrochloride, cysterine hydrochloride, and tris(2-carboxyethyl)phosphine hydrochloride. The reducing agent is preferably one that reduces disulfide bonds. The reducing agent may be used alone or in combination.

[0157] The reducing agent may be used without a solvent or may be used as a decomposition agent solution by diluting it with a solvent. The cured epoxy resin material of the present disclosure may be decomposed by immersing it in a decomposition agent solution containing a reducing agent. The amount of the decomposing agent solution used is not particularly limited and is determined depending on the shape of the cured epoxy resin material, the decomposition conditions, etc. The amount of the decomposer contained in the decomposer solution is, for example, preferably 1 to 1000 times, more preferably 1 to 100 times, and even more preferably 1 to 10 times, the amount of the epoxy resin cured product, on a mass basis.

[0158] The concentration of the reducing agent in the decomposition agent solution is not particularly limited, but is preferably 0.1% by mass to 99.9% by mass, more preferably 1% by mass to 80% by mass, and even more preferably 5% by mass to 50% by mass, for example.

[0159] The solvent used for dilution is not particularly limited as long as it can dissolve the reducing agent and decompose the cured epoxy resin material, and may be water or an organic solvent. Examples of organic solvents used for dilution include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,4-dioxane, tetrahydrofuran, methanol, and ethanol. In particular, polar organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide are preferred because they can completely dissolve the cured epoxy resin material.

[0160] The decomposer may contain, in addition to the reducing agent, an additive that accelerates the decomposition of the cured epoxy resin material. In particular, nitrogen-containing bases such as triethylamine, DBU, and ammonia are preferred because their addition has a high effect of accelerating the decomposition of the cured epoxy resin material.

[0161] In the method for decomposing a cured epoxy resin material according to the present disclosure, in order to accelerate the decomposition of the cured epoxy resin material, the material may be heated at 25°C to 150°C (preferably 25°C to 60°C) for 1 hour to 48 hours (preferably 1 hour to 8 hours), may be appropriately stirred, or may be subjected to ultrasonic treatment as needed. For example, the decomposition reaction of the cured epoxy resin material may be allowed to proceed for 8 hours at room temperature (25°C) or 80°C while stirring the cured epoxy resin material and the decomposing agent. In the method for decomposing an epoxy resin cured material according to the present disclosure, pressure may be applied at 0.1 MPa to 10 MPa (preferably 0.1 MPa to 1 MPa) to promote decomposition of the epoxy resin cured material.

[0162] By the method for decomposing an epoxy resin cured material according to the present disclosure, it is preferable that 80 mass % or more of the cured epoxy resin material is decomposed, more preferably 90 mass % or more, even more preferably 95 mass % or more, and particularly preferably 100 mass % is decomposed, i.e., the entire cured epoxy resin material is decomposed.

[0163] <Method for recovering reinforcing fibers from fiber-reinforced composite materials> A method for recovering reinforced fibers from a fiber-reinforced composite material of the present disclosure includes contacting the fiber-reinforced composite material of the present disclosure with a decomposition agent including a reducing agent. According to the method for recovering reinforcing fibers from a fiber-reinforced composite material of the present disclosure, the fiber-reinforced composite material of the present disclosure is brought into contact with a decomposing agent containing a reducing agent, whereby the cured epoxy resin contained in the fiber-reinforced composite material is decomposed and / or dissolved, making it possible to recover the reinforcing fibers.

[0164] The description of the decomposition agent containing a reducing agent in the method for recovering reinforcing fibers from a fiber-reinforced composite material, including definitions, examples, preferred embodiments, etc., is the same as the description of the decomposition agent containing a reducing agent in the <<Method for Decomposing an Epoxy Resin Cured Material>>.

[0165] In the method for recovering reinforced fibers from a fiber-reinforced composite material of the present disclosure, in order to promote decomposition and / or dissolution of the cured epoxy resin contained in the fiber-reinforced composite material, the material may be heated at 25°C to 150°C (preferably 25°C to 60°C) for 1 hour to 48 hours (preferably 1 hour to 8 hours), or may be stirred as appropriate, or may be subjected to ultrasonic treatment as necessary. For example, the decomposition and / or dissolution reaction of the cured epoxy resin contained in the fiber-reinforced composite material may be allowed to proceed while stirring the fiber-reinforced composite material and the decomposing agent at room temperature (25°C) or 80°C for 8 hours. In the method for recovering reinforcing fibers from a fiber-reinforced composite material according to the present disclosure, pressure may be applied at 0.1 MPa to 10 MPa (preferably 0.1 MPa to 1 MPa) to promote decomposition and / or dissolution of the cured epoxy resin contained in the fiber-reinforced composite material.

[0166] The method for recovering reinforcing fibers from a fiber-reinforced composite material according to the present disclosure may include decomposing and / or dissolving a cured epoxy resin contained in the fiber-reinforced composite material, and then recovering the reinforcing fibers. The method for recovering the reinforcing fibers is not particularly limited, and the long fibers can be recovered by winding them up, or by filtration. The recovered reinforcing fibers can be recycled into prepregs or fiber-reinforced composite materials, and in this process, if necessary, oil such as a sizing agent may be applied again. [Example]

[0167] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited thereto. The components and evaluation methods used in the examples and comparative examples are as follows.

[0168] The following epoxy resins and curing agents were prepared for use in the Examples and Comparative Examples. [Epoxy resin [A]] "jER825" (trade name) [bisphenol A diglycidyl ether, epoxy equivalent: 169 g / eq, manufactured by Mitsubishi Chemical Corporation] "jER828" (trade name) [bisphenol A diglycidyl ether, epoxy equivalent: 189 g / eq, manufactured by Mitsubishi Chemical Corporation] "jER834" (trade name) [bisphenol A diglycidyl ether, epoxy equivalent: 250 g / eq, manufactured by Mitsubishi Chemical Corporation] "jER1001" (trade name) [bisphenol A diglycidyl ether, epoxy equivalent: 475 g / eq, manufactured by Mitsubishi Chemical Corporation] "jER1008" (trade name) [bisphenol A diglycidyl ether, epoxy equivalent: 950 g / eq, manufactured by Mitsubishi Chemical Corporation] The above "jER" is a registered trademark.

[0169] [Hardening agent [B]] <Hardening agent [B1]> "DADS" [4,4'-dithiodianiline, active hydrogen equivalent: 62g / eq, manufactured by Tokyo Chemical Industry Co., Ltd.] "APTMDS" [1,3-bis(3-aminopropyl)tetramethyldisiloxane, active hydrogen equivalent: 62g / eq, manufactured by Tokyo Chemical Industry Co., Ltd.] <Curing agents other than curing agent [B1]> "MED-J" (product name: Curehard MED-J, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, active hydrogen equivalent: 71 g / eq, manufactured by Kumiai Chemical Co., Ltd.) The above "Curehard" is a registered trademark.

[0170] [Curing accelerator] "DBU" [1,5,7-triazabicyclodecene, manufactured by Tokyo Chemical Industry Co., Ltd.]

[0171] <Examples 1 to 4 and Comparative Examples 1 to 7> [1] Preparation of epoxy resin composition An epoxy resin and a curing agent, or an epoxy resin, a curing agent and a curing accelerator, were weighed out in the parts by mass shown in Table 1 below, and mixed using a stirrer at 80°C for 30 minutes to prepare an epoxy resin composition.

[0172] [2] Preparation of cured epoxy resin and measurement of its physical properties (2-1) Preparation of cured epoxy resin The epoxy resin composition prepared in [1] above was degassed in a vacuum and then poured into a silicone resin mold set to a thickness of 4 mm using a 4 mm silicone resin spacer. The epoxy resin composition in the silicone resin mold was then cured at 120°C for 2 hours, 150°C for 2 hours, and 180°C for 2 hours to obtain a 4 mm-thick cured epoxy resin product.

[0173] (2-2) Measurement of glass transition temperature (Tg) The glass transition temperature of the cured epoxy resin was measured in a nitrogen gas flow at a flow rate of 40 mL / min using a TA Instruments DSC Q2000 differential scanning calorimeter. 5 mg±1 mg of the cured epoxy resin prepared in (2-1) above was sampled and heated from 30°C to 350°C at a rate of 10°C / min. The inflection point in the transition process of the obtained curve was recorded as the glass transition temperature of the cured epoxy resin.

[0174] (2-3) Measurement of stress relaxation rate The epoxy resin composition prepared in [1] above was set on 8 mmφ aluminum parallel plates with a gap distance of 2 mm, and cured at a temperature of 120°C for 2 hours, at a temperature of 150°C for 2 hours, and at a temperature of 180°C for 2 hours to obtain an epoxy resin. The resulting epoxy resin cured product was then held at a temperature 40°C higher than the glass transition temperature for 2 minutes, and then subjected to a 6.25 x 10 -3 The modulus G generated when a displacement of 100 rad was applied was measured for 3600 seconds, and the resulting plot was recorded. Stress relaxation was measured using a TA Instruments Discovery DHR-2 rheometer in a nitrogen gas flow of 10 L / min. In the obtained time plot, the stress relaxation rate was calculated by the following formula. [1-((G(min)) / (G(0)))]×100 Here, G(0) is the modulus value at the start of application of the external force (i.e., 0 seconds after the start of application of the external force). G(min) is the minimum modulus value one hour after the start of application of the external force, in other words, the minimum modulus value up to 3600 seconds after the start of application of the external force. If the modulus value reaches the lower limit of measurement by the device within 3600 seconds, this value is used. If the modulus value does not reach the lower limit of measurement by the device within one hour after the start of application of the external force, this value is used. In the present disclosure, the modulus value G(0) at 0 seconds after the start of application of the external force was considered to be the same as the modulus value G(0.1) at 0.1 seconds after the start of application of the external force to determine the stress relaxation rate.

[0175] The results of the stress relaxation measurements are shown in Table 1 and FIG. In Example 3, stress was relaxed by application of an external force, and the stress relaxation rate 3600 seconds after the start of application of the external force was 99%. On the other hand, in Comparative Example 4, the stress relaxation rate 3600 seconds after the start of application of the external force was 76%.

[0176] (2-4) Stress relaxation mode separation analysis The modulus value G(t) at 200°C recorded in (2-3) above was analyzed according to the above-mentioned [Stress relaxation mode separation analysis]. The stress relaxation mode separation analysis was carried out in the range of 0 seconds to 3600 seconds, and the analysis was carried out in the following 25 modes. τi=1,2.5,4,5.5,7,8.5,10,25,40,55,70,85,100,250,400,550,700,850,1000,2500,4000,5500,7000,8500,10000

[0177] The results of the stress relaxation mode separation analysis for Examples 1 and 3 and Comparative Example 4 are shown in FIG. In Example 1, the relaxation mode group with a relaxation time of less than 200 seconds had a contribution rate of 61%, and the relaxation mode group with a relaxation time of 1000 seconds or more had a contribution rate of 23%. In Example 3, the relaxation mode group with a relaxation time of less than 200 seconds had a contribution rate of 51%, and the relaxation mode group with a relaxation time of 1000 seconds or more showed no contribution rate. In Comparative Example 4, the relaxation mode group with a relaxation time of less than 200 seconds had a contribution rate of 19%, and the relaxation mode group with a relaxation time of 1000 seconds or more had a contribution rate of 41%.

[0178] (2-5) Confirmation of remolding ability The cured epoxy resin prepared in (2-1) above was crushed into chips with three sides of 1 mm or less, and the resulting cured epoxy resin chips were used as samples. Next, 0.7 g of the sample was placed in a mold equipped with an 8 mm diameter cylindrical mold frame and preheated at 200°C for 5 minutes. A pressure of 25 MPa was applied in a press at 200°C for 30 minutes to prepare a remolded sample. The obtained remolded samples were visually observed. The remoldability was evaluated according to the following criteria, with A being in the practically acceptable range.

[0179] -standard- A: The surface of the remolded sample was smooth, and no grain boundaries of the chips were visible even when light was transmitted through it. B: The surface of the remolded sample was smooth, but turbidity due to the grain boundaries of the chip was observed when light was transmitted through it. C: The grain boundaries of the chip before molding were observed on the surface of the remolded sample.

[0180] (2-6) Confirmation of self-repairing ability The cured epoxy resin material prepared in (2-1) above was polished to a thickness of 2 mm, and a crack of approximately 2 mm was inserted using a razor. The material was then preheated to 120°C and placed on the sample stage of a transmission electron microscope equipped with a heat stage. The temperature was then increased to 200°C at a rate of 20°C / min, and finally held at 200°C for 15 minutes to prepare a self-repairing sample. The obtained self-repairing samples were observed using a transmission electron microscope, n = 5. The self-repairing property was judged according to the following criteria, with A being in the range acceptable for practical use.

[0181] -standard- A: The cracks in the self-repaired sample have almost completely disappeared. B: The crack in the self-repaired sample was partially reduced. C: No disappearance or shrinkage of cracks was observed in the self-repaired sample.

[0182] (2-7) Confirmation of resin decomposition The cured epoxy resin product prepared in (2-1) above was cut into pieces of 1 cm x 1 cm x 0.4 mm, and each piece was immersed in 40 mL of an N,N-dimethylformamide solution containing 4 mL of 1-thioglycerol and stirred at room temperature (25°C) and 80°C. The state of the solution after 8 hours was visually observed. The resin decomposition property was judged according to the following criteria, with A and B being considered to be within the range acceptable for practical use.

[0183] -standard- A: The cured epoxy resin completely decomposed at room temperature and became a homogeneous solution. B: The cured epoxy resin did not completely decompose at room temperature, but at 80°C, 80% by mass or more was decomposed. C: The cured epoxy resin material decomposed less than 80% by mass at both room temperature and 80°C.

[0184] (2-8) Compressive strength (CS) The epoxy resin composition prepared in [1] above was placed in an 8 mm diameter test tube and cured at 120°C for 2 hours, 150°C for 2 hours, and 180°C for 2 hours to obtain a cured epoxy resin. The cured epoxy resin was removed and cut to a length of 15 mm to obtain a cylindrical cured epoxy resin product measuring 15 mm x 8 mm diameter. The cylindrical cured epoxy resin was used as a sample and subjected to a compression test at a test speed of 0.2 mm / min according to a method in accordance with JIS K7171:2016 to measure the compressive strength.

[0185] The various physical properties of the cured resin products obtained by curing the obtained epoxy resin compositions are shown in Table 1. The degree of cure of the cured epoxy resin products obtained by curing the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 7 was measured by a method in accordance with JIS K 7148-1:2015 (DSC method), and was 99.9% or higher in all cases.

[0186] [Table 1]

[0187] From the above, it was found that the epoxy resin compositions of Examples 1 to 4 had excellent remoldability and self-repairing properties in the cured products, even though they used compounds containing dynamic covalent bond moieties in amounts less than the theoretical equivalent relative to the epoxy resin.

Claims

1. Contains at least an epoxy resin [A] and a curing agent [B], the average epoxy equivalent of the epoxy resin [A] is in the range of 320 g / eq or more and 5000 g / eq or less, the curing agent [B] contains at least a curing agent [B1] containing a dynamic covalent bond moiety Y, the curing agent [B1] contains active hydrogen, and the ratio (b1) / (a) of the molar amount (b1) of the active hydrogen to the molar amount (a) of the epoxy groups in the epoxy resin [A] is in the range of 0.25 or more and 2.0 or less.

2. 2. The epoxy resin composition according to claim 1, wherein, after the composition has been cured to a degree of cure of 90% or more to form a cured product, an external force is applied to the cured product at a temperature 40°C higher than the glass transition temperature of the cured product, and the resulting stress is measured; the stress relaxation rate is 80% or more one hour after the start of application of the external force.

3. 2. The epoxy resin composition according to claim 1, wherein the concentration of the dynamic covalent bonding moiety Y relative to the total mass of the epoxy resin [A] and the curing agent [B] is in the range of 0.05 mmol / g or more and 0.65 mmol / g or less.

4. 2. The epoxy resin composition according to claim 1, wherein the dynamic covalent bonding site Y undergoes concerted bond exchange without cleavage.

5. 2. The epoxy resin composition according to claim 1, wherein the curing agent [B1] comprises an amine-based curing agent represented by the following formula (2): 【Chemical 1】 In formula (2), R １ and R ２ each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an ether group, or a divalent group formed by combining two or more selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an ether group, and Y represents a dynamic covalent bond moiety.

6. 2. The epoxy resin composition according to claim 1, wherein the dynamic covalent bonding site Y comprises a disulfide bond.

7. 2. The epoxy resin composition according to claim 1, wherein the curing agent [B1] comprises an amine-based curing agent represented by the following formula (3): 【Chemistry 2】

8. A cured epoxy resin product obtained by curing the epoxy resin composition according to claim 1.

9. 9. The cured epoxy resin material according to claim 8, wherein 80 mass % or more of the cured epoxy resin material dissolves when the cured epoxy resin material is brought into contact with a decomposing agent containing a reducing agent and heated at 100°C for 48 hours.

10. A prepreg obtained by impregnating a fiber-reinforced substrate having reinforcing fibers with the epoxy resin composition according to claim 1 or 2, A prepreg having a content of the reinforcing fibers in the range of 25% by volume or more and 75% by volume or less relative to the total volume of the prepreg.

11. A fiber-reinforced composite material comprising the epoxy resin cured product according to claim 8 or 9 and a fiber-reinforced substrate having reinforcing fibers, A fiber-reinforced composite material in which the content of the reinforcing fibers is in the range of 25% by volume or more and 75% by volume or less relative to the total volume of the fiber-reinforced composite material.

12. 10. A method for repairing a cured epoxy resin material, comprising heating the cured epoxy resin material according to claim 8 or 9, which has voids therein, at a temperature equal to or higher than the glass transition temperature of the cured epoxy resin material, thereby repairing the voids.

13. A method for repairing a fiber-reinforced composite material, comprising heating the fiber-reinforced composite material described in claim 11, which has voids therein, at a temperature equal to or higher than the glass transition temperature of the fiber-reinforced composite material, thereby repairing the voids.

14. A method for remolding a cured epoxy resin material, comprising heating and pressurizing the cured epoxy resin material according to claim 8 or 9 at a temperature equal to or higher than the glass transition temperature of the cured epoxy resin material.

15. A method for remolding a fiber-reinforced composite material, comprising heating and pressurizing the fiber-reinforced composite material according to claim 11 at a temperature equal to or higher than the glass transition temperature of the fiber-reinforced composite material.

16. A method for decomposing an epoxy resin cured product, comprising contacting the epoxy resin cured product according to claim 8 or 9 with a decomposition agent containing a reducing agent.

17. A method for recovering reinforcing fibers from a fiber-reinforced composite material, comprising contacting the fiber-reinforced composite material according to claim 11 with a decomposition agent containing a reducing agent.

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