Glycidyl ether group-containing compound, curable resin composition, cured product, and laminate

Abstract

Provided are: a compound which is a curable resin and which can easily achieve repairability and remoldability in a cured product; a curable resin composition obtained using the compound; and a cured product thereof. A glycidyl ether group-containing compound used in the present invention is a hydroxyl group-containing compound in which a constituent unit A having one or more glycidyl ether groups and a constituent unit B different from the constituent unit A are linked by A-B-A, the structural unit A and the structural unit B are bonded by a reversible bond having a dissociation temperature of 120 DEG C or higher. The reversible bond is preferably a disulfide bond sandwiched by an aromatic ring and an addition structure obtained by Diels-Alder reaction of an anthracene type.

Description

Technical Field

[0001] The present invention relates to a glycidyl ether group-containing compound having a specific structure, a curable resin composition containing the same, a cured product, and a laminate containing a layer composed of the cured product. Background Art

[0002] Cured products obtained from epoxy resins have excellent heat resistance, mechanical strength, electrical properties, adhesion, etc., and are indispensable materials in various fields such as electrical / electronics, coatings, and adhesives.

[0003] On the other hand, cured products using thermosetting resins such as epoxy resins have low long-term reliability. For example, when the cured product of epoxy resin undergoes oxidative degradation, cracks may occur.

[0004] In addition, the cured product obtained by temporarily curing thermosetting resins such as epoxy resins cannot be dissolved (insoluble) in solvents, and will not melt (melt) at high temperatures. Therefore, it lacks recyclability and reusability. The cured product after use becomes waste, so reducing waste and alleviating the burden on the environment has become a problem.

[0005] Therefore, for cured products using epoxy resins and the like, there is a demand for solutions to the problems of extending the life and reducing waste, and among these solutions, imparting easy disassembly properties and repairability / reformability to the cured products is considered to be effective.

[0006] Under such circumstances, a method has been disclosed in which a thermally decomposable compound is added to the adhesive component of the reaction system in advance, and then the adhesive strength is reduced by heating to a certain extent after use to enable disassembly (for example, see Patent Document 1).

[0007] In addition, a method for forming a sealing material has been disclosed, in which, even if cracks or peeling occur in a sealing material using an epoxy resin or the like, self-repair can be achieved by using microcapsule particles containing a first thermosetting resin and a second thermosetting resin precursor (for example, refer to Patent Document 2).

[0008] In addition to the above, in order to impart repairability and re-molding properties, the use of reversible bonds such as dynamic covalent bonds and supramolecular bonds in cured products is also being actively studied.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2013-256557

[0012] Patent Document 2: Japanese Patent Application Publication No. 2017-041496 Summary of the invention

[0013] Problems to be solved by the invention

[0014] In the technology provided by the aforementioned patent document 1, the adhesive will be discarded after disassembly, and although the substrate as the adhesive can be recycled, there is still a problem of insufficient recyclability as a whole. In addition, in the technology of the aforementioned patent document 2, although it has a certain degree of self-repairability, it is not a solution from the perspective of so-called reuse, and there is still a problem of becoming waste when it is not needed. In addition, in the raw materials used for the aforementioned reversible bonds, their molecular mobility must be ensured, so there is a problem that only gel-like substances that lack mechanical strength can be used as raw materials. As far as the current situation is concerned, improvements are required in any of them. Therefore, the subject of the present invention is to provide a compound that is a curable resin but can easily achieve repairability / reformability when it is a cured product, and a curable resin composition and its cured product formed using the compound.

[0015] Methods for solving problems

[0016] As a result of detailed studies, the inventors of the present invention have found that the above-mentioned problems can be solved by using a compound having a specific structure and containing a glycidyl ether group and using it as a curable resin composition, thereby completing the invention.

[0017] That is, the present invention includes the following aspects.

[0018] [1] A compound containing a glycidyl ether group, characterized in that the compound contains a glycidyl ether group in which a structural unit A having one or more glycidyl ether groups and a structural unit B different from the aforementioned A are connected by ABA, and the aforementioned structural unit A and the aforementioned structural unit B are bonded by a reversible bond with a dissociation temperature of 120°C or more.

[0019] [2] The glycidyl ether group-containing compound according to [1], wherein the reversible bond is a covalent bond.

[0020] [3] A compound containing a glycidyl ether group as described in [2] above, wherein the reversible bond is any one of an addition structure formed by a Diels-Alder reaction with a dissociation temperature of 120°C or higher, a disulfide bond, an ester bond, a borate bond, a hemiamine acetal bond, an imine bond, an acylhydrazone bond, an olefin metathesis reaction, an alkoxyamine skeleton, and an amide bond.

[0021] [4] The glycidyl ether group-containing compound according to [2] or [3], wherein the reversible bond is an addition-type structure formed by an anthracene-type Diels-Alder reaction or a disulfide bond sandwiched between aromatic rings.

[0022] [5] The glycidyl ether group-containing compound according to any one of [1] to [4], wherein the structural unit B has an alkylene chain or an alkylene ether chain.

[0023] [6] The glycidyl ether group-containing compound according to [5], wherein the alkylene chain has 4 to 16 carbon atoms.

[0024] [7] The glycidyl ether group-containing compound as described in any one of [1] to [6] above, wherein the structural unit B further has a reversible bond that is the same as the reversible bond with a dissociation temperature of 120°C or above that is the link between the structural unit A and the structural unit B.

[0025] [8] A compound containing a glycidyl ether group, represented by the following general formula.

[0026] [Chemistry 1]

[0027]

[0028] [Ar in formula (2) is independently a structure containing an unsubstituted or substituted aromatic ring, and the structures derived from anthracene in formulas (1-1) and (1-2) may have a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent. G is a glycidyl group or a 2-methylglycidyl group. In the formula, ma is an integer of 1 to 10, and n is an average value of the number of repetitions and is 0 to 10. Z 1 It is the following formula (3), Z 2 It is the following formula (4), Z 3 It is the following formula (5), Z 4 Any one of the structures represented by the following formula (6) or (7), a plurality of which are present in one molecule, and they may be the same or different.

[0029] [Chemistry 2]

[0030]

[0031] [The aromatic ring in formula (3) may be substituted or unsubstituted, and * indicates a bonding point. G is the same as above, and -OG on the naphthalene ring in the formula may be bonded at any position.]

[0032] [Chemistry 3]

[0033]

[0034] [In formula (4),

[0035] Ar is independently a structure containing an unsubstituted or substituted aromatic ring,

[0036] R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group,

[0037] R is a hydrogen atom or a methyl group,

[0038] R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0039] n1 is an integer of 2 to 16, n2 is an average value of the repeating units and is 2 to 30,

[0040] k1 is the average of the number of repetitions and is in the range of 0.5 to 10.

[0041] p1 and p2 are each independently 0 to 5,

[0042] X is a structural unit represented by the following formula (4-1), and Y is a structural unit represented by the following formula (4-2),

[0043] [Chemistry 4]

[0044]

[0045] [In formula (4-1) and (4-2), Ar, R, R 1 , R 2 , R', n1, n2 are the same as above.]

[0046] m1 and m2 are average values ​​of the repetition numbers, and are each independently 0 to 25, and m1+m2≥1.

[0047] The bonding between the structural unit X represented by the aforementioned formula (4-1) and the structural unit Y represented by the aforementioned formula (4-2) may be random or block, and the total number of each structural unit X and Y present in one molecule is m1 and m2 respectively.]

[0048] [Chemistry 5]

[0049]

[0050] [In formula (5), n3 and n5 are the average values ​​of the number of repetitions, which are 0.5 to 10 respectively, n4 is an integer of 1 to 16, R ” are each independently a hydrogen atom, a methyl group or an ethyl group.]

[0051] [Chemistry 6]

[0052]

[0053] [Chemistry 7]

[0054]

[0055] [In formula (6) and (7), R 1 , R 2 , R', n1, n2 are the same as above.]

[0056] [9] A curable resin composition comprising as essential components the glycidyl ether group-containing compound as described in any one of [1] to [8] and a compound (I) reactive with the glycidyl ether group-containing compound.

[0057]

[10] The curable resin composition according to [9], wherein the compound (I) reactive with the glycidyl ether group-containing compound is a hydroxyl group-containing compound.

[0058]

[11] The curable resin composition according to

[10] , wherein the compound (I) reactive with the glycidyl ether group-containing compound is a hydroxyl group-containing compound having a reversible bond.

[0059]

[12] The curable resin composition according to

[11] , wherein the hydroxyl-containing compound having a reversible bond is a hydroxyl-containing compound represented by the following general formula.

[0060] [Chemistry 8]

[0061]

[0062] [Ar in formula (9) is independently a structure containing an unsubstituted or substituted aromatic ring, and the structures derived from anthracene in formulas (8-1) and (8-2) may have a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent.

[0063] In the formula, ma is an integer of 1 to 10, and n is the average value of the number of repetitions and is 0 to 10. 5 It is the following formula (10), Z 2 It is the following formula (11), Z 3 It is the following formula (12), Z 4 Any one of the structures represented by the following formula (13) or (14), a plurality of which are present in one molecule, and they may be the same or different.

[0064] [Chemistry 9]

[0065]

[0066] [The aromatic ring in formula (10) may be substituted or unsubstituted, and * indicates a bonding point. The hydroxyl group on the naphthalene ring in the formula indicates that it can be bonded at any position.]

[0067] [Chemistry 10]

[0068]

[0069] [In formula (11), Ar is the same as above,

[0070] Ar is independently a structure containing an unsubstituted or substituted aromatic ring,

[0071] R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group,

[0072] R is a hydrogen atom or a methyl group,

[0073] R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0074] n1 is an integer of 2 to 16, n2 is an average value of the repeating units and is 2 to 30,

[0075] k1 is the average of the number of repetitions and is in the range of 0.5 to 10.

[0076] p1 and p2 are each independently 0 to 5,

[0077] X is a structural unit represented by the following formula (11-1), and Y is a structural unit represented by the following formula (11-2),

[0078] [Chemistry 11]

[0079]

[0080] [In formula (11-1) and (11-2), Ar, R, R 1 , R 2 , R', n1, n2 are the same as above.]

[0081] m1 and m2 are average values ​​of the repetition numbers, and are each independently 0 to 25, and m1+m2≥1.

[0082] The bonding between the structural unit X represented by the aforementioned formula (11-1) and the structural unit Y represented by the aforementioned formula (11-2) may be random or block, and the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively.]

[0083] [Chemistry 12]

[0084]

[0085] [In formula (12), n3 and n5 are average values ​​of the number of repetitions, which are 0.5 to 10 respectively, n4 is an integer of 1 to 16, R ”are each independently a hydrogen atom, a methyl group or an ethyl group.]

[0086] [Chemistry 13]

[0087]

[0088] [Chemistry 14]

[0089]

[0090] [In formula (13) and (14), R 1 , R 2 , R', n1, n2 are the same as above.]

[0091]

[13] The curable resin composition as described in any one of [9] to

[12] above, further comprising an epoxy resin having an epoxy equivalent of 100 to 10,000 g / eq other than the glycidyl ether group-containing compound as described in any one of [1] to [8] above.

[0092]

[14] The curable resin composition according to

[13] , wherein the epoxy resin is represented by the following formula (15) and has an epoxy equivalent of 500 to 10,000 g / eq.

[0093] [Chemistry 15]

[0094]

[0095] [In formula (15), Ar is independently a structure containing an unsubstituted or substituted aromatic ring, X' is a structural unit represented by the following formula (15-1), and Y' is a structural unit represented by the following formula (15-2),

[0096] [Chemistry 16]

[0097]

[0098] [In formula (15-1) and (15-2), Ar is the same as above,

[0099] R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group,

[0100] R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0101] R 3 , R 4 , R 7 , R 8 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0102] R5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group,

[0103] n1 is an integer from 4 to 16,

[0104] n2 is the average value of the repeating units and is 2 to 30.]

[0105] R 11 , R 12 are each independently a glycidyl ether group or a 2-methylglycidyl ether group,

[0106] R 13 , R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0107] R 15 , R 16 is a hydrogen atom or a methyl group,

[0108] m3, m4, p1, p2, q are the average values ​​of the number of repetitions,

[0109] m3 and m4 are each independently 0 to 25, and m3+m4≥1,

[0110] p1 and p2 are each independently 0 to 5,

[0111] q is 0.5~5.

[0112] The bonding between the structural unit X' represented by the aforementioned formula (15-1) and the structural unit Y' represented by the aforementioned formula (15-2) may be random or block, and the total number of each structural unit X and Y present in one molecule is m3 and m4, respectively.

[0113]

[15] The curable resin composition according to any one of [9] to

[14] , wherein the concentration of the reversible bonds is 0.10 mmol / g or more relative to the total mass of the curable components in the curable resin composition.

[0114]

[16] The curable resin composition according to any one of [9] to

[15] , which is a self-healing composition or a composition for a reforming material.

[0115]

[17] A cured product obtained by curing the curable resin composition according to any one of [9] to

[16] .

[0116]

[18] A laminate comprising a substrate and a layer comprising the cured product according to

[17] above.

[0117]

[19] A heat-resistant member comprising the cured product as described in

[17] .

[0118]

[20] A method for producing a compound containing a glycidyl ether group, comprising using an intermediate of a conjugated diene represented by the following general formula (1-1)' or (1-2)' or a dienophilic intermediate, and synthesizing the compound containing a glycidyl ether group represented by the aforementioned formula (1-1) or (1-2) in situ during curing with a compound (I), wherein the aforementioned compound (I) is reactive with the aforementioned compound containing a glycidyl ether group.

[0119] [Chemistry 17]

[0120]

[0121] [where n, Z 2 , Z 3 Same as above.]

[0122]

[21] A cured product obtained by subjecting the aforementioned formula (1-1)', a maleimide having a glycidyl ether group, and a compound (I) reactive with the aforementioned compound having a glycidyl ether group as essential raw materials to a curing reaction.

[0123]

[22] A cured product obtained by subjecting the aforementioned formula (1-2)', anthracene having a glycidyl ether group, and a compound (I) reactive with the aforementioned compound having a glycidyl ether group as essential raw materials to a curing reaction.

[0124] Effects of the Invention

[0125] According to the present invention, repairability and remolding properties can be imparted to a cured product composed of a curable resin composition, thereby contributing to extending the life of the cured product itself and reducing waste. DETAILED DESCRIPTION

[0126] The present invention is not limited to the following embodiments, and it should be understood that appropriate design changes and improvements can be made based on the common knowledge of those skilled in the art without departing from the gist of the present invention.

[0127] The glycidyl ether group-containing compound as one embodiment of the present invention is characterized in that the glycidyl ether group-containing compound is formed by a structural unit A having one or more glycidyl ether groups and a structural unit B different from the aforementioned A being linked by ABA, and the aforementioned structural unit A and the aforementioned structural unit B are bonded by a reversible bond having a dissociation temperature of 120° C. or higher. In addition, the glycidyl ether group in the present invention not only means a glycidyl ether group having no substituent, but also includes a case where a substituent is present on a carbon atom.

[0128] By having such a structure, the compound containing a glycidyl ether group is introduced into the cross-linked structure through a curing reaction based on its glycidyl ether group. On the other hand, it still has reversibility after becoming a cured product, so that, in particular, the structural unit B can exist away from the cross-linked structure, and thus has a high molecular mobility even in the cured product. Therefore, when the cured product is impacted and cracks or crushed, the aforementioned reversible bond part is easily cut off, and on the other hand, the aforementioned reversible bond can reversibly reshape the bond in a low temperature region including room temperature, and exert functions such as repairability and reshaping. Because the aforementioned structural unit B can exist away from the cross-linked structure, it exhibits particularly high molecular mobility, showing low-temperature repairability and low-temperature reshaping. For example, even when the cured product formed by using the compound containing a glycidyl ether group of the present invention is crushed, by placing it at a low temperature including room temperature or in a warming / heating state, it is easy to repair the cured product based on the reversible bond, and it can also be reshaped after the cured product is crushed.

[0129] As the reversible bond having a dissociation temperature of 120°C or higher, there can be mentioned covalent bonds and non-covalent bonds. From the viewpoint of durability of the cured product, covalent bonds are preferred. On the other hand, from the viewpoint of shortening the repair time and reshaping time after the cured product is crushed, non-covalent bonds are preferred.

[0130] The aforementioned covalent bond system is not particularly limited, and examples thereof include an addition structure formed by a Diels-Alder reaction, a disulfide bond, an ester bond, a borate ester bond, a semiamine acetal bond, an imine bond, an acylhydrazone bond, an olefin metathesis reaction, an alkoxyamine skeleton, an amide bond, etc. Among them, from the viewpoint of heat resistance and hydrolysis resistance of the cured product, an addition structure formed by a Diels-Alder reaction of an anthracene type (a reversible bond composed of an anthracene structure and a maleimide structure) or a disulfide bond sandwiched by an aromatic ring is preferred.

[0131] The non-covalent bond system is not particularly limited, and examples thereof include van der Waals force, ionic bond, inclusion bond of cyclodextrin, hydrogen bond of ureidopyrimidinone unit or polyetherthiourea, and the like.

[0132] In order to introduce the addition structure formed by the Diels-Alder reaction of the anthracene type into the compound, from the viewpoint of simplicity of preparation, it is preferred to use anthracene having a reactive functional group on the ring and maleimide having a reactive functional group. The specific reversible bond partial structure can be represented by the following chemical formula. Based on the R part in the following formula in the structure derived from maleimide or various reactive functional groups on the ring of the structure derived from anthracene, it is bonded to other structural units, thereby introducing a reversible bond into the compound.

[0133] [Chemistry 18]

[0134]

[0135] In the Diels-Alder reaction, a conjugated diene and a dienophile undergo an addition reaction to form a six-membered ring. The Diels-Alder reaction is an equilibrium reaction, so a Retro-Diels-Alder reaction will occur at a specific temperature to dissociate (decrosslink). At this time, when the temperature (dissociation temperature) at which the Retro-Diels-Alder reaction occurs is low, decrosslinking will be performed in a high temperature region, the crosslinking density of the cured product will decrease, and the mechanical strength will decrease. Therefore, in the present invention, a Diels-Alder reaction unit with a high thermal stability combination having a dissociation temperature of more than 120°C is required. For example, the dissociation temperature of the Diels-Alder reaction unit composed of anthracene structure and maleimide structure is as high as 250°C or more, and it will not dissociate at least at about 200°C and maintain a crosslinked structure, and has excellent thermal stability. Therefore, the crosslinking density of the cured product can be suppressed from decreasing, and good mechanical strength can be maintained. In addition, when the obtained cured product is scratched or mechanical energy such as external force is applied, the CC bond of the Diels-Alder reaction unit has a lower bonding energy than a general covalent bond, so the CC bond of the Diels-Alder reaction unit is preferentially cut. However, in a temperature range lower than the dissociation temperature, the CC bond of the Diels-Alder reaction unit shifts its equilibrium toward the bonding direction to form an adduct (Diels-Alder reaction unit) again, so it is believed that the scratch can be repaired and reshaped.

[0136] As the aforementioned disulfide bond-containing compound, the following compounds can be cited. Similarly, by bonding various compounds via positions other than the disulfide bond site, such as hydroxyl, amino, and vinyl, a disulfide bond site can be introduced into a compound containing a glycidyl ether group. In this disulfide bond site, as described above, when the cured product is cut by external force, the disulfide bond is also preferentially cut, but below the dissociation temperature, the equilibrium shifts toward the bonding direction, thereby forming an SS bond again, and repairing and reshaping the wound can be performed.

[0137] [Chemistry 19]

[0138]

[0139] [Chemistry 20]

[0140]

[0141] Examples of the compound containing the alkoxyamine skeleton include the following compounds: As described above, a reversible bond can be introduced into the compound containing a glycidyl ether group by bonding to another compound via a terminal vinyl group (methacryloyl group).

[0142] [Chemistry 21]

[0143]

[0144] The aforementioned reversible bonds exist in at least two places in the target glycidyl ether group-containing compound. From the viewpoint of obtaining a structure with higher molecular mobility and facilitating adjustment of physical properties such as mechanical strength of the cured product, it is preferred that the structural unit B also has a plurality of reversible bonds of the same type as the reversible bonds between AB.

[0145] In addition, for the same reasons as above, the molecular weight of the structural unit B is preferably greater than a certain value, for example, the average molecular weight (Mw) is preferably greater than 28. When the structural unit B has a reversible bond, the molecular weight between the reversible bonds is preferably greater than 28. In addition, the structural unit B may also have the same crosslinkable functional group as the glycidyl ether group in the structural unit A, but from the viewpoint of more easily exhibiting the effect of the present invention, it is preferred that the crosslinkable (curable) functional group is not present.

[0146] In the structural unit B, when the glycidyl ether group-containing compound of the present invention is used as a structural adhesive, for example, it is preferred to have an alkylene chain or an alkylene ether chain from the viewpoint of further improving the flexibility of the cured product or the adaptability to the substrate. In this case, the alkylene chain is more preferably an alkylene chain having 2 to 30 carbon atoms, and most preferably an alkylene chain having 4 to 16 carbon atoms. The alkylene ether chain is not particularly limited, but is preferably an alkylene ether chain having 2 to 12 carbon atoms, and the average number of repetitions thereof is preferably in the range of 2 to 30.

[0147] The glycidyl ether group in the structural unit A may be any as long as it can react easily with other functional groups, but preferably a glycidyl ether group having no substituent on the carbon atom is preferred from the viewpoint of easy acquisition of raw materials and curability. In addition, the number of glycidyl ether groups in the structural unit A is not particularly limited, but is preferably within the range of 1 to 3, more preferably 1 to 2, from the viewpoint of easy acquisition of raw materials in industry and easy adjustment of the crosslinking density when forming a cured product.

[0148] The average molecular weight (Mw) of the glycidyl ether group-containing compound is not particularly limited, but is preferably 500 or more and preferably 50000 or less from the viewpoint of achieving mechanical strength, flexibility, and repair / reformability when forming a cured product. In addition, when there are multiple reversible bonds in the structural unit B other than between AB, the molecular weight per reversible bond is more preferably in the range of 300 to 10000 from the viewpoint of the reformability of the cured product.

[0149] The glycidyl ether group-containing compound which is one embodiment of the present invention is a compound represented by the following general formula.

[0150] [Chemistry 22]

[0151]

[0152] Ar in formula (2) is independently a structure containing an unsubstituted or substituted aromatic ring, and the structures derived from anthracene in formulas (1-1) and (1-2) may have a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent. G is a glycidyl group or a 2-methylglycidyl group. In the formula, ma is an integer of 1 to 10, and n is an average value of the number of repetitions and is 0 to 10. Z 1 It is the following formula (3), Z 2 It is the following formula (4), Z 3 It is the following formula (5), Z 4 Any one of the structures represented by the following formula (6) or (7), a plurality of which are present in one molecule, and they may be the same or different.

[0153] [Chemistry 23]

[0154]

[0155] [The aromatic ring in formula (3) may be substituted or unsubstituted, and * indicates a bonding point. G is the same as above, and -OG on the naphthalene ring in the formula may be bonded at any position.]

[0156] [Chemistry 24]

[0157]

[0158] In formula (4),

[0159] Ar is independently a structure containing an unsubstituted or substituted aromatic ring,

[0160] R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group,

[0161] R is a hydrogen atom or a methyl group,

[0162] R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0163] n1 is an integer of 2 to 16, n2 is an average value of the repeating units and is 2 to 30,

[0164] k1 is the average of the number of repetitions and is in the range of 0.5 to 10.

[0165] p1 and p2 are each independently 0 to 5,

[0166] X is a structural unit represented by the following formula (4-1), and Y is a structural unit represented by the following formula (4-2),

[0167] [Chemistry 25]

[0168]

[0169] [In formula (4-1) and (4-2), Ar, R, R 1 , R 2 , R', n1, n2 are the same as above.]

[0170] m1 and m2 are average values ​​of the repetition numbers, and are each independently 0 to 25, and m1+m2≥1.

[0171] The bonding between the structural unit X represented by the aforementioned formula (4-1) and the structural unit Y represented by the aforementioned formula (4-2) may be random or block, and the total number of each structural unit X and Y present in one molecule is m1 and m2 respectively.]

[0172] [Chemistry 26]

[0173]

[0174] [In formula (5), n3 and n5 are the average values ​​of the number of repetitions, which are 0.5 to 10 respectively, n4 is an integer of 1 to 16, R ” are each independently a hydrogen atom, a methyl group or an ethyl group.]

[0175] [Chemistry 27]

[0176]

[0177] [Chemistry 28]

[0178]

[0179] [In formula (6) and (7), R 1 , R 2 , R', n1, n2 are the same as above.]

[0180] The above-mentioned general formulae (1-1) and (1-2) have a reversible bond formed by anthracene and maleimide at the terminal in the molecule. The terminal maleimide structure in the general formula (1-1) and the terminal anthracene structure in the general formula (1-2) have one or more Zs of any structure represented by the above-mentioned general formula (3). 1 The glycidyl ether group or 2-methylglycidyl ether group contributes to the curing reaction in the curable resin composition described later. ma is Z in the structure derived from anthracene 1 The number is an integer of 1 to 10, but is preferably in the range of 1 to 4, more preferably 1 or 2, from the viewpoint of ease of obtaining raw materials industrially and ease of controlling the curing reaction.

[0181] The above general formula (2) has a disulfide bond in the molecule and contains one or more Z having any of the structures represented by the above general formula (3) at the molecular end. 1 The glycidyl ether group or 2-methylglycidyl ether group contributes to the curing reaction in the curable resin composition described below.

[0182] Z in the formula 1 It is a structural unit having a glycidyl ether group or a 2-methylglycidyl ether group represented by the above general formula (3). Among these, the following structural formula is preferred from the viewpoint of easy availability of raw materials and reactivity: G is a glycidyl ether group or a 2-methylglycidyl ether group.

[0183] [Chemistry 29]

[0184]

[0185] In the above general formulae (1-1) and (1-2), the site to which the structure derived from maleimide is connected is Z 3 , the site connecting the structure derived from anthracene is Z 2 In the above general formula (2), the site connecting the oxygen atoms is Z 4 , which are any of the structures represented by the aforementioned general formulae (4), (5), (6) and (7).

[0186] In the general formulae (1-1), (1-2) and (2), n is an average value of the number of repetitions and is in the range of 0 to 10, preferably 0 to 5.

[0187] Ar in these structural formulas is an aromatic ring which may have a substituent, and is not particularly limited. As an aromatic ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring can be cited. As a substituent, for example, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, and the like can be cited. The substituent on Ar is preferably such that no curing reaction occurs when used as a curable resin composition described later, because it is easier to show the effect of the present invention.

[0188] Among these, Ar is preferably any one of the structures represented by the following structural formulae.

[0189] [Chemistry 30]

[0190]

[0191] [The aromatic ring in the formula may be substituted or unsubstituted, and * indicates the bonding point.]

[0192] In addition, the structure represented by the following formula can also be mentioned as Ar.

[0193] [Chemistry 31]

[0194]

[0195] (In the formula, the aromatic ring may be substituted or unsubstituted, n6=1 to 4, and * indicates the bonding point.)

[0196] As the structure of Ar, the following is particularly preferred: * represents a bonding point.

[0197] [Chemistry 32]

[0198]

[0199] The repeating unit n1 in the general formula (4) and (4-1) is an integer of 2 to 16. When n1 is 4 or more, the deformation mode when forming a cured product is easily elastic. In addition, when n1 is 16 or less, the reduction in crosslinking density can be suppressed. It is preferably 4 to 15, and more preferably 6 to 12.

[0200] In the above general formulas (4) and (4-1), R 1 , R 2 Each of them is independently a hydrogen atom, a methyl group or an ethyl group, and each of R is independently a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferred.

[0201] n2 in the general formula (4) and (4-2) is an average value of the repeating units and is 2 to 30. Within this range, it is preferred from the viewpoint of achieving a good balance between the viscosity of the glycidyl ether group-containing compound and the crosslinking density of the resulting cured product. It is preferably 2 to 25, and more preferably 4 to 20.

[0202] In the general formulae (4) and (4-2), R' is a divalent hydrocarbon group having 2 to 12 carbon atoms. Within this range, the adhesive force is improved and the deformation mode of the cured product tends to be elastic. Preferably, R' is a divalent hydrocarbon group having 2 to 6 carbon atoms.

[0203] The divalent hydrocarbon group is not particularly limited, and examples thereof include linear or branched alkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, and aralkylene groups (a divalent group having an alkylene group and an arylene group).

[0204] Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Examples of the alkenylene group include vinylene, 1-methylvinylene, propenylene, butenylene, and pentenylene. Examples of the alkynylene group include ethynylene, propynylene, butynylene, pentynylene, and hexynylene. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene. Examples of the arylene group include phenylene, tolylene, xylylene, and naphthylene.

[0205] Among these, an ethylene group, a propylene group, and a tetramethylene group are preferred from the viewpoint of the balance between the availability of raw materials, the viscosity of the obtained glycidyl ether group-containing compound, and the flexibility when a cured product is formed.

[0206] R in the above general formulae (4) and (4-2) is independently a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.

[0207] In the general formula (4), m1 and m2 are respectively the average values ​​of the repeating numbers of the structural unit X and the structural unit Y, and are each independently 0 to 25, and m1+m2≥1. Preferably, m1 and m2 are respectively in the range of 0.5 to 10.

[0208] In the general formula (4), k1 is the average of the number of repetitions and is in the range of 0.5 to 5, preferably in the range of 0.5 to 2.

[0209] In the above general formula (5), n3 and n5 are average values ​​of the number of repetitions, which are 0.5 to 10, respectively; n4 is an integer of 1 to 16; R ”Each independently represents a hydrogen atom, a methyl group or an ethyl group. Among these, from the viewpoint of the ease of obtaining the raw materials and the mechanical properties of the obtained cured product, n3 is preferably in the range of 0.5 to 10, n5 is preferably in the range of 2 to 3, n4 is preferably an integer of 1 to 8, and R ” Preferred is a hydrogen atom.

[0210] In the above general formulas (6) and (7), R 1 , R 2 , R', n1, and n2 are the same as those described above, and the preferred embodiments are also the same as those described above.

[0211] Examples of the glycidyl ether group-containing compound of the present invention include the following, but are not limited thereto.

[0212] [Chemistry 33]

[0213]

[0214] [Chemistry 34]

[0215]

[0216] The method for producing the glycidyl ether group-containing compound according to one embodiment of the present invention is not particularly limited, and can be produced by using known reactions in stages according to the target structure, and raw materials can also be obtained by appropriately combining commercially available products. Representative synthesis methods are described below.

[0217] The above-mentioned general formulas (1-1) and (1-2) can be obtained by using a compound having two Diels-Alder reaction units as reversible bonds in the molecule, wherein the above-mentioned Diels-Alder reaction units are addition reaction parts formed by Diels-Alder reaction composed of an anthracene structure and a maleimide structure, and in the case of the general formula (1-1), Z 1 In the case of the general formula (1-2), a maleimide compound having a structure of 1 The structure of anthracene compounds.

[0218] The so-called Diels-Alder reaction, in which a conjugated diene such as an anthracene structure and a dienophile such as a maleimide structure undergo an addition reaction to form a six-membered ring, is an equilibrium reaction. At a temperature higher than the temperature at which the addition reaction is performed, the addition reaction part dissociates and returns to the original conjugated diene and dienophile, i.e., a reverse Diels-Alder reaction, which is widely known.

[0219] As the aforementioned Z 1The precursor of the maleimide compound having a structure of, that is, a maleimide compound having a hydroxyl group, may be any of the compounds listed below. Among these, hydroxyphenylmaleimide is preferred in terms of curability, and monohydroxyphenylmaleimide is particularly preferred in terms of the balance between reactivity and the physical properties of the cured product, as well as repairability and remolding properties. Among the monohydroxyphenylmaleimide, p-hydroxyphenylmaleimide is particularly preferred from the viewpoint of heat resistance. The hydroxyl group in the compound may be formed into a glycidyl ether group by a known method described in the examples, for example.

[0220] [Chemistry 35]

[0221]

[0222] As the aforementioned Z 1 The precursor of the anthracene compound having a structure of, that is, an anthracene compound having a hydroxyl group, can be any of the compounds listed below. Among these, from the viewpoint of good curability, 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene and hydroxyanthracene are more preferred, and from the perspective of the balance between reactivity and the physical properties of the cured product, as well as repairability and remolding properties, 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene and monohydroxyanthracene are particularly preferred. The hydroxyl group in the compound can be formed into a glycidyl ether group by a known method described in the examples, for example.

[0223] [Chemistry 36]

[0224]

[0225] In addition, the structures of the maleimide compound and the anthracene compound each independently include a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent. In addition, in the structures of the compounds listed in the above formula, an alkoxy group, an aralkyloxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group also include a case where various substituents are further bonded to the carbon atoms possessed by these groups.

[0226] The Diels-Alder reaction can be carried out by a known method. For example, the conjugated diene compound and the dienophile compound can be mixed in equimolar amounts or one of the components can be mixed in excess as appropriate, melted by heating or dissolved in a solvent, stirred at room temperature to 200° C. for 1 to 24 hours, and directly filtered and the solvent can be distilled off without purification, or the product can be obtained by a commonly used separation and purification method such as recrystallization, reprecipitation and chromatography.

[0227] The synthesis of sites other than the reversible bond can be performed by known methods. For example, a compound having a hydroxyl group at the terminal is obtained by reacting a diglycidyl ether of an aliphatic dihydroxy compound or an aliphatic divinyl ether with an aromatic hydroxy compound, and then reacting the compound with chloromethylanthracene, glycidyloxyanthracene, etc. to introduce an anthracene structure at the terminal, and then performing a Diels-Alder reaction with a maleimide compound having a glycidyl ether group as described above to obtain a compound represented by the general formula (1-1).

[0228] Alternatively, after obtaining a compound having a hydroxyl group at the end, it is epoxidized to convert the end into a glycidyl ether group, and then, by reacting it with hydroxyanthracene or the like, an anthracene structure is introduced at the end, and then, as described above, a Diels-Alder reaction is carried out with a maleimide compound having a glycidyl ether group, thereby obtaining a compound represented by the general formula (1-1).

[0229] Alternatively, an aromatic dihydroxy compound is reacted with a dihalogenated alkyl compound or a dihalogenated aralkyl compound to obtain a compound having a halogenated alkyl group at the end, which is then reacted with hydroxymethylanthracene or the like to introduce an anthracene structure into the end, and then subjected to a Diels-Alder reaction with a maleimide compound having a glycidyl ether group as described above, thereby obtaining a compound represented by the general formula (1-1).

[0230] The diglycidyl ether of the aliphatic dihydroxy compound is not particularly limited, and examples thereof include 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecandiol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl ether, and 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether. These diglycidyl ethers may be used alone or in combination of two or more.

[0231] Among these, compounds having a structure in which glycidyl groups are linked to both ends of an alkylene chain having 12 to 14 carbon atoms via ether groups are preferred, and 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, and 1,14-tetradecanediol diglycidyl ether are most preferably used, from the viewpoint of an excellent balance between flexibility and heat resistance of the obtained cured product.

[0232] The aliphatic divinyl ether is not particularly limited, and examples thereof include polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,10-decanediol divinyl ether and other linear alkylene divinyl ethers, and branched alkylene divinyl ethers such as neopentyl glycol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether and other divinyl ethers containing a cycloalkane structure, bisphenol A divinyl ether, bisphenol F divinyl ether, and hydroquinone divinyl ether. These may be used alone or in combination of two or more.

[0233] Among these, divinyl ethers having a polyether structure or a linear alkylene chain having 9 to 10 carbon atoms are preferred from the viewpoint of excellent balance between the flexibility and toughness of the obtained cured product, and polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, and 1,14-tetradecanediol diglycidyl ether are most preferably used.

[0234] The aromatic hydroxy compound is not particularly limited, and examples thereof include dihydroxybenzenes such as hydroquinone, resorcinol, and catechol, trihydroxybenzenes such as pyrogallol, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene, triphenylmethane-type phenols such as 4,4',4"-trihydroxytriphenylmethane, dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, 1,1'-methylenebis-(2,7-naphthalenediol) obtained by coupling dihydroxynaphthalenes, and 1,1'-binaphthyl. -2,2',7,7'-tetrol, 1,1'-oxybis-(2,7-naphthalene diol) and other tetrafunctional phenols, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane and 1,1-bis(4-hydroxyphenyl)-1-phenylethane and bis(4-hydroxyphenyl)sulfone and other bisphenols, 2,2'-biphenol, 4,4'-biphenol, (1,1'-biphenyl)-3,4-diol, 3,3'-dimethyl-(1,1'-biphenyl)-4,4'-diol, 3-methyl- Biphenols such as (1,1'-biphenyl)-4,4'-diol, 3,3',5,5'-tetramethylbiphenyl-2,2'-diol, 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 5-methyl-(1,1'-biphenyl)-3,4'-diol, 3'-methyl-(1,1'-biphenyl)-3,4'-diol, 4'-methyl-(1,1'-biphenyl)-3,4'-diol, phenols containing an alicyclic structure such as polyadducts of phenol and dicyclopentadiene and polyadducts of phenol and terpene compounds, naphthyl such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane Phenols, condensation products of phenols and phenylenedimethyl chloride or biphenylenedimethyl chloride, i.e., so-called Zylock type phenol resins, can be used alone or in combination of two or more. Furthermore, bifunctional phenol compounds having a structure in which a methyl group, a tert-butyl group or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds can also be cited. In addition, the aforementioned phenols containing an alicyclic structure and the aforementioned Zylock type phenol resin system can contain not only bifunctional components but also trifunctional components or more, and can be used directly or only bifunctional components can be taken out for use through purification steps such as chromatographic columns.

[0235] Among these, bisphenols are preferred from the viewpoint of excellent balance between flexibility and toughness when forming a cured product, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are preferred from the viewpoint of significant toughness-imparting performance. In addition, when moisture resistance of the cured product is important, phenols containing an alicyclic structure are preferably used.

[0236] As for the reaction ratio of the diglycidyl ether of the aforementioned aliphatic dihydroxy compound and the aforementioned aromatic hydroxy compound, it is preferred to react them within the range of the former / the latter being 1 / 1.01 to 1 / 5.0 (molar ratio). From the viewpoint of obtaining a cured product having a good balance between flexibility and heat resistance, (a1) / (a2) is preferably 1 / 1.02 to 1 / 3.0 (molar ratio).

[0237] The reaction of the diglycidyl ether of the aliphatic dihydroxy compound with the aromatic hydroxy compound is preferably carried out in the presence of a catalyst. As the catalyst, various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, phosphorus compounds such as triphenylphosphine, DMP-30, DMAP, chlorides, bromides, iodides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and benzyltributylammonium, quaternary ammonium salts such as chlorides, bromides, iodides such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, and benzyltributylammonium, triethylamine, N,N-dimethylbenzylamine, tertiary amines such as 1,8-diazabicyclo[5.4.0]undecene and 1,4-diazabicyclo[2.2.2]octane, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like imidazoles, etc. Among these, it is also possible to use two or more catalysts in combination. Among them, from the viewpoint of rapid reaction and high effect of reducing impurities, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred. The amount of these catalysts used is not particularly limited, and it is preferred to use 0.0001 to 0.01 moles relative to 1 mole of the phenolic hydroxyl group of the aforementioned aromatic hydroxy compound. The form of these catalysts is also not particularly limited, and they can be used in the form of aqueous solutions or in the form of solids.

[0238] In addition, the reaction of the diglycidyl ether of the aforementioned aliphatic dihydroxy compound and the aforementioned aromatic hydroxy compound can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of usable organic solvents include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propanol, butanol, and the like. The amount of the organic solvent used is generally 50 to 300% by mass, preferably 100 to 250% by mass, relative to the total mass of the raw materials introduced. These organic solvents can be used alone or in combination. In order to allow the reaction to proceed rapidly, it is preferably solvent-free. On the other hand, from the viewpoint of reducing impurities in the final product, dimethyl sulfoxide is preferably used.

[0239] The reaction temperature when performing the above reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing the impurities in the final product, the reaction temperature is preferably 100 to 160°C. In addition, when the degree of coloration of the obtained compound is large, an antioxidant or a reducing agent may be added to suppress this. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and trivalent phosphorus-containing phosphite compounds. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, dithionite, or salts thereof.

[0240] After the reaction is completed, neutralization or water washing treatment may be performed until the pH value of the reaction mixture reaches 3 to 7, preferably 5 to 7. Neutralization treatment and water washing treatment may be performed according to conventional methods. For example, when an alkaline catalyst is used, an acidic substance such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, oxalic acid, etc. may be used as a neutralizing agent. After neutralization or water washing treatment, the solvent may be distilled off under reduced pressure and heating as necessary to concentrate the product to obtain a compound.

[0241] As for the reaction ratio of the aforementioned aliphatic divinyl ether and the aforementioned aromatic hydroxy compound, it is preferred to react them within the range of the former / the latter being 1 / 1.01 to 1 / 5.0 (molar ratio). From the viewpoint of obtaining a cured product having a good balance between flexibility and heat resistance, (a1) / (a2) is preferably 1 / 1.02 to 1 / 3.0 (molar ratio).

[0242] The reaction of the diglycidyl ether of the aforementioned aliphatic dihydroxy compound with the aforementioned aromatic hydroxy compound can proceed fully even without using a catalyst, but from the viewpoint of selecting raw materials and increasing the reaction rate, a catalyst can be appropriately used. As catalysts that can be used here, there can be mentioned: inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, organic acids such as toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, and trifluoroacetic acid, aluminum chloride, ferric chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, boron trifluoride phenol complex, etc. Lewis acids, etc. With regard to the amount of catalyst used, in general, it is in the range of 10ppm to 1% by weight relative to the mass of the divinyl ether compound. At this time, it is preferred to select its type and amount in a manner to avoid the nuclear addition reaction of the vinyl group to the aromatic ring.

[0243] In addition, the reaction of the aliphatic divinyl ether and the aromatic hydroxy compound can be carried out without a solvent or in the presence of an organic solvent. Examples include aromatic organic solvents such as benzene, toluene, and xylene, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and alcohol organic solvents such as methanol, ethanol, isopropanol, and n-butanol. The amount of the organic solvent used is usually 50 to 300 mass %, preferably 100 to 250 mass %, relative to the total mass of the raw materials placed. These organic solvents can be used alone or in combination.

[0244] The reaction temperature for the above reaction is usually 50 to 150° C., and the reaction time is usually 0.5 to 10 hours. In order to prevent self-polymerization of the vinyl ether group, the reaction is preferably carried out under an oxygen atmosphere.

[0245] After the reaction is completed, when an organic solvent is used, it is removed under reduced pressure and heating. When a catalyst is used, it is deactivated with a deactivating agent as needed and then removed by washing with water or filtering to obtain a compound.

[0246] The compound having a hydroxyl group at the end thus obtained is reacted with chloromethylanthracene or the like. At this time, sodium hydroxide, potassium hydroxide, potassium carbonate or the like can be used as a catalyst, and toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide or the like can also be used as a solvent. The reaction temperature is room temperature to 200°C, and the reaction time is 1 to 24 hours. Thereafter, the catalyst is removed by filtration or the like, and extraction and removal of the solvent are performed, thereby obtaining the target compound. The Diels-Alder reaction of this compound is as described above.

[0247] The aliphatic hydroxy compound is not particularly limited, and examples thereof include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexanediol, 1,17-heptanediol, 1,18-octanediol, 1,19-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetra ,16-hexadecanediol, 2-methyl-1,11-undecandiol, 3-methyl-1,11-undecandiol, 2,6,10-trimethyl-1,11-undecandiol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, polyheptamethylene glycol diglycidyl ether, etc. can be used alone or in combination of two or more.

[0248] Among these, from the viewpoint of excellent balance between flexibility and heat resistance of the obtained cured product, dihydroxy compounds having a polyether structure or a linear alkylene chain having 12 to 14 carbon atoms are preferred, and polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol are most preferred.

[0249] The dihalogenated alkyl compound is not particularly limited, and examples thereof include 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-dichloroundecane, 1,12-dichlorododecane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1,9-dibromononane, 1,10-dibromodecane, 1,11-dibromodecane, and 1,12-dibromododecane. These compounds may be used alone or in combination of two or more.

[0250] The dihalogenated aralkyl compound is not particularly limited, and examples thereof include dichloroxylene, dichloromethylbiphenyl, dibromoxylene, dibromomethylbiphenyl, and the like. These compounds may be used alone or in combination of two or more.

[0251] As for the reaction ratio of the aforementioned aromatic dihydroxy compound and the dihalogenated alkyl compound or the dihalogenated aralkyl compound, it is preferred that the former / the latter be reacted in the range of 1 / 1.01 to 1 / 5.0 (molar ratio). From the viewpoint of obtaining a cured product having both flexibility and heat resistance in a good balance, (a1) / (a2) is preferably 1 / 1.02 to 1 / 3.0 (molar ratio).

[0252] The reaction of the aforementioned aromatic dihydroxy compound with a dihalogenated alkyl compound or a dihalogenated aralkyl compound is preferably carried out in the presence of a catalyst. As the aforementioned catalyst, various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, etc. Among these, it is also possible to use two or more catalysts at the same time. Among them, from the viewpoint of rapid reaction and high effect of reducing impurities, sodium hydroxide, potassium hydroxide and potassium carbonate are preferred. The amount of these catalysts used is not particularly limited, and it is preferably used 0.0001 to 10 moles relative to 1 mole of phenolic hydroxyl groups of the aforementioned aromatic hydroxy compounds. The form of these catalysts is also not particularly limited, and they can be used in the form of aqueous solutions or in the form of solids.

[0253] In addition, the reaction of the aforementioned aromatic dihydroxy compound with a dihalogenated alkyl compound or a dihalogenated aralkyl compound can be carried out without a solvent or in the presence of an organic solvent. As usable organic solvents, for example, toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide, etc. can be cited. The amount of the organic solvent used is usually 50 to 300 mass%, preferably 100 to 1000 mass%, relative to the total mass of the raw materials placed. These organic solvents can be used alone or in a variety of mixed uses.

[0254] The reaction temperature for the above reaction is usually room temperature to 150°C, and the reaction time is usually 1 to 24 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably room temperature to 100°C.

[0255] The compound having a halogenated alkyl group at the end thus obtained is reacted with hydroxymethylanthracene or the like. At this time, sodium hydroxide, potassium hydroxide, potassium carbonate or the like can be used as a catalyst, and toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide or the like can also be used as a solvent. The reaction temperature is room temperature to 200°C, and the reaction time is 1 to 24 hours. Thereafter, the catalyst is removed by filtration or the like, and extraction and removal of the solvent are performed, thereby obtaining the target compound. The Diels-Alder reaction of this compound is as described above.

[0256] The intermediate of the conjugated diene or the dienophilic intermediate before the Diels-Alder reaction can be represented by the following general formula (1-1)' or (1-2)'.

[0257] [Chemistry 37]

[0258]

[0259] [where n, Z 2 , Z 3 Same as above.]

[0260] The method for producing the compound having a disulfide bond as the reversible bond represented by the general formula (3) is also not particularly limited.

[0261] Examples of compounds that can be used as a raw material for the compound having a disulfide bond include the following.

[0262] [Chemistry 38]

[0263]

[0264] [Chemistry 39]

[0265]

[0266] The compound having a disulfide bond can be obtained by a known method. For example, a compound having a thiol group is oxidatively bonded. As an oxidizing agent, iodine or hydrogen peroxide is generally used. It can also be heated to melt or dissolved in a solvent, stirred at a temperature of room temperature to 200°C for 1 to 24 hours, and directly filtered and distilled to remove the solvent without purification, or it can be obtained by a commonly used separation and purification method such as recrystallization, reprecipitation and chromatography. After obtaining a compound containing a hydroxyl group as a precursor, a known method can be used to convert it into a glycidyl ether group.

[0267] The compound containing a glycidyl ether group of the present invention can be used in combination with a compound (I) reactive with the compound containing a glycidyl ether group to form a curable resin composition. The curable resin composition can be suitably used in various electrical / electronic component applications such as adhesives, coatings, photoresists, printed wiring boards, and semiconductor sealing materials.

[0268] Examples of the compound (I) reactive with the glycidyl ether group-containing compound include various known epoxy resin curing agents such as amine compounds, acid anhydrides, amide compounds, compounds containing phenolic hydroxyl groups, carboxylic acid compounds, and thiol compounds. The curing agent can be appropriately selected according to the physical properties of the target cured product, and in particular, a hydroxyl group-containing compound is preferably used from the viewpoints of mechanical strength, adhesion to a substrate, and the like.

[0269] Examples of the amine compound include trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N',N'-tetramethylpropylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenediamine, and Aliphatic amine compounds such as ethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, α-methylbenzylmethylamine, etc.

[0270] Alicyclic and heterocyclic amine compounds such as piperidine, piperazine, menthane diamine, isophorone diamine, methylmorpholine, ethylmorpholine, N,N',N"-tris(dimethylaminopropyl)hexahydro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxyspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N'-dimethylpiperazine, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU);

[0271] Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, pyridine, and picoline;

[0272] Modified amine compounds such as epoxide addition polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-terminated polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, amine imides, boron trifluoride-piperidine complexes, and boron trifluoride-monoethylamine complexes.

[0273] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0274] Examples of the compound containing a phenolic hydroxyl group include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadienol addition type resins, phenol aralkyl resins (siloc resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenolylethane resins, Polyphenol compounds such as naphthol novolac resin, naphthol-phenol co-condensation novolac resin, naphthol-cresol co-condensation novolac resin, biphenyl-modified phenol resin (a polyphenol compound in which a phenol core is connected via a dimethylene group), biphenyl-modified naphthol resin (a polyphenol compound in which a phenol core is connected via a dimethylene group), aminotriazine-modified phenol resin (a polyphenol compound in which a phenol core is connected via melamine, benzoguanamine, etc.), or alkoxy-containing aromatic ring-modified novolac resin (a polyphenol compound in which a phenol core and an alkoxy-containing aromatic ring are connected via formaldehyde).

[0275] Examples of the amide compounds include dicyandiamide and polyamidoamine, etc. Examples of the polyamidoamine include compounds obtained by reacting aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid, or carboxylic acid compounds such as fatty acids and dimer acids with aliphatic polyamines or polyamines having a polyoxyalkylene chain.

[0276] Examples of the carboxylic acid compound include carboxylic acid-terminated polyesters, polyacrylic acid, and carboxylic acid polymers such as maleic acid-modified polypropylene glycol.

[0277] The thiol compound is preferably a compound containing two or more thiol groups in two molecules. Examples thereof include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetra(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate), 1,3,4,6-tetra(2-mercaptoethyl)acetylene carbamide, 4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol.

[0278] In the case of using these curing agents, only one curing agent may be used, or two or more curing agents may be mixed. In addition, in applications such as bottom filling materials and general coating applications, it is preferred to use the aforementioned amine compounds, carboxylic acid compounds and / or anhydride compounds. In addition, in adhesives and flexible wiring substrate applications, from the viewpoints of workability, curability, and long-term stability, amine compounds, especially dicyandiamide, are preferred. In addition, in semiconductor sealing material applications, from the viewpoint of the heat resistance of the cured product, solid-state phenolic compounds are preferred. In addition, in battery applications, from the viewpoint of low-temperature curing, aliphatic amines or thiol compounds are preferred.

[0279] Furthermore, from the viewpoint of further exhibiting the effects of the present invention, the compound (I) reactive with the glycidyl ether group-containing compound is preferably a hydroxyl group-containing compound having a reversible bond.

[0280] Examples of the hydroxyl-containing compound having a reversible bond include a hydroxyl-containing compound in which a structural unit A' having one or more hydroxyl groups and a structural unit B' different from the aforementioned A' are connected by A'-B'-A', and the aforementioned structural unit A' and the aforementioned structural unit B' are bonded via a reversible bond. In this case, from the viewpoint of further exerting the effect of the present invention, the dissociation temperature of the aforementioned reversible bond is preferably 120° C. or higher.

[0281] Examples of the reversible bond include the same reversible bonds as those in the glycidyl ether group-containing compound of the present invention.

[0282] Examples of the hydroxyl group-containing compound having a reversible bond include compounds represented by the following formulas: Among these, compounds represented by the following formulas (8-1), (8-2), and (9) are preferably used from the viewpoint of the dissociation temperature of the reversible bond.

[0283] [Chemistry 40]

[0284]

[0285] [Ar in formula (9) is independently a structure containing an unsubstituted or substituted aromatic ring, and the structures derived from anthracene in formulas (8-1) and (8-2) and the structures derived from furan in formulas (8-3) and (8-4) may have a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent.

[0286] In the formula, ma is an integer of 1 to 10, mb is an integer of 1 to 4, and n is the average value of the number of repetitions and is 0 to 10. 5 It is the following formula (10), Z 2 It is the following formula (11), Z 3 It is the following formula (12), Z 4 Any one of the structures represented by the following formula (13) or (14), a plurality of which are present in one molecule, and they may be the same or different.

[0287] [Chemistry 41]

[0288]

[0289] [The aromatic ring in formula (10) may be substituted or unsubstituted, and * indicates a bonding point. The hydroxyl group on the naphthalene ring in the formula indicates that it can be bonded at any position.]

[0290] [Chemistry 42]

[0291]

[0292] [In formula (11),

[0293] Ar is independently a structure containing an unsubstituted or substituted aromatic ring,

[0294] R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group,

[0295] R is a hydrogen atom or a methyl group,

[0296] R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0297] n1 is an integer of 2 to 16, n2 is an average value of the repeating units and is 2 to 30,

[0298] k1 is the average of the number of repetitions and is in the range of 0.5 to 10.

[0299] p1 and p2 are each independently 0 to 5,

[0300] X is a structural unit represented by the following formula (11-1), and Y is a structural unit represented by the following formula (11-2),

[0301] [Chemistry 43]

[0302]

[0303] [In formula (11-1) and (11-2), Ar, R, R 1 , R 2 , R', n1, n2 are the same as above.]

[0304] m1 and m2 are average values ​​of the repetition numbers, and are each independently 0 to 25, and m1+m2≥1.

[0305] The bonding between the structural unit X represented by the aforementioned formula (11-1) and the structural unit Y represented by the aforementioned formula (11-2) may be random or block, and the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively.]

[0306] [Chemistry 44]

[0307]

[0308] [In formula (12), n3 and n5 are average values ​​of the number of repetitions, which are 0.5 to 10 respectively, n4 is an integer of 1 to 16, R ” are each independently a hydrogen atom, a methyl group or an ethyl group.]

[0309] [Chemistry 45]

[0310]

[0311] [Chemistry 46]

[0312]

[0313] [In formula (13) and (14), R 1 , R 2 , R', n1, n2 are the same as above.]

[0314] Specific examples of the hydroxyl group-containing compound having a reversible bond include compounds represented by the following structural formula.

[0315] [Chemistry 47]

[0316]

[0317] [Chemistry 48]

[0318]

[0319] These hydroxyl group-containing compounds correspond to intermediates (precursors) of the aforementioned glycidyl ether group-containing compounds of the present invention, and can be obtained by using commercially available raw materials such as maleimide, furan, anthracene, etc. having a hydroxyl group according to the aforementioned production method.

[0320] In addition, in the curable resin composition of the present invention, other epoxy resins other than the glycidyl ether group-containing compound of the present invention may be used in combination within a range not impairing the effects of the present invention.

[0321] Examples of the other epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AD ​​epoxy resins, polyhydroxybenzene epoxy resins, polyhydroxynaphthalene epoxy resins, biphenyl epoxy resins, tetramethylbiphenyl epoxy resins and other liquid epoxy resins, brominated epoxy resins such as brominated phenol novolac epoxy resins, solid bisphenol A epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, triphenylmethane epoxy resins, tetraphenylethane epoxy resins, dicyclopentane epoxy resins, and the like. Diene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensation novolac type epoxy resin, naphthol-cresol co-condensation novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl modified novolac type epoxy resin, etc. can be used alone or in combination of two or more. It is preferred to select and use them according to the target application, the physical properties of the cured product, etc.

[0322] Among these, from the viewpoint of an excellent balance between curability and the crosslinking density of the obtained cured product, it is preferred to use an epoxy resin having an epoxy equivalent of 100 to 10,000 g / eq, and it is particularly preferred to use an epoxy resin represented by the following formula (15) having an epoxy equivalent of 500 to 10,000 g / eq.

[0323] [Chemistry 49]

[0324]

[0325] [In formula (15), Ar is independently a structure containing an unsubstituted or substituted aromatic ring, X' is a structural unit represented by the following formula (15-1), and Y' is a structural unit represented by the following formula (15-2),

[0326] [Chemistry 50]

[0327]

[0328] [In formula (15-1) and (15-2), Ar is the same as above,

[0329] R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group,

[0330] R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0331] R 3 , R 4 , R 7 , R 8 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0332] R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group,

[0333] n1 is an integer from 4 to 16,

[0334] n2 is the average value of the repeating units and is 2 to 30.]

[0335] R 11 , R 12 are each independently a glycidyl ether group or a 2-methylglycidyl ether group,

[0336] R 13 , R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0337] R 15 , R 16 is a hydrogen atom or a methyl group,

[0338] m3, m4, p1, p2, q are the average values ​​of the number of repetitions,

[0339] m3 and m4 are each independently 0 to 25, and m3+m4≥1,

[0340] p1 and p2 are each independently 0 to 5,

[0341] q is 0.5~5.

[0342] The bonding between the structural unit X' represented by the aforementioned formula (15-1) and the structural unit Y' represented by the aforementioned formula (15-2) may be random or block, and the total number of each structural unit X and Y present in one molecule is m3 and m4, respectively.

[0343] The epoxy resin represented by the general formula (15) can be used alone to form a curable resin composition. From the viewpoint of imparting further flexibility to the cured product and facilitating easy disassembly, it is preferred to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq in combination.

[0344] The epoxy resin that can be used in combination has an epoxy equivalent in the range of 100 to 300 g / eq, and its structure is not limited. Examples thereof include liquid epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, polyhydroxybenzene epoxy resin, polyhydroxynaphthalene epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, brominated epoxy resins such as brominated phenol novolac epoxy resin, solid bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene-phenol epoxy resin, and the like. Addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensation novolac type epoxy resin, naphthol-cresol co-condensation novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl modified novolac type epoxy resin, etc., can be used alone or in combination of two or more, and it is preferred to select and use various types according to the target application, the physical properties of the cured product, etc.

[0345] Among these, it is preferred to use liquid epoxy resins having an epoxy equivalent of 100 to 300 g / eq, such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, polyhydroxybenzene epoxy resin, polyhydroxynaphthalene epoxy resin, biphenyl epoxy resin, and tetramethylbiphenyl epoxy resin. It is particularly preferred to use liquid epoxy resins having an epoxy equivalent of 100 to 300 g / eq, such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AD ​​epoxy resin.

[0346] The ratio of the epoxy resin represented by the general formula (15) to the epoxy resin having an epoxy equivalent of 100 to 300 g / eq is not particularly limited. From the viewpoint of easy phase separation in the cured product, the mass ratio of the former to the latter is 97:3 to 3:97, preferably 10:90 to 90:10, and particularly preferably 80:20 to 20:80. Phase separation in the cured product forms an island structure, which has both the adhesiveness and stress relaxation ability of the cured product, and in particular, exhibits high adhesiveness in a wide temperature range, and has the effect of reducing the molding shrinkage of the resin composition before and after heat curing.

[0347] The concentration of the reversible bond in the curable resin composition of the present invention is preferably 0.10 mmol / g or more relative to the total mass of the curable components in the curable resin composition. According to such a configuration, the repairability and remolding properties of the cured product obtained from the curable resin composition are both better. The concentration of the reversible bond is more preferably 0.10 to 3.00 mmol / g, and further preferably 0.15 to 2.00 mmol / g. In addition, in the case where the compound containing a glycidyl ether group of the present invention has multiple reversible bonds, or the compound containing a hydroxyl group having a reversible bond is used alone as a curing agent or in combination with other curing agents, the total concentration of the reversible bond is preferably 0.10 mmol / g or more relative to the total mass of the curable components in the curable resin composition, more preferably 0.10 to 3.00 mmol / g, and further preferably 0.15 to 2.00 mmol / g. In addition, the concentration of the reversible bond can be appropriately selected by the glass transition temperature defined by the tanδ peak top of the viscoelasticity measuring instrument (DMA) of the target cured product. For example, in the case where the glass transition temperature is used as a standard, if the glass transition temperature of the cured product is near room temperature, sufficient repairability and reshaping functions can be easily exhibited even at the low concentration side of the preferred range. On the other hand, if the glass transition temperature of the target cured product exceeds 100°C as a standard, it is easy to exhibit functions at the high concentration side of the preferred range. However, in the temperature range exceeding the glass transition temperature measured by DMA, the molecular mobility is generally high, and sufficient repairability and reshaping functions can be easily exhibited even at a low concentration of the compound containing a glycidyl ether group. Therefore, for example, by appropriately adjusting the aging temperature for repair or the heating temperature for reshaping, the effect of exhibiting the repairability and reshaping functions can also be adjusted. In this way, the relationship between the glass transition temperature of the cured product and the concentration of the reversible bond is not limited to these.

[0348] In the curable resin composition of the present invention, the ratio of the total amount of glycidyl ether groups to the total amount of active groups reactive with the glycidyl ether groups is not particularly limited. However, from the viewpoint of good mechanical properties and the like of the obtained cured product, the amount of active groups reactive with the glycidyl ether groups is preferably 0.4 to 1.5 equivalents per 1 equivalent of the total amount of glycidyl ether groups in the resin composition.

[0349] In addition, the curable resin composition may also contain a curing accelerator. As the aforementioned curing accelerator, various substances can be used, for example: urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, organic acid metal salts, Lewis acids, amine complex salts, etc. In the case of use as an adhesive, from the perspective of excellent workability and low-temperature curing, urea compounds, especially 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) are preferred. In the case of use as a semiconductor sealing material, from the perspective of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene is preferred among tertiary amines.

[0350] Examples of the phosphorus compound include primary phosphines such as alkyl phosphines such as ethyl phosphine and butyl phosphine, and phenyl phosphine; dialkyl phosphines such as dimethyl phosphine and dipropyl phosphine; secondary phosphines such as diphenyl phosphine and methylethyl phosphine; and tertiary phosphines such as trimethyl phosphine, triethyl phosphine and triphenyl phosphine.

[0351] Examples of the imidazole include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2 -phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, and the like.

[0352] Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

[0353] Examples of the urea compound include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, and N-(3-chloro-4-methylphenyl)-N′,N′-dimethylurea.

[0354] Furthermore, the curable resin composition of the present invention may be used in combination with other thermosetting resins or thermoplastic resins within a range not inhibiting the effects of the present invention.

[0355] Examples of other thermosetting resins include cyanate resins, resins having a benzoxazine structure, active ester resins, vinyl benzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc. When other thermosetting resins are used together, the amount used is not particularly limited as long as it does not hinder the effects of the present invention, and is preferably in the range of 1 to 50 parts by mass in 100 parts by mass of the curable resin composition.

[0356] Examples of the cyanate resin include bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin, bisphenol sulfide type cyanate resin, phenylene ether type cyanate resin, naphthylene ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol novolac type cyanate resin, cresol novolac type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin, dicyclopentadiene-phenol addition reaction type cyanate resin, phenol aralkyl type cyanate resin, naphthol novolac type cyanate resin, naphthol aralkyl type cyanate resin, naphthol-phenol co-condensation novolac type cyanate resin, naphthol-cresol co-condensation novolac type cyanate resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate resin, biphenyl-modified novolac type cyanate resin, and anthracene type cyanate resin. These may be used alone or in combination of two or more.

[0357] Among these cyanate resins, bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, polyhydroxynaphthalene type cyanate resin, naphthylene ether type cyanate resin, and novolac type cyanate resin are preferably used because they can obtain a cured product having excellent heat resistance. Dicyclopentadiene-phenol addition reaction type cyanate resin is preferred because it can obtain a cured product having excellent dielectric properties.

[0358] The resin having a benzoxazine structure is not particularly limited, and examples thereof include: a reaction product of bisphenol F, formalin and aniline (Fa-type benzoxazine resin), a reaction product of diaminodiphenylmethane, formalin and phenol (Pd-type benzoxazine resin), a reaction product of bisphenol A, formalin and aniline, a reaction product of dihydroxydiphenyl ether, formalin and aniline, a reaction product of diaminodiphenyl ether, formalin and phenol, a reaction product of dicyclopentadiene-phenol addition type resin, formalin and aniline, a reaction product of phenolphthalein, formalin and aniline, a reaction product of diphenyl sulfide, formalin and aniline, etc. These may be used alone or in combination of two or more.

[0359] As the above-mentioned active ester resin, there is no particular limitation. Generally speaking, it is preferred to use compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The above-mentioned active ester resin is preferably a resin obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferably an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxyl compound, and more preferably an active ester resin obtained from a carboxylic acid compound or its halide and a phenolic compound and / or a naphthol compound. As a carboxylic acid compound, for example: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or its halide. Examples of the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, and dicyclopentadiene-phenol addition type resins.

[0360] Specifically, preferred active ester resins include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated products of phenol novolacs, active ester resins that are benzoylated products of phenol novolacs, and the like. Among them, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred from the viewpoint of excellent improvement in peel strength.

[0361] Furthermore, various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolac resins of compounds containing phenolic hydroxyl groups and aromatic compounds containing alkoxy groups, phenol aralkyl resins (siloc resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylethane resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins and various vinyl polymers may also be used in combination.

[0362] More specifically, the various novolac resins include polymers obtained by reacting a compound containing a phenolic hydroxyl group such as phenol, phenylphenol, resorcinol, biphenyl, bisphenol A, bisphenol F, naphthol, dihydroxynaphthalene, and the like with an aldehyde compound under an acid catalyst condition.

[0363] Examples of the various vinyl polymers include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly(meth)acrylate, or copolymers thereof.

[0364] The so-called thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, cyclic polyolefin resin, etc. These thermoplastic resins may be used alone or in combination of two or more.

[0365] When using these other resins, the mixing ratio of the glycidyl ether group-containing compound of the present invention and the other resins can be arbitrarily set according to the application. From the viewpoint of not hindering the repairability and remolding properties exerted by the present invention, it is preferred that the other resins be in a ratio of 0.5 to 100 parts by mass relative to 100 parts by mass of the glycidyl ether group-containing compound of the present invention.

[0366] When the curable resin composition of the present invention is used for applications requiring high flame retardancy, a non-halogen flame retardant containing substantially no halogen atoms may be blended.

[0367] The aforementioned non-halogen flame retardants include, for example, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. There are no restrictions on their use. They can be used alone or in combination with multiple flame retardants of the same series. In addition, flame retardants of different series can also be used in combination.

[0368] The phosphorus-based flame retardant may be either inorganic or organic. Examples of the inorganic compound include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide.

[0369] In addition, for the purpose of preventing hydrolysis, etc., the red phosphorus is preferably subjected to surface treatment. Examples of the surface treatment method include: (i) a method of coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide and a thermosetting resin such as a phenol resin; (iii) a method of double coating with a thermosetting resin such as a phenol resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc.

[0370] The above-mentioned organophosphorus compounds include, for example, general-purpose organophosphorus compounds such as phosphate compounds, phosphonic acid compounds, phosphine acid compounds, phosphine oxide compounds, sulfide cyclic phosphorus compounds, and organic nitrogen-containing phosphorus compounds. Examples thereof include cyclic organophosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives thereof obtained by reacting them with compounds such as epoxy resins and phenol resins.

[0371] The amount of these phosphorus flame retardants can be appropriately selected according to the type of phosphorus flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all components such as non-halogen flame retardants and other fillers and additives, when red phosphorus is used as the non-halogen flame retardant, it is preferably blended in the range of 0.1 to 2.0 parts by mass. When an organic phosphorus compound is used, it is also preferably blended in the range of 0.1 to 10.0 parts by mass, and more preferably in the range of 0.5 to 6.0 parts by mass.

[0372] When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, a boron compound, zirconium oxide, a black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, or the like may be used in combination with the phosphorus-based flame retardant.

[0373] Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothioic acid compounds, etc., preferably a triazine compound, a cyanuric acid compound, or an isocyanuric acid compound.

[0374] Examples of the triazine compounds include, in addition to melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphoric acid, and triguanamine, (1) sulfated aminotriazine compounds such as formamidinylmelamine sulfate, melem sulfate, and melam sulfate; (2) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, and formguanamine, and formaldehyde; (3) mixtures of the co-condensates of the above (2) with phenol resins such as phenol formaldehyde condensates; and (4) compounds obtained by further modifying the above (2) and (3) with tung oil, isomerized linseed oil, and the like.

[0375] Examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate.

[0376] The amount of the nitrogen flame retardant can be appropriately selected according to the type of the nitrogen flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, the amount is preferably in the range of 0.05 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, based on 100 parts by mass of the resin composition containing all components such as the non-halogen flame retardant and other fillers and additives.

[0377] When the nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

[0378] The aforementioned silicone flame retardant can be used without particular limitation as long as it is an organic compound containing silicon atoms, and examples thereof include silicone oil, silicone rubber, silicone resin, etc. The amount of the aforementioned silicone flame retardant can be appropriately selected according to the type of silicone flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all components such as non-halogen flame retardants and other fillers and additives, it is preferably blended in the range of 0.05 to 20 parts by mass. In addition, when using the aforementioned silicone flame retardant, molybdenum compounds, aluminum oxide, etc. may also be used in combination.

[0379] Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass.

[0380] Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

[0381] Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

[0382] Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

[0383] Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

[0384] Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

[0385] The aforementioned low melting point glass may include, for example, Ceepree (Boxi Brown Company), hydrated glass SiO2-MgO-H2O, PbO-B2O3 system, ZnO-P2O5-MgO system, P2O5-B2O3-PbO-MgO system, P-Sn-OF system, PbO-V2O5-TeO2 system, Al2O3-H2O system, lead borosilicate system and other glassy compounds.

[0386] The amount of the inorganic flame retardant to be added can be appropriately selected according to the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, the amount of the inorganic flame retardant to be added is preferably in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass, based on 100 parts by mass of the resin composition containing all components such as the non-halogen flame retardant and other fillers and additives.

[0387] Examples of the organic metal salt flame retardant include ferrocene, acetylacetone metal complexes, organic metal carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, and compounds in which a metal atom is ionically or coordinately bonded to an aromatic compound or a heterocyclic compound.

[0388] The amount of the organic metal salt flame retardant can be appropriately selected according to the type of the organic metal salt flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, the amount is preferably in the range of 0.005 to 10 parts by mass in 100 parts by mass of the resin composition containing all components such as the non-halogen flame retardant and other fillers and additives.

[0389] The curable resin composition of the present invention may contain a filler. Examples of the filler include inorganic fillers and organic fillers. Examples of the inorganic filler include inorganic fine particles.

[0390] Examples of inorganic particles include aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide, silicon dioxide (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.) and the like, inorganic particles with excellent heat resistance include boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond and the like, inorganic particles with excellent thermal conductivity include metal fillers and / or metal-coated fillers using a metal element or alloy (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.), and inorganic particles with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, or potassium titanate, magnesium sulfate, sepiolite, etc. , vermiculite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; for inorganic particles with high refractive index, barium titanate, zirconium oxide, titanium oxide, etc.; as inorganic particles showing photocatalytic properties, titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead and other photocatalytic metals, composites of the above metals, oxides of these, etc.; for inorganic particles with excellent wear resistance, metals such as silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide, and composites and oxides of these, etc.; for inorganic particles with excellent conductivity, metals such as silver and copper, tin oxide, indium oxide, etc.; for inorganic particles with excellent insulation, silicon dioxide, etc.; for inorganic particles with excellent ultraviolet shielding, titanium oxide, zinc oxide, etc. These inorganic particles can be appropriately selected according to the purpose, and can be used alone or in combination. In addition, the above-mentioned inorganic fine particles have various properties in addition to the properties exemplified above, and therefore may be appropriately selected in accordance with the intended use.

[0391] For example, when using silicon dioxide as inorganic particles, it is not particularly limited, and known silicon dioxide particles such as powdered silicon dioxide or colloidal silicon dioxide can be used. As commercially available powdered silicon dioxide particles, for example: AEROSIL 50, 200 manufactured by Japan AEROSIL Co., Ltd., SHIELDEX H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Japan Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji SILYSIA Co., Ltd., SG FLAKE manufactured by Nippon Sheet Glass Co., Ltd., etc. can be cited.

[0392] In addition, commercially available colloidal silica includes, for example, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc.

[0393] Surface-modified silica particles may also be used, for example, silica particles obtained by surface-treating the silica particles with a reactive silane coupling agent having a hydrophobic group, and silica particles obtained by modifying the silica particles with a compound having a (meth)acryloyl group. Commercially available powdered silica modified with a compound having a (meth)acryloyl group includes AEROSIL RM50 and R711 manufactured by AEROSIL Co., Ltd. of Japan, and commercially available colloidal silica modified with a compound having a (meth)acryloyl group includes MIBK-SD manufactured by Nissan Chemical Industries, Ltd.

[0394] The shape of the silica particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous or irregular shapes may be used. The primary particle size is preferably in the range of 5 to 200 nm.

[0395] As titanium oxide particles, not only body pigments but also ultraviolet light responsive photocatalysts can be used, for example, anatase titanium oxide, rutile titanium oxide, brookite titanium oxide, etc. can be used. Furthermore, particles designed in a manner of responding to visible light by doping different types of elements in the crystal structure of titanium oxide can also be used. As elements doped into titanium oxide, anionic elements such as nitrogen, sulfur, carbon, fluorine, phosphorus, or cationic elements such as chromium, iron, cobalt, and manganese can be suitably used. In addition, in terms of form, powders, sols or slurries dispersed in organic solvents or water can be used. For commercially available powdered titanium oxide particles, for example: AEROSIL P-25 manufactured by Japan AEROSIL Co., Ltd., ATM-100 manufactured by TAYCA Co., Ltd., etc. can be cited. In addition, as commercially available slurry titanium oxide particles, for example: TKD-701 manufactured by TAYCA Co., Ltd., etc. can be cited.

[0396] The curable resin composition of the present invention may further contain a fibrous matrix. The fibrous matrix is ​​not particularly limited, but is preferably a fibrous matrix used in a fiber-reinforced resin, and examples thereof include inorganic fibers and organic fibers.

[0397] In addition to inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, and silicon carbide fiber, inorganic fibers such as carbon fiber, activated carbon fiber, graphite fiber, tungsten carbide fiber, silicon carbide fiber, ceramic fiber, natural fiber, mineral fibers such as basalt, boron nitride fiber, boron carbide fiber, and metal fiber can be cited. Examples of the above-mentioned metal fibers include aluminum fiber, copper fiber, brass fiber, stainless steel fiber, and steel fiber.

[0398] Examples of organic fibers include synthetic fibers made of resin materials such as polybenzobisoxazole, polyaramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as proteins, polypeptides, and alginic acid.

[0399] Among them, carbon fiber and glass fiber are preferred because they are widely used in industry. Among these, only one kind may be used or a plurality of kinds may be used simultaneously.

[0400] The fibrous matrix may be an aggregate of fibers, and the fibers may be continuous or discontinuous, woven or nonwoven. In addition, it may be a fiber bundle in which the fibers are arranged in one direction, or a sheet in which the fiber bundles are arranged. In addition, it may be a three-dimensional shape in which the aggregate of fibers has thickness.

[0401] In the curable resin composition of the present invention, a dispersion medium may be used for the purpose of adjusting the solid content and viscosity of the resin composition. As the dispersion medium, any liquid medium that does not impair the effects of the present invention may be used, and various organic solvents, liquid organic polymers, etc. may be mentioned.

[0402] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF) and dioxolane, esters such as methyl acetate, ethyl acetate, and butyl acetate, aromatics such as toluene and xylene, carbitol, cellosolve, methanol, isopropyl alcohol, butanol, and alcohols such as propylene glycol monomethyl ether. These can be used alone or in combination. Among them, methyl ethyl ketone is preferred from the perspective of volatility and solvent recovery during coating.

[0403] The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include acrylic polymer (FLOWLEN WK-20: Kyoeisha), special modified amine salt of phosphate ester (HIPLAAD ED-251: Kusumoto Chemicals), and modified acrylic block copolymer (DISPERBYK2000; BYK).

[0404] The resin composition of the present invention may contain other compounds, such as catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, reactive diluents, etc.

[0405] The resin composition of the present invention can be cured to obtain a cured product. When the resin composition is cured, it can be cured at room temperature or by heating. When the resin composition is thermally cured, it can be cured by heating once or by a multi-stage heating process.

[0406] In addition, the curable resin composition of the present invention can also be cured by active energy rays. In this case, a photocationic polymerization initiator can be used as a polymerization initiator. As active energy rays, visible light, ultraviolet rays, X-rays, electron beams, etc. can be used.

[0407] Examples of the photocationic polymerization initiator include arylsulfonium salts, aryliodonium salts, and specifically, arylsulfonium hexafluorophosphate, arylsulfonium hexafluoroantimonate, arylsulfonium tetrakis(pentafluoro)borate, tri(alkylphenyl)sulfonium hexafluorophosphate, etc. The photocationic polymerization initiator may be used alone or in combination of two or more.

[0408] The curable resin composition of the present invention can be prepared by uniformly mixing the above-mentioned components, and the method is not particularly limited. For example, it can be prepared by uniformly mixing using a pot mill, a ball mill, a bead mill, a roll mill, a homogenizer, a super grinder, a homodisper, a universal mixer, a Banbury mixer, a kneader, etc.

[0409] The curable resin composition of the present invention is prepared by dissolving the aforementioned compound containing a glycidyl ether group of the present invention and the aforementioned compound (I) reactive with the compound containing a glycidyl ether group, and further dissolving the aforementioned curing agent, filler, fibrous matrix, dispersion medium, and resins other than the aforementioned various compounds in a dispersion medium such as the aforementioned organic solvent as required. After dissolution, the solvent is distilled off and reduced pressure drying is performed in a vacuum oven or the like, thereby obtaining a curable resin composition. In addition, the curable resin composition of the present invention may also be a state in which the aforementioned constituent materials are uniformly mixed. At this time, it is preferably uniformly mixed with a mixer or the like. The proportion of each constituent material can be appropriately prepared according to the desired properties of the cured product such as mechanical strength, heat resistance, repairability and remolding. In addition, in the preparation of the curable resin composition, the specific mixing order of the constituent materials is not particularly limited.

[0410] The cured product of the present invention is obtained by curing the compound (I) reactive with the glycidyl ether group-containing compound by the glycidyl ether group-containing compound of the present invention. The curing method can be appropriately selected from known methods according to the properties of the compound (I) reactive with the glycidyl ether group-containing compound used.

[0411] As described above, the cured product of the present invention can exhibit a moderate crosslinking density because it is cured by the compound containing a glycidyl ether group of the present invention, thereby maintaining good mechanical strength. In addition, when the cured product of the present invention is scratched or mechanical energy such as an external force is applied, the reversible bond is cut, but since the equilibrium shifts toward the bonding direction, it is considered that an adduct is formed again, and the scratch can be repaired and reshaped.

[0412] The structure of the obtained cured product can be confirmed by infrared absorption (IR) spectroscopy using Fourier transform infrared spectroscopy (FT-IR) or the like, elemental analysis, X-ray scattering, or the like.

[0413] Regarding the cured product of one embodiment of the present invention, as described above, it can be obtained by using the glycidyl ether group-containing compound of the present invention as a component of the curable resin composition, but it is also possible to use an intermediate of the aforementioned conjugated diene or a dienophilic intermediate as an intermediate of the glycidyl ether group-containing compound, and use a compound that can undergo an addition reaction with it through a Diels-Alder reaction, so that during the curing process, the glycidyl ether group-containing compound is formed (in situ synthesis) and the cured product is formed at the same time.

[0414] For example, if the compound represented by the aforementioned formula (1-1)', the maleimide having a glycidyl ether group, and the compound (I) reactive with the aforementioned compound containing a glycidyl ether group are used as necessary raw materials and a curing reaction is carried out, during the curing reaction, the compound containing a glycidyl ether group represented by the aforementioned formula (1-1) can be obtained, and as the curing reaction proceeds, a cured product can be obtained. The maleimide having a glycidyl ether group that can be used at this time is the same as that described above.

[0415] In addition, if the compound represented by the aforementioned formula (1-2)', anthracene having a glycidyl ether group, and compound (I) reactive with the aforementioned compound containing a glycidyl ether group are used as necessary raw materials and a curing reaction is carried out, during the curing reaction, the compound containing a glycidyl ether group represented by the aforementioned formula (1-2) can be obtained, and as the curing reaction proceeds, a cured product can be obtained. The anthracene having a glycidyl ether group that can be used at this time is the same as that described above.

[0416] The curable resin composition of the present invention and the cured product produced using the curable resin composition are excellent in both heat resistance and repairability and have remolding properties, and can be used for the following applications.

[0417] The curable resin cured product of the present invention can be formed into a laminate by stacking with a substrate. As the substrate of the laminate, inorganic materials such as metals and glass, plastics, and organic materials such as wood can be appropriately used according to the purpose. It can be in the shape of a laminate, and can also have a flat plate, a sheet or a three-dimensional structure, or a three-dimensional shape. It can also be any shape according to the purpose such as the entire surface or a part having a curvature. In addition, the hardness, thickness, etc. of the substrate are also unrestricted. In addition, it is also possible to form a multilayer laminated body stacked in the order of the first substrate, the layer constituted by the cured product of the curable resin composition of the present invention, and the second substrate. The curable resin composition of the present embodiment is excellent in adhesion, so it can be suitably used as an adhesive for bonding the first substrate to the second substrate. In addition, the curable resin cured product of the present invention can also be used as a substrate, and the cured product of the present invention can be further stacked.

[0418] In addition, the curable resin cured product of the present invention can relax stress, and therefore can be particularly suitably used for bonding of different types of materials. For example, even if the substrate is a laminate of different types of materials such as a metal and / or metal oxide and the second substrate is a plastic layer, the stress relaxation ability of the cured product of the present invention can maintain the bonding strength.

[0419] In the laminated body formed by stacking the cured product of the present invention and the substrate, the layer containing the cured product can also be formed by directly coating or molding the substrate, and it is also okay to stack the formed layer. In the case of direct coating, as the coating method, it is not particularly limited, and can be cited: spraying, spin coating, dipping, roller coating, doctor coating, doctor roll method, doctor blade method, curtain coating, slit coating, screen printing, inkjet method, etc. In the case of direct molding, can be cited: in-mold molding, embedded molding, vacuum molding, extrusion lamination molding, compression molding, etc. In the case of stacking the formed composition, the uncured or semi-cured composition layer can be stacked and then cured, and the layer containing the cured product obtained by completely curing the composition can also be stacked for the substrate. In addition, it is also possible to coat the cured product of the present invention with a precursor that can become a substrate and solidify it so as to stack it, and it is also possible to bond the precursor that can become a substrate or the composition of the present invention in an uncured or semi-cured state and then solidify it. The precursor that can serve as the substrate is not particularly limited, and various curable resin compositions and the like can be mentioned.

[0420] The cured product obtained by using the curable resin composition of the present invention has particularly high adhesion to metals and / or metal oxides, and can therefore be particularly well used as a primer for metals. Examples of metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and materials obtained by combining these, and examples of metal oxides include single oxides and / or composite oxides of these metals. In particular, because of its excellent adhesion to iron, copper, and aluminum, it can be well used as an adhesive for iron, copper, and aluminum.

[0421] The curable resin composition of the present invention can be suitably used as the adhesive of the structural member in automobile, tram, civil engineering, electronic equipment (electronics), aircraft, aerospace industry field.Even if this adhesive is used for the bonding of different materials such as metal-nonmetal, it is also possible to maintain high adhesion without being affected by temperature environment changes, and it is not easy to peel off.In addition, this adhesive, except for structural member purposes, can also be used as the adhesive of the unit or module or housing of general affairs, medical use, carbon fiber, storage battery, etc., and can also be used as the adhesive for semiconductors such as optical component bonding, optical disc bonding, printed wiring board installation, grain bonding (die bonding) adhesive, bottom filler, BGA enhanced bottom filler, anisotropic conductive film, anisotropic conductive paste, etc. are installed.

[0422] When the curable resin composition of the present invention has a fibrous matrix and the fibrous matrix is ​​a reinforcing fiber, the curable resin composition containing the fibrous matrix can be used as a fiber-reinforced resin. There is no particular limitation on the method of making the composition contain the fibrous matrix as long as it is within the range that does not impair the effects of the present invention, and examples include a method of compounding the fibrous matrix and the composition by kneading, coating, impregnation, injection, pressure bonding, etc., and it can be appropriately selected according to the form of the fiber and the use of the fiber-reinforced resin.

[0423] There is no particular limitation on the method for molding the fiber-reinforced resin. If a plate-like product is to be manufactured, extrusion molding is generally used, but it can also be done by flat pressing. In addition, extrusion molding, blow molding, compression molding, vacuum molding, injection molding, etc. can be used. In addition, if a film-like product is to be manufactured, in addition to the melt extrusion method, a solution casting method can be used. In the case of using a melt molding method, examples include: blown film molding, casting molding, extrusion lamination molding, calendering molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, coating molding, etc. In addition, in the case of a resin cured with active energy rays, a cured product can be manufactured by using various curing methods that utilize active energy rays. In particular, when a thermosetting resin is used as the main component of the matrix resin, a molding method that includes prepregging the molding material and pressurizing and heating it by pressing or autoclave can be mentioned. In addition, resin transfer molding (RTM), vacuum assisted resin transfer molding (VaRTM), lamination molding, hand lay-up molding, etc. can be mentioned.

[0424] The curable resin composition of the present invention has good heat resistance and repairability, and has re-molding properties. Therefore, it can be used for large housings or engine cases, casting materials inside housings, gears, pulleys and other molding materials. These can be cured products of resin alone or reinforced with fibers such as glass chips.

[0425] The fiber-reinforced resin may be in the state of an uncured or semi-cured so-called prepreg. The product may also be circulated in the state of a prepreg and then finally cured to form a cured product. In the case of forming a laminate, it is preferred that a laminate in which each layer is closely attached is formed by laminating other layers after forming a prepreg and then finally curing. The mass ratio of the composition used at this time to the fibrous matrix is ​​not particularly limited, and it is generally preferred to prepare in a manner that the resin component in the prepreg is 20 to 60% by mass.

[0426] The cured product of the present invention has good heat resistance and repairability, and has re-molding properties, and can be used as heat-resistant materials and electronic materials. In particular, it can be suitably used in semiconductor sealing materials, circuit substrates, build-up films, build-up substrates, etc., or adhesives or photoresist materials. In addition, it can also be suitably used in the matrix resin of fiber-reinforced resins, and is particularly suitable as a high-heat-resistant prepreg. The heat-resistant components or electronic components thus obtained can be suitably used for various purposes, for example: industrial machinery parts, general machinery parts, automobile / railway / vehicle parts, aerospace / aviation related parts, electronic / electrical parts, building materials, container / packaging components, daily necessities, sports / leisure products, frame components for wind power generation, etc., but are not limited to these items.

[0427] Among them, the excellent characteristics of flexibility in the cured product can be brought into play, and it can be suitably used as an adhesive for structural members in the fields of automobiles, trams, civil engineering, electronic equipment, aircraft, and aerospace industries. Even if the adhesive of the present invention is used for bonding of different types of materials such as metal-nonmetal, it will not be affected by the change of temperature environment and can maintain high adhesion, and it is not easy to peel off. In addition, the adhesive of the present invention, in addition to the use of structural members, can also be used as an adhesive for general affairs, medical use, carbon fiber, cells or modules of batteries or housings, etc., and can include: adhesives for optical component bonding, adhesives for optical disc bonding, adhesives for printed wiring board installation, die bonding adhesives, semiconductor adhesives such as bottom fillers, BGA enhanced bottom fillers, anisotropic conductive films, anisotropic conductive pastes, etc., etc.

[0428] Representative products are described below as examples.

[0429] 1. Semiconductor sealing materials

[0430] As a method for obtaining a semiconductor sealing material from the resin composition of the present invention, there can be cited a method of fully melt-mixing the aforementioned resin composition and the curing accelerator and the inorganic filler and other compounding agents until they are uniform using an extruder, a kneader, a roller, etc. as required. At this time, fused silica is usually used as an inorganic filler, but in the case of using it as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, high crystalline silica, alumina, silicon nitride, etc. having a thermal conductivity higher than that of fused silica can be used. The filling rate is preferably to use an inorganic filler in the range of 30 to 95% by mass per 100 parts by mass of the curable resin composition, wherein, in order to achieve the improvement of flame retardancy, moisture resistance and resistance to solder cracking, and the reduction of the linear expansion coefficient, it is more preferably 70 parts by mass or more, and more preferably 80 parts by mass or more.

[0431] 2. Semiconductor devices

[0432] Semiconductor encapsulation molding of a semiconductor device obtained from the curable resin composition of the present invention includes a method of molding a semiconductor sealing material or molding using a transfer molding machine, injection molding machine, etc., and further heating at 50 to 250° C. for 2 to 10 hours.

[0433] 3. Printed circuit board

[0434] The method for obtaining a printed circuit board from the composition of the present invention includes laminating the above-mentioned prepregs by a conventional method, appropriately overlapping copper foils, and heat-compression bonding them at 170 to 300° C. under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0435] 4. Flexible substrate

[0436] As a method for producing a flexible substrate from the crosslinkable resin composition of the present invention, there can be mentioned a case where the production is carried out by a method consisting of the following three steps. The first step is a step of applying a crosslinkable resin composition containing a resin component, an organic solvent, etc. to an electrically insulating film using a coater such as a reverse roll coater or a notch wheel coater, the second step is a step of heating the electrically insulating film coated with the crosslinkable resin composition at 60 to 170° C. for 1 to 15 minutes using a heater to volatilize the solvent from the electrically insulating film and B-stage the crosslinkable resin composition, and the third step is a step of thermally pressing a metal foil to an adhesive using a heating roller or the like (the pressing pressure is preferably 2 to 200 N / cm and the pressing temperature is preferably 40 to 200° C.) with respect to the electrically insulating film having the crosslinkable resin composition B-staged. If sufficient adhesive performance can be obtained through the above three steps, it is not a problem to end here, but when complete adhesive performance is required, it is preferably further post-cured at 100 to 200° C. for 1 to 24 hours. The thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 μm.

[0437] 5. Build-up substrate

[0438] The method for obtaining a build-up substrate from the composition of the present invention can include, for example, the following steps. First, the above-mentioned composition appropriately mixed with rubber, filler, etc. is applied to a circuit substrate having a circuit formed thereon by spraying, curtain coating, etc., and then cured (step 1). After that, after opening a specific through-hole portion or the like as required, it is treated with a roughening agent, and the surface is washed with hot water to form a concave-convex, and then the process of plating a metal such as copper is performed (step 2). Such operations are repeated in sequence as required to form a resin insulating layer and a conductor layer of a specific circuit pattern by alternating layers (step 3). In addition, the opening of the through-hole portion is performed after the formation of the outermost resin insulating layer. In addition, the build-up substrate of the present invention can also be made by heating and pressing the copper foil with resin formed by semi-curing the above-mentioned resin composition on the copper foil at 170 to 300°C on the wiring substrate having a circuit, thereby omitting the steps of forming a roughened surface and plating treatment to produce a build-up substrate.

[0439] 6. Add-on film

[0440] As a method for obtaining a build-up film from the composition of the present invention, the composition can be applied to the surface of a support film (Y) as a substrate, and then the organic solvent is dried by heating or hot air blowing to form a layer (X) of the composition.

[0441] As the organic solvent used here, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and it is also preferred to use the organic solvent in a ratio of 30 to 60% by mass of the non-volatile component.

[0442] The thickness of the formed layer (X) is usually set to be greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit substrate is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer is preferably 10 to 100 μm. In addition, the layer (X) of the above-mentioned composition in the present invention can also be protected by a protective film described later. By protecting with a protective film, dirt or scratches can be prevented from being attached to the surface of the resin composition layer.

[0443] The aforementioned support film and protective film can include: polyolefins such as polyethylene, polypropylene, polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and further include: release paper or metal foils such as copper foil and aluminum foil. In addition, the support film and the protective film can also be subjected to a release treatment in addition to a matte treatment and a corona treatment. The thickness of the support film is not particularly limited, and is usually 10 to 150 μm, preferably used in the range of 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

[0444] The support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is heat cured, it is possible to prevent dirt and the like from being attached during the curing process. When peeling off after curing, the support film is usually subjected to a demolding treatment in advance.

[0445] The build-up film obtained as described above can be used to manufacture a multilayer printed circuit substrate. For example, in the case where layer (X) is protected by a protective film, after peeling these off, layer (X) is laminated on one or both sides of the circuit substrate in a manner that directly contacts the circuit substrate, for example, by vacuum lamination. The lamination method can be batch type or continuous type with a roller. In addition, the build-up film and the circuit substrate can be heated (preheated) in advance as required before lamination. Regarding the lamination conditions, it is preferred that the crimping temperature (lamination temperature) is 70 to 140°C, and the crimping pressure is preferably 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), preferably lamination is carried out under reduced pressure such that the air pressure is 20 mmHg (26.7 hPa) or less.

[0446] 7. Conductive paste

[0447] As a method of obtaining the conductive paste from the composition of the present invention, for example, there is a method of dispersing conductive particles in the composition. The conductive paste can be a circuit-connecting paste resin composition or an anisotropic conductive adhesive depending on the type of conductive particles used.

[0448] Example

[0449] Next, the present invention will be specifically described by way of Examples and Comparative Examples. Unless otherwise specified, "parts" and "%" are based on mass, but the present invention is not limited thereto.

[0450] 1 H and 13 C-NMR, FD-MS spectrum and GPC were measured under the following conditions.

[0451] 1 H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE

[0452] Magnetic field strength: 600MHz

[0453] Total times: 32 times

[0454] Solvent: CDCl3, DMSO-d6

[0455] Sample concentration: 30% by mass

[0456] 13 C-NMR: JEOL RESONANCE "JNM-ECA600"

[0457] Magnetic field strength: 150MHz

[0458] Total times: 320 times

[0459] Solvent: DMSO-d6

[0460] Sample concentration: 30% by mass

[0461] FD-MS: JMS-T100GC AccuTOF manufactured by JEOL Ltd.

[0462] Measurement range: m / z = 50.00 to 2000.00

[0463] Change rate: 25.6mA / min

[0464] Final current value: 40mA

[0465] Cathode voltage: -10kV

[0466] GPC: HLC-8320GPC manufactured by Tosoh Corporation

[0467] Chromatographic columns: "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0468] Detector: RI (differential refractometer)

[0469] Measurement conditions: 40°C

[0470] Mobile phase: tetrahydrofuran

[0471] Flow rate: 1ml / min

[0472] Standard: "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F" manufactured by Tosoh Corporation

[0473] The epoxy equivalent of the synthesized epoxy resin was measured in accordance with JIS K7236 to calculate the epoxy equivalent (g / eq).

[0474] Examples of a method for calculating the number of repeating units include calculation from GPC molecular weight measurement or analysis results using appropriate various equipment such as FD-MS and NMR.

[0475] Synthesis example 1

[0476] In a flask equipped with a thermometer and a stirrer, 151 g (1.0 mol) of 4-hydroxyacetanilide, 300 g of acetone, and 166 g (1.2 mol) of potassium carbonate were added, and the temperature was raised to reflux temperature. Then, 144 g (1.2 mol) of allyl bromide was added dropwise, and the mixture was allowed to react for another 7 hours. After cooling to room temperature, the potassium carbonate was removed by filtration, and the acetone and excess allyl bromide in the filtrate were removed under reduced pressure using an evaporator. The obtained solid was dissolved in 222 g of ethanol, 417 g (4.0 mol) of 35% hydrochloric acid aqueous solution was added dropwise, and the mixture was allowed to react at 60-65° C. for 12 hours. After cooling to room temperature, the mixture was neutralized with 880 g (4.4 mol) of 20% sodium hydroxide aqueous solution, and the mixture was separated three times with 373 g of ethyl acetate. After the organic layer was dehydrated with sodium sulfate, ethyl acetate was distilled off under reduced pressure using an evaporator to obtain 113 g (0.76 mol, yield 76%) of 4-allyloxyaniline.

[0477] [Chemistry 51]

[0478]

[0479] 82 g (0.84 mol) of maleic anhydride was added to a flask equipped with a thermometer and a stirrer, and dissolved in 1590 g of toluene and 9.0 g of DMF. While maintaining the temperature below 10°C in an ice bath, 113 g (0.76 mol) of 4-allyloxyaniline dissolved in 150 g of DMF was added dropwise, and the mixture was reacted at 25 degrees for 2 hours. Then 10 g of 95% sulfuric acid was added, and the mixture was reacted at 110°C for 5 hours, and then the toluene was removed by vacuum distillation. 1200 g of ethyl acetate was added and the mixture was separated three times, and then separated twice with a 2% aqueous sodium bicarbonate solution. After the organic layer was dehydrated with sodium sulfate, the ethyl acetate was removed by vacuum distillation using an evaporator to obtain 150 g (0.66 mol, yield 87%) of N-allyloxyphenylmaleimide.

[0480] [Chemistry 52]

[0481]

[0482] In a flask equipped with a thermometer and a stirrer, 150 g (0.66 mol) of N-allyloxyphenylmaleimide and 3390 g of dichloromethane were added and dissolved. While maintaining the temperature below 10°C in an ice bath, 1200 g of m-chlorobenzoic acid was added dropwise, and then reacted at room temperature for 72 hours. After neutralization with 402 g of a saturated aqueous sodium bicarbonate solution, 403 g of a saturated aqueous sodium sulfite solution was added dropwise. After removing the water layer, the liquid was separated three times with a 2% aqueous sodium bicarbonate solution and four times with water. After dehydrating the organic layer with sodium sulfate, the dichloromethane was removed under reduced pressure using an evaporator to obtain 60 g of a brown solid (0.24 mol, yield 37%). The epoxy equivalent is 299. By 1 H-NMR analysis confirmed that 4-glycidyloxyphenylmaleimide (M-1) was obtained. 1 H-NMR (DMSO-d6, 600MHz): 2.72-2.87(m,2H), 3.84-3.90(m,1H), 4.36(dd,1H), 4.39(dd,1H), 7.16(s,2H), 7.03-7.30(m,4H).

[0483] [Chemistry 53]

[0484]

[0485] Synthesis example 2

[0486] 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 76 g (0.33 mol) of bisphenol A (hydroxy equivalent 114 g / eq) were added to a flask equipped with a thermometer and a stirrer, and the temperature was raised to 140°C for 30 minutes, and then 2.6 g of a 4% sodium hydroxide aqueous solution was added. After that, the temperature was raised to 150°C for 30 minutes, and the mixture was further reacted at 150°C for 7 hours. Then, 61 g (0.32 mol) of 2-hydroxyanthracene was added, and the mixture was reacted at 150°C for 12 hours to obtain an anthracene compound (A-1). Regarding this compound, a peak of M+=1454 corresponding to the theoretical structure of m1=1 and n1=4 in the following formula was obtained by mass spectrometry, and thus the formation of the target compound was confirmed.

[0487] [Chemistry 54]

[0488]

[0489] Example 1

[0490] 582 g of the anthracene compound of Synthesis Example 2 in a flask equipped with a thermometer and a stirrer were added with 110 g (0.37 mol) of glycidyloxyphenylmaleimide obtained in Synthesis Example 1, 2620 g of methyl isobutyl ketone, and 2620 g of toluene, and the mixture was reacted at 80° C. for 17 hours to obtain a Diels-Alder reaction product (D-1). The epoxy equivalent was 1843. Regarding this compound, a peak of M+=1944 corresponding to the theoretical structure of m1=1, n1=4 in the following formula was obtained by mass spectrometry, thereby confirming the formation of the target compound.

[0491] [Chemistry 55]

[0492]

[0493] Synthesis example 3

[0494] In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, under a nitrogen atmosphere, 180 ml of dimethylacetamide was added to 38.8 g (0.20 mole) of 9-anthrone while immersed in an ice-water bath to form a slurry, and 110 g (0.22 mole) of an 8.09% aqueous sodium hydroxide solution was further added thereto. Next, 27.7 g (0.20 mole) of epibromohydrin dissolved in 40 ml of dimethylacetamide was added dropwise. After stirring for 1 hour, the ice-water bath was removed, 70 g of water was added, the precipitated solid was filtered out, and then dried under reduced pressure to obtain 23.6 g (yield 47%) of a solid. By 1 H-NMR analysis confirmed that 9-(2-glycidyloxy)anthracene (A-2) was obtained. 1 H-NMR (CDCl3, 600MHz): δ=2.79-2.96(m,2H), 3.54-3.62(m,1H), 4.17(dd,1H), 4. 50(dd,1H), 7.40-7.56(m,4H), 7.94-8.05(m,2H), 8.24(s,1H), 8.30-8.42(m,2H).

[0495] [Chemistry 56]

[0496]

[0497] Example 2

[0498] In a flask equipped with a thermometer, a stirrer, and a cooling tube, 12.5 g (0.05 mol) of 9-(2-glycidyloxy)anthracene obtained in Synthesis Example 3, 6.6 g (0.02 mol) of 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM manufactured by Yamato Chemical Industry Co., Ltd.), 62.5 g of methyl isobutyl ketone, and 62.5 g of toluene were added, and after nitrogen substitution, the mixture was reacted at 100°C for 7 hours. Thereafter, the precipitate was removed by filtration, and the organic solvent in the filtrate was removed by reduced pressure distillation at 50°C. Then, the mixture was dried under reduced pressure at 80°C to obtain 34.1 g of Diels-Alder reaction product (D-2). The epoxy equivalent of the obtained Diels-Alder reaction product (D-2) was 438 g / eq. Regarding this Diels-Alder reaction product (D-2), a peak of M+=819 was obtained by mass spectrometry, confirming the formation of the target compound.

[0499] [Chemistry 57]

[0500]

[0501] Example 3

[0502] The reaction was carried out in the same manner as in Example 2 except that 6.6 g (0.02 mole) of 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM manufactured by Yamato Chemical Industry Co., Ltd.) was replaced with 7.4 g (0.02 mole) of 4,4'-diphenylmethane bismaleimide (BMI-1000 manufactured by Yamato Chemical Industry Co., Ltd.), thereby obtaining 34.3 g of a Diels-Alder reaction product (D-3). The epoxy equivalent of the obtained Diels-Alder reaction product (D-3) was 495 g / eq. With respect to this Diels-Alder reaction product (D-3), a peak of M+=859 was obtained by a mass spectrometer, confirming the formation of the target compound.

[0503] [Chemistry 58]

[0504]

[0505] Synthesis example 4

[0506] According to the existing report (Scientific Reports, 10(1), 20214(2020)), an anthracene-modified product (A-3) having the following structure was synthesized.

[0507] [Chemistry 59]

[0508]

[0509] Example 4

[0510] In a flask equipped with a thermometer, a stirrer, and a cooling tube, 26.4 g (0.1 mol) of the anthracene modified product (A-3) obtained in Synthesis Example 4, 15.9 g (0.05 mol) of 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM manufactured by Yamato Chemical Industry Co., Ltd.), and 169.4 g of methyl isobutyl ketone were added, and after nitrogen substitution, the reaction was allowed to proceed at 110°C for 7 hours. Thereafter, the temperature was raised to 150°C, the methyl isobutyl ketone was distilled off under reduced pressure, and the mixture was cooled to room temperature to obtain 41.8 g of Diels-Alder reaction product (D-4). The epoxy equivalent of the obtained Diels-Alder reaction product (D-4) was 435 g / eq. With respect to this Diels-Alder reaction product (D-4), a peak of M+=847 was obtained by a mass spectrometer, confirming the formation of the target compound.

[0511] [Chemistry 60]

[0512]

[0513] Synthesis example 5

[0514] According to a prior report (Polymer, 82, 319 (2016)), a disulfide bond-containing epoxy resin (S-1) having the following structure was synthesized.

[0515] [Chemistry 61]

[0516]

[0517] Synthesis example 6

[0518] 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 190 g (0.76 mol) of 4,4'-dihydroxydiphenyl disulfide (hydroxy equivalent 125 g / eq) were added to a flask equipped with a thermometer and a stirrer. After heating to 140°C for 30 minutes, 3.2 g of a 4% sodium hydroxide aqueous solution was added. After that, the temperature was raised to 150°C for 30 minutes, and the mixture was further reacted at 150°C for 5 hours. After that, a neutralizing amount of sodium phosphate was added to obtain 635 g of a hydroxy compound (S-2) represented by the following formula. Regarding the hydroxy compound, a peak of M+=1424 corresponding to the theoretical structure of m1=1 and n1=11 in the following formula was obtained by a mass spectrometer, thereby confirming the formation of the target compound. The hydroxyl equivalent of this hydroxy compound (S-2) calculated by GPC was 750 g / eq, the average value of n1 was 10.6, and the average value of m1 was 1.09.

[0519] [Chemistry 62]

[0520]

[0521] Example 5

[0522] In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 37.5 g (0.025 mole) of the hydroxy compound (S-2) obtained in Synthesis Example 6, 750 mL of DMF, 69 g (0.5 mole) of potassium carbonate, and 69 g (0.5 mole) of epibromohydrin were added and dissolved while nitrogen purging was implemented. After heating to 60°C, stirring was continued for 20 hours. After cooling to room temperature, potassium carbonate was removed by filtration, 1000 g of water and chloroform were added, and the liquid was separated three times. After dehydrating the organic layer with sodium sulfate, the solvent was distilled off under reduced pressure using an evaporator to obtain 37.5 g of the epoxide (S-3) represented by the following structural formula. The epoxy equivalent of the obtained epoxide (S-3) is 806 g / eq. Regarding this epoxy resin, a peak of M+=1536 corresponding to the theoretical structure of m1=1 and n1=11 in the following formula was obtained by mass spectrometry, and thus the formation of the target compound was confirmed.

[0523] [Chemistry 63]

[0524]

[0525] Synthesis Example 7

[0526] In a flask equipped with a thermometer and a stirrer, 210 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Kogyo Co., Ltd.: epoxy equivalent 210 g / eq) and 145 g (0.58 mol) of 4,4'-dihydroxydiphenyl disulfide (hydroxy equivalent 125 g / eq) were added, and after heating to 140°C for 30 minutes, 3.6 g of a 4% aqueous sodium hydroxide solution was added. After that, the temperature was raised to 150°C for 30 minutes, and the mixture was further reacted at 150°C for 5 hours. After that, a neutralizing amount of sodium phosphate was added to obtain 355 g of a hydroxy compound (S-4) represented by the following formula. With respect to the hydroxy compound, a peak of M+=814 corresponding to the theoretical structure in the following formula was obtained by a mass spectrometer, thereby confirming the formation of the target compound. The hydroxy equivalent of this hydroxy compound (S-4) calculated by GPC is 1076 g / eq.

[0527] [Chemistry 64]

[0528]

[0529] Example 6

[0530] In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 53.8 g (0.025 mole) of the hydroxy compound (S-4) obtained in Synthesis Example 7, 750 mL of DMF, 69 g (0.5 mole) of potassium carbonate, and 69 g (0.5 mole) of epibromohydrin were added and dissolved while nitrogen purging was implemented. After heating to 60°C, stirring was continued for 20 hours. After cooling to room temperature, potassium carbonate was removed by filtration, 1000 g of water and chloroform were added, and the liquid was separated three times. After dehydrating the organic layer with sodium sulfate, the solvent was removed by decompression distillation using an evaporator to obtain 53.8 g of an epoxide (S-5) represented by the following structural formula. The epoxy equivalent of the obtained epoxide (S-5) is 1020 g / eq. Regarding the epoxy resin, a peak of M+=926 corresponding to the theoretical structure was obtained by a mass spectrometer, thereby confirming the formation of the target compound.

[0531] [Chemistry 65]

[0532]

[0533] Synthesis example 8

[0534] 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol ("Denacol EX-991L" manufactured by Nagase ChemteX: epoxy equivalent 445 g / eq) and 171 g (0.75 mol) of bisphenol A (hydroxy equivalent 114 g / eq) were added to a flask equipped with a thermometer and a stirrer, and the temperature was raised to 140°C over 30 minutes, and then 3.1 g of a 4% sodium hydroxide aqueous solution was added. Thereafter, the temperature was raised to 150°C over 30 minutes, and the mixture was further reacted at 150°C for 16 hours. Thereafter, a neutralizing amount of sodium phosphate was added to obtain 616 g of a hydroxy compound represented by the following formula (Ph-1). With respect to the hydroxy compound, a peak of M+=1380 corresponding to the theoretical structure of m1=1 and n1=11 in the following formula was obtained by mass spectrometry, and thus it was confirmed that a PTMG (polytetramethylene ether glycol) type (BPA: bisphenol A) hydroxy compound was contained. The hydroxyl equivalent of this hydroxy compound (Ph-1) calculated by GPC was 1080 g / eq, the average value of n1 was 10.6, and the average value of m1 was 0.76.

[0535] [Chemistry 66]

[0536]

[0537] Synthesis example 9

[0538] In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 200 g of the hydroxy compound Ph-1 obtained in Synthesis Example 5 was added while nitrogen was purged, and 437 g (4.72 mol) of epichlorohydrin and 118 g of n-butanol were added and dissolved. After the temperature was raised to 65° C., the pressure was reduced to the azeotropic pressure, and 6.66 g (0.08 mol) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours.

[0539] Next, stirring was continued for 0.5 hours under the same conditions. During this period, the distillate components distilled out due to azeotropy were separated by a Dean-Stark Trap, the water layer was removed, and the oil layer was returned to the reaction system while the reaction was carried out. After that, unreacted epichlorohydrin was distilled off by reduced pressure distillation. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to the obtained crude epoxy resin and dissolved.

[0540] Furthermore, 10 g of a 10% sodium hydroxide aqueous solution was added to the solution, and the mixture was reacted at 80° C. for 2 hours, and then washed three times with 50 g of water until the pH of the washing liquid became neutral.

[0541] Next, the system was dehydrated by azeotropy, and after precision filtration, the solvent was distilled off under reduced pressure to obtain 190 g of epoxy resin (Ep-1). The epoxy equivalent of the obtained epoxy resin (Ep-1) was 1192 g / eq. Regarding the epoxy resin Ep-1, a peak of M+=1492 corresponding to the theoretical structure of m1=1, n1=11, q=1, p1=0, p2=0 in the following formula was obtained by mass spectrometry, thus confirming that it contained PTMG-type (BPA) epoxy resin.

[0542] [Chemistry 67]

[0543]

[0544] Preparation of composition and cured product

[0545] According to the formula of Table 1 and Table 2 (the numbers in the table are based on mass), each compound was used and uniformly mixed by a mixer ("Awatori Rentaro ARV-200" manufactured by THINKY Co., Ltd.) to obtain a curable resin composition. The curable resin composition was sandwiched between an aluminum mirror plate ("JIS H 4000A1050P" manufactured by Engineering Test Service Co., Ltd.) using a silicone tube as a spacer, and heated and cured under specific conditions to obtain a cured product with a thickness of 0.7 mm.

[0546] <Remolding test>

[0547] The solidified product was frozen and crushed. 0.07 g of the crushed solidified product was placed in a 10 mm square, 0.5 mm thick mold frame and vacuum pressed under specific conditions. The appearance of the solidified product was visually observed. The judgment criteria are as follows.

[0548] A: The joints disappear and the cured product is integrated.

[0549] B: Some joints can be visually confirmed, but the cured product is integrated.

[0550] C: It forms lumps that fall apart with a little force.

[0551] <Repair test>

[0552] The produced solidified product was cut with a razor, and the generated cracked surfaces were brought into contact, and then aged in a dryer at 150° C. for 24 hours. After being taken out of the dryer, the cross sections of the solidified product were visually checked to see if they were joined. The judgment criteria are as follows.

[0553] A: Bonding. Even if the cured product is bent 90°, the bond does not separate.

[0554] B: Bonded. If the cured product is bent, the bonded portion dissociates.

[0555] C: Not joined.

[0556] [Table 1]

[0557]

[0558] [Table 2]

[0559]

[0560] EPICLON850-S: BPA type liquid epoxy resin, epoxy equivalent 188g / eq

[0561] DICY: dicyandiamide

[0562] DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

Claims

1. A compound containing a glycidyl ether group, It is characterized in that The compound containing a glycidyl ether group is formed by connecting a structural unit A having one or more glycidyl ether groups and a structural unit B different from the structural unit A via ABA, wherein the structural unit A and the structural unit B are bonded via a reversible bond having a dissociation temperature of 120° C. or higher.

2. The glycidyl ether group-containing compound according to claim 1, in, The reversible bond is a reversible bond of a covalent bond system.

3. The glycidyl ether group-containing compound according to claim 2, in, The reversible bond is any one of an addition structure formed by a Diels-Alder reaction with a dissociation temperature of 120° C. or higher, a disulfide bond, an ester bond, a borate ester bond, a hemiamine acetal bond, an imine bond, an acylhydrazone bond, an olefin metathesis reaction, an alkoxyamine skeleton, and an amide bond.

4. The glycidyl ether group-containing compound according to claim 3, in, The reversible bond is an addition-type structure formed by the Diels-Alder reaction of anthracene or a disulfide bond sandwiched by an aromatic ring.

5. The glycidyl ether group-containing compound according to claim 1, in, The structural unit B has an alkylene chain or an alkylene ether chain.

6. The glycidyl ether group-containing compound according to claim 5, in, The alkylene chain has 4 to 16 carbon atoms.

7. The glycidyl ether group-containing compound according to claim 1, in, The structural unit B further has the same reversible bond as the reversible bond having a dissociation temperature of 120° C. or higher as the linking site between the structural unit A and the structural unit B.

8. A compound containing a glycidyl ether group, represented by the following general formula: [Chemistry 1] Ar in formula (2) is independently a structure containing an unsubstituted or substituted aromatic ring, and the structures derived from anthracene in formulas (1-1) and (1-2) may have a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent; G is a glycidyl group or a 2-methylglycidyl group; wherein ma is an integer of 1 to 10, and n is an average value of the number of repetitions and is 0 to 10; Z 1 is the following formula (3), Z 2 It is the following formula (4), Z 3 It is the following formula (5), Z 4 Any one of the structures represented by the following formula (6) or (7), a plurality of which may be the same or different in one molecule; [Chemistry 2] The aromatic ring in formula (3) may be substituted or unsubstituted, * indicates the bonding point; G is the same as above, and -OG on the naphthalene ring in the formula indicates that it can be bonded at any position; [Chemistry 3] In formula (4), Ar is independently a structure containing an unsubstituted or substituted aromatic ring, R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, R is a hydrogen atom or a methyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, n1 is an integer of 2 to 16, n2 is an average value of the repeating units and is 2 to 30, k1 is the average of the number of repetitions and is in the range of 0.5 to 10. p1 and p2 are each independently 0 to 5, X is a structural unit represented by the following formula (4-1), and Y is a structural unit represented by the following formula (4-2), [Chemistry 4] In formula (4-1) and (4-2), Ar, R, R 1 , R 2 , R', n1, n2 are the same as above; m1 and m2 are the average values ​​of the number of repetitions, each independently ranging from 0 to 25, and m1+m2≥1; The bonding between the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) can be random or block, and the total number of each structural unit X and Y present in one molecule is m1 and m2 respectively; [Chemistry 5] In formula (5), n3 and n5 are the average values ​​of the number of repetitions, which are 0.5 to 10 respectively, n4 is an integer of 1 to 16, and R ” are each independently a hydrogen atom, a methyl group or an ethyl group; [Chemistry 6] [Chemistry 7] In formula (6) and (7), R 1 , R 2 , R', n1, n2 are the same as mentioned above. 9 . A curable resin composition comprising as essential components the glycidyl ether group-containing compound according to claim 1 and a compound (I) reactive with the glycidyl ether group-containing compound.

10. The curable resin composition according to claim 9, in, The compound (I) reactive with the glycidyl ether group-containing compound is a hydroxyl group-containing compound.

11. The curable resin composition according to claim 10, in, The compound (I) reactive with the glycidyl ether group-containing compound is a hydroxyl group-containing compound having a reversible bond.

12. The curable resin composition according to claim 11, in, The hydroxyl-containing compound having a reversible bond is a hydroxyl-containing compound represented by the following general formula: [Chemistry 8] Ar in formula (9) is independently a structure containing an unsubstituted or substituted aromatic ring, and the structures derived from anthracene in formulas (8-1) and (8-2) may have a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent; Wherein, ma is an integer of 1 to 10, n is the average value of the number of repetitions and is 0 to 10; Z 5 It is the following formula (10), Z 2 It is the following formula (11), Z 3 It is the following formula (12), Z 4 Any one of the structures represented by the following formula (13) or (14), a plurality of which may be the same or different in one molecule; [Chemistry 9] The aromatic ring in formula (10) may be substituted or unsubstituted, and * indicates a bonding point; the hydroxyl group on the naphthalene ring in the formula indicates that it can be bonded at any position; [Chemistry 10] In formula (11), Ar is the same as above, Ar is independently a structure containing an unsubstituted or substituted aromatic ring, R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, R is a hydrogen atom or a methyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, n1 is an integer of 2 to 16, n2 is an average value of the repeating units and is 2 to 30, k1 is the average of the number of repetitions and is in the range of 0.5 to 10. p1 and p2 are each independently 0 to 5, X is a structural unit represented by the following formula (11-1), and Y is a structural unit represented by the following formula (11-2), [Chemistry 11] In formula (11-1) and (11-2), Ar, R, R 1 , R 2 , R', n1, n2 are the same as above; m1 and m2 are the average values ​​of the number of repetitions, each independently ranging from 0 to 25, and m1+m2≥1; The bonding between the structural unit X represented by the formula (11-1) and the structural unit Y represented by the formula (11-2) can be random or block, and the total number of each structural unit X and Y present in one molecule is m1 and m2 respectively; [Chemistry 12] In formula (12), n3 and n5 are the average values ​​of the number of repetitions, which are 0.5 to 10 respectively, n4 is an integer of 1 to 16, and R ” are each independently a hydrogen atom, a methyl group or an ethyl group; [Chemistry 13] [Chemistry 14] In formula (13) and (14), R 1 , R 2 , R', n1, n2 are the same as mentioned above. 13 . The curable resin composition according to claim 9 , further comprising an epoxy resin having an epoxy equivalent of 100 to 10,000 g / eq other than the glycidyl ether group-containing compound according to claim 1 .

14. The curable resin composition according to claim 13, in, The epoxy resin is represented by the following formula (15), and the epoxy equivalent is 500 to 10000 g / eq; [Chemistry 15] In formula (15), Ar is independently a structure containing an unsubstituted or substituted aromatic ring, X' is a structural unit represented by the following formula (15-1), and Y' is a structural unit represented by the following formula (15-2), [Chemistry 16] In formula (15-1) and (15-2), Ar is the same as above, R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, R 3 , R 4 , R 7 , R 8 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, n 1 is an integer from 4 to 16, n 2 is the average value of the repeating units and is 2 to 30; R 11 , R 12 are each independently a glycidyl ether group or a 2-methylglycidyl ether group, R 13 , R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, R 15 , R 16 is a hydrogen atom or a methyl group, m3, m4, p1, p2, q are the average values ​​of the number of repetitions, m3 and m4 are each independently 0 to 25, and m3+m4≥1, p1 and p2 are each independently 0 to 5, q is 0.5 to 5; The bonding between the structural unit X' represented by the formula (15-1) and the structural unit Y' represented by the formula (15-2) can be random or block, and the total number of the structural units X and Y present in one molecule is m3 and m4 respectively.

15. The curable resin composition according to claim 9, in, The concentration of the reversible bonds is 0.10 mmol / g or more relative to the total mass of the curable components in the curable resin composition. 16 . The curable resin composition according to claim 9 , which is a self-healing composition or a composition for a reforming material. 17 . A cured product obtained by curing the curable resin composition according to claim 9 . 18 . A laminate comprising a substrate and a layer comprising the cured product according to claim 17 .

19. A heat-resistant member comprising the cured product according to claim 17.

20. A method for producing a compound containing a glycidyl ether group, comprising using an intermediate of a conjugated diene represented by the following general formula (1-1)' or (1-2)' or a dienophilic intermediate, and in situ synthesizing the compound containing a glycidyl ether group represented by the formula (1-1) or (1-2) during curing with a compound (I), wherein the compound (I) is reactive with the compound containing a glycidyl ether group; [Chemistry 17] In the formula, n, Z 2 , Z 3 Same as above.

21. A cured product obtained by subjecting the formula (1-1)', a maleimide having a glycidyl ether group and a compound (I) reactive with the compound having a glycidyl ether group as essential raw materials to a curing reaction.

22. A cured product obtained by subjecting the formula (1-2)', anthracene having a glycidyl ether group, and a compound (I) reactive with the compound having a glycidyl ether group as essential raw materials to a curing reaction.

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