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

Abstract

To provide: a compound capable of readily realizing repairability and reformability in a cured product, irrespective of being a curable resin; and a curable resin composition formed using the compound; and a cured product thereof.SOLUTION: The present invention uses a glycidyl ether group-containing compound that is a hydroxy group-containing compound obtained as a result of a structural unit A having one or more glycidyl ether groups and a structural unit B different from the structural unit A being connected in A-B-A, and is characterized in that the structural unit A and the structural unit B are bonded by reversible bonds having a dissociation temperature of 120°C or higher. The reversible bonds are preferably an adduct structure formed by an anthracene Diels-Alder reaction and a disulfide bond interposed between aromatic rings.SELECTED DRAWING: None

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 compound, a cured product, and a laminate containing a layer made of the cured product. [Background technology]

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

[0003] On the other hand, cured products using thermosetting resins such as epoxy resins have low long-term reliability. For example, when a cured product of an epoxy resin deteriorates due to oxidation, cracks may occur.

[0004] In addition, the cured product obtained by curing thermosetting resins such as epoxy resins cannot be dissolved in solvents (is insoluble) and does not dissolve even at high temperatures (is infusible), making it difficult to recycle or reuse. In addition, the cured product becomes waste after use, so there is a need to reduce waste and alleviate the burden on the environment.

[0005] Therefore, there is a demand for solutions to issues such as extending the lifespan and reducing waste for cured products made from epoxy resins, etc., and it is believed that an effective solution to these issues would be to give the cured products easy dismantling, repairability, and remoldability.

[0006] Against this background, a method has been disclosed in which a thermally decomposable compound is incorporated into a reactive adhesive component in advance, and then, after use, a certain amount of heat is applied to reduce the adhesive strength, making the product dismantlable (see, for example, Patent Document 1).

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

[0008] In addition to the above, active research is being conducted on the use of reversible bonds such as dynamic covalent bonds and supramolecular bonds in hardened materials in order to impart repairability and reshapeability. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] JP 2013-256557 A [Patent Document 2] JP 2017-041496 A Summary of the Invention [Problem to be solved by the invention]

[0010] In the technology provided in Patent Document 1, the adhesive after dismantling is discarded, and although the substrate to be bonded can be recycled, there is a problem that the overall recyclability is insufficient. In addition, in the technology in Patent Document 2, although it has a certain degree of self-repairability, it is not a solution in terms of reuse, and the problem of waste when it becomes unnecessary remains. In addition, since it is necessary to ensure the molecular mobility of the raw materials used in the reversible bond, there is a problem that the raw materials used are limited to gel-like substances with poor mechanical strength, and both are currently required to be improved. Therefore, the object of the present invention is to provide a compound that is a curable resin but can easily realize repairability and remolding in the cured product, and a curable resin composition and a cured product thereof made using the same. [Means for solving the problem]

[0011] Means for Solving the Problems The present inventors have conducted extensive research and found that the above-mentioned problems can be solved by using a glycidyl ether group-containing compound having a specific structure as a curable resin composition, thereby completing the invention.

[0012] That is, the present invention includes the following aspects. [1] A glycidyl ether group-containing compound comprising a structural unit A having one or more glycidyl ether groups and a structural unit B different from A, which are linked via an ABA bond, wherein the structural unit A and the structural unit B are linked via a reversible bond having a dissociation temperature of 120° C. or higher. [2] The glycidyl ether group-containing compound according to [1] above, wherein the reversible bond is a covalent bond. [3] The glycidyl ether group-containing compound according to [2], wherein the reversible bond is any one of an addition structure by a Diels-Alder reaction, a disulfide bond, an ester bond, a boronic acid ester bond, a hemiaminal bond, an imine bond, an acylhydrazone bond, an olefin metathesis reaction, an alkoxyamine skeleton, and an amide bond, each of which has a dissociation temperature of 120°C or higher. [4] The glycidyl ether group-containing compound according to [2] or [3] above, wherein the reversible bond is an anthracene-type Diels-Alder addition structure or a disulfide bond sandwiched between aromatic rings. [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. [6] The glycidyl ether group-containing compound according to [5] above, wherein the alkylene chain has 4 to 16 carbon atoms. [7] The glycidyl ether group-containing compound according to any one of [1] to [6], wherein the structural unit B further has a reversible bond identical to the reversible bond which is a linking site between the structural unit A and the structural unit B and has a dissociation temperature of 120° C. or higher. [8] A glycidyl ether group-containing compound represented by the following general formula:

[0013] [ka]

[0014] [Each Ar in formula (2) is independently a structure containing an aromatic ring which is unsubstituted or substituted, and the anthracene-derived structure 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 amido group, an alkyloxycarbonyl 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 the average number of repetitions which is 0 to 10. Z 1 is expressed by the following formula (3), Z 2 is expressed by the following formula (4), Z 3 is expressed by the following formula (5), Z 4 is either of the structures represented by the following formula (6) or (7), and each of the multiple structures present in one molecule may be the same or different.

[0015] [ka] [The aromatic ring in formula (3) may be substituted or unsubstituted, * represents a bonding point, G is the same as above, and -OG on the naphthalene ring in the formula indicates that it may be bonded to any position.]

[0016] [ka]

[0017] [In formula (4), Each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 each independently represents 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, and n2 is the average number of repeating units of 2 to 30. k1 is the average number of repetitions and is in the range of 0.5 to 10; p1 and p2 each independently represent 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),

[0018] [ka]

[0019] [In formulas (4-1) and (4-2), Ar, R, R 1 , R 2 , R', n1, and n2 are the same as above.] m1 and m2 are average values ​​of repetitions, each independently ranging from 0 to 25, and m1+m2≧1. However, the bond between the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively.

[0020] [ka] [In formula (5), n3 and n5 are average numbers of repetitions, each of which is 0.5 to 10, n4 is an integer of 1 to 16, and R ” are each independently a hydrogen atom, a methyl group, or an ethyl group.

[0021] [ka]

[0022] [ka] [In formulas (6) and (7), R 1 , R 2 , R', n1, and n2 are the same as above.

[0023] [9] A curable resin composition comprising, as essential components, the glycidyl ether group-containing compound according to any one of [1] to [8] above and a compound (I) reactive with the glycidyl ether group-containing compound.

[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.

[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.

[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:

[0024] [ka]

[0025] [Each Ar in formula (9) is independently a structure containing an aromatic ring which is unsubstituted or substituted, and the anthracene-derived structure 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 amido group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent. In the formula, ma is an integer of 1 to 10, and n is the average number of repetitions, which is 0 to 10. 5 is expressed by the following formula (10), Z 2 is expressed by the following formula (11), Z 3 is expressed by the following formula (12), Z 4 is either of the structures represented by the following formula (13) or (14), and each of the multiple structures present in one molecule may be the same or different.

[0026] [ka]

[0027] [The aromatic ring in formula (10) may be substituted or unsubstituted, and * represents a bonding point. The hydroxyl group on the naphthalene ring in the formula may be bonded to any position.]

[0028] [ka]

[0029] [In the formula (11), Ar is the same as defined above, Each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 each independently represents 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, and n2 is the average number of repeating units of 2 to 30. k1 is the average number of repetitions and is in the range of 0.5 to 10; p1 and p2 each independently represent 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),

[0030] [ka]

[0031] [In formulas (11-1) and (11-2), Ar, R, R 1 , R 2 , R', n1, and n2 are the same as above.] m1 and m2 are average values ​​of repetitions, each independently ranging from 0 to 25, and m1+m2≧1. However, the bond between the structural unit X represented by the formula (11-1) and the structural unit Y represented by the formula (11-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively.

[0032] [ka] In formula (12), n3 and n5 are average numbers of repetitions, each of which is 0.5 to 10, n4 is an integer of 1 to 16, and R ” are each independently a hydrogen atom, a methyl group, or an ethyl group.

[0033] [ka]

[0034] [ka] [In formulas (13) and (14), R 1 , R 2 , R', n1, and n2 are the same as above.

[0035]

[13] The curable resin composition according to any one of the above [9] to

[12] , 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 any one of the above [1] to [8].

[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.

[0036] [ka] [In formula (15), each Ar independently represents a structure having 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):

[0037] [ka]

[0038] [In the formulas (15-1) and (15-2), Ar is the same as defined above, R 1 , R 2 each independently represents 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 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 each independently represents a hydrogen atom or a methyl group, n1 is an integer from 4 to 16, n2 is the average number of repeating units and is between 2 and 30. R 11 , R 12 each independently represents a glycidyl ether group or a 2-methylglycidyl ether group; R 13 , R 14 each independently represents 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, and q are the average values ​​of the repetitions. m3 and m4 each independently represents 0 to 25, and m3+m4≧1; p1 and p2 each independently represent 0 to 5; q is 0.5 to 5. However, the bond between the structural unit X' represented by the formula (15-1) and the structural unit Y' represented by the formula (15-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m3 and m4, respectively.

[0039]

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

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

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

[15] above, which is a self-repairing composition or a remolding material composition.

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

[16] above.

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

[17] .

[19] A heat-resistant component containing the cured product described in

[17] above.

[20] A method for producing a glycidyl ether group-containing compound, comprising in situ synthesizing the glycidyl ether group-containing compound represented by the formula (1-1) or (1-2) in the process of curing the compound with a compound (I) reactive with the glycidyl ether group-containing compound, using a conjugated diene intermediate or a diene parent intermediate represented by the following general formula (1-1)' or (1-2)':

[0040] [ka] [In the formula, n, Z 2 , Z 3 is the same as above.

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

[22] A cured product obtained by curing reaction of the above formula (1-2)', an anthracene having a glycidyl ether group, and a compound (I) reactive with the above glycidyl ether group-containing compound as essential raw materials. Effect of the Invention

[0041] According to the present invention, it is possible to impart repairability and remoldability to a cured product made of a curable resin composition, which can contribute to extending the life of the cured product itself and reducing waste. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] Next, the embodiments for carrying out the present invention will be described in detail. It should be understood that the present invention is not limited to the following embodiments, and that appropriate changes and improvements in the design may be made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention.

[0043] The glycidyl ether group-containing compound according to one embodiment of the present invention is a glycidyl ether group-containing compound in which a structural unit A having one or more glycidyl ether groups and a structural unit B different from A are linked via ABA, and is characterized in that the structural unit A and the structural unit B are linked via a reversible bond having a dissociation temperature of 120° C. or higher. Note that the glycidyl ether group in the present invention does not only refer to a glycidyl ether group having no substituent, but also includes those having a substituent on a carbon atom.

[0044] By having such a structure, the glycidyl ether group-containing compound is incorporated into the crosslinked structure by the curing reaction based on the glycidyl ether group. On the other hand, by having reversibility even after becoming a cured product, the structural unit B in particular can exist apart from the crosslinked structure, and therefore has high molecular mobility even in the cured product. For this reason, when the cured product is subjected to an impact, cracks occur, or it is crushed, it is easy to break at the reversible bond part, but on the other hand, the reversible bond can be reversibly reshaped even in a low temperature range including room temperature, and can exhibit functions such as repairability and reshapeability. Since the structural unit B exists apart from the crosslinked structure, it exhibits particularly high molecular mobility, and shows low-temperature repairability and low-temperature reshapeability. For example, even if the cured product made of the glycidyl ether group-containing compound of the present invention is crushed, the cured product can be easily repaired based on the reversible bond by placing it at a low temperature including room temperature or in a heated or heated state, and it is also possible to reshape the cured product after crushing it.

[0045] The reversible bond having a dissociation temperature of 120° C. or higher may be a covalent bond or a non-covalent bond, and from the viewpoint of durability of the cured product, a covalent bond is preferred, whereas from the viewpoint of short repair time or remolding time after crushing of the cured product, a non-covalent bond is preferred.

[0046] The covalent bond system is not particularly limited, and examples thereof include an addition type structure by a Diels-Alder reaction, a disulfide bond, an ester bond, a boronic acid ester bond, a hemiaminal bond, an imine bond, an acylhydrazone bond, an olefin metathesis reaction, an alkoxyamine skeleton, an amide bond, etc. Among them, from the viewpoint of the heat resistance and hydrolysis resistance of the cured product, an addition type structure by a Diels-Alder reaction of an anthracene type (a reversible bond consisting of an anthracene structure and a maleimide structure) and a disulfide bond sandwiched between aromatic rings are preferred.

[0047] The non-covalent bond system is not particularly limited, but examples thereof include van der Waals forces, ionic bonds, inclusion bonds of cyclodextrin, and hydrogen bonds of ureidopyrimidinone units and polyether thiourea.

[0048] In order to introduce the anthracene-type Diels-Alder reaction-based addition structure into a compound, a method using an anthracene having a reactive functional group on the ring and a maleimide having a reactive functional group is preferred because of its simple manufacturing process. A specific reversible bond partial structure can be represented by the following chemical formula. A reversible bond can be introduced into a compound by bonding with other structural units based on the R portion in the following formula in the maleimide-derived structure or various reactive functional groups on the ring of the anthracene-derived structure.

[0049] [ka]

[0050] In the Diels-Alder reaction, a conjugated diene and a parent diene undergo an addition reaction to form a six-membered ring. Since the Diels-Alder reaction is an equilibrium reaction, a Retro-Diels-Alder reaction occurs at a certain temperature, resulting in dissociation (decrosslinking). At this time, if the temperature at which the Retro-Diels-Alder reaction occurs (dissociation temperature) is low, decrosslinking occurs in a high temperature range, and the crosslink density of the cured product decreases, resulting in a decrease in mechanical strength. Therefore, in the present invention, it is necessary that the Diels-Alder reaction unit has a dissociation temperature of 120°C or higher and is a combination of high thermal stability. For example, a Diels-Alder reaction unit consisting of an anthracene structure and a maleimide structure has a high dissociation temperature of 250°C or higher, and does not dissociate at least at about 200°C, maintaining the crosslinked structure, and has excellent thermal stability. Therefore, it is possible to suppress the decrease in crosslink density of the cured product, and to maintain good mechanical strength. In addition, when mechanical energy such as scratches or external force is applied to the resulting cured product, the CC bond of the Diels-Alder reaction unit is preferentially broken because the bond energy of the CC bond is lower than that of a normal covalent bond. However, in the temperature range lower than the dissociation temperature, the CC bond of the Diels-Alder reaction unit shifts the equilibrium toward the bond, forming an adduct (Diels-Alder reaction unit) again, which is thought to enable repair of the scratches and remolding.

[0051] The compounds containing the disulfide bond include the following compounds. Similarly, by bonding various compounds to sites other than the disulfide bond site, such as hydroxyl groups, amino groups, and vinyl groups, it is possible to incorporate disulfide bond sites into glycidyl ether group-containing compounds. In the disulfide bond site, similarly to the above, when the cured product is cut by external force, the disulfide bond is preferentially cut, but below the dissociation temperature, the equilibrium shifts toward the bond, and the SS bond is formed again, making it possible to repair the damage and reshape.

[0052] [ka]

[0053] [ka]

[0054] Examples of the compound containing the alkoxyamine skeleton include the following compounds. As described above, by bonding with other compounds via the terminal vinyl group (methacryloyl group), it is possible to incorporate a reversible bond into the glycidyl ether group-containing compound.

[0055] [ka]

[0056] The above-mentioned reversible bond will be present at at least two places in the target glycidyl ether group-containing compound, but from the viewpoints of obtaining a structure with higher molecular mobility and facilitating adjustment of physical properties such as the mechanical strength of the cured product, it is preferable that the structural unit B also has a plurality of reversible bonds of the same type as the reversible bond between A and B.

[0057] For the same reasons as above, the molecular weight of the structural unit B is preferably at least a certain size, and for example, the average molecular weight (Mw) is preferably at least 28. When the structural unit B has a reversible bond, the molecular weight between the reversible bonds is preferably at least 28. Although the structural unit B may have a crosslinkable functional group similar to the glycidyl ether group in the structural unit A, it is preferable that the structural unit B does not have a crosslinkable (curable) functional group from the viewpoint of more easily achieving the effects of the present invention.

[0058] In order to enable the cured product to exhibit greater flexibility or better conformability to a substrate when the glycidyl ether group-containing compound of the present invention is used, for example, as a structural adhesive, it is preferable for the structural unit B to have an alkylene chain or an alkylene ether chain, and in this case, the alkylene chain more preferably has 2 to 30 carbon atoms, and most preferably has 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 is preferably in the range of 2 to 30.

[0059] The glycidyl ether group in the structural unit A may be any as long as it can easily react with other functional groups, but from the viewpoint of availability of raw materials and curability, it is preferable that the glycidyl ether group does not have a substituent on the carbon atom. Also, the number of glycidyl ether groups in the structural unit A is not particularly limited, but from the viewpoint of industrial availability of raw materials and easy adjustment of crosslink density when cured, it is preferably in the range of 1 to 3, more preferably 1 to 2.

[0060] The average molecular weight (Mw) of the glycidyl ether group-containing compound is not particularly limited, but from the viewpoint of achieving both mechanical strength, flexibility, and repairability and remoldability when the compound is cured, it is preferably 500 or more and preferably 50000 or less. In addition, when the compound has a plurality of reversible bonds other than between A and B, for example, in the structural unit B, it is more preferable that the molecular weight per reversible bond is in the range of 300 to 10000 from the viewpoint of remoldability and the like of the cured product.

[0061] The glycidyl ether group-containing compound according to one embodiment of the present invention is a compound represented by the following general formula:

[0062] [ka]

[0063] In formula (2), Ar each independently represents a structure containing an aromatic ring having a substituent or no substituent, and the anthracene-derived structure in formulae (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 alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group as a substituent. G represents a glycidyl group or a 2-methylglycidyl group. In the formula, ma represents an integer of 1 to 10, and n represents the average number of repetitions, which is 0 to 10. Z 1 is expressed by the following formula (3), Z 2 is expressed by the following formula (4), Z 3 is expressed by the following formula (5), Z 4 is either of the structures represented by the following formula (6) or (7), and each of the multiple structures present in one molecule may be the same or different.

[0064] [ka] [The aromatic ring in formula (3) may be substituted or unsubstituted, * represents a bonding point, G is the same as above, and -OG on the naphthalene ring in the formula indicates that it may be bonded to any position.]

[0065] [ka]

[0066] In formula (4), Each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 each independently represents 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, and n2 is the average number of repeating units of 2 to 30. k1 is the average number of repetitions and is in the range of 0.5 to 10; p1 and p2 each independently represent 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),

[0067] [ka] [In formulas (4-1) and (4-2), Ar, R, R 1 , R 2 , R', n1, and n2 are the same as above.] m1 and m2 are average values ​​of repetitions, each independently ranging from 0 to 25, and m1+m2≧1. However, the bond between the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively.

[0068] [ka] [In formula (5), n3 and n5 are average numbers of repetitions, each of which is 0.5 to 10, n4 is an integer of 1 to 16, and R ” are each independently a hydrogen atom, a methyl group, or an ethyl group.

[0069] [ka]

[0070] [ka] [In formulas (6) and (7), R 1 , R 2 , R', n1, and n2 are the same as above.

[0071] The general formulae (1-1) and (1-2) have a reversible bond formed by anthracene and maleimide at the end of 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 Z1 structures represented by the general formula (3), and this glycidyl ether group or 2-methylglycidyl ether group contributes to the curing reaction in the curable resin composition described later. ma is the number of Z1 in the anthracene-derived structure and is an integer of 1 to 10, but is preferably in the range of 1 to 4, more preferably 1 or 2, from the viewpoints of industrial availability of raw materials and ease of control of the curing reaction.

[0072] The general formula (2) has a disulfide bond in the molecule, and the molecular end has a structure containing an aromatic ring having one or more Z1, which is any structure represented by the general formula (3). This glycidyl ether group or 2-methylglycidyl ether group contributes to the curing reaction in the curable resin composition described later.

[0073] In the formula, Z1 is a structural unit having a glycidyl ether group or a 2-methylglycidyl ether group, as represented by the above general formula (3), and among these, from the viewpoints of availability of raw materials and reactivity, the following structural formula is preferred: G is a glycidyl ether group or a 2-methylglycidyl ether group.

[0074] [ka]

[0075] In the general formulae (1-1) and (1-2), the moiety linking the maleimide-derived structures is Z3, the moiety linking the anthracene-derived structures is Z2, and in the general formula (2), the moiety linking the oxygen atoms together is Z4, which are any of the structures represented by the general formulae (4), (5), (6), and (7), respectively.

[0076] In the general formulae (1-1), (1-2) and (2), n is the average number of repetitions and is in the range of 0 to 10, preferably 0 to 5.

[0077] In these structural formulas, Ar is an aromatic ring which may have a substituent, and is not particularly limited. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Examples of the substituent include a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group. It is preferable that the substituent on Ar does not cause a curing reaction when used as a curable resin composition later, because the effect of the present invention is more easily expressed.

[0078] Among these, Ar is preferably any of the structures represented by the following structural formulas.

[0079] [ka] (The aromatic ring in the formula may be substituted or unsubstituted, and * represents a point of attachment.)

[0080] Further, structures represented by the following formulas are also included as Ar.

[0081] [ka] (In the formula, the aromatic ring may be substituted or unsubstituted, n6=1 to 4, and * represents a bonding point.)

[0082] The following structures are particularly preferred for Ar: * represents a bonding point.

[0083] [ka]

[0084] In the general formulas (4) and (4-1), the repeating unit n1 is an integer of 2 to 16. When n1 is 4 or more, the deformation mode of the cured product is likely to be elastic deformation. When n1 is 16 or less, a decrease in crosslink density can be suppressed. It is preferably 4 to 15, and more preferably 6 to 12.

[0085] In the general formula (4) and (4-1), R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, and R are each independently a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferred.

[0086] In the general formulas (4) and (4-2), n2 is the average value of the repeating units and is 2 to 30. This range is preferable because it provides a good balance between the viscosity of the glycidyl ether group-containing compound and the crosslink density of the resulting cured product. It is preferably 2 to 25, and more preferably 4 to 20.

[0087] In the general formulas (4) and (4-2), R' is a divalent hydrocarbon group having 2 to 12 carbon atoms. Within this range, the adhesive strength 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.

[0088] 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 (divalent groups having an alkylene group and an arylene group).

[0089] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the alkenylene group include a vinylene group, a 1-methylvinylene group, a propenylene group, a butenylene group, and a pentenylene group. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, and a hexynylene group. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.

[0090] Among these, ethylene, propylene and tetramethylene groups are preferred from the viewpoints of the balance between the availability of raw materials, the viscosity of the resulting glycidyl ether group-containing compound and the flexibility of the cured product.

[0091] In the general formulas (4) and (4-2), R is each independently a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable.

[0092] In the general formula (4), m1 and m2 are the average values ​​of the repeating numbers of the structural unit X and the structural unit Y, respectively, and are each independently 0 to 25, and m1+m2≧1. Preferably, m1 and m2 are each in the range of 0.5 to 10.

[0093] In addition, k1 in the general formula (4) is the average number of repetitions and is in the range of 0.5 to 5, and preferably in the range of 0.5 to 2.

[0094] In the general formula (5), n3 and n5 are the average number of repetitions, each of which is 0.5 to 10, n4 is an integer of 1 to 16, and R ”are each independently a hydrogen atom, a methyl group, or an ethyl group. Among these, from the viewpoints of availability of raw materials and mechanical properties of the resulting cured product, it is preferable that n3 is in the range of 0.5 to 10, n5 is in the range of 2 to 3, and n4 is preferably an integer of 1 to 8. ” is preferably a hydrogen atom.

[0095] In the general formulas (6) and (7), R 1 , R 2 , R', n1, and n2 are the same as above, and the preferred ones are also the same as above.

[0096] Examples of the glycidyl ether group-containing compound of the present invention include, but are not limited to, those shown below.

[0097] [ka]

[0098] [ka]

[0099] The method for producing the glycidyl ether group-containing compound according to one embodiment of the present invention is not particularly limited, and the compound may be produced stepwise using known reactions depending on the target structure, and may also be obtained by appropriately combining commercially available raw materials. Representative synthesis methods are described below.

[0100] The general formulae (1-1) and (1-2) have, as reversible bonds, two Diels-Alder reaction units, which are addition reaction moieties formed by a Diels-Alder reaction consisting of an anthracene structure and a maleimide structure, in the molecule, and can be obtained by using a maleimide compound having the structure Z1 in the general formula (1-1) and an anthracene compound having the structure Z1 in the general formula (1-2).

[0101] The so-called Diels-Alder reaction, in which a conjugated diene such as an anthracene structure and a parent diene such as a maleimide structure undergo an addition reaction to form a six-membered ring, is an equilibrium reaction. It is widely known that at temperatures higher than the temperature at which the addition reaction proceeds, the addition reaction site dissociates, returning the original conjugated diene and parent diene, and a retro-Diels-Alder reaction takes place.

[0102] The maleimide compound having a hydroxyl group, which is a precursor of the maleimide compound having the structure Z1, can be any of the compounds listed in the following formula. Among these, hydroxyphenylmaleimide is preferred in terms of curability, and monohydroxyphenylmaleimide is particularly preferred in terms of the balance between reactivity, cured product properties, and repairability and remolding properties. Among the monohydroxyphenylmaleimides, parahydroxyphenylmaleimide is particularly preferred in terms of heat resistance. The hydroxyl group in the compound can be converted to a glycidyl ether group by a known method such as that described in the examples.

[0103] [ka]

[0104] The anthracene compound having a hydroxyl group, which is a precursor of the anthracene compound having the structure Z1, can be any of the compounds listed in the following formula. Among these, 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene and hydroxyanthracene are preferred because of their good curability, and 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene and monohydroxyanthracene are particularly preferred in terms of the balance between reactivity and cured product properties, as well as repairability and remolding ability. The hydroxyl group in the compound can be converted to a glycidyl ether group by a known method, for example, as described in the examples.

[0105] [ka]

[0106] The maleimide compound and anthracene compound structures each include those having, independently of one another, a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl 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, the alkoxy group, the aralkyloxy group, the aryloxy group, the carboxy group, the alkyloxycarbonyl group, the aryloxycarbonyl group, the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group also include those having various substituents bonded to the carbon atoms they have.

[0107] The Diels-Alder reaction may be carried out by a known method. For example, a conjugated diene compound and a parent diene compound are mixed in equimolar amounts, or one of the components may be in excess, and the mixture is melted by heating or dissolved in a solvent, and stirred at room temperature to 200° C. for 1 to 24 hours. The product may be obtained by filtration or solvent distillation without purification, or by a commonly used isolation and purification method such as recrystallization, reprecipitation, or chromatography.

[0108] The synthesis of the site other than the reversible bond can be performed by a known method. For example, a compound having a hydroxyl group at the end is obtained by reacting a diglycidyl ether of an aliphatic dihydroxy compound or an aliphatic divinyl ether with an aromatic hydroxy compound, and then an anthracene structure is introduced at the end by reacting with chloromethylanthracene, glycidyloxyanthracene, etc., and further, a Diels-Alder reaction is performed with a maleimide compound having a glycidyl ether group according to the above, thereby obtaining a compound represented by the general formula (1-1).

[0109] Alternatively, a compound having a hydroxy group at the terminal is obtained, and then epoxidized to convert the terminal into a glycidyl ether group. Thereafter, the compound is reacted with hydroxyanthracene or the like to introduce an anthracene structure at the terminal. Furthermore, the compound represented by the general formula (1-1) can be obtained by carrying out a Diels-Alder reaction with a maleimide compound having a glycidyl ether group as described above.

[0110] 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 terminal, which is then reacted with hydroxymethylanthracene or the like to introduce an anthracene structure at the terminal, and further, a Diels-Alder reaction is carried out with a maleimide compound having a glycidyl ether group as described above to obtain a compound represented by the general formula (1-1).

[0111] 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-pentadecanediol 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 may be used alone or in combination of two or more kinds.

[0112] Among these, compounds having a structure in which glycidyl groups are linked via ether groups to both ends of an alkylene chain having 12 to 14 carbon atoms are preferred because they provide an excellent balance between flexibility and heat resistance of the resulting cured product, and it is most preferred to use 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, or 1,14-tetradecanediol diglycidyl ether.

[0113] The aliphatic divinyl ether is not particularly limited, and examples thereof include divinyl ethers of linear alkylene groups such as polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, and 1,10-decanediol divinyl ether, and divinyl ethers of branched alkylene groups such as neopentyl glycol divinyl ether, divinyl ethers containing a cycloalkane structure such as 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether, and pentacyclopentadecanediol divinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, and hydroquinone divinyl ether. These may be used alone or in combination of two or more.

[0114] Among these, divinyl ethers having a polyether structure or a linear alkylene chain having 9 to 10 carbon atoms are preferred because they provide an excellent balance between flexibility and toughness of the resulting cured product, and it is most preferred to use polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, or 1,14-tetradecanediol diglycidyl ether.

[0115] The aromatic hydroxy compound is not particularly limited, and examples thereof include dihydroxybenzenes such as hydroquinone, resorcin, 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; tetrafunctional phenols such as 1,1'-methylenebis-(2,7-naphthalenediol), 1,1'-binaphthalene-2,2',7,7'-tetraol, and 1,1'-oxybis-(2,7-naphthalenediol) obtained by coupling reaction of dihydroxynaphthalenes; 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, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, 2,2'-biphenol, 4,4'-biphenol, (1,1'-biphenyl)-3,4-diol, 3,3'-Dimethyl-(1,1'-biphenyl)-4,4'-diol, 3-Methyl-(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,Examples of the phenols include biphenols such as 4'-diol, polyaddition products of phenol and dicyclopentadiene, and polyaddition products of phenol and terpene compounds, naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane, and the so-called Xylok-type phenolic resins which are condensation reaction products of phenol and phenylene dimethyl chloride or biphenylene dimethyl chloride. These may be used alone or in combination of two or more. In addition, bifunctional phenolic compounds having a structure in which the aromatic nucleus of each of the above compounds is substituted with a methyl group, a t-butyl group, or a halogen atom as a substituent may also be used. The phenols containing an alicyclic structure and the Xylok-type phenolic resins may contain not only bifunctional components but also trifunctional or higher components at the same time, and may be used as they are, or may be used by isolating only the bifunctional components after a purification process such as a column.

[0116] Among these, bisphenols are preferred because they provide an excellent balance between flexibility and toughness when cured, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferred because they provide outstanding toughness. In addition, when importance is attached to the moisture resistance of the cured product, it is preferred to use phenols containing an alicyclic structure.

[0117] The reaction ratio of the diglycidyl ether of the aliphatic dihydroxy compound to the aromatic hydroxy compound is preferably in the range of 1 / 1.01 to 1 / 5.0 (molar ratio) of the former / the latter, and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is in the range of 1 / 1.02 to 1 / 3.0 (molar ratio).

[0118] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound is preferably carried out in the presence of a catalyst.Various catalysts can be used, such as 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, chlorides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, and benzyltributylammonium, bromides, and iodides, quaternary ammonium salts such as chlorides, bromides, and iodides such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, and benzyltributylphosphonium, tertiary amines such as triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, and 1,4-diazabicyclo[2.2.2]octane, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. These catalysts may be used in combination of two or more kinds. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds quickly and the amount of impurities is highly reduced. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 moles per mole of the phenolic hydroxyl group of the aromatic hydroxy compound. The form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in the form of a solid.

[0119] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, and butyl alcohol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination. In order to carry out the reaction quickly, it is preferable to use no solvent, while it is preferable to use dimethyl sulfoxide in order to reduce impurities in the final product.

[0120] The reaction temperature in carrying out the reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. The reaction temperature is preferably 100 to 160°C in terms of reducing impurities in the final product. In addition, if the resulting compound is significantly colored, an antioxidant or a reducing agent may be added to suppress the coloration. The antioxidant is not particularly limited, but examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphorous ester compounds containing a trivalent phosphorus atom. The reducing agent is not particularly limited, but examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0121] After the reaction is completed, the reaction mixture may be neutralized or washed until the pH value is 3 to 7, preferably 5 to 7. The neutralization and washing may be performed according to a conventional method. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, or oxalic acid may be used as a neutralizing agent. After the neutralization or washing, the solvent may be distilled off under reduced pressure and heating, if necessary, to concentrate the product, thereby obtaining a compound.

[0122] The reaction ratio of the aliphatic divinyl ether and the aromatic hydroxy compound is preferably in the range of 1 / 1.01 to 1 / 5.0 (molar ratio) of the former / the latter, and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is in the range of 1 / 1.02 to 1 / 3.0 (molar ratio).

[0123] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently without using a catalyst, but it can be used appropriately from the viewpoint of selecting raw materials and increasing the reaction rate. Examples of catalysts that can be used here include 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, and Lewis acids such as aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, and boron trifluoride phenol complex. The amount of catalyst used is usually in the range of 10 ppm to 1% by weight based on the mass of the divinyl ether compound. In this case, it is preferable to select the type and amount of catalyst used so as not to cause a nuclear addition reaction of the vinyl group to the aromatic ring.

[0124] The reaction between 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 of the organic solvent 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, isopropyl alcohol, and normal butanol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.

[0125] The reaction temperature when carrying out the above reaction is usually 50 to 150° C., and the reaction time is usually 0.5 to 10 hours. In this case, in order to prevent self-polymerization of the vinyl ether group, the reaction is preferably carried out in an oxygen atmosphere.

[0126] After completion of the reaction, if an organic solvent was used, it is removed under reduced pressure and heating, and if a catalyst was used, it is deactivated with a deactivator or the like as necessary, and then removed by washing with water or filtration, whereby the compound can be obtained.

[0127] 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 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 the target compound can be obtained by extraction, solvent removal, or the like. The Diels-Alder reaction of this compound is as described above.

[0128] 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, and 1,16-hexadecanediol. Examples of the polyglyceryl ether include diol, 2-methyl-1,11-undecanediol, 3-methyl-1,11-undecanediol, 2,6,10-trimethyl-1,11-undecanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, and polyheptamethylene glycol diglycidyl ether. These may be used alone or in combination of two or more.

[0129] Among these, it is preferable to use a dihydroxy compound having a polyether structure or a linear alkylene chain having 12 to 14 carbon atoms, because the resulting cured product has an excellent balance between flexibility and heat resistance, and it is most preferable to use polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,12-dodecanediol, 1,13-tridecanediol, or 1,14-tetradecanediol.

[0130] 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-dibromoundecane, and 1,12-dibromododecane. These compounds may be used alone or in combination of two or more.

[0131] The dihalogenated aralkyl compound is not particularly limited, and examples thereof include dichloroxylene, dichloromethylbiphenyl, dibromoxylene, dibromomethylbiphenyl, and the like. These may be used alone or in combination of two or more kinds.

[0132] The reaction ratio of the aromatic dihydroxy compound to the dihalogenated alkyl compound or dihalogenated aralkyl compound is preferably in the range of 1 / 1.01 to 1 / 5.0 (molar ratio) of the former / the latter, and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is 1 / 1.02 to 1 / 3.0 (molar ratio).

[0133] The reaction between the aromatic dihydroxy compound and the dihalogenated alkyl compound or dihalogenated aralkyl 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, calcium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Two or more of these catalysts may be used in combination. Among them, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred because the reaction proceeds quickly and the effect of reducing the amount of impurities is high. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 10 moles per mole of the phenolic hydroxyl group of the aromatic hydroxy compound. The form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in the form of a solid.

[0134] The reaction of the aromatic dihydroxy compound with the dihalogenated alkyl compound or dihalogenated aralkyl compound can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, and dimethylformamide. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 1000% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.

[0135] The reaction temperature when carrying out the above reaction is usually room temperature to 150° C., and the reaction time is usually 1 to 24 hours. The reaction temperature is preferably room temperature to 100° C. in order to reduce impurities in the final product.

[0136] 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 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 the target compound can be obtained by extraction, solvent removal, or the like. The Diels-Alder reaction of this compound is as described above.

[0137] The conjugated diene intermediate or the dienophile intermediate before the Diels-Alder reaction can be represented by the following general formula (1-1)' or (1-2)'.

[0138] [ka] [In the formula, n, Z 2 , Z 3 is the same as above.

[0139] The method for producing the compound having a disulfide bond as a reversible bond represented by the general formula (3) is not particularly limited.

[0140] The compounds that can be used as the raw material for the compound having a disulfide bond include the following.

[0141] [ka]

[0142] [ka]

[0143] The compound having a disulfide bond may be prepared by a known method. For example, a compound having a thiol group is oxidatively bonded. Iodine, hydrogen peroxide, etc. are generally used as the oxidizing agent. The compound is melted by heating or dissolved in a solvent, stirred at room temperature to 200°C for 1 to 24 hours, and can be obtained by filtration or solvent distillation without purification, or by a commonly used isolation and purification method such as recrystallization, reprecipitation, and chromatography. After obtaining the precursor hydroxyl group-containing compound, a known method can be used to convert it into a glycidyl ether group.

[0144] The glycidyl ether group-containing compound of the present invention can be used in combination with a compound (I) having reactivity with the glycidyl ether group-containing compound to form a curable resin composition. The curable resin composition can be suitably used for various electric and electronic material applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulation materials.

[0145] Examples of the compound (I) reactive with the glycidyl ether group-containing compound include various known curing agents for epoxy resins, such as amine compounds, acid anhydrides, amide compounds, phenolic hydroxyl group-containing compounds, carboxylic acid compounds, and thiol compounds. The curing agent can be appropriately selected depending on the physical properties of the desired cured product, but it is preferable to use a hydroxyl group-containing compound, particularly from the viewpoint of mechanical strength and adhesion to the substrate.

[0146] Examples of the amine compound include trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N',N'-tetramethylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetramethylhexamethylenediamine ... aliphatic amine compounds such as triethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, and α-methylbenzylmethylamine;

[0147] Alicyclic and heterocyclic amine compounds such as piperidine, piperazine, menthanediamine, isophoronediamine, 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, 1,8-diazabicyclo-[5.4.0]-undecene (DBU);

[0148] Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, and picoline;

[0149] Examples of modified amine compounds include epoxy compound-added polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, aminimide, boron trifluoride-piperidine complex, and boron trifluoride-monoethylamine complex.

[0150] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic polypropylene glycol anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0151] Examples of the phenolic hydroxyl group-containing compound 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, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, Examples of polyhydric phenol compounds include tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which a phenol nucleus is linked via a bismethylene group), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which a phenol nucleus is linked via a bismethylene group), aminotriazine-modified phenol resin (a polyhydric phenol compound in which a phenol nucleus is linked via melamine, benzoguanamine, or the like), and alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked via formaldehyde).

[0152] Examples of the amide-based compound include dicyandiamide and polyamidoamine, etc. Examples of the polyamidoamine include those obtained by reacting an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, etc., or a carboxylic acid compound such as a fatty acid or a dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain, etc.

[0153] Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyesters, polyacrylic acid, and maleic acid-modified polypropylene glycol.

[0154] The thiol compound preferably contains two or more thiol groups in two molecules. For example, 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexaneedithiol, 1,10-decanedithiol, and the like.

[0155] When using these curing agents, only one type of curing agent may be used, or two or more types may be mixed. In applications such as underfill materials and general coating applications, it is preferable to use the amine compounds, carboxylic acid compounds, and / or acid anhydride compounds. In applications such as adhesives and flexible wiring boards, amine compounds, particularly dicyandiamide, are preferred from the viewpoints of workability, curability, and long-term stability. In applications such as semiconductor encapsulation materials, solid-type phenol compounds are preferred from the viewpoint of heat resistance of the cured product. In applications such as batteries, aliphatic amines and thiol compounds are preferred from the viewpoint of low-temperature curing.

[0156] From the viewpoint of being able to further exert the effects of the present invention, it is preferable that the compound (I) reactive with the glycidyl ether group-containing compound is a hydroxyl group-containing compound having a reversible bond.

[0157] The hydroxyl-containing compound having a reversible bond may be a hydroxyl-containing compound in which a structural unit A' having one or more hydroxyl groups and a structural unit B' different from the A' are linked by A'-B'-A', and the structural unit A' and the structural unit B' are linked by a reversible bond. In this case, the dissociation temperature of the reversible bond is preferably 120° C. or higher, from the viewpoint of further achieving the effects of the present invention.

[0158] The reversible bond may be the same as the reversible bond in the glycidyl ether group-containing compound of the present invention.

[0159] Examples of the hydroxyl-containing compound having a reversible bond include those represented by the following formulae: Among these, from the viewpoint of the dissociation temperature of the reversible bond, it is preferable to use the compounds represented by the following formulae (8-1), (8-2) and (9).

[0160] [ka]

[0161] [Each Ar in formula (9) is independently a structure containing an aromatic ring which is unsubstituted or substituted, and the anthracene-derived structure in formulae (8-1) and (8-2) and the furan-derived structure in formulae (8-3) and (8-4) may have a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amido group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent. In the formula, ma is an integer of 1 to 10, mb is an integer of 1 to 4, and n is the average number of repetitions, which is 0 to 10. 5 is expressed by the following formula (10), Z 2 is expressed by the following formula (11), Z 3 is expressed by the following formula (12), Z 4 is either of the structures represented by the following formula (13) or (14), and each of the multiple structures present in one molecule may be the same or different.

[0162] [ka] [The aromatic ring in formula (10) may be substituted or unsubstituted, and * represents a bonding point. The hydroxyl group on the naphthalene ring in the formula may be bonded to any position.]

[0163] [ka] [In formula (11), Each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 each independently represents 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, and n2 is the average number of repeating units of 2 to 30. k1 is the average number of repetitions and is in the range of 0.5 to 10; p1 and p2 each independently represent 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),

[0164] [ka] [In formulas (11-1) and (11-2), Ar, R, R 1 , R 2 , R', n1, and n2 are the same as above.] m1 and m2 are average values ​​of repetitions, each independently ranging from 0 to 25, and m1+m2≧1. However, the bond between the structural unit X represented by the formula (11-1) and the structural unit Y represented by the formula (11-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively.

[0165] [ka] [In formula (12), n3 and n5 are average numbers of repetitions, each of which is 0.5 to 10, n4 is an integer of 1 to 16, and R ” are each independently a hydrogen atom, a methyl group, or an ethyl group.

[0166] [ka]

[0167] [ka] [In formulas (13) and (14), R 1 , R 2 , R', n1, and n2 are the same as above.

[0168] Specific examples of the hydroxyl-containing compound having a reversible bond include those represented by the following structural formulas.

[0169] [ka]

[0170] [ka]

[0171] These hydroxyl group-containing compounds correspond to intermediates (precursors) of the above-mentioned glycidyl ether group-containing compound of the present invention, and therefore can be obtained by using commercially available raw materials such as maleimide, furan, and anthracene having a hydroxyl group according to the above-mentioned production method.

[0172] Furthermore, in the curable resin composition of the present invention, epoxy resins other than the glycidyl ether group-containing compound of the present invention can be used in combination within the range that does not impair the effects of the present invention.

[0173] Examples of the other epoxy resins include liquid epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD ​​type epoxy resins, polyhydroxybenzene type epoxy resins, polyhydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type epoxy resins; brominated epoxy resins such as brominated phenol novolac type epoxy resins; solid bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, and tetraphenylethane type epoxy resins. Examples of such epoxy resins include dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resins, biphenyl modified novolac type epoxy resins, and the like. These may be used alone or in combination of two or more kinds, and it is preferable to select and use various types depending on the intended use, the physical properties of the cured product, and the like.

[0174] Among these, it is preferable to use an epoxy resin having an epoxy equivalent of 100 to 10,000 g / eq in combination from the viewpoint of achieving an excellent balance between the curability and the crosslink density of the resulting cured product, and it is particularly preferable to use an epoxy resin represented by the following formula (15) and having an epoxy equivalent of 500 to 10,000 g / eq.

[0175] [ka] [In formula (15), each Ar independently represents a structure having 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):

[0176] [ka]

[0177] [In the formulas (15-1) and (15-2), Ar is the same as defined above, R 1 , R 2 each independently represents 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 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 each independently represents a hydrogen atom or a methyl group, n1 is an integer from 4 to 16, n2 is the average number of repeating units and is between 2 and 30. R 11 , R 12 each independently represents a glycidyl ether group or a 2-methylglycidyl ether group; R 13 , R 14 each independently represents 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, and q are the average values ​​of the repetitions. m3 and m4 each independently represent 0 to 25, and m3+m4≧1; p1 and p2 each independently represent 0 to 5; q is 0.5 to 5. However, the bond between the structural unit X' represented by the formula (15-1) and the structural unit Y' represented by the formula (15-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m3 and m4, respectively.

[0178] The epoxy resin represented by the general formula (15) may be used alone in combination to form a curable resin composition. However, from the viewpoint of imparting further flexibility to the cured product and making it easier to dismantle, it is also preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq in combination.

[0179] The epoxy resin that can be used in combination is not limited in structure as long as its epoxy equivalent is in the range of 100 to 300 g / eq. Examples of the epoxy resin include liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, and tetramethylbiphenyl type epoxy resin; brominated epoxy resins such as brominated phenol novolac type epoxy resin; solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclohexyl ether type epoxy resin, and the like. Examples of such epoxy resins include isopropyl alcohol-based epoxy resins, isopropyl alcohol-based epoxy resins, and the like. Examples of such epoxy resins include isopropyl alcohol-based epoxy resins, isopropyl alcohol-based epoxy resins, and the like. Examples of such epoxy resins include isopropyl alcohol-based epoxy resins, isopropyl alcohol-based epoxy resins, and the like. Examples of such epoxy resins include isopropyl alcohol-based epoxy resins, isopropyl alcohol-based epoxy resins, and the like.

[0180] Among these, it is preferable to use liquid epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD ​​type epoxy resins, polyhydroxybenzene type epoxy resins, polyhydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type epoxy resins, and it is particularly preferable to use epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AD ​​... the like, each having an epoxy equivalent of 100 to 300 g / eq.

[0181] 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, but from the viewpoint of facilitating 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 results in a sea-island structure, which achieves both adhesiveness and stress relaxation ability of the cured product, exhibits high adhesive strength in a particularly wide temperature range, and has the effect of reducing the molding shrinkage rate before and after heat curing of the resin composition.

[0182] The concentration of the reversible bond in the curable resin composition of the present invention is preferably 0.10 mmol / g or more with respect to the total mass of the curable components in the curable resin composition. According to such a configuration, both the repairability and remolding property of the cured product obtained from the curable resin composition are further improved. The concentration of the reversible bond is more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. In addition, when the glycidyl ether group-containing compound of the present invention has a plurality of reversible bonds, or when the hydroxyl group-containing compound having the reversible bond is used alone or in combination with another curing agent as a curing agent, the concentration as the sum of the reversible bonds is preferably 0.10 mmol / g or more with respect to the total mass of the curable components in the curable resin composition, more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. The concentration of the reversible bond can be appropriately selected based on the glass transition temperature defined by the tan δ peak top of the dynamic viscoelasticity measuring device (DMA) of the target cured product. For example, when the glass transition temperature is used as a guideline, if the glass transition temperature of the cured product is near room temperature, sufficient repairability and reshapeability functions are likely to be expressed 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 guideline, the functions are likely to be expressed at the high concentration side of the preferred range. However, in the temperature range exceeding the glass transition temperature measured by DMA, molecular mobility is generally high, and sufficient repairability and reshapeability functions are likely to be expressed even at a low concentration of the glycidyl ether group-containing compound, so that, for example, the effect of expressing the repairability and reshapeability functions can be adjusted by appropriately adjusting the aging temperature for repair and the heating temperature for reshaping. Thus, the relationship between the glass transition temperature of the cured product and the concentration of the reversible bond is not limited to these.

[0183] The ratio of the total number of glycidyl ether groups to the total number of active groups capable of reacting with the glycidyl ether groups in the curable resin composition of the present invention is not particularly limited, but in terms of good mechanical properties and the like of the resulting cured product, it is preferable that the amount of active groups capable of reacting with the glycidyl ether groups be 0.4 to 1.5 equivalents per equivalent of the total number of glycidyl ether groups in the resin composition.

[0184] The curable resin composition may contain a curing accelerator. Various types of curing accelerators can be used, including urea compounds, phosphorus compounds, tertiary amines, imidazole, imidazoline, organic acid metal salts, Lewis acids, and amine complex salts. When used as an adhesive, urea compounds, particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), are preferred because of their excellent workability and low-temperature curing properties. When used as a semiconductor encapsulating material, triphenylphosphine is preferred as a phosphorus compound, and 1,8-diazabicyclo-[5.4.0]-undecene is preferred as a tertiary amine because of their excellent curing properties, heat resistance, electrical properties, and moisture resistance reliability.

[0185] Examples of the phosphorus compound include alkyl phosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine, dialkyl phosphines such as dimethylphosphine and dipropylphosphine, secondary phosphines such as diphenylphosphine and methylethylphosphine, and tertiary phosphines such as trimethylphosphine, triethylphosphine and triphenylphosphine.

[0186] 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, and 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 Midazole, 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-di(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, etc.

[0187] Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

[0188] 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.

[0189] The curable resin composition of the present invention may be used in combination with other thermosetting resins or thermoplastic resins within the range that does not impair the effects of the present invention.

[0190] Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, active ester resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc. When the other thermosetting resins described above are used in combination, the amount of use is not particularly limited as long as it does not inhibit the effects of the present invention, but is preferably in the range of 1 to 50 parts by mass in 100 parts by mass of the curable resin composition.

[0191] Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenyl Examples of the cyanate ester resin include tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolac type cyanate ester resin, naphthol-cresol co-condensed novolac type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolac type cyanate ester resin, anthracene type cyanate ester resin, etc. These may be used alone or in combination of two or more.

[0192] Among these cyanate ester resins, it is preferable to use bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthylene ether type cyanate ester resin, and novolac type cyanate ester resin, in that a cured product having excellent heat resistance can be obtained, and it is preferable to use dicyclopentadiene-phenol addition reaction type cyanate ester resin in that a cured product having excellent dielectric properties can be obtained.

[0193] 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. Each of these may be used alone, or two or more of them may be used in combination.

[0194] The active ester resin is not particularly limited, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or halides thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, 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, phloroglucin, benzenetriol, and dicyclopentadiene-phenol adduct resins.

[0195] Specific examples of the active ester resin include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins which are acetylated phenol novolac, and active ester resins which are benzoylated phenol novolac. Of these, the active ester resins containing a dicyclopentadiene-phenol addition structure and the active ester resins containing a naphthalene structure are more preferred in terms of their excellent ability to improve peel strength.

[0196] Furthermore, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and various vinyl polymers may be used in combination.

[0197] More specifically, the various novolak resins include polymers obtained by reacting a phenolic hydroxyl group-containing compound, such as phenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A or bisphenol F, naphthol, or dihydroxynaphthalene, with an aldehyde compound under acid catalyst conditions.

[0198] Examples of the various vinyl polymers include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly(meth)acrylate, or copolymers thereof.

[0199] 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, and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

[0200] When these other resins are used, the blending ratio of the glycidyl ether group-containing compound of the present invention to the other resins can be set arbitrarily depending on the application. From the viewpoint of not impairing the repairability and remoldability exhibited by the present invention, however, the blending ratio of the other resins is preferably 0.5 to 100 parts by mass per 100 parts by mass of the glycidyl ether group-containing compound of the present invention.

[0201] When the curable resin composition of the present invention is used in an application requiring high flame retardancy, a non-halogen flame retardant substantially containing no halogen atoms may be blended therein.

[0202] Examples of the non-halogen flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. There are no limitations on the use of these flame retardants. They may be used alone or in combination with a plurality of flame retardants of the same type. Also, flame retardants of different types may be used in combination.

[0203] The phosphorus-based flame retardant may be either inorganic or organic. Examples of inorganic compounds 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.

[0204] The red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like. 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 phenolic resin, and (iii) a method of doubly coating with a thermosetting resin such as a phenolic resin on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc.

[0205] Examples of the organophosphorus compound include general-purpose organophosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as 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 reacted with compounds such as epoxy resins and phenol resins.

[0206] The amount of these phosphorus-based flame retardants to be added is appropriately selected depending on the type of phosphorus-based flame retardant, other components of the resin composition, and the desired level of flame retardancy. For example, in 100 parts by mass of a resin composition containing all of the non-halogenated flame retardants and other fillers and additives, when red phosphorus is used as the non-halogenated flame retardant, it is preferably added in a range of 0.1 to 2.0 parts by mass, and when an organic phosphorus compound is used, it is similarly preferably added in a range of 0.1 to 10.0 parts by mass, and more preferably added in a range of 0.5 to 6.0 parts by mass.

[0207] When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dyes, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. may be used in combination with the phosphorus-based flame retardant.

[0208] Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines, with triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds being preferred.

[0209] Examples of the triazine compounds include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, and the like, as well as (1) aminotriazine sulfate compounds such as guanylmelamine 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 (2) with phenolic resins such as phenol-formaldehyde condensates, and (4) compounds obtained by further modifying (2) and (3) with tung oil, isomerized linseed oil, or the like.

[0210] Examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate.

[0211] The amount of the nitrogen-based flame retardant to be blended is appropriately selected depending on the type of nitrogen-based flame retardant, other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend in an amount of 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives.

[0212] When the nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, etc. may be used in combination.

[0213] The silicone flame retardant can be used without any 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 silicone flame retardant is appropriately selected according to the type of silicone flame retardant, other components of the resin composition, and the desired level of flame retardancy, but it is preferable to mix it in the range of 0.05 to 20 parts by mass in 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives. When using the silicone flame retardant, a molybdenum compound, alumina, etc. may be used in combination.

[0214] Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.

[0215] Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

[0216] 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.

[0217] 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.

[0218] Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

[0219] Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

[0220] Examples of the low-melting glass include glassy compounds such as Seapley (Boxey Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3, ZnO-P2O5-MgO, P2O5-B2O3-PbO-MgO, P-Sn-OF, PbO-V2O5-TeO2, Al2O3-H2O, and lead borosilicate.

[0221] The amount of the inorganic flame retardant to be blended is appropriately selected depending on the type of inorganic flame retardant, other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend in an amount of 0.05 to 20 parts by mass, and more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives.

[0222] Examples of the organometallic salt flame retardant include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organocobalt salt compounds, organosulfonic acid metal salts, and compounds in which a metal atom is ionic- or coordinate-bonded to an aromatic compound or a heterocyclic compound.

[0223] The amount of the organometallic salt flame retardant to be blended is appropriately selected depending on the type of organometallic salt flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend in an amount of 0.005 to 10 parts by mass per 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers, additives, etc.

[0224] 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.

[0225] Examples of inorganic fine particles include those with excellent heat resistance, such as alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine amorphous silica); those with excellent thermal conductivity, such as boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, and diamond; those with excellent electrical conductivity, such as metal fillers and / or metal-coated fillers using simple metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, and stainless steel); and those with excellent barrier properties, such as minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, and the like. , aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; those with a high refractive index include barium titanate, zirconia oxide, titanium oxide, etc.; those exhibiting photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of the above metals, and oxides thereof; those with excellent wear resistance include metals such as silica, alumina, zirconia, magnesium oxide, etc., composites and oxides thereof; those with excellent electrical conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; those with excellent insulation properties include silica, etc.; those with excellent ultraviolet shielding properties include titanium oxide, zinc oxide, etc. These inorganic fine particles can be selected appropriately depending on the application, and can be used alone or in combination of multiple types. In addition, the above inorganic fine particles have various properties other than those listed as examples, so they can be selected appropriately according to the application.

[0226] For example, when silica is used as inorganic fine particles, known silica fine particles such as powdered silica and colloidal silica can be used without any particular limitation. Commercially available powdered silica fine particles include, for example, Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG Flake manufactured by Nippon Sheet Glass Co., Ltd.

[0227] Examples of commercially available colloidal silica include methanol silica sol, 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, and ST-OL, all of which are manufactured by Nissan Chemical Industries, Ltd.

[0228] Surface-modified silica fine particles may be used, for example, the silica fine particles are surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth)acryloyl group. Commercially available powdered silica modified with a compound having a (meth)acryloyl group includes Aerosil RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth)acryloyl group includes MIBK-SD, etc. manufactured by Nissan Chemical Industries, Ltd.

[0229] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous shapes can be used. The primary particle size is preferably in the range of 5 to 200 nm.

[0230] As the titanium oxide fine particles, not only extender pigments but also ultraviolet light responsive photocatalysts can be used, for example, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, etc. can be used. Furthermore, particles designed to respond to visible light by doping different elements into the crystal structure of titanium oxide can also be used. As the element to be doped into titanium oxide, anion elements such as nitrogen, sulfur, carbon, fluorine, phosphorus, etc., and cationic elements such as chromium, iron, cobalt, manganese, etc. are preferably used. In addition, as the form, powder, sol dispersed in an organic solvent or water, or slurry can be used. As commercially available powdered titanium oxide fine particles, for example, Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by Teika Co., Ltd., etc. can be used. In addition, as commercially available slurry-like titanium oxide fine particles, for example, TKD-701 manufactured by Teika Co., Ltd., etc. can be used.

[0231] The curable resin composition of the present invention may further contain a fibrous substrate. The fibrous substrate is not particularly limited, but is preferably one used in fiber-reinforced resins, such as inorganic fibers and organic fibers.

[0232] Examples of inorganic fibers include inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, tungsten carbide fibers, silicon carbide fibers (silicon carbide fibers), ceramic fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0233] Examples of organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, 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 protein, polypeptide, and alginic acid.

[0234] Among these, carbon fiber and glass fiber are preferred because they have a wide range of industrial applications. Of these, only one type may be used, or a plurality of types may be used simultaneously.

[0235] The fibrous substrate may be an assembly of fibers, the fibers may be continuous or discontinuous, and may be in the form of a woven or nonwoven fabric. It may also be a fiber bundle in which the fibers are aligned in one direction, or in the form of a sheet in which fiber bundles are arranged. It may also be a three-dimensional shape in which a thickness is added to an assembly of fibers.

[0236] The curable resin composition of the present invention may contain a dispersion medium for the purpose of adjusting the solid content and viscosity of the resin composition. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and examples of the dispersion medium include various organic solvents and liquid organic polymers.

[0237] 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; and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These can be used alone or in combination, but of these, methyl ethyl ketone is preferred from the standpoint of volatility during coating and solvent recovery.

[0238] The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include acrylic polymers (Floren WK-20: Kyoeisha), amine salts of special modified phosphate esters (HIPLAAD ED-251: Kusumoto Chemicals), and modified acrylic block copolymers (DISPERBYK2000; BYK-Chemie).

[0239] 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 control agents, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, and reactive diluents.

[0240] The resin composition of the present invention can be cured to obtain a cured product. When curing, the resin composition may be cured at room temperature or by heating. When performing heat curing, the resin composition may be cured by one heating step or may be cured by multiple heating steps.

[0241] The curable resin composition of the present invention can also be cured by active energy rays. In that case, a photocationic polymerization initiator may be used as the polymerization initiator. The active energy rays may be visible light, ultraviolet light, X-rays, electron beams, etc.

[0242] Examples of the photocationic polymerization initiator include aryl-sulfonium salts and aryl-iodonium 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 kinds.

[0243] 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, the composition can be prepared by uniformly mixing the components using a pot mill, a ball mill, a bead mill, a roll mill, a homogenizer, a super mill, a homodisper, a universal mixer, a Banbury mixer, a kneader, or the like.

[0244] The curable resin composition of the present invention is prepared by dissolving the above-mentioned glycidyl ether group-containing compound of the present invention and the compound (I) having reactivity with the above-mentioned glycidyl ether group-containing compound, and further dissolving the above-mentioned curing agent, filler, fibrous substrate, dispersion medium, and resin other than the above-mentioned various compounds in a dispersion medium such as the above-mentioned organic solvent, if necessary. After dissolving, the solvent is distilled off and the curable resin composition can be obtained by drying under reduced pressure using a vacuum oven or the like. The curable resin composition of the present invention may be in a state in which the above-mentioned constituent materials are uniformly mixed. At this time, it is preferable to mix uniformly using a mixer or the like. The blending ratio of each constituent material can be appropriately adjusted according to the desired characteristics of the cured product, such as mechanical strength, heat resistance, repairability, and remoldability. In addition, in the preparation of the curable resin composition, the specific order of mixing the constituent materials is not particularly limited.

[0245] The cured product of the present invention is obtained by curing a compound (I) reactive with the glycidyl ether group-containing compound with the glycidyl ether group-containing compound of the present invention. The curing method can be appropriately selected and adopted from known methods depending on the properties of the compound (I) reactive with the glycidyl ether group-containing compound used.

[0246] The cured product of the present invention is cured by the glycidyl ether group-containing compound of the present invention as described above, and therefore can maintain good mechanical strength by exhibiting a suitable crosslinking density. In addition, when mechanical energy such as scratches or external force is applied to the cured product of the present invention, the reversible bond is broken, but the equilibrium shifts in the bond direction, so that an adduct is formed again, which is considered to enable repair of the scratches and remolding.

[0247] 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.

[0248] As described above, the cured product, which is one embodiment of the present invention, can be obtained by using the glycidyl ether group-containing compound of the present invention as one component of a curable resin composition. However, it is also possible to use the above-mentioned conjugated diene intermediate or dienophile intermediate, which is an intermediate of the glycidyl ether group-containing compound, in combination with a compound capable of addition reaction by Diels-Alder reaction, and form the glycidyl ether group-containing compound during the curing process (while synthesizing in situ) to obtain a cured product.

[0249] For example, when a curing reaction is carried out using the compound represented by the formula (1-1)', a maleimide having a glycidyl ether group, and a compound (I) having reactivity with the glycidyl ether group-containing compound as essential raw materials, the glycidyl ether group-containing compound represented by the formula (1-1) can be obtained in the course of the curing reaction, and a cured product can be obtained as the curing reaction progresses. The maleimide having a glycidyl ether group that can be used in this case is the same as that described above.

[0250] In addition, when a curing reaction is carried out using the compound represented by the formula (1-2)', an anthracene having a glycidyl ether group, and a compound (I) having reactivity with the glycidyl ether group-containing compound as essential raw materials, the glycidyl ether group-containing compound represented by the formula (1-2) can be obtained in the course of the curing reaction, and a cured product can be obtained as the curing reaction progresses. The anthracene having a glycidyl ether group that can be used in this case is the same as that described above.

[0251] The curable resin composition of the present invention and a cured product produced from the curable resin composition are excellent in both heat resistance and repairability, and are also remoldable, and are useful for the following applications.

[0252] The curable resin cured product of the present invention can be laminated with a substrate to form a laminate. The substrate of the laminate may be an inorganic material such as metal or glass, or an organic material such as plastic or wood, and may be used as appropriate depending on the application. The substrate may be in the shape of a laminate, a flat plate, a sheet, or a three-dimensional structure, or may be three-dimensional. The substrate may have any shape according to the purpose, such as a shape having a curvature on the entire surface or in a part. There is no restriction on the hardness, thickness, etc. of the substrate. The first substrate, a layer made of the cured product of the curable resin composition of the present invention, and a second substrate may be laminated in this order to form a multilayer laminate. The curable resin composition of the present embodiment has excellent adhesiveness, and can be suitably used as an adhesive for bonding a first substrate and a second substrate. The curable resin cured product of the present invention may be used as a substrate, and the cured product of the present invention may be further laminated.

[0253] In addition, the cured product of the curable resin of the present invention can relieve stress, and therefore can be suitably used for bonding different materials. For example, even in a laminate in which the substrate is a metal and / or metal oxide and the second substrate is a different material such as a plastic layer, the adhesive strength is maintained due to the stress relaxation ability of the cured product of the present invention.

[0254] In the laminate obtained by laminating the cured product of the present invention and the substrate, the layer containing the cured product may be formed by direct coating or molding on the substrate, or an already molded product may be laminated. When directly coating, the coating method is not particularly limited, and examples thereof include spraying, spin coating, dip coating, roll coating, blade coating, doctor roll, doctor blade, curtain coating, slit coating, screen printing, and inkjet. When directly molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, and press molding. When laminating a molded composition, an uncured or semi-cured composition layer may be laminated and then cured, or a layer containing a cured product obtained by completely curing the composition may be laminated on the substrate. In addition, the cured product of the present invention may be laminated by coating a precursor that can be a substrate and curing it, or the precursor that can be a substrate or the composition of the present invention may be adhered in an uncured or semi-cured state and then cured. The precursor that can be a substrate is not particularly limited, and examples thereof include various curable resin compositions.

[0255] 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 be particularly well used as a primer for metals. Metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials thereof, and metal oxides include single oxides and / or composite oxides of these metals. In particular, the cured product has excellent adhesion to iron, copper, and aluminum, and can be particularly well used as an adhesive for iron, copper, and aluminum.

[0256] The curable resin composition of the present invention can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry. Even when used to bond different materials such as between metal and nonmetal, the adhesive can maintain high adhesion without being affected by changes in temperature environment, and peeling is unlikely to occur. In addition to structural member applications, the adhesive can also be used as an adhesive for general office use, medical use, carbon fiber, storage battery cells, modules, and cases, and can be used as an adhesive for bonding optical components, an adhesive for bonding optical disks, an adhesive for mounting printed wiring boards, a die bonding adhesive, an adhesive for semiconductors such as underfill, an underfill for reinforcing BGA, an anisotropic conductive film, an anisotropic conductive paste, and other mounting adhesives.

[0257] When the curable resin composition of the present invention has a fibrous substrate, and the fibrous substrate is a reinforcing fiber, the curable resin composition containing the fibrous substrate can be used as a fiber-reinforced resin. The method of adding the fibrous substrate to the composition is not particularly limited as long as it does not impair the effects of the present invention, and includes methods of compounding the fibrous substrate and the composition by kneading, coating, impregnation, injection, pressure bonding, etc., and can be appropriately selected depending on the form of the fiber and the use of the fiber-reinforced resin.

[0258] There is no particular limitation on the method of molding the fiber-reinforced resin. If a plate-shaped product is to be manufactured, an extrusion molding method is generally used, but it can also be manufactured by a flat press. In addition, extrusion molding, blow molding, compression molding, vacuum molding, injection molding, etc. can be used. If a film-shaped product is to be manufactured, in addition to the melt extrusion method, a solution casting method can be used. When a melt molding method is used, examples of the method include inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. In addition, in the case of a resin that is cured by active energy rays, a cured product can be manufactured using various curing methods using active energy rays. In particular, when a thermosetting resin is used as the main component of the matrix resin, examples of the molding method include a molding method in which the molding material is made into a prepreg and pressurized and heated by a press or autoclave, and other examples of the molding method include RTM (Resin Transfer Molding) molding, VaRTM (Vacuum assist Resin Transfer Molding) molding, lamination molding, and hand layup molding.

[0259] The curable resin composition of the present invention, when used in a cured product, has good heat resistance and repairability, and is also remoldable, and can therefore be used as a molding material for large cases, motor housings, casting materials for the inside of cases, gears, pulleys, etc. These may be cured products of the resin alone, or may be cured products reinforced with fibers such as glass chips.

[0260] The fiber reinforced resin can form a state called an uncured or semi-cured prepreg. After distributing the product in the prepreg state, final curing may be performed to form a cured product. When forming a laminate, it is preferable to form a prepreg, then laminate other layers and then perform final curing, since this allows the formation of a laminate in which each layer is in close contact with each other. The mass ratio of the composition and the fibrous substrate used at this time is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60 mass%.

[0261] The cured product of the present invention has good heat resistance and repairability, and has remoldability, and can be used as a heat-resistant material and an electronic material. In particular, it can be suitably used for semiconductor encapsulation materials, circuit boards, build-up films, build-up boards, adhesives, and resist materials. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a highly heat-resistant prepreg. The heat-resistant and electronic components thus obtained can be suitably used for various applications, such as industrial machine parts, general machine parts, automobile, railway, and vehicle parts, space and aviation-related parts, electronic and electrical parts, building materials, containers and packaging materials, daily necessities, sports and leisure goods, and housing members for wind power generation, but are not limited thereto.

[0262] In particular, the adhesive can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry, taking advantage of the excellent flexibility of the cured product. The adhesive of the present invention can maintain high adhesion without being affected by changes in temperature environment, even when used to bond different materials such as between metal and nonmetal, and peeling is unlikely to occur. In addition to structural member applications, the adhesive of the present invention can also be used as an adhesive for general office use, medical use, carbon fiber, storage battery cells, modules, and cases, and examples thereof include adhesives for bonding optical components, adhesives for bonding optical disks, adhesives for mounting printed wiring boards, die bonding adhesives, adhesives for semiconductors such as underfills, underfills for reinforcing BGAs, and mounting adhesives such as anisotropic conductive films and anisotropic conductive pastes.

[0263] Below, we will explain some representative products by giving examples.

[0264] 1. Semiconductor encapsulation materials As a method for obtaining a semiconductor encapsulation material from the resin composition of the present invention, the resin composition, the curing accelerator, and compounding agents such as inorganic fillers are melt-mixed sufficiently until homogeneous using an extruder, kneader, roll, etc. as necessary. In this case, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulation material for power transistors and power ICs, it is preferable to use highly filled crystalline silica, alumina, silicon nitride, etc., which have a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc. The filling rate is preferably in the range of 30 to 95 mass% per 100 parts by mass of the curable resin composition, and among them, in order to improve flame retardancy, moisture resistance, and solder crack resistance and to reduce the linear expansion coefficient, it is more preferable that the inorganic filler is 70 parts by mass or more, and even more preferable that the inorganic filler is 80 parts by mass or more.

[0265] 2. Semiconductor Devices The semiconductor package molding for obtaining a semiconductor device from the curable resin composition of the present invention can be carried out by molding the semiconductor encapsulating material using a casting machine, a transfer molding machine, an injection molding machine or the like, and then heating the molded product at 50 to 250°C for 2 to 10 hours.

[0266] 3. Printed Circuit Boards A method for obtaining a printed circuit board from the composition of the present invention includes laminating the above prepreg by a conventional method, appropriately overlaying copper foil, and heat-pressing the laminate at 170 to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0267] 4. Flexible board The method for producing a flexible substrate from the crosslinkable resin composition of the present invention includes a method comprising the following three steps: The first step is to apply the crosslinkable resin composition containing a resin component, an organic solvent, etc., to an electrical insulating film using a coater such as a reverse roll coater or a comma coater, the second step is to heat the electrical insulating film to which the crosslinkable resin composition has been applied at 60 to 170°C for 1 to 15 minutes using a heater to volatilize the solvent from the electrical insulating film and to bring the crosslinkable resin composition to a B-stage, and the third step is to thermocompress (preferably a compression pressure of 2 to 200 N / cm and a compression temperature of 40 to 200°C) a metal foil to an adhesive on the electrical insulating film to which the crosslinkable resin composition has been brought to a B-stage using a heating roll or the like. If sufficient adhesive performance is obtained by going through the above three steps, the process may be terminated here, but if complete adhesive performance is required, it is preferable to further post-cure under conditions of 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.

[0268] 5. Build-up board The method for obtaining a build-up board from the composition of the present invention includes, for example, the following steps. First, the above composition, which is appropriately blended with rubber, filler, etc., is applied to a circuit board on which a circuit is formed by using a spray coating method, a curtain coating method, etc., and then cured (step 1). Then, if necessary, a predetermined through-hole portion or the like is drilled, treated with a roughening agent, and the surface is washed with hot water to form unevenness, and a metal such as copper is plated (step 2). These operations are repeated as desired, and a resin insulating layer and a conductor layer of a predetermined circuit pattern are alternately built up to form the build-up (step 3). Note that the through-hole portion is drilled after the formation of the outermost resin insulating layer. In addition, the build-up board of the present invention can also be produced by forming a roughened surface by heating and pressing the resin-coated copper foil, which is obtained by semi-curing the resin composition on the copper foil, on a wiring board on which a circuit is formed, at 170 to 300 ° C., thereby omitting the steps of forming a roughened surface and plating.

[0269] 6. Build-up film A build-up film can be obtained from the composition of the present invention by applying the composition to the surface of a support film (Y) as a substrate, and then drying the organic solvent by heating or blowing hot air or the like to form a layer of the composition (X).

[0270] As the organic solvent used here, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosolve, butyl carbitol, etc., aromatic hydrocarbons such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and it is also preferable to use them in a proportion such that the nonvolatile content is 30 to 60 mass%.

[0271] The thickness of the layer (X) formed is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The layer (X) of the composition in the present invention may be protected with a protective film described below. By protecting the layer with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin composition layer and prevent scratches.

[0272] The above-mentioned support film and protective film may be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a matte treatment, a corona treatment, or a release treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0273] The support film (Y) is peeled off after laminating it 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, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0274] A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, when the layer (X) is protected with a protective film, the protective film is peeled off, and then the layer (X) is laminated, for example, by a vacuum lamination method, on one or both sides of the circuit board so as to be in direct contact with the circuit board. The lamination method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably performed under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0275] 7.Conductive paste A method for obtaining a conductive paste from the composition of the present invention includes, for example, dispersing conductive particles in the composition. The conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used. EXAMPLES

[0276] The present invention will now be described in detail with reference to examples and comparative examples, in which "parts" and "%" are by weight unless otherwise specified, and the present invention is not limited thereto.

[0277] 1H and 13 C-NMR, FD-MS spectrum, and GPC were measured under the following conditions.

[0278] 1 H-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 600MHz Number of times: 32 Solvent: CDCl3, DMSO-d6 Sample concentration: 30% by mass

[0279] 13 C-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 150MHz Number of times: 320 Solvent: DMSO-d6 Sample concentration: 30% by mass

[0280] FD-MS: JEOL Ltd. "JMS-T100GC AccuTOF" Measurement range: m / z=50.00~2000.00 Rate of change: 25.6mA / min Final current value: 40mA Cathode voltage: -10kV

[0281] GPC: Tosoh Corporation "HLC-8320GPC" Column: Tosoh Corporation "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" Detector: RI (Differential Refractometer) Measurement conditions: 40℃ Mobile phase: Tetrahydrofuran Flow rate: 1ml / min Standard: Tosoh Corporation "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F"

[0282] The epoxy equivalent of the synthesized epoxy resin was measured according to JIS K7236, and the epoxy equivalent (g / eq) was calculated.

[0283] The number of repeating units can be calculated, for example, from the results of GPC molecular weight measurement, or various appropriate instrumental analyses such as FD-MS and NMR.

[0284] Synthesis Example 1 151g (1.0 mol) of 4-hydroxyacetanilide, 300g of acetone, and 166g (1.2 mol) of potassium carbonate were charged in a flask equipped with a thermometer and a stirrer, and the temperature was raised to the reflux temperature. Then, 144g (1.2 mol) of allyl bromide was dropped and reacted for another 7 hours. The mixture was cooled to room temperature, the potassium carbonate was removed by filtration, and the acetone and excess allyl bromide in the filtrate were distilled off under reduced pressure using an evaporator. The obtained solid was dissolved in 222g of ethanol, 417g (4.0 mol) of 35% aqueous hydrochloric acid was dropped, and the mixture was reacted at 60 to 65°C for 12 hours. After cooling to room temperature, the mixture was neutralized with 880g (4.4 mol) of 20% aqueous sodium hydroxide solution, and separated three times with 373g of ethyl acetate. The organic layer was dehydrated with sodium sulfate, and then ethyl acetate was distilled off under reduced pressure using an evaporator to obtain 113 g (0.76 mol, yield 76%) of 4-allyloxyaniline.

[0285] [ka]

[0286] 82g (0.84 mol) of maleic anhydride was added to a flask equipped with a thermometer and a stirrer, and dissolved in 1590g of toluene and 9.0g of DMF. While keeping the temperature below 10°C in an ice bath, 113g (0.76 mol) of 4-allyloxyaniline dissolved in 150g of DMF was added dropwise, and the mixture was reacted at 25°C for 2 hours. Subsequently, 10g of 95% sulfuric acid was added, and the mixture was reacted at 110°C for 5 hours, after which the toluene was distilled off under reduced pressure. 1200g of ethyl acetate was added and separated three times, and then separated twice with a 2% aqueous sodium bicarbonate solution. The organic layer was dehydrated with sodium sulfate, and the ethyl acetate was distilled off under reduced pressure using an evaporator to obtain 150g (0.66 mol, yield 87%) of N-allyloxyphenylmaleimide.

[0287] [ka]

[0288] In a flask equipped with a thermometer and a stirrer, 150g (0.66 mol) of N-allyloxyphenylmaleimide and 3390g of dichloromethane were charged and dissolved. While keeping the temperature below 10°C in an ice bath, 1200g of m-chlorobenzoic acid was added dropwise, and then the mixture was reacted at room temperature for 72 hours. After neutralization with 402g of saturated aqueous sodium hydrogen carbonate solution, 403g of saturated aqueous sodium sulfite solution was added dropwise. After removing the water layer, the mixture was separated three times with 2% aqueous sodium hydrogen carbonate solution and four times with water. After dehydrating the organic layer with sodium sulfate, dichloromethane was distilled off under reduced pressure using an evaporator to obtain 60g (0.24 mol, yield 37%) of a brown solid. The epoxy equivalent was 299. 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).

[0289] [ka]

[0290] Synthesis Example 2 In a flask equipped with a thermometer and a stirrer, 445g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase Chemtex's "Denacol EX-991L": epoxy equivalent 445g / eq) and 76g (0.33 mol) of bisphenol A (hydroxyl equivalent 114g / eq) were added, and the temperature was raised to 140°C over 30 minutes, after which 2.6g of 4% aqueous sodium hydroxide solution was added. The temperature was then raised to 150°C over 30 minutes, and the mixture was further reacted at 150°C for 7 hours. Subsequently, 61g (0.32 mol) of 2-hydroxyanthracene was added and reacted at 150°C for 12 hours to obtain anthracene compound (A-1). The compound showed a peak of M+=1454, which corresponds to the theoretical structure of m1=1 and n1=4 in the following formula, in the mass spectrum, and the production of the target compound was confirmed.

[0291] [ka]

[0292] Example 1 110g (0.37 mol) of glycidyloxyphenylmaleimide obtained in Synthesis Example 1, 2620g of methyl isobutyl ketone, and 2620g of toluene were added to 582g of the anthracene compound of Synthesis Example 2 in a flask equipped with a thermometer and a stirrer, and reacted at 80°C for 17 hours to obtain a Diels-Alder reaction product (D-1). The epoxy equivalent was 1843. The compound showed a peak of M+=1944 in the mass spectrum, which corresponds to the theoretical structure of m1=1 and n1=4 in the following formula, and the production of the target compound was confirmed.

[0293] [ka]

[0294] Synthesis Example 3 In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 38.8g (0.20 mol) of 9-anthrone was added to 180ml of dimethylacetamide to form a slurry while immersing it in an ice-water bath under a nitrogen atmosphere, and 110g (0.22 mol) of 8.09% aqueous sodium hydroxide solution was added thereto. Then, 27.7g (0.20 mol) of epibromohydrin dissolved in 40ml of dimethylacetamide was added dropwise. After stirring for 1 hour, the ice-water bath was removed, 70g of water was added, and the precipitated solid was filtered and dried under reduced pressure to obtain 23.6g of solid (yield 47%). 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).

[0295] [ka]

[0296] Example 2 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 Daiwa Kasei Kogyo Co., Ltd.), 62.5 g of methyl isobutyl ketone, and 62.5 g of toluene were charged, and after nitrogen replacement, 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 distilled off under reduced pressure at 50 ° C. Then, the mixture was dried under reduced pressure at 80 ° C., and 34.1 g of Diels-Alder reaction product (D-2) was obtained. The epoxy equivalent of the obtained Diels-Alder reaction product (D-2) was 438 g / eq. This Diels-Alder reaction product (D-2) had a peak of M + = 819 in the mass spectrum, and the production of the target compound was confirmed.

[0297] [ka]

[0298] Example 3 The reaction was carried out in the same manner as in Example 2, except that 6.6 g (0.02 mol) of 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM manufactured by Daiwa Chemical Industry Co., Ltd.) was replaced with 7.4 g (0.02 mol) of 4,4'-diphenylmethane bismaleimide (BMI-1000 manufactured by Daiwa Chemical Industry Co., Ltd.), and 34.3 g of Diels-Alder reaction product (D-3) was obtained. The epoxy equivalent of the obtained Diels-Alder reaction product (D-3) was 495 g / eq. This Diels-Alder reaction product (D-3) gave a peak of M+=859 in the mass spectrum, and the production of the target compound was confirmed.

[0299] [ka]

[0300] Synthesis Example 4 According to a previous report (Scientific Reports, 10(1), 20214(2020)), the anthracene modified product (A-3) having the following structure was synthesized.

[0301] [ka]

[0302] Example 4 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 Daiwa Kasei Kogyo Co., Ltd.), and 169.4 g of methyl isobutyl ketone were charged, and after nitrogen replacement, the mixture was reacted at 110 ° C for 7 hours. Thereafter, the temperature was raised to 150 ° C, and 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. This Diels-Alder reaction product (D-4) had a peak of M + = 847 in the mass spectrum, and the production of the target compound was confirmed.

[0303] [ka]

[0304] Synthesis Example 5 According to a previous report (Polymer, 82, 319 (2016)), a disulfide bond-containing epoxy resin (S-1) with the following structure was synthesized.

[0305] [ka]

[0306] Synthesis Example 6 In a flask equipped with a thermometer and a stirrer, 445g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445g / eq) and 190g (0.76 mol) of 4,4'-dihydroxydiphenyl disulfide (hydroxyl equivalent 125g / eq) were added, and the temperature was raised to 140°C over 30 minutes, after which 3.2g of 4% aqueous sodium hydroxide solution was added. The temperature was then raised to 150°C over 30 minutes, and the reaction was continued at 150°C for 5 hours. Then, a neutralizing amount of sodium phosphate was added to obtain 635g of a hydroxy compound (S-2) represented by the following formula. The hydroxy compound showed a peak of M+=1424, which corresponds to the theoretical structure of m1=1 and n1=11 in the following formula, in the mass spectrum, and the production of the target compound was confirmed. 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.

[0307] [ka]

[0308] Example 5 In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 37.5g (0.025 mol) of the hydroxy compound (S-2) obtained in Synthesis Example 6, 750mL of DMF, 69g (0.5 mol) of potassium carbonate and 69g (0.5 mol) of epibromohydrin were added and dissolved while purging with nitrogen gas. After heating to 60°C, stirring was continued for 20 hours. After cooling to room temperature, potassium carbonate was removed by filtration, and 1000g each of water and chloroform were added and separated three times. The organic layer was dehydrated with sodium sulfate, and the solvent was distilled off under reduced pressure using an evaporator to obtain 37.5g of the epoxy compound (S-3) represented by the following structural formula. The epoxy equivalent of the obtained epoxy compound (S-3) was 806g / eq. The mass spectrum of this epoxy resin showed a peak of M+=1536, which corresponds to the theoretical structure of m1=1, n1=11 in the following formula, confirming the production of the target compound.

[0309] [ka]

[0310] Synthesis Example 7 210g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthetic Co., Ltd.: epoxy equivalent 210g / eq) and 145g (0.58 mol) of 4,4'-dihydroxydiphenyl disulfide (hydroxyl equivalent 125g / eq) were added to a flask equipped with a thermometer and a stirrer, and the temperature was raised to 140°C over 30 minutes, after which 3.6g of 4% aqueous sodium hydroxide solution was added. The temperature was then raised to 150°C over 30 minutes, and the reaction was continued at 150°C for 5 hours. Thereafter, a neutralizing amount of sodium phosphate was added to obtain 355g of a hydroxy compound (S-4) represented by the following formula. The hydroxy compound showed a peak of M+=814 corresponding to the theoretical structure in the following formula in the mass spectrum, confirming the production of the target compound. The hydroxy compound (S-4) had a hydroxyl equivalent of 1076g / eq calculated from GPC.

[0311] [ka]

[0312] Example 6 In a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 53.8 g (0.025 mol) of the hydroxy compound (S-4) obtained in Synthesis Example 7, 750 mL of DMF, 69 g (0.5 mol) of potassium carbonate, and 69 g (0.5 mol) of epibromohydrin were added and dissolved while purging with nitrogen gas. After heating to 60°C, stirring was continued for 20 hours. After cooling to room temperature, potassium carbonate was removed by filtration, and 1000 g each of water and chloroform were added and separated three times. After dehydrating the organic layer with sodium sulfate, the solvent was distilled under reduced pressure using an evaporator to obtain 53.8 g of an epoxy compound (S-5) represented by the following structural formula. The epoxy equivalent of the obtained epoxy compound (S-5) was 1020 g / eq. The epoxy resin had a peak of M+=926 corresponding to the theoretical structure in the mass spectrum, and the production of the target compound was confirmed.

[0313] [ka]

[0314] Synthesis Example 8 A flask equipped with a thermometer and a stirrer was charged with 445g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445g / eq) and 171g (0.75 mol) of bisphenol A (hydroxyl equivalent 114g / eq), and the temperature was raised to 140°C over 30 minutes, after which 3.1g of 4% aqueous sodium hydroxide solution was added. The temperature was then raised to 150°C over 30 minutes, and the mixture was further reacted at 150°C for 16 hours. A neutralizing amount of sodium phosphate was then added to obtain 616g of a hydroxy compound represented by the following formula (Ph-1). The hydroxy compound was confirmed to contain a PTMG (polytetramethylene ether glycol) type (BPA: bisphenol A) hydroxy compound, since a peak of M+=1380 corresponding to the theoretical structure of m1=1 and n1=11 in the following formula was obtained in the mass spectrum. 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.

[0315] [ka]

[0316] Synthesis Example 9 In a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 200 g of the hydroxy compound Ph-1 obtained in Synthesis Example 5, 437 g (4.72 mol) of epichlorohydrin and 118 g of n-butanol were added and dissolved while purging with nitrogen gas. After heating to 65°C, the pressure was reduced to an azeotropic pressure, and 6.66 g (0.08 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Next, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropy was separated using a Dean-Stark trap, the water layer was removed, and the oil layer was returned to the reaction system while the reaction was continued. After that, the unreacted epichlorohydrin was distilled off by vacuum distillation. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 10 g of a 10% aqueous solution of sodium hydroxide was added to this solution, and the mixture was reacted at 80° C. for 2 hours, after which the mixture was washed three times with 50 g of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after microfiltration, 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. The epoxy resin Ep-1 was confirmed to contain a PTMG type (BPA) epoxy resin, since a peak of M+=1492 was obtained in the mass spectrum, which corresponds to the theoretical structure of m1=1, n1=11, q=1, p1=0, and p2=0 in the following formula.

[0317] [ka]

[0318] Preparation of composition and cured product A curable resin composition was obtained by mixing each compound uniformly in a mixer (Thinky Corporation's "Awatori Rentaro ARV-200") according to the formulations in Tables 1 and 2 (the numbers in the tables are by weight). This curable resin composition was sandwiched between aluminum mirror plates (Engineering Test Service Corporation's "JIS H 4000 A1050P") using a silicon tube as a spacer, and heat curing was performed under specified conditions to obtain a cured product with a thickness of 0.7 mm.

[0319] <Remolding test> The prepared hardened product was freeze-pulverized. 0.07 g of the pulverized hardened product was placed in a 10 mm square, 0.5 mm thick mold and vacuum-pressed under specified conditions. The appearance of the obtained hardened product was visually observed. The evaluation criteria were as follows: A: The seams disappeared and the hardened material became one piece. B: Some of the seams are visible to the naked eye, but the hardened material has become one piece. C: It had a solidified shape and broke apart when light pressure was applied.

[0320] <Repair Test> The cured product was cut with a razor, the resulting fractured surfaces were brought into contact with each other, and then aged in a dryer at 150°C for 24 hours. After removing from the dryer, the cut surfaces of the cured products were visually inspected for adhesion. The criteria for evaluation were as follows: A: The bond does not come apart even when the cured product is bent 90 degrees. B: The material is bonded, and when the hardened material is bent, the bond comes apart. C: No bonding.

[0321] [Table 1]

[0322] [Table 2]

[0323] EPICLON850-S: BPA-type liquid epoxy resin, epoxy equivalent 188g / eq DICY: Dicyandiamide DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea

Claims

1. A glycidyl ether group-containing compound comprising a structural unit A having one or more glycidyl ether groups and a structural unit B different from A, linked in an A-B-A manner, wherein the structural unit A and the structural unit B are connected by a disulfide bond which is a reversible bond with a dissociation temperature of 120°C or higher, and the glycidyl ether group-containing compound represented by the following general formula (2). 【Chemistry 1】 [In formula (2), each Ar independently contains an unsubstituted or substituted aromatic ring, n is the average value of the number of repeats and ranges from 0 to 10, Z ４ The structure is one of the structures represented by the following formulas (6) or (7), and each of the multiple structures in a single molecule may be the same or different. G is a glycidyl group or a 2-methylglycidyl group. 【Chemistry 2】 【Transformation 3】 In formulas (6) and (7), R 1 , R ２ Each of the following is independently a hydrogen atom, a methyl group, or an ethyl group; R' is a divalent hydrocarbon group with 2 to 12 carbon atoms; n1 is an integer from 2 to 16; and n2 is the average value of the repeating units, from 2 to 30. [* represents a bond point]

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

3. The glycidyl ether group-containing compound according to claim 2, wherein the alkylene chain has 4 to 16 carbon atoms.

4. The glycidyl ether group-containing compound according to claim 1, wherein the molecular weight per reversible disulfide bond is in the range of 300 to 10,000.

5. A glycidyl ether group-containing compound according to claim 1, which is represented by any of the following general formulas. 【Chemistry 4】 (In the formula, G, n, n1, n2, and R' are the same as described above.)

6. A curable resin composition comprising a glycidyl ether group-containing compound according to any one of claims 1 to 5 and a compound (I) that is reactive with the glycidyl ether group-containing compound as essential components.

7. The curable resin composition according to claim 6, wherein the compound (I) that is reactive with the glycidyl ether group-containing compound is dicyandiamide or diaminodiphenyl sulfone.

8. Furthermore, the curable resin composition according to claim 6, comprising an epoxy resin having an epoxy equivalent of 100 to 10,000 g / eq, other than the glycidyl ether group-containing compound described in any one of claims 1 to 5.

9. The curable resin composition according to claim 6, wherein the concentration of reversible bonds relative to the total mass of curable components in the curable resin composition is 0.10 mmol / g or more.

10. A curable resin composition according to claim 6, wherein the curable resin composition is a self-healing composition or a composition for remolding materials.

11. A cured product obtained by curing the curable resin composition according to claim 6.

12. A laminate comprising a base material and a layer containing the cured product described in claim 11.

13. A heat-resistant member containing the cured product described in claim 11.

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