Hydrogenated acid group-containing compound, curable resin composition, cured product, and laminate

Abstract

Provided are: a compound which, while being a curable resin, can easily exhibit recoverability / re-moldability when being in the form of a cured product; a curable resin composition obtained using same; and a cured product thereof. Used in the present invention is a hydroxyl group-containing compound characterized in that: a structural unit A having one or more hydroxyl groups and a structural unit B that is different from the structural unit A are linked in the form A-B-A; and the structural unit A and the structural unit B are bonded by a reversible bond having a dissociation temperature of 120ºC or higher. This reversible bond is preferably an addition type structure formed by an anthracene type Diels-Alder reaction or a disulfide bond held between aromatic rings.

Description

[Technical Field]

[0001] The present invention relates to a hydroxyl 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, and adhesive properties, making them indispensable materials in a variety of fields, including electrical and electronic applications, 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 epoxy resin deteriorates due to oxidation, cracks may occur.

[0004] Furthermore, the cured products obtained by hardening thermosetting resins such as epoxy resins cannot be dissolved in solvents (are insoluble) and are insoluble even at high temperatures (are infusible), making them difficult to recycle or reuse. As a result, the cured products become waste after use, and therefore reducing waste and mitigating the burden on the environment has become a challenge.

[0005] Therefore, there is a need to solve the problems of extending the lifespan and reducing waste for cured products made from epoxy resins and other materials, and it is thought that giving the cured products the ability to be easily dismantled, repaired, and remolded would be an effective way to solve these problems.

[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 after use, the adhesive strength is reduced by applying a certain amount of heat, making the adhesive dismantlable (see, for example, Patent Document 1).

[0007] Furthermore, 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 second thermosetting resin precursor (see, for example, Patent Document 2).

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

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-256557 [Patent Document 2] Japanese Patent Application Publication No. 2017-041496 Summary of the Invention [Problem to be solved by the invention]

[0010] In the technology provided in Patent Document 1, the adhesive is discarded after disassembly, and although the substrate to be bonded is recyclable, there is a problem of insufficient recyclability overall. Furthermore, the technology in Patent Document 2 has a certain degree of self-repairing ability, but it is not a solution from the perspective of reuse, and the problem of waste when it is no longer needed remains. Furthermore, since the raw materials used in the reversible bonding must ensure their molecular mobility, there is a problem that the raw materials used are limited to gel-like substances with poor mechanical strength. Improvements are currently required in both areas. Therefore, the object of the present invention is to provide a compound that is a curable resin but can easily achieve repairability and remoldability in the cured product, as well as a curable resin composition and a cured product thereof made therefrom. [Means for solving the problem]

[0011] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by using a hydroxyl group-containing compound having a specific structure as a curable resin composition, and have completed the present invention.

[0012] That is, the present invention includes the following aspects. [1] A hydroxyl group-containing compound comprising a structural unit A having one or more hydroxyl groups and a structural unit B different from A, linked via ABA, 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 hydroxyl group-containing compound according to [1], wherein the reversible bond is a covalent reversible bond. [3] The hydroxyl group-containing compound according to [1] or [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, all of which have a dissociation temperature of 120°C or higher. [4] The hydroxyl group-containing compound according to any one of [1] to [3], wherein the reversible bond is an anthracene-type Diels-Alder addition structure or a disulfide bond sandwiched between aromatic rings. [5] The hydroxyl 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 hydroxyl group-containing compound according to [5] above, wherein the alkylene chain has 4 to 16 carbon atoms. [7] The hydroxyl 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 that is the linking site between the structural unit A and the structural unit B and has a dissociation temperature of 120°C or higher. [8] A hydroxyl group-containing compound represented by the following general formula:

[0013] [ka]

[0014] [Each Ar in formula (2) is independently a structure containing an unsubstituted or substituted aromatic ring, 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 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 the formula, ma is an integer of 1 to 10, and n is the average number of repeating groups, 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 a plurality of such structures in one molecule may be the same or different.

[0015] [ka] [The aromatic ring in formula (3) may be substituted or unsubstituted, and * represents the point of attachment. The hydroxyl group on the naphthalene ring in the formula may be attached to any position.]

[0016] [ka]

[0017] [In formula (4), Ar each independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R is a hydrogen atom or a methyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; n1 is an integer of 2 to 16, 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 a number from 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 the repetitions, each independently ranging from 0 to 25, and m1+m2≧1. However, the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be bonded randomly or in blocks, 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 the average numbers of repeats, 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 hydroxyl group-containing compound according to any one of [1] to [8] above and a compound (I) reactive with the hydroxyl group-containing compound.

[10] The curable resin composition according to [9], wherein the concentration of reversible bonds in the hydroxyl group-containing compound relative to the total mass of the curable components in the curable resin composition is 0.10 mmol / g or more.

[11] The curable resin composition according to [9] or

[10] , wherein the compound (I) reactive with the hydroxyl group-containing compound is an epoxy resin.

[12] The curable resin composition according to

[11] , further comprising a curing agent for epoxy resins other than the hydroxyl group-containing compound.

[13] The curable resin composition according to

[11] or

[12] , wherein the epoxy resin is represented by the following formula (8) and has an epoxy equivalent of 500 to 10,000 g / eq:

[0024] [ka] [In formula (8), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, X' is a structural unit represented by the following general formula (8-1), and Y' is a structural unit represented by the following general formula (8-2):

[0025] [ka]

[0026] [In the formulas (8-1) and (8-2), Ar is the same as defined above, R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; R 3 , R 4 , R 7 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, 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 are each independently 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 a number from 0 to 5; q is 0.5 to 5. However, the bond between X' represented by the general formula (8-2) and Y' represented by the general formula (8-3) may be random or block, and the total number of the structural units X' and Y' present in one molecule is m3 and m4, respectively.

[0027]

[14] The curable resin composition according to

[13] , wherein the epoxy resin is represented by the following formula (9):

[0028] [ka] [In formula (9), p1, p2, q, and m4 are average values ​​of the repetitions, and p1 is 0 to 5, p2 is 0 to 5, q is 0.5 to 5, and m4 is 0 to 25, respectively.]

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

[14] , wherein the curable resin composition is a self-repairing composition or a remolding material composition.

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

[14] above.

[17] A laminate having a substrate and a layer containing the cured product described in

[16] .

[18] A heat-resistant member containing the cured product according to

[16] above.

[19] A conjugated diene intermediate or a dienophile intermediate represented by the following general formula (1-1)' or (1-2)'.

[0029] [ka] [In the formula, n, Z 2 , Z 3 is the same as above.]

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

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

[22] A cured product obtained by curing the essential raw materials, which are the compound of the formula (1-2)', an anthracene having a hydroxyl group, and a compound (I) reactive with the hydroxyl group-containing compound. [Effects of the Invention]

[0030] According to the present invention, it is possible to impart repairability and remoldability to a cured product made from a curable resin composition, which can contribute to extending the life of the cured product itself and reducing waste. DETAILED DESCRIPTION OF THE INVENTION

[0031] 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 design changes, improvements, etc. may be made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention.

[0032] A hydroxyl group-containing compound according to one embodiment of the present invention is a hydroxyl group-containing compound formed by linking a structural unit A having one or more hydroxyl groups and a structural unit B different from A 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.

[0033] With this structure, the hydroxyl group-containing compound is incorporated into the crosslinked structure through a curing reaction based on its hydroxyl group. On the other hand, because the cured product remains reversible, structural unit B, in particular, can exist away from the crosslinked structure, resulting in high molecular mobility even in the cured product. Therefore, when the cured product is subjected to impact, cracks occur, or is crushed, the reversible bond is easily broken at the reversible bond. On the other hand, the reversible bond can be reversibly reformed even at low temperatures, including room temperature, thereby exhibiting functions such as repairability and reshapeability. Because structural unit B exists away from the crosslinked structure, it exhibits particularly high molecular mobility, demonstrating low-temperature repairability and low-temperature reshapeability. For example, even when a cured product made using the hydroxyl 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 low temperatures, including room temperature, or under heated or heated conditions. Furthermore, the cured product can also be crushed and then reshaped based on the reversible bond.

[0034] The reversible bond having a dissociation temperature of 120°C or higher may be a covalent bond or a non-covalent bond, with a covalent bond being preferred from the viewpoint of durability of the cured product, while a non-covalent bond is preferred from the viewpoint of short recovery time and remolding time after crushing the cured product.

[0035] The covalent bond system is not particularly limited, and examples thereof include an addition structure formed by a Diels-Alder reaction, a disulfide bond, an ester bond, a 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 these, from the viewpoint of the heat resistance and hydrolysis resistance of the cured product, an addition structure formed by a Diels-Alder reaction of an anthracene type (a reversible bond consisting of an anthracene structure and a maleimide structure) and a disulfide bond sandwiched between aromatic rings are preferred.

[0036] 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 thioureas.

[0037] To introduce the anthracene-type Diels-Alder reaction 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 it is a simple manufacturing method. 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 moiety in the following formula in the maleimide-derived structure or various reactive functional groups on the ring of the anthracene-derived structure.

[0038] [ka]

[0039] In the Diels-Alder reaction, a conjugated diene and a parent diene undergo an addition reaction to form a six-membered ring. Because the Diels-Alder reaction is an equilibrium reaction, a Retro-Diels-Alder reaction occurs at a certain temperature, resulting in dissociation (decrosslinking). If the temperature at which the Retro-Diels-Alder reaction occurs (dissociation temperature) is low, decrosslinking occurs in a high temperature range, resulting in a decrease in the crosslink density of the cured product and a decrease in mechanical strength. Therefore, in the present invention, a combination of Diels-Alder reaction units with a dissociation temperature of 120°C or higher and high thermal stability is required. 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 around 200°C, maintaining the crosslinked structure and exhibiting excellent thermal stability. This prevents a decrease in the crosslink density of the cured product and maintains good mechanical strength. Furthermore, if the resulting cured product is subjected to mechanical energy such as scratches or external force, the C-C bond of the Diels-Alder reaction unit will be preferentially broken because the bond energy of the C-C bond is lower than that of a normal covalent bond. However, at temperatures lower than the dissociation temperature, the equilibrium of the C-C bond of the Diels-Alder reaction unit shifts toward the bond, forming an adduct (Diels-Alder reaction unit) again, which is thought to enable repair of scratches and remolding.

[0040] Examples of compounds containing disulfide bonds include the compounds shown below. Similarly, by bonding various compounds to sites other than the disulfide bond sites, such as hydroxyl groups, amino groups, or vinyl groups, it is possible to incorporate disulfide bond sites into hydroxyl group-containing compounds. As described above, even at these disulfide bond sites, when the cured product is cut by external force, the disulfide bond is preferentially broken. However, at temperatures below the dissociation temperature, the equilibrium shifts toward the bond, and SS bonds are formed again, allowing the damage to be repaired and the product to be reshaped.

[0041] [ka]

[0042] [ka]

[0043] Examples of the compound containing the alkoxyamine skeleton include the compounds shown below. As described above, by bonding to another compound via the terminal vinyl group (methacryloyl group), it becomes possible to incorporate a reversible bond into the hydroxyl group-containing compound.

[0044] [ka]

[0045] The aforementioned reversible bond will be present at at least two places in the target hydroxyl 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 structural unit B also has multiple reversible bonds of the same type as the reversible bond between A and B.

[0046] For the same reasons as above, the molecular weight of the structural unit B is preferably at least a certain size, and for example, its 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. Note that the structural unit B may have a crosslinkable functional group similar to the hydroxyl group in the structural unit A, but from the viewpoint of more easily achieving the effects of the present invention, it is preferable that the structural unit B does not have a crosslinkable (curable) functional group.

[0047] In order to enable the cured product to exhibit greater flexibility or better conformability to the substrate when the hydroxyl 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 thereof is preferably in the range of 2 to 30.

[0048] The hydroxyl group in the structural unit A may be alcoholic or aromatic as long as it can easily react with other functional groups. For example, when combined with an epoxy resin described below to form a curable resin composition, an aromatic hydroxyl group is generally preferred. The number of hydroxyl groups in the structural unit A is not particularly limited, but is preferably in the range of 1 to 3, more preferably 1 to 2, from the viewpoints of industrial availability of raw materials and ease of adjusting the crosslink density when formed into a cured product.

[0049] The average molecular weight (Mw) of the hydroxyl group-containing compound is not particularly limited, but from the viewpoint of achieving both mechanical strength, flexibility, and repairability / reformability in a cured product, it is preferably 500 or more and preferably 50,000 or less. Furthermore, when there are multiple 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 10,000 from the viewpoint of the reformability of the cured product.

[0050] The hydroxyl group-containing compound according to one embodiment of the present invention is a compound represented by the following general formula:

[0051] [ka]

[0052] In formula (2), Ar each independently represents a structure containing an unsubstituted or substituted aromatic ring, 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 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 the formula, ma is an integer of 1 to 10, and n is the average number of repeating groups, 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 a plurality of such structures in one molecule may be the same or different.

[0053] [ka] [The aromatic ring in formula (3) may be substituted or unsubstituted, and * represents the point of attachment. The hydroxyl group on the naphthalene ring in the formula may be attached to any position.]

[0054] [ka]

[0055] [In formula (4), Ar each independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R is a hydrogen atom or a methyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; n1 is an integer of 2 to 16, 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 a number from 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),

[0056] [ka]

[0057] [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 the repetitions, each independently ranging from 0 to 25, and m1+m2≧1. However, the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be bonded randomly or in blocks, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively.

[0058] [ka]

[0059] In formula (5), n3 and n5 are the average values ​​of the 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.

[0060] [ka]

[0061] [ka] [In formulas (6) and (7), R 1 , R 2 , R', n1, and n2 are the same as above.]

[0062] The general formulas (1-1) and (1-2) have a reversible bond formed between an anthracene structure and a maleimide structure at the end of the molecule. The terminal maleimide structure in general formula (1-1) and the terminal anthracene structure in general formula (1-2) have one or more Z1 structures represented by general formula (3), and this hydroxyl group contributes to the curing reaction in the curable resin composition described below. ma is the number of Z1 in the anthracene-derived structure and is an integer of 1 to 10. From the viewpoints of industrial availability of raw materials and ease of control of the curing reaction, ma is preferably in the range of 1 to 4, and more preferably 1 or 2.

[0063] The general formula (2) has a disulfide bond in the molecule, and the molecular terminal has a structure containing an aromatic ring having one or more Z1, which is any structure represented by the general formula (3). This hydroxyl group contributes to the curing reaction in the curable resin composition described below.

[0064] In the formula, Z1 is an aromatic hydroxyl group or an alcoholic hydroxyl group represented by the general formula (3) above. Among these, those having the following structural formula are preferred from the viewpoints of availability of raw materials and reactivity.

[0065] [ka]

[0066] In the general formulas (1-1) and (1-2), the site linking the maleimide-derived structures is Z3, the site linking the anthracene-derived structures is Z2, and in the general formula (2), the site linking the oxygen atoms is Z4, which are any of the structures represented by the general formulas (4), (5), (6), and (7), respectively.

[0067] In the general formulae (1-1), (1-2) and (2), n is the average number of repeating units, and is 0 to 10, preferably 0 to 5.

[0068] In these structural formulas, Ar is an aromatic ring which may have a substituent, and is not particularly limited. Examples of aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Examples of substituents 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 this makes it easier to exhibit the effects of the present invention.

[0069] Among these, Ar preferably has any of the structures represented by the following structural formulas.

[0070] [ka] (The aromatic ring in the formula may be substituted or unsubstituted, and * represents the point of attachment.)

[0071] In addition, structures represented by the following formulas are also included as Ar.

[0072] [ka] (In the formula, the aromatic ring may be substituted or unsubstituted, n6=1 to 4, and * represents a point of attachment.)

[0073] The following structures are particularly preferred for Ar: * represents a bonding point.

[0074] [ka]

[0075] 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 tends to be elastic deformation. Furthermore, 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.

[0076] 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.

[0077] 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 hydroxyl group-containing compound and the crosslink density of the resulting cured product. It is preferably 2 to 25, and more preferably 4 to 20.

[0078] 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.

[0079] 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).

[0080] Examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups. Examples of alkenylene groups include vinylene, 1-methylvinylene, propenylene, butenylene, and pentenylene groups. Examples of alkynylene groups include ethynylene, propynylene, butynylene, pentynylene, and hexynylene groups. Examples of cycloalkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene groups. Examples of arylene groups include phenylene, tolylene, xylylene, and naphthylene groups.

[0081] Among these, ethylene, propylene, and tetramethylene groups are preferred from the viewpoint of the balance between the availability of raw materials, the viscosity of the resulting hydroxyl group-containing compound, and the flexibility of the cured product.

[0082] In the general formulas (4) and (4-2), R each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferred.

[0083] 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.

[0084] Furthermore, k1 in the general formula (4) is the average number of repetitions and is in the range of 0.5 to 5, preferably 0.5 to 2.

[0085] In the general formula (5), n3 and n5 are the average number of repeating units, 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. R ” is preferably a hydrogen atom.

[0086] 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.

[0087] Examples of the hydroxyl group-containing compound of the present invention include, but are not limited to, those shown below.

[0088] [ka]

[0089] [ka]

[0090] The method for producing the hydroxyl 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.

[0091] The general formulas (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).

[0092] The 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, resulting in a retro-Diels-Alder reaction.

[0093] Examples of the maleimide compound having the structure Z1 include any of the compounds listed in the following formulas. 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 ability. Among the monohydroxyphenylmaleimides, parahydroxyphenylmaleimide is particularly preferred in terms of heat resistance.

[0094] [ka]

[0095] Examples of the anthracene compound having the structure Z1 include any of the compounds listed in the following formulas: 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, cured product properties, and repairability and reshapeability.

[0096] [ka]

[0097] The structures of the maleimide compound and the anthracene compound 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. Furthermore, in the structures of the compounds listed in the above formulas, 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 further bonded to the carbon atoms thereof.

[0098] 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 optionally 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 resulting product can be obtained directly without purification by filtration or solvent distillation, or by a commonly used isolation and purification method such as recrystallization, reprecipitation, or chromatography.

[0099] The synthesis of the moieties other than the reversible bond can be performed by a known method. For example, a diglycidyl ether of an aliphatic dihydroxy compound or an aliphatic divinyl ether is reacted with an aromatic hydroxy compound to obtain a compound having a hydroxy group at the terminal, and then the compound is reacted with chloromethylanthracene, glycidyloxyanthracene, 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 hydroxy group as described above to obtain a compound represented by the general formula (1-1).

[0100] Alternatively, a compound having a terminal hydroxy group 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. Further, a Diels-Alder reaction is carried out with a maleimide compound having a hydroxy group as described above, thereby obtaining a compound represented by the general formula (1-1).

[0101] Alternatively, an aromatic dihydroxy compound may be reacted with a dihalogenated alkyl compound or a dihalogenated aralkyl compound to obtain a compound having a halogenated alkyl group at the terminal, which may then be reacted with hydroxymethylanthracene or the like to introduce an anthracene structure at the terminal. Furthermore, the compound may be subjected to a Diels-Alder reaction with a maleimide compound having a hydroxyl group, as described above, to obtain a compound represented by the general formula (1-1).

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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 in 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.

[0106] The aromatic hydroxy compound is not particularly limited, and examples thereof include dihydroxybenzenes such as hydroquinone, resorcinol, and catechol; trihydroxybenzenes such as pyrogallol, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene; triphenylmethane-type phenols such as 4,4',4"-trihydroxytriphenylmethane; dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; 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 suitable phenolic compounds include biphenols such as 4'-diol, alicyclic structure-containing phenols such as polyadducts of phenol and dicyclopentadiene and polyadducts of phenol and terpene compounds, naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane, and 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. Further examples include bifunctional phenolic compounds in which the aromatic nucleus of each of the above compounds is substituted with a methyl group, t-butyl group, or halogen atom. The alicyclic structure-containing phenolic compounds and the Xylok-type phenolic resins may contain not only bifunctional components but also trifunctional or higher functional components. These compounds may be used as is, or the bifunctional components may be isolated and used after purification using a column or other purification process.

[0107] Among these, bisphenols are preferred because they have 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 of their outstanding toughness-imparting properties.Furthermore, when importance is placed on the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

[0108] 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 1 / 1.1 to 1 / 3.0 (molar ratio).

[0109] The reaction of the diglycidyl ether of the aliphatic dihydroxy compound with the aromatic hydroxy compound is preferably carried out in the presence of a catalyst.Various catalysts can be used, including 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, bromides, and iodides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, and benzyltributylammonium, 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. Two or more of these catalysts may be used in combination. Among these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because they allow the reaction to proceed quickly and are highly effective in reducing the amount of impurities. 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.

[0110] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of organic solvents 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. The use of no solvent is preferred to rapidly carry out the reaction, while the use of dimethyl sulfoxide is preferred to reduce impurities in the final product.

[0111] The reaction temperature for the reaction is typically 50 to 180°C, and the reaction time is typically 1 to 10 hours. A reaction temperature of 100 to 160°C is preferred to reduce impurities in the final product. If the resulting compound exhibits significant coloration, an antioxidant or a reducing agent may be added to suppress this. The antioxidant is not particularly limited, but examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite 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.

[0112] After the reaction is complete, the reaction mixture may be neutralized or washed with water until the pH reaches 3 to 7, preferably 5 to 7. The neutralization and washing may be carried out 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 neutralization or washing, the solvent may be distilled off under reduced pressure and heating, if necessary, and the product may be concentrated to obtain the compound.

[0113] The reaction ratio of the aliphatic divinyl ether 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 1 / 1.02 to 1 / 3.0 (molar ratio).

[0114] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently without a catalyst, but a catalyst can be used appropriately to select the raw materials and increase the reaction rate. Examples of catalysts that can be used 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 wt.% based on the mass of the divinyl ether compound. In this case, it is preferable to select the type and amount of catalyst to avoid a nucleation reaction of the vinyl group to the aromatic ring.

[0115] The reaction between the aliphatic divinyl ether and the aromatic hydroxy compound can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of suitable organic solvents 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 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.

[0116] The reaction temperature when carrying out the reaction is usually 50 to 150° C., and the reaction time is usually 0.5 to 10 hours. In this case, the reaction is preferably carried out in an oxygen atmosphere to prevent self-polymerization of the vinyl ether group.

[0117] 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, thereby obtaining a compound.

[0118] The compound having a terminal hydroxyl group thus obtained is reacted with chloromethylanthracene or the like. 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. The catalyst is then removed by filtration, 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.

[0119] 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-hexadecane. Examples of the diglycidyl 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.

[0120] Among these, it is preferable to use dihydroxy compounds with a polyether structure or a linear alkylene chain having 12 to 14 carbon atoms, as this provides an excellent balance between flexibility and heat resistance of the resulting cured product, and it is most preferable to use polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,12-dodecanediol, 1,13-tridecanediol, or 1,14-tetradecanediol.

[0121] 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.

[0122] The dihalogenated aralkyl compound is not particularly limited, and examples thereof include dichloroxylene, dichloromethylbiphenyl, dibromoxylene, dibromomethylbiphenyl, etc., and these compounds may be used alone or in combination of two or more.

[0123] 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).

[0124] The reaction of the aromatic dihydroxy compound with the dihalogenated alkyl compound or dihalogenated aralkyl compound is preferably carried out in the presence of a catalyst. Various catalysts can be used, including alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and 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 these, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred because they promote rapid reaction and are highly effective in reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but is preferably 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 a solid.

[0125] The reaction of the aromatic dihydroxy compound with the alkyl dihalide compound or aralkyl dihalide compound can be carried out without a solvent or in the presence of an organic solvent. Usable organic solvents include, for example, 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.

[0126] The reaction temperature when carrying out the 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.

[0127] The compound having a halogenated alkyl group at the end obtained in this manner is reacted with hydroxymethylanthracene or the like. 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. The catalyst is then removed by filtration, 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 conjugated diene intermediate or dienophile intermediate before the Diels-Alder reaction can be represented by the following general formula (1-1)' or (1-2)'.

[0129] [ka] [In the formula, n, Z 2 , Z 3 is the same as above.]

[0130] The method for producing the compound having a disulfide bond as a reversible bond represented by the general formula (3) is not particularly limited.

[0131] The compounds that can be used as raw materials for the compound having a disulfide bond include the following:

[0132] [ka]

[0133] [ka]

[0134] The compound having a disulfide bond can be prepared by a known method. For example, a compound having this group is oxidatively bonded. Iodine, hydrogen peroxide, or the like is commonly used as an oxidizing agent. The compound is melted by heating or dissolved in a solvent and stirred at room temperature to 200°C for 1 to 24 hours. The compound can be obtained by filtration or solvent distillation without further purification, or by commonly used isolation and purification methods such as recrystallization, reprecipitation, and chromatography.

[0135] The hydroxyl group-containing compound of the present invention can be used in combination with a compound (I) reactive with the hydroxyl group-containing compound to form a curable resin composition, which can be suitably used in various electrical and electronic materials such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulation materials.

[0136] Examples of the compound (I) reactive with the hydroxyl group-containing compound include melamine compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, guanamine compounds, glycoluril compounds, urea compounds, resole resins, epoxy resins, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, hexamethylenetetramine and modified products thereof, and oxazoline compounds.

[0137] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound of hexamethylol melamine in which 1 to 6 methylol groups are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and a compound of hexamethylol melamine in which 1 to 6 methylol groups are acyloxymethylated.

[0138] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, a compound of tetramethylolguanamine in which 1 to 4 methylol groups are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, and a compound of tetramethylolguanamine in which 1 to 4 methylol groups are acyloxymethylated.

[0139] Examples of the glycoluril compound include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

[0140] Examples of the urea compound include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0141] Examples of the resole resin include polymers obtained by reacting a phenolic hydroxyl group-containing compound, such as phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, or dihydroxynaphthalene, with an aldehyde compound under alkaline catalytic conditions.

[0142] 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; 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 phenolic resin-type epoxy resins, and biphenyl-modified novolac type epoxy resins. These may be used alone or in combination of two or more types, 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.

[0143] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0144] Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.

[0145] Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0146] Examples of the acid anhydride include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4'-(isopropylidene)diphthalic anhydride, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

[0147] The concentration of the reversible bond in the curable resin composition of the present invention is preferably 0.10 mmol / g or more relative to the total mass of the curable components in the curable resin composition. This configuration further improves both the repairability and remoldability of the cured product obtained from the curable resin composition. 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. The concentration of the reversible bond in the present invention can be appropriately selected based on the glass transition temperature of the target cured product, defined by the tan δ peak top of a dynamic mechanical analyzer (DMA). 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 remoldability functions are likely to be exhibited even at the lower concentration end of the preferred range. On the other hand, if the glass transition temperature of the target cured product is above 100°C, these functions are likely to be exhibited at the higher concentration end of the preferred range. However, in the temperature range above the glass transition temperature measured by DMA, molecular mobility is generally high, and sufficient repairability and reshapeability functions are likely to be exhibited even if the concentration of the hydroxyl group-containing compound is low, so the effect of exhibiting repairability and reshapeability functions can be adjusted, for example, 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 reversible bonds is not limited to these.

[0148] As the compound (I) reactive with the hydroxyl group-containing compound, it is particularly preferable to use an epoxy resin, since this results in a curable resin composition that is excellent in curability and in the mechanical strength and heat resistance of the cured product.

[0149] The epoxy resin may be an epoxy resin represented by the following formula (8) and having an epoxy equivalent of 500 to 10,000 g / eq.

[0150] [ka] [In formula (8), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, X' is a structural unit represented by the following general formula (8-1), and Y' is a structural unit represented by the following general formula (8-2):

[0151] [ka]

[0152] [In the formulas (8-1) and (8-2), Ar is the same as defined above, R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; R 3 , R 4 , R 7 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, n1 is an integer from 2 to 16, n2 is the average number of repeating units and is between 2 and 30. R 11 , R 12 are each independently 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 a number from 0 to 5; q is between 0.5 and 5. However, the bond between X' represented by the general formula (8-2) and Y' represented by the general formula (8-3) may be random or block, and the total number of the structural units X' and Y' present in one molecule is m3 and m4, respectively.

[0153] The epoxy resin may be an epoxy resin represented by the following formula (9): By using such an epoxy resin, the effects of repairability and remoldability of the cured epoxy resin product are improved, and a good balance between flexibility and toughness is achieved.

[0154] [ka] [In formula (9), p1, p2, q, and m4 are average values ​​of the repetitions, and p1 is 0 to 5, p2 is 0 to 5, q is 0.5 to 5, and m4 is 0 to 25, respectively.]

[0155] The epoxy resin represented by the general formula (8) or (9) may be used alone in combination with the hydroxyl group-containing compound of the present invention to form a curable resin. However, from the viewpoint of imparting even greater 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.

[0156] The epoxy resins that can be used in combination are not limited in structure as long as they have an epoxy equivalent in the range of 100 to 300 g / eq. Examples 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, tetraphenylethane type epoxy resins; and dicyclopentasiloxane type epoxy resins. Examples of suitable epoxy resins include anthradiene-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, and biphenyl-modified novolac type epoxy resins. These may be used alone or in combination of two or more types, and it is preferable to select and use various types depending on the intended use, the physical properties of the cured product, etc.

[0157] 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, which have an epoxy equivalent of 100 to 300 g / eq.

[0158] The ratio of the epoxy resin represented by general formula (8) or (9) 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 balances the adhesiveness and stress relaxation ability of the cured product, exhibits high adhesive strength over a particularly wide temperature range, and has the effect of reducing the mold shrinkage rate before and after heat curing of the resin composition.

[0159] Furthermore, when the hydroxyl group-containing compound of the present invention is combined with an epoxy resin to prepare a curable resin composition, a curing agent for epoxy resins may be blended.

[0160] Examples of the curing agent that can be used here 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.

[0161] 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;

[0162] 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), etc.

[0163] Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, picoline, etc.;

[0164] Examples of the 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.

[0165] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0166] 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 adduct resins, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, Examples of polyhydric phenol compounds include tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked via bismethylene groups), aminotriazine-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via melamine, benzoguanamine, or the like), and alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0167] Examples of the amide compounds 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, or azelaic acid, or a carboxylic acid compound such as a fatty acid or dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain.

[0168] Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.

[0169] The thiol compound preferably contains two or more thiol groups in one molecule. 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-hexanedithiol, 1,10-decanedithiol, and the like.

[0170] When using these curing agents, only one type of curing agent may be used, or two or more types may be mixed. For applications such as underfill materials and general coating applications, it is preferable to use the amine-based compounds, carboxylic acid-based compounds, and / or acid anhydride-based compounds. For applications such as adhesives and flexible wiring boards, amine-based compounds, particularly dicyandiamide, are preferred in terms of workability, curability, and long-term stability. For applications as semiconductor encapsulation materials, solid phenol-based compounds are preferred in terms of the heat resistance of the cured product. For applications as batteries, aliphatic amines and thiol compounds are preferred in terms of low-temperature curing.

[0171] The amounts of epoxy resin and curing agent used are not particularly limited, but in terms of the good mechanical properties of the resulting cured product, it is preferable to use amounts such that the amount of active groups reactive with epoxy groups, including the hydroxyl group-containing cured product of the present invention, is 0.4 to 1.5 equivalents per equivalent of the total epoxy groups in the resin composition.

[0172] Furthermore, when an epoxy resin is used, a curing accelerator may be contained. Various curing accelerators can be used, including urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, 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 due to their excellent workability and low-temperature curing properties. When used as a semiconductor encapsulating material, triphenylphosphine is a preferred phosphorus compound, and 1,8-diazabicyclo[5.4.0]undecene is a preferred tertiary amine due to their excellent curability, heat resistance, electrical properties, and moisture resistance reliability.

[0173] 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.

[0174] 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 1-isopropylimidazole. 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 Imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole Examples include 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, and 1-benzyl-2-phenylimidazole hydrochloride.

[0175] Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

[0176] 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.

[0177] 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.

[0178] 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 used 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 per 100 parts by mass of the curable resin composition.

[0179] 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 suitable cyanate ester resins include tetraphenylethane-type cyanate ester resins, dicyclopentadiene-phenol addition reaction-type cyanate ester resins, phenol aralkyl-type cyanate ester resins, naphthol novolac-type cyanate ester resins, naphthol aralkyl-type cyanate ester resins, naphthol-phenol co-condensed novolac-type cyanate ester resins, naphthol-cresol co-condensed novolac-type cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolac-type cyanate ester resins, and anthracene-type cyanate ester resins. These may be used alone or in combination of two or more.

[0180] Among these cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, polyhydroxynaphthalene-type cyanate ester resins, naphthylene ether-type cyanate ester resins, and novolac-type cyanate ester resins are preferred in that they can give cured products with particularly excellent heat resistance, and dicyclopentadiene-phenol addition reaction-type cyanate ester resins are preferred in that they can give cured products with excellent dielectric properties.

[0181] Resins having a benzoxazine structure are 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 a dicyclopentadiene-phenol adduct resin, formalin, and aniline, a reaction product of phenolphthalein, formalin, and aniline, and a reaction product of diphenyl sulfide, formalin, and aniline. These may be used alone or in combination of two or more.

[0182] The active ester resin is not particularly limited, but compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester resin is preferably one 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. From the viewpoint of improving heat resistance, active ester resins obtained from a carboxylic acid compound or its halide and a hydroxy compound are preferred, and active ester resins obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound are more preferred. Examples of carboxylic acid compounds 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 phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-phenol adduct resins.

[0183] Specific examples of preferred active ester resins 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, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred in terms of their excellent ability to improve peel strength.

[0184] 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 phenolic resins, biphenyl-modified naphthol resins, aminotriazine-modified phenolic resins, and various vinyl polymers may be used in combination.

[0185] 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.

[0186] 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, as well as copolymers thereof.

[0187] Thermoplastic resins refer to resins that can be melt-molded by heating. Specific examples include polyethylene resins, polypropylene resins, polystyrene resins, rubber-modified polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-styrene (AS) resins, polymethyl methacrylate resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyethylene terephthalate resins, ethylene vinyl alcohol resins, cellulose acetate resins, ionomer resins, polyacrylonitrile resins, polyamide resins, polyacetal resins, polybutylene terephthalate resins, polylactic acid resins, polyphenylene ether resins, modified polyphenylene ether resins, polycarbonate resins, polysulfone resins, polyphenylene sulfide resins, polyetherimide resins, polyethersulfone resins, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyetheretherketone resins, polyketone resins, liquid crystal polyester resins, fluororesins, syndiotactic polystyrene resins, and cyclic polyolefin resins. These thermoplastic resins can be used alone or in combination of two or more.

[0188] When using these other resins, the blending ratio of the hydroxyl group-containing compound of the present invention to the other resins can be set arbitrarily depending on the application. However, from the viewpoint of not impairing the repairability and remoldability exhibited by the present invention, it is preferable that the other resins be used in a ratio of 0.5 to 100 parts by mass per 100 parts by mass of the hydroxyl group-containing compound of the present invention.

[0189] The curable resin composition of the present invention may also contain a curing accelerator. Examples of the curing accelerator include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and boron trifluoride monoethylamine complex; organic acid compounds such as thiodipropionic acid; benzoxazine compounds such as thiodiphenolbenzoxazine and sulfonylbenzoxazine; and sulfonyl compounds. These may be used alone or in combination of two or more. The amount of these catalysts added is preferably in the range of 0.001 to 15 parts by mass per 100 parts by mass of the curable resin composition.

[0190] When the curable resin composition of the present invention is used in an application requiring high flame retardancy, a non-halogen flame retardant containing substantially no halogen atoms may be blended therein.

[0191] 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 multiple flame retardants of the same type may be used, or different flame retardants may be used in combination.

[0192] 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.

[0193] The red phosphorus is preferably surface-treated to prevent 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, or 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 top of a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide.

[0194] Examples of the organic phosphorus compound include general-purpose organic phosphorus 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 organic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives thereof obtained by reacting these with compounds such as epoxy resins and phenolic resins.

[0195] The amount of these phosphorus-based flame retardants to be added is selected appropriately depending on the type of phosphorus-based flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, when red phosphorus is used as the non-halogenated flame retardant, it is preferably added in an amount of 0.1 to 2.0 parts by mass, relative to 100 parts by mass of the resin composition containing all of the non-halogenated flame retardants and other fillers and additives. When an organic phosphorus compound is used, it is similarly preferably added in an amount of 0.1 to 10.0 parts by mass, and more preferably added in an amount of 0.5 to 6.0 parts by mass.

[0196] 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.

[0197] 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.

[0198] 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) or (3) with tung oil, isomerized linseed oil, or the like.

[0199] Examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate.

[0200] The amount of the nitrogen-based flame retardant to be blended is selected appropriately depending on the type of nitrogen-based flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend it 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.

[0201] When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

[0202] The silicone flame retardant can be any organic compound containing silicon atoms, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicone flame retardant to be added is appropriately selected depending on the type of silicone flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to add the silicone flame retardant in an amount of 0.05 to 20 parts by mass per 100 parts by mass of the resin composition containing the non-halogen flame retardant and other fillers and additives. When using the silicone flame retardant, a molybdenum compound, alumina, etc. may also be used in combination.

[0203] Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.

[0204] Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

[0205] 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.

[0206] 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.

[0207] Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

[0208] Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

[0209] Examples of the low-melting glass include glassy compounds such as Shepley (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.

[0210] The amount of the inorganic flame retardant to be blended is selected as appropriate depending on the type of inorganic 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 0.05 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.

[0211] Examples of the organometallic salt flame retardant include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, and compounds in which a metal atom is ionic- or coordinate-bonded to an aromatic compound or a heterocyclic compound.

[0212] 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 it in the range 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.

[0213] 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.

[0214] 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 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, as well as potassium titanate, magnesium sulfate, sepiolite, and zonolite. Examples of inorganic particles include tin, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, and magnesium hydroxide; those with a high refractive index include barium titanate, zirconia oxide, and titanium oxide; 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, and lead, as well as composites of these metals and oxides thereof; those with excellent abrasion resistance include metals such as silica, alumina, zirconia, and magnesium oxide, as well as composites and oxides thereof; those with excellent conductivity include metals such as silver and copper, tin oxide, and indium oxide; those with excellent insulation properties include silica; and those with excellent UV blocking properties include titanium oxide and zinc oxide. These inorganic particles can be selected appropriately depending on the application and can be used alone or in combination. Furthermore, the above inorganic particles have various properties in addition to those listed as examples, so they can be selected appropriately depending on the application.

[0215] For example, when silica is used as inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica or colloidal silica can be used. 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.

[0216] 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.

[0217] Surface-modified silica fine particles may also be used, for example, the silica fine particles that have been surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth)acryloyl group. Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, etc. manufactured by Nissan Chemical Industries, Ltd.

[0218] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or irregularly shaped particles can be used. The primary particle diameter is preferably in the range of 5 to 200 nm.

[0219] Titanium oxide microparticles can be used not only as extender pigments but also as ultraviolet light-responsive photocatalysts, such as anatase titanium oxide, rutile titanium oxide, and brookite titanium oxide. Furthermore, particles designed to respond to visible light by doping different elements into the crystalline structure of titanium oxide can also be used. Suitable elements for doping titanium oxide include anionic elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cationic elements such as chromium, iron, cobalt, and manganese. The titanium oxide can be used in the form of a powder, a sol dispersed in an organic solvent or water, or a slurry. Commercially available powdered titanium oxide microparticles include, for example, Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd. and ATM-100 manufactured by Teika Co., Ltd. Commercially available slurry-type titanium oxide microparticles include, for example, TKD-701 manufactured by Teika Co., Ltd.

[0220] 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.

[0221] 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.

[0222] Examples of organic fibers include synthetic fibers made from 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.

[0223] 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 two or more types may be used simultaneously.

[0224] The fibrous substrate may be an assembly of fibers, with continuous or discontinuous fibers, in the form of a woven or nonwoven fabric, in the form of a fiber bundle in which fibers are aligned in one direction, or in the form of a sheet in which fiber bundles are arranged, or in the form of a three-dimensional shape in which a thickness is added to an assembly of fibers.

[0225] 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.

[0226] 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 methyl ethyl ketone is preferred from the standpoint of volatility during coating and solvent recovery.

[0227] The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include an acrylic polymer (Floren WK-20: Kyoeisha), an amine salt of a special modified phosphate ester (HIPLAAD ED-251: Kusumoto Chemicals), and a modified acrylic block copolymer (DISPERBYK2000: BYK-Chemie).

[0228] 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 modifiers, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, and reactive diluents.

[0229] A cured product can be obtained by curing the resin composition of the present invention. When curing, curing can be performed at room temperature or by heating. When performing thermal curing, curing can be performed by heating once or through multiple heating steps.

[0230] The curable resin composition of the present invention can also be cured by active energy rays. In this case, a photocationic polymerization initiator may be used as the polymerization initiator. Examples of active energy rays that can be used include visible light, ultraviolet light, X-rays, and electron beams.

[0231] 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.

[0232] The curable resin composition of the present invention can be prepared by uniformly mixing the above-mentioned components, and the method for doing so 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.

[0233] The curable resin composition of the present invention is prepared by dissolving the hydroxyl group-containing compound of the present invention and the compound (I) reactive with the hydroxyl group-containing compound, as well as the curing agent, filler, fibrous substrate, dispersion medium, and resins other than the various compounds described above, in a dispersion medium such as the organic solvent. After dissolution, the solvent is distilled off and the resulting mixture is dried under reduced pressure using a vacuum oven or the like to obtain a curable resin composition. The curable resin composition of the present invention may also be in a state in which the aforementioned constituent materials are uniformly mixed. In this case, uniform mixing is preferably performed using a mixer or the like. The blending ratio of each constituent material can be appropriately adjusted depending on the desired properties of the cured product, such as mechanical strength, heat resistance, repairability, and remoldability. Furthermore, the order in which the constituent materials are mixed is not particularly limited when preparing the curable resin composition.

[0234] The cured product of the present invention is obtained by curing a compound (I) reactive with a hydroxyl group-containing compound with the hydroxyl group-containing compound of the present invention. The curing method can be appropriately selected from known methods depending on the properties of the compound (I) reactive with a hydroxyl group-containing compound used.

[0235] The cured product of the present invention is cured by the hydroxyl group-containing compound of the present invention as described above, and thus can maintain good mechanical strength by exhibiting an appropriate crosslink density. Furthermore, when the cured product of the present invention is subjected to mechanical energy such as scratching or external force, the reversible bonds are broken, but the equilibrium shifts in the bond direction, and an adduct is formed again, which is thought to enable repair of the scratch and remolding.

[0236] The structure of the resulting 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.

[0237] As described above, the cured product, which is one embodiment of the present invention, can be obtained by using the hydroxyl group-containing compound of the present invention as one component of a curable resin composition. However, it is also possible to use the aforementioned conjugated diene intermediate or dienophilic intermediate, which is an intermediate of the hydroxyl group-containing compound, in combination with a compound capable of addition reaction by Diels-Alder reaction, and form the hydroxyl group-containing compound during the curing process (while synthesizing in situ) to obtain a cured product.

[0238] For example, when a curing reaction is carried out using the above formula (1-1)', a maleimide having a hydroxyl group, and a compound (I) reactive with the hydroxyl group-containing compound as essential raw materials, the hydroxyl group-containing compound represented by the above formula (1-1) can be obtained during the curing reaction, and as the curing reaction progresses, a cured product can be obtained. The maleimide having a hydroxyl group that can be used in this case is the same as described above.

[0239] Furthermore, when a curing reaction is carried out using the above-mentioned formula (1-2)', an anthracene having a hydroxyl group, and the compound (I) reactive with the hydroxyl group-containing compound as essential raw materials, the hydroxyl group-containing compound represented by the above-mentioned formula (1-2) can be obtained in the course of the curing reaction, and further, as the curing reaction progresses, a cured product can be obtained. The anthracene having a hydroxyl group that can be used in this case is the same as above.

[0240] 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.

[0241] The cured curable resin of the present invention can be laminated with a substrate to form a laminate. The substrate of the laminate can be inorganic materials such as metal and glass, or organic materials such as plastic and wood, as appropriate for the application. The substrate may be in the form of a laminate, such as a flat plate, a sheet, or a three-dimensional structure, or may be three-dimensional. Any shape depending on the purpose, such as one with cured surface or partial curvature, may be used. There are no limitations on the hardness or thickness of the substrate. A multilayer laminate may also be formed by laminating a first substrate, a layer made of the cured product of the curable resin composition of the present invention, and a second substrate in this order. Because the curable resin composition of this embodiment has excellent adhesive properties, it can be suitably used as an adhesive for bonding a first substrate and a second substrate. Alternatively, the cured curable resin of the present invention may be used as a substrate, and the cured product of the present invention may be further laminated.

[0242] Furthermore, the cured curable resin of the present invention can relieve stress and is therefore particularly suitable for use in bonding dissimilar materials. For example, even in a laminate in which the substrate is a metal and / or metal oxide and the second substrate is a dissimilar material such as a plastic layer, the adhesive strength is maintained due to the stress-relieving ability of the cured resin of the present invention.

[0243] In a laminate obtained by laminating the cured product of the present invention and a 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, dipping, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, screen printing, and inkjet printing. When directly molding, examples thereof 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 fully cured cured product of the composition may be laminated on the substrate. Alternatively, the cured product of the present invention may be laminated by coating a precursor capable of serving as a substrate and curing it, or the precursor capable of serving as a substrate or the composition of the present invention may be adhered in an uncured or semi-cured state and then cured. The precursor capable of serving as a substrate is not particularly limited, and examples thereof include various curable resin compositions.

[0244] The cured product obtained using the curable resin composition of the present invention has particularly high adhesion to metals and / or metal oxides, making it particularly suitable for use as a primer for metals. Examples of metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials thereof, while examples of metal oxides include single oxides and / or composite oxides of these metals. Because of its particularly excellent adhesive strength to iron, copper, and aluminum, it can be suitably used as an adhesive for iron, copper, and aluminum.

[0245] The curable resin composition of the present invention can be suitably used as an adhesive for structural components in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry. Even when used to bond dissimilar materials, such as metals and non-metals, the adhesive maintains high adhesion without being affected by changes in temperature and is resistant to peeling. In addition to structural applications, the adhesive can also be used for general office and medical applications, carbon fiber, and storage battery cells, modules, and cases. It can also be used as an adhesive for bonding optical components, bonding optical disks, mounting printed wiring boards, die bonding adhesives, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films, anisotropic conductive pastes, and other mounting applications.

[0246] 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 for incorporating the fibrous substrate into the composition is not particularly limited as long as the effects of the present invention are not impaired. Examples include methods for combining the fibrous substrate and the composition by methods such as kneading, coating, impregnation, injection, and pressure bonding, and the method can be selected appropriately depending on the form of the fiber and the application of the fiber-reinforced resin.

[0247] The method for molding fiber-reinforced resins is not particularly limited. To produce plate-shaped products, extrusion molding is commonly used, but flat presses are also possible. Other methods that can be used include extrusion molding, blow molding, compression molding, vacuum molding, and injection molding. To produce film-shaped products, melt extrusion and solution casting can be used. Examples of melt molding methods include inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. For resins that are cured with active energy rays, cured products can be produced 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 molding methods include prepreg molding of the molding material and pressurizing and heating it using a press or autoclave. Other examples include RTM (Resin Transfer Molding), Vacuum-assisted Resin Transfer Molding (VaRTM), laminate molding, and hand layup molding.

[0248] The curable resin composition of the present invention provides a cured product thereof that has good heat resistance and repairability, and is also remoldable, and therefore can 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 cured products reinforced with fiber such as glass chips.

[0249] Fiber-reinforced resins can be formed into an uncured or semi-cured state known as a 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 the prepreg, then stack other layers, and then perform final curing, since this allows the formation of a laminate in which each layer is tightly adhered. The mass ratio of the composition and fibrous substrate used in this case is not particularly limited, but it is generally preferable to prepare the prepreg so that the resin content is 20 to 60 mass%.

[0250] The cured product of the present invention has good heat resistance and repairability, and is remoldable, making it suitable for use as a heat-resistant material and an electronic material. It is particularly suitable for use in semiconductor encapsulants, circuit boards, build-up films, build-up boards, adhesives, and resist materials. It is also suitable for use 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 used in a variety of applications, including, but not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace and aviation-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, and housing components for wind power generation.

[0251] In particular, by taking advantage of the excellent flexibility of the cured product, 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. Even when used to bond dissimilar materials, such as between metals and non-metals, the adhesive of the present invention can maintain high adhesion without being affected by changes in the temperature environment and is less likely to peel. 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, and storage battery cells, modules, and cases, etc., including adhesives for bonding optical components, adhesives for bonding optical disks, adhesives for mounting printed wiring boards, die bonding adhesives, semiconductor adhesives such as underfills, BGA reinforcing underfills, and mounting adhesives such as anisotropic conductive films and anisotropic conductive pastes.

[0252] Below, we will explain some representative products by giving examples.

[0253] 1.Semiconductor encapsulation materials A method for obtaining a semiconductor encapsulating material from the resin composition of the present invention includes thoroughly melt-mixing the resin composition, a curing accelerator, and compounding ingredients such as an inorganic filler, as needed, using an extruder, kneader, roll, or the like until homogeneous. In this process, fused silica is typically used as the inorganic filler. However, when used as a high-thermal-conductivity semiconductor encapsulating material for power transistors and power ICs, highly filled inorganic fillers such as crystalline silica, alumina, and silicon nitride, which have higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, and silicon nitride may be used. The inorganic filler is preferably used in an amount of 30 to 95% by weight per 100 parts by weight of the curable resin composition. In particular, a filler amount of 70 parts by weight or more, and even more preferably 80 parts by weight or more, is preferred to improve flame retardancy, moisture resistance, and solder crack resistance and to reduce the linear expansion coefficient.

[0254] 2. Semiconductor Devices A semiconductor package molding method for obtaining a semiconductor device from the curable resin composition of the present invention includes 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.

[0255] 3. Printed Circuit Board A method for obtaining a printed circuit board from the composition of the present invention includes laminating the prepreg by a conventional method, appropriately overlaying copper foil, and heat-pressing the laminate under a pressure of 1 to 10 MPa at 170 to 300°C for 10 minutes to 3 hours.

[0256] 4. Flexible substrate A 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 electrically insulating film using a coater such as a reverse roll coater or a comma coater; the second step is to heat the electrically 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 electrically insulating film and B-stage the crosslinkable resin composition; and the third step is to thermocompression bond a metal foil to the adhesive of the electrically insulating film containing the B-stage crosslinkable resin composition using a heated roll or the like (the compression pressure is preferably 2 to 200 N / cm and the compression temperature is preferably 40 to 200°C). If sufficient adhesive properties are obtained by going through the above three steps, the process may be terminated here, but if complete adhesive properties are required, it is preferable to further post-cure the resin composition at 100 to 200° C. for 1 to 24 hours. The thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 μm.

[0257] 5. Build-up board A method for obtaining a build-up substrate from the composition of the present invention includes, for example, the following steps. First, the composition, which is appropriately blended with rubber, filler, and the like, is applied to a circuit board on which a circuit has been formed using a spray coating method, curtain coating method, or the like, and then cured (Step 1). Next, if necessary, predetermined through-holes or the like are drilled, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, followed by plating with a metal such as copper (Step 2). These operations are sequentially repeated as desired to alternately build up resin insulating layers and conductor layers of a predetermined circuit pattern (Step 3). Note that drilling of through-holes is performed after the formation of the outermost resin insulating layer. Alternatively, the build-up substrate of the present invention can be produced by forming a roughened surface by heat-pressing a copper foil, in which the resin composition has been semi-cured on a copper foil, onto a wiring board on which a circuit has been formed, at 170 to 300°C, thereby eliminating the plating step.

[0258] 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).

[0259] The organic solvent used here is preferably, for example, a ketone such as acetone, methyl ethyl ketone, or cyclohexanone; an acetate ester such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, or carbitol acetate; a carbitol such as cellosolve or butyl carbitol; an aromatic hydrocarbon such as toluene or xylene; dimethylformamide, dimethylacetamide, or N-methylpyrrolidone; and it is preferably used in a proportion such that the nonvolatile content is 30 to 60% by mass.

[0260] 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 a 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. In addition, the layer (X) of the composition in the present invention may be protected with a protective film described below. Protection with a protective film can prevent adhesion of dust and the like to the surface of the resin composition layer and scratches.

[0261] Examples of the support film and protective film include 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, corona treatment, or release treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0262] The support film (Y) is peeled off after laminating it onto 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.

[0263] A multilayer printed circuit board can be produced using the build-up film obtained as described above. For example, if the layer (X) is protected by a protective film, the 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 x 10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably carried out under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0264] 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. Depending on the type of conductive particles used, the conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive. [Example]

[0265] The present invention will now be described in more detail with reference to examples and comparative examples, in which "parts" and "%" are by mass unless otherwise specified. The present invention is not limited thereto.

[0266] 1H and 13 C-NMR, FD-MS spectrum, and GPC were measured under the following conditions.

[0267] 1 H-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 600MHz Accumulation count: 32 times Solvent: DMSO-d6 Sample concentration: 30% by mass

[0268] 13 C-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 150MHz Accumulation count: 320 times Solvent: DMSO-d6 Sample concentration: 30% by mass

[0269] FD-MS: JEOL Ltd. "JMS-T100GC AccuTOF" Measurement range: m / z = 50.00 to 2000.00 Rate of change: 25.6mA / min Final current value: 40mA Cathode voltage: -10kV

[0270] GPC: Tosoh Corporation "HLC-8320GPC" Column: Tosoh Corporation "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Measurement conditions: 40°C Mobile phase: tetrahydrofuran Flow rate: 1ml / min Standard: Tosoh Corporation "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F"

[0271] The epoxy equivalent of the synthesized epoxy resin was measured in accordance with JIS K7236, and the epoxy equivalent (g / eq) was calculated.

[0272] Examples of methods for calculating the number of repeating units include calculation from the results of GPC molecular weight measurement, and various appropriate instrumental analyses such as FD-MS and NMR.

[0273] Synthesis Example 1 A flask equipped with a thermometer, condenser, and stirrer was charged with 420 g (1.0 mol) of 1,12-dodecanediol diglycidyl ether (manufactured by Yokkaichi Synthetic Co., Ltd.; epoxy equivalent: 210 g / eq) and 342 g (1.5 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq). The mixture was heated to 140 °C over 30 minutes, and then 3.8 g of 4% aqueous sodium hydroxide solution was added. The mixture was then heated to 150 °C over 30 minutes and reacted at 150 °C for 3 hours. The mixture was then cooled to 80 °C, and 762 g of methyl isobutyl ketone, 762 g of water, and a neutralization amount of sodium phosphate were added. The aqueous layer was then removed. The solvent was then distilled off under reduced pressure to obtain 750 g of the hydroxy compound (Ph-1). This hydroxy compound (Ph-1) was confirmed to contain a hydroxy compound having a structure represented by the following structural formula (Ph) because a peak at M+=771 was confirmed in the mass spectrum. 1 The hydroxyl group equivalent calculated by H-NMR was 633 g / eq, and the average value of m in the following structural formula (Ph) was 1.9.

[0274] [ka]

[0275] Synthesis Example 2 A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 63.3 g (0.10 mol) of the hydroxy compound (Ph-1) obtained in Synthesis Example 1, 167 g (1.8 mol) of epichlorohydrin, and 55 g of n-butanol were added and dissolved. After heating to 65°C, the pressure was reduced to an azeotropic pressure, and 16.7 g (0.2 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under the same conditions for 0.5 hours. During this time, the azeotropic distillate was separated using a Dean-Stark trap, the aqueous layer was removed, and the oil layer was returned to the reaction system while the reaction was continued. Unreacted epichlorohydrin was then removed by vacuum distillation. 20 g of methyl isobutyl ketone and 20 g of n-butanol were added to the resulting crude epoxy resin and dissolved. Further, 1.0 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 65.0 g of epoxy compound (Ep-1) represented by the following structural formula (Ep). The epoxy equivalent of the obtained epoxy compound (Ep-1) was 670 g / eq. Mass spectrometry showed a peak of M+ = 883, which corresponds to the theoretical structure of m1 = 1, n1 = 12, q = 1, p1 = 0, and p2 = 0 in the following structural formula (Ep), confirming that the epoxy compound contained the compound represented by the following structural formula (Ep).

[0276] [ka]

[0277] Synthesis Example 3 The same reaction as in Synthesis Example 1 was performed, except that the amount of bisphenol A (hydroxyl equivalent: 114 g / eq) used in Synthesis Example 1 was changed from 342 g (1.5 mol) to 240 g (1.05 mol), yielding 645 g of hydroxy compound (Ph-2). Mass spectrometry of this hydroxy compound (Ph-2) revealed a peak at M+ = 771, corresponding to the theoretical structure of m1 = 1 and n1 = 12 in structural formula (Ph), confirming that it contained the target hydroxy compound. The hydroxyl equivalent of this hydroxy compound (Ph-2) calculated by GPC was 2000 g / eq, and the average value of m in structural formula (Ph) was 6.9.

[0278] Synthesis Example 4 The same reaction as in Synthesis Example 2 was carried out, except that 63.3 g of the hydroxy compound (Ph-2) obtained in Synthesis Example 3 was used instead of 63.3 g of the hydroxy compound obtained in Synthesis Example 1, to obtain 64 g of epoxy compound (Ep-2). The epoxy equivalent of the obtained epoxy compound (Ep-2) was 2320 g / eq. Mass spectrometry of this epoxy compound (Ep-2) revealed a peak at M+ = 883, which corresponds to the theoretical structure of m1 = 1, n1 = 12, p1 = 0, p2 = 0, and q = 1 in structural formula (Ep), confirming that it contains the compound represented by the structural formula (Ep).

[0279] Example 1 A thermometer, a condenser, and a stirrer were equipped, and 63.3 g (0.10 mol) of the hydroxy compound (Ph-1) obtained in Synthesis Example 1, 22.7 g (0.10 mol) of 9-chloromethylanthracene, and 55.3 g (0.40 mol) of potassium carbonate were charged, followed by nitrogen substitution. 344 g of acetone was then added and dissolved, and the mixture was allowed to react at reflux temperature for 12 hours. After cooling to room temperature, the potassium carbonate was removed by filtration, and the acetone in the filtrate was distilled off under reduced pressure using an evaporator. The resulting liquid was diluted with 230 g of toluene, and 230 g of water was added and separated three times. The organic layer was dehydrated with sodium sulfate, and the toluene was distilled off under reduced pressure using an evaporator to obtain 61.7 g of anthracene compound (A-1). 1 The molecular weight per mole of anthracene calculated by H-NMR was 919 g / eq.

[0280] [ka]

[0281] Example 2 A flask equipped with a thermometer, stirrer, and condenser was charged with 46.0 g (0.050 mol) of the anthracene compound (A-1) obtained in Example 1, 4.69 g (0.015 mol) of 1,6'-bismaleimido-(2,2,4-trimethyl)hexane (BMI-THM, manufactured by Daiwa Chemical Industry Co., Ltd.), and 50.7 g of toluene. After purging with nitrogen, the mixture was reacted at 60°C for 10 hours. Next, 3.78 g (0.020 mol) of 4-hydroxyphenylmaleimide was added, and the mixture was reacted at 80°C for 10 hours. The mixture was then heated to 140°C, the toluene was distilled off under reduced pressure, and the mixture was cooled to room temperature to obtain a Diels-Alder reaction product (D-1). The yield was 54.4 g. The molecular weight measured by GPC was Mn = 2.5 × 10 3 , Mw=10.0×10 3 It was.

[0282] [ka]

[0283] Example 3 A flask equipped with a thermometer, a condenser, and a stirrer was charged with 49.8 g (0.05 mol) of polytetramethylene oxide 2,000 (manufactured by Fujifilm Wako Co., Ltd., acid value = 56.3 mg KOH / g, average value of n calculated from the acid value = 27.4), 11.3 g (0.05 mol) of 9-chloromethylanthracene, 14.6 g (0.125 mol) of 48% aqueous potassium hydroxide solution, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 61.1 g of toluene, and nitrogen substitution was performed. The mixture was then reacted at 60°C for 14 hours. After cooling to room temperature, 100 g of water and a neutralizing amount of sodium phosphate were added, and the mixture was separated three times. The organic layer was dehydrated with sodium sulfate, and the toluene was distilled off under reduced pressure using an evaporator to obtain 48.9 g of anthracene compound (A-2). 1The molecular weight per mole of anthracene calculated by H-NMR was 1684 g / eq.

[0284] [ka]

[0285] Example 4 A flask equipped with a thermometer, stirrer, and condenser was charged with 42.1 g (0.025 mol) of the anthracene compound (A-2) obtained in Example 3, 2.3 g (0.0073 mol) of 1,6'-bismaleimido-(2,2,4-trimethyl)hexane (BMI-THM, manufactured by Daiwa Chemical Industry Co., Ltd.), and 44.4 g of toluene. After purging with nitrogen, the mixture was reacted at 60°C for 10 hours. Next, 1.97 g (0.0104 mol) of 4-hydroxyphenylmaleimide was added and the mixture was reacted at 80°C for 10 hours. The mixture was then heated to 140°C, the toluene was distilled off under reduced pressure, and the mixture was cooled to room temperature to obtain Diels-Alder reaction product (D-2). The yield was 46.3 g. The molecular weights measured by GPC were Mn = 2.7 × 103 and Mw = 7.6 × 103.

[0286] [ka]

[0287] Example 5 A flask equipped with a thermometer, stirrer, and condenser was charged with 37.6 g (0.1 mol) of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (BIP-ANT, manufactured by Asahi Organic Chemicals Co., Ltd.), 15.9 g (0.05 mol) of 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM, manufactured by Daiwa Chemical Industry Co., Ltd.), and 214.2 g of methyl isobutyl ketone. After purging with nitrogen, the mixture was reacted at 110 °C for 7 hours. The temperature was then raised to 150 °C, and the methyl isobutyl ketone was distilled off under reduced pressure. The mixture was then cooled to room temperature to obtain 52.1 g of Diels-Alder reaction product (D-3). This Diels-Alder reaction product (D-3) exhibited a peak of M+ = 1071 in the mass spectrum, confirming the production of the target compound.

[0288] [ka]

[0289] Example 6 A flask equipped with a thermometer and stirrer was charged with 445 g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 190 g (0.76 mol) of 4,4'-dihydroxydiphenyl disulfide (hydroxyl equivalent 125 g / eq). The mixture was heated to 140 °C over 30 minutes, after which 3.2 g of 4% aqueous sodium hydroxide solution was added. The mixture was then heated to 150 °C over 30 minutes and allowed to react at 150 °C for 5 hours. A neutralizing amount of sodium phosphate was then added, yielding 635 g of a hydroxy compound represented by the following formula (S-1). Mass spectrometry of this hydroxy compound (S-1) confirmed the formation of the target compound, as it exhibited a peak at M+ = 1424, which corresponds to the theoretical structure of m1 = 1 and n1 = 11 in the following formula. The hydroxyl equivalent of this hydroxy compound (S-1) calculated by GPC was 750 g / eq, the average value of n1 was 10.6, and the average value of m1 was 1.09.

[0290] [ka]

[0291] Synthesis Example 5 A flask equipped with a thermometer and stirrer was charged with 445 g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 86 g (0.75 mol) of bisphenol A (hydroxyl equivalent 114 g / eq). The mixture was heated to 140°C over 30 minutes, after which 3.4 g of 4% aqueous sodium hydroxide solution was added. The mixture was then heated to 150°C over 30 minutes and allowed to react at 150°C for 16 hours. A neutralizing amount of sodium phosphate was then added, yielding 531 g of a hydroxy compound represented by the following formula: The mass spectrum of this hydroxy compound showed a peak at M+ = 1380, which corresponds to the theoretical structure of m1 = 1 and n1 = 11 in the following formula, confirming the production of the target compound. The hydroxyl equivalent weight of this hydroxy compound (Ph-3) calculated by GPC was 1136 g / eq, the average value of n1 was 10.6, and the average value of m1 was 1.82.

[0292] [ka]

[0293] Preparation of composition and cured product A curable resin composition was obtained by uniformly mixing each compound in a mixer (Thinky Corporation's "Awatori Rentaro ARV-200") according to the formulations shown in Tables 1 to 4 (the numbers in the tables are by mass). This curable resin composition was sandwiched between aluminum mirror plates (Engineering Test Service Co., Ltd.'s "JIS H 4000 A1050P") using a silicone tube as a spacer, and heat-cured under specified conditions to obtain a cured product with a thickness of 0.7 mm.

[0294] <Remolding test> The cured product was freeze-pulverized. 0.07 g of the pulverized cured product was placed in a 10 mm square, 0.5 mm thick mold and vacuum-pressed under specified conditions. The appearance of the resulting cured product was visually observed. The evaluation criteria were as follows: A: The seams disappeared and the hardened material became one piece. B: Some joints are visible to the naked eye, but the cured product has become one piece. C: It had a solidified shape and broke apart when light pressure was applied.

[0295] <Repair test> The cured product was punched into a dumbbell shape (JIS K 7161-2-1BA) using a punching blade to prepare test specimens. The breaking stress and tensile elongation were evaluated in accordance with JIS K 7162-2 at 23°C using a tensile tester (Shimadzu Corporation, Autograph AG-IS) (test speed: 2 mm / min). The breaking stress and tensile elongation of the tensile test were evaluated after aging the test specimens at 150°C for 24 hours (initial). In addition, the center of the test specimen was cut with a razor, and the cut surfaces were butted together. The specimens were then aged at 150°C for 24 hours, and the tensile test was similarly performed and evaluated (after repair). The repair rate (%) was calculated from the obtained breaking stress and tensile elongation rate based on the formula (value after repair / initial value)×100%.

[0296] [Table 1]

[0297] EPICLON 850-S: BPA-type liquid epoxy resin, epoxy equivalent weight 188g / eq BMI-TMH: 1,6'-bismaleimido-(2,3,4-trimethyl)hexane 4-HPMI: 4-hydroxyphenylmaleimide DICY: Dicyandiamide DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea

[0298] [Table 2]

[0299] [Table 3]

[0300] BPF: Bisphenol F

[0301] [Table 4]

Claims

1. a hydroxyl group-containing compound represented by the following general formula: one or more compounds (I) reactive with the hydroxyl group-containing compound selected from the group consisting of melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resole resins, epoxy resins, isocyanate compounds, azide compounds, compounds containing an alkenyl ether group, acid anhydrides, hexamethylenetetramine and modified compounds thereof, and oxazoline compounds, each of which is substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group; A curable resin composition comprising the above as an essential component. 【Chemical 1】 [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 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. The maleimide-derived structure may have 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 the formulas, m-a is an integer of 1 to 10, and n is the average number of repeating groups, which is 0 to 10. Z １ is the following formula (3), Z ２ is the following formula (4), Z ３ is any of the structures represented by the following formula (5), and a plurality of such structures in one molecule may be the same or different. 【Chemistry 2】 [The aromatic ring in formula (3) is an unsubstituted or substituted aromatic ring, and * indicates a bonding point. The hydroxyl group on the naphthalene ring in the formula may be bonded to any position.] 【Chemistry 3】 [In formula (4), Each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R is a hydrogen atom or a methyl group; R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; n1 is an integer of 2 to 16, and n2 is the average number of repeating units of 2 to 30. k1 is the average number of repeats and ranges from 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): 【Chemistry 4】 [In formula (4-1) (4-2), Ar, R, R 1 , R 2 , R′, n1, and n2 are the same as above.] m1 and m2 are the average values ​​of the repeats, each independently ranging from 0 to 25, and m1+m2≧1. However, the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be bonded randomly or in blocks, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively. 【Chemistry 5】 [In formula (5), n3 and n5 are the average number of repeats, 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.

2. 2. The curable resin composition according to claim 1, wherein the concentration of reversible bonds in the hydroxyl group-containing compound relative to the total mass of the curable components in the curable resin composition is 0.10 mmol / g or more.

3. 2. The curable resin composition according to claim 1, wherein the compound (I) reactive with the hydroxyl group-containing compound is an epoxy resin.

4. The curable resin composition according to claim 3, further comprising a curing agent for epoxy resins other than the hydroxyl group-containing compound.

5. The curable resin composition according to claim 3, wherein the epoxy resin is represented by the following formula (8) and has an epoxy equivalent of 500 to 10,000 g / eq: 【Chemistry 6】 [In formula (8), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, X' is a structural unit represented by the following general formula (8-1), and Y' is a structural unit represented by the following general formula (8-2): 【Chemistry 7】 [In formulas (8-1) and (8-2), Ar is the same as defined above, R １ , R ２ are each independently a hydrogen atom, a methyl group, or an ethyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; R ３ , R ４ , R ７ , R ８ each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R ５ , R ６ , R ９ , R １０ are each independently a hydrogen atom or a methyl group, n1 is an integer from 4 to 16, n2 is the average number of repeating units and is 2 to 30.] R １１ , R １２ are each independently a glycidyl ether group or a 2-methylglycidyl ether group, R １３ , R １４ 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 X' represented by the general formula (8-2) and Y' represented by the general formula (8-3) 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.

6. The curable resin composition according to claim 5, wherein the epoxy resin is represented by the following formula (9): 【Chemistry 8】 [In formula (9), p1, p2, q, and m4 are average values ​​of repetitions, and each independently p1 is 0 to 5, p2 is 0 to 5, q is 0.5 to 5, and m4 is 0 to 25.]

7. The curable resin composition according to claim 1, which is a self-repairing composition or a remolding material composition.

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

9. A laminate comprising a substrate and a layer comprising the cured product according to claim 8.

10. A heat-resistant member comprising the cured product according to claim 8.

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