Acid-containing compounds, curing resin components, cured products, and laminations.

Abstract

To provide a compound which can easily achieve recovery property and re-moldability in a cured product while being a curable resin, a curable resin composition using the same, and a cured product of the same.SOLUTION: A hydroxyl group-containing compound is obtained by coupling a structural unit A having one or more hydroxyl groups and a structural unit B different from the A in an A-B-A manner, wherein the structural unit A and the structural unit B are bonded to each other by a reversible bond at a dissociation temperature of 120°C or higher. The reversible bond is preferably an addition type structure by anthracene type Diels-Alder reaction, and a disulfide bond sandwiched aromatic rings.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a hydroxyl group-containing compound having a specific structure, a curable resin composition containing the same, a cured product, and a laminate containing a layer comprising the cured product.

Background Art

[0002] A cured product obtained from an epoxy resin is excellent in heat resistance, mechanical strength, electrical properties, adhesiveness, etc., and is an indispensable material in various fields such as electric and electronic, paints, adhesives, etc.

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

[0004] In addition, a cured product obtained by once curing a thermosetting resin such as an epoxy resin cannot be dissolved in a solvent (insoluble) and also does not dissolve even at high temperatures (infusible). Therefore, it has poor recyclability and reusability, and since the cured product after use becomes waste, it is an issue to reduce waste and the environmental load.

[0005] Therefore, there is a demand for solving the problems of extending the life and reducing waste in cured products using epoxy resins and the like. For solving these problems, it is considered effective to impart easy disassembly, reparability, and reshaping properties to the cured products.

[0006] Under such a background, a method has been disclosed in which a compound having pyrolytic properties in advance is blended with a reaction system adhesive component, and after use, the adhesive strength is reduced by heating to a certain extent to enable disassembly (see, for example, Patent Document 1).

[0007] Furthermore, a method has been disclosed for creating a self-healing encapsulant by using microcapsule particles containing a first thermosetting resin and a second thermosetting resin precursor, even if cracks or delamination occur in an encapsulant using epoxy resin or the like (see, for example, Patent Document 2).

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

[0009] [Patent Document 1] Japanese Patent Publication No. 2013-256557 [Patent Document 2] Japanese Patent Publication No. 2017-041496 [Overview of the project] [Problems that the invention aims to solve]

[0010] In the technology provided in Patent Document 1, the adhesive is discarded after dismantling, and although the substrate to which the adhesive is applied is recyclable, there is a problem of insufficient overall recyclability. In addition, the technology in Patent Document 2 has a certain degree of self-healing properties, but it is not a solution from the perspective of reuse, and the problem of waste when it is no longer needed remains. Furthermore, in the raw materials involved in the reversible bonding, it is necessary to ensure their molecular mobility, which limits the use of raw materials to gel-like substances with poor mechanical strength, and improvements are needed in all of these cases. Therefore, the object of the present invention is to provide a compound that is a curable resin, yet can easily achieve repairability and remolding properties in the cured product, and a curable resin composition using the same and its cured product. [Means for solving the problem]

[0011] As a result of diligent research, the inventors discovered 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 thus completed the invention.

[0012] In other words, the present invention encompasses the following aspects. [1] A hydroxyl group-containing compound comprising structural unit A having one or more hydroxyl groups and structural unit B different from A, linked by ABA, characterized in that structural unit A and structural unit B are linked by 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 one of the following: an addition structure by a Diels-Alder reaction with a dissociation temperature of 120°C or higher, 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, or an amide bond. [4] The hydroxyl group-containing compound according to any one of [1] to [3] above, wherein the reversible bond is an addition structure formed by an anthracene-type Diels-Alder reaction or a disulfide bond sandwiched between aromatic rings. [5] The hydroxyl group-containing compound according to any one of [1] to [4] above, wherein the structural unit B has an alkylene chain or an alkylene ether chain. [6] The hydroxyl group-containing compound according to [5], 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 the same reversible bond as the reversible bond with a dissociation temperature of 120°C or higher that is the linking site between structural unit A and structural unit B. [8] A hydroxyl group-containing compound represented by the following general formula.

[0013] [ka]

[0014] [In formula (2), each Ar independently contains an unsubstituted or substituted aromatic ring, and the anthracene-derived structures in formulas (1-1) and (1-2) may have a halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. In the formula, ma is an integer from 1 to 10, and n is the average value of the number of repetitions from 0 to 10. Z 1 This is given by the following equation (3), Z 2 This is given by the following equation (4), Z 3 This is given by the following equation (5), Z 4 The structure is one of the structures represented by the following formulas (6) or (7), and each of the multiple structures in a single molecule may be identical or different.

[0015] [ka] [The aromatic ring in formula (3) may be substituted or unsubstituted, and * indicates a bond point. The hydroxyl group on the naphthalene ring in the formula may be bonded at any position.]

[0016] [ka]

[0017] [In formula (4), Each Ar independently has a structure with an unsubstituted or substituted aromatic ring. R 1 , R 2 Each of these is 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 with 2 to 12 carbon atoms. n1 is an integer between 2 and 16, and n2 is the average value of the repeating units, between 2 and 30. k1 is the average number of repetitions and is in the range of 0.5 to 10. p1 and p2 are independently between 0 and 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] [Chemical formula]

[0019] [In formulas (4-1) and (4-2), Ar, R, R 1 , R 2 , R’, n1, and n2 are the same as defined above.] m1 and m2 are average values of the repetition, and are each independently 0 to 25, and m1 + m2 ≥ 1. However, the combination of the structural unit X represented by the formula (4-1) and the structural unit Y represented by the formula (4-2) may be random or block, and the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively.]

[0020] [Chemical formula] [In formula (5), n3 and n5 are average values of the repetition numbers, and are each 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] [Chemical formula]

[0022] [Chemical formula] [In formulas (6) and (7), R 1 , R 2 , R’, n1, and n2 are the same as defined 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 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) that is 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 10000 g / eq.

[0024] [ka] [In formula (8), each Ar independently has a structure that is either unsubstituted or has a 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 equations (8-1) and (8-2), Ar is the same as described above. R 1 , R 2 Each of these is independently a hydrogen atom, a methyl group, or an ethyl group. R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. R 3 , R 4 , R 7 , R 8 Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R 5 , R 6 , R 9 , R 10 Each of these is independently a hydrogen atom or a methyl group. n1 is an integer between 4 and 16. n² is the average value of the repetition unit, ranging from 2 to 30. R 11 , R 12 Each of these is independently a glycidyl ether group or a 2-methylglycidyl ether group. R 13 , R 14 Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R 15 , R 16 is a hydrogen atom or a methyl group, m3, m4, p1, p2, and q are repeated mean values. m3 and m4 are independently between 0 and 25, and m3 + m4 ≥ 1. p1 and p2 are independently between 0 and 5. q is between 0.5 and 5. However, the bonding between X' represented by the general formula (8-2) and Y' represented by the general formula (8-3) may be random or blocky, and the total number of each structural unit X' and Y' present in one molecule is m3 and m4, respectively.

[0027]

[14] The epoxy resin is a curable resin composition according to

[13] , represented by the following formula (9).

[0028] [ka] [In equation (9), p1, p2, q, and m4 are repeated average values, and independently, p1 is between 0 and 5, p2 is between 0 and 5, q is between 0.5 and 5, and m4 is between 0 and 25.]

[15] A curable resin composition in which the curable resin composition described in any of [9] to

[14] above is a self-healing composition or a composition for remolding material.

[16] A cured product obtained by curing any of the curable resin compositions described in [9] to

[14] above.

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

[16] .

[18] A heat-resistant member containing the cured product described in

[16] above.

[19] A conjugated diene intermediate or parent diene intermediate represented by the following general formulas (1-1)' and (1-2)'.

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

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

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

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

[0030] According to the present invention, it is possible to impart repairability and remolding properties to cured products made from a curable resin composition, thereby contributing to extending the lifespan of the cured products themselves and reducing waste. [Modes for carrying out the invention]

[0031] Next, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments, and it should be understood that appropriate design changes, improvements, etc., can be made based on the ordinary knowledge of those skilled in the art, without departing from the spirit of the invention.

[0032] A hydroxyl group-containing compound as one embodiment of the present invention is a hydroxyl group-containing compound in which structural unit A having one or more hydroxyl groups and structural unit B different from A are linked by ABA, characterized in that structural unit A and structural unit B are linked by a reversible bond having a dissociation temperature of 120°C or higher.

[0033] Due to this configuration, the hydroxyl group-containing compound is incorporated into the crosslinked structure by a curing reaction based on its hydroxyl groups. On the other hand, because it remains reversible even after curing, structural unit B in particular can exist detached from the crosslinked structure, thus exhibiting high molecular mobility even in the cured product. Therefore, if the cured product is subjected to impact, cracks may occur, or it may be pulverized, the reversible bonds are easily broken. However, these reversible bonds can be reversibly reformed even in low-temperature regions, including room temperature, exhibiting functions such as repairability and reformability. Structural unit B, existing detached from the crosslinked structure, exhibits particularly high molecular mobility, resulting in low-temperature repairability and low-temperature reformability. For example, even if a cured product using the hydroxyl group-containing compound of the present invention is pulverized, the cured product can be easily repaired based on the reversible bonds by placing it in a low-temperature state, including room temperature, or under heated conditions, and it is also possible to reform the pulverized cured product.

[0034] Examples of reversible bonds with a dissociation temperature of 120°C or higher include covalent and non-covalent bonds. From the viewpoint of durability of the cured product, covalent bonds are preferred. On the other hand, from the viewpoint of short repair and reshaping times after pulverization of the cured product, non-covalent bonds are preferred.

[0035] The aforementioned covalent bonding system is not particularly limited, but examples include addition structures formed by Diels-Alder reactions, disulfide bonds, ester bonds, boronic acid ester bonds, hemiaminal bonds, imine bonds, acylhydrazone bonds, olefin metathesis reactions, alkoxyamine skeletons, and amide bonds. Among these, addition structures formed by Diels-Alder reactions of the anthracene type (reversible bonds consisting of an anthracene structure and a maleimide structure) and disulfide bonds sandwiched between aromatic rings are preferred from the viewpoint of heat resistance and hydrolysis resistance of the cured product.

[0036] The aforementioned non-covalent bonding system is not particularly limited, but examples include van der Waals forces, ionic bonds, inclusion bonds of cyclodextrins, and hydrogen bonds of ureidopyrimidinone units and polyetherthioureas.

[0037] To introduce the aforementioned anthracene-type addition structure into a compound via a Diels-Alder reaction, a method using anthracene having a reactive functional group on its ring and maleimide having a reactive functional group is preferred due to its simple preparation. A specific reversible bond substructure can be represented by the following chemical formula. Reversible bonds can be introduced into a compound by bonding the R portion in the following formula from the maleimide-derived structure or various reactive functional groups on the ring of the anthracene-derived structure with other structural units.

[0038] [ka]

[0039] The Diels-Alder reaction involves the addition reaction of a conjugated diene and a parent diene to form a six-membered ring. Since the Diels-Alder reaction is an equilibrium reaction, a retro-Diels-Alder reaction occurs at a predetermined temperature, leading to dissociation (de-crosslinking). If the temperature at which the retro-Diels-Alder reaction occurs (dissociation temperature) is low, de-crosslinking occurs in a high-temperature range, reducing the crosslinking density of the cured product and decreasing its mechanical strength. Therefore, in this invention, it is necessary to have a Diels-Alder reaction unit with a combination of structures that has high thermal stability and a dissociation temperature of 120°C or higher. 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 maintains its crosslinked structure without dissociating at least around 200°C, thus exhibiting excellent thermal stability. As a result, the decrease in the crosslinking density of the cured product can be suppressed, and good mechanical strength can be maintained. Furthermore, if mechanical energy such as scratches or external forces are applied to the resulting cured product, the CC bonds of the Diels-Alder reaction unit will be preferentially cleaved because their bond energy is lower than that of ordinary covalent bonds. However, in the temperature range below the dissociation temperature, the equilibrium shifts in the bond direction, so it is thought that the adduct (Diels-Alder reaction unit) can be reformed, allowing for repair of scratches and reshaping.

[0040] Examples of compounds containing the disulfide bond include the following compounds. Similarly, by bonding various compounds to sites other than the disulfide bond site, such as hydroxyl groups, amino groups, and vinyl groups, it is possible to incorporate the disulfide bond site into the hydroxyl group-containing compound. In this disulfide bond site as well, even if the cured product is cut by an external force, the disulfide bond will be preferentially broken. However, below the dissociation temperature, the equilibrium shifts in the direction of bonding, so that the SS bond is reformed, allowing for repair of damage and reshaping.

[0041] [ka]

[0042] [ka]

[0043] Examples of compounds containing the alkoxyamine skeleton are listed below. Similar to the above, by bonding with other compounds via a terminal vinyl group (methacryloyl group), it is possible to incorporate a reversible bond into the hydroxyl group-containing compound.

[0044] [ka]

[0045] As mentioned above, at least two reversible bonds will be present in the target hydroxyl group-containing compound. However, from the viewpoint 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] Furthermore, for the same reasons as described above, it is preferable that the molecular weight of structural unit B be above a certain size, for example, that its average molecular weight (Mw) is 28 or more. If reversible bonds are present in structural unit B, it is preferable that the molecular weight between the reversible bonds is 28 or more. Although crosslinking functional groups similar to the hydroxyl groups in structural unit A may be present in structural unit B, it is preferable that crosslinking (curing) functional groups are not present in structural unit B from the viewpoint of more easily exhibiting the effects of the present invention.

[0047] The structural unit B preferably contains an alkylene chain or an alkylene ether chain, from the viewpoint of enabling greater flexibility or conformability to the substrate by the cured product when the hydroxyl group-containing compound of the present invention is used, for example, as a structural adhesive. In this case, the alkylene chain is more preferably 2 to 30 carbon atoms, and most preferably 4 to 16 carbon atoms. The alkylene ether chain is not particularly limited, but is preferably an alkylene ether chain with 2 to 12 carbon atoms, and the average number of repeats is preferably in the range of 2 to 30.

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

[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 repair / remodeling properties in the cured product, it is preferably 500 or more, and preferably 50,000 or less. Furthermore, if there are multiple reversible bonds other than between A and B, for example within structural unit B, it is more preferable from the viewpoint of the remodeling properties of the cured product that the molecular weight per reversible bond is in the range of 300 to 10,000.

[0050] One embodiment of the present invention is a hydroxyl group-containing compound represented by the following general formula.

[0051] [ka]

[0052] In formula (2), each Ar independently contains an unsubstituted or substituted aromatic ring, and the anthracene-derived structures in formulas (1-1) and (1-2) may have a halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. In the formula, ma is an integer from 1 to 10, and n is the average value of the number of repetitions from 0 to 10. 1 This is given by the following equation (3), Z 2 This is given by the following equation (4), Z 3 This is given by the following equation (5), Z 4 The structure is one of the structures represented by the following formulas (6) or (7), and each of the multiple structures in a single molecule may be identical or different.

[0053] [ka] [The aromatic ring in formula (3) may be substituted or unsubstituted, and * indicates a bond point. The hydroxyl group on the naphthalene ring in the formula may be bonded at any position.]

[0054] [ka]

[0055] [In formula (4), Each Ar independently has a structure with an unsubstituted or substituted aromatic ring. R 1 , R 2 Each of these is 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 with 2 to 12 carbon atoms. n1 is an integer between 2 and 16, and n2 is the average value of the repeating units, between 2 and 30. k1 is the average number of repetitions and is in the range of 0.5 to 10. p1 and p2 are independently between 0 and 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 repeated average values, each independently ranging from 0 to 25, and m1 + m2 ≥ 1. However, the bonding between structural unit X represented by formula (4-1) and structural unit Y represented by formula (4-2) may be random or block-like, and the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively.

[0058] [ka]

[0059] In equation (5), n3 and n5 are the average values ​​of the number of repetitions, ranging from 0.5 to 10, and n4 is an integer ranging from 1 to 16. ” Each of these is 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 reversible bonds formed intramolecularly and at the terminal between an anthracene structure and a maleimide structure. The terminal maleimide structure in general formula (1-1) and the terminal anthracene structure in general formula (1-2) have one or more Z1 groups which are any of the structures represented by general formula (3), and these hydroxyl groups contribute to the curing reaction in the curable resin composition described later. ma is the number of Z1 groups in the anthracene-derived structure and is an integer from 1 to 10, but from the viewpoint of ease of obtaining industrial raw materials and ease of controlling the curing reaction, it is preferably in the range of 1 to 4, and more preferably 1 or 2.

[0063] The general formula (2) has a disulfide bond within the molecule, and the molecular end contains an aromatic ring having one or more Z1 groups that are any of the structures represented by the general formula (3). This hydroxyl group contributes to the curing reaction in the curable resin composition described later.

[0064] In the formula, Z1 is an aromatic hydroxyl group or an alcoholic hydroxyl group represented by the general formula (3) above, but among these, the one with the following structural formula is preferred from the viewpoint of ease of raw material availability and reactivity.

[0065] [ka]

[0066] In the above general formulas (1-1) and (1-2), the site connecting the maleimide-derived structure is Z3, the site connecting the anthracene-derived structure is Z2, and in the above general formula (2), the site connecting the oxygen atoms is Z4, and each of these is one of the structures represented by the above general formulas (4), (5), (6), and (7).

[0067] In the general formulas (1-1), (1-2), and (2) above, n is the average value of the number of repetitions, and is between 0 and 10, preferably in the range of 0 to 5.

[0068] In these structural formulas, Ar is an aromatic ring that may have substituents and is not particularly limited. Examples of aromatic rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Examples of substituents include halogen atoms, alkoxy groups, aralkyloxy groups, aryloxy groups, nitro groups, amide groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, cyano groups, alkyl groups, cycloalkyl groups, aralkyl groups, and aryl groups. It is preferable that the substituents on Ar do not undergo a curing reaction when used in a subsequent curable resin composition, as this allows the effects of the present invention to be more easily expressed.

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

[0070] [ka] [The aromatic rings in the formula may be substituted or unsubstituted, and * represents a bonding point.]

[0071] Furthermore, structures represented by the following formula can also be considered as Ar.

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

[0073] The following structures of Ar are particularly preferred. * indicates a bond point.

[0074] [ka]

[0075] In the general formulas (4) and (4-1) above, the repeating unit n1 is an integer between 2 and 16. When n1 is 4 or greater, the deformation mode of the cured product tends to be elastic deformation. Also, when n1 is 16 or less, the decrease in crosslinking density can be suppressed. Preferably, it is between 4 and 15, and more preferably between 6 and 12.

[0076] In the above general formulas (4) and (4-1), R 1 , R 2 Each of these is independently a hydrogen atom, a methyl group, or an ethyl group, and each of these is independently a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferred.

[0077] In the general formulas (4) and (4-2) above, n2 is the average value of the repeating units and is between 2 and 30. This range is preferable because it provides a good balance between the viscosity of the hydroxyl group-containing compound and the crosslinking density of the resulting cured product. Preferably it is between 2 and 25, and more preferably between 4 and 20.

[0078] In the general formulas (4) and (4-2) above, 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 deformation. Preferably, R' is a divalent hydrocarbon group having 2 to 6 carbon atoms.

[0079] The aforementioned divalent hydrocarbon group is not particularly limited and can include linear or branched alkylene groups, alkenylene groups, alkylylene 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. Examples of alkenylene groups include vinylene, 1-methylvinylene, propenylene, butenylene, and pentenylene. Examples of alkylene groups include ethynylene, propynylene, butynylene, pentynylene, and hexynylene. Examples of cycloalkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene. Examples of arylene groups include phenylene, torylene, xylylene, and naphthylene.

[0081] Among these, ethylene groups, propylene groups, and tetramethylene groups are preferred from the viewpoint of the ease of obtaining 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) above, R is independently either a hydrogen atom or a methyl group. Of these, a hydrogen atom is preferred.

[0083] In the general formula (4) above, m1 and m2 are the average values ​​of the repeating structural units X and Y, respectively, and are independently between 0 and 25, with m1 + m2 ≥ 1. Preferably, m1 and m2 are in the range of 0.5 to 10.

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

[0085] In the general formula (5) above, n3 and n5 are the average values ​​of the number of repetitions, ranging from 0.5 to 10, and n4 is an integer ranging from 1 to 16, R ”Each of these is independently a hydrogen atom, a methyl group, or an ethyl group. Among these, from the viewpoint of ease of raw material availability and the mechanical properties of the resulting cured product, n3 is preferably in the range of 0.5 to 10, n5 is preferably in the range of 2 to 3, and n4 is preferably an integer from 1 to 8, R ” It is preferable that it is a hydrogen atom.

[0086] In the above general formulas (6) and (7), R 1 , R 2 R', n1, and n2 are the same as described above, and the preferred ones are also the same as described above.

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

[0088] [ka]

[0089] [ka]

[0090] The method for producing a hydroxyl group-containing compound, which is one embodiment of the present invention, is not particularly limited and can be produced stepwise using known reactions depending on the desired structure, and can also be obtained by appropriately combining commercially available raw materials. A typical synthesis method is described below.

[0091] The general formulas (1-1) and (1-2) above have two Diels-Alder reaction units within the molecule, which are addition reaction sites formed by a Diels-Alder reaction consisting of an anthracene structure and a maleimide structure, as reversible bonds. Furthermore, in general formula (1-1), a maleimide compound having the Z1 structure is used, and in general formula (1-2), an anthracene compound having the Z1 structure is used.

[0092] The so-called Diels-Alder reaction, in which a conjugated diene such as an anthracene structure is added to a parent diene such as a maleimide structure 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, a reverse reaction called the retro-Diels-Alder reaction occurs, in which the addition reaction site dissociates and returns to the original conjugated diene and parent diene.

[0093] Examples of maleimide compounds having the structure of Z1 include any of the compounds listed in the following formula. Among these, hydroxyphenylmaleimide is preferred in terms of curability, and monohydroxyphenylmaleimide is particularly preferred in terms of the balance between reactivity, cured product properties, and repairability and remodeling properties. Among monohydroxyphenylmaleimides, parahydroxyphenylmaleimide is particularly preferred from the viewpoint of heat resistance.

[0094] [ka]

[0095] An anthracene compound having the structure of Z1 can be any of the compounds listed in the following formula. Among these, 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene and hydroxyanthracene are preferred due to 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 remodelability.

[0096] [ka]

[0097] Furthermore, the structures of the maleimide compounds and anthracene compounds described above each include those that independently have a hydrogen atom, halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. In addition, in the structures of the compounds listed in the above formula, the alkoxy group, aralkyloxy group, aryloxy group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group, and aryl group also include those in which various substituents are further bonded to the carbon atoms they possess.

[0098] The Diels-Alder reaction can be carried out using known methods. For example, the conjugated diene compound and the parent diene compound can be mixed in equimolar amounts, or in some cases, with an excess of one component, heated and melted, or dissolved in a solvent, and stirred at room temperature to 200°C for 1 to 24 hours. The result can then be obtained by filtration or solvent removal without further purification, or by commonly used isolation and purification methods such as recrystallization, reprecipitation, and chromatography.

[0099] The synthesis of parts other than the reversible bond can be done by known methods. For example, by reacting a diglycidyl ether or aliphatic divinyl ether of an aliphatic dihydroxy compound with an aromatic hydroxy compound to obtain a compound having a hydroxyl group at the terminal, and then reacting it with chloromethylanthracene, glycidyloxyanthracene, etc. to introduce an anthracene structure at the terminal, and further by carrying out a Diels-Alder reaction with a maleimide compound having a hydroxyl group in accordance with the above, the compound represented by the general formula (1-1) can be obtained.

[0100] Alternatively, a compound having a hydroxyl group at the terminal can be obtained, then epoxidized to form a glycidyl ether group at the terminal, and subsequently reacted with hydroxyanthracene or the like to introduce an anthracene structure at the terminal. Furthermore, by carrying out a Diels-Alder reaction with a maleimide compound having a hydroxyl group in accordance with the above, the compound represented by the general formula (1-1) can be obtained.

[0101] Alternatively, an aromatic dihydroxy compound can be reacted with a dihalogenated alkyl compound or a dihalogenated aralkyl compound to obtain a compound having a halogenated alkyl group at the terminal, and then reacted with hydroxymethylanthracene or the like to introduce an anthracene structure at the terminal. Furthermore, by carrying out a Diels-Alder reaction with a maleimide compound having a hydroxyl group in accordance with the above, the compound represented by the general formula (1-1) can be obtained.

[0102] The diglycidyl ether of the aliphatic dihydroxy compound is not particularly limited, and examples 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, 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether, and others, which may be used alone or in combination of two or more.

[0103] Among these, compounds having a structure in which glycidyl groups are linked to both ends of an alkylene chain having 12 to 14 carbon atoms via ether groups are preferred because they offer an excellent balance between the flexibility and heat resistance of the resulting cured product. Most preferably, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, and 1,14-tetradecanediol diglycidyl ether are used.

[0104] The aliphatic divinyl ether is not particularly limited and includes, for example, divinyl ethers with 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 with branched alkylene groups such as neopentyl glycol divinyl ether, divinyl ether containing cycloalkane structures such as 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecanedimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether, and pentacyclopentadecanediol divinyl ether, and bisphenol A divinyl ether, bisphenol F divinyl ether, and hydroquinone divinyl ether, which may be used alone or in combination of two or more types.

[0105] Among these, polyether structures or divinyl ethers of linear alkylene chains having 9 to 10 carbon atoms are preferred due to their excellent balance of flexibility and toughness in the resulting cured product. Most preferably, polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, and 1,14-tetradecanediol diglycidyl ether are used.

[0106] The aromatic hydroxy compounds are not particularly limited, and include, for example, 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'-methylenebisu(2,7-naphthalenediol), 1,1'-binaphthalene-2,2',7,7'-tetraol, and 1,1'-oxybisu(2,7-naphthalenediol), obtained by coupling reactions of dihydroxynaphthalenes; and bis(4-H Bisphenols such as 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 include biphenols such as 4'-diols, alicyclic structure-containing phenols such as polyadditives of phenol and dicyclopentadiene, and polyadditives of phenol and terpene compounds, naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane, and so-called Zyloc-type phenolic resins which are condensation reaction products of phenol and phenylene dimethyl chloride or biphenylene dimethyl chloride. These may be used individually or in combination of two or more. Furthermore, bifunctional phenolic compounds in which a methyl group, t-butyl group, or halogen atom is substituted as a substituent on the aromatic kernel of each of the above compounds are also examples. Note that the alicyclic structure-containing phenols and the Zyloc-type phenolic resins may contain not only bifunctional components but also trifunctional or more functional components simultaneously. They 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 due to their excellent balance of flexibility and toughness when cured, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferred due to their remarkable toughness-imparting properties. Furthermore, when moisture resistance of the cured product is important, 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 / latter, and it is preferable that (a1) / (a2) is 1 / 1.1 to 1 / 3.0 (molar ratio) in order to obtain a cured product that has a good balance of flexibility and heat resistance.

[0109] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound is preferably carried out in the presence of a catalyst. Various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; phosphorus compounds such as triphenylphosphine; 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. These catalysts may be used in combination of two or more types. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds rapidly and they have a high effect 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 phenolic hydroxyl group of the aromatic hydroxy compound. The form of these catalysts is also not particularly limited and may be used in aqueous solution form or in solid form.

[0110] Furthermore, the reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound can be carried out without a solvent or in the presence of an organic solvent. Examples of 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 organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, relative to the total mass of the raw materials. These organic solvents can be used individually or in mixtures of several types. Solvent-free use is preferred for rapid reaction, while the use of dimethyl sulfoxide is preferred in terms of reducing impurities in the final product.

[0111] The reaction temperature for the above reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. A reaction temperature of 100 to 160°C is preferred in order to reduce impurities in the final product. If the resulting compound is highly discolored, antioxidants or reducing agents may be added to suppress this discoloration. Antioxidants are not particularly limited, but examples include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing trivalent phosphorus atoms. Reducing agents are not particularly limited, but examples include hypophosphorous acid, phosphite, thiosulfite, sulfite, hydrosulfite, or salts thereof.

[0112] After the reaction is complete, the reaction mixture may be neutralized or washed with water until its pH is 3 to 7, preferably 5 to 7. Neutralization and washing can be carried out according to conventional methods. For example, when a basic catalyst is used, acidic substances such as hydrochloric acid, sodium monohydrogen phosphate, p-toluenesulfonic acid, or oxalic acid can be used as neutralizing agents. After neutralization or washing, the solvent can be removed under reduced pressure and heating if necessary to concentrate the product and 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), and it is preferable that (a1) / (a2) is 1 / 1.02 to 1 / 3.0 (molar ratio) in order to obtain a cured product that has a good balance of flexibility and heat resistance.

[0114] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently without the use of a catalyst, but a catalyst may be used as appropriate in terms of selecting the starting materials and increasing the reaction rate. Examples of catalysts that can be used here include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; organic acids such as toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, and trifluoroacetic acid; and Lewis acids such as aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, and boron trifluoride phenol complex. The amount of catalyst used is usually in the range of 10 ppm to 1% by weight relative to the mass of the divinyl ether compound. In this case, it is preferable to select the type and amount of catalyst so as not to cause a nucleation reaction of the vinyl group to the aromatic ring.

[0115] Furthermore, the reaction between the aliphatic divinyl ether and the aromatic hydroxy compound can be carried out without a solvent or in the presence of an organic solvent. Examples of 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 alcoholic organic solvents such as methanol, ethanol, and isopropyl alcohol n-butanol. The amount of organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, relative to the total mass of the raw materials. These organic solvents can be used individually or in mixtures of several types.

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

[0117] After the reaction is complete, if an organic solvent was used, it can be removed under reduced pressure heating. If a catalyst was used, it can be deactivated with an inactivator or the like as necessary, and then removed by washing with water or filtration to obtain the compound.

[0118] The compound having a hydroxyl group at its terminus, obtained in this manner, is reacted with chloromethylanthracene or the like. Sodium hydroxide, potassium hydroxide, potassium carbonate, etc., can be used as catalysts, and toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide, etc., can be used as solvents. The reaction temperature is room temperature to 200°C, and the reaction time is 1 to 24 hours. Afterward, the catalyst is removed by filtration, etc., and the target compound can be obtained by extraction, solvent removal, etc. The Diels-Alder reaction with this compound is as described above.

[0119] The aliphatic hydroxy compounds are not particularly limited, and include, for example, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, and 1,16-hexadecanediol. Examples include diols, 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, polyheptamethylene glycol diglycidyl ether, etc., which may be used individually or in combination of two or more types.

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

[0121] The aforementioned alkyl dihalide compounds are not particularly limited, and examples 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, 1,12-dibromododecane, etc., which may be used alone or in combination of two or more.

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

[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) for the former / latter, and is preferably (a1) / (a2) is 1 / 1.02 to 1 / 3.0 (molar ratio) in order to obtain a cured product that has a good balance of flexibility and heat resistance.

[0124] The reaction between the aromatic dihydroxy compound and the alkyl dihalide compound or aralkyl dihalide compound is preferably carried out in the presence of a catalyst. Various catalysts can be used, such as alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, 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 the reaction proceeds rapidly and they have a high effect 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 10 moles per mole of phenolic hydroxyl group of the aromatic hydroxy compound. The form of these catalysts is also not particularly limited and may be used in aqueous solution form or in solid form.

[0125] Furthermore, the reaction between the aromatic dihydroxy compound and the dihalogenated alkyl compound or dihalogenated aralkyl compound can be carried out without a solvent or in the presence of an organic solvent. Examples of organic solvents that can be used include toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, and dimethylformamide. The amount of organic solvent used is usually 50 to 300% by mass, preferably 100 to 1000% by mass, relative to the total mass of the raw materials. These organic solvents can be used individually or in mixtures of several types.

[0126] The reaction temperature for the above-mentioned reaction is usually room temperature to 150°C, and the reaction time is usually 1 to 24 hours. From the viewpoint of reducing impurities in the final product, a reaction temperature of room temperature to 100°C is preferable.

[0127] The compound having a halogenated alkyl group at the terminal, obtained in this manner, is reacted with hydroxymethylanthracene or the like. Sodium hydroxide, potassium hydroxide, potassium carbonate, etc., can be used as catalysts, and toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide, etc., can be used as solvents. The reaction temperature is room temperature to 200°C, and the reaction time is 1 to 24 hours. Afterward, the catalyst is removed by filtration, etc., and the target compound can be obtained by extraction, solvent removal, etc. The Diels-Alder reaction with this compound is as described above.

[0128] The conjugated diene intermediate or parent diene intermediate before the Diels-Alder reaction can be represented by the following general formulas (1-1)' and (1-2)'.

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

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

[0131] The following compounds can be listed as raw materials for the aforementioned compounds having disulfide bonds:

[0132] [ka]

[0133] [ka]

[0134] The compound having the disulfide bond can be obtained using known methods. For example, the compound having the disulfide bond can be bonded oxidatively. Iodine and hydrogen peroxide are commonly used as oxidizing agents. It can be obtained by heating and melting or dissolving in a solvent, stirring at room temperature to 200°C for 1 to 24 hours, and then filtering or removing the solvent without further purification. Alternatively, it can be obtained 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 compound (I), which is reactive with the hydroxyl group-containing compound, to form a curable resin composition. The curable resin composition can be suitably used in various electrical and electronic component applications such as adhesives, paints, photoresists, printed circuit boards, and semiconductor encapsulation materials.

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

[0137] Examples of the melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylmelamine are methoxymethylated, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, and compounds in which 1 to 6 methylol groups of hexamethylmelamine are acyloxymethylated.

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

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

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

[0141] Examples of resol resins include polymers obtained by reacting phenolic hydroxyl group-containing compounds such as phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene with aldehyde compounds under alkaline catalytic conditions.

[0142] The epoxy resins include, for example, 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, 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 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 copolymer novolac type epoxy resins, naphthol-cresol copolymer novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, biphenyl-modified novolac type epoxy resins, etc. These can be used individually or in combination of two or more types, and it is preferable to select and use them according to the intended application and the physical properties of the cured product.

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

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

[0145] Examples of compounds containing double bonds such as the 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 aforementioned acid anhydrides 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, dodecenyl succinic 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. With such a configuration, both the repairability and remodelability of the cured product obtained from the curable resin composition are further improved. The aforementioned 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, defined by the tanδ peak top of the dynamic viscoelasticity measuring instrument (DMA) of the target cured product. For example, when using the glass transition temperature as a guideline, if the glass transition temperature of the cured product is near room temperature, sufficient repairability and remodelability functions are more likely to be exhibited even at the lower end of the preferred range of concentrations. On the other hand, if the glass transition temperature of the target cured product is above 100°C as a guideline, the functions are more likely to be exhibited at the higher end of the preferred range of concentrations. However, in the temperature range exceeding the glass transition temperature measured by DMA, molecular mobility is generally high, and sufficient repair and remodeling functions tend to be exhibited even at low concentrations of hydroxyl group-containing compounds. Therefore, the effect of exhibiting repair and remodeling functions can be adjusted, for example, by adjusting the aging temperature for repair and the heating temperature for remodeling as needed. 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) that reacts with the hydroxyl group-containing compound, epoxy resin is particularly preferred because it results in a curable resin composition with excellent curability, mechanical strength of the cured product, heat resistance, and other properties.

[0149] As the epoxy resin, an epoxy resin represented by the following formula (8) and having an epoxy equivalent of 500 to 10000 g / eq may be used.

[0150] [ka] [In formula (8), each Ar independently has a structure that is either unsubstituted or has a 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 equations (8-1) and (8-2), Ar is the same as described above. R 1 , R 2 Each of these is independently a hydrogen atom, a methyl group, or an ethyl group. R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. R 3 , R 4 , R 7 , R 8 Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R 5 , R 6 , R 9 , R 10 Each of these is independently a hydrogen atom or a methyl group. n1 is an integer between 2 and 16. n² is the average value of the repetition unit, ranging from 2 to 30. R 11 , R 12 Each of these is independently a glycidyl ether group or a 2-methylglycidyl ether group. R 13 , R 14 Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R 15 , R 16 is a hydrogen atom or a methyl group, m3, m4, p1, p2, and q are repeated mean values. m3 and m4 are independently between 0 and 25, and m3 + m4 ≥ 1. p1 and p2 are independently between 0 and 5. q is between 0.5 and 5. However, the bonding between X' represented by the general formula (8-2) and Y' represented by the general formula (8-3) may be random or blocky, and the total number of each structural unit X' and Y' present in one molecule is m3 and m4, respectively.

[0153] As the epoxy resin, an epoxy resin represented by the following formula (9) may be used. By using such an epoxy resin, the repairability and remolding properties of the cured epoxy resin are improved, and a good balance between flexibility and toughness is achieved.

[0154] [ka] [In equation (9), p1, p2, q, and m4 are repeated average values, and independently, p1 is between 0 and 5, p2 is between 0 and 5, q is between 0.5 and 5, and m4 is between 0 and 25.]

[0155] The epoxy resin represented by the general formula (8) or (9) may be used alone or in combination with the hydroxyl group-containing compound of the present invention to form a curable resin. However, from the viewpoint of further imparting flexibility to the cured product and easily exhibiting easy decomposition properties, it is also preferable to use an epoxy resin with an epoxy equivalent of 100 to 300 g / eq in combination.

[0156] The epoxy resins that can be used in combination as described above only need to have an epoxy equivalent in the range of 100 to 300 g / eq, and their structure is not limited. For example, 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, tetramethylbiphenyl type epoxy resin, etc., 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, dicyclopeptide Examples include antadien-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 copolymer novolac type epoxy resins, naphthol-cresol copolymer novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, biphenyl-modified novolac type epoxy resins, etc. These can be used individually or in combination of two or more types, and it is preferable to select and use them according to the intended application and the physical properties of the cured product.

[0157] Among these, it is preferable to use an epoxy resin with an epoxy equivalent of 100 to 300 g / eq from among 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. In particular, it is preferable to use an epoxy resin with an epoxy equivalent of 100 to 300 g / eq from among bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin.

[0158] There are no particular limitations on the ratio of the epoxy resin represented by the general formula (8) or (9) and the epoxy resin having an epoxy equivalent of 100 to 300 g / eq used. However, from the viewpoint of easy phase separation in the cured product, the mass ratio of the former to the latter is 97:3 to 3:97, preferably 10:90 to 90:10, and particularly preferably 80:20 to 20:80. Phase separation in the cured product results in a sea-island structure, achieving both adhesiveness and stress relaxation ability in the cured product, exhibiting high adhesive strength over a wide temperature range, and reducing the molding shrinkage rate of the resin composition before and after heat curing.

[0159] Furthermore, when combining the hydroxyl group-containing compound of the present invention with an epoxy resin to form a curable resin composition, an epoxy resin curing agent may be added.

[0160] Examples of curing agents 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 compounds 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, and Aliphatic amine compounds such as tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane(triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, α-methylbenzylmethylamine, and other aliphatic amine compounds;

[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, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU);

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

[0164] Examples include epoxy compound-added polyamines, Michael-added polyamines, Mannich-added polyamines, thiourea-added polyamines, ketone-blocked polyamines, dicyandiamides, guanidines, organic acid hydrazides, diaminomaleonitriles, amineimides, boron trifluoride-piperidine complexes, boron trifluoride-monoethylamine complexes, and other modified amine compounds.

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

[0166] The phenolic hydroxyl group-containing compounds 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 phenol resins, dicyclopentadienephenol addition type resins, phenol aralkyl resins (Zyloc resins), naphthol aralkyl resins, and trimethylol methane resins. Examples of polyhydric phenol compounds include tetraphenyloleethane 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 the phenol nucleus is linked by a bismethylene group), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which the phenol nucleus is linked by a bismethylene group), aminotriazine-modified phenol resin (a polyhydric phenol compound in which the phenol nucleus is linked by melamine, benzoguanamine, etc.), and alkoxy-group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which the phenol nucleus and alkoxy-group-containing aromatic ring are linked by formaldehyde).

[0167] Examples of the amide compounds include dicyandiamide and polyamidoamine. Examples of polyamidoamines include those obtained by reacting aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid, or carboxylic acid compounds such as fatty acids and dimer acids, with aliphatic polyamines or polyamines having polyoxyalkylene chains.

[0168] Examples of the carboxylic acid compound include carboxylic acid-terminated polyesters, polyacrylic acid, maleic acid-modified polypropylene glycols, and other carboxylic acid polymers.

[0169] The thiol compound is preferably one that contains two or more thiol groups in one molecule. Examples include 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)glycoluryl, 4-butanedithiol, 1,6-hexanedithiol, and 1,10-decandithiol.

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

[0171] While there are no particular restrictions on the amount of epoxy resin and curing agent used, it is preferable that the amount of reactive groups that can react with epoxy groups, including the hydroxyl group-containing curing product of the present invention, be such that the mechanical properties of the resulting cured product are good.

[0172] Furthermore, when epoxy resin is used, a curing accelerator may be included. Various curing accelerators can be used, but examples include 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 preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene is preferred among tertiary amines due to their excellent curability, heat resistance, electrical properties, and moisture resistance reliability.

[0173] Examples of the phosphorus compounds include alkylphosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine; dialkylphosphines 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 imidazoles 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- Sopropylimidazole, 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- Midazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole Examples include isocyanuric acid adducts, 2-methylimidazole isocyanuric acid adducts, 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 compounds include 2-methylimidazoline and 2-phenylimidazoline.

[0176] Examples of the urea compounds 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] Furthermore, the curable resin composition of the present invention may be used in combination with other thermosetting resins or thermoplastic resins, to the extent that they do not impair the effects of the present invention.

[0178] Other thermosetting resins include, for example, cyanate ester resins, resins having a benzoxazine structure, activated ester resins, vinyl benzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride. When using any of the above-mentioned other thermosetting resins in combination, the amount used is not particularly limited as long as it does not hinder the effects of the present invention, but it 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 resins 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, and triphenyl Examples include rumethane-type cyanate ester resins, 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, anthracene-type cyanate ester resins, and the like. These may be used individually or in combination of two or more types.

[0180] Among these cyanate ester resins, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthylene ether type cyanate ester resin, and novolac type cyanate ester resin are preferred for obtaining cured products with excellent heat resistance, while dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferred for obtaining cured products with excellent dielectric properties.

[0181] There are no particular restrictions on the resin having a benzoxazine structure, but examples include the reaction product of bisphenol F, formalin, and aniline (Fa-type benzoxazine resin), the reaction product of diaminodiphenylmethane, formalin, and phenol (Pd-type benzoxazine resin), the reaction product of bisphenol A, formalin, and aniline, the reaction product of dihydroxydiphenyl ether, formalin, and aniline, the reaction product of diaminodiphenyl ether, formalin, and phenol, the reaction product of dicyclopentadiene-phenol addition resin, formalin, and aniline, the reaction product of phenolphthalein, formalin, and aniline, and the reaction product of diphenyl sulfide, formalin, and aniline. These may be used individually or in combination of two or more types.

[0182] There are no particular restrictions on the activated ester resin, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred. The activated ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, activated ester resins obtained from a carboxylic acid compound or its halide and a hydroxy compound are preferred, and activated 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, etc., or their halides. 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 addition resins.

[0183] As the active ester resin, specifically, active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated phenol novolacs, and active ester resins that are benzoylated phenol novolacs are preferred, and among these, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred in that they are excellent at improving peel strength.

[0184] Furthermore, various novolac resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolac resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zyloc resins), naphthol aralkyl resins, trimethylol methane resins, tetraphenyloleethane resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and various vinyl polymers may be used in combination.

[0185] The aforementioned novolac resins include, more specifically, polymers obtained by reacting phenolic hydroxyl group-containing compounds such as phenol, phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene with aldehyde compounds under acid-catalyzed conditions.

[0186] The aforementioned vinyl polymers include homopolymers or copolymers thereof of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricycline, and poly(meth)acrylate.

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

[0188] When using these other resins, the blending ratio of the hydroxyl group-containing compound of the present invention to the other resin can be arbitrarily set depending on the application. However, from the viewpoint of not hindering the repairability and remolding properties achieved by the present invention, it is preferable that the ratio is 0.5 to 100 parts by mass of the other resin to 100 parts by mass of the hydroxyl group-containing compound of the present invention.

[0189] Furthermore, the curable resin composition of the present invention may also contain a curing accelerator. Examples of curing accelerators 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 individually 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] Furthermore, when the curable resin composition of the present invention is used in applications requiring high flame retardancy, a non-halogen flame retardant that substantially does not contain halogen atoms may be incorporated.

[0191] Examples of the non-halogen-based flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organometallic salt-based flame retardants, etc. There are no restrictions on their use; they can be used individually, multiple flame retardants of the same type can be used together, or flame retardants of different types can be used in combination.

[0192] The phosphorus-based flame retardant can be either inorganic or organic. Examples of inorganic compounds include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate, as well as inorganic nitrogen-containing phosphorus compounds such as phosphate amides.

[0193] Also, the red phosphorus is preferably subjected to surface treatment for the purpose of preventing hydrolysis or the like. Examples of the surface treatment method include (i) a method of coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide and a thermosetting resin such as a phenolic resin; (iii) a method of double coating with a thermosetting resin such as a phenolic resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc.

[0194] The organic phosphorus compound includes, for example, 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 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus compounds, and derivatives obtained by reacting the same with compounds such as epoxy resins and phenolic resins.

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

[0196] When using the phosphorus-based flame retardant, it may be used in combination with hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dyes, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc.

[0197] Examples of the nitrogen-based flame retardants include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, etc. Triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred.

[0198] Examples of the triazine compounds include melamine, acetoguanamine, benzoguanamine, melem, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, etc. In addition, for example, (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate, (2) condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, etc. with melamines such as melamine, benzoguanamine, acetoguanamine, formoguanamine, etc. and formaldehyde, (3) mixtures of the condensates of (2) with phenolic resins such as phenol-formaldehyde condensates, (4) those obtained by further modifying (2) and (3) with tung oil, isomerized linseed oil, etc.

[0199] Examples of the cyanuric acid compounds include cyanuric acid, melamine cyanurate, etc.

[0200] The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all of the non-halogen-based flame retardant and other fillers and additives, it is preferably blended in the range of from 0.05 to 10 parts by mass, and more preferably in the range of from 0.1 part by mass to 5 parts by mass.

[0201] When using the nitrogen-based flame retardant, it may be used in combination with metal hydroxides, molybdenum compounds, etc.

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

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

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

[0205] Examples of the aforementioned metal oxides 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 aforementioned metal carbonate compounds 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 aforementioned metal powders include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

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

[0209] Examples of the low-melting-point glass include glassy compounds such as Sheeplee (Voxui-Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3 system, ZnO-P2O5-MgO system, P2O5-B2O3-PbO-MgO system, P-Sn-OF system, PbO-V2O5-TeO2 system, Al2O3-H2O system, and lead borosilicate system.

[0210] The amount of inorganic flame retardant to be blended is appropriately selected depending on the type of inorganic flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. For example, it is preferable to blend it in the range of 0.05 to 20 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass, per 100 parts by mass of the resin composition containing the non-halogenated flame retardant and all other fillers and additives.

[0211] Examples of the organometallic salt-based flame retardants include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organocobalt salt compounds, organosulfonic acid metal salts, and compounds in which a metal atom is ionically bonded or coordinately bonded to an aromatic compound or heterocyclic compound.

[0212] The amount of the organometallic salt flame retardant is appropriately selected depending on the type of organometallic salt flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. For example, it is preferable to include it in an amount of 0.005 to 10 parts by mass per 100 parts by mass of the resin composition containing the non-halogenated flame retardant and all other fillers and additives.

[0213] The curable resin composition of the present invention may contain a filler. Examples of fillers include inorganic fillers and organic fillers. Examples of inorganic fillers include inorganic fine particles.

[0214] Examples of inorganic fine particles include, for example, those with excellent heat resistance: alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine amorphous silica, etc.); those with excellent thermal conductivity: boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.; those with excellent electrical conductivity: metal fillers and / or metal-coated fillers using elemental metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); those with excellent barrier properties: minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite. Examples of inorganic nanoparticles include aluminum borate, calcium carbonate, titanium dioxide, barium sulfate, zinc oxide, and magnesium hydroxide; those with high refractive index include barium titanate, zirconia oxide, and titanium dioxide; 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 the aforementioned metals and their oxides; those with excellent wear resistance include metals such as silica, alumina, zirconia, and magnesium oxide, and their composites and oxides; 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 ultraviolet shielding properties include titanium dioxide and zinc oxide. These inorganic nanoparticles can be selected as appropriate depending on the application, and may be used individually or in combination of multiple types. Furthermore, since the above inorganic nanoparticles have various properties other than those listed as examples, they should be selected as appropriate for the application.

[0215] For example, when using silica as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used. Examples of commercially available powdered silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildeck H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Chemical Ltd., SG flakes manufactured by Nippon Sheet Glass Co., Ltd., and the like.

[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, ST-OL, etc. manufactured by Nissan Chemical Industries, Ltd.

[0217] Silica fine particles with surface modification may also be used. For example, those obtained by surface-treating the silica fine particles with a reactive silane coupling agent having a hydrophobic group, or those modified with a compound having a (meth)acryloyl group can be mentioned. 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-shaped, plate-shaped, fibrous, or irregularly shaped particles can be used. The primary particle diameter is preferably in the range of 5 to 200 nm.

[0219] As titanium dioxide nanoparticles, not only extender pigments but also UV-responsive photocatalysts can be used, such as anatase-type titanium dioxide, rutile-type titanium dioxide, and brookite-type titanium dioxide. Furthermore, particles designed to respond to visible light by doping different elements into the crystal structure of titanium dioxide can also be used. Suitable elements for doping titanium dioxide include anionic elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cationic elements such as chromium, iron, cobalt, and manganese. In terms of form, it can be used as a powder, a sol dispersed in an organic solvent or water, or a slurry. Examples of commercially available powdered titanium dioxide nanoparticles include Aerosil P-25 from Nippon Aerosil Co., Ltd. and ATM-100 from Teika Co., Ltd. Examples of commercially available slurry-type titanium dioxide nanoparticles include TKD-701 from 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 those used in fiber-reinforced resins are preferred, and examples include inorganic fibers and organic fibers.

[0221] Inorganic fibers include carbon fibers, glass fibers, boron fibers, alumina fibers, 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 above-mentioned 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 (poly-p-phenylenebenzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as proteins, polypeptides, and alginic acid.

[0223] Among these, carbon fiber and glass fiber are preferred because they have a wide range of industrial applications. Only one of these materials may be used, or multiple materials may be used simultaneously.

[0224] The fibrous matrix may be an aggregate of fibers, and the fibers may be continuous or discontinuous, and may be woven or unwoven. It may also be a bundle of fibers aligned in one direction, or a sheet made of arranged fiber bundles. Furthermore, it may be a three-dimensional shape with thickness given to the aggregate of fibers.

[0225] The curable resin composition of the present invention may use a dispersion medium to adjust the solid content and viscosity of the resin composition. The dispersion medium can be any liquid medium that does not impair the effects of the present invention, and examples include various organic solvents and liquid organic polymers.

[0226] Examples of the aforementioned organic solvents 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 in terms of volatility during coating and solvent recovery.

[0227] The aforementioned liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples include acrylic polymers (Floren WK-20: Kyoeisha), amine salts of specially modified phosphate esters (HIPLAAD ED-251: Kusumoto Kasei), and modified acrylic block copolymers (DISPERBYK2000: Bic Chemie).

[0228] The resin composition of the present invention may contain other compounds. Examples include catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, reactive diluents, and the like.

[0229] A cured product can be obtained by curing the resin composition of the present invention. Curing can be performed at room temperature or by heating. When performing thermal curing, curing may be performed in a single heating step or through a multi-stage heating process.

[0230] Furthermore, the curable resin composition of the present invention can also be cured using active energy rays. In this case, a photocationic polymerization initiator may be used as the polymerization initiator. As the active energy ray, visible light, ultraviolet light, X-rays, electron beams, etc., can be used.

[0231] Examples of photocationic polymerization initiators include aryl sulfonium salts and aryl iodonium salts. Specifically, aryl sulfonium hexafluorophosphate, aryl sulfonium hexafluoroantimonate, aryl sulfonium tetrakis(pentafluoro)borate, and tri(alkylphenyl)sulfonium hexafluorophosphate can be used. Photocationic polymerization initiators may be used alone or in combination of two or more.

[0232] The curable resin composition of the present invention can be prepared by uniformly mixing the aforementioned components, and the method of preparation is not particularly limited. For example, it can be prepared by uniformly mixing using a pot mill, ball mill, bead mill, roll mill, homogenizer, super mill, homodisper, universal mixer, Banbury mixer, kneader, etc.

[0233] The curable resin composition of the present invention is obtained by dissolving the hydroxyl group-containing compound of the present invention and compound (I) which is reactive with the hydroxyl group-containing compound, and optionally the aforementioned curing agent, filler, fibrous substrate, dispersion medium, and resins other than the aforementioned various compounds, in a dispersion medium such as the aforementioned organic solvent. After dissolution, the solvent is removed by distillation, and the curable resin composition can be obtained by drying under reduced pressure in a vacuum oven or the like. The curable resin composition of the present invention may also be obtained in a state in which the aforementioned constituent materials are uniformly mixed. In this case, it is preferable to mix them uniformly in a mixer or the like. The mixing ratio of each constituent material can be appropriately adjusted according to the desired properties of the cured product, such as mechanical strength, heat resistance, repairability, and remoldingability. Furthermore, there are no particular limitations on the specific mixing order of the constituent materials in the preparation of the curable resin composition.

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

[0235] As described above, the cured product of the present invention is cured with the hydroxyl group-containing compound of the present invention, and by exhibiting an appropriate crosslinking density, it is possible to maintain good mechanical strength. Furthermore, when mechanical energy such as scratches or external forces is applied to the cured product of the present invention, the reversible bonds are broken, but since the equilibrium shifts in the direction of bonding, it is thought that adducts will be formed again, making it possible to repair scratches and reshape the product.

[0236] The structure of the resulting cured product can be confirmed by infrared absorption (IR) spectroscopy using Fourier transform infrared spectroscopy (FT-IR), elemental analysis, X-ray scattering, etc.

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

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

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

[0240] The curable resin composition of the present invention and the cured product produced using this curable resin composition are excellent in both heat resistance and repairability, and are also remoldable, making them useful for the following applications.

[0241] The curable resin cured product of the present invention can be laminated by laminating it with a substrate. The substrate of the laminate may be an inorganic material such as metal or glass, or an organic material such as plastic or wood, depending on the application. The laminate may be in the shape of a flat plate, a sheet, or a three-dimensional structure, or it may be three-dimensional. It may be any shape depending on the purpose, such as having curvature on the entire surface or in part. There are also no restrictions on the hardness, thickness, etc., of the substrate. Alternatively, a multilayer laminate may 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 that order. Since the curable resin composition of this embodiment has excellent adhesive properties, it can be suitably used as an adhesive to bond the first substrate and the second substrate. Alternatively, the curable resin cured product of the present invention may be used as a substrate, and the cured product of the present invention may be further laminated.

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

[0243] In a laminate formed by laminating a cured product of the present invention with a substrate, the layer containing the cured product may be formed by direct coating or molding onto the substrate, or a pre-molded layer may be laminated. When direct coating is performed, there are no particular limitations on the coating method, and examples include spray coating, spin coating, dip coating, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, screen printing, and inkjet coating. When direct molding is performed, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination, 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 product of the composition may be laminated onto the substrate. Furthermore, the cured product of the present invention may be laminated by coating a precursor that can serve as a substrate with it and curing it, or the precursor that can serve as a substrate or the composition of the present invention may be bonded in an uncured or semi-cured state and then cured. There are no particular limitations on the precursor that can serve as a substrate, and examples include various curable resin compositions.

[0244] The cured products obtained using the curable resin composition of the present invention exhibit particularly high adhesion to metals and / or metal oxides, making them particularly suitable for use as primers for metals. Examples of metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials thereof. Examples of metal oxides include individual oxides and / or composite oxides of these metals. In particular, the composition exhibits excellent adhesion to iron, copper, and aluminum, making it suitable for use 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 members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the aerospace industry. Even when used to bond dissimilar materials, such as metal-nonmetallic materials, this adhesive maintains high adhesion regardless of temperature changes, and is less prone to peeling. In addition to its use in structural members, this adhesive can also be used as an adhesive for general office use, medical applications, carbon fiber, battery cells, modules, and cases, and as an adhesive for bonding optical components, bonding optical discs, mounting printed circuit boards, die bonding, underfills, BGA reinforcement underfills, anisotropic conductive films, and anisotropic conductive pastes.

[0246] If 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 it does not impair the effects of the present invention, and examples include compounding the fibrous substrate and the composition by kneading, coating, impregnation, injection, or compression, which can be appropriately selected depending on the form of the fibers and the application of the fiber-reinforced resin.

[0247] There are no particular limitations on the method of molding fiber-reinforced resins. For plate-shaped products, extrusion molding is common, but it is also possible by flat pressing. In addition, extrusion molding, blow molding, compression molding, vacuum molding, injection molding, etc., can be used. When manufacturing film-shaped products, in addition to molten extrusion, solution casting can be used, and when using molten molding methods, examples include inflation film molding, cast molding, extrusion lamination molding, calendering, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. Furthermore, in the case of resins that harden with active energy rays, cured products can be manufactured using various hardening methods that utilize active energy rays. In particular, when thermosetting resins are the main component of the matrix resin, molding methods that involve pre-pregging the molding material and heating it under pressure by pressing or autoclaving are mentioned, as well as RTM (Resin Transfer Molding) molding, VaRTM (Vacuum Assist Resin Transfer Molding) molding, lamination molding, and hand lay-up molding.

[0248] The curable resin composition of the present invention can be used for large cases, motor housings, casting materials for the inside of cases, gears, pulleys, and other molding materials, as the cured products obtained using it have good heat resistance and repairability, as well as remoldability. These may be cured products of the resin alone, or cured products reinforced with fibers such as glass chips.

[0249] Fiber-reinforced resins can form an uncured or semi-cured state called 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 first, then laminate the other layers, and then perform final curing, as this allows for the formation of a laminate in which each layer is tightly bonded. The mass ratio of the composition and fibrous substrate used at this time is not particularly limited, but it is generally preferable to prepare the prepreg so that the resin content is 20 to 60% by mass.

[0250] The cured product of the present invention exhibits excellent heat resistance and repairability, as well as remolding properties, making it suitable for use as a heat-resistant material and an electronic material. In particular, it is suitably used as a semiconductor encapsulant, circuit board, build-up film, build-up substrate, adhesive, and resist material. It is also suitably used as a matrix resin for fiber-reinforced resins, and is especially suitable as a high-heat-resistant prepreg. The heat-resistant and electronic components thus obtained can be suitably used in a variety of applications, including, but are not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, and wind turbine enclosure components.

[0251] In particular, taking advantage of its excellent flexibility in cured products, it can be suitably used as an adhesive for structural components in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the aerospace industry. The adhesive of the present invention can maintain high adhesion regardless of changes in temperature environment, even when used to bond dissimilar materials such as metal-nonmetal, and is less prone to peeling. In addition to structural component applications, the adhesive of the present invention can also be used as an adhesive for general office use, medical use, carbon fiber, battery cells, modules and cases, etc. Examples include adhesives for bonding optical components, adhesives for bonding optical discs, adhesives for mounting printed circuit boards, die bonding adhesives, semiconductor adhesives such as underfills, underfills for BGA reinforcement, anisotropic conductive films, anisotropic conductive pastes, and other mounting adhesives.

[0252] The following will provide examples of representative products.

[0253] 1. Semiconductor encapsulation materials A method for obtaining a semiconductor encapsulating material from the resin composition of the present invention involves thoroughly melting and mixing the resin composition, a curing accelerator, and compounding agents such as inorganic fillers using an extruder, needle, roll, etc., as needed, until the mixture is uniform. In this case, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulating material for power transistors and power ICs, it is preferable to use a higher filler content of crystalline silica, alumina, silicon nitride, etc., which have higher thermal conductivity than fused silica, or to use fused silica, crystalline silica, alumina, silicon nitride, etc. The filler content is preferably in the range of 30 to 95% by mass of inorganic filler per 100 parts by mass of curable resin composition, and in particular, 70 parts by mass or more is more preferable, and 80 parts by mass or more is even more preferable, in order to improve flame retardancy, moisture resistance, solder crack resistance, and the coefficient of linear expansion.

[0254] 2. Semiconductor equipment A semiconductor package molding method for obtaining a semiconductor device from the curable resin composition of the present invention involves molding the semiconductor encapsulating material by casting, or using a transfer molding machine, injection molding machine, etc., and then heating it 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 above-mentioned prepreg by a conventional method, layering copper foil as appropriate, and then heat-pressing it at 170 to 300°C for 10 minutes to 3 hours under pressure of 1 to 10 MPa.

[0256] 4. Flexible substrate A method for producing a flexible substrate from the crosslinkable resin composition of the present invention includes the following three-step method. The first step is to apply the crosslinkable resin composition, which contains resin components and organic solvents, to an electrical insulating film using a coating machine such as a reverse roll coater or comma coater. The second step is to heat the electrical insulating film coated with the crosslinkable resin composition using a heater at 60 to 170°C for 1 to 15 minutes to evaporate the solvent from the electrical insulating film and B-stage the crosslinkable resin composition. The third step is to heat-press a metal foil onto the B-staged electrical insulating film using a heating roll or the like to bond it to an adhesive (preferably with a bonding pressure of 2 to 200 N / cm and a bonding temperature of 40 to 200°C). If sufficient adhesive performance is obtained through the three steps described above, the process can be terminated here. However, if complete adhesive performance is required, it is preferable to further cure the resin at 100-200°C for 1-24 hours. The thickness of the resin composition layer after final curing is preferably in the range of 5-100 μm.

[0257] 5. Build-up board A method for obtaining a build-up substrate from the composition of the present invention includes the following steps, for example: First, the composition, which contains rubber, fillers, etc., in appropriate proportions, is applied to a circuit board with a circuit formed on it using a spray coating method, a curtain coating method, etc., and then cured (Step 1). After that, holes such as predetermined through-holes are drilled as needed, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and then plated with a metal such as copper (Step 2). These operations are repeated sequentially as desired to alternately build up and form a resin insulating layer and a conductor layer of a predetermined circuit pattern (Step 3). Note that the drilling of through-holes is performed after the formation of the outermost resin insulating layer. Furthermore, the build-up substrate of the present invention can also be manufactured by forming a roughened surface and omitting the plating process by heating and pressing a resin-coated copper foil, which has the resin composition semi-cured on a copper foil, onto a wiring board with a circuit formed on it at 170 to 300°C.

[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) which is a base material, and then drying the organic solvent by heating or blowing hot air to form a layer (X) of the composition.

[0259] The organic solvents used here preferably include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and it is preferable to use them in a proportion that results in a non-volatile content of 30 to 60% by mass.

[0260] The thickness of the formed layer (X) 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, it is preferable that the thickness of the resin composition layer be 10 to 100 μm. The above composition layer (X) in this invention may be protected by a protective film, which will be described later. By protecting it with a protective film, it is possible to prevent dust and other debris from adhering to the surface of the resin composition layer and to prevent scratches.

[0261] The aforementioned support film and protective film can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and also release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be treated with matte finish, corona finish, or release finish. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0262] The support film (Y) described above is peeled off after lamination to the circuit board or after an insulating layer is formed by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film has heat cured, it is possible to prevent the adhesion of dust and other contaminants during the curing process. When peeling off after curing, the support film is usually treated with a release agent beforehand.

[0263] A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, if layer (X) is protected by a protective film, these are peeled off, and then layer (X) is laminated to one or both sides of the circuit board so that it is in direct contact with the circuit board, for example, by vacuum lamination. The lamination method may be batch or continuous on 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 temperature (lamination temperature) of 70 to 140°C and a pressure of 1 to 11 kgf / cm2 (9.8 × 10⁻⁶). 4 ~107.9×10 4 N / m 2 It is preferable to use this method, and it is preferable to laminate under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0264] 7. Conductive paste One method for obtaining a conductive paste from the composition of the present invention is to disperse 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. [Examples]

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

[0266] 1H and 13 ¹¹¹NMR, FD-MS spectra, and GPC were measured under the following conditions.

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

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

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

[0270] GPC: HLC-8320GPC manufactured by Tosoh Corporation Column: Tosoh Corporation's "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" Detector: RI (Differential Refractive Index Meter) Measurement conditions: 40℃ Mobile phase: tetrahydrofuran Flow rate: 1ml / min Standard: Tosoh Corporation's "PStQuick A", "PStQuick B", "PStQuick E", and "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 GPC molecular weight measurement and calculation from the results of appropriate instrumental analyses such as FD-MS and NMR.

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

[0274] [ka]

[0275] Synthesis Example 2 In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 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 while purging with nitrogen gas. After raising the temperature to 65°C, the pressure was reduced to the azeotropic pressure, and 16.7 g (0.2 mol) of 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. Next, stirring was continued under the same conditions for 0.5 hours. During this time, the distillate that distilled off by azeotropy 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 continued. After that, the unreacted epichlorohydrin was removed by vacuum distillation. 20 g of methyl isobutyl ketone and 20 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Furthermore, 1.0 g of a 10% sodium hydroxide aqueous solution was added to this solution and reacted at 80°C for 2 hours. After that, the solution was washed three times with 50 g of water until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropy, and after microfiltration, the solvent was removed 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 revealed a peak at M+=883, corresponding to the theoretical structure of m1=1, n1=12, q=1, p1=0, p2=0 in the following structural formula (Ep), confirming that the epoxy compound contains the compound represented by the following structural formula (Ep).

[0276] [ka]

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

[0278] Synthesis Example 4 The reaction was carried out in the same manner as in Synthesis Example 2, except that 63.3 g of the hydroxy compound obtained in Synthesis Example 1 was replaced with 63.3 g of the hydroxy compound (Ph-2) obtained in Synthesis Example 3, yielding 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) yielded a peak at M+=883, which corresponds to the theoretical structure of structural formula (Ep) with m1=1, n1=12, p1=0, p2=0, q=1, confirming that it contains the compound represented by the structural formula (Ep).

[0279] Example 1 In Synthesis Example 1, which was equipped with a thermometer, condenser, and stirrer, 63.3 g (0.10 mol) of the hydroxy compound (Ph-1), 22.7 g (0.10 mol) of 9-chloromethylanthracene, and 55.3 g (0.40 mol) of potassium carbonate were charged, and nitrogen purging was performed. Then, 344 g of acetone was added to dissolve the compounds, and the mixture was reacted at the reflux temperature for 12 hours. After cooling to room temperature, potassium carbonate was removed by filtration, and the acetone in the filtrate was removed by vacuum distillation using an evaporator. The obtained liquid was diluted with 230 g of toluene, and 230 g of water was added, and three liquid-liquid steps were performed. After dehydrating the organic layer with sodium sulfate, toluene was removed by vacuum distillation using an evaporator to obtain 61.7 g of anthracene compound (A-1). 1 The molecular weight of anthracene per mole, calculated from 1H-NMR, was 919 g / eq.

[0280] [ka]

[0281] Example 2 In a flask equipped with a thermometer, stirrer, and condenser, 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'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM, manufactured by Yamato Chemical Industries, Ltd.), and 50.7 g of toluene were charged. 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 charged, and the mixture was reacted at 80°C for 10 hours. Subsequently, the temperature was raised to 140°C, toluene was removed by distillation under reduced pressure, and the mixture was cooled to room temperature to obtain the Diels-Alder reaction product (D-1). The yield was 54.4 g. The molecular weight measured by GPC was Mn = 2.5 × 10⁻⁶. 3 Mw = 10.0 × 10 3 That was the case.

[0282] [ka]

[0283] Example 3 In a flask equipped with a thermometer, condenser, and stirrer, 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% potassium hydroxide aqueous solution, 3.22 g (0.01 mol) of tetrabutylammonium bromide, and 61.1 g of toluene were charged, and the flask was purged with nitrogen. The reaction was then carried out at 60°C for 14 hours. After cooling to room temperature, 100 g of water and the amount of sodium phosphate to neutralize the mixture were added, and three liquid-liquid steps were performed. After dehydrating the organic layer with sodium sulfate, toluene was removed by vacuum distillation using an evaporator to obtain 48.9 g of anthracene compound (A-2). 1The molecular weight of anthracene per mole, calculated from 1H-NMR, was 1684 g / eq.

[0284] [ka]

[0285] Example 4 In a flask equipped with a thermometer, stirrer, and condenser, 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'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM, manufactured by Yamato Chemical Industries, Ltd.), and 44.4 g of toluene were charged. 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 charged, and the mixture was reacted at 80°C for 10 hours. Subsequently, the temperature was raised to 140°C, toluene was removed by distillation under reduced pressure, and the mixture was cooled to room temperature to obtain the 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 In a flask equipped with a thermometer, stirrer, and condenser, 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 Yamato Chemical Industries, Ltd.), and 214.2 g of methyl isobutyl ketone were charged. After purging with nitrogen, the mixture was reacted at 110°C for 7 hours. Subsequently, the temperature was raised to 150°C, and the methyl isobutyl ketone was removed by distillation under reduced pressure. The mixture was then cooled to room temperature to obtain 52.1 g of the Diels-Alder reaction product (D-3). Mass spectrometry of this Diels-Alder reaction product (D-3) yielded a peak with M+=1071, confirming the formation of the target compound.

[0288] [ka]

[0289] Example 6 In a flask equipped with a thermometer and stirrer, 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 group equivalent 125 g / eq) were added. The mixture was heated to 140°C for 30 minutes, and then 3.2 g of 4% sodium hydroxide aqueous solution was added. The mixture was then heated to 150°C for 30 minutes, and the reaction was continued at 150°C for 5 hours. After that, sodium phosphate was added to neutralize the mixture, yielding 635 g of the hydroxy compound represented by the following formula (S-1). The mass spectrum of the hydroxy compound (S-1) showed a peak at M+=1424, corresponding to the theoretical structure with m1=1 and n1=11 in the following formula, thus confirming the formation of the target compound. The hydroxyl group equivalent of this hydroxy compound (S-1), calculated from GPC, was 750 g / eq, with an average value of 10.6 for n1 and an average value of 1.09 for m1.

[0290] [ka]

[0291] Synthesis Example 5 In a flask equipped with a thermometer and stirrer, 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 group equivalent 114 g / eq) were added. The mixture was heated to 140°C for 30 minutes, and then 3.4 g of 4% sodium hydroxide aqueous solution was added. The mixture was then heated to 150°C for 30 minutes, and the reaction was continued at 150°C for 16 hours. After that, sodium phosphate was added to neutralize the reaction, yielding 531 g of the hydroxy compound represented by the following formula. The formation of the target compound was confirmed by obtaining a peak at M+=1380 in the mass spectrum, which corresponds to the theoretical structure of m1=1, n1=11 in the following formula. The hydroxyl group equivalent of this hydroxy compound (Ph-3), calculated from GPC, was 1136 g / eq, with an average value of 10.6 for n1 and an average value of 1.82 for m1.

[0292] [ka]

[0293] Preparation of composition and cured product Each compound was used in the formulations shown in Tables 1-4 (numbers in the tables are by mass) and uniformly mixed in a mixer (Awatori Rentaro ARV-200, manufactured by Thinky Co., Ltd.) to obtain a curable resin composition. This curable resin composition was sandwiched between aluminum mirror plates (JIS H 4000 A1050P, manufactured by Engineering Test Service Co., Ltd.) with a silicone tube as a spacer, and heat curing was performed under predetermined conditions to obtain a cured product with a thickness of 0.7 mm.

[0294] <Remolding Test> The prepared cured material was freeze-dried and pulverized. 0.07g of the pulverized cured material was placed in a 10mm square, 0.5mm thick mold and vacuum-pressed under specified conditions. The appearance of the resulting cured material was visually inspected. The criteria for evaluation are as follows. A: The seams disappeared, and the hardened material became one. B: Some seams are visible to the naked eye, but the hardened material has become one solid mass. C: It had a solidified shape, but it crumbled when light force was applied.

[0295] <Restoration Test> The prepared hardened material was punched out into a dumbbell shape (JIS K 7161-2-1BA) using a punching blade, and these were used as test specimens. Using a tensile testing machine (Shimadzu Corporation "Autograph AG-IS"), the fracture stress and tensile elongation were evaluated in accordance with JIS K 7162-2 at a measurement environment of 23°C (test speed: 2 mm / min). The fracture stress and tensile elongation of the specimens in the tensile test were evaluated after aging the specimens at 150°C for 24 hours (initial). In addition, specimens that were cut through the center with a razor, the cut surfaces were joined together, and then aged at 150°C for 24 hours were similarly subjected to tensile tests and evaluated (post-repair). The repair rate (%) was calculated based on the obtained fracture stress and tensile elongation using the formula (value after repair / initial value) × 100%.

[0296] [Table 1]

[0297] EPICLON 850-S: BPA-type liquid epoxy resin, epoxy equivalent 188 g / eq BMI-TMH: 1,6'-Bismaleimide-(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 conjugated diene intermediate or parent diene intermediate represented by the following general formulas (1-1)', (1-2)', and which must have a reversible bond between an anthracene structure and a maleimide structure via a Diels-Alder reaction. 【Chemistry 1】 [The anthracene-derived structure in formulas (1-1)' and (1-2)' may have a halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. The maleimide-derived structure may have an alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. In the formulas, n is the average value of the number of repetitions, from 0 to 10. Z ２ This is given by the following equation (4), Z ３ The structure is one of the structures represented by the following formula (5), and each of the multiple structures in a single molecule may be identical or different. 【Chemistry 2】 [In formula (4), Each Ar independently has a structure with an unsubstituted or substituted aromatic ring. R 1 , R 2 Each of these is 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 with 2 to 12 carbon atoms. n1 is an integer between 2 and 16, and n2 is the average value of the repeating units, between 2 and 30. k1 is the average number of repetitions and is in the range of 0.5 to 10. p1 and p2 are independently between 0 and 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), 【Transformation 3】 [In formula (4-1) (4-2), Ar, R, R 1 , R 2 R', n1, and n2 are the same as described above. m1 and m2 are repeated average values, each independently ranging from 0 to 25, and m1 + m2 ≥ 1. However, the bonding between structural unit X represented by formula (4-1) and structural unit Y represented by formula (4-2) may be random or block-like, and the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively. 【Chemistry 4】 [In equation (5), n3 and n5 are the average values ​​of the number of repetitions, ranging from 0.5 to 10, and n4 is an integer ranging from 1 to 16, R ” Each of these is independently a hydrogen atom, a methyl group, or an ethyl group.

2. The conjugated diene intermediate or parent diene intermediate according to claim 1, wherein the conjugated diene intermediate or parent diene intermediate represented by the general formulas (1-1)' and (1-2)' has a structure derived from 1,6'-bismaleimide-(2,2,4-trimethyl)hexane.

3. A curable resin composition comprising, as essential, a conjugated diene intermediate represented by formula (1-1)' in claim 1, a maleimide having a hydroxyl group, and a compound (I) that is reactive with a hydroxyl group-containing compound.

4. A curable resin composition comprising, as essential, the parenthetical diene intermediate represented by formula (1-2)' in claim 1, an anthracene having a hydroxyl group, and compound (I) that is reactive with a hydroxyl group-containing compound.

5. The curable resin composition according to claim 3 or 4, wherein the concentration of reversible bonds formed by the Diels-Alder reaction between anthracene structures and maleimide structures in the curable resin composition is 0.10 mmol / g or more.

6. The curable resin composition according to claim 3 or 4, wherein the compound (I) that is reactive with the hydroxyl group-containing compound is an epoxy resin.

7. Furthermore, the curable resin composition according to claim 6, further comprising a curing agent for epoxy resins.

8. The curable resin composition according to claim 6, wherein the epoxy resin is represented by the following formula (8) and has an epoxy equivalent of 500 to 10,000 g / eq. 【Transformation 5】 [In formula (8), each Ar independently has a structure that is either unsubstituted or has a 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), 【Transformation 6】 [In equations (8-1) and (8-2), Ar is the same as described above.] R １ 、 R ２ is independently a hydrogen atom, a methyl group or an ethyl group, respectively, R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. R ３ , R ４ , R ７ , R ８ Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R ５ , R ６ , R ９ , R １０ Each of these is independently a hydrogen atom or a methyl group. n1 is an integer between 4 and 16. n² is the average value of the repeating units, ranging from 2 to 30. R １１ , R １２ Each of these is independently a glycidyl ether group or a 2-methylglycidyl ether group. R １３ , R １４ Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R １５ , R １６ is a hydrogen atom or a methyl group, m3, m4, p1, p2, and q are repeated average values, m3 and m4 are independently between 0 and 25, and m3 + m4 ≥ 1. p1 and p2 are independently between 0 and 5. q is between 0.5 and 5. However, the bonding between X' represented by the general formula (8-2) and Y' represented by the general formula (8-3) may be random or blocky, and the total number of each structural unit X' and Y' present in one molecule is m3 and m4, respectively.

9. The curable resin composition according to claim 6, wherein the epoxy resin is represented by the following formula (9). 【Transformation 7】 [In equation (9), p1, p2, q, and m4 are repeated average values, and independently, p1 is between 0 and 5, p2 is between 0 and 5, q is between 0.5 and 5, and m4 is between 0 and 25.]

10. A curable resin composition according to claim 3 or 4, wherein the curable resin composition is any one of a self-healing composition, an easily disassembled composition, or a composition for remolding material.

11. A cured product obtained by curing the curable resin composition according to claim 3 or 4.

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

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

14. A hydroxyl group-containing compound represented by the following general formula (1-1) The intermediate of the conjugated diene represented by formula (1-1)' in claim 1, Maleimide having a hydroxyl group, Compound (I) that is reactive with a hydroxyl group-containing compound, In the curing process of a curable resin composition that requires, A method for producing hydroxyl group-containing compounds. 【Transformation 8】 [The anthracene-derived structure in formula (1-1) may have a halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. The maleimide-derived structure may have an alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. In the formula, n is the average value of the number of repetitions, from 0 to 10. Z １ is one of the structures represented by the following formula (3), Z ２ Z ３ The same applies as described above, and each of the multiple elements within a single molecule may be identical or different. 【Chemistry 9】 [The aromatic ring in formula (3) may be substituted or unsubstituted, and * indicates a bonding site. The hydroxyl group on the naphthalene ring in the formula may be bonded at any position.]

15. A method for producing a hydroxyl group-containing compound according to claim 14, wherein the compound (I) that is reactive with the hydroxyl group-containing compound is an epoxy resin.

16. A hydroxyl group-containing compound represented by the following general formula (1-2) The parent diene intermediate represented by formula (1-2)' in claim 1, Anthracene having a hydroxyl group, Compound (I) that is reactive with a hydroxyl group-containing compound, In the curing process of a curable resin composition that requires, A method for producing hydroxyl group-containing compounds. 【Chemistry 10】 [The anthracene-derived structure in formula (1-2) may have a halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. The maleimide-derived structure may have a alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. In the formula, m-a is an integer from 1 to 10, and n is the average value of the number of repetitions from 0 to 10. Z １ is one of the structures represented by the following formula (3), Z ２ Z ３ The same applies as described above, and each of the multiple elements within a single molecule may be identical or different. 【Chemistry 11】 [The aromatic ring in formula (3) may be substituted or unsubstituted, and * indicates a bonding site. The hydroxyl group on the naphthalene ring in the formula may be bonded at any position.]

17. A method for producing a hydroxyl group-containing compound according to claim 16, wherein the compound (I) that is reactive with the hydroxyl group-containing compound is an epoxy resin.

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