Curable resin composition, cured product, laminate, and curable compound

Abstract

To provide a compound which, while being a curable resin, makes it possible to easily achieve quick dismantlability, repairability, reformability and the like in a cured product; a curable resin composition prepared using the compound; and a cured product of the composition.SOLUTION: There is used a curable resin composition characterized by comprising a curable compound (A) having in its molecule one or more anthracene structures and two or more curable functional groups (a), a compound (B) containing a parent diene structure, and a compound (C) having reactivity with the curable functional groups (a). Each of the curable functional groups is preferably a hydroxyl group or a glycidyl ether group, and the compound (B) containing the parent diene structure is preferably bismaleimide.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition containing a curable compound having a specific structure, a cured product, and a laminate containing a layer made of the cured product. [Background technology]

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

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

[0004] Furthermore, the cured product obtained by curing thermosetting resins is insoluble in solvents and infusible even at high temperatures, making it difficult to recycle or reuse. Therefore, the cured product becomes waste after use, creating challenges in reducing waste and mitigating the burden on the environment. Furthermore, because of their high adhesive properties, there are also challenges in that their ease of disassembly and reusability after use is limited.

[0005] Therefore, cured products made from thermosetting resins are required to have a long life, reduce waste, and be reusable, and it is thought that giving them the ability to repair, reshape, and disassemble them will be effective in achieving this.

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

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

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

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

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

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

[0012] That is, the present invention includes the following aspects. [1] A curable compound (A) having one or more anthracene structures and two or more curable functional groups (a) in the molecule; a compound (B) containing a dienophile structure; a compound (C) reactive with the curable functional group (a); A curable resin composition comprising: [2] The curable resin composition according to [1], wherein the curable functional group (a) is a hydroxyl group or a glycidyl ether group. [3] The curable resin composition according to [1] or [2], further comprising an alkylene chain or an alkylene ether chain in the curable compound (A). [4] The curable resin composition according to any one of [1] to [3], wherein the compound containing a dienophilic structure is a compound having two or more maleimide groups. [5] The curable resin composition according to any one of [1] to [4], wherein the curable functional group (a) is a hydroxyl group, and the compound (C) reactive with the curable functional group (a) is an epoxy resin. [6] The curable resin composition according to any one of [1] to [5], wherein the curable functional group (a) is a glycidyl ether group, and the compound (C) reactive with the curable functional group (a) is a curing agent for epoxy resins. [7] The curable resin composition according to any one of [1] to [6], wherein the concentration of reversible bonds formed by Diels-Alder reaction relative to the total mass of the curable components in the curable resin composition is 0.10 mmol / g or more. [8] The curable resin composition according to any one of [1] to [7], which is one or more compositions selected from the group consisting of an easily dismantlable composition, a repairable composition, and a composition for a remolding material. [9] A cured product obtained by curing the curable resin composition according to any one of [1] to [8].

[10] A laminate having a substrate and a layer containing the cured product according to [9].

[11] A heat-resistant member containing the cured product according to [9].

[12] A curable compound represented by any one of the following general formulas (1) to (3):

[0013] [ka]

[0014] [In formulas (1) to (3), R represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group; Z1 is any one of the following (Z1-1) to (Z1-7),

[0015] [ka]

[0016] [In formulas (Z1-1), (Z1-2), (Z1-3), (Z1-4), (Z1-5), (Z1-6), (Z1-7), Ar each independently represents a structure having an unsubstituted or substituted aromatic ring, R 11 , R 12 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 13 , R 14 is a hydrogen atom or a methyl group, R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R' are each independently a divalent hydrocarbon group having 2 to 12 carbon atoms, n is the average value of the repeating units and is 0.5 to 10. n1 is an integer from 4 to 16, n2 is the average value of the repeating units and is 2 to 30. In formula (Z1-1), X is a structural unit represented by the following general formula (Z1-1-1), and Y is a structural unit represented by the following general formula (Z1-1-2):

[0017] [ka]

[0018] <In formulas (Z1-1-1) and (Z1-1-2), Ar, R 1 , R 2 , R', n1, and n2 are the same as above; R 3 , R 4 , R 7 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group. m1, m2, m3, m4, m5, m6, p1, p2, and q are the average values ​​of the repetitions, m1, m2, m3, m4, m5, and m6 each independently represent 0 to 25, and m1+m2≧1; p1 and p2 each independently represent a number from 0 to 5; q is 0.5 to 5. However, the bond between X represented by the general formula (Z1-1-1) and Y represented by the general formula (Z1-1-2) may be random or block, and the total number of structural units X and Y present in one molecule is m1 and m2, respectively. In addition, the aromatic ring containing the anthracene skeleton in formulas (1) to (3) may have a substituent. The lines in the formulas indicate that the ring may be connected at any point on the ring. [Effects of the Invention]

[0019] According to the present invention, it is possible to impart easy dismantling, repairability, and remoldability to a cured product made from a curable resin composition, thereby contributing to extending the life of the cured product itself and reducing waste. DETAILED DESCRIPTION OF THE INVENTION

[0020] Next, the embodiments for carrying out the present invention will be described in detail. It should be understood that the present invention is not limited to the following embodiments, and that appropriate design changes, improvements, etc. may be made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention.

[0021] A curable resin composition according to one embodiment of the present invention is characterized by containing a curable compound (A) having one or more anthracene structures and two or more curable functional groups (a) in the molecule, a compound (B) containing a diene-containing structure, and a compound (C) reactive with the curable functional groups (a).

[0022] By adopting such a configuration, in the process of obtaining a cured product, the curable resin composition undergoes a Diels-Alder reaction between the anthracene structure in the curable compound (A) and the dienophile in the compound (B) containing a dienophile structure, forming a reversible bond. At the same time, the curing reaction forms a covalent bond between the curable functional group (a) in the compound (A) and the compound (C). Therefore, the obtained cured product has both a reversible bond formed by the Diels-Alder reaction and a permanent crosslinked structure (covalent bond) obtained by the reaction between the curable functional group (a) and the compound (C) that can react with it.

[0023] Such cured products have a reversible crosslinking structure, so when the cured product is subjected to impact, cracks occur, or is crushed, the reversible bonds are easily cleaved, resulting in easy disassembly. Meanwhile, the reversible bonds reversibly reform even at low temperatures, including room temperature, allowing for functions such as repairability and reshaping. For example, even if the cured product of the present invention is crushed, the reversible bonds allow the cured product to be easily repaired by placing it at low temperatures, including room temperature, or under heated or heated conditions. Furthermore, the cured product can be crushed and then reshaped. Furthermore, the Diels-Alder reaction due to the anthracene structure has a high bonding temperature and is durable even at relatively high temperatures, so that it can be handled in the same way as cured products obtained from thermosetting resins at normal temperature ranges.

[0024] On the other hand, a permanent crosslinked structure is formed in the cured product by forming a covalent bond between the curable functional group and compound (C). In particular, since compound (A) has two or more curable functional groups (a), a three-dimensional crosslinked structure can be formed by the curing reaction, and the cured product can also be endowed with mechanical strength and heat resistance.

[0025] The curable compound (A) is not particularly limited as long as it has one or more anthracene structures and two or more curable functional groups (a) as described above.

[0026] The curable functional group is not particularly limited and examples thereof include a vinyl group, an epoxy group, a hydroxyl group, an isocyanate group, a carboxyl group, etc. Among these, a hydroxyl group or a glycidyl ether group which may have a substituent is preferred from the viewpoints of thermosetting, industrial ease of availability of raw materials, and an excellent balance of the heat resistance, water resistance, moist heat resistance, etc. of the resulting cured product. Furthermore, from the viewpoints of industrial ease of availability of raw materials and ease of adjusting the crosslink density when the cured product is obtained, the number of curable functional groups in one molecule is preferably in the range of 2 to 5, more preferably 2 to 3.

[0027] Furthermore, it is preferable that the compound (A) contains a flexible structure. The inclusion of a flexible structure can impart greater flexibility and toughness to the cured product itself. Therefore, even in applications where cracks are likely to occur, the compound can absorb impacts. Furthermore, when used as an adhesive between substrates with different thermal expansion coefficients, the compound exhibits excellent substrate conformability. Furthermore, the reversible bond described above contributes to the durability of the cured product by exhibiting easy disassembly and repairability. Examples of the flexible structure include partial structures that do not contain aromatic rings or alicyclic structures, such as alkylene chains and alkylene ether chains. In this case, the alkylene chain preferably contains 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 containing 2 to 12 carbon atoms, and the average number of repeating units is preferably in the range of 2 to 30. Furthermore, the flexible structure may contain multiple identical or different structures per molecule.

[0028] Furthermore, the molecular weight of the curable compound according to one embodiment of the present invention is not particularly limited and can be appropriately adjusted depending on the intended use of the curable resin composition comprising the compound (B) having a dienophilic structure and the compound (C) reactive with the curable functional group (a), as described below. For example, when the resulting curable resin composition is used for solventless adhesive applications, it is preferable that the composition has fluidity at room temperature. From this perspective, the molecular weight of the curable compound (A) is preferably in the range of 500 to 50,000 in terms of weight average molecular weight. From the viewpoint of the cured density of the resulting cured product, it is also preferable to adjust the equivalent weight of the curable functional group. For example, when the compound has an epoxy group, the epoxy equivalent is preferably in the range of 200 to 30,000 g / eq, and when the compound has a hydroxyl group, the hydroxyl equivalent is preferably in the range of 200 to 30,000 g / eq, from the viewpoint of ease of handling.

[0029] Examples of the curable compound (A) include compounds represented by any of the following general formulas (1) to (3).

[0030] [ka]

[0031] [In formulas (1) to (3), R represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group; Z1 is any one of the following (Z1-1) to (Z1-7),

[0032] [ka]

[0033] [In formulas (Z1-1), (Z1-2), (Z1-3), (Z1-4), (Z1-5), (Z1-6), (Z1-7), Ar each independently represents a structure having an unsubstituted or substituted aromatic ring, R 11 , R 12 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 13 , R 14 is a hydrogen atom or a methyl group, R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R' are each independently a divalent hydrocarbon group having 2 to 12 carbon atoms, n is the average value of the repeating units and is 0.5 to 10. n1 is an integer from 4 to 16, n2 is the average value of the repeating units and is 2 to 30. In formula (Z1-1), X is a structural unit represented by the following general formula (Z1-1-1), and Y is a structural unit represented by the following general formula (Z1-1-2):

[0034] [ka]

[0035] <In formulas (Z1-1-1) and (Z1-1-2), Ar, R 1 , R 2 , R', n1, and n2 are the same as above; R 3 , R 4 , R 7 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group. m1, m2, m3, m4, m5, m6, p1, p2, and q are the average values ​​of the repetitions, m1, m2, m3, m4, m5, and m6 each independently represent 0 to 25, and m1+m2≧1; p1 and p2 each independently represent a number from 0 to 5; q is between 0.5 and 5. However, the bond between X represented by the general formula (Z1-1-1) and Y represented by the general formula (Z1-1-2) may be random or block, and the total number of structural units X and Y present in one molecule is m1 and m2, respectively. In addition, the aromatic ring containing the anthracene skeleton in formulas (1) to (3) may have a substituent. The lines in the formulas indicate that the ring may be connected at any point on the ring.

[0036] In the general formula, Ar is an aromatic ring which may have a substituent, and is not particularly limited. Examples of aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Examples of substituents include a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group. It is preferable that the substituent on Ar does not cause a curing reaction when used as a curable resin composition, as this makes it easier to achieve the effects of the present invention.

[0037] Among these, Ar is preferably any of the structures represented by the following structural formulas: In the formula, the line indicates that the ring may be connected at any point on the ring.

[0038] [ka] (The aromatic ring in the formula may be substituted or unsubstituted, and * represents the point of attachment.)

[0039] In addition, structures represented by the following formulas are also included as Ar.

[0040] [ka] (In the formula, the aromatic ring may be substituted or unsubstituted, n6=1 to 4, and * represents a point of attachment.)

[0041] The following structures are particularly preferred for Ar: * represents a bonding point.

[0042] [ka]

[0043] In the general formula, the repeating unit n1 is an integer of 2 to 16. When n1 is 4 or more, the deformation mode of the cured product tends to be elastic deformation. Furthermore, when n1 is 16 or less, a decrease in crosslink density can be suppressed. It is preferably 4 to 15, and more preferably 6 to 12.

[0044] In the general formula, R 1 , R 2 R are each independently a hydrogen atom, a methyl group, or an ethyl group, and are preferably a hydrogen atom. 13 , R 14 , R 5 , R 6 , R 9 , R 10 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0045] In the general formula, n2 is the average value of the repeating units and is 2 to 30. This range is preferable because it provides a good balance between the viscosity of the curable compound and the crosslink density of the resulting cured product. It is preferably 2 to 25, and more preferably 4 to 20.

[0046] In the general formula, 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 is likely to be elastic. Preferably, R' is a divalent hydrocarbon group having 2 to 6 carbon atoms.

[0047] The divalent hydrocarbon group is not particularly limited, and examples thereof include linear or branched alkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, and aralkylene groups (divalent groups having an alkylene group and an arylene group).

[0048] Examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups. Examples of alkenylene groups include vinylene, 1-methylvinylene, propenylene, butenylene, and pentenylene groups. Examples of alkynylene groups include ethynylene, propynylene, butynylene, pentynylene, and hexynylene groups. Examples of cycloalkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, and cyclohexylene groups. Examples of arylene groups include phenylene, tolylene, xylylene, and naphthylene groups.

[0049] Among these, ethylene, propylene and tetramethylene groups are preferred from the viewpoint of the balance between the availability of raw materials, the viscosity of the resulting curable compound and the flexibility of the cured product.

[0050] In the general formula, m1 and m2 are the average values ​​of the repeating numbers of the structural unit X and the structural unit Y, respectively, and are each independently 0 to 25, and m1+m2≧1. Preferably, m1 and m2 are each in the range of 0.5 to 10. m1 and m2 are each independently 0 to 25, and preferably in the range of 0.5 to 10.

[0051] Examples of the curable compound of the present invention include, but are not limited to, those represented by the following formulae:

[0052] [ka]

[0053] [ka]

[0054] In the above structural formulas, R is a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group; n1 is an integer of 4 to 16; n2 and m are average values ​​of the number of repeating units; n2 is 2 to 30; and m is 0.5 to 10.

[0055] The curable compound according to one embodiment of the present invention can be synthesized by a known method. For example, the compound represented by the general formula (1) can be easily obtained by elongation reaction using an anthracene diol and a polyglycidyl ether compound, a polyvinyl ether, or a polyhalogenated alkylene compound, using an excess of anthracene diol when the curable reactive group is a hydroxyl group, or using an excess of a polyglycidyl ether compound when the curable reactive group is a glycidyl ether group. In this case, the polyglycidyl ether compound may be a single compound or a combination of compounds with different structures. Furthermore, other hydroxyl-containing compounds may be used in combination as long as they do not impair the curing effect of the present invention.

[0056] Examples of the anthracene diol include the following: The anthracene skeleton described below may have various substituents, but from the viewpoint of easily achieving the effects of the present invention, it is preferable that the substituents are non-reactive.

[0057] [ka]

[0058] The polyglycidyl ether compound is not particularly limited, but is preferably a diglycidyl ether compound because it is easy to prepare the curable compound (A).Furthermore, from the viewpoint of easily introducing a flexible structure into the curable compound (A), it is preferable to use a diglycidyl ether compound containing an alkylene chain or an alkylene ether chain.

[0059] The glycidyl ether compound having an alkylene chain or an alkylene ether chain is not particularly limited, and examples of diglycidyl ethers having an alkylene chain include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol diglycidyl ether, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl ether, and 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether. Examples of glycidyl ether compounds having an alkylene ether chain include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, and polyheptamethylene glycol diglycidyl ether. These compounds may contain organic chlorine impurities produced during the glycidyl etherification of hydroxy compounds, or may contain organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) represented by the following structure. These glycidyl ether compounds may be used alone or in combination of two or more.

[0060] [ka]

[0061] Among these, it is preferable to use 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether, because they provide an excellent balance between flexibility and heat resistance of the resulting cured product.

[0062] When the curable reactive group is a hydroxyl group, the reaction ratio of the glycidyl ether compound having an alkylene chain or alkylene ether chain to the anthracene diol is preferably in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio), and from the viewpoint of a well-balanced combination of flexibility and heat resistance of the resulting cured product, the reaction ratio is preferably 1.0 / 1.02 to 1.0 / 3.0 (molar ratio). Alternatively, when the curable reactive group is a glycidyl ether group, the reaction ratio is preferably in the range of 1.01 / 1.0 to 5.0 / 1.0 (molar ratio), and from the viewpoint of a well-balanced combination of flexibility and heat resistance of the resulting cured product, the reaction ratio is preferably 1.02 / 1.0 to 3.0 / 1.0 (molar ratio).

[0063] The reaction between the glycidyl ether compound having an alkylene chain or an alkylene ether chain and the anthracene diol is preferably carried out in the presence of a catalyst. Various catalysts can be used, including, 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. Two or more of these catalysts may be used in combination. Among these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds quickly and the amount of impurities is highly reduced. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 moles per mole of hydroxyl groups in the anthracene diol. The form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in the form of a solid.

[0064] The reaction between the glycidyl ether compound having an aliphatic alkylene chain or an alkylene ether chain and the anthracene diol can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of organic solvents that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, and butyl alcohol. The amount of organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination. The use of no solvent is preferred to rapidly carry out the reaction, while the use of dimethyl sulfoxide is preferred to reduce impurities in the final product.

[0065] The reaction temperature for the reaction is typically 50 to 180°C, and the reaction time is typically 1 to 10 hours. A reaction temperature of 100 to 160°C is preferred to reduce impurities in the final product. If the resulting compound exhibits significant coloration, an antioxidant or a reducing agent may be added to suppress this. The antioxidant is not particularly limited, but examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. The reducing agent is not particularly limited, but examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0066] After the reaction is complete, the reaction mixture may be neutralized or washed with water until the pH reaches 3 to 7, preferably 5 to 7. The neutralization and washing may be carried out according to a conventional method. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, or oxalic acid may be used as a neutralizing agent. After neutralization or washing, the solvent may be distilled off under reduced pressure and heating, if necessary, and the product may be concentrated to obtain the compound.

[0067] The polyvinyl ether compound is not particularly limited, but is preferably a divinyl ether compound because it is easy to prepare the curable compound (A).Furthermore, from the viewpoint of easily introducing a flexible structure into the curable compound (A), it is preferable to use an aliphatic divinyl ether compound containing an alkylene chain or an alkylene ether chain.

[0068] The reaction between the aliphatic divinyl ether and the anthracene diol can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of suitable organic solvents include aromatic organic solvents such as benzene, toluene, and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohol-based organic solvents such as methanol, ethanol, isopropyl alcohol, and normal butanol. The amount of organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.

[0069] The reaction temperature when carrying out the reaction is usually 50 to 150° C., and the reaction time is usually 0.5 to 10 hours. In this case, the reaction is preferably carried out in an oxygen atmosphere to prevent self-polymerization of the vinyl ether group.

[0070] After completion of the reaction, if an organic solvent was used, it is removed under reduced pressure and heating, and if a catalyst was used, it is deactivated with a deactivator or the like as necessary, and then removed by washing with water or filtration, thereby obtaining a compound.

[0071] The polyhalogenated alkylene compound is not particularly limited, but a dihalogenated alkylene compound is preferred because it is easy to prepare the curable compound (A).

[0072] The reaction ratio of the dihalogenated alkylene compound to the anthracene diol is preferably in the range of 1.0 / 1.01 to 1 / 5.0 (molar ratio), and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance in the resulting cured product, the molar ratio is preferably 1.0 / 1.1 to 1.0 / 3.0.

[0073] The reaction between the anthracene diol and the dihalogenated alkylene compound is preferably carried out in the presence of a basic compound. Various basic compounds can be used, including, for example, 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 basic compounds may be used in combination. Among these, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred because they allow the reaction to proceed rapidly and are highly effective in reducing the amount of impurities. The amount of these basic compounds used is not particularly limited, but is preferably 0.0001 to 10 moles per mole of hydroxyl groups in the anthracene diol. The form of these basic compounds is also not particularly limited, and they may be used in the form of an aqueous solution or a solid. A catalyst can also be used in the reaction, and examples of catalysts that can be used include quaternary ammonium salts such as tetra-n-butylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydroxide, tetra-n-butylammonium iodide, tetra-ethylammonium chloride, benzyltributylammonium bromide, benzyltriethylammonium bromide, hexadecyltriethylammonium chloride, tetramethylammonium chloride, and hexadecyltrimethylammonium chloride; crown ethers; and potassium iodide.

[0074] The reaction between the anthracene diol and the dihalogenated alkylene compound can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of organic solvents that can be used include toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, and dimethylformamide. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 1000% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.

[0075] The reaction temperature when carrying out the reaction is usually room temperature to 150°C, and the reaction time is usually 1 to 24 hours. The reaction temperature is preferably room temperature to 100°C in order to reduce impurities in the final product.

[0076] Alternatively, a diglycidyl ether of an aliphatic dihydroxy compound, an aliphatic divinyl ether, or a dihalogenated alkylene compound may be reacted with an aromatic hydroxy compound to obtain a compound having a terminal hydroxyl group, which may then be epoxidized to convert the terminal into a glycidyl ether group, and then the compound may be reacted with the above-mentioned anthracene diol to obtain the curable compound (A).

[0077] As the diglycidyl ether of the aliphatic dihydroxy compound, the compounds described above as glycidyl ether group-containing compounds having an alkylene chain or an alkylene ether chain can be used in the same manner. The same applies to preferred compounds.

[0078] The aliphatic divinyl ether is not particularly limited, and examples thereof include divinyl ethers of linear alkylene groups such as polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, and 1,10-decanediol divinyl ether, and divinyl ethers of branched alkylene groups such as neopentyl glycol divinyl ether, and divinyl ethers containing a cycloalkane structure such as 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether, and pentacyclopentadecanediol divinyl ether. These divinyl ethers may be used alone or in combination of two or more.

[0079] Among these, divinyl ethers having a polyether structure or a linear alkylene structure are preferred because they provide an excellent balance between flexibility and toughness in the resulting cured product, and it is most preferred to use polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, or 1,14-tetradecanediol diglycidyl ether.

[0080] The dihalogenated alkylene compound is not particularly limited, and examples thereof include 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-dichloroundecane, 1,12-dichlorododecane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1,9-dibromononane, 1,10-dibromodecane, 1,11-dibromoundecane, and 1,12-dibromododecane. These compounds may be used alone or in combination of two or more.

[0081] The aromatic hydroxy compound is not particularly limited, and examples thereof include dihydroxybenzenes such as hydroquinone, resorcinol, and catechol; trihydroxybenzenes such as pyrogallol, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene; triphenylmethane-type phenols such as 4,4',4"-trihydroxytriphenylmethane; dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; tetrafunctional phenols such as 1,1'-methylenebis-(2,7-naphthalenediol), 1,1'-binaphthalene-2,2',7,7'-tetraol, and 1,1'-oxybis-(2,7-naphthalenediol) obtained by coupling reaction of dihydroxynaphthalenes; bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, 2,2'-biphenol, 4,4'-biphenol, (1,1'-biphenyl)-3,4-diol, 3,3'-dimethyl-(1,1'-biphenyl)-4,4'-diol, 3-methyl-(1,1'-biphenyl)-4,4'-diol, 3,3',5,5'-tetramethylbiphenyl-2,2'-diol, 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 5-methyl-(1,1'-biphenyl)-3,4'diol, 3'-methyl-(1,1'-biphenyl)-3,4'diol, 4'-methyl-(1,1'-biphenyl)-3,Examples of suitable phenolic compounds include biphenols such as 4'-diol, alicyclic structure-containing phenols such as polyadducts of phenol and dicyclopentadiene and polyadducts of phenol and terpene compounds, naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane, and so-called Xylok-type phenolic resins, which are condensation reaction products of phenol and phenylene dimethyl chloride or biphenylene dimethyl chloride. These may be used alone or in combination of two or more. Further examples include bifunctional phenolic compounds in which the aromatic nucleus of each of the above compounds is substituted with a methyl group, t-butyl group, or halogen atom. The alicyclic structure-containing phenolic compounds and the Xylok-type phenolic resins may contain not only bifunctional components but also trifunctional or higher functional components. These compounds may be used as is, or the bifunctional components may be isolated and used after purification using a column or other purification process.

[0082] Among these, bisphenols are preferred because they have an excellent balance between flexibility and toughness when cured, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferred because of their outstanding toughness-imparting properties.Furthermore, when importance is placed on the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

[0083] The reaction ratio of the diglycidyl ether of the aliphatic dihydroxy compound to the aromatic hydroxy compound is preferably in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio) of the former / the latter, and is preferably 1.0 / 1.02 to 1.0 / 3.0 (molar ratio) in order to provide a well-balanced combination of flexibility and heat resistance of the resulting cured product.

[0084] The reaction of the diglycidyl ether of the aliphatic dihydroxy compound with the aromatic hydroxy compound is preferably carried out in the presence of a catalyst.Various catalysts can be used, including alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, phosphorus compounds such as triphenylphosphine, chlorides, bromides, and iodides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, and benzyltributylammonium, quaternary ammonium salts such as chlorides, bromides, and iodides such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, and benzyltributylphosphonium, tertiary amines such as triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, and 1,4-diazabicyclo[2.2.2]octane, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. Two or more of these catalysts may be used in combination. Among these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because they allow the reaction to proceed quickly and are highly effective in reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 moles per mole of the phenolic hydroxyl group of the aromatic hydroxy compound. The form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in the form of a solid.

[0085] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of organic solvents that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, and butyl alcohol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination. The use of no solvent is preferred to rapidly carry out the reaction, while the use of dimethyl sulfoxide is preferred to reduce impurities in the final product.

[0086] The reaction temperature for the reaction is typically 50 to 180°C, and the reaction time is typically 1 to 10 hours. A reaction temperature of 100 to 160°C is preferred to reduce impurities in the final product. If the resulting compound exhibits significant coloration, an antioxidant or a reducing agent may be added to suppress this. The antioxidant is not particularly limited, but examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. The reducing agent is not particularly limited, but examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0087] After the reaction is complete, the reaction mixture may be neutralized or washed with water until the pH reaches 3 to 7, preferably 5 to 7. The neutralization and washing may be carried out according to a conventional method. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, or oxalic acid may be used as a neutralizing agent. After neutralization or washing, the solvent may be distilled off under reduced pressure and heating, if necessary, and the product may be concentrated to obtain the compound.

[0088] The reaction ratio of the aliphatic divinyl ether to the aromatic hydroxy compound is preferably in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio), and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance of the resulting cured product, the molar ratio is preferably 1.0 / 1.02 to 1.0 / 3.0.

[0089] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently without a catalyst, but a catalyst can be used appropriately to select the raw material and increase the reaction rate. Examples of catalysts that can be used include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; organic acids such as toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, and trifluoroacetic acid; and Lewis acids such as aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, and boron trifluoride phenol complex. The amount of catalyst used is usually in the range of 10 ppm to 1% by mass relative to the mass of the divinyl ether compound. In this case, it is preferable to select the type and amount of catalyst used so as not to cause a nucleation reaction of the vinyl group to the aromatic ring.

[0090] The reaction between the aliphatic divinyl ether and the aromatic hydroxy compound can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of suitable organic solvents include aromatic organic solvents such as benzene, toluene, and xylene; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohol organic solvents such as methanol, ethanol, isopropyl alcohol, and normal butanol. The amount of organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.

[0091] The reaction temperature when carrying out the reaction is usually 50 to 150° C., and the reaction time is usually 0.5 to 10 hours. In this case, the reaction is preferably carried out in an oxygen atmosphere to prevent self-polymerization of the vinyl ether group.

[0092] After completion of the reaction, if an organic solvent was used, it is removed under reduced pressure and heating, and if a catalyst was used, it is deactivated with a deactivator or the like as necessary, and then removed by washing with water or filtration, thereby obtaining a compound.

[0093] The reaction ratio of the dihalogenated alkylene compound to the aromatic hydroxy compound is preferably in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio), and from the viewpoint of providing a well-balanced combination of flexibility and heat resistance in the resulting cured product, the molar ratio is preferably 1.0 / 1.1 to 1.0 / 3.0.

[0094] The reaction between the aromatic hydroxy compound and the dihalogenated alkylene compound is preferably carried out in the presence of a basic compound. Various basic compounds can be used, including, for example, 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 basic compounds may be used in combination. Among these, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred because they allow the reaction to proceed rapidly and are highly effective in reducing the amount of impurities. The amount of these basic compounds used is not particularly limited, but is preferably 0.0001 to 10 moles per mole of the phenolic hydroxyl group of the aromatic hydroxy compound. The form of these basic compounds is also not particularly limited, and they may be used in the form of an aqueous solution or a solid. A catalyst can also be used in the reaction, and examples of catalysts that can be used include quaternary ammonium salts such as tetra-n-butylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydroxide, tetra-n-butylammonium iodide, tetra-ethylammonium chloride, benzyltributylammonium bromide, benzyltriethylammonium bromide, hexadecyltriethylammonium chloride, tetramethylammonium chloride, and hexadecyltrimethylammonium chloride; crown ethers; and potassium iodide.

[0095] The reaction between the aromatic hydroxy compound and the dihalogenated alkylene compound can be carried out in the absence of a solvent or in the presence of an organic solvent. Usable organic solvents include, for example, toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, and dimethylformamide. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 1000% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination.

[0096] The reaction temperature when carrying out the reaction is usually room temperature to 150°C, and the reaction time is usually 1 to 24 hours. The reaction temperature is preferably room temperature to 100°C in order to reduce impurities in the final product.

[0097] The method for the glycidyl etherification reaction of the precursor (intermediate) hydroxy compound obtained above is not particularly limited, and examples thereof include a method of reacting a phenolic hydroxyl group with epihalohydrin, a method of olefinating the phenolic hydroxyl group and then oxidizing the carbon-carbon double bond of the olefin with an oxidizing agent, etc. Among these, the method using epihalohydrin is preferred in terms of ease of obtaining raw materials and ease of reaction.

[0098] Examples of methods using epihalohydrin include adding 0.3 to 100 moles of epihalohydrin per mole of aromatic hydroxyl groups of the hydroxy compound obtained above, and then reacting the mixture at a temperature of 20 to 120°C for 0.5 to 10 hours while adding 0.9 to 2.0 moles of a basic catalyst per mole of aromatic hydroxyl groups of the hydroxy compound all at once or gradually. The greater the excess amount of epihalohydrin added, the closer the resulting epoxy resin will be to its theoretical structure, and the more effectively it can suppress the formation of secondary hydroxyl groups resulting from the reaction of unreacted aromatic hydroxyl groups with epoxy groups. From this perspective, a range of 2.5 to 100 equivalents is preferred. The basic catalyst may be a solid or an aqueous solution thereof. When an aqueous solution is used, it may be continuously added, and water and epihalohydrin may be continuously distilled from the reaction mixture under reduced pressure or under normal pressure, followed by liquid separation to remove water and return epihalohydrin to the reaction mixture continuously.

[0099] When reacting epihalohydrin, a promoter such as a quaternary ammonium salt may be used in combination for the purpose of improving the reaction rate. Various quaternary ammonium salts can be used, and examples thereof include tetra-n-butylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydroxide, tetra-n-butylammonium iodide, tetra-ethylammonium chloride, benzyltributylammonium bromide, benzyltriethylammonium bromide, hexadecyltriethylammonium chloride, tetramethylammonium chloride, and hexadecyltrimethylammonium chloride.

[0100] In industrial production, all of the epihalohydrin charged in the first batch of epoxy resin production is fresh, but from the next batch onwards, it is preferred to use epihalohydrin recovered from the crude reaction product in combination with fresh epihalohydrin equivalent to the amount consumed and lost in the reaction. The epihalohydrin used in this case is not particularly limited, but examples include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferred because of its easy availability.

[0101] The basic catalyst is not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferred because of their excellent catalytic activity in the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. When used, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55 mass %, or may be used in solid form.

[0102] The use of an organic solvent in combination can also increase the reaction rate in the synthesis of the epoxy resin. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol; cellosolves such as methyl cellosolve and ethyl cellosolve; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide. These organic solvents may be used alone or in combination of two or more, as appropriate, to adjust the polarity.

[0103] The reaction product of these glycidylation reactions is washed with water, and then the unreacted epihalohydrin and the organic solvent used are removed by distillation under heating and reduced pressure. Furthermore, to obtain an epoxy resin with even less hydrolyzable halogen, the resulting epoxy resin can be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to further carry out the reaction. In this case, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present to improve the reaction rate.

[0104] When a phase transfer catalyst is used, the amount thereof is preferably in the range of 0.1 to 3.0% by mass based on the epoxy resin used. After completion of the reaction, the salt formed is removed by filtration, washing with water, etc., and the solvent, such as toluene or methyl isobutyl ketone, is distilled off under heating and reduced pressure to obtain a high-purity resin.

[0105] The resin having a glycidyl ether group at the end obtained in this manner is reacted with anthracene diol in the same manner as above, whereby the curable compound (A) of the present invention can be obtained.

[0106] Furthermore, as for the compound (A) represented by the general formula (2), a compound (A) having a glycidyl ether group as the curable reactive group can be obtained by reacting aminoanthracene with the polyglycidyl ether compound. In this case, the preferred polyglycidyl ether compound is a diglycidyl ether compound, as described above, and further, for the same reason, it is preferable to use a compound having an alkylene chain or an alkylene ether chain.

[0107] Examples of the aminoanthracene include the following: As described below, the anthracene skeleton may have various substituents, but from the viewpoint of easily achieving the effects of the present invention, it is preferable that the substituent is non-reactive.

[0108] [ka]

[0109] The reaction ratio of the glycidyl ether compound to the aminoanthracene is preferably in the range of 1.01 / 1.0 to 5.0 / 1.0 (molar ratio) of the former / the latter, and is preferably 1.02 / 1.0 to 3.0 / 1.0 (molar ratio) in order to provide a cured product having a good balance between flexibility and heat resistance.

[0110] The reaction of the glycidyl ether compound with the aminoanthracene is preferably carried out in the presence of a catalyst.Various catalysts can be used, including alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, phosphorus compounds such as triphenylphosphine, chlorides, bromides, and iodides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, and benzyltributylammonium, quaternary ammonium salts such as chlorides, bromides, and iodides such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, and benzyltributylphosphonium, tertiary amines such as triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, and 1,4-diazabicyclo[2.2.2]octane, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. Two or more of these catalysts may be used in combination. Among these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because they allow the reaction to proceed quickly and are highly effective in reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but it is preferable to use 0.0001 to 0.01 moles per mole of glycidyl ether group in the glycidyl ether compound. The form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in the form of a solid.

[0111] The reaction between the glycidyl ether compound and the aminoanthracene can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of organic solvents that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, and butyl alcohol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination. The use of no solvent is preferred to rapidly carry out the reaction, while the use of dimethyl sulfoxide is preferred to reduce impurities in the final product.

[0112] The reaction temperature for the reaction is typically 50 to 160°C, and the reaction time is typically 1 to 10 hours. A reaction temperature of 100 to 130°C is preferred to reduce impurities in the final product. If the resulting compound exhibits significant coloration, an antioxidant or a reducing agent may be added to suppress this. The antioxidant is not particularly limited, but examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite ester compounds containing a trivalent phosphorus atom. The reducing agent is not particularly limited, but examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0113] After the reaction is complete, the reaction mixture may be neutralized or washed with water until the pH reaches 3 to 7, preferably 5 to 7. The neutralization and washing may be carried out according to a conventional method. For example, when a basic catalyst is used, an acidic substance such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, or oxalic acid may be used as a neutralizing agent. After neutralization or washing, the solvent may be distilled off under reduced pressure and heating, if necessary, and the product may be concentrated to obtain the compound.

[0114] By reacting the compound having an anthracene structure terminated in a diglycidyl ether group obtained in this manner with a compound having two or more hydroxyl groups, a compound can be obtained in which the curable functional group (a) is a hydroxyl group.

[0115] Furthermore, as the compound (A) represented by the general formula (3), a compound (A) in which the curable reactive group is a glycidyl ether group can be obtained by using the following anthracene-containing compound containing a hydroxyl group as a raw material and reacting it with a polyglycidyl ether compound in the same manner as above. In this case, the preferred polyglycidyl ether compound is a diglycidyl ether compound as above, and further, for the same reason, it is preferable to use a compound having an alkylene chain or an alkylene ether chain as above.

[0116] [ka]

[0117] Furthermore, by further reacting with an aromatic hydroxy compound in the same manner as above, a compound (A) in which the curable reactive group is a hydroxy group can be obtained.

[0118] Furthermore, as the compound (A) represented by the general formula (3), an anthracene-containing compound containing an epoxy group, such as the one shown below, can be used as a raw material and reacted with an aromatic hydroxy compound in the same manner as above to obtain a compound (A) in which the curable reactive group is a hydroxy group. In this case, as with the aromatic hydroxy compound, bisphenols are preferred, and for the same reasons, bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are also preferred. Furthermore, when importance is placed on the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

[0119] [ka]

[0120] Furthermore, in the same manner as above, this can be epoxidized to convert the terminal to a glycidyl ether group, thereby obtaining a compound (A) in which the curable reactive group is an epoxy group.

[0121] The cured product of one embodiment of the present invention comprises a compound (B) having a diene-philic structure, which is reversibly bonded to the anthracene structure in the curable compound (A) by a Diels-Alder reaction. The compound (B) having a diene-philic structure may be monofunctional, but is preferably bifunctional or higher in order to impart better performance to the cured product.

[0122] The reversible bond formed by the Diels-Alder reaction is a reaction in which a conjugated diene and a parent diene undergo an addition reaction to form a six-membered ring. Because the Diels-Alder reaction is an equilibrium reaction, a retro-Diels-Alder reaction occurs at a certain temperature, resulting in dissociation (decrosslinking). This reversibility is maintained even after the cured product (three-dimensional crosslinked product) is formed. Therefore, when the cured product is subjected to mechanical energy such as scratches or external force, the C-C bond of the Diels-Alder reaction unit is preferentially cleaved because the C-C bond has lower bond energy than a normal covalent bond. However, at temperatures lower than the dissociation temperature, the equilibrium shifts toward the C-C bond of the Diels-Alder reaction unit, and an adduct (Diels-Alder reaction unit) is again formed, which is thought to enable repair of scratches and reshaping.

[0123] The compound (B) containing a dienophilic structure is not particularly limited, and examples thereof include compounds having a maleimide group, an acryloyl group, a vinyl ketone group, an acetylene group, an allyl group, a diazo group, a nitro group, a benzoquinone skeleton, etc. Among these, compounds having a maleimide group are preferred from the viewpoint of the balance between the reactivity when used as a curable resin composition and the ease of dismantling and remolding of the cured product. Furthermore, compounds having two or more maleimide groups per molecule are preferred from the viewpoint of further enhancing the effect of remolding.

[0124] Examples of the compound having a maleimide group include the following compounds:

[0125] [ka]

[0126] The n3, n5, n6, n7, n8, and n9 are the average values ​​of the number of repetitions, each of which is 0.5 to 10, and n4 is an integer of 1 to 16. ” are each independently a hydrogen atom, a methyl group, or an ethyl group.

[0127] The maleimide group-containing compounds include those each independently having a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group as a substituent. Furthermore, in the structures of the compounds listed in the formula above, the alkoxy group, the aralkyloxy group, the aryloxy group, the carboxy group, the alkyloxycarbonyl group, the aryloxycarbonyl group, the alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group also include those having various substituents further bonded to their carbon atoms.

[0128] The curable resin composition of one embodiment of the present invention essentially comprises the curable compound (A), a compound (B) containing a diene-philic structure, and a compound (C) reactive with the curable functional group (a). In this case, the compound (A) may be reacted with the compound (B) in advance, and then the curing reaction with the compound (C) may be carried out. However, from the viewpoint of ease of handling, it is preferable to react the compounds (A) to (C) simultaneously.

[0129] The compound (C) reactive with the terminal curable functional group is not particularly limited.

[0130] When the terminal curable functional group is a hydroxyl group, examples of the compound (C) include melamine compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, guanamine compounds, glycoluril compounds, urea compounds, resole resins, epoxy resins, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, hexamethylenetetramine and modified products thereof, oxazoline compounds, etc. Among these, epoxy resins are preferred from the viewpoints of good curability and ease of handling.

[0131] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound of hexamethylol melamine in which 1 to 6 methylol groups are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and a compound of hexamethylol melamine in which 1 to 6 methylol groups are acyloxymethylated.

[0132] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, a compound of tetramethylolguanamine in which 1 to 4 methylol groups are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, and a compound of tetramethylolguanamine in which 1 to 4 methylol groups are acyloxymethylated.

[0133] Examples of the glycoluril compound include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

[0134] Examples of the urea compound include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0135] Examples of the resole resin include polymers obtained by reacting a phenolic hydroxyl group-containing compound, such as phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, or dihydroxynaphthalene, with an aldehyde compound under alkaline catalytic conditions.

[0136] Examples of the epoxy resin include liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, and tetramethylbiphenyl type epoxy resin; brominated epoxy resins such as brominated phenol novolac type epoxy resin; solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin; Examples of such epoxy resins include dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resin-type epoxy resins, and biphenyl-modified novolac type epoxy resins. These may be used alone or in combination of two or more types, and it is preferable to select and use various types depending on the intended use, the physical properties of the cured product, and the like.

[0137] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0138] Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.

[0139] Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0140] Examples of the acid anhydride include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4'-(isopropylidene)diphthalic anhydride, and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

[0141] Furthermore, when the curable functional group in the curable compound is a hydroxyl group and this is combined with an epoxy resin to form a curable resin composition, a curing agent for the epoxy resin may be blended.

[0142] Examples of the curing agent that can be used here include various known curing agents for epoxy resins, such as amine compounds, acid anhydrides, amide compounds, phenolic hydroxyl group-containing compounds, carboxylic acid compounds, and thiol compounds.

[0143] Examples of the amine compound include trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N',N'-tetramethylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetramethylhexamethylenediamine ... Aliphatic amine compounds such as triethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, and α-methylbenzylmethylamine;

[0144] Alicyclic and heterocyclic amine compounds such as piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N,N',N"-tris(dimethylaminopropyl)hexahydro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxyspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N'-dimethylpiperazine, 1,8-diazabicyclo-[5.4.0]-undecene (DBU), etc.

[0145] Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, and picoline;

[0146] Examples of the modified amine compounds include epoxy compound-added polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, aminimide, boron trifluoride-piperidine complex, and boron trifluoride-monoethylamine complex.

[0147] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0148] Examples of the phenolic hydroxyl group-containing compound include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol adduct resins, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, Examples of polyhydric phenol compounds include tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked via bismethylene groups), aminotriazine-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via melamine, benzoguanamine, or the like), and alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0149] Examples of the amide compounds include dicyandiamide and polyamidoamine, etc. Examples of the polyamidoamine include those obtained by reacting an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid, or a carboxylic acid compound such as a fatty acid or dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain.

[0150] Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.

[0151] The thiol compound preferably contains two or more thiol groups in one molecule. For example, 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, and the like.

[0152] When using these curing agents, only one type of curing agent may be used, or two or more types may be mixed. For applications such as underfill materials and general coating applications, it is preferable to use the amine-based compounds, carboxylic acid-based compounds, and / or acid anhydride-based compounds. For applications such as adhesives and flexible wiring boards, amine-based compounds, particularly dicyandiamide, are preferred in terms of workability, curability, and long-term stability. For applications as semiconductor encapsulation materials, solid phenol-based compounds are preferred in terms of the heat resistance of the cured product. For applications as batteries, aliphatic amines and thiol compounds are preferred in terms of low-temperature curing.

[0153] Furthermore, when an epoxy resin is used, a curing accelerator may be contained. Various curing accelerators can be used, including urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, organic acid metal salts, Lewis acids, and amine complex salts. When used as an adhesive, urea compounds, particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), are preferred due to their excellent workability and low-temperature curing properties. When used as a semiconductor encapsulating material, triphenylphosphine is a preferred phosphorus compound, and 1,8-diazabicyclo[5.4.0]undecene is a preferred tertiary amine due to their excellent curability, heat resistance, electrical properties, and moisture resistance reliability.

[0154] Examples of the phosphorus compound include alkyl phosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine, dialkyl phosphines such as dimethylphosphine and dipropylphosphine, secondary phosphines such as diphenylphosphine and methylethylphosphine, and tertiary phosphines such as trimethylphosphine, triethylphosphine and triphenylphosphine.

[0155] Examples of the imidazole include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, and 1-isopropylimidazole. isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole Imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole Examples include isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and 1-benzyl-2-phenylimidazole hydrochloride.

[0156] Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

[0157] Examples of the urea compound include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, and N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea.

[0158] When the terminal curable functional group is a glycidyl ether group, examples of the compound (C) include various known curing agents for epoxy resins, such as amine compounds, acid anhydrides, amide compounds, phenolic hydroxyl group-containing compounds, carboxylic acid compounds, thiol compounds, etc. The curing agent can be appropriately selected depending on the physical properties of the desired cured product, but it is preferable to use a hydroxyl group-containing compound, particularly from the viewpoints of mechanical strength, adhesion to the substrate, etc.

[0159] Examples of the amine compound include trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N',N'-tetramethylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetramethylhexamethylenediamine ... Aliphatic amine compounds such as triethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, and α-methylbenzylmethylamine;

[0160] Alicyclic and heterocyclic amine compounds such as piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N,N',N"-tris(dimethylaminopropyl)hexahydro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxyspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N'-dimethylpiperazine, 1,8-diazabicyclo-[5.4.0]-undecene (DBU), etc.

[0161] Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, picoline, etc.;

[0162] Examples of the modified amine compounds include epoxy compound-added polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, aminimide, boron trifluoride-piperidine complex, and boron trifluoride-monoethylamine complex.

[0163] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0164] Examples of the phenolic hydroxyl group-containing compound include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol adduct resins, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, Examples of polyhydric phenol compounds include tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked via bismethylene groups), aminotriazine-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via melamine, benzoguanamine, or the like), and alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0165] Examples of the amide compounds include dicyandiamide and polyamidoamine, etc. Examples of the polyamidoamine include those obtained by reacting an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid, or a carboxylic acid compound such as a fatty acid or dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain.

[0166] Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.

[0167] The thiol compound preferably contains two or more thiol groups in two molecules. For example, 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, and the like.

[0168] When using these curing agents, only one type of curing agent may be used, or two or more types may be mixed. For applications such as underfill materials and general coating applications, it is preferable to use the amine-based compounds, carboxylic acid-based compounds, and / or acid anhydride-based compounds. For applications such as adhesives and flexible wiring boards, amine-based compounds, particularly dicyandiamide, are preferred in terms of workability, curability, and long-term stability. For applications as semiconductor encapsulation materials, solid phenol-based compounds are preferred in terms of the heat resistance of the cured product. For applications as batteries, aliphatic amines and thiol compounds are preferred in terms of low-temperature curing.

[0169] The concentration of the reversible bond in the curable resin composition of the present invention is preferably 0.10 mmol / g or more relative to the total mass of the curable components in the curable resin composition. This configuration further improves the ease of disassembly, repairability, and remoldability of the cured product obtained from the curable resin composition. The concentration of the reversible bond is more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. The concentration of the reversible bond in the present invention can be appropriately selected based on the glass transition temperature of the target cured product, defined by the tan δ peak top of a dynamic mechanical analyzer (DMA). For example, when the glass transition temperature is used as a guideline, if the glass transition temperature of the cured product is near room temperature, sufficient repairability and remoldability functions are likely to be exhibited even at the lower concentration end of the preferred range. On the other hand, if the glass transition temperature of the target cured product is above 100°C, these functions are likely to be exhibited at the higher concentration end of the preferred range. However, in the temperature range above the glass transition temperature measured by DMA, molecular mobility is generally high, and sufficient repairability and remoldability functions are likely to be exhibited even if the concentration of the phenolic hydroxyl group-containing compound is low, so the effect of exhibiting repairability and remoldability functions can be adjusted, for example, by appropriately adjusting the aging temperature for repair and the heating temperature for remold. Thus, the relationship between the glass transition temperature of the cured product and the concentration of reversible bonds is not limited to these.

[0170] The curable resin composition of the present invention may be an epoxy resin represented by the following formula (4) and having an epoxy equivalent of 500 to 10,000 g / eq, since this results in a curable resin composition that is excellent in curability and in the mechanical strength and heat resistance of the cured product. In particular, when the terminal curable functional group is a hydroxyl group, the following epoxy resin may be used as the above-mentioned compound (III).

[0171] [ka] [In formula (4), each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, X is a structural unit represented by the following general formula (4-1), and Y is a structural unit represented by the following general formula (4-2),

[0172] [ka]

[0173] R 1 , R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; R 3 , R 4 , R 7 , R 8 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, n1 is an integer from 2 to 16, n2 is the average number of repeating units and is between 2 and 30. R 21 , R 22 are each independently a glycidyl ether group or a 2-methylglycidyl ether group, R 11 , R 12 each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 13 , R 14 is a hydrogen atom or a methyl group, m1, m2, p1, p2, and q are the average values ​​of the repetitions, m1 and m2 each independently represent 0 to 25, and m1+m2≧1; p1 and p2 each independently represent a number from 0 to 5; q is between 0.5 and 5. However, the bond between X represented by the general formula (2-2) and Y represented by the general formula (2-3) may be random or block, and the total number of structural units X and Y present in one molecule is m1 and m2, respectively.

[0174] The epoxy resin represented by the general formula (4) may be used alone in combination to form a curable resin composition, but from the viewpoint of further imparting flexibility to the cured product and making it easier to dismantle, it is also preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq in combination.

[0175] The epoxy resins that can be used in combination are not limited in structure as long as they have an epoxy equivalent in the range of 100 to 300 g / eq. Examples include liquid epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD ​​type epoxy resins, polyhydroxybenzene type epoxy resins, polyhydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type epoxy resins; brominated epoxy resins such as brominated phenol novolac type epoxy resins; solid bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins; and dicyclopentasiloxane type epoxy resins. Examples of suitable epoxy resins include anthradiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, and biphenyl-modified novolac type epoxy resins. These may be used alone or in combination of two or more types, and it is preferable to select and use various types depending on the intended use, the physical properties of the cured product, etc.

[0176] Among these, it is preferable to use liquid epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD ​​type epoxy resins, polyhydroxybenzene type epoxy resins, polyhydroxynaphthalene type epoxy resins, biphenyl type epoxy resins, and tetramethylbiphenyl type epoxy resins, and it is particularly preferable to use epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AD ​​... the like, which have an epoxy equivalent of 100 to 300 g / eq.

[0177] The ratio of the epoxy resin represented by general formula (4) to the epoxy resin having an epoxy equivalent of 100 to 300 g / eq is not particularly limited, but from the viewpoint of facilitating phase separation in the cured product, the mass ratio of the former to the latter is 97:3 to 3:97, preferably 10:90 to 90:10, and particularly preferably 80:20 to 20:80. Phase separation in the cured product results in a sea-island structure, which balances the adhesiveness and stress relaxation ability of the cured product, exhibits high adhesive strength over a particularly wide temperature range, and has the effect of reducing the mold shrinkage rate before and after heat curing of the resin composition.

[0178] The curable resin composition of the present invention may be used in combination with other thermosetting resins or thermoplastic resins within the range that does not impair the effects of the present invention.

[0179] Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, active ester resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc. When the other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as it does not inhibit the effects of the present invention, but is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the curable resin composition.

[0180] Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenyl Examples of suitable cyanate ester resins include tetraphenylethane-type cyanate ester resins, dicyclopentadiene-phenol addition reaction-type cyanate ester resins, phenol aralkyl-type cyanate ester resins, naphthol novolac-type cyanate ester resins, naphthol aralkyl-type cyanate ester resins, naphthol-phenol co-condensed novolac-type cyanate ester resins, naphthol-cresol co-condensed novolac-type cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolac-type cyanate ester resins, and anthracene-type cyanate ester resins. These may be used alone or in combination of two or more.

[0181] Among these cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, polyhydroxynaphthalene-type cyanate ester resins, naphthylene ether-type cyanate ester resins, and novolac-type cyanate ester resins are preferred in that they can give cured products with particularly excellent heat resistance, and dicyclopentadiene-phenol addition reaction-type cyanate ester resins are preferred in that they can give cured products with excellent dielectric properties.

[0182] Resins having a benzoxazine structure are not particularly limited, and examples thereof include a reaction product of bisphenol F, formalin, and aniline (Fa-type benzoxazine resin), a reaction product of diaminodiphenylmethane, formalin, and phenol (Pd-type benzoxazine resin), a reaction product of bisphenol A, formalin, and aniline, a reaction product of dihydroxydiphenyl ether, formalin, and aniline, a reaction product of diaminodiphenyl ether, formalin, and phenol, a reaction product of a dicyclopentadiene-phenol adduct resin, formalin, and aniline, a reaction product of phenolphthalein, formalin, and aniline, and a reaction product of diphenyl sulfide, formalin, and aniline. These may be used alone or in combination of two or more.

[0183] The active ester resin is not particularly limited, but compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance, active ester resins obtained from a carboxylic acid compound or its halide and a hydroxy compound are preferred, and active ester resins obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound are more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or halides thereof. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-phenol adduct resins.

[0184] Specific examples of preferred active ester resins include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins which are acetylated phenol novolac, and active ester resins which are benzoylated phenol novolac. Of these, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred in terms of their excellent ability to improve peel strength.

[0185] Furthermore, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Xylok resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, aminotriazine-modified phenolic resins, and various vinyl polymers may be used in combination.

[0186] More specifically, the various novolak resins include polymers obtained by reacting a phenolic hydroxyl group-containing compound such as phenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A or bisphenol F, naphthol, or dihydroxynaphthalene with an aldehyde compound under acid catalyst conditions.

[0187] Examples of the various vinyl polymers include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly(meth)acrylate, as well as copolymers thereof.

[0188] Thermoplastic resins refer to resins that can be melt-molded by heating. Specific examples include polyethylene resins, polypropylene resins, polystyrene resins, rubber-modified polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, acrylonitrile-styrene (AS) resins, polymethyl methacrylate resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyethylene terephthalate resins, ethylene vinyl alcohol resins, cellulose acetate resins, ionomer resins, polyacrylonitrile resins, polyamide resins, polyacetal resins, polybutylene terephthalate resins, polylactic acid resins, polyphenylene ether resins, modified polyphenylene ether resins, polycarbonate resins, polysulfone resins, polyphenylene sulfide resins, polyetherimide resins, polyethersulfone resins, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyetheretherketone resins, polyketone resins, liquid crystal polyester resins, fluororesins, syndiotactic polystyrene resins, and cyclic polyolefin resins. These thermoplastic resins can be used alone or in combination of two or more.

[0189] When using these other resins, the blending ratio of the phenolic hydroxyl group-containing compound of the present invention to the other resins can be set arbitrarily depending on the application. However, from the viewpoint of not impairing the repairability and remoldability exhibited by the present invention, it is preferable that the other resins be used in a ratio of 0.5 to 100 parts by mass per 100 parts by mass of the phenolic hydroxyl group-containing compound of the present invention.

[0190] The curable resin composition of the present invention may also contain a curing accelerator. Examples of the curing accelerator include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and boron trifluoride monoethylamine complex; organic acid compounds such as thiodipropionic acid; benzoxazine compounds such as thiodiphenolbenzoxazine and sulfonylbenzoxazine; and sulfonyl compounds. These may be used alone or in combination of two or more. The amount of these catalysts added is preferably in the range of 0.001 to 15 parts by mass per 100 parts by mass of the curable resin composition.

[0191] When the curable resin composition of the present invention is used in an application requiring high flame retardancy, a non-halogen flame retardant containing substantially no halogen atoms may be blended therein.

[0192] Examples of the non-halogen flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. There are no limitations on the use of these flame retardants. They may be used alone, or multiple flame retardants of the same type may be used, or different flame retardants may be used in combination.

[0193] The phosphorus-based flame retardant may be either inorganic or organic. Examples of inorganic compounds include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide.

[0194] The red phosphorus is preferably surface-treated to prevent hydrolysis and the like. Examples of the surface treatment method include (i) a method of coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof; (ii) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide, and a thermosetting resin such as a phenolic resin; and (iii) a method of doubly coating with a thermosetting resin such as a phenolic resin on top of a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide.

[0195] Examples of the organic phosphorus compound include general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as cyclic organic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives thereof obtained by reacting these with compounds such as epoxy resins and phenolic resins.

[0196] The amount of these phosphorus-based flame retardants to be added is selected appropriately depending on the type of phosphorus-based flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, when red phosphorus is used as the non-halogenated flame retardant, it is preferably added in an amount of 0.1 to 2.0 parts by mass, relative to 100 parts by mass of the resin composition containing all of the non-halogenated flame retardants and other fillers and additives. When an organic phosphorus compound is used, it is similarly preferably added in an amount of 0.1 to 10.0 parts by mass, and more preferably added in an amount of 0.5 to 6.0 parts by mass.

[0197] When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dyes, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. may be used in combination with the phosphorus-based flame retardant.

[0198] Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazines, with triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds being preferred.

[0199] Examples of the triazine compounds include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, and the like, as well as (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate, (2) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, and formguanamine and formaldehyde, (3) mixtures of the co-condensates of (2) with phenolic resins such as phenol-formaldehyde condensates, and (4) compounds obtained by further modifying (2) or (3) with tung oil, isomerized linseed oil, or the like.

[0200] Examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate.

[0201] The amount of the nitrogen-based flame retardant to be blended is selected appropriately depending on the type of nitrogen-based flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend it in an amount of 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives.

[0202] When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

[0203] The silicone flame retardant can be any organic compound containing silicon atoms, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicone flame retardant to be added is appropriately selected depending on the type of silicone flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to add the silicone flame retardant in an amount of 0.05 to 20 parts by mass per 100 parts by mass of the resin composition containing the non-halogen flame retardant and other fillers and additives. When using the silicone flame retardant, a molybdenum compound, alumina, etc. may also be used in combination.

[0204] Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.

[0205] Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

[0206] Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

[0207] Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

[0208] Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

[0209] Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

[0210] Examples of the low-melting glass include glassy compounds such as Shepley (Boxey Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3, ZnO-P2O5-MgO, P2O5-B2O3-PbO-MgO, P-Sn-OF, PbO-V2O5-TeO2, Al2O3-H2O, and lead borosilicate.

[0211] The amount of the inorganic flame retardant to be blended is selected as appropriate depending on the type of inorganic flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend in an amount of 0.05 to 20 parts by mass, and more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives.

[0212] Examples of the organometallic salt flame retardant include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, and compounds in which a metal atom is ionic- or coordinate-bonded to an aromatic compound or a heterocyclic compound.

[0213] The amount of the organometallic salt flame retardant to be blended is appropriately selected depending on the type of organometallic salt flame retardant, the other components of the resin composition, and the desired level of flame retardancy. For example, it is preferable to blend it in the range of 0.005 to 10 parts by mass per 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers, additives, etc.

[0214] The curable resin composition of the present invention may contain a filler. Examples of the filler include inorganic fillers and organic fillers. Examples of the inorganic filler include inorganic fine particles.

[0215] Examples of inorganic fine particles include those with excellent heat resistance such as alumina, magnesia, titania, zirconia, and silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine amorphous silica); those with excellent thermal conductivity such as boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, and diamond; those with excellent electrical conductivity such as metal fillers and / or metal-coated fillers using metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, and stainless steel); and those with excellent barrier properties such as minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, as well as potassium titanate, magnesium sulfate, sepiolite, and zonolite. Examples of inorganic particles include tin, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, and magnesium hydroxide; those with a high refractive index include barium titanate, zirconia oxide, and titanium oxide; those exhibiting photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, and lead, as well as composites of these metals and oxides thereof; those with excellent abrasion resistance include metals such as silica, alumina, zirconia, and magnesium oxide, as well as composites and oxides thereof; those with excellent conductivity include metals such as silver and copper, tin oxide, and indium oxide; those with excellent insulation properties include silica; and those with excellent UV blocking properties include titanium oxide and zinc oxide. These inorganic particles can be selected appropriately depending on the application and can be used alone or in combination. Furthermore, the above inorganic particles have various properties in addition to those listed as examples, so they can be selected appropriately depending on the application.

[0216] For example, when silica is used as inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica or colloidal silica can be used. Commercially available powdered silica fine particles include, for example, Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG Flake manufactured by Nippon Sheet Glass Co., Ltd.

[0217] Examples of commercially available colloidal silica include methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL, all of which are manufactured by Nissan Chemical Industries, Ltd.

[0218] Surface-modified silica fine particles may also be used, for example, the silica fine particles that have been surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth)acryloyl group. Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, etc. manufactured by Nissan Chemical Industries, Ltd.

[0219] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or irregularly shaped particles can be used. The primary particle diameter is preferably in the range of 5 to 200 nm.

[0220] Titanium oxide microparticles can be used not only as extender pigments but also as ultraviolet light-responsive photocatalysts, such as anatase titanium oxide, rutile titanium oxide, and brookite titanium oxide. Furthermore, particles designed to respond to visible light by doping different elements into the crystalline structure of titanium oxide can also be used. Suitable elements for doping titanium oxide include anionic elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cationic elements such as chromium, iron, cobalt, and manganese. The titanium oxide can be used in the form of a powder, a sol dispersed in an organic solvent or water, or a slurry. Commercially available powdered titanium oxide microparticles include, for example, Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd. and ATM-100 manufactured by Teika Co., Ltd. Commercially available slurry-type titanium oxide microparticles include, for example, TKD-701 manufactured by Teika Co., Ltd.

[0221] The curable resin composition of the present invention may further contain a fibrous substrate. The fibrous substrate is not particularly limited, but is preferably one used in fiber-reinforced resins, such as inorganic fibers and organic fibers.

[0222] Examples of inorganic fibers include inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, tungsten carbide fibers, silicon carbide fibers (silicon carbide fibers), ceramic fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0223] Examples of organic fibers include synthetic fibers made from resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as protein, polypeptide, and alginic acid.

[0224] Among these, carbon fiber and glass fiber are preferred because they have a wide range of industrial applications. Of these, only one type may be used, or two or more types may be used simultaneously.

[0225] The fibrous substrate may be an assembly of fibers, with continuous or discontinuous fibers, in the form of a woven or nonwoven fabric, in the form of a fiber bundle in which fibers are aligned in one direction, or in the form of a sheet in which fiber bundles are arranged, or in the form of a three-dimensional shape in which a thickness is added to an assembly of fibers.

[0226] The curable resin composition of the present invention may contain a dispersion medium for the purpose of adjusting the solid content and viscosity of the resin composition. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and examples of the dispersion medium include various organic solvents and liquid organic polymers.

[0227] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatics such as toluene and xylene; and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These can be used alone or in combination, but methyl ethyl ketone is preferred from the standpoint of volatility during coating and solvent recovery.

[0228] The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include an acrylic polymer (Floren WK-20: Kyoeisha), an amine salt of a special modified phosphate ester (HIPLAAD ED-251: Kusumoto Chemicals), and a modified acrylic block copolymer (DISPERBYK2000: BYK-Chemie).

[0229] The resin composition of the present invention may contain other compounds, such as catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, and reactive diluents.

[0230] A cured product can be obtained by curing the resin composition of the present invention. When curing, curing can be performed at room temperature or by heating. When performing thermal curing, curing can be performed by heating once or through multiple heating steps.

[0231] The curable resin composition of the present invention can also be cured by active energy rays. In this case, a photocationic polymerization initiator may be used as the polymerization initiator. Examples of active energy rays that can be used include visible light, ultraviolet light, X-rays, and electron beams.

[0232] Examples of the photocationic polymerization initiator include aryl-sulfonium salts and aryl-iodonium salts, and specifically, arylsulfonium hexafluorophosphate, arylsulfonium hexafluoroantimonate, arylsulfonium tetrakis(pentafluoro)borate, tri(alkylphenyl)sulfonium hexafluorophosphate, etc. The photocationic polymerization initiator may be used alone or in combination of two or more kinds.

[0233] The curable resin composition of the present invention can be prepared by uniformly mixing the above-mentioned components, and the method for doing so is not particularly limited. For example, the composition can be prepared by uniformly mixing the components using a pot mill, a ball mill, a bead mill, a roll mill, a homogenizer, a super mill, a homodisper, a universal mixer, a Banbury mixer, a kneader, or the like.

[0234] The curable resin composition of the present invention is prepared by dissolving the curable compound, the compound (III) reactive therewith, and optionally the curing agent, filler, fibrous substrate, dispersion medium, and resins other than the various compounds described above, in a dispersion medium such as the organic solvent. After dissolution, the solvent is distilled off, and the resulting mixture is dried under reduced pressure using a vacuum oven or the like to obtain a curable resin composition. The curable resin composition of the present invention may also be in a state in which the constituent materials are uniformly mixed. In this case, it is preferable to mix the materials uniformly using a mixer or the like. The blending ratio of each constituent material can be appropriately adjusted depending on the desired properties of the cured product, such as mechanical strength, heat resistance, repairability, and remoldability. Furthermore, the order in which the constituent materials are mixed is not particularly limited when preparing the curable resin composition.

[0235] The cured product of the present invention is obtained by curing the curable resin composition of the present invention. The curing method can be appropriately selected and adopted from known methods depending on the properties of the composition used.

[0236] The cured product of the present invention can maintain good mechanical strength by exhibiting an appropriate crosslink density as described above. Furthermore, when mechanical energy such as scratches or external force is applied to the cured product of the present invention, the reversible bonds are broken, resulting in easy disassembly. Furthermore, the equilibrium shifts in the direction of the bonds, which is thought to re-form adducts, enabling repair of scratches and remolding.

[0237] The structure of the resulting cured product can be confirmed by infrared absorption (IR) spectroscopy using Fourier transform infrared spectroscopy (FT-IR) or the like, elemental analysis, X-ray scattering, or the like.

[0238] The curable resin composition of the present invention and a cured product produced from the curable resin composition are excellent in both ease of dismantling and repairability, and are also remoldable, and are useful for the following applications.

[0239] The cured curable resin of the present invention can be laminated with a substrate to form a laminate. The substrate of the laminate can be inorganic materials such as metal and glass, or organic materials such as plastic and wood, as appropriate for the application. The substrate may be in the form of a laminate, such as a flat plate, a sheet, or a three-dimensional structure, or may be three-dimensional. Any shape depending on the purpose, such as one with cured surface or partial curvature, may be used. There are no limitations on the hardness or thickness of the substrate. A multilayer laminate may also be formed by laminating a first substrate, a layer made of the cured product of the curable resin composition of the present invention, and a second substrate in this order. Because the curable resin composition of this embodiment has excellent adhesive properties, it can be suitably used as an adhesive for bonding a first substrate and a second substrate. Alternatively, the cured curable resin of the present invention may be used as a substrate, and the cured product of the present invention may be further laminated.

[0240] Furthermore, the cured curable resin of the present invention can relieve stress and is therefore particularly suitable for use in bonding dissimilar materials. For example, even in a laminate in which the substrate is a metal and / or metal oxide and the second substrate is a dissimilar material such as a plastic layer, the adhesive strength is maintained due to the stress-relieving ability of the cured resin of the present invention.

[0241] In a laminate obtained by laminating the cured product of the present invention and a substrate, the layer containing the cured product may be formed by direct coating or molding on the substrate, or an already molded product may be laminated. When directly coating, the coating method is not particularly limited, and examples thereof include spraying, spin coating, dipping, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, screen printing, and inkjet printing. When directly molding, examples thereof include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, and press molding. When laminating a molded composition, an uncured or semi-cured composition layer may be laminated and then cured, or a layer containing a fully cured cured product of the composition may be laminated on the substrate. Alternatively, the cured product of the present invention may be laminated by coating a precursor capable of serving as a substrate and curing it, or the precursor capable of serving as a substrate or the composition of the present invention may be adhered in an uncured or semi-cured state and then cured. The precursor capable of serving as a substrate is not particularly limited, and examples thereof include various curable resin compositions.

[0242] The cured product obtained using the curable resin composition of the present invention has particularly high adhesion to metals and / or metal oxides, making it particularly suitable for use as a primer for metals. Examples of metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials thereof, while examples of metal oxides include single oxides and / or composite oxides of these metals. Because of its particularly excellent adhesive strength to iron, copper, and aluminum, it can be suitably used as an adhesive for iron, copper, and aluminum.

[0243] The curable resin composition of the present invention can be suitably used as an adhesive for structural components in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry. Even when used to bond dissimilar materials, such as metals and non-metals, the adhesive maintains high adhesion without being affected by changes in temperature and is resistant to peeling. In addition to structural applications, the adhesive can also be used for general office and medical applications, carbon fiber, and storage battery cells, modules, and cases. It can also be used as an adhesive for bonding optical components, bonding optical disks, mounting printed wiring boards, die bonding adhesives, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films, anisotropic conductive pastes, and other mounting applications.

[0244] When the curable resin composition of the present invention has a fibrous substrate, and the fibrous substrate is a reinforcing fiber, the curable resin composition containing the fibrous substrate can be used as a fiber-reinforced resin. The method for incorporating the fibrous substrate into the composition is not particularly limited as long as the effects of the present invention are not impaired. Examples include methods for combining the fibrous substrate and the composition by methods such as kneading, coating, impregnation, injection, and pressure bonding, and the method can be selected appropriately depending on the form of the fiber and the application of the fiber-reinforced resin.

[0245] The method for molding fiber-reinforced resins is not particularly limited. To produce plate-shaped products, extrusion molding is commonly used, but flat presses are also possible. Other methods that can be used include extrusion molding, blow molding, compression molding, vacuum molding, and injection molding. To produce film-shaped products, melt extrusion and solution casting can be used. Examples of melt molding methods include inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. For resins that are cured with active energy rays, cured products can be produced using various curing methods using active energy rays. In particular, when a thermosetting resin is used as the main component of the matrix resin, examples of molding methods include prepreg molding of the molding material and pressurizing and heating it using a press or autoclave. Other examples include RTM (Resin Transfer Molding), Vacuum-assisted Resin Transfer Molding (VaRTM), laminate molding, and hand layup molding.

[0246] The curable resin composition of the present invention provides a cured product thereof that has good heat resistance and repairability, and is also remoldable, and therefore can be used as a molding material for large cases, motor housings, casting materials for the inside of cases, gears, pulleys, etc. These may be cured products of the resin alone, or cured products reinforced with fiber such as glass chips.

[0247] Fiber-reinforced resins can be formed into an uncured or semi-cured state known as a prepreg. After distributing the product in the prepreg state, final curing may be performed to form a cured product. When forming a laminate, it is preferable to form the prepreg, then stack other layers, and then perform final curing, since this allows the formation of a laminate in which each layer is tightly adhered. The mass ratio of the composition and fibrous substrate used in this case is not particularly limited, but it is generally preferable to prepare the prepreg so that the resin content is 20 to 60 mass%.

[0248] The cured product of the present invention has good heat resistance and repairability, and is remoldable, making it suitable for use as a heat-resistant material and an electronic material. It is particularly suitable for use in semiconductor encapsulants, circuit boards, build-up films, build-up boards, adhesives, and resist materials. It is also suitable for use as a matrix resin for fiber-reinforced resins, and is particularly suitable as a highly heat-resistant prepreg. The heat-resistant and electronic components thus obtained can be used in a variety of applications, including, but not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace and aviation-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, and housing components for wind power generation.

[0249] In particular, by taking advantage of the excellent flexibility of the cured product, the adhesive can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry. Even when used to bond dissimilar materials, such as between metals and non-metals, the adhesive of the present invention can maintain high adhesion without being affected by changes in the temperature environment and is less likely to peel. In addition to structural member applications, the adhesive of the present invention can also be used as an adhesive for general office use, medical use, carbon fiber, and storage battery cells, modules, and cases, etc., including adhesives for bonding optical components, adhesives for bonding optical disks, adhesives for mounting printed wiring boards, die bonding adhesives, semiconductor adhesives such as underfills, BGA reinforcing underfills, and mounting adhesives such as anisotropic conductive films and anisotropic conductive pastes.

[0250] Below, we will explain some representative products by giving examples.

[0251] 1.Semiconductor encapsulation materials A method for obtaining a semiconductor encapsulating material from the resin composition of the present invention includes thoroughly melt-mixing the resin composition, a curing accelerator, and compounding ingredients such as an inorganic filler, as needed, using an extruder, kneader, roll, or the like until homogeneous. In this process, fused silica is typically used as the inorganic filler. However, when used as a high-thermal-conductivity semiconductor encapsulating material for power transistors and power ICs, highly filled inorganic fillers such as crystalline silica, alumina, and silicon nitride, which have higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, and silicon nitride may be used. The inorganic filler is preferably used in an amount of 30 to 95% by weight per 100 parts by weight of the curable resin composition. In particular, a filler amount of 70 parts by weight or more, and even more preferably 80 parts by weight or more, is preferred to improve flame retardancy, moisture resistance, and solder crack resistance and to reduce the linear expansion coefficient.

[0252] 2. Semiconductor Devices A semiconductor package molding method for obtaining a semiconductor device from the curable resin composition of the present invention includes molding the semiconductor encapsulating material using a casting machine, a transfer molding machine, an injection molding machine, or the like, and then heating the molded product at 50 to 250°C for 2 to 10 hours.

[0253] 3. Printed Circuit Board A method for obtaining a printed circuit board from the composition of the present invention includes laminating the prepreg by a conventional method, appropriately overlaying copper foil, and heat-pressing the laminate under a pressure of 1 to 10 MPa at 170 to 300°C for 10 minutes to 3 hours.

[0254] 4. Flexible substrate A method for producing a flexible substrate from the crosslinkable resin composition of the present invention includes a method comprising the following three steps: The first step is to apply the crosslinkable resin composition containing a resin component, an organic solvent, etc. to an electrically insulating film using a coater such as a reverse roll coater or a comma coater; the second step is to heat the electrically insulating film to which the crosslinkable resin composition has been applied at 60 to 170°C for 1 to 15 minutes using a heater to volatilize the solvent from the electrically insulating film and B-stage the crosslinkable resin composition; and the third step is to thermocompression bond a metal foil to the adhesive of the electrically insulating film containing the B-stage crosslinkable resin composition using a heated roll or the like (the compression pressure is preferably 2 to 200 N / cm and the compression temperature is preferably 40 to 200°C). If sufficient adhesive properties are obtained by going through the above three steps, the process may be terminated here, but if complete adhesive properties are required, it is preferable to further post-cure the resin composition at 100 to 200° C. for 1 to 24 hours. The thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 μm.

[0255] 5. Build-up board A method for obtaining a build-up substrate from the composition of the present invention includes, for example, the following steps. First, the composition, which is appropriately blended with rubber, filler, and the like, is applied to a circuit board on which a circuit has been formed using a spray coating method, curtain coating method, or the like, and then cured (Step 1). Next, if necessary, predetermined through-holes or the like are drilled, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, followed by plating with a metal such as copper (Step 2). These operations are sequentially repeated as desired to alternately build up resin insulating layers and conductor layers of a predetermined circuit pattern (Step 3). Note that drilling of through-holes is performed after the formation of the outermost resin insulating layer. Alternatively, the build-up substrate of the present invention can be produced by forming a roughened surface by heat-pressing a copper foil, in which the resin composition has been semi-cured on a copper foil, onto a wiring board on which a circuit has been formed, at 170 to 300°C, thereby eliminating the plating step.

[0256] 6. Build-up film A build-up film can be obtained from the composition of the present invention by applying the composition to the surface of a support film (Y) as a substrate, and then drying the organic solvent by heating or blowing hot air or the like to form a layer of the composition (X).

[0257] The organic solvent used here is preferably, for example, a ketone such as acetone, methyl ethyl ketone, or cyclohexanone; an acetate ester such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, or carbitol acetate; a carbitol such as cellosolve or butyl carbitol; an aromatic hydrocarbon such as toluene or xylene; dimethylformamide, dimethylacetamide, or N-methylpyrrolidone; and it is preferably used in a proportion such that the nonvolatile content is 30 to 60% by mass.

[0258] The thickness of the layer (X) formed is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. In addition, the layer (X) of the composition in the present invention may be protected with a protective film described below. Protection with a protective film can prevent adhesion of dust and the like to the surface of the resin composition layer and scratches.

[0259] Examples of the support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; polycarbonate; polyimide; and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a matte treatment, corona treatment, or release treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0260] The support film (Y) is peeled off after laminating it onto a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0261] A multilayer printed circuit board can be produced using the build-up film obtained as described above. For example, if the layer (X) is protected by a protective film, the film is peeled off, and then the layer (X) is laminated, for example, by a vacuum lamination method, on one or both sides of the circuit board so as to be in direct contact with the circuit board. The lamination method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination. The lamination conditions are preferably a pressure bonding temperature (lamination temperature) of 70 to 140°C and a pressure bonding pressure of 1 to 11 kgf / cm2 (9.8 x 10 4 ~107.9×10 4 N / m 2 ), and lamination is preferably carried out under reduced air pressure of 20 mmHg (26.7 hPa) or less.

[0262] 7.Conductive paste A method for obtaining a conductive paste from the composition of the present invention includes, for example, dispersing conductive particles in the composition. Depending on the type of conductive particles used, the conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive. [Example]

[0263] The present invention will now be described in more detail with reference to examples and comparative examples, in which "parts" and "%" are by mass unless otherwise specified. The present invention is not limited thereto.

[0264] FD-MS spectrum and GPC were measured under the following conditions. FD-MS: JEOL Ltd. "JMS-T100GC AccuTOF" Measurement range: m / z = 50.00 to 2000.00 Rate of change: 25.6mA / min Final current value: 40mA Cathode voltage: -10kV

[0265] GPC: Tosoh Corporation "HLC-8320GPC" Column: Tosoh Corporation "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Measurement conditions: 40°C Mobile phase: tetrahydrofuran Flow rate: 1ml / min Standard: Tosoh Corporation "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F"

[0266] The epoxy equivalent of the synthesized epoxy resin was measured in accordance with JIS K7236, and the epoxy equivalent (g / eq) was calculated.

[0267] Examples of methods for calculating the number of repeating units include calculation from the results of GPC molecular weight measurement and various appropriate instrumental analyses such as FD-MS.

[0268] Example 1 A flask equipped with a thermometer and stirrer was charged with 445 g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 64.4 g (0.33 mol) of 2-aminoanthracene (active hydrogen equivalent 96.6 g / eq). The temperature was raised to 130°C over 2 hours and the reaction was allowed to proceed for 20 hours. After this, 509.4 g of epoxy resin (Ep-1) was obtained. The epoxy equivalent of the resulting epoxy resin (Ep-1) was 1343 g / eq. Mass spectrometry of this epoxy resin (Ep-1) confirmed that it contained the desired epoxy resin (Ep-1), as it exhibited a peak at M+ = 1607, corresponding to the theoretical structure of the following structural formula (Ep-1) with m = 1 and n = 8.

[0269] [ka]

[0270] Example 2 509.4 g (0.19 mol) of the epoxy resin (Ep-1) obtained in Example 1 and 40 g (0.38 mol) of diethanolamine were charged, and the temperature was raised to 80°C over 1 hour, after which the reaction was carried out for 11 hours. 549.4 g of hydroxy compound (Ph-1) was then obtained. Mass spectrometry of this hydroxy compound (Ph-1) revealed a peak of M+ = 1817, which corresponds to the theoretical structure of the following structural formula (Ph-1) where m = 1 and n = 8, confirming that it contained the target hydroxy compound (Ph-1).

[0271] [ka]

[0272] Example 3 A flask equipped with a thermometer and stirrer was charged with 203 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthetic Co., Ltd.; epoxy equivalent: 203 g / eq) and 92 g (0.48 mol) of 2-aminoanthracene (active hydrogen equivalent: 96.6 g / eq). The temperature was raised to 125°C over 2 hours and then reacted for 14 hours. After this, 287 g of epoxy resin (Ep-2) was obtained. The epoxy equivalent of the resulting epoxy resin (Ep-2) was 4142 g / eq. Mass spectrometry of this epoxy resin (Ep-2) confirmed that it contained the desired epoxy resin (Ep-2), as it exhibited a peak at M+ = 822, which corresponds to the theoretical structure of the following structural formula (Ep-2) where n is 1.

[0273] [ka]

[0274] Example 4 A flask equipped with a thermometer and stirrer was charged with 188 g (0.5 mol) of EPICLON 850S (DIC Corporation, bisphenol-type liquid epoxy resin, epoxy equivalent: 188 g / eq) and 48.3 g (0.25 mol) of 2-aminoanthracene (active hydrogen equivalent: 96.6 g / eq). The temperature was raised to 125°C over 2 hours and then the reaction was allowed to proceed for 14 hours. After this, 225 g of epoxy resin (Ep-3) was obtained. The epoxy equivalent of the resulting epoxy resin (Ep-3) was 510 g / eq. Mass spectrometry of this epoxy resin (Ep-3) confirmed that it contained the desired epoxy compound (Ep-3), as a peak at M+ = 874 was obtained, corresponding to the theoretical structure of the following structural formula (Ep-3) where n is 1.

[0275] [ka]

[0276] Example 5 A flask equipped with a thermometer, condenser, and stirrer was charged with 40.0 g (0.10 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthetic Co., Ltd.; epoxy equivalent: 200 g / eq) and 25.1 g (0.066 mol) of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (manufactured by Asahi Organic Chemicals Co., Ltd.; BIP-ANT). The temperature was raised to 140 °C over 30 minutes, and then 0.33 g of 4% aqueous sodium hydroxide solution was added. The temperature was then raised to 150 °C over 30 minutes and the reaction was continued at 150 °C for 20 hours. The mixture was then cooled to 80 °C, and 65 g of methyl isobutyl ketone, 65 g of water, and a neutralization amount of sodium phosphate were added. The aqueous layer was then removed. The solvent was then distilled off under reduced pressure to obtain 60.3 g of epoxy resin (Ep-4). The epoxy equivalent of the obtained epoxy resin (Ep-4) was 1030 g / eq. Mass spectrometry of this epoxy resin (Ep-4) showed a peak of M+=1005, which corresponds to the theoretical structure of m=1 in the following structural formula (A-1), confirming that it contained the target epoxy resin (Ep-4).

[0277] [ka]

[0278] Example 6 The same reaction procedure as in Example 5 was repeated, except that 40.0 g (0.10 mol) of 1,12-dodecanediol diglycidyl ether was replaced with 89.0 g (0.10 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq). 125.5 g of epoxy resin (Ep-5) was obtained. The epoxy equivalent of the resulting epoxy resin (Ep-5) was 1970 g / eq. Mass spectrometry of this epoxy resin (Ep-5) revealed a peak at M+ = 2223, corresponding to the theoretical structure of m = 1, n = 11 in the following structural formula (Ep-5), confirming that it contained the desired epoxy resin (Ep-5).

[0279] [ka]

[0280] Example 7 41.2 g (0.02 mol) of the epoxy resin (Ep-4) obtained in Example 5 (epoxy equivalent: 1030 g / eq) and 4.8 g (0.021 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq) were charged, and the mixture was heated to 140°C over 30 minutes. Then, 0.5 g of a 20% aqueous sodium hydroxide solution was added. The mixture was then heated to 150°C over 30 minutes and allowed to react at 150°C for 16 hours. The mixture was then cooled to 80°C, and 45 g of methyl isobutyl ketone, 45 g of water, and a neutralizing amount of sodium phosphate were added. The aqueous layer was removed. The solvent was then distilled off under reduced pressure, and a neutralizing amount of sodium phosphate was added to obtain 43.1 g of a hydroxy compound (Ph-2). The hydroxy equivalent of the resulting hydroxy compound (Ph-2) was calculated by GPC to be 12840 g / eq. This hydroxy compound (Ph-2) was confirmed to contain the target hydroxy compound (Ph-2) because a peak of M+=1461 was obtained in the mass spectrum, which corresponds to the theoretical structure of m=1 in the following structural formula (A-3).

[0281] [ka]

[0282] Example 8 A flask equipped with a thermometer, condenser, and stirrer was charged with 445 g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 69.3 g (0.33 mol) of 2,6-dihydroxyanthracene (hydroxyl equivalent 105 g / eq). The temperature was raised to 140 °C over 30 minutes, and then 2.6 g of 4% aqueous sodium hydroxide solution was added. The temperature was then raised to 150 °C over 30 minutes and the reaction was continued at 150 °C for 6 hours. A neutralizing amount of sodium phosphate was then added, yielding 491 g of epoxy resin (Ep-6). The epoxy equivalent of the resulting epoxy resin (Ep-6) was 1700 g / eq. This epoxy resin (Ep-6) was confirmed to contain the target epoxy resin (Ep-6) because a peak of M+=2754 was obtained in the mass spectrum, which corresponds to the theoretical structure of m=1, n=8 in the following structural formula (Ep-6).

[0283] [ka]

[0284] Example 9 A flask equipped with a thermometer, condenser, and stirrer was charged with 200 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthetic Co., Ltd.; epoxy equivalent: 200 g / eq) and 69.3 g (0.33 mol) of 2,6-dihydroxyanthracene (hydroxyl equivalent: 105 g / eq). The temperature was raised to 140°C over 30 minutes, after which 2.6 g of 4% aqueous sodium hydroxide solution was added. The temperature was then raised to 150°C over 30 minutes and the reaction continued at 150°C for 6 hours. A neutralizing amount of sodium phosphate was then added, yielding 255 g of epoxy resin (Ep-7). The epoxy equivalent of the resulting epoxy resin (Ep-7) was 1440 g / eq. This epoxy resin (Ep-7) was confirmed to contain the target epoxy resin (Ep-7) because a peak of M+=838, which corresponds to the theoretical structure of m=1 in the following structural formula (Ep-7), was obtained in the mass spectrum.

[0285] [ka]

[0286] Example 10 89 g (0.05 mol) of the epoxy resin (Ep-7) obtained in Example 9 and 12.0 g (0.053 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq) were charged, and the mixture was heated to 140°C over 30 minutes. Then, 1.0 g of 20% aqueous sodium hydroxide solution was added. The mixture was then heated to 150°C over 30 minutes and allowed to react at 150°C for 12 hours. A neutralizing amount of sodium phosphate was then added, yielding 95 g of hydroxy compound (Ph-3). The hydroxy equivalent of the resulting hydroxy compound (Ph-3) was calculated by GPC to be 19,200 g / eq. This hydroxy compound (Ph-3) was confirmed to contain the desired hydroxy compound (Ph-3) because a peak at M+ = 1294, corresponding to the theoretical structure of the following structural formula (Ph-3) with m = 1, was observed in the mass spectrum.

[0287] [ka]

[0288] Synthesis Example 1 A flask equipped with a thermometer, condenser, and stirrer was charged with 56.4 g (0.15 mol) of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (BIP-ANT, manufactured by Asahi Organic Chemicals Co., Ltd.), 56.4 g of methanol, and 222.0 g (2.4 mol) of epichlorohydrin. After dissolving at 60 °C, 25.0 g (0.30 mol) of 48% caustic soda was added dropwise via a dropping funnel over 30 minutes, and the reaction was continued at 60 °C for 9 hours. The mixture was then washed four times with 114 g of purified water, and the organic layer was concentrated under reduced pressure to obtain a resinous product. The resinous product was left to cool and then crushed in a mortar and stirred with 540 g of methanol to precipitate crystals. The crystals were then filtered and dried to obtain 67.7 g of epoxy resin (Ep-8). The epoxy equivalent of the resulting epoxy resin (Ep-8) was 248 g / eq.

[0289] Example 11 Hydroxy Compound (Ph-4) 49.6 g (0.1 mol) of the epoxy resin (Ep-8) obtained in Synthesis Example 1 and 58.4 g (0.2 mol) of triphenylolmethane (Gunei Chemical Industry Co., Ltd. "TPM-100", hydroxyl equivalent 97 g / eq) were charged, and the mixture was heated to 140°C over 30 minutes. 1.0 g of a 20% aqueous sodium hydroxide solution was then charged. The mixture was then heated to 150°C over 30 minutes and allowed to react at 150°C for 12 hours. A neutralizing amount of sodium phosphate was then added, yielding 105 g of hydroxy compound (Ph-4). The hydroxyl equivalent of the resulting hydroxy compound (Ph-4) was calculated by GPC to be 300 g / eq.

[0290] [ka]

[0291] Example 12 A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 100 g of the hydroxy compound Ph-4 obtained in Synthesis Example 11, 215 g (2.3 mol) of epichlorohydrin, and 65 g of n-butanol were added and dissolved. After heating to 65°C, the pressure was reduced to an azeotropic pressure, and 35.4 g (0.43 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under the same conditions for 0.5 hours. During this time, the distillate distilled 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 was continued. Unreacted epichlorohydrin was then removed by vacuum distillation. 90 g of methyl isobutyl ketone and 90 g of n-butanol were added to the resulting crude epoxy resin and dissolved. Further, 10 g of a 10% aqueous solution of sodium hydroxide was added to this solution, and the mixture was reacted at 80° C. for 2 hours, after which the mixture was washed three times with 60 g of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 113 g of epoxy resin (Ep-9). The epoxy equivalent of the obtained epoxy resin (Ep-9) was 356 g / eq.

[0292] [ka]

[0293] Synthesis Example 2 A flask equipped with a thermometer and stirrer was charged with 445 g (0.5 mol) of polytetramethylene glycol diglycidyl ether (Nagase ChemteX "Denacol EX-991L": epoxy equivalent 445 g / eq) and 171 g (0.75 mol) of bisphenol A (hydroxyl equivalent 114 g / eq). The mixture was heated to 140 °C over 30 minutes, and then 3.1 g of 4% aqueous sodium hydroxide solution was added. The mixture was then heated to 150 °C over 30 minutes and further reacted at 150 °C for 16 hours. A neutralizing amount of sodium phosphate was then added, yielding 616 g of a hydroxy compound represented by the following formula (Ph-2). Mass spectrometry of this hydroxy compound revealed a peak at M+ = 1380, corresponding to the theoretical structure of m1 = 1 and n1 = 11 in the following formula, confirming that it contained a PTMG (polytetramethylene ether glycol) type (BPA: bisphenol A) hydroxy compound. The hydroxyl equivalent weight of this hydroxy compound (Ph-5) calculated by GPC was 1080 g / eq, the average value of n1 was 10.6, and the average value of m1 was 0.76.

[0294] [ka]

[0295] Synthesis Example 3 A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 200 g of the hydroxy compound Ph-5 obtained in Synthesis Example 2, 437 g (4.72 mol) of epichlorohydrin, and 118 g of n-butanol were added and dissolved. After heating to 65°C, the pressure was reduced to an azeotropic pressure, and 6.66 g (0.08 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under the same conditions for 0.5 hours. During this time, the azeotropic distillate was separated using a Dean-Stark trap, the aqueous layer was removed, and the oil layer was returned to the reaction system while the reaction was continued. Unreacted epichlorohydrin was then removed by vacuum distillation. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to the resulting crude epoxy resin and dissolved. Further, 10 g of a 10% aqueous solution of sodium hydroxide was added to this solution, and the mixture was reacted at 80° C. for 2 hours, after which the mixture was washed three times with 50 g of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 190 g of epoxy resin (Ep-10). The epoxy equivalent of the obtained epoxy resin (Ep-10) was 1192 g / eq. Mass spectrometry showed a peak at M+ = 1492, which corresponds to the theoretical structure of m1 = 1, n1 = 11, q = 1, p1 = 0, and p2 = 0 in the following formula, confirming that the epoxy resin (Ep-10) contains a PTMG-type (BPA) epoxy resin.

[0296] [ka]

[0297] Preparation of composition and cured product A curable resin composition was obtained by mixing each compound uniformly in a mixer (Thinky Corporation's "Awatori Rentaro ARV-200") according to the formulation shown in the table (the numbers in the table are by mass). This curable resin composition was sandwiched between aluminum mirror plates (Engineering Test Service Co., Ltd.'s "JIS H 4000 A1050P") using a silicone tube as a spacer, and heat-cured under specified conditions to obtain a cured product with a thickness of 0.7 mm.

[0298] <Tensile elongation> The resulting cured product was punched into a dumbbell shape (JIS K 7161-2-1BA) using a punching blade to prepare test specimens. Tensile tests were performed on these specimens using a tensile testing machine (Shimadzu Corporation's "Autograph AG-IS") in accordance with JIS K 7162-2, and the elongation at break was evaluated at a measurement temperature of 23°C (test speed: 2 mm / min).

[0299] <Remolding test> The cured product was freeze-pulverized. 0.07 g of the pulverized cured product was placed in a 10 mm square, 0.5 mm thick mold and vacuum-pressed under specified conditions. The appearance of the resulting cured product was visually observed. The evaluation criteria were as follows: A: The seams disappeared and the hardened material became one piece. B: Some joints are visible to the naked eye, but the cured product has become one piece. C: It had a solidified shape and broke apart when light pressure was applied.

[0300] <Repair test> The cured product was cut with a razor, the resulting fractured surfaces were brought into contact with each other, and then aged in a dryer at 150°C for 24 hours. After removing from the dryer, the cured product was visually inspected for adhesion between the cross sections. The evaluation criteria were as follows: A: The bonded part does not separate even when the cured product is bent 90 degrees. B: The bond is formed, and when the cured product is bent, the bond comes apart. C: No bonding.

[0301] [Table 1]

[0302] [Table 2]

[0303] [Table 3]

[0304] [Table 4]

[0305] [Table 5]

[0306] [Table 6]

[0307] [Table 7]

[0308] The formulations shown in the table are as follows: E-850S: Bisphenol A liquid epoxy resin (DIC Corporation, epoxy equivalent weight 188g / eq) TD-2131: Phenol novolac phenolic resin (DIC Corporation, hydroxyl equivalent: 104 g / eq) BMI-TMH: 1,6'-bismaleimido-(2,2,4-trimethyl)hexane DICY: Dicyandiamide ("DICY7" manufactured by Mitsubishi Chemical Corporation) DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DIC Corporation, "B-605-IM") TPP: Triphenylphosphine (Tokyo Chemical Industry Co., Ltd.)

Claims

1. A curable compound (I) represented by any one of the following general formulas (1) to (3): 【Chemical 1】 [In formulas (1) to (3), R represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group; Z １ is as follows (Z １ -1) to (Z １ -7) 【Chemistry 2】 [Formula (Z １ -1), (Z １ -2), (Z １ -3), (Z １ -4), (Z １ -5), (Z １ -6), (Z １ -7), among Each Ar independently represents a structure having an unsubstituted or substituted aromatic ring, R １１ , R １２ each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R １３ , R １４ is a hydrogen atom or a methyl group, R １ , R ２ are each independently a hydrogen atom, a methyl group, or an ethyl group, R' are each independently a divalent hydrocarbon group having 2 to 12 carbon atoms; n is the average value of the repeating units and is 0.5 to 10; n1 is an integer from 4 to 16, n2 is the average value of the repeating units and is 2 to 30. Expression (Z １ X in the formula (Z １ -1-1), and Y is a structural unit represented by the following general formula (Z １ -1-2) is a structural unit represented by 【Chemistry 3】 <Formula (Z １ -1-1), (Z １ -1-2) Middle, Ar, R １ , R ２ , R′, n1, and n2 are the same as above; R ３ , R ４ , R ７ , R ８ each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R ５ , R ６ , R ９ , R １０ are each independently a hydrogen atom or a methyl group. m1, m2, m3, m4, m5, m6, p1, p2, and q are the average values ​​of the repetitions, m1, m2, m3, m4, m5, and m6 each independently represent 0 to 25, and m1+m2≧1; p1 and p2 each independently represent 0 to 5; q is 0.5 to 5. However, the general formula (Z １ -1-1) and X represented by the general formula (Z １ The bond to Y represented by (1-1-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively. In addition, the aromatic ring containing the anthracene skeleton in formulas (1) to (3) may have a substituent. The lines in the formulas indicate that the ring may be connected at any point. * indicates a point of attachment.]

2. A curable compound (II) containing a reversible bond formed by a Diels-Alder reaction between a structure having an anthracene skeleton in a curable compound (I) represented by any one of general formulas (1) to (3) of claim 1 and a compound (B) containing a dienophilic structure.

3. The curable compound (II) according to claim 2, wherein the compound (B) having a dienophilic structure is a compound having two or more maleimide groups.

4. A curable compound (I) represented by any one of general formulas (1) to (3) of claim 1; and a compound (B) having a dienophilic structure, thereby allowing the cured product to contain reversible bonds formed by a Diels-Alder reaction.

5. The method for producing a cured product according to claim 4, wherein the compound (B) having a dienophilic structure is a compound having two or more maleimide groups.

6. The method for producing a cured product according to claim 4, further comprising using in combination a compound (C) reactive with a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group in the curable compound (I) represented by any one of general formulas (1) to (3) of claim 1.

7. A method for producing a cured product using the curable compound (II) containing a reversible bond according to claim 2, which allows the cured product to contain a reversible bond formed by a Diels-Alder reaction.

8. The method for producing a cured product according to claim 7, further comprising using in combination a compound (C) reactive with a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group in the curable compound (II) containing a reversible bond according to claim 2.

9. The method for producing a cured product according to any one of claims 4 to 8, wherein the cured product has any one of the functions of easy dismantling, repairability, and remoldability.

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