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

Abstract

Provided are: a compound which is a curable resin and which can easily achieve easy disintegration, reworkability, remoldability and the like in a cured product; a curable resin composition which is obtained using the compound; and a cured product of the curable resin composition. Specifically, a curable resin composition is used which 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 dienophile structure, and a compound (C) reactive with the curable functional groups (a). The curable functional group is preferably a hydroxyl group or a glycidyl ether group, and the compound (B) containing the dienophile structure is preferably bismaleimide.

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 formed of the cured product. Background Art

[0002] Cured products obtained by thermally curing phenolic resins, epoxy resins, etc. have excellent heat resistance, mechanical strength, electrical properties, adhesiveness, etc., and are essential materials in various fields such as electric / electronic, coatings, and adhesives.

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

[0004] In addition, a cured product obtained by once curing a thermosetting resin is insoluble in a solvent (insoluble) and does not dissolve even at high temperatures (infusible), so it lacks recyclability and reusability. The used cured product becomes waste, so reducing waste and alleviating the environmental load have become issues. In addition, due to its high adhesive performance, there are also issues such as limited disassemblability and reusability after use.

[0005] Therefore, for cured products using thermosetting resins, long life, reduction of waste, and reusability are required, and it is considered effective to endow them with reparability, re-moldability, and disassemblability.

[0006] Under such circumstances, the following method has been disclosed: by previously blending a compound having thermal decomposability into the reaction system adhesive component, the adhesive strength is reduced by performing a certain heating after use, enabling disassembly (for example, refer to Patent Document 1).

[0007] In addition, the following method has been disclosed: in a sealing material using an epoxy resin or the like, even when cracks or peeling occur, a self-healing sealing material can be made by using a first thermosetting resin and microcapsule particles encapsulating a second thermosetting resin precursor substance (for example, refer to Patent Document 2).

[0008] In addition to the above, in order to endow reparability / remoldability, research using reversible bonds such as dynamic covalent bonds and supramolecular bonds in cured products is also being actively carried out.

[0009] Prior Art Documents

[0010] Patent Documents

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

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

[0013] Problems to be Solved by the Invention

[0014] In the technology provided in the above Patent Document 1, the adhesive after disassembly is discarded, and the base material as the adherend can be recycled, but there is still a problem of insufficient overall recyclability. In addition, in the technology of the above Patent Document 2, although it has a certain degree of self-healing property, it is not a solution from the perspective of so-called reuse, and there is still a problem of becoming waste when not needed. In addition, among the raw materials used for the above reversible bond, it is necessary to ensure its molecular mobility, so there is a problem that only a gel-like substance lacking mechanical strength can be used as the raw material. At present, improvement is required in either case. Therefore, an object of the present invention is to provide a compound that is a curable resin but can easily achieve easy disassembly property, repair property, remolding property, etc. in the cured product, and a curable resin composition and a cured product using the compound.

[0015] Means for Solving the Problems

[0016] The present inventors conducted in-depth research and found that by using a curable compound having a specific structure and using it as a curable resin composition, the above problems can be solved, and thus the invention was completed.

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

[0018] [1] A curable resin composition, characterized by containing:

[0019] A curable compound (A) having one or more anthracene structures and two or more curable functional groups (a) in the molecule,

[0020] A compound (B) containing a dienophile structure, and

[0021] A compound (C) reactive with the above curable functional group (a).

[0022] [2] The curable resin composition according to [1], wherein the above curable functional group (a) is a hydroxyl group or a glycidyl ether group.

[0023] [3] The curable resin composition according to [1] or [2], wherein the above curable compound (A) further has an alkylene chain or an alkylene ether chain.

[0024] [4] The curable resin composition according to any one of [1] to [3], wherein the above compound containing a dienophile structure is a compound having two or more maleimide groups.

[0025] [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.

[0026] [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 resin.

[0027] [7] The curable resin composition according to any one of [1] to [6], wherein the concentration of the reversible bond formed by the Diels - Alder reaction is 0.10 mmol / g or more relative to the total mass of the curable components in the curable resin composition.

[0028] [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 a readily decomposable composition, a repair composition, and a composition for a remolding material.

[0029] [9] A cured product obtained by curing the curable resin composition according to any one of [1] to [8].

[0030]

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

[0031]

[11] A heat - resistant member containing the cured product described in [9].

[0032]

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

[0033] [Chemical formula 1]

[0034]

[0035] [In formulas (1) to (3), R is a hydroxyl group, a glycidyl ether group, or a 2 - methylglycidyl ether group,

[0036] Z1 is any one of the following (Z1 - 1) to (Z1 - 7),

[0037] [Chemical formula 2]

[0038]

[0039] [In formulas (Z1 - 1), (Z1 - 2), (Z1 - 3), (Z1 - 4), (Z1 - 5), (Z1 - 6), (Z1 - 7),

[0040] Each Ar is independently a structure containing an unsubstituted or substituted aromatic ring,

[0041] R 11 and R 12 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0042] R 13 and R 14 are a hydrogen atom or a methyl group,

[0043] R 1 and R 2 are each independently a hydrogen atom, a methyl group or an ethyl group,

[0044] Each R' is independently a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0045] n is the average value of the repeating unit and is 0.5 to 10,

[0046] n1 is an integer of 4 to 16,

[0047] n2 is the average value of the repeating unit and is 2 to 30;

[0048] In the 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),

[0049] [Chemical formula 3]

[0050]

[0051] In <formulas (Z1-1-1) and (Z1-1-2)>, Ar, R 1 and R 2 are the same as those described above, and R', n1, n2 are the same as those described above,

[0052] R 3 and R 4 and R 7 and R 8 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0053] R 5 and R 6 and R 9 and R 10 are each independently a hydrogen atom or a methyl group.〉

[0054] m1, m2, m3, m4, m5, m6, p1, p2, q are the average values of the repetitions,

[0055] m1, m2, m3, m4, m5, and m6 are each independently 0 to 25, and m1 + m2 ≥ 1.

[0056] p1 and p2 are each independently 0 to 5.

[0057] q is 0.5 to 5.

[0058] Among them, the bonding of X represented by the above general formula (Z1-1-1) and Y represented by the above general formula (Z1-1-2) can be random or block. The total numbers of the respective structural units X and Y present in one molecule are m1 and m2, respectively.

[0059] Moreover, the aromatic ring containing an anthracene skeleton in formulas (1) to (3) may have substituents. In addition, the lines in the formulas indicate that they can be connected at any position on the ring.

[0060] Advantages of the Invention

[0061] According to the present invention, it is possible to impart easy disassembly / repairability and reshaping property to the cured product formed from the curable resin composition, which can contribute to the long life of the cured product itself and the reduction of waste. Detailed Embodiments

[0062] Next, the modes 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 design changes, improvements, etc. can be appropriately made based on the general knowledge of those skilled in the art without departing from the gist of the present invention.

[0063] The curable resin composition according to one mode 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 dienophile structure, and a compound (C) reactive with the above curable functional group (a).

[0064] With such a configuration, in the process of obtaining a cured product from the above curable resin composition, a Diels-Alder reaction occurs 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, in the curing reaction, the curable functional group (a) in the above compound (A) and the compound (C) are covalently bonded to form a bond. Therefore, the obtained cured product becomes a cured product having a reversible bond formed by the Diels-Alder reaction, a curable functional group (a), and a permanent crosslinked structure (covalent bond) obtained by the reaction with the compound (C) capable of reacting therewith.

[0065] Since the crosslinked structure of such a cured product is reversible, when the cured product is impacted to generate cracks or is crushed, it is easy to be cut at the above-mentioned reversible bond portion and exhibit easy disassembly. On the other hand, even in a low-temperature region including room temperature, the above-mentioned reversible bond can be reversibly remolded into a bond, exhibiting functions such as reparability and remoldability. For example, even when the cured product of the present invention is crushed, by placing it in a low temperature including room temperature, heating / heating state, based on the reversible bond, it is easy to repair the cured product. In addition, it is also possible to remold the cured product after crushing it. It should be noted that since the bonding temperature of the Diels-Alder reaction based on the anthracene structure is high and it has durability even in a relatively high-temperature region, in a normal temperature region, it can be treated in the same manner as a cured product obtained from a thermosetting resin.

[0066] On the other hand, by forming a covalent bond between the curable functional group and the compound (C), a permanent crosslinked structure is formed in the cured product. In particular, since the above-mentioned compound (A) has two or more curable functional groups (a), a three-dimensional crosslinked structure can be formed through a curing reaction, and mechanical strength and heat resistance can also be imparted to the cured product.

[0067] As the above-mentioned curable compound (A), it is only necessary to have one or more anthracene structures and two or more curable functional groups (a) as described above, and there is no particular limitation on the others.

[0068] The above-mentioned curable functional group is not particularly limited. For example, vinyl, epoxy group, hydroxyl group, isocyanate group, carboxyl group, etc. can be cited. Among them, from the viewpoints of thermosetting, easy availability of industrial raw materials, and excellent balance of heat resistance, water resistance, and heat and humidity resistance of the obtained cured product, a hydroxyl group or a glycidyl ether group that may have a substituent is preferred. In addition, from the viewpoints of easy availability of industrial raw materials and easy adjustment of the crosslinking density when forming a cured product, the number of curable functional groups in one molecule is preferably in the range of 2 to 5, more preferably 2 to 3.

[0069] In addition, among the above-mentioned compound (A), a soft structure is preferably present. By including a soft structure, it is possible to further impart softness and toughness to the cured product itself. Therefore, it has the following characteristics: even at the site of use where cracks are likely to occur, it can absorb the impact, or even when used as an adhesive between substrates with different coefficients of thermal expansion, the substrate followability is more excellent. On this basis, by exhibiting the easy decomposability, reparability, etc. based on the above-mentioned reversible bonds, it also contributes to the durability of the cured product. As the above-mentioned soft structure, for example, partial structures such as an alkylene chain and an alkylene ether chain that do not contain an aromatic ring or an alicyclic structure can be cited. At this time, as the alkylene chain, the number of carbon atoms is more preferably 2 to 30, and particularly preferably 4 to 16. There is no particular limitation on the above-mentioned alkylene ether chain, and an alkylene ether chain having 2 to 12 carbon atoms is preferred, and the average value of the repetition number is preferably in the range of 2 to 30. Furthermore, the above-mentioned soft structure may have a plurality of the same or different structures in one molecule.

[0070] Furthermore, the molecular weight of the curable compound as one aspect of the present invention is not particularly limited, and can be appropriately adjusted according to the compound (B) having a dienophile structure described later, the use of the curable resin composition using the compound (C) having reactivity with the curable functional group (a), etc. For example, when the obtained curable resin composition is used for solvent-free adhesive applications, etc., it is preferably fluid at room temperature. From this viewpoint, 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. In addition, from the viewpoint of the curing density of the obtained cured product, it is preferable to adjust the equivalent weight of the curable functional group. For example, from the aspect of easy operation, when having an epoxy group, the epoxy equivalent weight is preferably in the range of 200 to 30,000 g / eq, and when having a hydroxyl group, the hydroxyl equivalent weight is preferably in the range of 200 g to 30,000 g / eq.

[0071] Examples of the above-mentioned curable compound (A) include compounds represented by any one of the following general formulas (1) to (3).

[0072] [Chemical formula 4]

[0073]

[0074] [In formulas (1) to (3), R is a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group,

[0075] Z1 is any one of the following (Z1-1) to (Z1-7),

[0076] [Chemical formula 4]

[0077]

[0078] [In formulas (Z1-1), (Z1-2), (Z1-3), (Z1-4), (Z1-5), (Z1-6), and (Z1-7),

[0079] each Ar is independently a structure containing an unsubstituted or substituted aromatic ring,

[0080] R 11 and R 12 are each independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group,

[0081] R 13 and R 14 are a hydrogen atom or a methyl group,

[0082] R 1 and R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group,

[0083] each R' is independently a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0084] n is the average value of the repeating unit and is 0.5 to 10,

[0085] n1 is an integer from 4 to 16,

[0086] n2 is the average value of the repeating unit and is 2 to 30.

[0087] 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),

[0088] [Chemical formula 5]

[0089]

[0090] [In formulas (Z1-1-1) and (Z1-1-2), Ar, R 1 and R 2 and R', n1, and n2 are the same as above,

[0091] R 3 and R 4 and R 7 and R 8 are each independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group,

[0092] R 5 and R 6 and R 9 and R 10 are each independently a hydrogen atom or a methyl group.〉

[0093] m1, m2, m3, m4, m5, m6, p1, p2, and q are the repeated average values.

[0094] m1, m2, m3, m4, m5, and m6 are each independently 0 to 25, and m1 + m2 ≥ 1.

[0095] p1 and p2 are each independently 0 to 5.

[0096] q is 0.5 to 5.

[0097] Among them, the bonding of X represented by the above general formula (Z1-1-1) and Y represented by the above general formula (Z1-1-2) can be random or block, and the total numbers of the respective structural units X and Y present in one molecule are m1 and m2, respectively.

[0098] Moreover, the aromatic ring containing an anthracene skeleton in formulas (1) to (3) may have substituents. In addition, the lines in the formulas indicate that they can be connected at any position on the ring.

[0099] Ar in the above general formula is an aromatic ring that may have substituents and is not particularly limited. Examples of the aromatic ring include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring. Examples of the substituents include: halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, aryl group, etc. The substituents on Ar are preferably those that do not undergo a curing reaction when used as a curable resin composition, because it is easier to exhibit the effects of the present invention.

[0100] Among them, as Ar, it is preferably any one of the structures represented by the following structural formulas. In addition, the lines in the formulas indicate that they can be connected at any position on the ring.

[0101] [Chemical formula 6]

[0102]

[0103] [The aromatic ring in the formula may be substituted or unsubstituted, and * represents the bonding point.]

[0104] In addition, as Ar, structures represented by the following formulas can also be cited.

[0105] [Chemical formula 7]

[0106]

[0107] (In the formula, the aromatic ring may be substituted or unsubstituted, n6 = 1 to 4, and * represents the bonding point.)

[0108] As the structure of the above Ar, the following structure is particularly preferred. * represents the bonding point.

[0109] [Chemical Formula 8]

[0110]

[0111] The repeating unit n1 in the above general formula is an integer from 2 to 16. By making n1 4 or more, the deformation mode of the cured product is likely to be elastic deformation. In addition, by making n1 16 or less, a decrease in the crosslinking density can be suppressed. It is preferably from 4 to 15, more preferably from 6 to 12.

[0112] R in the above general formula 1 and R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom. R 13 and R 14 and R 5 and R 6 and R 9 and R 10 are a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0113] The n2 in the above general formula is the average value of the repeating units and is from 2 to 30. If it is within this range, it is preferable in terms of the balance between the viscosity of the curable compound and the crosslinking density of the resulting cured product. It is preferably from 2 to 25, more preferably from 4 to 20.

[0114] R' in the above general formula is a divalent hydrocarbon group having 2 to 12 carbon atoms. If it is within this range, the adhesive force is increased and the deformation mode of the cured product is likely to be elastic deformation. Preferably, R' is a divalent hydrocarbon group having 2 to 6 carbon atoms.

[0115] The divalent hydrocarbon group is not particularly limited, and examples thereof include: linear or branched alkylene, alkenylene, alkynylene, cycloalkylene, arylene, aralkyl (a divalent group having an alkylene and an arylene), etc.

[0116] Examples of the alkylene include: methylene, ethylene, propylene, butylene, pentylene, hexylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Examples of the alkenylene include: vinylidene, 1-methylvinylidene, propenylene, butenylene, pentenylene, etc. Examples of the alkynylene include: acetylene, propyne, butyne, pentyne, hexyne, etc. Examples of the cycloalkylene include: cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, etc. Examples of the arylene include: phenylene, tolylene, xylylene, naphthylene, etc.

[0117] Among them, from the viewpoints of ease of obtaining raw materials, the viscosity of the resulting curable compound, and the balance of the softness when forming a cured product, ethylene, propylene, and tetramethylene are preferred.

[0118] In the above general formula, m1 and m2 are the average values of the repetitions of the above structural units X and Y, respectively, each independently being 0 to 25, and m1 + m2 ≥ 1. Preferably, each of m1 and m2 is in the range of 0.5 to 10. m1 and m2 are each independently 0 to 25, preferably in the range of 0.5 to 10, respectively.

[0119] As the curable compound of the present invention, for example, the curable compounds shown below can be cited, but are not limited to these.

[0120] [Chemical formula 9]

[0121]

[0122] [Chemical formula 10]

[0123]

[0124] In each of 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 the average values of repetitions, n2 represents 2 to 30, and m represents 0.5 to 10.

[0125] The curable compound as one aspect of the present invention can be synthesized by a known method. For example, the compound represented by the above general formula (1) can be easily obtained by using anthracenediol and a polyglycidyl ether compound, a polyvinyl ether or a polyhaloalkylene compound, and in the case where the curable reaction group is a hydroxyl group, using an excessive amount of anthracenediol, or in the case where the glycidyl ether group is the curable reaction group, using an excessive amount of the polyglycidyl ether compound for an elongation reaction. At this time, the polyglycidyl ether compound can be a single compound or a combination of a plurality of compounds having different structures. In addition, other hydroxyl group-containing compounds can also be used in combination within the range not impairing the curing of the present invention.

[0126] As the above anthracenediol, for example, the following substances can be cited. Various substituents can be present on the anthracene skeleton described below, and from the viewpoint of easily exhibiting the effects of the present invention, it is preferably a substituent having no reactivity.

[0127] [Chemical formula 11]

[0128]

[0129] The above polyglycidyl ether compound is not particularly limited, and from the aspect of easily adjusting the curable compound (A), a diglycidyl ether compound is preferred. Further, from the viewpoint of easily introducing a soft structure into the curable compound (A), a diglycidyl ether compound containing an alkylene chain and an alkylene ether chain is preferably used.

[0130] The glycidyl ether compound having an alkylene chain or an alkylene ether chain as described above is not particularly limited. For example, as the diglycidyl ether having an alkylene chain, 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, 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether, etc. can be cited. In addition, as the glycidyl ether compound having an alkylene ether chain, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, polyheptamethylene glycol diglycidyl ether, etc. can be cited. They may contain organic chlorine impurities generated in the glycidyl etherification of the hydroxy compound, and may also contain organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) shown by the following structure. These glycidyl ether compounds can be used alone or in combination of two or more.

[0131] [Chemical Formula 12]

[0132]

[0133] Among them, from the viewpoint of excellent balance between the flexibility and heat resistance of the obtained cured product, 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, polytetramethylene glycol diglycidyl ether.

[0134] Regarding the reaction ratio of the glycidyl ether compound having an alkylene chain or an alkylene ether chain to the above-mentioned anthracenediol, when the curable reaction group is a hydroxyl group, it is preferably reacted in the range of the former / latter being 1.0 / 1.01 to 1.0 / 5.0 (molar ratio), and from the aspect of well-balancedly having the flexibility and heat resistance of the obtained cured product, it is preferably 1.0 / 1.02 to 1.0 / 3.0 (molar ratio). Alternatively, when the glycidyl ether group is used as the curable reaction group, it is preferably reacted in the range of the former / latter being 1.01 / 1.0 to 5.0 / 1.0 (molar ratio), and from the aspect of well-balancedly having the flexibility and heat resistance of the obtained cured product, it is preferably 1.02 / 1.0 to 3.0 / 1.0 (molar ratio).

[0135] The reaction of the glycidyl ether compound having an alkylene chain or an alkylene ether chain with the above-mentioned anthracenediol is preferably carried out in the presence of a catalyst. As the above-mentioned catalyst, various catalysts can be used, for example: alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, phosphorus compounds such as triphenylphosphine, DMP-30, DMAP, quaternary ammonium salts such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium chlorides, bromides, iodides, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium chlorides, bromides, iodides, etc., tertiary amines such as triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, 1,4-diazabicyclo[2.2.2]octane, imidazoles such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc. Two or more kinds of these catalysts can also be used in combination. Among them, from the viewpoints of rapid progress of the reaction and high effect of reducing the amount of impurities, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred. The amount of these catalysts used is not particularly limited, and preferably 0.0001 to 0.01 mol is used relative to 1 mol of the hydroxyl group of the above-mentioned anthracenediol. The form of these catalysts is also not particularly limited, and they can be used in the form of an aqueous solution or in the form of a solid.

[0136] In addition, the reaction of the glycidyl ether compound having an alkylene chain or an alkylene ether chain with the above-mentioned anthracenediol can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include: methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propanol, butanol, etc. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, relative to the total mass of the raw materials charged. These organic solvents can be used alone or in combination of multiple kinds. For rapid progress of the reaction, no solvent is preferred. On the other hand, from the aspect of being able to reduce the impurities of the final product, dimethyl sulfoxide is preferably used.

[0137] As the reaction temperature when carrying out the above reaction, it is usually 50 to 180 °C, and the reaction time is usually 1 to 10 hours. From the viewpoint of being able to reduce the impurities of the final product, the reaction temperature is preferably 100 to 160 °C. In addition, when the resulting compound is highly colored, in order to suppress this situation, an antioxidant or a reducing agent can be added. There is no particular limitation on the antioxidant, for example: hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, phosphite compounds containing a trivalent phosphorus atom, etc. There is no particular limitation on the reducing agent, for example: hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, bisulfite or their salts, etc.

[0138] After the above reaction is completed, neutralization or washing with water may also be carried out until the pH value of the reaction mixture reaches 3 to 7, preferably 5 to 7. The neutralization treatment and the washing with water can be carried out according to conventional methods. For example, in the case of using a basic catalyst, acidic substances such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as neutralizing agents. After the neutralization or washing with water treatment, if necessary, the solvent can be distilled off under reduced pressure and heating to concentrate the product, and the compound can be obtained.

[0139] The above vinyl ether compound is not particularly limited, and from the aspect of easily adjusting the curable compound (A), a divinyl ether compound is preferred. Further, from the viewpoint of easily introducing a soft structure into the curable compound (A), an aliphatic divinyl ether compound containing an alkylene chain and an alkylene ether chain is preferably used.

[0140] In addition, the reaction of the above aliphatic divinyl ether with the above anthracenediol can be carried out without a solvent or in the presence of an organic solvent. Examples include aromatic organic solvents such as benzene, toluene, and xylene; ketone-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 n-butanol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. These organic solvents can be used alone or in combination of multiple kinds.

[0141] The reaction temperature during the above reaction is usually 50 to 150 °C, and the reaction time is usually 0.5 to 10 hours. At this time, in order to prevent the self-polymerization of the vinyl ether group, the reaction is preferably carried out in an oxygen atmosphere.

[0142] After the above reaction is completed, in the case of using an organic solvent, it is removed under reduced pressure and heating, and in the case of using a catalyst, it is deactivated with a deactivator or the like as needed and removed by washing and filtration operations, whereby the compound can be obtained.

[0143] The above polyhaloalkylene compound is not particularly limited, and from the aspect of easily adjusting the curable compound (A), a dihaloalkylene compound is preferred.

[0144] Regarding the reaction ratio of the above dihaloalkylene compound to anthracenediol, the reaction is preferably carried out in the range of the former / latter being 1.0 / 1.01 to 1 / 5.0 (molar ratio), and from the aspect of well-balancedly combining the softness and heat resistance of the obtained cured product, the former / latter is preferably 1.0 / 1.1 to 1.0 / 3.0 (molar ratio).

[0145] The reaction of the above-mentioned anthracenediol with the dihaloalkylene compound is preferably carried out in the presence of a basic compound. As the above-mentioned basic compound, various basic compounds can be used, for example: alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, etc. Two or more of these basic compounds can also be used in combination. Among them, from the viewpoints of rapid progress of the reaction and high effect of reducing the amount of impurities, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred. The amount of use of these basic compounds is not particularly limited, and 0.0001 to 10 moles are preferably used relative to 1 mole of the hydroxyl group of the above-mentioned anthracenediol. The form of these basic compounds is also not particularly limited, and they can be used in the form of an aqueous solution or in the form of a solid. In addition, a catalyst can also be used in the reaction, and quaternary ammonium salts such as tetrabutylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium iodide, tetraethylammonium chloride, benzyltributylammonium bromide, benzyltriethylammonium bromide, cetyltriethylammonium chloride, tetramethylammonium chloride, cetyltrimethylammonium chloride, crown ethers, potassium iodide, etc. can be used.

[0146] In addition, the reaction of the above-mentioned anthracenediol with the dihaloalkylene compound can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include: toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide, etc. The amount of use of the organic solvent is usually 50 to 300% by mass, preferably 100 to 1000% by mass, relative to the total mass of the raw materials charged. These organic solvents can be used alone or in combination of multiple kinds.

[0147] As the reaction temperature when carrying out the above reaction, it is usually from room temperature to 150 °C, and the reaction time is usually 1 to 24 hours. From the viewpoint of being able to reduce the impurities in the final product, the reaction temperature is preferably from room temperature to 100 °C.

[0148] In addition, the diglycidyl ether of an aliphatic dihydroxy compound or an aliphatic divinyl ether or a dihaloalkylene compound can be reacted with an aromatic hydroxy compound to obtain a compound having a hydroxyl group at the end, then it is epoxidized to make the end a glycidyl ether group, and then it is reacted with the above-mentioned anthracenediol to prepare the curable compound (A).

[0149] As the diglycidyl ether of the above-mentioned aliphatic dihydroxy compound, the substances 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 preferred compounds are also the same.

[0150] The aliphatic divinyl ether is not particularly limited. For example, it may include: divinyl ethers of polyethylene glycol, divinyl ethers of polypropylene glycol, divinyl ethers of polytetramethylene glycol, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,10-decanediol divinyl ether and other divinyl ethers of linear alkylene groups, as well as divinyl ethers of branched alkylene groups such as neopentyl glycol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecane diol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecane dimethanol divinyl ether, pentacyclopentadecane diol divinyl ether and other divinyl ethers containing cycloalkane structures. They can be used alone or in combination of two or more.

[0151] Among them, from the aspect of excellent balance between the flexibility and toughness of the obtained cured product, divinyl ethers having a polyether structure or a linear alkylene structure are preferred, and polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether are most preferably used.

[0152] The above-mentioned dihaloalkylene compound is not particularly limited. For example, it may include: 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-dichloroundecane, 1,12-dichlorododecane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1,9-dibromononane, 1,10-dibromodecane, 1,11-dibromoundecane, 1,12-dibromododecane, etc. They can be used alone or in combination of two or more.

[0153] As the above-mentioned aromatic hydroxyl compounds, there is no particular limitation, 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'-tetrol, and 1,1'-oxybis(2,7-naphthalenediol) obtained by coupling 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, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; biphenols such as 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, and 4'-methyl-(1,1'-biphenyl)-3,4'-diol; phenols containing an alicyclic structure such as an adduct of phenol and dicyclopentadiene and an adduct of phenol and a terpene compound; naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane; and a condensation reaction product of phenol and phenylene dimethyl chloride or biphenylene dimethyl chloride, namely, a so-called XYLOK-type phenolic resin. These can be used alone or in combination of two or more. Further, a bifunctional phenolic compound having a structure in which a methyl group, a tert-butyl group, or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds can also be cited. It should be noted that the above-mentioned phenols containing an alicyclic structure and the above-mentioned XYLOK-type phenolic resin can contain not only bifunctional components but also trifunctional or higher-functional components at the same time, and can be used directly. In addition, only bifunctional components can be taken out through a purification process such as a column for use.

[0154] Among them, from the viewpoint of excellent balance between flexibility and toughness when forming a cured product, bisphenols are preferred. In particular, from the viewpoint of remarkable performance in imparting toughness, bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are preferred. In addition, when the moisture resistance of the cured product is emphasized, phenols containing an alicyclic structure are preferably used.

[0155] Regarding the reaction ratio of the diglycidyl ether of the aliphatic dihydroxy compound to the aromatic hydroxy compound described above, it is preferably in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio) of the former / latter, and from the aspect of well-balancedly having both the flexibility and heat resistance of the obtained cured product, it is preferably 1.0 / 1.02 to 1.0 / 3.0 (molar ratio).

[0156] The reaction of the diglycidyl ether of the aliphatic dihydroxy compound to the aromatic hydroxy compound described above is preferably carried out in the presence of a catalyst. As the above catalyst, various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, phosphorus compounds such as triphenylphosphine, DMP-30, DMAP, quaternary ammonium salts such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium chlorides, bromides, iodides, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium chlorides, bromides, iodides, etc., tertiary amines such as triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, 1,4-diazabicyclo[2.2.2]octane, imidazoles such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc. Two or more catalysts can also be used in combination. Among them, from the viewpoints of rapid reaction progress and high impurity reduction effect, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred. The usage amount of these catalysts is not particularly limited, and preferably 0.0001 to 0.01 moles are used relative to 1 mole of the phenolic hydroxyl group of the aromatic hydroxy compound described above. The form of these catalysts is also not particularly limited, and they can be used in the form of an aqueous solution or in the form of a solid.

[0157] In addition, the reaction of the diglycidyl ether of the aliphatic dihydroxy compound to the aromatic hydroxy compound described above can be carried out without a solvent or in the presence of an organic solvent. As the organic solvent that can be used, for example, methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propanol, butanol, etc. can be cited. As the usage amount of the organic solvent, it is usually 50 to 300% by mass, preferably 100 to 250% by mass, relative to the total mass of the raw materials input. These organic solvents can be used alone or in combination of multiple kinds. For rapid reaction progress, no solvent is preferred. On the other hand, from the aspect of being able to reduce the impurities of the final product, dimethyl sulfoxide is preferably used.

[0158] As the reaction temperature for the above reaction, it is generally 50 to 180 °C, and the reaction time is generally 1 to 10 hours. From the viewpoint of being able to reduce the impurities of the final product, the reaction temperature is preferably 100 to 160 °C. In addition, when the resulting compound is highly colored, an antioxidant or a reducing agent can be added to suppress this situation. There is no particular limitation on the antioxidant, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing a trivalent phosphorus atom. There is no particular limitation on the reducing agent, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, bisulfite or their salts.

[0159] After the above reaction is completed, neutralization or water washing treatment can also be carried out until the pH value of the reaction mixture reaches 3 to 7, preferably 5 to 7. The neutralization treatment and water washing treatment can be carried out according to conventional methods. For example, in the case of using a basic catalyst, acidic substances such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as neutralizing agents. After the neutralization or water washing treatment, if necessary, the solvent can be distilled off under reduced pressure and heating to concentrate the product to obtain the compound.

[0160] Regarding the reaction ratio of the above aliphatic divinyl ether to the above aromatic hydroxy compound, it is preferably carried out within the range of the former / latter being 1.0 / 1.01 to 1.0 / 5.0 (molar ratio). From the aspect of well-balancedly combining the softness and heat resistance of the resulting cured product, it is preferably 1.0 / 1.02 to 1.0 / 3.0 (molar ratio).

[0161] The reaction of the diglycidyl ether of the above aliphatic dihydroxy compound with the above aromatic hydroxy compound proceeds sufficiently even without using a catalyst, but from the aspects of raw material selection and increasing the reaction rate, it can be appropriately used. Examples of the catalyst that can be used here include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, organic acids such as toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, and trifluoroacetic acid, and Lewis acids such as aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, and boron trifluoride phenol complex. The amount of the catalyst used is generally in the range of 10 ppm to 1% by mass relative to the mass of the divinyl ether compound. At this time, it is preferably selected in terms of avoiding the nucleophilic addition reaction of the vinyl group to the aromatic ring and the amount used.

[0162] In addition, the reaction of the above-mentioned aliphatic divinyl ether and the above-mentioned aromatic hydroxyl compound can be carried out without a solvent or in the presence of an organic solvent. Examples thereof 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 n-butanol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, relative to the total mass of the raw materials charged. These organic solvents can be used alone or in combination of two or more.

[0163] As the reaction temperature when carrying out the above reaction, it is usually 50 to 150 °C, and the reaction time is usually 0.5 to 10 hours. At this time, in order to prevent the self-polymerization of the vinyl ether group, it is preferable to carry out the reaction in an oxygen atmosphere.

[0164] After the above reaction is completed, in the case of using an organic solvent, it is removed by heating under reduced pressure. In the case of using a catalyst, it is inactivated with an inactivator or the like as needed and removed by washing with water and filtration operations, whereby the compound can be obtained.

[0165] Regarding the reaction ratio of the above-mentioned dihaloalkylene compound and the aromatic hydroxyl compound, it is preferably carried out in the range of the former / latter being 1.0 / 1.01 to 1.0 / 5.0 (molar ratio). From the aspect of well-balancing the flexibility and heat resistance of the obtained cured product, the former / latter is preferably 1.0 / 1.1 to 1.0 / 3.0 (molar ratio).

[0166] The reaction of the above-mentioned aromatic hydroxyl compound and the dihaloalkylene compound is preferably carried out in the presence of a basic compound. As the above-mentioned basic compound, various basic compounds can be used. For example, it includes 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 can also be used in combination. Among them, from the viewpoints of rapid progress of the reaction and high effect of reducing the amount of impurities, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred. The amount of these basic compounds used is not particularly limited, and preferably 0.0001 to 10 moles are used relative to 1 mole of the phenolic hydroxyl group of the above-mentioned aromatic hydroxyl compound. The form of these basic compounds is not particularly limited either, and they can be used in the form of an aqueous solution or in a solid form. In addition, a catalyst can also be used in combination during the reaction, and quaternary ammonium salts such as tetrabutylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium iodide, tetraethylammonium chloride, benzyltributylammonium bromide, benzyltriethylammonium bromide, cetyltriethylammonium chloride, tetramethylammonium chloride, and cetyltrimethylammonium chloride, crown ethers, potassium iodide, etc. can be used.

[0167] In addition, the reaction between the above aromatic hydroxyl compound and the dihaloalkylene compound can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include: toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide, etc. 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 of multiple kinds.

[0168] As the reaction temperature for carrying out the above reaction, it is usually from room temperature to 150°C, and the reaction time is usually 1 to 24 hours. From the viewpoint of being able to reduce the impurities in the final product, the reaction temperature is preferably from room temperature to 100°C.

[0169] The method for the glycidyl etherification reaction of the above-obtained precursor (intermediate) hydroxyl compound is not particularly limited, and examples include: a method of reacting a phenolic hydroxyl group with epihalohydrin, a method of olefinating a phenolic hydroxyl group and oxidizing the carbon-carbon double bond of the olefin using an oxidizing agent, etc. Among them, from the aspects of raw material availability and ease of reaction, the method using epihalohydrin is preferably used.

[0170] As a method using epihalohydrin, for example, the following method can be cited: relative to 1 mole of the aromatic hydroxyl group of the above-obtained hydroxyl compound, 0.3 to 100 moles of epihalohydrin is added. In this mixture, while adding a basic catalyst of 0.9 to 2.0 moles relative to 1 mole of the aromatic hydroxyl group of the hydroxyl compound all at once or slowly, the reaction is carried out at a temperature of 20 to 120°C for 0.5 to 10 hours. Regarding the addition amount of this epihalohydrin, the more excessive the epihalohydrin is, the closer the obtained epoxy resin is to the theoretical structure, and the formation of secondary hydroxyl groups due to the reaction between unreacted aromatic hydroxyl groups and epoxy groups can be more inhibited. From this viewpoint, a range of 2.5 to 100 equivalents is particularly preferred. This basic catalyst can be a solid or an aqueous solution thereof. In the case of using an aqueous solution, the following method can be used: while continuously adding, water and epihalohydrin are continuously distilled out from the reaction mixture under reduced pressure or normal pressure, and further liquid separation is carried out to remove water, and the epihalohydrin is continuously returned to the reaction mixture.

[0171] When reacting epihalohydrin, in order to increase the reaction rate, a promoter such as a quaternary ammonium salt can be used in combination. As the above quaternary ammonium salt, various quaternary ammonium salts can be used, and examples include: tetra-n-butylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydroxide, tetra-n-butylammonium iodide, tetraethylammonium chloride, benzyltributylammonium bromide, benzyltriethylammonium bromide, cetyltriethylammonium chloride, tetramethylammonium chloride, cetyltrimethylammonium chloride, etc.

[0172] It should be noted that in industrial production, in the initial batches of epoxy resin production, all the epichlorohydrin input is new epichlorohydrin. However, after the next batch, it is preferred to use a combination of the epichlorohydrin recovered from the crude reaction product and the new epichlorohydrin equivalent to the consumed and disappeared parts in the reaction. At this time, the epichlorohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, etc. Among them, from the aspect of easy availability, epichlorohydrin is preferred.

[0173] In addition, the basic catalyst is not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, from the viewpoint of excellent catalytic activity in the epoxy resin synthesis reaction, alkali metal hydroxides are preferred, and examples thereof include sodium hydroxide, potassium hydroxide, etc. When used, these alkali metal hydroxides can be used in the form of an aqueous solution of about 10 to 55% by mass, or can be used in a solid form.

[0174] In addition, by using an organic solvent in combination, the reaction rate in the synthesis of epoxy resin can be increased. As such an organic solvent, there is no particular limitation, and examples thereof include: ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol, and tert-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 can be used alone, and in addition, in order to adjust the polarity, two or more of them can be used in combination as appropriate.

[0175] After washing the reactants of these glycidylating reactions with water, the unreacted epichlorohydrin and the used organic solvent are distilled off by distillation under heating and reduced pressure. In addition, in order to further form an epoxy resin with less hydrolyzable halogen, the obtained 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 is added to further react. At this time, in order to increase the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether can be present.

[0176] As the amount of use of the phase transfer catalyst when used, it is preferably in the range of 0.1 to 3.0% by mass based on the epoxy resin used. After the reaction is completed, the generated salt is removed by filtration, washing with water, etc., and then the solvents such as toluene and methyl isobutyl ketone are distilled off under heating and reduced pressure, whereby a high-purity resin can be obtained.

[0177] By reacting the resin having a glycidyl ether group at the terminal obtained in the same manner as above with anthracenediol, the curable compound (A) in the present invention can be obtained.

[0178] In addition, as the compound (A) represented by the above general formula (2), a compound (A) having a glycidyl ether group as a curable reactive group can be obtained by reacting aminoanthracene with the above polyglycidyl ether compound. At this time, similarly to the above, the preferred polyglycidyl ether compound is a diglycidyl ether compound, and for the same reason as above, the above compound having an alkylene chain and an alkylene ether chain is preferably used.

[0179] As the above aminoanthracene, for example, the following aminoanthracene can be mentioned. As described below, various substituents can be present on the anthracene skeleton, but from the viewpoint of easily exerting the effects of the present invention, non-reactive substituents are preferred.

[0180] [Chemical 13]

[0181]

[0182] Regarding the reaction ratio of the above glycidyl ether compound and the above aminoanthracene, it is preferably reacted in the range of 1.01 / 1.0 to 5.0 / 1.0 (molar ratio) of the former / latter, and from the aspect of well-balancedly combining the flexibility and heat resistance of the obtained cured product, it is preferably 1.02 / 1.0 to 3.0 / 1.0 (molar ratio).

[0183] The reaction of the above glycidyl ether compound and the above aminoanthracene is preferably carried out in the presence of a catalyst. As the above catalyst, various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, phosphorus-based compounds such as triphenylphosphine, DMP-30, DMAP, quaternary ammonium salts such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium chlorides, bromides, iodides, and tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium chlorides, bromides, iodides, etc., tertiary amines such as triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, 1,4-diazabicyclo[2.2.2]octane, and imidazoles such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc. Two or more of these catalysts can also be used in combination. Among them, from the viewpoints of rapid reaction progress and high effect of reducing the amount of impurities, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred. The usage amount of these catalysts is not particularly limited, and preferably 0.0001 to 0.01 mol is used relative to 1 mol of the glycidyl ether group of the above glycidyl ether compound. The form of these catalysts is also not particularly limited, and they can be used in the form of an aqueous solution or in the form of a solid.

[0184] In addition, the reaction of the above glycidyl ether compound with the above aminoanthracene can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propanol, butanol, etc. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, relative to the total mass of the raw materials input. These organic solvents can be used alone or in combination of multiple kinds. In order to carry out the reaction rapidly, it is preferably without a solvent. On the other hand, from the aspect of being able to reduce the impurities of the final product, it is preferably to use dimethyl sulfoxide.

[0185] As the reaction temperature when carrying out the above reaction, it is usually 50 to 160 °C, and the reaction time is usually 1 to 10 hours. From the viewpoint of being able to reduce the impurities of the final product, the reaction temperature is preferably 100 to 130 °C. In addition, when the obtained compound is highly colored, in order to suppress this situation, an antioxidant or a reducing agent can be added. There is no particular limitation on the antioxidant. For example, hindered phenol-based compounds such as 2,6-dialkylphenol derivatives, divalent sulfur-based compounds, phosphite-based compounds containing a trivalent phosphorus atom, etc. can be cited. There is no particular limitation on the reducing agent. For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, bisulfite or their salts, etc. can be cited.

[0186] After the above reaction is completed, neutralization or washing treatment can also be carried out until the pH value of the reaction mixture reaches 3 to 7, preferably 5 to 7. The neutralization treatment and the washing treatment can be carried out according to the conventional method. For example, in the case of using a basic catalyst, acidic substances such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, oxalic acid, etc. can be used as the neutralizing agent. After carrying out the neutralization or washing treatment, if necessary, the solvent can be distilled off under reduced pressure and heating to concentrate the product to obtain the compound.

[0187] By reacting the thus obtained compound having an anthracene structure with a terminal diglycidyl ether group with a compound having two or more hydroxyl groups, a compound having a curable functional group (a) of a hydroxyl group can be obtained.

[0188] In addition, as the compound (A) represented by the above general formula (3), a hydroxyl group-containing anthracene compound as described below is used as a raw material. Similarly to the above, a compound (A) having a curable reaction group of a glycidyl ether group can be obtained by reacting with a polyglycidyl ether compound. At this time, similarly to the above, the preferred polyglycidyl ether compound is a diglycidyl ether compound. Further for the same reason, it is preferably to use the above compound having an alkylene chain and an alkylene ether chain.

[0189] [Chemical formula 14]

[0190]

[0191] In addition, in the same manner as described above, by reacting with an aromatic hydroxy compound, a compound (A) having a curable reactive group of a hydroxy group can be obtained.

[0192] In addition, as the compound (A) represented by the above general formula (3), an anthracene compound containing an epoxy group as described below is used as a raw material. In the same manner as described above, by reacting with an aromatic hydroxy compound, a compound (A) having a curable reactive group of a hydroxy group can be obtained. At this time, in the same manner as described above, the preferred aromatic hydroxy compound is preferably a bisphenol, and for the same reason further, bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are preferred. In addition, when the moisture resistance of the cured product is emphasized, a phenol containing an alicyclic structure is preferably used.

[0193] [Chemical Formula 15]

[0194]

[0195] In addition, in the same manner as described above, by epoxidizing it to make the terminal a glycidyl ether group, a compound (A) having a curable reactive group of an epoxy group can be obtained.

[0196] The cured product as one embodiment of the present invention includes a reversible bond formed by a Diels-Alder reaction between an anthracene structure in the above curable compound (A) and a compound (B) having a dienophile structure. As the compound (B) having a dienophile structure, a monofunctional compound can be used, but in order to further impart properties to the cured product, a compound having 2 or more functional groups is preferred.

[0197] The reversible bonding based on the above Diels-Alder reaction is a reaction in which a conjugated diene and a dienophile undergo an addition reaction to form a 6-membered ring. The Diels-Alder reaction is an equilibrium reaction, so at a predetermined temperature, a retro-Diels-Alder reaction occurs and dissociation (decrosslinking) proceeds. This reversibility is also maintained after becoming a cured product (three-dimensional crosslinked body). Therefore, when mechanical energy such as damage or external force is applied to the cured product, the C-C bond of the Diels-Alder reaction unit has a lower bond energy than a normal covalent bond, and thus the C-C bond of the Diels-Alder reaction unit is preferentially cleaved. However, it is considered that in the temperature region lower than the dissociation temperature, the equilibrium of the C-C bond of the Diels-Alder reaction unit shifts toward the bonding direction, so an adduct (Diels-Alder reaction unit) is formed again, and damage repair and reshaping can be performed.

[0198] The above compound (B) containing a dienophile structure is not particularly limited, and examples thereof include compounds having a maleimide group, an acryloyl group, a vinyl ketone group, an ethynyl group, an allyl group, a diazo group, a nitro group, a benzoquinone skeleton, etc. Among them, from the viewpoint of the balance between reactivity when used as a curable resin composition and the easy disassembly / reformability of the cured product, etc., it is preferable to use a compound having a maleimide group. Further, from the viewpoint of being able to further exhibit the reformability effect, a compound having two or more maleimide groups in one molecule is preferable.

[0199] As the above compound having a maleimide group, for example, the following compounds can be cited.

[0200] [Chemical Formula 16]

[0201]

[0202] The above n3, n5, n6, n7, n8, n9 are the average values of the repetition numbers, each being 0.5 to 10, n4 is an integer of 1 to 16, and R ” are each independently a hydrogen atom, a methyl group or an ethyl group.

[0203] It should be noted that the above compounds having a maleimide group each independently include compounds having a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent. Further, in the structures of the compounds listed in the above formula, the alkoxy group, aralkyloxy group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group and aryl group also include groups in which various substituents are further bonded to the carbon atoms they have.

[0204] As a curable resin composition according to one aspect of the present invention, the above curable compound (A), a compound (B) containing a dienophile structure, and a compound (C) reactive with the above curable functional group (a) are essential. At this time, after the above compound (A) and the above compound (B) are pre-reacted, the curing reaction with the compound (C) can be carried out, but from the viewpoint of easy operation, it is preferable to react the above compounds (A) to (C) simultaneously.

[0205] The compound (C) reactive with the terminal curable functional group is not particularly limited.

[0206] When the curable functional group at the terminal is a hydroxyl group, examples of the above compound (C) include: melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, novolac resins, epoxy resins, isocyanate compounds, azide compounds, compounds containing double bonds such as vinyl ether groups, acid anhydrides, hexamethylenetetramine and its modified products, oxazoline compounds, etc., which are substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl groups. Among them, from the viewpoints of good curability and good handling, epoxy resins are preferred.

[0207] Examples of the above melamine compounds include: hexahydroxymethyl melamine, hexamethoxymethyl melamine, compounds in which 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine are methoxymethylated, hexamethoxyethyl melamine, hexacyloxymethyl melamine, compounds in which 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine are acyloxymethylated, etc.

[0208] Examples of the above guanamine compounds include: tetrahydroxymethyl guanamine, tetramethoxymethyl guanamine, tetramethoxymethyl benzoguanamine, compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxy guanamine, compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl guanamine are acyloxymethylated, etc.

[0209] Examples of the above glycoluril compounds include: 1,3,4,6-tetra(methoxymethyl) glycoluril, 1,3,4,6-tetra(butoxymethyl) glycoluril, 1,3,4,6-tetra(hydroxymethyl) glycoluril, etc.

[0210] Examples of the above urea compounds include: 1,3-bis(hydroxymethyl) urea, 1,1,3,3-tetra(butoxymethyl) urea, 1,1,3,3-tetra(methoxymethyl) urea, etc.

[0211] Examples of the above novolac resins include: polymers obtained by reacting phenolic hydroxyl group-containing compounds such as alkylphenols (such as phenol, cresol, xylenol, etc.), phenylphenol, resorcinol, biphenyl, bisphenols (such as bisphenol A, bisphenol F, etc.), naphthol, and dihydroxynaphthalene with aldehyde compounds under alkaline catalytic conditions.

[0212] Examples of the above epoxy resins 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, tetramethylbiphenyl type epoxy resin, etc.; brominated epoxy resins such as brominated phenol novolac type epoxy resin; solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthalene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolac type epoxy resin, etc. They can be used alone or in combination of two or more. Preferably, various selections are made according to the target use, physical properties of the cured product, etc. for use.

[0213] Examples of the above isocyanate compounds include: toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, etc.

[0214] Examples of the above azide compounds include: 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylenebisazide, 4,4'-oxybisazide, etc.

[0215] Examples of the above compounds containing double bonds such as vinyl ether groups 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, trimethylolpropane trivinyl ether, etc.

[0216] Examples of the above acid anhydrides include: aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 3,3’,4,4’-benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4’-(isopropylidene) diphthalic anhydride, 4,4’-(hexafluoroisopropylidene) diphthalic anhydride; alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, trialkyltetrahydrophthalic anhydride, etc.

[0217] Furthermore, when the curable functional group in the curable compound is a hydroxyl group and it is combined with an epoxy resin to form a curable resin composition, a curing agent for epoxy resin can be added.

[0218] 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-based compounds, and thiol compounds.

[0219] Examples of the above amine compounds include aliphatic amine compounds such as 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, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, α-methylbenzylmethylamine;

[0220] 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-tetraoxaspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N’-dimethylpiperazine, 1,8-diazabicyclo-[5.4.0]-undecene (DBU);

[0221] aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, methylpyridine;

[0222] modified amine compounds such as epoxy compound-added polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-capped polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, amine imides, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, etc.

[0223] Examples of the above-mentioned acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

[0224] Examples of the above-mentioned phenolic hydroxyl group-containing compounds include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; phenol novolak resins; cresol novolak resins; aromatic hydrocarbon formaldehyde resin-modified phenolic resins; dicyclopentadiene phenol addition resins; phenol aralkyl resins (Celor resins); naphthol aralkyl resins; trimethylolmethane resins; tetraphenylethane resins; naphthol novolak resins; naphthol-phenol co-condensed novolak resins; naphthol-cresol co-condensed novolak resins; biphenyl-modified phenolic resins (polyphenol compounds in which phenolic nuclei are connected by dimethylene groups); biphenyl-modified naphthol resins (polynaphthol compounds in which phenolic nuclei are connected by dimethylene groups); amino triazine-modified phenolic resins (polyphenol compounds in which phenolic nuclei are connected by melamine, benzoguanamine, etc.); aromatic ring-modified phenolic novolak resins containing alkoxy groups (polyphenol compounds in which phenolic nuclei and aromatic rings containing alkoxy groups are connected by formaldehyde), and other polyphenol compounds.

[0225] Examples of the above-mentioned amide compounds include dicyandiamide, polyamidoamine, etc. Examples of the above-mentioned polyamidoamine include polyamidoamines obtained by reacting aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fatty acids, carboxylic acid compounds such as dimer acids, with aliphatic polyamines, polyamines having a polyoxyalkylene chain, etc.

[0226] Examples of the above-mentioned carboxylic acid compounds include carboxylic acid-terminated polyesters, polyacrylic acid, carboxylic acid polymers such as maleic acid-modified polypropylene glycol, etc.

[0227] As the above mercapto compound, it preferably contains two or more mercapto groups in one molecule. Examples thereof include: 3,3'-dithiobispropionic acid, trimethylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate), ethylene glycol dimercaptoacetate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)ethyl]-isocyanuric acid ester, 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, etc.

[0228] When using these curing agents, only one type of curing agent can be used, or two or more types can be mixed. It should be noted that in applications such as underfill materials and general coating applications, it is preferable to use the above amine compounds, carboxylic acid compounds, and / or acid anhydride compounds. In addition, in applications such as adhesives and flexible printed circuit boards, from the aspects of workability, curability, and long-term stability, amine compounds are preferred, and dicyandiamide is particularly preferred. In addition, in applications such as semiconductor encapsulation materials, from the aspect of the heat resistance of the cured product, solid phenolic compounds are preferred. In addition, in battery applications, from the aspect of low-temperature curing, aliphatic amines and mercapto compounds are preferred.

[0229] In addition, when using epoxy resins, a curing accelerator can also be included. As the above curing accelerator, various curing accelerators can be used. Examples thereof include: urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, organic acid metal salts, Lewis acids, amine complexes, etc. When used as an adhesive, from the aspects of excellent workability and low-temperature curability, urea compounds are preferred, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) is particularly preferred. When used as a semiconductor encapsulation material, from the aspects of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene is preferred among tertiary amines.

[0230] As the above phosphorus compounds, examples thereof include: alkylphosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine; dialkylphosphines such as dimethylphosphine and dipropylphosphine; secondary phosphines such as diphenylphosphine and methylethylphosphine; tertiary phosphines such as trimethylphosphine, triethylphosphine, and triphenylphosphine, etc.

[0231] As the above-mentioned imidazoles, for example, there may be mentioned: imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, and the like.

[0232] As the above-mentioned imidazoline compounds, for example, there may be mentioned: 2-methylimidazoline, 2-phenylimidazoline, and the like.

[0233] As the above-mentioned urea compounds, for example, there may be mentioned: p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea, and the like.

[0234] When the curable functional group at the terminal is a glycidyl ether group, as the above-mentioned compound (C), for example, there may be mentioned various known curing agents for epoxy resins such as amine compounds, acid anhydrides, amide compounds, phenolic hydroxyl group-containing compounds, carboxylic acid-based compounds, and thiol compounds. As the above-mentioned curing agent, it can be appropriately selected according to the physical properties of the target cured product. In particular, from the viewpoints of mechanical strength, adhesion to the substrate, etc., a hydroxyl group-containing compound is preferably used.

[0235] Examples of the above amine compounds include: aliphatic amine compounds such as 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, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, α-methylbenzylmethylamine;

[0236] 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-tetraoxaspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N’-dimethylpiperazine, 1,8-diazabicyclo-[5.4.0]-undecene (DBU);

[0237] aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, methylpyridine;

[0238] modified amine compounds such as epoxy compound-added polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-blocked polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, etc.

[0239] Examples of the above acid anhydrides include: phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

[0240] 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, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; phenol novolak resins; cresol novolak resins; aromatic hydrocarbon formaldehyde resin-modified phenolic resins; dicyclopentadiene phenol addition resins; phenol aralkyl resins (Cailock resins); naphthol aralkyl resins; trimethylolmethane resins; tetraphenylethane resins; naphthol novolak resins; naphthol-phenol co-condensed novolak resins; naphthol-cresol co-condensed novolak resins; biphenyl-modified phenolic resins (polyphenol compounds in which phenolic nuclei are connected by dimethylene groups); biphenyl-modified naphthol resins (polynaphthol compounds in which phenolic nuclei are connected by dimethylene groups); amino triazine-modified phenolic resins (polyphenol compounds in which phenolic nuclei are connected by melamine, benzoguanamine, etc.); aromatic ring-modified novolak resins containing alkoxy groups (polyphenol compounds in which phenolic nuclei and aromatic rings containing alkoxy groups are connected by formaldehyde), and other polyphenol compounds.

[0241] Examples of the amide compound include dicyandiamide, polyamide-type amines, etc. Examples of the polyamide-type amines include polyamide-type amines obtained by reacting aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fatty acids, carboxylic acid compounds such as dimer acid, with aliphatic polyamines, polyamines having a polyoxyalkylene chain, etc.

[0242] Examples of the carboxylic acid compound include carboxylic acid-terminated polyesters, polyacrylic acids, maleic acid-modified polypropylene glycols, and other carboxylic acid polymers.

[0243] The thiol compound preferably contains two or more thiol groups in two molecules. Examples include 3,3'-dithiobispropionic acid, trimethylolpropane tris(mercaptoacetate), pentaerythritol tetra(mercaptoacetate), ethylene glycol dimercaptoacetate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanuric acid ester, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate), 1,3,4,6-tetra(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.

[0244] When using these curing agents, only one type of curing agent may be used, or two or more types may be mixed. It should be noted that in applications such as underfill materials and general coating applications, it is preferable to use the above-mentioned amine compounds, carboxylic acid compounds, and / or acid anhydride compounds. In addition, in applications such as adhesives and flexible printed circuit boards, from the viewpoints of workability, curability, and long-term stability, amine compounds are preferable, and dicyandiamide is particularly preferable. In addition, in applications of semiconductor encapsulating materials, from the viewpoint of the heat resistance of the cured product, solid phenolic compounds are preferable. In addition, in battery applications, from the viewpoint of low-temperature curing, aliphatic amines and thiol compounds are preferable.

[0245] Relative to the total mass of the curable components in the curable resin composition, the concentration of the reversible bonds in the curable resin composition of the present invention is preferably 0.10 mmol / g or more. According to such a configuration, both the disintegratability / reparability and the remoldability of the cured product obtained from the curable resin composition become better. The concentration of the above-mentioned reversible bonds is more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. It should be noted that the concentration of the reversible bonds of the present invention can be appropriately selected according to the glass transition temperature defined by the tanδ peak of the dynamic viscoelasticity measuring instrument (DMA) of the target cured product. For example, in the case of taking the glass transition temperature as a reference, if the glass transition temperature of the cured product is near room temperature, sufficient reparability and remoldability functions are easily exhibited even on the low-concentration side of the preferred range. On the other hand, if the glass transition temperature of the target cured product exceeds 100 °C as a standard, the functions are easily exhibited on the high-concentration side of the preferred range. However, in the temperature region exceeding the glass transition temperature measured by DMA, the molecular mobility is usually high, and sufficient reparability and remoldability functions are easily exhibited even when the concentration of the phenolic hydroxyl group-containing compound is low. Therefore, for example, by appropriately adjusting the aging temperature for repair and the heating temperature for remolding, the expression effects of the reparability and remoldability functions can also be adjusted. Thus, the relationship between the glass transition temperature of the cured product and the concentration of the reversible bonds is not limited to these.

[0246] As the curable resin composition of the present invention, from the aspect of becoming a curable resin composition having excellent curability, mechanical strength, heat resistance, etc., an epoxy resin represented by the following formula (4) and having an epoxy equivalent of 500 to 10,000 g / eq can be used. Especially when the curable functional group at the end is a hydroxyl group, the following epoxy resin can be used as the above-mentioned compound (III).

[0247] [Chemical 17]

[0248]

[0249] [In formula (4), each Ar independently represents a structure containing an unsubstituted or substituted aromatic ring, X represents a structural unit represented by the following general formula (4-1), Y represents a structural unit represented by the following general formula (4-2),

[0250] [Chemical formula 18]

[0251]

[0252] R 1 、R 2 each independently represents a hydrogen atom, a methyl group or an ethyl group,

[0253] R' is a divalent hydrocarbon group having 2 to 12 carbon atoms,

[0254] R 3 、R 4 、R 7 、R 8 each independently represents a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0255] R 5 、R 6 、R 9 、R 10 each independently represents a hydrogen atom or a methyl group,

[0256] n1 is an integer from 2 to 16,

[0257] n2 is the average value of the repeating unit and is from 2 to 30.]

[0258] R 21 、R 22 each independently represents a glycidyl ether group or a 2-methylglycidyl ether group,

[0259] R 11 、R 12 each independently represents a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group,

[0260] R 13 、R 14 is a hydrogen atom or a methyl group,

[0261] m1, m2, p1, p2, q are the average values of the repetitions,

[0262] m1, m2 each independently are from 0 to 25, and m1 + m2 ≥ 1,

[0263] p1, p2 each independently are from 0 to 5,

[0264] q is from 0.5 to 5.

[0265] Among them, the bond between X represented by the above general formula (2-2) and Y represented by the above general formula (2-3) can be random or block, and the total numbers of the respective structural units X and Y present in one molecule are m1 and m2, respectively.

[0266] The epoxy resin represented by the above general formula (4) can be combined alone to form a curable resin composition. However, from the viewpoint of further imparting softness to the cured product and easily exhibiting disintegratability, it is further preferred to use in combination an epoxy resin having an epoxy equivalent of 100 to 300 g / eq.

[0267] As the epoxy resin that can be used in combination, it is only necessary that its epoxy equivalent is in the range of 100 to 300 g / eq, and its structure is not limited. For example, there can be mentioned: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin and other liquid epoxy resins, 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, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthalene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-novolac type epoxy resin, naphthol-cresol co-novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolac type epoxy resin, etc. These can be used alone or in combination of two or more, and it is preferably variously selected and used according to the target use, physical properties of the cured product, etc.

[0268] Among them, it is preferred to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq among liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, and it is particularly preferred to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq among bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin.

[0269] The use ratio of the epoxy resin represented by the above general formula (4) to the epoxy resin having an epoxy equivalent of 100 to 300 g / eq is not particularly limited. From the viewpoint of easy phase separation in the cured product, the mass ratio of the former to the latter is 97:3 to 3:97, preferably 10:90 to 90:10, and particularly preferably 80:20 to 20:80. By causing phase separation in the cured product, a sea-island structure is formed, which has both the adhesiveness and stress relaxation ability of the cured product. In particular, it exhibits high adhesive force in a wide temperature range and has the effect of reducing the molding shrinkage rate before and after heat curing of the resin composition.

[0270] In addition, within the range not hindering the effects of the present invention, other thermosetting resins and thermoplastic resins can also be used in combination with the curable resin composition of the present invention.

[0271] Examples of other thermosetting resins include: cyanate ester resins, resins having a benzoxazine structure, reactive ester resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc. When using the above other thermosetting resins in combination, the amount used is not particularly limited as long as the effects of the present invention are not hindered, and it is preferably in the range of 1 to 50 parts by mass in 100 parts by mass of the curable resin composition.

[0272] Examples of the above cyanate ester resins include: bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol thioether type cyanate ester resin, phenylene ether type cyanate ester resin, naphthalene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak type cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolak type cyanate ester resin, anthracene type cyanate ester resin, etc. They can be used alone or in combination of two or more.

[0273] Among these cyanate ester resins, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthalene ether type cyanate ester resin, and novolak type cyanate ester resin are preferably used in terms of obtaining a cured product with excellent heat resistance, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferably used in terms of obtaining a cured product with excellent dielectric properties.

[0274] As the resin having a benzoxazine structure, there is no particular limitation, and examples thereof include: reaction products of bisphenol F, formalin, and aniline (F-a type benzoxazine resin), reaction products of diaminodiphenylmethane, formalin, and phenol (P-d type benzoxazine resin), reaction products of bisphenol A, formalin, and aniline, reaction products of dihydroxydiphenyl ether, formalin, and aniline, reaction products of diaminodiphenyl ether, formalin, and phenol, reaction products of dicyclopentadiene-phenol addition type resin, formalin, and aniline, reaction products of phenolphthalein, formalin, and aniline, reaction products of diphenyl sulfide, formalin, and aniline, and the like. They can be used alone respectively, or two or more of them can be used in combination.

[0275] As the above-mentioned active ester resin, there is no particular limitation, and compounds having two or more highly reactive ester groups in one molecule such as phenolic esters, benzenethiol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are usually preferably used. The above-mentioned active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. or their halides. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-phenol addition type resin, etc.

[0276] Specifically, as the active ester resin, an active ester resin system containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin which is an acetylated product of phenol novolac, an active ester resin which is a benzoylated product of phenol novolac, etc. are preferred. Among them, from the aspect of excellent improvement in peel strength, an active ester resin containing a dicyclopentadiene-phenol addition structure and an active ester resin containing a naphthalene structure are more preferred.

[0277] Furthermore, various novolak resins, alicyclic diene compounds such as dicyclopentadiene, addition polymerization resins of phenolic compounds with phenolic compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (such as resol resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylethane resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, amino triazine-modified phenolic resins, and various vinyl polymers can also be used in combination.

[0278] More specifically, the above various novolak resins include polymers obtained by reacting phenolic hydroxyl group-containing compounds such as phenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene with aldehyde compounds under the condition of an acid catalyst.

[0279] Examples of the above various vinyl polymers include homopolymers or copolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, and poly(meth)acrylate.

[0280] A thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include: polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, cyclic olefin resin, etc. These thermoplastic resins can be used alone or in combination of two or more.

[0281] When using these other resins, the blending ratio of the phenolic hydroxyl group-containing compound of the present invention and the other resins can be arbitrarily set according to the use. From the viewpoint of not hindering the restorability and re-moldability exerted by the present invention, relative to 100 parts by mass of the phenolic hydroxyl group-containing compound of the present invention, the other resin is preferably in a proportion of 0.5 to 100 parts by mass.

[0282] In addition, a curing accelerator may be used in combination in the curable resin composition of the present invention. Examples of the curing accelerator include: tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus-based 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 thiodiphenol benzoxazine and sulfonyl benzoxazine; sulfonyl compounds and the like. They may be used alone respectively, or two or more of them may be used in combination. In 100 parts by mass of the curable resin composition, the addition amount of these catalysts is preferably in the range of 0.001 to 15 parts by mass.

[0283] In addition, in the case of applications where high flame retardancy is required for the curable resin composition of the present invention, a non-halogen-based flame retardant substantially free of halogen atoms can be incorporated.

[0284] Examples of the above non-halogen-based flame retardants include: phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon-based flame retardants, inorganic-based flame retardants, organic metal salt-based flame retardants, etc. There are no restrictions when using these, and they can be used alone, or multiple flame retardants of the same system can be used. In addition, flame retardants of different systems can also be used in combination.

[0285] Any of inorganic or organic types can be used for the above phosphorus-based flame retardants. Examples of inorganic compounds include: ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide.

[0286] In addition, for the purpose of preventing hydrolysis, etc., it is preferable to perform surface treatment on the above red phosphorus. Examples of the surface treatment method include: (i) a method of coating treatment with inorganic compounds 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 treatment with a mixture of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide and a thermosetting resin such as phenolic resin; (iii) a method of double coating treatment with a thermosetting resin such as phenolic resin on the film of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc.

[0287] Regarding the above-mentioned organophosphorus compounds, for example, in addition to general organophosphorus compounds such as phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, the following can also be cited: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organophosphorus compounds, and derivatives obtained by reacting them with compounds such as epoxy resins and phenolic resins.

[0288] As the compounding amount of these phosphorus-based flame retardants, it can be appropriately selected according to the type of phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of a resin composition containing all components such as a non-halogen-based flame retardant and other fillers and additives, when using red phosphorus as the non-halogen-based flame retardant, it is preferably compounded in the range of 0.1 part by mass to 2.0 parts by mass. When using an organic phosphorus compound, it is similarly preferably compounded in the range of 0.1 part by mass to 10.0 parts by mass, and more preferably compounded in the range of 0.5 part by mass to 6.0 parts by mass.

[0289] In addition, when using the above-mentioned phosphorus-based flame retardants, hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dyes, calcium carbonate, zeolites, zinc molybdate, activated carbon, etc. can also be used together with the phosphorus-based flame retardants.

[0290] Examples of the above-mentioned nitrogen-based flame retardants include: triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, etc., and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred.

[0291] Regarding the above-mentioned triazine compounds, in addition to, for example, melamine, acetoguanamine, benzoguanamine, mellon, mellite, succinoguanamine, ethylidene di-melamine, melamine polyphosphate, triguanamine, etc., the following can also be cited: (1) sulfuric acid amidotriazine compounds such as sulfuric acid guanidylmelamine, sulfuric acid melamine, sulfuric acid mellite; (2) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol and melamine-based compounds such as melamine, benzoguanamine, acetoguanamine, methylguanamine and formaldehyde; (3) mixtures of the co-condensates in (2) and phenolic resin-based compounds such as phenol-formaldehyde condensates; (4) triazine compounds obtained by further modifying the above (2) and (3) with tung oil, isomerized linseed oil, etc.

[0292] Examples of the above-mentioned cyanuric acid compounds include cyanuric acid, melamine cyanurate, etc.

[0293] As the compounding quantity of the above nitrogen-based flame retardant, it can be appropriately selected according to the type of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all components such as a non-halogen-based flame retardant and other filler materials and additives, it is preferably compounded in the range of 0.05 to 10 parts by mass, and more preferably in the range of 0.1 part by mass to 5 parts by mass.

[0294] In addition, when using the above nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, etc. can be used in combination.

[0295] The above silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom. For example, silicone oil, silicone rubber, silicone resin, etc. can be cited. As the compounding quantity of the above silicone-based flame retardant, it can be appropriately selected according to the type of the silicone-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all components such as a non-halogen-based flame retardant and other filler materials and additives, it is preferably compounded in the range of 0.05 to 20 parts by mass. In addition, when using the above silicone-based flame retardant, a molybdenum compound, aluminum oxide, etc. can be used in combination.

[0296] Examples of the above inorganic flame retardants include: metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low-melting-point glasses, etc.

[0297] Examples of the above metal hydroxides include: aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, etc.

[0298] Examples of the above metal oxides include: zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide, etc.

[0299] Examples of the above metal carbonate compounds include: zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate, etc.

[0300] Examples of the above metal powders include: aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc.

[0301] Examples of the above boron compounds include: zinc borate, zinc metaborate, barium metaborate, boric acid, borax, etc.

[0302] Examples of the above low melting point glass include: Ceepree (Bokusui-Brown Co., Ltd.), hydrated glass SiO2-MgO-H2O, PbO-B2O3 system, ZnO-P2O5-MgO system, P2O5-B2O3-PbO-MgO system, P-Sn-O-F system, PbO-V2O5-TeO2 system, Al2O3-H2O system, lead borosilicate system and other glassy compounds.

[0303] As the compounding amount of the above inorganic flame retardant, it can be appropriately selected according to the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all components such as a non-halogen flame retardant and other filler materials and additives, it is preferably compounded in the range of 0.05 parts by mass to 20 parts by mass, and more preferably compounded in the range of 0.5 parts by mass to 15 parts by mass.

[0304] Examples of the above organometallic salt-based flame retardants include: ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, organocobalt salt compounds, organosulfonic acid metal salts, compounds formed by ionic bonding or coordination bonding between metal atoms and aromatic compounds or heterocyclic compounds, etc.

[0305] As the compounding amount of the above organometallic salt-based flame retardant, it can be appropriately selected according to the type of the organometallic salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all components such as a non-halogen flame retardant and other filler materials and additives, it is preferably compounded in the range of 0.005 parts by mass to 10 parts by mass.

[0306] 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.

[0307] As inorganic fine particles, for example, as inorganic fine particles with excellent heat resistance, they are alumina, magnesia, titanium dioxide, zirconia, silica (quartz, fumed silica, precipitated silica, silica anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.); as inorganic fine particles with excellent heat conduction, they are boron nitride, aluminum nitride, alumina, titanium oxide, magnesia, zinc oxide, silica, diamond, etc.; as inorganic fine particles with excellent conductivity, they are metal fillers and / or metal-coated fillers using elemental metals or alloys (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); as inorganic fine particles with excellent barrier properties, they are minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, green earth, etc., potassium titanate, magnesium sulfate, sepiolite, vermiculite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; as inorganic fine particles with a high refractive index, they are barium titanate, zirconia, titanium oxide, etc.; as inorganic fine particles showing photocatalytic properties, they are photocatalyst metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., complexes of the above metals, their oxides, etc.; as inorganic fine particles with excellent abrasion resistance, they are metals such as silica, alumina, zirconia, magnesia, etc., and their complexes and oxides, etc.; as inorganic fine particles with excellent conductivity, they are metals such as silver, copper, etc., tin oxide, indium oxide, etc.; as inorganic fine particles with excellent insulation properties, they are silica, etc.; as inorganic fine particles with excellent ultraviolet shielding properties, they are titanium oxide, zinc oxide, etc. These inorganic fine particles can be appropriately selected according to the use, and can be used alone or in combination of multiple kinds. In addition, the above inorganic fine particles have various other properties in addition to the properties mentioned, so they can be appropriately selected in combination with the use.

[0308] For example, when using silica as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used. As commercially available powdered silica fine particles, for example, there can be mentioned: AEROSIL 50, 200 manufactured by Nippon Aerosil Co., Ltd., SHIELDEX H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji SYLYSIA Co., Ltd., SG FLAKE manufactured by Nippon Sheet Glass Co., Ltd., etc.

[0309] In addition, as commercially available colloidal silica, for example, there can be mentioned: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. manufactured by Nissan Chemical Industries, Ltd.

[0310] Surface-modified silica fine particles can also be used. For example, there can be mentioned: silica fine particles obtained by subjecting the above-mentioned silica fine particles to surface treatment with a reactive silane coupling agent having a hydrophobic group, and silica fine particles modified with a compound having a (meth)acryloyl group. As commercially available powdery silica modified with a compound having a (meth)acryloyl group, there can be mentioned AEROSIL RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and as commercially available colloidal silica modified with a compound having a (meth)acryloyl group, there can be mentioned MIBK-SD manufactured by Nissan Chemical Industries, Ltd.

[0311] The shape of the above-mentioned silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous or irregularly shaped silica fine particles can be used. In addition, the primary particle size is preferably in the range of 5 to 200 nm.

[0312] As titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used. For example, anatase titanium oxide, rutile titanium oxide, brookite titanium oxide, etc. can be used. Furthermore, particles designed to respond to visible light by doping foreign elements in the crystal structure of titanium oxide can also be used. As elements doped in titanium oxide, anion elements such as nitrogen, sulfur, carbon, fluorine, phosphorus, etc., and cation elements such as chromium, iron, cobalt, manganese, etc. can be suitably used. In addition, as the form, powders, sols or slurries dispersed in an organic solvent or water can be used. As commercially available powdery titanium oxide fine particles, for example, there can be mentioned AEROSIL P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by TAYCA Corporation, etc. In addition, as commercially available slurry-like titanium oxide fine particles, for example, there can be mentioned TKD-701 manufactured by TAYCA Corporation.

[0313] The curable resin composition of the present invention may further contain a fibrous matrix. The above-mentioned fibrous matrix is not particularly limited, and fibrous matrices for fiber-reinforced resins are preferred, and inorganic fibers and organic fibers can be mentioned.

[0314] As inorganic fibers, in addition to inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers, etc., there can also be mentioned: carbon fibers, activated carbon fibers, graphite fibers, tungsten carbide fibers, silicon carbide fibers (siliconcarbide fiber), ceramic fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers. As the above-mentioned metal fibers, for example, there can be mentioned: aluminum fibers, copper fibers, brass fibers, stainless steel fibers, steel fibers.

[0315] Examples of the organic fiber include synthetic fibers made of resin materials such as polybenzazole, aromatic polyamide, PBO (poly(p-phenylene 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.

[0316] Among them, carbon fiber and glass fiber are preferred because of their wide industrial utilization range. One of them can be used alone, or multiple of them can be used simultaneously.

[0317] The above fibrous matrix can be a fiber aggregate. The fibers can be continuous or discontinuous, can be in the form of a woven fabric or a non-woven fabric. In addition, it can be a fiber bundle formed by arranging the fibers neatly in one direction, or a sheet formed by arranging the fiber bundles. In addition, it can also be a three-dimensional shape formed by giving the fiber aggregate a thickness.

[0318] For the purpose of adjusting the solid content and viscosity of the resin composition, a dispersion medium can be used in the curable resin composition of the present invention. As the dispersion medium, any liquid medium that does not impair the effects of the present invention can be used, and various organic solvents, liquid organic polymers, etc. can be cited.

[0319] Examples of the above organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatics such as toluene and xylene; carbitol, cellosolve, methanol, isopropyl alcohol, butanol, propylene glycol monomethyl ether, etc. alcohols. They can be used alone or in combination. Among them, from the aspects of volatility during coating and solvent recovery, methyl ethyl ketone is preferred.

[0320] The above liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. Examples include acrylic polymers (FLOWLEN WK-20: Kyoeisha Chemical Co., Ltd.), amine salts of special modified phosphates (HIPLAAD ED-251: Kusumoto Chemicals, Ltd.), modified acrylic block copolymers (DISPERBYK 2000; BYK-Chemie GmbH), etc.

[0321] The resin composition of the present invention can also have other additives. Examples include catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, reactive diluents, etc.

[0322] By curing the resin composition of the present invention, a cured product can be obtained. When curing it, curing can be carried out at normal temperature or by heating. In the case of thermal curing, it can be cured by one-time heating or through multi-stage heating processes.

[0323] In addition, the curable resin composition of the present invention can also be cured using active energy rays. At this time, it is sufficient to use a photo cationic polymerization initiator as the polymerization initiator. As the active energy rays, visible light, ultraviolet rays, X-rays, electron rays, etc. can be used.

[0324] Examples of the photo cationic polymerization initiator include aryl-sulfonium salts, aryl-iodonium salts, etc. Specifically, arylsulfonium hexafluorophosphate, arylsulfonium hexafluoroantimonate, arylsulfonium tetra(pentafluoro)borate, tris(alkylphenyl)sulfonium hexafluorophosphate, etc. can be used. The photo cationic polymerization initiator can be used alone or in combination of two or more.

[0325] The curable resin composition of the present invention can be prepared by uniformly mixing the above-mentioned respective components, and there is no particular limitation on the method. For example, it can be prepared by uniformly mixing using a pot mill, ball mill, bead mill, roll mill, homogenizer, super mill, homodisper, universal mixer, Banbury mixer, kneader, etc.

[0326] Regarding the curable resin composition of the present invention, the above-mentioned curable compound, the compound (III) that can react with it, and, if necessary, the above-mentioned curable agent, filler, fibrous matrix, dispersion medium, and resins other than the above various compounds are dissolved in the dispersion medium such as the above-mentioned organic solvent. After dissolution, the solvent is distilled off, and vacuum drying is carried out using a vacuum oven or the like, whereby a curable resin composition can be obtained. In addition, the curable resin composition of the present invention can be a composition in a state where the above-mentioned constituent materials are uniformly mixed. At this time, it is preferably uniformly mixed using a mixer or the like. The blending ratio of each constituent material can be appropriately prepared according to the characteristics such as the mechanical strength, heat resistance, reparability, and reprocessability of the desired cured product. In addition, in the production of the curable resin composition, there is no particular limitation on the mixing order of the specific constituent materials.

[0327] 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 according to the properties of the composition used and a known method can be adopted.

[0328] The cured product of the present invention exhibits a moderate crosslinking density as described above, and thus can maintain good mechanical strength. In addition, when mechanical energy such as damage or external force is applied to the cured product of the present invention, the reversible bond is broken, so it exhibits easy disassembly. Furthermore, the equilibrium shifts toward the bonding direction, so it is considered that the adduct is formed again, and damage repair and re-molding can be performed.

[0329] The structure of the obtained cured product can be confirmed by infrared absorption (IR) spectrometry such as Fourier transform infrared spectroscopy (FT-IR), elemental analysis method, X-ray scattering method, etc.

[0330] Both the easy disassembly property and the reparability of the curable resin composition of the present invention and the cured product made from the curable resin composition are excellent, and it has re-moldability, so it is useful in the following applications.

[0331] The curable resin cured product of the present invention can be made into a laminate by laminating with a substrate. As the substrate of the laminate, inorganic materials such as metal and glass, organic materials such as plastic and wood can be appropriately used according to the use, and it can be the shape of the laminate, and can have a flat plate, sheet, or three-dimensional structure, or can be three-dimensional. It can also be any shape corresponding to the purpose, such as a shape with curvature on the whole surface or a part. In addition, there are no restrictions on the hardness, thickness, etc. of the substrate. In addition, it can also be made into a multi-layer laminate laminated in the order of the first substrate, the layer formed by the cured product of the curable resin composition of the present invention, and the second substrate. The curable resin composition of the present embodiment has excellent adhesiveness, so it can be suitably used as an adhesive for bonding the first substrate and the second substrate. In addition, the curable resin cured product of the present invention can be used as a substrate, and the cured product of the present invention can be further laminated.

[0332] In addition, the curable resin cured product of the present invention can relieve stress, so it is particularly suitable for bonding different types of materials. For example, even if the substrate is a laminate of different types of materials such as metal and / or metal oxide and the second substrate is a plastic layer, the adhesive force can be maintained by the stress relief ability of the cured product of the present invention.

[0333] In a laminate formed by laminating the cured product of the present invention with a substrate, the layer containing the cured product can be formed by directly coating or molding the substrate, or by laminating the already formed layers. In the case of direct coating, there is no particular limitation on the coating method, and examples include: spraying method, spin coating method, dipping method, roll coating method, blade coating method, knife-over-roll method, doctor blade method, curtain coating method, slot coating method, screen printing method, inkjet method, etc. In the case of direct molding, examples include: in-mold molding, insert molding, vacuum molding, extrusion lamination molding, compression molding, etc. In the case of laminating the already formed composition, it is possible to laminate the uncured or semi-cured composition layers and then cure them, or to laminate a layer containing the cured product obtained by completely curing the composition on the substrate. In addition, it is possible to laminate by coating a precursor that can become a substrate on the cured product of the present invention and curing it, or to bond the precursor that can become a substrate or the composition of the present invention in an uncured or semi-cured state and then cure it. There is no particular limitation on the precursor that can become a substrate, and examples include various curable resin compositions, etc.

[0334] The cured product obtained by using the curable resin composition of the present invention has particularly high adhesiveness to metals and / or metal oxides, and thus can be particularly preferably used as a metal primer. Examples of the metal include: copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and materials formed by combining them. Examples of the metal oxide include single oxides and / or composite oxides of these metals. In particular, the adhesiveness to iron, copper, and aluminum is excellent, and thus it can be preferably used as an adhesive for iron, copper, and aluminum.

[0335] The curable resin composition of the present invention can be suitably used as an adhesive for structural members in the fields of automobiles, trams, civil engineering, electronic devices, airplanes, and aerospace industries. For example, even when used in the adhesion of different materials such as between metal and non-metal, this adhesive can maintain high adhesiveness without being affected by changes in temperature environment, and it is not likely to cause peeling, etc. In addition, in addition to the use for structural members, this adhesive can also be used as an adhesive for general office use, medical use, carbon fiber, battery units or modules or casings, etc., and can also be used as an adhesive for optical component bonding, optical disc bonding, printed wiring board mounting, die bonding adhesive, underfill, etc. for semiconductors, underfill for BGA reinforcement, anisotropic conductive film, anisotropic conductive paste, etc. for mounting.

[0336] When the curable resin composition of the present invention has a fibrous matrix and the fibrous matrix is a reinforcing fiber, the curable resin composition containing the fibrous matrix can be used as a fiber-reinforced resin. Regarding the method of making the composition contain the fibrous matrix, there is no particular limitation as long as the effects of the present invention are not impaired. Examples include methods of compounding the fibrous matrix with the composition by kneading, coating, impregnating, injecting, press-bonding, etc., and these methods can be appropriately selected according to the form of the fiber and the use of the fiber-reinforced resin.

[0337] There is no particular limitation on the method of molding the fiber-reinforced resin. If manufacturing a plate-like product, generally an extrusion molding method is used, but it can also be by flat pressing. In addition, an extrusion molding method, blow molding method, compression molding method, vacuum molding method, injection molding method, etc. can be used. Also, if manufacturing a film-like product, in addition to the melt extrusion method, a solution casting method can also be used. In the case of using a melt molding method, examples include: blown film molding, casting molding, extrusion lamination molding, calendering molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, coating molding, etc. In addition, in the case of a resin cured by active energy rays, various curing methods using active energy rays can be used to manufacture a cured product. In particular, in the case where a thermosetting resin is the main component of the matrix resin, examples include a molding method of prepreging the molding material and performing pressure heating by pressing or autoclave. In addition to this, resin transfer molding (RTM), vacuum-assisted resin transfer molding (VaRTM), lamination molding, hand lay-up molding, etc. can also be cited.

[0338] Since the curable resin composition of the present invention has good heat resistance and reparability of the cured product using it, and has re-moldability, it can be used for molding materials such as large shells, engine casings, casting materials inside the casing, gears, pulleys, etc. They can be cured products of the resin alone or cured products reinforced with fibers such as glass chips.

[0339] The fiber-reinforced resin can be in an uncured or semi-cured state called prepreg. It is also possible to make the product flow in the prepreg state and then perform final curing to form a cured product. In the case of forming a laminate, by laminating other layers after forming the prepreg and then performing final curing, a laminate with each layer closely bonded can be formed, so this is preferred. As the mass ratio of the composition and the fibrous matrix used at this time, there is no particular limitation, and it is usually preferably prepared such that the resin component in the prepreg is 20 to 60% by mass.

[0340] The cured product of the present invention has good heat resistance and reparability, and has re-moldability, and can be used as a heat-resistant material and an electronic material. In particular, it can be suitably used for semiconductor encapsulating materials, circuit boards, build-up films, build-up substrates, etc., adhesives, and resist materials. In addition, it can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance. The heat-resistant members and electronic members thus obtained can be suitably used for various purposes, for example, industrial machine parts, general machine parts, parts of automobiles / railways / vehicles, etc., aerospace / aeronautics-related parts, electronic / electrical parts, building materials, container / packaging members, daily necessities, sports / leisure goods, housing members for wind power generation, etc., but are not limited to these.

[0341] Among them, it exhibits excellent flexibility of the cured product and can be suitably used as an adhesive for structural members in the fields of automobiles, trams, civil engineering, electronic devices, airplanes, and aerospace industries. For example, even when the adhesive of the present invention is used for bonding between different raw materials such as metal-nonmetal, it can maintain high adhesiveness without being affected by changes in temperature environment, and it is not easy to cause peeling, etc. In addition, the adhesive of the present invention can be used as an adhesive for general office use, medical use, carbon fiber, battery units or modules or casings, etc., in addition to the use for structural members. Examples of the adhesive include adhesives for optical component bonding, adhesives for optical disc bonding, adhesives for printed wiring board mounting, chip bonding adhesives, semiconductor adhesives such as underfill materials, BGA reinforcement underfill materials, anisotropic conductive films, anisotropic conductive pastes, and other mounting adhesives.

[0342] Hereinafter, representative products will be exemplified.

[0343] 1. Semiconductor encapsulating material

[0344] As a method for obtaining a semiconductor encapsulating material from the resin composition of the present invention, there may be mentioned a method of sufficiently melting and mixing compounding agents such as the above resin composition, a curing accelerator, and an inorganic filler until uniform using an extruder, a kneader, a roll, etc. as needed. At this time, as the inorganic filler, fused silica is usually used, but in the case of using it as a high thermal conductivity semiconductor encapsulating material for power transistors and power ICs, crystalline silica, alumina, silicon nitride, etc. with a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc. can be used. Regarding the filling rate, it is preferably used in the range of 30 to 95% by mass of the inorganic filler with respect to 100 parts by mass of the curable resin composition. Among them, in order to achieve an improvement in flame retardancy, moisture resistance, resistance to solder cracking, and a reduction in the linear expansion coefficient, it is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more.

[0345] 2. Semiconductor device

[0346] As for the semiconductor package molding of a semiconductor device obtained from the curable resin composition of the present invention, examples include: a method of casting the above semiconductor sealing material, or a method of molding using a transfer molding machine, an injection molding machine, etc., and then heating at 50 to 250°C for 2 to 10 hours.

[0347] 3. Printed circuit board

[0348] As a method for obtaining a printed circuit board from the composition of the present invention, examples include: a method of laminating the above prepreg by a conventional method, appropriately overlapping copper foils, and heating and pressing at 170 to 300°C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[0349] 4. Flexible substrate

[0350] As a method for manufacturing a flexible substrate from the crosslinkable resin composition of the present invention, examples include: a method manufactured by a method consisting of the following three steps. The first step is a step of coating a crosslinkable resin composition containing a resin component, an organic solvent, etc. on an electrically insulating film using a coater such as a reverse roll coater or a comma coater; the second step is a step of heating the electrically insulating film coated with the crosslinkable resin composition at 60 to 170°C for 1 to 15 minutes using a heating machine to volatilize the solvent from the electrically insulating film and B-stage the crosslinkable resin composition; the third step is a step of thermocompression bonding (the bonding pressure is preferably 2 to 200 N / cm, and the bonding temperature is preferably 40 to 200°C) a metal foil to an adhesive on the B-staged electrically insulating film of the crosslinkable resin composition using a heating roll or the like. It should be noted that if sufficient bonding performance can be obtained through the above three steps, it may end here, but in the case where complete bonding performance is required, it is further preferably post-cured under the conditions of 100 to 200°C for 1 to 24 hours. The thickness of the finally cured resin composition layer is preferably in the range of 5 to 100 μm.

[0351] 5. Multilayer substrate

[0352] The method for obtaining a laminated substrate from the composition of the present invention may, for example, include the following steps. First, a step of applying the above composition appropriately mixed with rubber, filler, etc. onto a circuit substrate having a circuit formed thereon using a spraying method, a curtain coating method, etc., and then curing it (step 1). Then, after opening a predetermined via hole portion or the like as needed, treating it with a roughening agent, performing hot water cleaning on its surface to form irregularities, and then performing a treatment of plating a metal such as copper (step 2). As needed, such operations are sequentially repeated, and a step of alternately laminating to form a resin insulating layer and a conductor layer of a predetermined circuit pattern (step 3). It should be noted that the opening of the via hole portion is performed after forming the outermost resin insulating layer. In addition, the laminated substrate of the present invention can also be manufactured by heat-pressing a copper foil with resin obtained by semi-curing the resin composition on a wiring substrate having a circuit formed thereon at 170 to 300 °C to form a roughened surface, and omitting the plating treatment step.

[0353] 6. Laminated film

[0354] As a method for obtaining a laminated film from the composition of the present invention, it can be manufactured by applying the above composition onto the surface of a support film (Y) as a substrate, and then drying the organic solvent by heating or blowing hot air, etc. to form a layer (X) of the composition.

[0355] As the organic solvent used herein, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used. In addition, it is preferably used in a proportion of 30 to 60% by mass of the non-volatile component.

[0356] The thickness of the formed layer (X) is usually equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit substrate is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer preferably has a thickness of 10 to 100 μm. It should be noted that the layer (X) of the above composition in the present invention can also be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the attachment of dirt, etc. and damage on the surface of the resin composition layer.

[0357] Examples of the above-mentioned support film and protective film include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET") and polyethylene naphthalate; polycarbonate, polyimide; and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that for the support film and protective film, in addition to matting treatment and corona treatment, release treatment can also be carried out. The thickness of the support film is not particularly limited, usually 10 to 150 μm, and preferably used in the range of 25 to 50 μm. In addition, the thickness of the protective film is preferably set to 1 to 40 μm.

[0358] The above-mentioned support film (Y) is peeled off after being laminated on the 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 laminated film is heat cured, it is possible to prevent the adhesion of dirt and the like during the curing process. In the case of peeling off after curing, usually, the support film is pre-treated with a release treatment.

[0359] The laminated film obtained as described above can be used to manufacture a multilayer printed circuit board. For example, when the layer (X) is protected by a protective film, after peeling them off, the layer (X) is laminated on one or both sides of the circuit board in direct contact with the circuit board by, for example, a vacuum lamination method. The lamination method can be intermittent or continuous using a roller. In addition, if necessary, the laminated film and the circuit board can be heated (preheated) as required before lamination. Regarding the lamination conditions, it is preferable to set the crimping temperature (lamination temperature) to 70 to 140 °C, and it is preferable to set the crimping pressure to 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and it is preferable to carry out lamination under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0360] 7. Conductive paste

[0361] As a method for obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing conductive particles in the composition can be cited. The above-mentioned conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive according to the type of conductive particles used.

[0362] Examples

[0363] Next, the present invention will be specifically described by way of examples and comparative examples. Hereinafter, unless otherwise specified, "parts" and "%" are based on mass. The present invention is not limited thereto.

[0364] FD-MS spectra and GPC were measured under the following conditions.

[0365] FD-MS: "JMS-T100GC AccuTOF" manufactured by JEOL Ltd.

[0366] Measurement range: m / z = 50.00 - 2000.00

[0367] Rate of change: 25.6 mA / min

[0368] Final current value: 40 mA

[0369] Cathode voltage: -10 kV

[0370] GPC: "HLC-8320GPC" manufactured by Tosoh Corporation

[0371] Column: "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0372] Detector: RI (Differential refractive index meter)

[0373] Measurement conditions: 40 °C

[0374] Mobile phase: Tetrahydrofuran

[0375] Flow rate: 1 ml / min

[0376] Standards: "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F" manufactured by Tosoh Corporation

[0377] Regarding the epoxy equivalent of the synthesized epoxy resin, it is measured in accordance with JIS K7236, and the epoxy equivalent (g / eq) is calculated.

[0378] As a calculation method for the number of repeating units, examples can be given of calculations based on the analysis results of various appropriate equipment such as GPC molecular weight measurement and FD-MS.

[0379] Example 1

[0380] In a flask equipped with a thermometer and a stirrer, 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol (Nagase ChemteX's "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) were added. After heating to 130 °C over 2 hours, the reaction was carried out for 20 hours. Then, 509.4 g of epoxy resin (Ep-1) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-1) was 1343 g / eq. Regarding this epoxy resin (Ep-1), a peak of M+ = 1607 corresponding to the theoretical structure of m = 1, n = 8 of the following structural formula (Ep-1) was obtained by mass spectrometry, thereby confirming the presence of the target epoxy resin (Ep-1).

[0381] [Chemical formula 19]

[0382]

[0383] Example 2

[0384] 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. After heating to 80 °C over 1 hour, the reaction was carried out for 11 hours. Then, 549.4 g of a hydroxy compound (Ph-1) was obtained. Regarding this hydroxy compound (Ph-1), a peak of M+ = 1817 corresponding to the theoretical structure of m = 1, n = 8 of the following structural formula (Ph-1) was obtained by mass spectrometry, thereby confirming the presence of the target hydroxy compound (Ph-1).

[0385] [Chemical formula 20]

[0386]

[0387] Example 3

[0388] In a flask equipped with a thermometer and a stirrer, 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) were charged. After heating to 125 °C over 2 hours, the reaction was carried out for 14 hours. Then, 287 g of epoxy resin (Ep-2) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-2) was 4142 g / eq. Regarding this epoxy resin (Ep-2), a peak of M+ = 822 corresponding to the theoretical structure with n = 1 of the following structural formula (Ep-2) was obtained by mass spectrometry, thereby confirming the presence of the target epoxy resin (Ep-2).

[0389] [Chemical formula 21]

[0390]

[0391] Example 4

[0392] In a flask equipped with a thermometer and a stirrer, 188 g (0.5 mol) of EPICLON 850S (bisphenol type liquid epoxy resin with an epoxy equivalent of 188 g / eq, manufactured by DIC Corporation) and 48.3 g (0.25 mol) of 2-aminoanthracene (active hydrogen equivalent of 96.6 g / eq) were charged. After heating to 125 °C over 2 hours, the reaction was carried out for 14 hours. Then, 225 g of epoxy resin (Ep-3) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-3) was 510 g / eq. Regarding this epoxy resin (Ep-3), a peak of M+ = 874 corresponding to the theoretical structure with n = 1 in the following structural formula (Ep-3) was obtained by mass spectrometry, and thus it was confirmed that the target epoxy compound (Ep-3) was contained.

[0393] [Chemical formula 22]

[0394]

[0395] Example 5

[0396] In a flask equipped with a thermometer, a condenser, and a stirrer, 40.0 g (0.10 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthesis Co., Ltd.: epoxy equivalent 200 g / eq) and 25.1 g (0.066 mol) of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (BIP-ANT manufactured by Asahi Organic Chemicals Co., Ltd.) were charged. After heating to 140 °C over 30 minutes, 0.33 g of 4% aqueous sodium hydroxide solution was added. Then, it was heated to 150 °C over 30 minutes and further reacted at 150 °C for 20 hours. Then, it was cooled to 80 °C, 65 g of methyl isobutyl ketone, 65 g of water, and a neutralizing amount of sodium phosphate were added, and the aqueous layer was removed. Subsequently, the solvent was 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. Regarding this epoxy resin (Ep-4), a peak of M+ = 1005 corresponding to the theoretical structure with m = 1 in the following structural formula (A-1) was obtained by mass spectrometry, and thus it was confirmed that the target epoxy resin (Ep-4) was contained.

[0397] [Chemical formula 23]

[0398]

[0399] Example 6

[0400] Forty grams (0.10 mol) of the diglycidyl ether of 1,12-dodecanediol in Example 5 was changed to 89.0 g (0.10 mol) of the diglycidyl ether of polytetramethylene glycol (“Denacol EX-991L” manufactured by Nagase ChemteX; epoxy equivalent: 445 g / eq). Otherwise, the reaction was carried out in the same manner as in Example 5 to obtain 125.5 g of an epoxy resin (Ep-5). The epoxy equivalent of the obtained epoxy resin (Ep-5) was 1970 g / eq. For this epoxy resin (Ep-5), a peak of M+ = 2223 corresponding to the theoretical structure with m = 1 and n = 11 in the following structural formula (Ep-5) was obtained by mass spectrometry, thereby confirming the presence of the target epoxy resin (Ep-5).

[0401] [Chemical formula 24]

[0402]

[0403] Example 7

[0404] Forty-one point two grams (0.02 mol) of the epoxy resin (Ep-4) (epoxy equivalent: 1030 g / eq) obtained in Example 5 and 4.8 g (0.021 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq) were charged. After heating to 140 °C over 30 minutes, 0.5 g of a 20% aqueous sodium hydroxide solution was added. Then, the temperature was raised to 150 °C over 30 minutes, and the reaction was further carried out at 150 °C for 16 hours. Then, the mixture was cooled to 80 °C, 45 g of methyl isobutyl ketone, 45 g of water, and a neutralizing amount of sodium phosphate were added, and the aqueous layer was removed. Subsequently, the solvent was 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 hydroxyl equivalent of the obtained hydroxy compound (Ph-2) calculated by GPC was 12840 g / eq. For this hydroxy compound (Ph-2), a peak of M+ = 1461 corresponding to the theoretical structure with m = 1 in the following structural formula (A-3) was obtained by mass spectrometry, thereby confirming the presence of the target hydroxy compound (Ph-2).

[0405] [Chemical formula 25]

[0406]

[0407] Example 8

[0408] In a flask equipped with a thermometer, a cooling tube, and a stirrer, 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol (Nagase ChemteX's "Denacol EX-991L": epoxy equivalent 445 g / eq) and 69.3 g (0.33 mol) of 2,6-dihydroxyanthracene (hydroxyl equivalent 105 g / eq) were charged. After heating to 140 °C over 30 minutes, 2.6 g of a 4% aqueous sodium hydroxide solution was added. Then, the temperature was raised to 150 °C over 30 minutes, and the reaction was further carried out at 150 °C for 6 hours. Then, a neutralizing amount of sodium phosphate was added to obtain 491 g of an epoxy resin (Ep-6). The epoxy equivalent of the obtained epoxy resin (Ep-6) was 1700 g / eq. Regarding this epoxy resin (Ep-6), a peak of M+ = 2754 corresponding to the theoretical structure of m = 1 and n = 8 in the following structural formula (Ep-6) was obtained by mass spectrometry, thereby confirming the presence of the target epoxy resin (Ep-6).

[0409] [Chemical formula 26]

[0410]

[0411] Example 9

[0412] In a flask equipped with a thermometer, a cooling tube, and a stirrer, 200 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthesis Co., Ltd.: epoxy equivalent 200 g / eq) and 69.3 g (0.33 mol) of 2,6-dihydroxyanthracene (hydroxyl equivalent 105 g / eq) were charged. After heating to 140 °C over 30 minutes, 2.6 g of a 4% aqueous sodium hydroxide solution was added. Then, the temperature was raised to 150 °C over 30 minutes, and the reaction was further carried out at 150 °C for 6 hours. Then, a neutralizing amount of sodium phosphate was added to obtain 255 g of an epoxy resin (Ep-7). The epoxy equivalent of the obtained epoxy resin (Ep-7) was 1440 g / eq. Regarding this epoxy resin (Ep-7), a peak of M+ = 838 corresponding to the theoretical structure of m = 1 in the following structural formula (Ep-7) was obtained by mass spectrometry, thereby confirming the presence of the target epoxy resin (Ep-7).

[0413] [Chemical formula 27]

[0414]

[0415] Example 10

[0416] 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. After heating to 140 °C over 30 minutes, 1.0 g of a 20% aqueous sodium hydroxide solution was added. Then, the temperature was raised to 150 °C over 30 minutes and further reacted at 150 °C for 12 hours. Then, a neutralizing amount of sodium phosphate was added to obtain 95 g of a hydroxyl compound (Ph-3). The hydroxyl equivalent of the obtained hydroxyl compound (Ph-3) calculated by GPC was 19,200 g / eq. Regarding this hydroxyl compound (Ph-3), a peak of M+ = 1294 corresponding to the theoretical structure of m = 1 of the following structural formula (Ph-3) was obtained by mass spectrometry, and thus it was confirmed that the target hydroxyl compound (Ph-3) was contained.

[0417] [Chemical formula 28]

[0418]

[0419] Synthesis Example 1

[0420] In a flask equipped with a thermometer, a condenser, and a stirrer, 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 were charged. After dissolving at 60 °C, 25.0 g (0.30 mol) of 48% caustic soda was added dropwise over 30 minutes using a dropping funnel, and the reaction was carried out at 60 °C for 9 hours. Then, after washing 4 times with 114 g of pure water, the organic layer was concentrated under reduced pressure to obtain the resinous target product. The resinous product after standing and cooling was coarsely crushed in a mortar, stirred together with 540 g of methanol to precipitate crystals, filtered, and dried to obtain 67.7 g of an epoxy resin (Ep-8). The epoxy equivalent of the obtained epoxy resin (Ep-8) was 248 g / eq.

[0421] Example 11 Hydroxyl Compound (Ph-4)

[0422] 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. After heating to 140 °C over 30 minutes, 1.0 g of a 20% aqueous sodium hydroxide solution was added. Then, the temperature was raised to 150 °C over 30 minutes and further reacted at 150 °C for 12 hours. Then, a neutralizing amount of sodium phosphate was added to obtain 105 g of a hydroxyl compound (Ph-4). The hydroxyl equivalent of the obtained hydroxyl compound (Ph-4) calculated by GPC was 300 g / eq.

[0423] [Chemical formula 29]

[0424]

[0425] Example 12

[0426] While purging a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer with nitrogen, 100 g of the hydroxy compound Ph-4 obtained in Synthesis Example 11, 215 g (2.3 moles) of epichlorohydrin, and 65 g of n-butanol were added and dissolved. After heating to 65°C, the pressure was reduced to the azeotropic pressure, and 35.4 g (0.43 mole) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours.

[0427] Next, stirring was continued for 0.5 hour under the same conditions. During this period, the distillate components distilled off by azeotropy were separated with a Dean-Stark Trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Then, unreacted epichlorohydrin was distilled off by vacuum distillation. 90 g of methyl isobutyl ketone and 90 g of n-butanol were added to the obtained crude epoxy resin and dissolved.

[0428] Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution, and after reacting at 80°C for 2 hours, it was washed repeatedly 3 times with 60 g of water until the pH of the washing liquid became neutral.

[0429] Next, the system was dehydrated by azeotropy, and after precision filtration, the solvent was distilled off under reduced pressure to obtain 113 g of an epoxy resin (Ep-9). The epoxy equivalent of the obtained epoxy resin (Ep-9) was 356 g / eq.

[0430] [Chemical formula 30]

[0431]

[0432] Synthesis Example 2

[0433] In a flask equipped with a thermometer and a stirrer, 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol (“Denacol EX-991L” manufactured by Nagase ChemteX; epoxy equivalent: 445 g / eq) and 171 g (0.75 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq) were added. After heating to 140°C over 30 minutes, 3.1 g of a 4% aqueous sodium hydroxide solution was added. Then, the temperature was raised to 150°C over 30 minutes, and the reaction was carried out at 150°C for 16 hours. Then, a neutralizing amount of sodium phosphate was added to obtain 616 g of a hydroxy compound represented by the following formula (Ph-2). For this hydroxy compound, a peak of M+ = 1380 corresponding to the theoretical structure with m1 = 1 and n1 = 11 in the following formula was obtained by mass spectrometry, thereby confirming the presence of a hydroxy compound containing PTMG (polytetramethylene ether glycol) type (BPA: bisphenol A). The hydroxy equivalent 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.

[0434] [Chemical formula 31]

[0435]

[0436] Synthesis Example 3

[0437] In a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, while performing nitrogen purging, 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 the azeotropic pressure, and 6.66 g (0.08 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours.

[0438] Next, stirring was continued under the same conditions for 0.5 hour. During this period, the distillate components distilled off by azeotropy were separated with a water separator, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Then, unreacted epichlorohydrin was removed by vacuum distillation. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to the obtained crude epoxy resin and dissolved.

[0439] Furthermore, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution, and after reacting at 80°C for 2 hours, it was washed repeatedly with 50 g of water three times until the pH of the washing solution became neutral.

[0440] Next, the system was dehydrated by azeotropy. After precise filtration, 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. Regarding this epoxy resin (Ep-10), a peak of M+ = 1492 corresponding to the theoretical structure of m1 = 1, n1 = 11, q = 1, p1 = 0, p2 = 0 in the following formula was obtained by mass spectrometry, thereby confirming the presence of a PTMG type (BPA) epoxy resin.

[0441] [Chemical formula 32]

[0442]

[0443] Preparation of Composition and Cured Product

[0444] According to the formulation in the table (the numbers in the table are based on mass), each compound was used and uniformly mixed with a mixer ("Defoaming and Kneading Machine Awatori Rentaro ARV-200" manufactured by THINKY Corporation) to obtain a curable resin composition. The curable resin composition was sandwiched between an aluminum mirror plate ("JIS H4000 A1050P" manufactured by Engineering Test Service Co., Ltd.) with a silicone tube as a spacer and heat-cured under predetermined conditions to obtain a cured product with a thickness of 0.7 mm.

[0445] <Tensile Elongation>

[0446] The obtained cured product was punched into a dumbbell shape (JIS K 7161-2-1BA) using a punching blade and used as a test piece. Using a tensile testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation), the tensile test of this test piece was carried out in accordance with JIS K 7162-2, and the elongation at break at a measurement environment of 23°C (test speed: 2 mm / min) was evaluated.

[0447] <Re-molding Test>

[0448] The produced cured product was cryogenically pulverized. 0.07 g of the pulverized cured product was placed in a mold box with a side length of 10 mm and a thickness of 0.5 mm, and vacuum pressing was carried out under predetermined conditions. The appearance of the obtained cured product was visually observed. The judgment criteria are as follows.

[0449] A: The joint disappeared and the cured product was integrated.

[0450] B: Some joints could be visually confirmed, but the cured product was integrated.

[0451] C: It formed a lumpy shape and dispersed when slightly stressed.

[0452] <Repair Test>

[0453] Cut the cured product made with a razor. After bringing the resulting fracture surfaces into contact, age them in a dryer at 150 °C for 24 hours. After taking them out of the dryer, visually confirm whether the cross-sections of the cured products are joined to each other. The judgment criteria are as follows.

[0454] A: Joined. Even if the cured product is bent 90°, the joined part does not dissociate.

[0455] B: Joined. If the cured product is bent, the joined part dissociates.

[0456] C: Not joined.

[0457] [Table 1]

[0458]

[0459] [Table 2]

[0460]

[0461] [Table 3]

[0462]

[0463] [Table 4]

[0464]

[0465] [Table 5]

[0466]

[0467] [Table 6]

[0468]

[0469] [Table 7]

[0470]

[0471] It should be noted that the respective complexes shown in the table are as follows.

[0472] E-850S: Bisphenol A liquid epoxy resin (manufactured by DIC Corporation, epoxy equivalent 188 g / eq)

[0473] TD-2131: Phenolic novolac type phenolic resin (manufactured by DIC Corporation, hydroxyl equivalent 104 g / eq)

[0474] BMI-TMH: 1,6'-bismaleimide-(2,2,4-trimethyl)hexane

[0475] DICY: Dicyandiamide ("DICY7" manufactured by Mitsubishi Chemical Corporation)

[0476] DCMU: 3-(3,4-Dichlorophenyl)-1,1-dimethylurea ("B-605-IM" manufactured by DIC Corporation)

[0477] TPP: Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.).

Claims

1. A curable resin composition, characterized in that, Comprising: 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, and A compound (C) reactive with the curable functional group (a).

2. The curable resin composition according to claim 1, wherein, The curable functional group (a) is a hydroxyl group or a glycidyl ether group.

3. The curable resin composition according to claim 1, wherein, The curable compound (A) further has an alkylene chain or an alkylene ether chain.

4. The curable resin composition according to claim 1, wherein, The compound containing a dienophile structure is a compound having two or more maleimide groups.

5. The curable resin composition according to claim 2, 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 claim 2, 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 resin.

7. The curable resin composition according to any one of claims 1 to 6, wherein, Relative to the total mass of the curable components in the curable resin composition, the concentration of the reversible bond formed by the Diels - Alder reaction is 0.10 mmol / g or more.

8. The curable resin composition according to claim 7, which is one or more compositions selected from the group consisting of a dissociable composition, a reparative composition, and a composition for remolding material.

9. A cured product obtained by curing the curable resin composition according to claim 7.

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

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

12. A curable compound represented by any one of the following general formulas (1) to (3), [Chemical formula 1] In formulas (1) to (3), R is 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), [Chemical formula 2] In formulas (Z1 - 1), (Z1 - 2), (Z1 - 3), (Z1 - 4), (Z1 - 5), (Z1 - 6), (Z1 - 7), Ar is each independently a structure containing an unsubstituted or substituted aromatic ring, R 11 and R 12 are each independently a hydroxyl group, glycidyl ether group or 2-methylglycidyl ether group, R 13 and R 14 is a hydrogen atom or a methyl group R 1 、R 2 Each independently represents a hydrogen atom, a methyl group or an ethyl group, R' is each independently a divalent hydrocarbon group having 2 to 12 carbon atoms, n is the average value of the repeating unit and is 0.5 to 10, n1 is an integer of 4 to 16, n2 is the average value of the repeating unit and is 2 to 30; X in formula (Z1 - 1) 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), [Chemical formula 3] In formulas (Z1-1-1) and (Z1-1-2), Ar, R 1 , R 2 , R', n1, and n2 are the same as described 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 Each independently represents a hydrogen atom or a methyl group; m1, m2, m3, m4, m5, m6, p1, p2, q are the average values of the repetitions, m1, m2, m3, m4, m5, m6 are each independently 0 to 25, and m1 + m2 ≥ 1, p1, p2 are each independently 0 to 5, q is 0.5 to 5; Among them, The bonding of X represented by the general formula (Z1 - 1 - 1) and Y represented by the general formula (Z1 - 1 - 2) can be random or block, and the total number of each structural unit X, Y present in one molecule is m1, m2 respectively. Further, the aromatic rings containing an anthracene skeleton in formulas (1) to (3) may have substituents, and the lines in the formulas indicate that they may be connected at any position on the rings.

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