Sclerotic resin composition, cured product, laminate, and sclerotic compound

Abstract

Provided are: a compound which, while being a curable resin, can make it possible to easily achieve quick dismantlability, repairability, reformability and the like in a cured product; a curable resin composition prepared using the compound; and a cured product of the composition. More specifically, there is used a curable resin composition characterized by comprising a curable compound (A) having at least one anthracene structure and at least two curable functional groups (a) in the molecule thereof, a compound (B) containing a parent diene structure, and a compound (C) having reactivity with the curable functional groups (a). Each of the curable functional groups is preferably a hydroxyl group or a glycidyl ether group, and the compound (B) containing the parent diene structure is preferably bismaleimide.

Description

Technical Field

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

Background Art

[0002] Cured products obtained by thermosetting phenolic resins, epoxy resins, etc. are excellent in heat resistance, mechanical strength, electrical properties, adhesiveness, etc., and are indispensable materials in various fields such as electric and electronic, paints, and adhesives.

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

[0004] In addition, cured products obtained by once curing thermosetting resins cannot be dissolved in solvents (insoluble) and do not melt even at high temperatures (infusible). Therefore, they are poor in recyclability and reusability. Since the cured products after use become waste, it has become an issue to reduce waste and the environmental load. Also, due to their high adhesive performance, there is an issue that the disassembly and reusability after use are limited.

[0005] Therefore, there is a demand for long life, waste reduction, and reusability of cured products using thermosetting resins. For this, it is considered effective to impart reparability, reshaping ability, and disassembly ability.

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

[0007] In addition, even when cracks or peeling occur in a sealing material using an epoxy resin or the like, a technique for obtaining a self-healing sealing material by using a first thermosetting resin and microcapsule particles encapsulating a second thermosetting resin precursor has been disclosed (see, for example, Patent Document 2).

[0008] In addition to the above, in order to impart reparability and reshaping properties, research using reversible bonds such as dynamic covalent bonds and supramolecular bonds in the cured product has also been actively conducted.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] In the technique provided in Patent Document 1, the adhesive after disassembly is to be discarded, and although the base material as the adherend is recyclable, there is a problem that the recyclability as a whole is insufficient. Further, in the technique of Patent Document 2, although it has a certain degree of self-healing property, it is not a solution from the viewpoint of reuse, and the problem of waste when it becomes unnecessary remains. In addition, in the raw materials used for the reversible bond, since it is necessary to ensure its molecular mobility, there is a problem that the use of raw materials is limited to gel-like substances with poor mechanical strength. In any case, improvement is required at present. Therefore, an object of the present invention is to provide a compound that can easily achieve easy disassembly, reparability, reshaping property, etc. in a cured product while being a curable resin, a curable resin composition using the same, and a cured product thereof.

Means for Solving the Problems

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

[0012] That is, the present invention includes the following aspects. 〔1〕A curable compound (A) having one or more anthracene structures and two or more curable functional groups (a) in the molecule, A compound (B) containing a parent diene structure, A compound (C) reactive with the curable functional group (a), A curable resin composition characterized by containing the above. 〔2〕The curable resin composition according to 〔1〕, wherein the curable functional group (a) is a hydroxyl group or a glycidyl ether group. 〔3〕Furthermore, the curable resin composition according to 〔1〕 or 〔2〕, which has an alkylene chain or an alkylene ether chain in the curable compound (A). 〔4〕The curable resin composition according to any one of 〔1〕 to 〔3〕, wherein the compound containing the parent diene structure has two or more maleimide groups. 〔5〕The curable resin composition according to any one of 〔1〕 to 〔4〕, wherein the curable functional group (a) is a hydroxyl group and the compound (C) reactive with the curable functional group (a) is an epoxy resin. 〔6〕The curable resin composition according to any one of 〔1〕 to 〔5〕, wherein the curable functional group (a) is a glycidyl ether group and the compound (C) reactive with the curable functional group (a) is a curing agent for an epoxy resin. 〔7〕The curable resin composition according to any one of 〔1〕 to 〔6〕, wherein the concentration of the reversible bond by the Diels - Alder reaction is 0.10 mmol / g or more with respect to the total mass of the curable components in the curable resin composition. 〔8〕The curable resin composition according to any one of 〔1〕 to 〔7〕, which is one or more compositions selected from the group consisting of an easily decomposable composition, a reparable composition, and a composition for a remolding material. 〔9〕A cured product obtained by curing the curable resin composition according to any one of 〔1〕 to 〔8〕. A laminate having a substrate and a layer containing the cured product described in [9]. 〔11〕A heat-resistant member containing the cured product described in [9]. 〔12〕A curable compound represented by any one of the following general formulas (1) to (3).

[0013] [Chemical formula]

[0014] (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),

[0015] [Chemical formula]

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

[0017] [Chemical formula]

[0018] 〈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 are each independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group.〉 m1, m2, m3, m4, m5, m6, p1, p2, and q are average values of repetition, m1, m2, m3, m4, m5, and m6 are each independently 0 to 25, and m1 + m2 ≥ 1. p1 and p2 are each independently 0 to 5. q is 0.5 to 5. However, the bond between X represented by the general formula (Z1-1-1) and Y represented by the general formula (Z1-1-2) may be random or block, indicating that the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively. Also, the aromatic ring containing the anthracene skeleton in formulas (1) to (3) may have a substituent. Note that the lines in the formula indicate that they may be connected at any position on the ring. [Advantages of the Invention]

[0019] According to the present invention, it is possible to impart easy disassembly, reparability, and recyclability to a cured product made of a curable resin composition, contributing to extending the lifespan of the cured product itself and reducing waste.

Mode for Carrying Out the Invention

[0020] Next, the mode 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 ordinary knowledge of those skilled in the art without departing from the gist of the present invention.

[0021] The curable resin composition as one form of the present invention contains 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 parent diene structure, and a compound (C) having reactivity with the curable functional group (a).

[0022] With such a configuration, in the process of obtaining a cured product, a Diels - Alder reaction occurs between the anthracene structure in the curable compound (A) and the parent diene in the compound (B) containing a parent diene structure, forming a reversible bond. At the same time, in the curing reaction, a covalent bond is formed between the curable functional group (a) in the compound (A) and the compound (C). Therefore, the obtained cured product has a cured product that concurrently has a reversible bond due to the Diels - Alder reaction, a curable functional group (a), and a permanent cross - linked structure (covalent bond) obtained by the reaction of the curable functional group (a) with the compound (C) capable of reacting therewith.

[0023] Since such a cured product has reversibility in its crosslinked structure, when the cured product is subjected to impact and cracks are generated or it is pulverized, it is easily cleaved at the reversible bonding portion, exhibiting easy disassembly. On the other hand, the reversible bond can reversibly reform the bond even in a low temperature region including room temperature, and can exhibit functions such as reparability and reshaping ability. For example, even when the cured product of the present invention is pulverized, by placing it in a low temperature including room temperature or a heating / heating state, based on the reversible bond, the cured product can be easily repaired, and it is also possible to reshape the pulverized cured product. In addition, since the Diels-Alder reaction by the anthracene structure has a high bonding temperature and has durability even in a relatively high temperature region, it can be handled in the same manner as a cured product obtained from a thermosetting resin in the normal temperature region.

[0024] 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 compound (A) has two or more curable functional groups (a), it is possible to form a three-dimensional crosslinked structure by a curing reaction, and mechanical strength and heat resistance can be imparted to the cured product.

[0025] As the curable compound (A), as described above, it may have one or more anthracene structures and two or more curable functional groups (a), and the others are not particularly limited.

[0026] The curable functional group is not particularly limited, and examples thereof include a vinyl group, an epoxy group, a hydroxyl group, an isocyanate group, a carboxy group, etc. Among these, from the viewpoints of thermosetting, easy availability of industrial raw materials, and excellent balance of heat resistance, water resistance, heat and humidity resistance, etc. of the obtained cured product, a hydroxyl group or a glycidyl ether group which may have a substituent is preferable. Also, from the viewpoint of easy availability of industrial raw materials and easy adjustment of the crosslinking density when forming a cured product, etc., the number of curable functional groups in one molecule is preferably in the range of 2 to 5, and more preferably 2 to 3.

[0027] In addition, the compound (A) preferably has a flexible structure. By including a flexible structure, flexibility and toughness can be further imparted to the cured product itself. Therefore, even at the site of use where cracks are likely to occur, the impact can be absorbed, or when used as an adhesive between substrates with different coefficients of thermal expansion, it has excellent substrate followability. Moreover, the reversibility and repairability due to the aforementioned reversible bonds contribute to the durability of the cured product. Examples of the flexible structure include partial structures that do not contain aromatic rings or alicyclic structures, such as alkylene chains and alkylene ether chains. At this time, the alkylene chain preferably has 2 to 30 carbon atoms, and particularly preferably 4 to 16 carbon atoms. The alkylene ether chain is not particularly limited, but is preferably an alkylene ether chain having 2 to 12 carbon atoms, and the average value of the repeating number is preferably in the range of 2 to 30. Furthermore, the flexible structure may have a plurality of the same or different structures in one molecule.

[0028] Furthermore, the molecular weight of the curable compound which is one embodiment of the present invention is not particularly limited, and can be appropriately adjusted according to the use of the curable resin composition using the compound (B) having a parent diene structure described later and the compound (C) having reactivity with the curable functional group (a). For example, when the obtained curable resin composition is used for solventless 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. Also, 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, the epoxy equivalent weight in the case of having an epoxy group is preferably in the range of 200 to 30,000 g / eq, and the hydroxyl equivalent weight in the case of having a hydroxyl group is preferably in the range of 200 to 30,000 g / eq because it is easy to handle.

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

[0030]

Chem.

[0031] 〔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),

[0032]

Chem.

[0033] [In formulas (Z1-1), (Z1-2), (Z1-3), (Z1-4), (Z1-5), (Z1-6), and (Z1-7), Ar is each independently a structure having an unsubstituted or substituted aromatic ring, R 11 、R 12 are each independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 13 、R 14 is a hydrogen atom or a methyl group, R 1 、R 2 are each independently a hydrogen atom, a methyl group, or an ethyl group, R’ is each independently a divalent hydrocarbon group having 2 to 12 carbon atoms, n is the average value of the repeating units and is 0.5 to 10, n1 is an integer of 4 to 16, n2 is the average value of the repeating units 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),

[0034]

Chem.

[0035] 〈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 are each independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group.〉 m1, m2, m3, m4, m5, m6, p1, p2, and q are average values of repetition, m1, m2, m3, m4, m5, and m6 are each independently from 0 to 25, and m1 + m2 ≥ 1, p1 and p2 are each independently from 0 to 5, q is from 0.5 to 5. However, the bonding between X represented by the general formula (Z1-1-1) and Y represented by the general formula (Z1-1-2) may be random or block, indicating that the total numbers of the respective structural units X and Y present in one molecule are m1 and m2, respectively. Also, the aromatic ring containing the anthracene skeleton in formulas (1) to (3) may have a substituent. Note that the lines in the formula indicate that they may be connected at any position on the ring.]

[0036] Ar in the general formula is an aromatic ring which may have a substituent and is not particularly limited. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Examples of the substituent include a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, etc. It is preferable that the substituent on Ar does not cause a curing reaction when used as the curable resin composition, because the effects of the present invention are more likely to be exhibited.

[0037] Among these, Ar is preferably any of the structures represented by the following structural formulas. In the formulas, the lines indicate that they may be connected at any position on the ring.

[0038]

Chemical formula

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

[0040]

Chemical formula

[0041] The following structures of Ar are particularly preferable. * represents a bonding point.

[0042]

Chemical formula

[0043] In the general formula, the repeating unit n1 is an integer of 2 to 16. When n1 is 4 or more When it is made into a cured product, the deformation mode is likely to be elastic deformation. Further, when n1 is 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.

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

[0045] In the general formula, n2 is an average value of the repeating units and is from 2 to 30. This range is preferable in terms of achieving a good 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.

[0046] In the general formula, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms. Within this range, the adhesive strength is improved and the deformation mode of the cured product is likely to be elastic deformation. Preferably, R' is a divalent hydrocarbon group having 2 to 6 carbon atoms.

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

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

[0049] Among these, from the viewpoints of ease of obtaining raw materials, the viscosity of the resulting curable compound, and the balance of flexibility when formed into a cured product, an ethylene group, a propylene group, or a tetramethylene group is preferred.

[0050] In the general formula, m1 and m2 are respectively the average values of the repetitions of the aforementioned structural unit X and structural unit Y, each independently being 0 to 25, and m1 + m2 ≥ 1. Preferably, m1 and m2 are each in the range of 0.5 to 10. It is preferable that m1 and m2 are each independently 0 to 25 and each in the range of 0.5 to 10.

[0051] Examples of the curable compound of the present invention include, but are not limited to, those represented below.

[0052]

Chemical formula

[0053]

Chemical formula

[0054] 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 average values of repetition, n2 is 2 to 30, and m represents 0.5 to 10.

[0055] The curable compound which is one form of the present invention can be synthesized by a known method. For example, the compound represented by the general formula (1) can be easily obtained by using anthracenediol and a polyglycidyl ether compound, a polyvinyl ether or a polyhalogenated alkylene compound, and using an excessive amount of anthracenediol when the curable reactive group is a hydroxyl group, or using an excessive amount of the polyglycidyl ether compound for an extension reaction when the glycidyl ether group is the curable reactive group. At this time, the polyglycidyl ether compound may be composed of a single one or a plurality of those having different structures may be used in combination. Further, other hydroxyl group-containing compounds may be used in combination as long as the curing of the present invention is not impaired.

[0056] Examples of the anthracenediol include the following. Although various substituents may be present on the anthracene skeleton described below, from the viewpoint of easily exhibiting the effects of the present invention, it is preferable that the substituent has no reactivity.

[0057]

Chemical formula

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

[0059] The glycidyl ether compound having the alkylene chain or alkylene ether chain 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, and the like can be mentioned. Further, 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, and the like can be mentioned. These may contain organic chlorine impurities generated in the glycidyl etherification of hydroxy compounds, and may contain organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) represented by the following structure. These glycidyl ether compounds may be used alone or in combination of two or more.

[0060]

Chemical formula

[0061] Among these, 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, or polytetramethylene glycol diglycidyl ether.

[0062] When the reaction ratio of the glycidyl ether compound having the alkylene chain or alkylene ether chain to the anthracenediol is such that the hydroxyl group is the curable reactive group, it is preferably reacted in the range of former / latter = 1.0 / 1.01 to 1.0 / 5.0 (molar ratio), and from the viewpoint of achieving a good balance between 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 the curable reactive group, it is preferably reacted in the range of former / latter = 1.01 / 1.0 to 5.0 / 1.0 (molar ratio), and from the viewpoint of achieving a good balance between the flexibility and heat resistance of the obtained cured product, it is preferably 1.02 / 1.0 to 3.0 / 1.0 (molar ratio).

[0063] The reaction between the glycidyl ether compound having the alkylene chain or alkylene ether chain and the anthracenediol is preferably carried out in the presence of a catalyst. As the catalyst, various ones 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; quaternary ammonium salts such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium chlorides, bromides, iodides, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium chlorides, bromides, iodides; 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. These may be used in combination of two or more kinds of catalysts. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred in terms of the rapid progress of the reaction and the high effect of reducing the amount of impurities. The usage amount of these catalysts is not particularly limited, but it is preferably 0.0001 to 0.01 mol per 1 mol of the hydroxyl group of the anthracenediol. The form of these catalysts is not particularly limited either, and they may be used in the form of an aqueous solution or in a solid form.

[0064] In addition, the reaction between the glycidyl ether compound having the fatty alkylene chain or alkylene ether chain and the 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, propyl alcohol, butyl alcohol, and the like. 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 charged raw materials. These organic solvents can be used alone or in combination of several types. To carry out the reaction rapidly, no solvent is preferred, while from the viewpoint of reducing impurities in the final product, the use of dimethyl sulfoxide is preferred.

[0065] The reaction temperature when carrying out the reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably 100 to 160°C. Further, when the obtained compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol-based compounds such as 2,6-dialkylphenol derivatives, divalent sulfur-based compounds, and phosphite-based compounds containing trivalent phosphorus atoms. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0066] After the completion of the reaction, neutralization or washing with water can also be carried out until the pH value of the reaction mixture becomes 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, when a basic catalyst is used, acidic substances such as hydrochloric acid, sodium monohydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as neutralizing agents. After the neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure and heating to concentrate the product, and the compound can be obtained.

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

[0068] Also, the reaction between the aliphatic divinyl ether and the anthracenediol can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent include aromatic organic solvents such as benzene, toluene, and xylene, ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and alcohol-based organic solvents such as methanol, ethanol, isopropyl alcohol, and normal butanol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the charged raw materials. These organic solvents can be used alone or in combination of several kinds.

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

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

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

[0072] The reaction ratio of the dihalogenated alkylene compound to anthracenediol is preferably in the range of 1.0 / 1.01 to 1 / 5.0 (molar ratio) of the former to the latter. From the viewpoint of achieving a good balance between the flexibility and heat resistance of the resulting cured product, it is preferable that the former / latter is 1.0 / 1.1 to 1.0 / 3.0 (molar ratio).

[0073] The reaction between the anthracenediol and the dihalogenated alkylene compound is preferably carried out in the presence of a basic compound. Various basic compounds can be used as the basic compound. For example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate can be mentioned. Two or more basic compounds may be used in combination. Among them, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferable from the viewpoints of rapid progress of the reaction and high effect of reducing the amount of impurities. The amount of these basic compounds used is not particularly limited, but it is preferably 0.0001 to 10 moles per 1 mole of the hydroxyl group of the anthracenediol. The form of these basic compounds is not particularly limited either, and they may be used in the form of an aqueous solution or in a solid form. In addition, a catalyst can also be used in combination in the reaction, such as tetra-n-butylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydroxide, tetra-n-butylammonium iodide, tetra-ethylammonium chloride, benzyltributylammonium bromide, benzyltriethylammonium bromide, hexadecyltriethylammonium chloride, tetramethylammonium chloride, hexadecyltrimethylammonium chloride and other quaternary ammonium salts, crown ethers, potassium iodide, etc. um salts, crown ethers, potassium iodide, etc. can be used.

[0074] Also, the reaction between the anthracenediol and the dihalogenated alkylene 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, and the like. 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 charged raw materials. These organic solvents can be used alone or in combination of several kinds.

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

[0076] Alternatively, after reacting a diglycidyl ether of an aliphatic dihydroxy compound or an aliphatic divinyl ether or a dihalogenated alkylene compound with an aromatic hydroxy compound to obtain a compound having a hydroxyl group at the terminal, epoxidizing this to make the terminal a glycidyl ether group, and then reacting this with the aforementioned anthracenediol, a curable compound (A) can also be obtained.

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

[0078] The aliphatic divinyl ether is not particularly limited. For example, polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,10-decanediol divinyl ether and other divinyl ethers of linear alkylene groups, and neopentyl glycol Divinyl ethers of branched alkylene groups such as neopentyl glycol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecanedimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether, pentacyclopentadecanediol divinyl ether and other divinyl ethers containing cycloalkane structures can be mentioned. They can be used alone or in combination of two or more.

[0079] Among these, divinyl ethers having a polyether structure or a linear alkylene structure are preferred from the viewpoint of excellent balance between the flexibility and toughness of the resulting cured product. It is most preferable to use 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.

[0080] The dihalogenated alkylene compound is not particularly limited. For example, 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. may be mentioned. It may be used alone or in combination of two or more kinds.

[0081] The aromatic hydroxy compound is not particularly limited. For example, dihydroxybenzenes such as hydroquinone, resorcinol, and catechol; trihydroxybenzenes such as pyrogallol, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene; triphenylmethane-type phenols such as 4,4’,4”-trihydroxytriphenylmethane; dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; tetrafunctional phenols such as 1,1’-methylenebis(2,7-naphthalenediol), 1,1’-binaphthalene-2,2’,7,7’-tetraol, and 1,1’-oxybis(2,7-naphthalenediol) obtained by subjecting dihydroxynaphthalenes to a coupling reaction; 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, 4’-methyl-(1,1’-biphenyl)-3,Biphenols such as 4'-diol, adducts of phenol and dicyclopentadiene, and alicyclic structure-containing phenols such as adducts of phenol and terpene compounds, bis(2-hydroxy-1-naphthyl)methane, and naphthols such as bis(2-hydroxy-1-naphthyl)propane, and so-called Zylok-type phenol resins which are condensation reaction products of phenol and phenylenedimethyl chloride or biphenylenedimethyl chloride can be mentioned. They may be used alone or in combination of two or more. Furthermore, bifunctional phenol compounds having a structure in which a methyl group, a t-butyl group, or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds can also be mentioned. Incidentally, the alicyclic structure-containing phenols and the Zylok-type phenol resins may contain not only bifunctional components but also trifunctional or higher-functional components at the same time, and they may be used as they are, or only bifunctional components may be taken out and used after passing through a purification process such as a column.,

[0082] Among these, biphenols are preferable from the viewpoint of excellent balance between flexibility and toughness when formed into a cured product, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferable from the viewpoint of remarkable performance in imparting toughness. Also, when importance is attached to the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

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

[0084] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound is preferably carried out in the presence of a catalyst. Various catalysts can be used. For example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate; phosphorus compounds such as triphenylphosphine; chlorides, bromides, iodides of quaternary ammonium salts such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium; chlorides, bromides, iodides of quaternary phosphonium salts such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium; 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 of these catalysts may be used in combination. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred because the reaction proceeds rapidly and the effect of reducing the amount of impurities is high. The amount of these catalysts used is not particularly limited, but it is preferably 0.0001 to 0.01 mol per 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound. The form of these catalysts is not particularly limited either, and they may be used in the form of an aqueous solution or in a solid form.

[0085] In addition, the reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, butyl alcohol, and the like. 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 charged raw materials. These organic solvents can be used alone or in combination of several kinds. To carry out the reaction promptly, no solvent is preferred. On the other hand, from the viewpoint of reducing impurities in the final product, the use of dimethyl sulfoxide is preferred.

[0086] The reaction temperature when carrying out the reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably 100 to 160°C. Also, when the coloring of the obtained compound is large, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0087] After completion of the reaction, neutralization or washing with water can be carried out until the pH value of the reaction mixture becomes 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, when a basic catalyst is used, acidic substances such as hydrochloric acid, sodium monohydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as neutralizing agents. After the neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure and heating to concentrate the product, and the compound can be obtained.

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

[0089] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently without using a catalyst, but it can be appropriately used from the viewpoints of raw material selection and increasing the reaction rate. 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 usually in the range of 10 ppm to 1% by mass based on the mass of the divinyl ether compound. At this time, it is preferable to select the type and amount used so as not to cause a nucleophilic addition reaction of the vinyl group to the aromatic ring.

[0090] Also, the reaction between the aliphatic divinyl ether and the aromatic hydroxy compound can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent include aromatic organic solvents such as benzene, toluene, and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohol-based organic solvents such as methanol, ethanol, isopropyl alcohol, and normal butanol. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the charged raw materials. These organic solvents can be used alone or in combination of several types.

[0091] When carrying out the above reaction, the reaction temperature 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 under an oxygen atmosphere is preferred.

[0092] After the completion of the above reaction, when an organic solvent is used, it is removed under heating under reduced pressure. When a catalyst is used, it is deactivated with a deactivator or the like if necessary, and removed by washing with water or filtration operation, whereby the compound can be obtained.

[0093] The reaction ratio of the alkylene dihalide compound to the aromatic hydroxy compound is preferably in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio) of the former to the latter. From the viewpoint of well-balancing the flexibility and heat resistance of the obtained cured product, it is preferable that the former / latter is 1.0 / 1.1 to 1.0 / 3.0 (molar ratio).

[0094] The reaction between the aromatic hydroxy compound and the alkylene dihalide compound is preferably carried out in the presence of a basic compound. As the basic compound, various ones can be used. For example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and alkali metal carbonates such as sodium carbonate, potassium carbonate, etc. can be mentioned. Two or more basic compounds may be used in combination. Among them, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferable in terms of the rapid progress of the reaction and the high effect of reducing the amount of impurities. The amount of these basic compounds used is not particularly limited, but it is preferably 0.0001 to 10 moles per mole of the phenolic hydroxyl group of the aromatic hydroxy compound. The form of these basic compounds is not particularly limited either, and they may be used in the form of an aqueous solution or in a solid form. Also, a catalyst can be used in combination in the reaction, such as tetra-n-butylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydroxide, tetra-n-butylammonium iodide, tetra-ethylammonium chloride, benzyltri butylammonium bromide, benzyltriethylammonium bromide, hexadecyltriethylammonium chloride, tetramethylammonium chloride, hexadecyltrimethylammonium chloride and other quaternary ammonium salts, crown ethers, potassium iodide, etc. can be used.

[0095] Also, the reaction between the aromatic hydroxy compound and the alkylene dihalide 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 charged raw materials. These organic solvents can be used alone or in a mixture of several types.

[0096] When carrying out the reaction, the reaction temperature is usually from room temperature to 150°C, and the reaction time is usually from 1 to 24 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably from room temperature to 100°C.

[0097] There is no particular limitation on the method for the glycidyl etherification reaction of the precursor (intermediate) hydroxy compound obtained above. 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 with an oxidizing agent, etc. Among these, the method using epihalohydrin is preferable because raw materials are easily available and the reaction is easy.

[0098] As a method using epihalohydrin, for example, 0.3 to 100 moles of epihalohydrin are added to 1 mole of the aromatic hydroxyl group of the hydroxy compound obtained above, and 0.9 to 2.0 moles of a basic catalyst per 1 mole of the aromatic hydroxyl group of the hydroxy compound are added all at once or gradually to this mixture, and the reaction is carried out at a temperature of 20 to 120°C for 0.5 to 10 hours. The larger the excess amount of epihalohydrin added, the closer the resulting epoxy resin is to the theoretical structure, and the formation of secondary hydroxyl groups caused by the reaction between unreacted aromatic hydroxyl groups and epoxy groups can be suppressed. From this viewpoint, it is preferably in the range of 2.5 to 100 equivalents. This basic catalyst may be solid or its aqueous solution may be used. When using an aqueous solution, it is added continuously, and water and epihalohydrin are continuously distilled out from the reaction mixture under reduced pressure or normal pressure, and further separated to remove water and continuously return epihalohydrin to the reaction mixture.

[0099] When reacting epihalohydrin, an accelerator such as a quaternary ammonium salt may be used in combination for the purpose of improving the reaction rate. Various quaternary ammonium salts can be used. For example, tetra-n-butylammonium bromide, benzyltriethylammonium chloride, cetyltrimethylammonium bromide, cetylpyridinium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium hydroxide, tetra-n-butylammonium iodide, tetra-ethylammonium chloride, benzyltributylammonium bromide, ben zyltriethylammonium bromide, hexadecyltriethylammonium chloride, tetramethylammonium chloride, hexadecyltrimethylammonium chloride, etc. can be mentioned.

[0100] In industrial production, when starting the production of epoxy resin, all of the charged epihalohydrin is newly used in the first batch. However, after the second batch and later, it is preferable to use a combination of epihalohydrin recovered from the crude reaction product and new epihalohydrin corresponding to the amount consumed and lost in the reaction. At this time, the epihalohydrin to be used is not particularly limited. For example, epichlorohydrin, epibromohydrin, etc. can be mentioned. Among them, epichlorohydrin is preferable because it is easily available.

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

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

[0103] After washing the reaction products of these glycidylation reactions with water, unreacted epihalohydrin and the organic solvent used in combination are distilled off under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is 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 carry out the reaction. At this time, for the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present.

[0104] When using a phase transfer catalyst, the amount used 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 further, a high-purity resin can be obtained by distilling off solvents such as toluene and methyl isobutyl ketone under heating and reduced pressure.

[0105] By reacting the resin having a glycidyl ether group at the terminal obtained in this way with anthracenediol in the same manner as described above, the curable compound (A) in the present invention can be obtained.

[0106] As the compound (A) represented by the general formula (2), a compound (A) having a curable reactive group as a glycidyl ether group can be obtained by reacting aminoanthracene with the polyglycidyl ether compound. At this time, a preferable polyglycidyl ether compound is a diglycidyl ether compound as described above. For the same reason as above, it is preferable to use a compound having the above-mentioned alkylene chain or alkylene ether chain.

[0107] Examples of the aminoanthracene include the following. As described below, various substituents may be present on the anthracene skeleton, but from the viewpoint of easily achieving the effects of the present invention, it is preferable that the substituent has no reactivity.

[0108]

Chemical formula

[0109] The reaction ratio of the glycidyl ether compound to the aminoanthracene is preferably in the range of 1.01 / 1.0 to 5.0 / 1.0 (molar ratio) of the former to the latter, and from the viewpoint of well-balancing the flexibility and heat resistance of the obtained cured product, it is preferably 1.02 / 1.0 to 3.0 / 1.0 (molar ratio).

[0110] The reaction between the glycidyl ether compound and the aminoanthracene is preferably carried out in the presence of a catalyst. As the catalyst, various ones 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; chlorides, bromides, iodides of quaternary ammonium salts such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium; chlorides, bromides, iodides of quaternary phosphonium salts such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium; 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. These may be used in combination of two or more kinds of catalysts. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferable from the viewpoints that the reaction proceeds rapidly and the effect of reducing the amount of impurities is high. The usage amount of these catalysts is not particularly limited, but it is preferably 0.0001 to 0.01 mol per 1 mol of the glycidyl ether group of the glycidyl ether compound. The form of these catalysts is not particularly limited either, and they may be used in the form of an aqueous solution or in a solid form.

[0111] In addition, the reaction between the glycidyl ether compound and the 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, propyl alcohol, butyl alcohol, and the like. 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 charged raw materials. These organic solvents can be used alone or in combination of several types. To carry out the reaction rapidly, no solvent is preferred, while the use of dimethyl sulfoxide is preferred from the viewpoint of reducing impurities in the final product.

[0112] When carrying out the reaction, the reaction temperature is usually 50 to 160°C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably 100 to 130°C. Further, when the obtained compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0113] After completion of the reaction, neutralization or washing with water can be carried out until the pH value of the reaction mixture becomes 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, when a basic catalyst is used, acidic substances such as hydrochloric acid, sodium monohydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as neutralizing agents. After the neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure and heating to concentrate the product, and the compound can be obtained.

[0114] By reacting a compound having an anthracene structure with a diglycidyl ether group at the terminal thus obtained with a compound having two or more hydroxyl groups, a compound having a curable functional group (a) as a hydroxyl group can be obtained.

[0115] Further, as the compound (A) represented by the general formula (3), an anthracene-containing compound containing a hydroxyl group as described below is used as a raw material, and in the same manner as above, by reacting with a polyglycidyl ether compound, a compound (A) having a curable reaction group as a glycidyl ether group can be obtained. At this time, a preferable polyglycidyl ether compound is a diglycidyl ether compound as described above, and for the same reason as above, it is preferable to use a compound having the above-mentioned alkylene chain or alkylene ether chain.

[0116]

Chemical formula

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

[0118] Further, as the compound (A) represented by the general formula (3), an anthracene-containing compound containing an epoxy group as described below is used as a raw material, and in the same manner as above, by reacting with an aromatic hydroxy compound, a compound (A) having a curable reaction group as a hydroxy group can be obtained. At this time, a preferable aromatic hydroxy compound is bisphenols as described above, and for the same reason as above, bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are preferable. Also, when emphasizing the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

[0119]

Chemical formula

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

[0121] The cured product which is one embodiment of the present invention includes a reversible bond by a Diels - Alder reaction between the anthracene structure in the curable compound (A) described above and a compound (B) having a parent diene structure. The compound (B) having the parent diene structure may be monofunctional, but is preferably bifunctional or more for imparting performance to the cured product.

[0122] The reversible bond by the Diels - Alder reaction is a reaction in which a conjugated diene and a parent diene undergo an addition reaction to form a six - membered ring. Since the Diels - Alder reaction is an equilibrium reaction, a Retro - Diels - Alder reaction occurs at a predetermined temperature and dissociation (depolymerization) takes place. Since this reversibility is maintained even after the cured product (three - dimensional cross - linked body) is formed, when mechanical energy such as a scratch or an external force is applied to the cured product, the C - C bond of the Diels - Alder reaction unit has a lower bond energy compared to a normal covalent bond, so the C - C bond of the Diels - Alder reaction unit is preferentially cleaved. However, the C - C bond of the Diels - Alder reaction unit moves the equilibrium in the bonding direction in a temperature region lower than the dissociation temperature, so it is considered that an adduct (Diels - Alder reaction unit) is formed again, enabling repair of scratches and remolding.

[0123] The compound (B) containing the parent diene structure is not particularly limited, and examples thereof include compounds having a maleimide group, an acryloyl group, a vinyl ketone group, an acetylene group, an allyl group, a diazo group, a nitro group, a benzoquinone skeleton, etc. Among these, from the viewpoint of the balance between the reactivity when used as a curable resin composition and the easy disassembly and remoldability of the cured product, it is preferable to use a compound having a maleimide group. Also, from the viewpoint of being able to further exhibit the effect of remoldability, it is preferable that the compound has two or more maleimide groups in one molecule.

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

[0125]

Chemical formula

[0126] The above n3, n5, n6, n7, n8, n9 are average values of the number of repetitions, 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.

[0127] In addition, each of the compounds having a maleimide group independently has a hydrogen atom, a halogen atom, an alkoxy group, an aralkyl-oxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group as a substituent. Further, in the structure of the compounds listed in the above formula, the alkoxy group, the aralkyl-oxy group, the aryloxy group, the carboxy group, the alkyloxycarbonyl group, the aryloxycarbonyl group, the alkyl group, the cycloalkyl group, the aralkyl group and the aryl group include those in which various substituents are further bonded to the carbon atoms they have.

[0128] The curable resin composition which is one embodiment of the present invention essentially comprises the above curable compound (A), a compound (B) containing a parent diene structure, and a compound (C) having reactivity with the curable functional group (a). At this time, the compound (A) and the compound (B) may be reacted in advance and then subjected to a curing reaction with the compound (C), but from the viewpoint of easy handling, it is preferable to react using the compounds (A) to (C) simultaneously.

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

[0130] When the curable functional group at the terminal is a hydroxyl group, examples of the compound (C) include a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resol resin, an epoxy resin, an isocyanate compound, an azide compound, a compound containing a double bond such as an alkenyl ether group, an acid anhydride, hexamethylenetetramine and its modified products, an oxazoline compound, etc., which are substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Among them, from the viewpoint of good curability and easy handling, an epoxy resin is preferably used.

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

[0132] Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethyl benzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxy guanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are acyloxymethylated, etc.

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

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

[0135] The resol resin is, for example, a polymer obtained by reacting a phenolic hydroxyl group-containing compound such as phenol, alkylphenol such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A and bisphenol F, naphthol, dihydroxynaphthalene, etc. with an aldehyde compound under alkaline catalyst conditions.

[0136] The epoxy resin is, for example, liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc., brominated epoxy resins such as brominated phenol novolak type epoxy resin, solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak 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, naphthylene ether type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resin, etc. These can be used alone or in combination of two or more, and it is preferably selected and used variously according to the intended use and physical properties of the cured product, etc.

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

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

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

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

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

[0142] Examples of the curing agent that can be used herein 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.

[0143] Examples of the amine compound 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, etc.;

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

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

[0146] 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. can be mentioned.

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

[0148] Examples of the phenolic hydroxyl group-containing compound include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; phenol novolak resins; cresol novolak resins; aromatic hydrocarbon formaldehyde resin-modified phenol resins; dicyclopentadiene phenol addition type resins; phenol aralkyl resins (Zylok resins); naphthol aralkyl resins; trimethylolmethane resins; tetraphenylol ethane resins; naphthol novolak resins; naphthol-phenol co-condensed novolak resins; naphthol-cresol co-condensed novolak resins; biphenyl-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by bismethylene groups); biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol nuclei are linked by bismethylene groups); aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, etc.); and alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde).

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

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

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

[0152] When using these curing agents, the curing agent may be used alone or two or more kinds may be mixed. In addition, in applications such as underfill materials and general paint applications, it is preferable to use the amine-based compound, carboxylic acid-based compound, and / or acid anhydride-based compound. Also, in applications such as adhesives and flexible printed circuit boards, an amine-based compound, particularly dicyandiamide, is preferable from the viewpoints of workability, curability, and long-term stability. Further, in applications for semiconductor encapsulation materials, a solid type phenolic compound is preferable from the viewpoint of the heat resistance of the cured product. Also, in battery applications, aliphatic amines and thiol compounds are preferable from the viewpoint of low-temperature curing.

[0153] Also, when using an epoxy resin, it may contain a curing accelerator. Various curing accelerators can be used. For example, urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, metal organic salts, Lewis acids, amine complex salts, etc. can be mentioned. When used for adhesive applications, urea compounds, especially 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), are preferred because of their excellent workability and low-temperature curability. When used for semiconductor encapsulation materials, triphenylphosphine is preferred among phosphorus-based compounds, and 1,8-diazabicyclo-[5.4.0]-undecene is preferred among tertiary amines because of their excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc.

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

[0155] Examples of the imidazole include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 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 isocyanurate adduct, 2-methylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, and the like.

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

[0157] Examples of the urea compound include 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.

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

[0159] Examples of the amine compound 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;

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

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

[0162] 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. are included.

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

[0164] Examples of the phenolic hydroxyl group-containing compound include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; phenol novolak resins; cresol novolak resins; aromatic hydrocarbon formaldehyde resin-modified phenol resins; dicyclopentadiene phenol addition type resins; phenol aralkyl resins (zylok resins); naphthol aralkyl resins; trimethylolmethane resins; tetraphenylol ethane resins; naphthol novolak resins; naphthol-phenol co-condensed novolak resins; naphthol-cresol co-condensed novolak resins; biphenyl-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by bismethylene groups); biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol nuclei are linked by bismethylene groups); aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, etc.); and alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde).

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

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

[0167] As the thiol compound, it is preferably one containing two or more thiol groups in one molecule. For example, 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc. can be mentioned.

[0168] When using these curing agents, the curing agent may be used alone or two or more kinds may be mixed. In addition, in applications such as underfill materials and general paint applications, it is preferable to use the amine-based compound, carboxylic acid-based compound, or acid anhydride-based compound. Also, in applications such as adhesives and flexible printed circuit boards, an amine-based compound, particularly dicyandiamide, is preferable from the viewpoints of workability, curability, and long-term stability. Further, in semiconductor encapsulation material applications, a solid type phenolic compound is preferable from the viewpoint of the heat resistance of the cured product. Also, in battery applications, aliphatic amines and thiol compounds are preferable from the viewpoint of low-temperature curing.

[0169] The concentration of the reversible bond in the curable resin composition of the present invention is preferably 0.10 mmol / g or more with respect to the total mass of the curable components in the curable resin composition. According to such a configuration, the easy disassembly property, reparability, and reshaping property of the cured product obtained from the curable resin composition are all further improved. The concentration of the aforementioned reversible bond is more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. The concentration of the reversible bond of the present invention can be appropriately selected according to the glass transition temperature and the like defined at the tanδ peak top of the dynamic viscoelasticity measuring instrument (DMA) of the target cured product. For example, when using the glass transition temperature as a reference, if the glass transition temperature of the cured product is near room temperature, even in the low-concentration side of the preferred range, sufficient reparability and reshaping property functions are likely to be exhibited. On the other hand, if the glass transition temperature of the target cured product exceeds 100°C as a reference, the functions are likely to be exhibited on the high-concentration side of the preferred range. However, in the temperature region exceeding the glass transition temperature measured by DMA, generally the molecular mobility is high, and even when the concentration of the phenolic hydroxyl group-containing compound is low, sufficient reparability and reshaping property functions are likely to be exhibited. Therefore, for example, by appropriately adjusting the aging temperature for repair and the heating temperature for reshaping in a timely manner, the expression effect of the reparability and reshaping property functions can be adjusted. Thus, the relationship between the glass transition temperature of the cured product and the concentration of the reversible bond is not limited to these.

[0170] As the curable resin composition of the present invention, since it becomes a curable resin composition excellent in curability, mechanical strength, heat resistance, etc. in the cured product, an epoxy resin represented by the following formula (4) and having an epoxy equivalent of 500 to 10,000 g / eq may be used. Particularly when the terminal curable functional group is a hydroxyl group, the following epoxy resin may be used as the aforementioned compound (III).

[0171]

Chemical formula

[0172]

Chemical formula

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

[0174] The epoxy resin represented by the general formula (4) may be used alone or in combination to form a curable resin composition. However, from the viewpoint of further imparting flexibility to the cured product and easily exhibiting easy disassembly properties, it is more preferable to further use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq in combination.

[0175] The epoxy resin that can be used in combination only needs to have an epoxy equivalent in the range of 100 to 300 g / eq, and its structure is not limited. For example, liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, brominated epoxy resins such as brominated phenol novolak type epoxy resin, solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak 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, naphthylene ether type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resin, etc. can be mentioned. They may be used alone or in combination of two or more, and it is preferable to select and use variously according to the intended use and the physical properties of the cured product.

[0176] Among these, it is preferable 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, and tetramethylbiphenyl type epoxy resin. Among bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD type epoxy resin, it is particularly preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq.

[0177] The usage ratio of the epoxy resin represented by the general formula (4) and the epoxy resin having an epoxy equivalent of 100 to 300 g / eq is not particularly limited. However, from the viewpoint of easy phase separation in the cured product, the mass ratio of the former to the latter is 97:3 to 3:97, preferably 10:90 to 90:10, and particularly preferably 80:20 to 20:80. By phase separation in the cured product, a sea-island structure is formed, and both the adhesiveness and stress relaxation ability of the cured product are achieved. In particular, a high adhesive force is exhibited in a wide temperature range, and there is an effect of reducing the molding shrinkage rate before and after heat curing of the resin composition.

[0178] In addition, the curable resin composition of the present invention may be used in combination with other thermosetting resins and thermoplastic resins as long as the effects of the present invention are not impaired.

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

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

[0181] Among these cyanate ester resins, in terms of obtaining a cured product with particularly excellent heat resistance, it is preferable to use bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthylene ether type cyanate ester resin, novolac type cyanate ester resin. In terms of obtaining a cured product with excellent dielectric properties, dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable.

[0182] The resin having a benzoxazine structure is not particularly limited. For example, 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 adduct type resin, formalin, and aniline, reaction products of phenolphthalein, formalin, and aniline, reaction products of diphenyl sulfide, formalin, and aniline, etc. can be mentioned. These may be used alone or in combination of two or more kinds.

[0183] The active ester resin is not particularly limited, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The 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. Particularly 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, phloroglucin, benzenetriol, dicyclopentadiene-phenol addition type resin, etc.

[0184] Specific examples of the active ester resin include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated phenol novolacs, active ester resins that are benzoylated phenol novolacs, etc. Among them, in terms of excellent improvement in peel strength, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred.

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

[0186] More specifically, the various novolak resins include polymers obtained by reacting phenolic 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 acid catalyst conditions.

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

[0188] 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 polyolefin resin, and the like. These thermoplastic resins can be used alone or in combination of two or more.

[0189] When using these other resins, the blending ratio of the phenolic hydroxyl group-containing compound of the present invention and the other resin can be arbitrarily set according to the application. However, from the viewpoint of not inhibiting the restorability and remoldability achieved by the present invention, it is preferable that the other resin is in a ratio of 0.5 to 100 parts by mass with respect to 100 parts by mass of the phenolic hydroxyl group-containing compound of the present invention.

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

[0191] When the curable resin composition of the present invention is used for applications that require high flame retardancy, a non-halogen-based flame retardant that substantially does not contain a halogen atom may be blended.

[0192] Examples of the non-halogen-based flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic-based flame retardants, and organometallic salt-based flame retardants. There are no particular restrictions on their use, and they may be used alone, or a plurality of flame retardants of the same type may be used, or different types of flame retardants may be used in combination.

[0193] Both inorganic and organic phosphorus-based flame retardants can be used. Examples of the inorganic compound 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.

[0194] Further, it is preferable that the red phosphorus is surface-treated for the purpose of preventing hydrolysis or the like. Examples of the surface treatment method include (i) a method of coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) a method of coating with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide and a thermosetting resin such as a phenol resin; (iii) a method of double coating with a thermosetting resin such as a phenol resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc.

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

[0196] The compounding amount of these phosphorus-based flame retardants is appropriately selected depending on the type of the phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, when red phosphorus is used as a non-halogen-based flame retardant in 100 parts by mass of a resin composition containing all of a non-halogen-based flame retardant and other fillers and additives, it is preferably compounded in the range of 0.1 part by mass to 2.0 parts by mass. When an organic phosphorus compound is used, 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.

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

[0198] Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, etc., and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred.

[0199] Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, etc. In addition, for example, (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate, (2) condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, etc. with melamines such as melamine, benzoguanamine, acetoguanamine, formoguanamine, etc. and formaldehyde, (3) mixtures of the condensates of (2) with phenolic resins such as phenol formaldehyde condensates, (4) those obtained by further modifying (2) and (3) with tung oil, isomerized linseed oil, etc.

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

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

[0202] When using the nitrogen-based flame retardant, metal hydroxides, molybdenum compounds, etc. may be used in combination.

[0203] The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom. Examples thereof include silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone-based flame retardant is 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, it is preferably blended in the range of 0.05 to 20 parts by mass in 100 parts by mass of the resin composition containing all of the non-halogen-based flame retardant and other fillers and additives. When using the silicone-based flame retardant, a molybdenum compound, alumina, etc. may be used in combination.

[0204] Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glasses, etc.

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

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

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

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

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

[0210] Examples of the low melting point glass include glassy compounds such as Seepley (manufactured by Boxi Brown), 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, and lead borosilicate system.

[0211] The compounding amount of the inorganic flame retardant is appropriately selected depending on 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 of the non-halogen-based flame retardant and other fillers and additives, it is preferably compounded in the range of 0.05 part by mass to 20 parts by mass, and more preferably compounded in the range of 0.5 part by mass to 15 parts by mass.

[0212] Examples of the organometallic salt-based flame retardant include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, and a compound in which a metal atom and an aromatic compound or a heterocyclic compound are ionically bonded or coordinately bonded.

[0213] The compounding amount of the organometallic salt-based flame retardant is appropriately selected depending on 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 of the non-halogen-based flame retardant and other fillers and additives, it is preferably compounded in the range of 0.005 part by mass to 10 parts by mass.

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

[0215] Examples of inorganic fine particles include, for those with excellent heat resistance, alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine amorphous silica, etc.); for those with excellent thermal conductivity, boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.; for those with excellent conductivity, metal fillers and / or metal-coated fillers using simple metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); for those with excellent barrier properties, minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, etc. and potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; for those with a high refractive index, barium titanate, zirconium oxide, titanium oxide, etc.; for those exhibiting photocatalytic properties, photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of the above metals, their oxides, etc.; for those with excellent wear resistance, metals such as silica, alumina, zirconia, magnesium oxide, etc., and their composites and oxides, etc.; for those with excellent conductivity, metals such as silver, copper, etc., tin oxide, indium oxide, etc.; for those with excellent insulation properties, silica, etc.; for those with excellent ultraviolet shielding properties, titanium oxide, zinc oxide, etc. These inorganic fine particles may be appropriately selected according to the application and may be used alone or in combination of multiple types. Also, since the above inorganic fine particles have various properties other than those listed in the examples, they may be selected according to the application in a timely manner.

[0216] For example, when using silica as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdered silica and colloidal silica can be used. Examples of commercially available powdered silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Chemical Ltd., SG Flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

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

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

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

[0220] As the titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used. For example, anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, etc. can be used. Furthermore, particles designed to respond to visible light by doping a hetero element into the crystal structure of titanium oxide can also be used. As the element to be doped into titanium oxide, anion elements such as nitrogen, sulfur, carbon, fluorine, phosphorus, etc. and cation elements such as chromium, iron, cobalt, manganese, etc. are preferably used. Also, as the form, powders, sols or slurries dispersed in an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by Tayca Corporation, etc. Examples of commercially available slurry-type titanium oxide fine particles include TKD-701 manufactured by Tayca Corporation, etc.

[0221] The curable resin composition of the present invention may further contain a fibrous substrate. The fibrous substrate is not particularly limited, but those used in fiber-reinforced resins are preferred, and examples include inorganic fibers and organic fibers.

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

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

[0224] Among them, carbon fiber and glass fiber are preferable because they have a wide range of industrial applications. Only one of these may be used, or a plurality of types may be used simultaneously.

[0225] The fibrous substrate may be an aggregate of fibers, and the fibers may be continuous, discontinuous, woven, or non-woven. Further, it may be a fiber bundle in which the fibers are aligned in one direction, or a sheet-like structure in which the fiber bundles are arranged side by side. Further, it may have a three-dimensional shape in which the aggregate of fibers has a thickness.

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

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

[0228] The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include acrylic polymers (Flowlen WK-20: Kyoeisha Chemical Co., Ltd.), amine salts of special modified phosphoric esters (HIPLAAD ED-251: Kusumoto Chemicals, Ltd.), and modified acrylic block copolymers (DISPERBYK 2000; BYK-Chemie).

[0229] The resin composition of the present invention may have other formulations. For example, 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. can be mentioned.

[0230] By curing the resin composition of the present invention, a cured product can be obtained. When curing, curing may be performed at room temperature or by heating. When performing thermal curing, it may be cured by a single heating, or it may be cured through a multi-step heating process.

[0231] In addition, the curable resin composition of the present invention can also be cured with active energy rays. In that case, a photo cationic polymerization initiator may be used as the polymerization initiator. As the active energy rays, visible light, ultraviolet rays, X-rays, electron beams, etc. can be used.

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

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

[0234] The curable resin composition of the present invention dissolves the aforementioned curable compound, compound (III) capable of reacting therewith, and further, if necessary, the aforementioned optional curing agent, filler, fibrous substrate, dispersion medium, and resin other than the aforementioned various compounds in a dispersion medium such as the aforementioned organic solvent. After dissolution, the solvent is distilled off, and the curable resin composition can be obtained by drying under reduced pressure using a vacuum oven or the like. Further, the curable resin composition of the present invention may be in a state where the aforementioned constituent materials are uniformly mixed. At this time, it is preferably uniformly mixed with a mixer or the like. The blending ratio of each constituent material can be appropriately adjusted according to the properties of the desired cured product, such as mechanical strength, heat resistance, reparability, and remoldability. Further, in the production of the curable resin composition, the mixing order of the specific constituent materials is not particularly limited.

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

[0236] The cured product of the present invention can maintain good mechanical strength by expressing an appropriate crosslink density as described above. Further, when mechanical energy such as a scratch or external force is applied to the cured product of the present invention, the reversible bond is broken, so that easy disassembly is exhibited. Furthermore, since the equilibrium moves in the bonding direction, it is considered that an adduct is formed again, enabling repair of scratches and remolding.

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

[0238] The curable resin composition of the present invention and the cured product produced by the curable resin composition are excellent in both easy disassembly and reparability, and have remoldability, and are useful for the following applications.

[0239] The cured product of the curable resin of the present invention can be made into a laminate by laminating it with a substrate. As the substrate of the laminate, inorganic materials such as metals and glass, organic materials such as plastics and wood, etc. may be used appropriately according to the application, and it may also be the shape of the laminate, such as a flat plate, a sheet shape, or may have a three-dimensional structure, or may be three-dimensional. It may have any shape according to the purpose, such as having a curvature on the whole or a part. Also, there are no restrictions on the hardness, thickness, etc. of the substrate. Further, it may be a multilayer laminate formed by laminating a first substrate, a layer made of the cured product of the curable resin composition of the present invention, and a second substrate in this order. Since the curable resin composition of the present embodiment is excellent in adhesiveness, it can be suitably used as an adhesive for bonding the first substrate and the second substrate. Also, the cured product of the curable resin of the present invention may be used as a substrate, and further, the cured product of the present invention may be laminated.

[0240] Also, since the cured product of the curable resin of the present invention can relieve stress, it can be particularly suitably used for bonding dissimilar materials. For example, even in a laminate of dissimilar materials where the substrate is a metal and / or a metal oxide and the second substrate is a plastic layer, the adhesive strength is maintained due to the stress relaxation ability of the cured product of the present invention.

[0241] In a laminate formed by laminating a cured product of the present invention and a substrate, the layer containing the cured product may be formed directly on the substrate by coating or molding, or a pre-formed one may be laminated. When directly coating, the coating method is not particularly limited, and examples include spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, screen printing method, inkjet method, etc. When directly molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, etc. When laminating a molded composition, an uncured or semi-cured composition layer may be laminated and then cured, or a layer containing a cured product obtained by completely curing the composition may be laminated on the substrate. Further, a precursor that can serve as a substrate may be coated on the cured product of the present invention and cured to effect lamination, or the precursor that can serve as a substrate or the composition of the present invention may be adhered in an uncured or semi-cured state and then cured. The precursor that can serve as a substrate is not particularly limited, and examples include various curable resin compositions.

[0242] The cured product obtained 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 primer for metals. Examples of the metal include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and materials obtained by combining these. Examples of the metal oxide include single oxides and / or composite oxides of these metals. Since it has excellent adhesion particularly to iron, copper, and aluminum, it can be preferably used as an adhesive for iron, copper, and aluminum.

[0243] The curable resin composition of the present invention can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering, electronics, aircraft, and space industries. When used as an adhesive for bonding different materials such as between metal and non-metal, this adhesive can maintain high adhesiveness without being affected by changes in temperature environment, and peeling and the like are less likely to occur. In addition to being used for structural members, this adhesive can also be used as an adhesive for general office use, medical use, carbon fiber, cells, modules, and cases of storage batteries, etc. It can be used as an adhesive for optical component bonding, an adhesive for bonding optical discs, an adhesive for printed wiring board mounting, a die bonding adhesive, a semiconductor adhesive such as underfill, an underfill for BGA reinforcement, an anisotropic conductive film, an anisotropic conductive paste, and other adhesives for mounting.

[0244] When the curable resin composition of the present invention has a fibrous substrate and the fibrous substrate is a reinforcing fiber, the curable resin composition containing the fibrous substrate can be used as a fiber-reinforced resin. The method of incorporating the fibrous substrate into the composition is not particularly limited as long as the effects of the present invention are not impaired. Examples of methods for compounding the fibrous substrate and the composition include kneading, coating, impregnating, injecting, and pressing. These methods can be appropriately selected according to the form of the fiber and the use of the fiber-reinforced resin.

[0245] The method for molding the fiber-reinforced resin is not particularly limited. If a plate-shaped product is to be manufactured, the extrusion molding method is common, but it is also possible with a flat press. In addition, it is possible to use an extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, etc. Also, if a film-shaped product is to be manufactured, in addition to the melt extrusion method, the solution casting method can be used. When using a melt molding method, inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, coating molding, etc. can be mentioned. Also, in the case of a resin cured by active energy rays, a cured product can be manufactured using various curing methods using active energy rays. In particular, when a thermosetting resin is the main component of the matrix resin, there is a molding method in which the molding material is prepreged and then pressure-heated by a press or an autoclave. In addition, RTM (Resin Transfer Molding) molding, VaRTM (Vacuum assist Resin Transfer Molding) molding, lamination molding, hand lay-up molding, etc. can be mentioned.

[0246] Since the cured product using the curable resin composition of the present invention has both good heat resistance and reparability and has remoldability, it can be used as a molding material for large cases, motor housings, in-mold injection materials inside the case, gears, pulleys, etc. These may be cured products of resin alone or fiber-reinforced cured products such as glass chips.

[0247] The fiber-reinforced resin can form a state called uncured or semi-cured prepreg. After distributing the product in the prepreg state, final curing may be performed to form a cured product. When forming a laminate, after forming the prepreg, laminating other layers and then performing final curing can form a laminate in which each layer is in close contact, which is preferable. The mass ratio of the composition and the fibrous substrate used at this time is not particularly limited, but usually, it is preferably prepared so that the resin content in the prepreg is 20 to 60% by mass.

[0248] The cured product of the present invention has excellent heat resistance and reparability, and also has reshaping properties, and can be used as a heat-resistant material and an electronic material. In particular, it can be suitably used for semiconductor encapsulants, circuit boards, build-up films, build-up boards, etc., as well as adhesives and resist materials. 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 applications, for example, industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

[0249] Among them, taking advantage of the excellent flexibility of the cured product, it can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering, electronics, aircraft, and space industries. The adhesive of the present invention can maintain high adhesiveness without being affected by changes in the temperature environment even when used for bonding different materials such as between metal and non-metal, and peeling and the like are less likely to occur. In addition to being used for structural members, the adhesive of the present invention can also be used as an adhesive for general office use, medical use, carbon fiber, cells, modules, and cases of storage batteries, etc., and adhesives for bonding optical components, adhesives for bonding optical disks, adhesives for mounting printed wiring boards, die bonding adhesives, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, anisotropic conductive films, anisotropic conductive pastes, and other adhesives for mounting.

[0250] Hereinafter, examples will be given and described for representative products.

[0251] 1. Semiconductor Encapsulation Material As a method for obtaining a semiconductor encapsulant from the resin composition of the present invention, a method of sufficiently melt-mixing the resin composition, a curing accelerator, and compounding agents such as an inorganic filler until uniform using an extruder, kneader, roll, etc. as needed can be mentioned. At that time, fused silica is usually used as the inorganic filler. However, when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, high filling of crystalline silica, alumina, silicon nitride, etc. with a higher thermal conductivity than fused silica, or the use of fused silica, crystalline silica, alumina, silicon nitride, etc. is preferable. The filling rate is preferably in the range of 30 to 95% by mass of the inorganic filler per 100 parts by mass of the curable resin composition. Among them, in order to improve flame retardancy, moisture resistance, solder crack resistance, and reduce the linear expansion coefficient, 70 parts by mass or more is more preferable, and 80 parts by mass or more is even more preferable.

[0252] 2. Semiconductor device As semiconductor package molding for obtaining a semiconductor device from the curable resin composition of the present invention, a method of molding the above semiconductor encapsulant using a casting mold, a transfer molding machine, an injection molding machine, etc., and further heating at 50 to 250 °C for 2 to 10 hours can be mentioned.

[0253] 3. Printed circuit board As a method for obtaining a printed circuit board from the composition of the present invention, a method of laminating the above prepreg by a conventional method, appropriately stacking a copper foil, and thermocompression bonding at 170 to 300 °C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa can be mentioned.

[0254] 4. Flexible substrate As a method for manufacturing a flexible substrate from the crosslinkable resin composition of the present invention, there is a method comprising the following three steps. The first step is a step of applying a crosslinkable resin composition containing a resin component, an organic solvent, etc. to an electrically insulating film using a coater such as a reverse roll coater or a comma coater. The second step is 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 a metal foil to an adhesive (the bonding pressure is preferably 2 to 200 N / cm and the bonding temperature is preferably 40 to 200 ° C) to the electrically insulating film on which the crosslinkable resin composition has been B-staged, using a heating roll or the like. Note that if sufficient adhesion performance is obtained through the above three steps, it may be ended here, but if complete adhesion performance is required, it is preferable to further post-cure under the conditions of 100 to 200 ° C for 1 to 24 hours. The thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 μm.

[0255] 5. Build-up substrate Examples of the method for obtaining a build-up substrate from the composition of the present invention include the following steps. First, a step of applying the above composition appropriately blended with rubber, filler, etc. to a circuit board having a circuit formed thereon using a spray coating method, a curtain coating method, etc., and then curing it (step 1). Then, after perforating a predetermined through-hole portion or the like as necessary, treating it with a roughening agent, forming irregularities by hot washing its surface, and plating a metal such as copper (step 2). Such operations are sequentially repeated as desired to alternately build up a resin insulating layer and a conductor layer of a predetermined circuit pattern (step 3). Note that the perforation of the through-hole portion is performed after the formation of the outermost resin insulating layer. In addition, the build-up substrate of the present invention can also be produced by heat-pressure bonding a copper foil with resin obtained by semi-curing the resin composition on a copper foil to a wiring board having a circuit formed thereon at 170 to 300 ° C to form a roughened surface and omitting the step of plating treatment.

[0256] 6. Build-up Film As a method for obtaining a build-up film from the composition of the present invention, the composition is applied to the surface of a support film (Y) as a base material, and then the organic solvent is dried by heating or blowing hot air, etc. to form a layer (X) of the composition. It can be manufactured by doing so.

[0257] Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. It is preferably used, and it is preferably used at a ratio such that the non-volatile content is 30 to 60% by mass.

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

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

[0260] 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 build-up film is heat cured, it is possible to prevent the adhesion of dust and the like in the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment.

[0261] A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, when the layer (X) is protected by a protective film, after peeling these, the layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch type or a continuous type using a roll. Further, if necessary, the build-up film and the circuit board may be heated (preheated) as necessary before lamination. The lamination conditions preferably have a crimping temperature (lamination temperature) of 70 to 140°C, a crimping pressure of 1 to 11 kgf / cm2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0262] 7. Conductive Paste 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 mentioned. The above conductive paste can be a circuit connection paste resin composition or an anisotropic conductive adhesive depending on the type of conductive particles used.

Examples

[0263] Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The present invention is not limited thereby.

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

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

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

[0267] As a method for calculating the number of repeating units, calculation from appropriate various instrumental analysis results such as GPC molecular weight measurement and FD-MS can be exemplified.

[0268] Example 1 Into 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 64.4 g (0.33 mol) of 2-aminoanthracene (active hydrogen equivalent: 96.6 g / eq) were charged. After heating up to 130°C over 2 hours, the mixture was reacted for 20 hours. Thereafter, 509.4 g of an epoxy resin (Ep-1) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-1) was 1343 g / eq. Since a peak of M+ = 1607 corresponding to the theoretical structure of m = 1 and n = 8 in the following structural formula (Ep-1) was obtained in the mass spectrum of this epoxy resin (Ep-1), it was confirmed that the epoxy resin (Ep-1) contained the target epoxy resin (Ep-1).

[0269] [Chemical formula]

[0270] Example 2 509.4 g (0.19 mol) of the epoxy resin (Ep-1) obtained in Example 1 and 40 g (0.38 mol) of diethanolamine were charged. After heating up to 80°C over 1 hour, the mixture was reacted for 11 hours. Thereafter, 549.4 g of a hydroxy compound (Ph-1) was obtained. Since a peak of M+ = 1817 corresponding to the theoretical structure of m = 1 and n = 8 in the following structural formula (Ph-1) was obtained in the mass spectrum of this hydroxy compound (Ph-1), it was confirmed that the hydroxy compound (Ph-1) contained the target hydroxy compound (Ph-1).

[0271] [Chemical formula]

[0272] Example 3 Into a flask equipped with a thermometer and a stirrer, 203 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei 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 up to 125 °C over 2 hours, the mixture was reacted for 14 hours. Thereafter, 287 g of an epoxy resin (Ep-2) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-2) was 4142 g / eq. From the fact that a peak of M+ = 822 corresponding to the theoretical structure with n = 1 in the following structural formula (Ep-2) was obtained in the mass spectrum of this epoxy resin (Ep-2), it was confirmed that the target epoxy resin (Ep-2) was contained.

[0273]

Chemical formula

[0274] Example 4 Into a flask equipped with a thermometer and a stirrer, 188 g (0.5 mol) of EPICLON 850S (bisphenol type liquid epoxy resin manufactured by DIC Corporation, epoxy equivalent 188 g / eq) and 48.3 g (0.25 mol) of 2-aminoanthracene (active hydrogen equivalent 96.6 g / eq) were charged. After heating up to 125 °C over 2 hours, the mixture was reacted for 14 hours. Thereafter, 225 g of an epoxy resin (Ep-3) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-3) was 510 g / eq. From the fact that a peak of M+ = 874 corresponding to the theoretical structure with n = 1 in the following structural formula (Ep-3) was obtained in the mass spectrum of this epoxy resin (Ep-3), it was confirmed that the target epoxy compound (Ep-3) was contained.

[0275]

Chemical formula

[0276] Example 5 Into a flask equipped with a thermometer, a cooling tube, and a stirrer, 40.0 g (0.10 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei 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 Materials Co., Ltd.) were charged. After heating up to 140 °C over 30 minutes, 0.33 g of a 4% aqueous sodium hydroxide solution was charged. Then, it took 30 minutes to heat up to 150 °C, and the reaction was further carried out at 150 °C for 20 hours. Then, it was cooled to 80 °C, 65 g of methyl isobutyl ketone, 65 g of water, and sodium phosphate in a neutralizing amount were added, and the aqueous layer was removed. Next, the solvent was distilled off under reduced pressure to obtain 60.3 g of an epoxy resin (Ep-4). The epoxy equivalent of the obtained epoxy resin (Ep-4) was 1030 g / eq. Since a peak of M+ = 1005 corresponding to the theoretical structure with m = 1 in the following structural formula (A-1) was obtained in the mass spectrum of this epoxy resin (Ep-4), it was confirmed that the target epoxy resin (Ep-4) was contained.

[0277] [Chemical formula]

[0278] Example 6 Except that 40.0 g (0.10 mol) of diglycidyl ether of 1,12-dodecanediol in Example 5 was changed to 89.0 g (0. 10 mol) of diglycidyl ether of polytetramethylene glycol (「Denacol EX-991L」manufactured by Nagase ChemteX; epoxy equivalent: 445 g / eq), 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. Since 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 in the mass spectrum of this epoxy resin (Ep-5), it was confirmed that the target epoxy resin (Ep-5) was contained.

[0279] [Chemical formula]

[0280] Example 7 41.2 g (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 up to 140 °C over 30 minutes, 0.5 g of a 20% aqueous sodium hydroxide solution was charged. Then, it took 30 minutes to heat up to 150 °C, and the reaction was further carried out at 150 °C for 16 hours. Then, it 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. Next, the solvent was distilled off under reduced pressure, a neutralizing amount of sodium phosphate was added, and 43.1 g of the hydroxy compound (Ph-2) was obtained. The hydroxyl equivalent calculated from the GPC of the obtained hydroxy compound (Ph-2) was 12,840 g / eq. Since a peak of M+ = 1461 corresponding to the theoretical structure of m = 1 of the following structural formula (A-3) was obtained in the mass spectrum of this hydroxy compound (Ph-2), it was confirmed that the target hydroxy compound (Ph-2) was contained.

[0281] [Chemical formula]

[0282] Example 8 Into a flask equipped with a thermometer, a cooling tube, and a stirrer, 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol (“Denacol EX-991L” manufactured by Nagase ChemteX Corporation; 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 up to 140 °C over 30 minutes, 2.6 g of a 4% aqueous sodium hydroxide solution was charged. Then, it took 30 minutes to heat up to 150 °C, 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. Since 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 spectrum for this epoxy resin (Ep-6), it was confirmed that the target epoxy resin (Ep-6) was contained.

[0283] [Chemical formula]

[0284] Example 9 Into 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 Gosei 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 up to 140 °C over 30 minutes, 2.6 g of a 4% aqueous sodium hydroxide solution was charged. Then, it took 30 minutes to heat up to 150 °C, 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. Since a peak of M+ = 838 corresponding to the theoretical structure of m = 1 in the following structural formula (Ep-7) was obtained by mass spectrum for this epoxy resin (Ep-7), it was confirmed that the target epoxy resin (Ep-7) was contained.

[0285] [Chemical]

[0286] Example 10 89 g (0.05 mol) of the epoxy resin (Ep-7) obtained in Example 9 and 12.0 g (0.053 mol) of bisphenol A (hydroxyl equivalent weight 114 g / eq) were charged, and after heating up to 140 °C over 30 minutes, 1.0 g of a 20% aqueous sodium hydroxide solution was charged. Then, it took 30 minutes to heat up to 150 °C, and the reaction was further carried out at 150 °C for 12 hours. Then, the neutralizing amount of sodium phosphate was added to obtain 95 g of a hydroxy compound (Ph-3). The hydroxyl equivalent weight calculated from the GPC of the obtained hydroxy compound (Ph-3) was 19,200 g / eq. Since a peak of M+ = 1294 corresponding to the theoretical structure of m = 1 of the following structural formula (Ph-3) was obtained in the mass spectrum of this hydroxy compound (Ph-3), it was confirmed that the hydroxy compound (Ph-3) contained the target hydroxy compound (Ph-3).

[0287] [Chemical]

[0288] Synthesis Example 1 9-(4-Hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (BIP-ANT manufactured by Asahi Organic Materials Co., Ltd.) 56.4 g (0.15 mol), 56.4 g of methanol, and 222.0 g (2.4 mol) of epichlorohydrin were put into a flask equipped with a thermometer, a condenser, and a stirrer, dissolved at 60 °C, and then 25.0 g (0.30 mol) of 48% caustic soda was added dropwise from a dropping funnel over 30 minutes, and the reaction was carried out at 60 °C for 9 hours. Then, it was washed 4 times with 114 g of pure water, and the organic layer was concentrated under reduced pressure to obtain a resinous target product. The resinous product cooled by standing was crushed in a mortar, stirred 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 weight of the obtained epoxy resin (Ep-8) was 248 g / eq.

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

[0290] [Chemical formula]

[0291] Example 12 While purging with nitrogen gas, 100 g of the hydroxy compound Ph-4 obtained in Synthesis Example 11, 215 g (2.3 mol) of epichlorohydrin, and 65 g of n-butanol were added to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer and dissolved. After raising the temperature to 65 °C, the pressure was reduced to the pressure at which azeotropy occurs, and 35.4 g (0.43 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Next, stirring was continued for 0.5 hour under the same conditions. During this time, the distillate distilled by azeotropy was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer into the reaction system. Thereafter, unreacted epichlorohydrin was distilled off by distillation under reduced pressure. 90 g of methyl isobutyl ketone and 90 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Furthermore, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 °C for 2 hours, and then washing with 60 g of water was repeated 3 times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropy, and after passing through fine filtration, the solvent was distilled off under reduced pressure to obtain 113 g of the epoxy resin (Ep-9). The epoxy equivalent weight of the obtained epoxy resin (Ep-9) was 356 g / eq.

[0292]

Chem.

[0293] Synthesis Example 2 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol (“Denacol EX-991L” manufactured by Nagase ChemteX Corporation; epoxy equivalent: 445 g / eq) and 171 g (0.75 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq) were added to a flask equipped with a thermometer and a stirrer. After heating up to 140° C. over 30 minutes, 3.1 g of a 4% aqueous sodium hydroxide solution was added. Then, it took 30 minutes to heat up to 150° C., and the reaction was further carried out at 150° C. for 16 hours. Then, sodium phosphate in a neutralizing amount was added to obtain 616 g of a hydroxy compound represented by the following formula (Ph-2). Since a peak of M+=1380 corresponding to the theoretical structure of m1 = 1 and n1 = 11 in the following formula was obtained in the mass spectrum of the hydroxy compound, it was confirmed that the hydroxy compound contained a PTMG (polytetramethylene ether glycol) type (BPA: bisphenol A) hydroxy compound. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-5) was 1080 g / eq, the average value of n1 was 10.6, and the average value of m1 was 0.76

[0294]

Chem.

[0295] Synthesis Example 3 While purging with nitrogen gas, 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 to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer and dissolved. After heating up to 65° C., the pressure was reduced to the pressure at which azeotropy occurs, and 6.66 g (0.08 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours Next, stirring was continued for 0.5 hours under the same conditions. During this period, the distillate distilled off by azeotropy was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer into the reaction system. Thereafter, unreacted epichlorohydrin was distilled off by vacuum distillation. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Furthermore, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution, and after reacting at 80 °C for 2 hours, washing with 50 g of water was repeated 3 times until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through precision filtration, the solvent was distilled off under reduced pressure to obtain 190 g of an epoxy resin (Ep-10). The epoxy equivalent of the obtained epoxy resin (Ep-10) was 1192 g / eq. Since 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 in the mass spectrum for the epoxy resin (Ep-10), it was confirmed that it contained a PTMG type (BPA) epoxy resin.

[0296]

Chemical formula

[0297] Preparation of Composition and Cured Product Using each compound according to the formulation in the table (the numbers in the table are based on mass), they were uniformly mixed with a mixer ("Avatori Rentaaro ARV-200" manufactured by Shinky Co., Ltd.) to obtain a curable resin composition. This curable resin composition was sandwiched between aluminum mirror plates ("JIS H 4000 A1050P" manufactured by Engineering Test Services Co., Ltd.) using a silicon tube as a spacer, and heat curing was carried out under predetermined conditions to obtain a cured product with a thickness of 0.7 mm.

[0298] <Tensile elongation rate> The obtained cured product was punched into a dumbbell shape (JIS K 7161-2-1BA) using a punching blade, and this was used as a test piece. The tensile test of this test piece was conducted in accordance with JIS K 7162-2 using a tensile testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation), and the elongation at break at a measurement environment of 23°C was evaluated (test speed: 2 mm / min).

[0299] <Reforming test> The prepared cured product was cryogenically pulverized. 0.07 g of the pulverized cured product was placed in a mold with a size of 10 mm square and a thickness of 0.5 mm, and vacuum pressing was performed under predetermined conditions. The appearance of the obtained cured product was visually observed. The judgment criteria are as follows. A: The joint disappeared and the cured product was integrated. B: The joint could be partially visually confirmed, but the cured product was integrated. C: It had a solidified shape and broke apart when a light force was applied.

[0300] <Repair test> The prepared cured product was cut with a razor, and after bringing the resulting fracture surfaces into contact, aging was performed at 150°C for 24 hours in a dryer. After taking it out of the dryer, the presence or absence of bonding between the cross-sections of the cured product was visually confirmed. The judgment criteria are as follows. A: It bonded, and the bonded part did not dissociate even when the cured product was bent at 90° B: It bonded, and the bonded part dissociated when the cured product was bent. C: It did not bond.

[0301]

Table 1

[0302]

Table 2

[0303]

Table 3

[0304]

Table 4

[0305]

Table 5

[0306]

Table 6

[0307]

Table 7

[0308] Note that each formulation shown in the table is as follows. E-850S: Bisphenol A liquid epoxy resin (manufactured by DIC Corporation, epoxy equivalent 188 g / eq) TD-2131: Phenol novolac type phenol resin (manufactured by DIC Corporation, hydroxyl equivalent 104 g / eq) BMI-TMH: 1,6’-bismaleimide-(2,2,4-trimethyl)hexane DICY: Dicyandiamide (manufactured by Mitsubishi Chemical Corporation “DICY7”) DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea) (manufactured by DIC Corporation “B-605-IM”) TPP: Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)

Claims

1. A curable compound represented by any one of the following general formulas (1) to (3), A compound (B) containing a dienephilic structure; a compound (C) having reactivity with a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, which is the curable functional group (a) in the curable compound (A); A curable resin composition comprising: A curable resin composition, wherein a concentration of reversible bonds by Diels-Alder reaction relative to a total mass of the curable components in the curable resin composition is in the range of 0.10 to 3.00 mmol / g. 【Chemistry 1】 In the formulas (1) to (3), R represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group; Z １ is as follows (Z １ -1) to (Z １ -7) 【Chemistry 2】 [Formula (Z １ -1), (Z １ -2), (Z １ -3), (Z １ -4), (Z １ -5), (Z １ -6), (Z １ -7), among Each Ar is independently a structure having an unsubstituted or substituted aromatic ring, R １１ , R １２ each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R １３ , R １４ is a hydrogen atom or a methyl group, R １ , R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group, Each R' is independently a divalent hydrocarbon group having 2 to 12 carbon atoms; n is the average value of the repeating units and is from 0.5 to 10; n1 is an integer from 4 to 16, n2 is the average value of the repeating units and is from 2 to 30. Expression (Z １ X in formula (Z １ -1-1), and Y is a structural unit represented by the following general formula (Z １ -1-2) is a structural unit represented by 【Chemistry 3】 <Formula (Z １ -1-1), (Z １ -1-2) Middle, Ar, R １ , R ２ , R′, n1, and n2 are the same as above; R ３ , R ４ , R ７ , R ８ each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R ５ , R ６ , R ９ , R １０ are each independently a hydrogen atom or a methyl group. m1, m2, m3, m4, m5, m6, p1, p2, and q are the average values ​​of the repetitions, m1, m2, m3, m4, m5, and m6 each independently represent 0 to 25, and m1+m2≧1; p1 and p2 each independently represent 0 to 5; q is 0.5 to 5. However, the general formula (Z １ -1-1) and X represented by the general formula (Z １ The bonds to Y represented by the formula (1-1-2) may be random or block, and the total numbers of the structural units X and Y present in one molecule are m1 and m2, respectively. In addition, the aromatic ring containing the anthracene skeleton in formulas (1) to (3) may have a substituent. The lines in the formulas indicate that the ring may be connected at any point. * indicates a bonding point.]

2. 2. The curable resin composition according to claim 1, wherein the compound (B) having a dienophilic structure is a compound having two or more maleimide groups.

3. The curable resin composition according to claim 1, wherein the curable functional group (a) in the curable compound (A) is a hydroxyl group, and the compound (C) reactive with the hydroxyl group, glycidyl ether group, or 2-methylglycidyl ether group, which is the curable functional group (a), is an epoxy resin.

4. The curable resin composition according to claim 1, wherein the curable functional group (a) in the curable compound (A) is a glycidyl ether group, and the compound (C) having reactivity with the curable functional group (a), which is a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, is a curing agent for epoxy resins.

5. The curable resin composition according to any one of claims 1 to 4, which is one or more compositions selected from the group consisting of an easily dismantled composition, a repairable composition, and a remolding material composition.

6. A cured product obtained by curing the curable resin composition according to claim 5.

7. A laminate comprising a substrate and a layer comprising the cured product according to claim 6.

8. A heat-resistant member comprising the cured product according to claim 6.

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