Epoxy resin composition, cured product thereof, and disassembly method

Abstract

To provide: an epoxy resin composition which, while being an epoxy resin composition, allows the cured product to readily achieve reparability, easy disassembly, and re-formability; a cured product thereof; and a disassembly method.SOLUTION: An epoxy resin composition of the present embodiment comprises an epoxy resin (A) having a specific structure and having an epoxy equivalent of 500 to 10,000 g / eq, an epoxy resin (B) having an epoxy equivalent of 100 to 300 g / eq, a glycidyl ether group-containing compound (C) having a molecular weight of 1000 or more, and expandable particles (D), wherein the glycidyl ether group-containing compound (C) has a specific structure having a reversible bond.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an epoxy resin composition, a cured product thereof, and a disassembly method using a disassembly adhesive material.

Background Art

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

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

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

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

[0006] For example, as a technology for weight reduction of automobiles, airplanes, etc., it is essential to improve the performance of adhesives for structural materials. On the other hand, achieving high adhesive performance also contributes to the production of products that are difficult to recycle, and the dismantling and reusability after use are limited. Against the backdrop of the increasing environmental awareness these days, it is also important to develop an adhesive that can be easily peeled off after the usage period while maintaining high adhesive performance. Against such a background, the development of easily dismantlable adhesives has been actively carried out. Generally, the thermal melting of thermoplastic resins is often utilized. In recent years, however, technologies have also been proposed in which a thermosetting resin is premixed with a thermally expandable material or a thermally decomposable compound, and after use, mainly by applying thermal energy, the adhesive force is reduced to cause peeling (see, for example, Patent Documents 1 and 2).

[0007] Further, even when cracks or peeling occur in a sealing material using an epoxy resin or the like, a technique for making 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 3).

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0009] However, in the technology of Patent Document 1, basically, a conventional epoxy resin composition is used as an adhesive, and as a result, foaming by the thermally expandable material in the cured product (adhesive layer) is hardly sufficiently exhibited, so that the peelability may be insufficient or, due to the brittleness of the adhesive layer, it may not be cleanly removed. In addition, in the technology of Patent Document 2, since a thermally decomposable compound is contained in advance, there is a complexity in use that it is necessary to highly control the heating temperature during the curing reaction. In particular, when using a metal substrate with high thermal conductivity, it cannot be denied that heat may be applied to the adhesive too much in an unexpected place, resulting in problems. Also, the adhesive after disassembly will be discarded. Although the substrate as the adherend is recyclable, there is a problem that the overall recyclability is insufficient. In addition, in the technology of Patent Document 3, although it has a certain degree of self-healing property, it is not a solution from the perspective of reuse, and the problem of waste when it becomes unnecessary remains. Also, 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 the raw materials is limited to gel-like substances with poor mechanical strength. Currently, in any case, improvement is required. Therefore, an object of the present invention is to provide a compound that can easily achieve easy disassembly, reparability, and reshaping properties in a cured product while being a curable resin, an epoxy resin composition using the same, its cured product, and a disassembly method using a disassembly adhesive material.

Means for Solving the Problems

[0010] As a result of intensive studies, the present inventors have found that the above problems can be solved by using a glycidyl ether group-containing compound having a specific structure and an epoxy resin having a specific structure, and blending thermally expandable particles in the resin composition, and completed the invention.

[0011] That is, the present invention includes the following aspects. 〔1〕 An epoxy resin (A) having an epoxy equivalent of 500 to 10,000 g / eq represented by the following general formula (1), An epoxy resin (B) having an epoxy equivalent of 100 to 300 g / eq, A glycidyl ether group-containing compound (C) represented by the following general formula (4) and having a molecular weight of 1000 or more, An epoxy resin composition characterized by containing thermally expandable particles (D). [Chemical formula] 〔In formula (1), each Ar independently has a structure having an unsubstituted or substituted aromatic ring, X is a structural unit represented by the following general formula (2), and Y is a structural unit represented by the following general formula (3). [Chemical formula] [In formulas (2) and (3), Ar is the same as described above, 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 4 to 16, and n2 is from 2 to 30 as the average value of repeating units.] R 11 and R 12 are each independently a glycidyl ether group or a 2-methylglycidyl ether group, R 13 and R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, R 15 and R 16 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 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 (2) and Y represented by the general formula (3) may be random or block, and the total number of each structural unit X and Y present in one molecule is represented by m1 and m2, respectively. ]]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0012] According to the present invention, it is possible to impart easy disassembly, reparability, and remoldability to a cured product made of an epoxy resin composition, contributing to the extension of the lifespan of the cured product itself and the reduction of waste.

Embodiments for Carrying Out the Invention

[0013] Next, embodiments for carrying out the present invention will be described in detail. It should be understood that the present invention is not limited to the following embodiments, and modifications and improvements in design can be appropriately made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention.

[0014] (Epoxy Resin Composition) An epoxy resin composition as one form (this embodiment) of the present invention contains an epoxy resin (A) having an epoxy equivalent of 500 to 10,000 g / eq represented by the above general formula (1), an epoxy resin (B) having an epoxy equivalent of 100 to 300 g / eq, a glycidyl ether group-containing compound (C) represented by the above general formula (4) and having a molecular weight of 1000 or more, and thermally expandable particles (D). The epoxy resin composition of this embodiment preferably further contains a compound (I) having reactivity with the glycidyl ether group-containing compound (C). The epoxy resin composition of this embodiment may, if necessary, contain other epoxy resins other than the epoxy resin (A), the epoxy resin (B), and the glycidyl ether group-containing compound (C) according to this embodiment. Further, the epoxy resin composition of this embodiment may, if necessary, contain a curing accelerator, other thermosetting resins or thermoplastic resins, a non-halogen-based flame retardant, a filler not belonging to the thermally expandable particles (D) according to this embodiment, or a dispersion medium, etc. Hereinafter, each component will be described in detail.

[0015] [Epoxy resin (A)]

[0016] The epoxy resin (A) contained in the epoxy resin composition of this embodiment is an epoxy resin having an epoxy equivalent of 500 to 10,000 g / eq represented by the following general formula (1). [Chemical formula] 〔In formula (1), each Ar is independently a structure having an unsubstituted or substituted aromatic ring, X is a structural unit represented by the following general formula (2), and Y is a structural unit represented by the following general formula (3), [Chemical formula] [In formulas (2) and (3), Ar is the same as described above, R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, R’ is a divalent hydrocarbon group having 2 to 12 carbon atoms, R 3 , R 4 , R 7 , R 8 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, n1 is an integer of 4 to 16, n2 is an average value of repeating units and is 2 to 30.] R 11 , R 12 are each independently a glycidyl ether group or a 2-methylglycidyl ether group, R 13 , R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, R 15 , R 16is a hydrogen atom or a methyl group, m1, m2, p1, p2, and q are average values of repetition, m1 and m2 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 (2) and Y represented by the general formula (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. ]]

[0017] It contains a structural unit X represented by the general formula (2) and / or a structural unit Y represented by the general formula (3) in the above structure, and the presence of an alkylene chain or a polyether chain in each structural unit enables the cured product to exhibit high flexibility. In particular, the flexibility due to the alkylene chain can follow the thermal expansion of the substrate when used as an adhesive, and the polyether chain can contribute to the improvement of the coating property and processability of the epoxy resin composition because it has the effect of lowering the viscosity of the epoxy resin (A) itself.

[0018] In the epoxy resin (A), the structural units X and Y may each have them alone, or may have both the structural units X and Y in one molecule. At this time, X and Y may be in a block bond or a random bond, and the total number of the structural unit X and the structural unit Y contained in one molecule indicates m1 and m2, respectively.

[0019] Ar in the general formula (1) representing the epoxy resin (A), Ar in the general formula (2) representing the structural unit X, and Ar in the general formula (3) representing the structural unit Y all have a structure having an unsubstituted or substituted aromatic ring. However, this aromatic ring is not particularly limited, and examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.

[0020] Among these, as Ar, it is preferably any structure represented by the following structural formula (ar).

[0021]

Chem.

[0022] Also, the structures represented by the following formulas can also be cited as Ar.

[0023]

Chem.

[0024] The aromatic ring possessed by Ar may be substituted or unsubstituted. When Ar has a substituent, the substituent is preferably an alkyl group, a halogen atom, a glycidyl ether group, a 2-methylglycidyl ether group, etc. Preferably, it is unsubstituted, or an alkyl group, a glycidyl ether group, a 2-methylglycidyl ether group. The number of substituents is preferably 2 or less per aromatic ring, more preferably 1 or less, and particularly preferably unsubstituted.

[0025] As the structure of the above Ar, the following are particularly preferred. * represents the bonding point.

[0026]

Chem.

[0027] As particularly preferred structures of Ar having a substituent, the following structures can be cited. * represents the bonding point.

[0028]

Chem.

[0029] In the structural unit X represented by the general formula (2), as the repeating unit n1, it is an integer of 4 to 16. When n1 is 4 or more, the adhesive strength is improved and the deformation mode of the cured product becomes elastic deformation. Also, when n1 is 16 or less, a decrease in the crosslinking density can be suppressed. It is preferably 4 to 15, and more preferably 6 to 12.

[0030] In the structural unit X represented by the general formula (2), R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, and R 3 , R 4 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, and R 5 , R 6 are each independently a hydrogen atom or a methyl group.

[0031] Among these, it is preferable that R 3 , R 4 are hydroxyl groups, and it is preferable that R 5 , R 6 are hydrogen atoms.

[0032] In the structural unit Y represented by the general formula (3), n2 is the average value of the repeating units and is 2 to 30. This range is preferable from the viewpoint that the balance between the viscosity of the epoxy resin (A) and the crosslinking density of the obtained cured product is good. It is preferably 2 to 25, and more preferably 4 to 20.

[0033] In the structural unit Y represented by the general formula (3), R' is a divalent hydrocarbon group having 2 to 12 carbon atoms. In this range, the adhesive strength is improved and the deformation mode of the cured product becomes elastic deformation. Preferably, R' is a divalent hydrocarbon group having 2 to 6 carbon atoms.

[0034] The divalent hydrocarbon group is not particularly limited, and examples thereof include linear or branched alkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, aralkylene groups (divalent groups having an alkylene group and an arylene group), and the like.

[0035] 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, a hexamethylene group, and the like. Examples of the alkenylene group include a vinylene group, a 1-methylvinylene group, a propenylene group, a butenylene group, a pentenylene group, and the like. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, and the like. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and the like. Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, a naphthylene group, and the like.

[0036] Among these, from the viewpoints of easy availability of raw materials, the viscosity of the obtained epoxy resin (A), and the balance of flexibility when formed into a cured product, an ethylene group, a propylene group, or a tetramethylene group is preferable.

[0037] In the structural unit Y represented by the general formula (3), R 7 , R 8 are each independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, and R 9 , R 10 are each independently a hydrogen atom or a methyl group. R 7 , R 8 is preferably a hydroxyl group, and R 9 , R 10 is preferably a hydrogen atom.

[0038] As described above, the epoxy resin (A) used in the present embodiment is represented by the general formula (1). In the general formula (1), m1 and m2 are respectively the average values of the repetitions of the aforementioned structural unit X and structural unit Y, and are each independently 0 to 25, and m1 + m2 ≥ 1.

[0039] Also, R in the general formula (1) 11 and R 12 are each independently a glycidyl ether group or a 2-methyl glycidyl ether group, and R 13 and R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methyl glycidyl ether group, and R 15 and R 16 are a hydrogen atom or a methyl group, and p1, p2, and q are average values of repetitions, p1 and p2 are each independently 0 to 5, and q is 0.5 to 5. Among these, it is preferable that R 11 and R 12 are glycidyl ether groups, it is preferable that R 13 and R 14 are hydroxyl groups, and it is preferable that R 15 and R 16 are hydrogen atoms. Also, it is preferable that p1 and p2 are 0 to 2, and it is preferable that q is 0.5 to 2.

[0040] Furthermore, the epoxy equivalent of the epoxy resin (A) used in the present embodiment is 500 to 10,000 g / eq. By being in this range, the balance between the flexibility and crosslink density of the obtained cured product becomes excellent. From the viewpoint of ease of handling and a more balanced flexibility and crosslink density, it is preferably in the range of 600 to 8,000 g / eq, and more preferably in the range of 800 to 5,000 g / eq.

[0041] Among the epoxy resins (A) in the present embodiment, examples of those having both the structural unit X and the structural unit Y in one molecule include resins having the following structural formulas.

[0042] [Chemical formula]

[0043]

Chem.

[0044]

Chem.

[0045]

Chem.

[0046]

Chem.

[0047]

Chem.

[0048]

Chem.

[0049]

Chem.

[0050]

Chem.

[0051]

Chem.

[0052]

Chem.

[0053] [Chemical formula]

[0054] In each of the above structural formulas (A-1) to (A-12), ran represents a random bond, G is a glycidyl group, R' represents a divalent hydrocarbon group having 2 to 12 carbon atoms, n1 is an integer of 4 to 16, n2 is an average value of repeating units and is 2 to 30, m1, m2, p1, p2, and q are average values of repetition, m1 and m2 are each independently 0.5 to 25, p1 and p2 are each independently 0 to 5, and q is 0.5 to 5. However, each of the repeating units present in the repeating unit may be the same or different.

[0055] Among the above structural formulas, from the viewpoint of excellent physical property balance of the obtained cured product, it is most preferable to use those represented by the structural formulas (A-1), (A-2), (A-3), (A-5), (A-7), (A-8), and (A-9).

[0056] Among the epoxy resins (A), examples of the epoxy resin having the above-mentioned structural unit X include resins represented by the following structural formulas.

[0057] [Chemical formula]

[0058] [Chemical formula]

[0059] [Chemical formula]

[0060] [Chemical formula]

[0061] [Chemistry]

[0062] [Chemistry]

[0063] [Chemistry]

[0064] [Chemistry]

[0065] [Chemistry]

[0066] [Chemistry]

[0067] [Chemistry]

[0068] [Chemistry]

[0069] In the above structural formulas (A-13) to (A-24), G is a glycidyl group, n1 is an integer from 4 to 16, m1, p1, p2, and q are average values of repetitions, m1 is from 0.5 to 25, p1 and p2 are each independently from 0 to 5, and q is from 0.5 to 5. However, each repeating unit existing in the repeating unit may be the same or different from each other.

[0070] Among the above structural formulas, those represented by the structural formulas (A-13), (A-14), (A-15), (A-17), (A-19), (A-20), and (A-21) are preferably used because of their excellent balance of physical properties of the resulting cured product.

[0071] Among the epoxy resins (A), examples of the epoxy resin having the aforementioned structural unit Y include resins represented by the following structural formulas.

[0072]

Chemical formula

[0073]

Chemical formula

[0074]

Chemical formula

[0075]

Chemical formula

[0076]

Chemical formula

[0077]

Chemical formula

[0078]

Chemical formula

[0079]

Chemical formula

[0080] [Chemistry]

[0081] [Chemistry]

[0082] [Chemistry]

[0083] [Chemistry]

[0084] In each of the above structural formulas (A-25) to (A-36), G is a glycidyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, n2 is the average value of the repeating units and is 2 to 30, m2, p1, p2, and q are average values of the repetitions, m2 is 0.5 to 25, p1 and p2 are each independently 0 to 5, and q is 0.5 to 5. However, the respective repeating units present in the repeating units may be the same or different.

[0085] Among the above structural formulas, those represented by the structural formulas (A-25), (A-26), (A-27), (A-29), (A-31), (A-32), and (A-33) are most preferably used because of the excellent balance of physical properties of the resulting cured product.

[0086] <Manufacturing method of epoxy resin (A)> The method for producing the epoxy resin (A) according to this embodiment is not particularly limited. For example, a diglycidyl ether (a1) of a dihydroxy compound having an alkylene chain and a polyether chain and an aromatic hydroxy compound (a2) are reacted in a molar ratio (a1) / (a2) in the range of 1 / 1.01 to 1 / 5.0 to obtain a hydroxy compound [corresponding to a precursor or an intermediate of the epoxy resin (A)], and then reacting with epihalohydrin (a3) is preferable from the viewpoints of easy availability of raw materials and easy reaction.

[0087] In the product obtained by the reaction of reacting the diglycidyl ether (a1) of a dihydroxy compound having an alkylene chain and a polyether chain with the aromatic hydroxy compound (a2) to obtain a hydroxy compound, unreacted aromatic hydroxy compound (a2) may be contained. However, in the synthesis of the epoxy resin (A) used in this embodiment, it may be directly used for the reaction with epihalohydrin (a3) in the next step, or the unreacted aromatic hydroxy compound (a2) may be removed. However, from the viewpoint of the balance between toughness and flexibility of the cured product obtained from the epoxy resin composition of this embodiment containing the obtained epoxy resin (A), the abundance ratio of the unreacted aromatic hydroxy compound (a2) in the hydroxy compound used in the next step is preferably in the range of 0.1 to 30% by mass.

[0088] The method for removing the unreacted aromatic hydroxy compound (a2) is not particularly limited and can be carried out according to various methods. For example, column chromatography separation method using the difference in polarity, distillation fractionation method using the difference in boiling point, alkali aqueous solution extraction method using the difference in solubility in alkaline water, etc. can be mentioned. Among them, the alkali aqueous solution extraction method is preferable in terms of efficiency etc. because it does not involve thermal denaturation. At this time, as the organic solvent used to dissolve the target substance, those that do not mix with water such as toluene and methyl isobutyl ketone can be used, but it is particularly preferable to use methyl isobutyl ketone from the viewpoint of solubility with the target substance.

[0089] The diglycidyl ether (a1) of the dihydroxy compound having the alkylene chain and polyether 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, etc. can be mentioned. Further, as the diglycidyl ether having a polyether chain, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, polyheptamethylene glycol diglycidyl ether, etc. can be mentioned. These may contain organic chlorine impurities generated in the glycidyl etherification of the hydroxy compound, and may contain organic chlorine such as 1-chloromethyl-2-glycidyl ether (chloromethyl form) represented by the following structure. These diglycidyl ethers may be used alone or in combination of two or more.

[0090]

Chemical formula

[0091] Among these, from the viewpoint of excellent balance between the flexibility and heat resistance of the resulting 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, and polytetramethylene glycol diglycidyl ether.

[0092] Further, by reacting the diglycidyl ether having the above-mentioned alkylene chain and the diglycidyl ether having a polyether chain with the aromatic hydroxy compound (a2) simultaneously, a hydroxy compound having both the structural unit X and the structural unit Y can be obtained, and by reacting this further with the epihalohydrin (a3), an epoxy resin (A) having both the structural unit X and the structural unit Y can be obtained.

[0093] The aromatic hydroxy compound (a2) 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 coupling reaction of dihydroxynaphthalenes; bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 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 the so-called Zylok type phenol resins which are condensation reaction products of phenol and phenylenedimethyl chloride or biphenylenedimethyl chloride may be mentioned, and they may be used alone or in combination of two or more. Further, 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 may 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 in the present invention, they may be used as they are, or after a purification step such as a column, only bifunctional components may be taken out and used.,

[0094] Among these, bisphenols are preferable from the viewpoint of excellent balance between flexibility and toughness when cured, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferable from the viewpoint of remarkable toughness imparting performance. Further, when importance is attached to the curability and heat resistance of the cured product, dihydroxynaphthalenes are preferable, and 2,7-dihydroxynaphthalene is particularly preferable from the viewpoint of remarkable imparting of rapid curability. Further, when importance is attached to the moisture resistance of the cured product, it is preferable to use a compound containing an alicyclic structure.,

[0095] The reaction ratio of the diglycidyl ether (a1) of the dihydroxy compound having an alkylene chain and a polyether chain and the aromatic hydroxy compound (a2) is preferably used at (a1) / (a2) of 1 / 1.01 to 1 / 5.0 (molar ratio) from the viewpoint of reaction efficiency, and more preferably (a1) / (a2) is 1 / 1.02 to 1 / 3.0 (molar ratio).

[0096] The reaction of the diglycidyl ether (a1) of the dihydroxy compound having the alkylene chain and polyether chain with the aromatic hydroxy compound (a2) 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 chlorides, bromides, iodides of DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, chlorides, bromides, iodides of 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 in terms of the rapid progress of the reaction and the high effect of reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but it is preferably 0.0001 to 0.1 mol per 1 mol of the aromatic hydroxyl group in the aromatic hydroxy compound (a2). The form of these catalysts is also not particularly limited, and they may be used in the form of an aqueous solution or in a solid form.

[0097] Further, the reaction between the diglycidyl ether (a1) of the dihydroxy compound having an alkylene chain and a polyether chain and the aromatic hydroxy compound (a2) 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. For quickly carrying out the reaction, no solvent is preferred, while the use of dimethyl sulfoxide is preferred in terms of reducing impurities in the final product.

[0098] When carrying out the reaction, the reaction temperature is usually 50 to 180°C, and the reaction time is usually 1 to 30 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 significant, 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-based compounds, and phosphite ester 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.

[0099] After 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 dihydrogen 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 a hydroxy compound can be obtained.

[0100] By using a glycidyl ether having the alkylene chain and a glycidyl ether having a polyether chain in combination, a hydroxy compound having both of the structural unit X and the structural unit Y can be obtained. At this time, preferable structures include, for example, compounds represented by the following structural formulas.

[0101]

Chemical formula

[0102]

Chemical formula

[0103]

Chemical formula

[0104]

Chemical formula

[0105]

Chemical formula

[0106]

Chemical formula

[0107]

Chemical formula

[0108]

Chemical formula

[0109]

Chemical formula

[0110] [Chemistry]

[0111] [Chemistry]

[0112] [Chemistry]

[0113] In each of the above structural formulas, ran represents a random bond, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, n1 is an integer from 4 to 16, n2 is an average value of repeating units and is from 2 to 30, and m1 and m2 are average values of repetitions and are independently from 0.5 to 25. However, each repeating unit existing in the repeating unit may be the same or different.

[0114] Moreover, by using the glycidyl ether having the alkylene chain as a raw material, a hydroxy compound having the structural unit X can be obtained. At this time, preferred structures include, for example, compounds represented by the following structural formulas.

[0115] [Chemistry]

[0116] [Chemistry]

[0117] [Chemistry]

[0118] [Chemistry]

[0119] [Chemical]

[0120] [Chemical]

[0121] [Chemical]

[0122] [Chemical]

[0123] [Chemical]

[0124] [Chemical]

[0125] [Chemical]

[0126] [Chemical]

[0127] In each of the above structural formulas, n1 is an integer from 4 to 16, m1 is the average value of the repetition, and is from 0.5 to 25.

[0128] Further, by using the glycidyl ether having the polyether chain as a raw material, a hydroxy compound having the structural unit Y can be obtained. At this time, preferred structures include, for example, compounds represented by the following structural formulas.

[0129]

Chem.

[0130]

Chem.

[0131]

Chem.

[0132]

Chem.

[0133]

Chem.

[0134]

Chem.

[0135]

Chem.

[0136]

Chem.

[0137]

Chem.

[0138]

Chem.

[0139]

Chem.

[0140]

Chem.

[0141] In each of the above structural formulas, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, n2 is an average value of repeating units and is 2 to 30, and m2 is an average value of repetitions and is 0.5 to 25. However, each repeating unit existing in the repeating unit may be the same or different from each other.

[0142] In the method for producing the epoxy resin (A), there is no particular limitation on the method of 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 (a3) is preferable in terms of easy availability of raw materials and easy reaction.

[0143] As a method using epihalohydrin (a3), for example, 0.3 to 100 moles of epihalohydrin (a3) is added to 1 mole of the aromatic hydroxyl group of the hydroxy compound obtained above, and to this mixture, 0.9 to 2.0 moles of a basic catalyst per 1 mole of the aromatic hydroxyl group of the hydroxy compound is added all at once or gradually, and the reaction is carried out at a temperature of 20 to 120 ° C for 0.5 to 10 hours. The addition amount of this epihalohydrin (a3) is such that the more the excess amount of epihalohydrin (a3) increases, the closer the obtained epoxy resin becomes to the theoretical structure, and the formation of secondary hydroxyl groups generated by the reaction of unreacted aromatic hydroxyl groups and epoxy groups can be suppressed. From such a 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 continuously added, and water and epihalohydrin (a3) are continuously distilled off from the reaction mixture under reduced pressure or normal pressure, and further separated to remove water and the epihalohydrin (a3) is continuously returned to the reaction mixture.

[0144] When carrying out industrial production, all of the charged epihalohydrin (a3) is new in the first batch of epoxy resin production, but from the second batch onwards, it is preferable to use a combination of epihalohydrin (a3) recovered from the crude reaction product and new epihalohydrin (a3) corresponding to the amount consumed and lost in the reaction. At this time, the epihalohydrin (a3) to be used is not particularly limited, and examples include epichlorohydrin, epibromohydrin, etc. Among them, epichlorohydrin is preferable because it is easily available.

[0145] 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 from the viewpoint of excellent catalytic activity in the epoxy resin synthesis reaction, and examples include sodium hydroxide, potassium hydroxide, etc. When using, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55% by mass, or may be used in a solid form.

[0146] 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. For example, 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 can be mentioned. These organic solvents may be used alone or, in order to adjust the polarity, two or more kinds may be used in combination as appropriate.

[0147] After washing the reactants of these glycidylation reactions with water, unreacted epihalohydrin (a3) 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 a crown ether may be present.

[0148] 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 completion of the reaction, the generated salt is removed by filtration, washing with water, etc., and further, a high-purity epoxy resin can be obtained by distilling off solvents such as toluene and methyl isobutyl ketone under heating and reduced pressure.

[0149] [Epoxy Resin (B)]

[0150] As the epoxy resin (B) contained in the epoxy resin of the present embodiment, its epoxy equivalent may be in the range of 100 to 300 g / eq, and its structure is not limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin and other liquid epoxy resins, brominated epoxy resins such as brominated phenol novolac type epoxy resin, solid bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolac type epoxy resin, etc. can be mentioned. They may be used alone or in combination of two or more, and it is preferably selectively used according to the intended use, physical properties of the cured product, etc.

[0151] 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 them, it is particularly preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq among bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD type epoxy resin.

[0152] In this embodiment, the usage ratio of the epoxy resin (A) and the epoxy resin (B) is not particularly limited. However, from the viewpoint of easy phase separation in the cured product, the mass ratio (A):(B) of the epoxy resin (A) and the epoxy resin (B) is 90:10 to 10:90, preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70. By phase separation in the cured product, a sea-island structure is formed, achieving both the adhesiveness and stress relaxation ability of the cured product, exhibiting high adhesive strength particularly in a wide temperature range, and having the effect of reducing the molding shrinkage rate before and after heat curing of the resin composition.

[0153] [Glycidyl ether group-containing compound (C)] The glycidyl ether group-containing compound (C) contained in the epoxy resin composition of this embodiment is a glycidyl ether group-containing compound (C) represented by the following general formula (4). [Chemical formula] 〔In the furan-derived structure in formula (4), a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group may be contained as a substituent. n is the average value of the repetition number and is 0.5 to 10, and m is an integer of 1 to 4. Z 1 is the following formula (5), Z 2 is the following formulas (6A) and (6B), Z 3 is any of the structures represented by the following formulas (7-1) to (7-3), and each of them may be the same or different in one molecule. [Chemical formula] 〔The aromatic ring in formula (5) may be substituted or unsubstituted, and * represents the bonding point. G is a glycidyl group or a 2-methylglycidyl group, and -OG on the naphthalene ring in the formula indicates that it may be bonded at any position.〕 [Chemical formula] [Chemical formula] [In formulas (6A) and (6B), Ar is each independently a structure having an unsubstituted or substituted aromatic ring, R 1 , R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, R is a hydrogen atom or a methyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, n1 is an integer from 4 to 16, and n2 is an average value of repeating units and is from 2 to 30, k1 is an average of the number of repetitions and is in the range of 0.5 to 5, p1 and p2 are each independently from 0 to 5, X is a structural unit represented by the following formula (6-1), and Y is a structural unit represented by the following formula (6-2), [Chemical formula] [In formulas (6-1) and (6-2), Ar, R, R 1 , R 2 , R', n1, and n2 are the same as defined above.] m1 and m2 are average values of repetitions, each independently from 0 to 25, and m1 + m2 ≥ 1. However, the bonding between the structural unit X represented by the formula (6-1) and the structural unit Y represented by the formula (6-2) may be random or block, and the total number of each of the structural units X and Y present in one molecule is m1 and m2, respectively.] [Chemical formula] [Chemical formula] [Chemical formula] [In Formulas (7-1) to (7-3), n3 and n5 are average values of the number of repetitions, each being 0.5 to 10, n4 is an integer of 1 to 16, and R” is independently a hydrogen atom, a methyl group or an ethyl group.]

[0154] The glycidyl ether group-containing compound of this embodiment is characterized in that a maleimide structure and a furan structure are bonded by a reversible bond due to a Diels-Alder reaction.

[0155] By having such a configuration, the glycidyl ether group-containing compound is incorporated into a crosslinked structure by a curing reaction based on its glycidyl ether group. On the other hand, even after becoming a cured product, due to its reversibility, it has high molecular mobility in the cured product. From this, when the cured product is subjected to an impact and cracks are generated or it is crushed, it is easily cleaved at the reversible bond 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 properties. Since the structural unit B exists away from the crosslinked structure, it exhibits particularly high molecular mobility and shows low temperature reparability and low temperature reshaping. For example, even when a cured product using the glycidyl ether group-containing compound of the present invention is crushed, it can be easily repaired based on the reversible bond by placing it in a low temperature including room temperature or a heating state, and it is also possible to reshape the cured product after crushing it.

[0156] In order to introduce a furan-type addition structure (reversible bond) due to the Diels-Alder reaction into the compound, furan having a reactive functional group on the ring and maleimide having a reactive functional group are used. The specific reversible bond partial structure can be represented by the following chemical formula. By bonding other structural units based on the R portion in the following formula in the maleimide-derived structure and various reactive functional groups on the ring of the furan-derived structure, a reversible bond can be introduced into the compound.

[0157] [Chemical formula]

[0158] In the Diels - Alder reaction, a conjugated diene and a dienophile undergo an addition reaction to form a six - membered ring. Since the Diels - Alder reaction is an equilibrium reaction, at a given temperature, the Retro - Diels - Alder reaction occurs and dissociation (depolymerization) takes place. When mechanical energy such as damage or external force is applied to the resulting cured product, the C - C bond in the Diels - Alder reaction unit has a lower bond energy compared to ordinary covalent bonds, so the C - C bond in the Diels - Alder reaction unit is preferentially cleaved. From this, the cured product exhibits easy disassembly. Also, the C - C bond in the Diels - Alder reaction unit has an equilibrium shift in the bonding direction in a temperature range lower than the dissociation temperature, so it is considered that an adduct (Diels - Alder reaction unit) is formed again, enabling repair of damage and remolding.

[0159] In the reversible bond formed by the Diels - Alder reaction, the reversible bond formed by the Diels - Alder reaction with the furan structure and the maleimide structure undergoes dissociation (depolymerization) due to the Retro - Diels - Alder reaction occurring around 120°C. Therefore, the heating temperature required for the cured product to exhibit easy disassembly can be reduced, and it is excellent in easy disassembly for applications where high - temperature heating is not suitable.

[0160] Regarding the average molecular weight (Mw) of the glycidyl ether group - containing compound (C), from the viewpoints of the mechanical strength, flexibility, and the compatibility of easy disassembly and repair / remolding properties when it is made into a cured product, it is 1000 or more. Also, it is preferably 50000 or less. Further, when having reversible bonds other than the terminal part, from the viewpoints of easy disassembly and remolding properties of the cured product, etc., the molecular weight per reversible bond is more preferably in the range of 300 to 10000.

[0161] In the general formula (4), a reversible bond formed by furan and maleimide is present at the terminal within the molecule. The terminal furan structure in the general formula (4) has Z1 which is any of the structures represented by the general formula (5). This glycidyl ether group or 2-methylglycidyl ether group contributes to the curing reaction in the epoxy resin composition described later.

[0162] Z in the formula 1 is a structural unit having a glycidyl ether group or 2-methylglycidyl ether group represented by the general formula (5). Among these, from the viewpoints of ease of obtaining raw materials and reactivity, those having the following structural formula are preferred. G is a glycidyl group or 2-methylglycidyl group.

[0163]

Chem.

[0164] In the general formula (4), the site connecting the furan-derived structure is Z2, and the site connecting the maleimide-derived structure is Z 3 is. Z 2 is any of the structures represented by the general formulas (6A) and (6B), and Z 2 is any of the structures represented by (7-1) to (7-3).

[0165] Z2 in the formula is those represented by the general formulas (6A) and (6B). Among these, from the viewpoints of ease of obtaining raw materials, reactivity, and the balance of toughness and flexibility of the resulting compound, those having the following structural formula are preferred.

[0166]

Chem.

[0167] n in the general formula (4) is the average value of the repetition number and is 0.5 to 10, preferably in the range of 0.5 to 5.

[0168] In the foregoing structural formula, Ar is an aromatic ring which may have substituents 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. The substituent on Ar is preferably one that does not cause a curing reaction when used as the subsequent epoxy resin composition, because the effects of the present embodiment are more likely to be exhibited.

[0169] Among these, as Ar, it is preferable that it is any structure represented by the following structural formula.

[0170] [Chemical formula] 〔The aromatic ring in the formula may be substituted or unsubstituted, and * represents a bonding point.〕

[0171] Also, a structure represented by the following formula is also cited as Ar.

[0172] [Chemical formula] (In the formula, the aromatic ring may be substituted or unsubstituted, n6 = 1 to 4, and * represents a bonding point.)

[0173] As the structure of the foregoing Ar, the following are particularly preferable. * represents a bonding point.

[0174] [Chemical formula]

[0175] In the general formulas (6A), (6B) and (6-1), the repeating unit n1 is an integer of 2 to 16. When n1 is 4 or more, the deformation mode of the cured product tends to be elastic deformation. Also, when n1 is 16 or less, a decrease in the crosslinking density can be suppressed. It is preferably 4 to 15, and more preferably 6 to 12.

[0176] In the general formulas (6A), (6B) and (6-1), R1 and R2 are each independently a hydrogen atom, a methyl group or an ethyl group, and R is each independently a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable.

[0177] In the general formulas (6A), (6B) and (6-2), n2 is an average value of repeating units and is 2 to 30. This range is preferable because the balance between the viscosity of the glycidyl ether group-containing compound (C) and the crosslinking density of the resulting cured product is good. It is preferably 2 to 25, and more preferably 4 to 20.

[0178] In the general formulas (6A), (6B) and (6-2), R' is a divalent hydrocarbon group having 2 to 12 carbon atoms. Within this range, the adhesive strength is improved and the deformation mode of the cured product tends to be elastic deformation. Preferably, R' is a divalent hydrocarbon group having 2 to 6 carbon atoms.

[0179] The divalent hydrocarbon group is not particularly limited, and examples thereof include linear or branched alkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, aralkylen groups (divalent groups having an alkylene group and an arylene group), and the like.

[0180] 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.

[0181] Among these, from the viewpoints of easy availability of raw materials, the viscosity of the glycidyl ether group-containing compound (C) obtained, and the balance of flexibility when formed into a cured product, it is preferably an ethylene group, a propylene group, or a tetramethylene group.

[0182] In the general formulas (6A), (6B), and (6-2), each R is independently a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferred.

[0183] In the general formulas (6A) and (6B), m1 and m2 are respectively the average values of the repetitions of the aforementioned structural unit X and structural unit Y, and are each independently from 0 to 25, and m1 + m2 ≧ 1. Preferably, m1 and m2 are each in the range of 0.5 to 10.

[0184] Further, in the general formulas (6A) and (6B), k1 is the average of the number of repetitions and is in the range of 0.5 to 5, and preferably in the range of 0.5 to 2.

[0185] In the general formulas (7-1) to (7-3), n3 and n5 are average values of the number of repetitions, each being from 0.5 to 10, n4 is an integer from 1 to 16, and R” is each independently a hydrogen atom, a methyl group, or an ethyl group. Among these, from the viewpoints of ease of obtaining raw materials, mechanical properties of the resulting cured product, etc., it is preferable that n3 is in the range of 0.5 to 10, n5 is in the range of 2 to 3, it is preferable that n4 is an integer from 1 to 8, and it is preferable that R” is a hydrogen atom.

[0186] Examples of the glycidyl ether group-containing compound (C) of the present embodiment include, but are not limited to, those represented below.

[0187]

Chemical formula

[0188]

Chemical formula

[0189] The method for producing the glycidyl ether group-containing compound (C) of the present embodiment is not particularly limited. Depending on the target structure, it may be produced step by step using known reactions, or it can be obtained by appropriately combining commercially available products as raw materials. Representative synthesis methods are described below.

[0190] The compound represented by the general formula (4) has two Diels-Alder reaction units in the molecule, which are addition reaction parts formed by a Diels-Alder reaction composed of a furan structure and a maleimide structure as reversible bonds, and in the general formula (4), Z 1 can be obtained by using a furan compound having the structure of.

[0191] The so-called Diels-Alder reaction, in which a conjugated diene such as a furan structure and a dienophile such as a maleimide structure undergo an addition reaction to form a six-membered ring, is an equilibrium reaction. It is widely known that at a temperature higher than the temperature at which the addition reaction proceeds, a retro-Diels-Alder reaction occurs, in which the addition reaction part dissociates and returns to the original conjugated diene and dienophile.

[0192] Said Z 1 Examples of the furan compound having a hydroxyl group, which is a precursor of the furan compound having the structure of

[0193]

Chemical formula

[0194] Among the above formulas, the following compounds are particularly preferable in terms of the balance of reactivity, physical properties of the cured product, and easy disassembly, reparability, and remoldability.

[0195]

Chemical formula

[0196] In addition, the structures of the above furan compounds each independently include those having a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group as a substituent. In addition, in the structures of the compounds listed in the above formulas, those in which various substituents are further bonded to the carbon atoms they have are also included for the alkoxy group, aralkyloxy group, aryloxy group, carboxy group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group, and aryl group.

[0197] The Diels-Alder reaction may be carried out by using known methods. For example, an equimolar amount of a conjugated diene compound and a dienophile compound are mixed, and in some cases, one of the components is taken in excess. They are heated and melted or dissolved in a solvent, stirred at a temperature of room temperature to 110 °C for 1 to 24 hours, and can be obtained by filtration or distilling off the solvent without purification, or can also be obtained by commonly used isolation and purification methods such as recrystallization, reprecipitation, and chromatography.

[0198] Regarding the synthesis of sites other than the reversible bond, it can be synthesized by known methods. For example, after reacting a diglycidyl ether of an aliphatic dihydroxy compound or an aliphatic divinyl ether with an aromatic hydroxy compound to obtain a compound having a hydroxy group at the terminal, it is reacted with glycidyloxyphenylmaleimide or the like to introduce a maleimide structure at the terminal. Further, according to the above, by performing a Diels-Alder reaction with a furan compound having a glycidyl ether group, the compound represented by the general formula (4) can be obtained.

[0199] Or, after obtaining a compound having a hydroxy group at the terminal, it is epoxidized to make the terminal a glycidyl ether group, and then reacted with hydroxyphenylmaleimide or the like to introduce a maleimide structure at the terminal. Further, according to the above, by performing a Diels-Alder reaction with a furan compound having a glycidyl ether group, the compound represented by the general formula (4) can be obtained.

[0200] Or, after reacting an aromatic dihydroxy compound with an alkyl dihalide compound or an aralkyl dihalide compound to obtain a compound having a halogenated alkyl group at the terminal, it is reacted with hydroxyphenylmaleimide or the like to introduce a maleimide structure at the terminal. Further, according to the above, by performing a Diels-Alder reaction with a furan compound having a glycidyl ether group, the compound represented by the general formula (4) can be obtained.

[0201] The diglycidyl ether of the aliphatic dihydroxy compound is not particularly limited. For example, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl ether, 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether, etc. may be mentioned. It may be used alone or in combination of two or more kinds.

[0202] Among these, from the viewpoint of excellent balance between the flexibility and heat resistance of the resulting cured product, it is preferably a compound having a structure in which glycidyl groups are linked via ether groups at both ends of an alkylene chain having 12 to 14 carbon atoms. It is most preferable to use 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, or 1,14-tetradecanediol diglycidyl ether.

[0203] 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 with linear alkylene groups, and neopentyl glycol divinyl ether and other divinyl ethers with branched alkylene groups, 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, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroquinone divinyl ether, etc. may be mentioned. They may be used alone or in combination of two or more.

[0204] Among these, divinyl ethers having a polyether structure or a linear alkylene chain with 9 to 10 carbon atoms 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.

[0205] 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 coupling reaction of dihydroxynaphthalenes; bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; 2,2’-biphenol, 4,4’-biphenol, (1,1’-biphenyl)-3,4-diol, 3,3’-dimethyl-(1,1‘-biphenyl)-4,4’-diol, 3-methyl-(1,1’-biphenyl)-4,4’-diol, 3,3’,5,5’-tetramethylbiphenyl-2,2’-diol, 3,3’,5,5’-tetramethylbiphenyl-4,4’-diol, 5-methyl-(1,1’-biphenyl)-3,4’-diol, 3’-methyl-(1,1’-biphenyl)-3,4’-diol, 4’-methyl-(1,1’-biphenyl)-3,Biphenols such as 4'-diol, polyadducts of phenol and dicyclopentadiene, and alicyclic structure-containing phenols such as polyadducts 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 may be mentioned, and 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 may 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 after a purification step such as a column, only bifunctional components may be taken out and used.,

[0206] Among these, bisphenols are preferable because of their excellent balance of flexibility and toughness when made into a cured product, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferable because of their remarkable performance in imparting toughness. Also, when emphasizing the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

[0207] The reaction ratio of the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound is preferably in the range of 1 / 1.01 to 1 / 5.0 (molar ratio) of the former to the latter, and from the point of achieving a good balance of flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is 1 / 1.02 to 1 / 3.0 (molar ratio).

[0208] 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 can be used in combination. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred from the viewpoints of rapid progress of the reaction and high impurity reduction effect. 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.

[0209] Moreover, 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 as a mixture of several kinds. 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.

[0210] When carrying out the reaction, the reaction temperature 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 coloring of the obtained compound is significant, 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-based 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.

[0211] After the 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 hydrogen 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 to obtain the compound.

[0212] The reaction ratio of the aliphatic divinyl ether and the aromatic hydroxy compound is preferably in the range of 1 / 1.01 to 1 / 5.0 (molar ratio) for the former / latter, and from the viewpoint of achieving a good balance between the flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is 1 / 1.02 to 1 / 3.0 (molar ratio).

[0213] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently even without using a catalyst, but it can be used as appropriate 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 weight 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 nuclear addition reaction of the vinyl group to the aromatic ring.

[0214] 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 organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohol organic solvents such as methanol, ethanol, isopropyl alcohol, and normal butanol. The amount of the organic solvent used is usually 50 to 300% by weight, preferably 100 to 250% by weight, based on the total mass of the charged raw materials. These organic solvents can be used alone or in combination of several types.

[0215] When carrying out the above reaction, the reaction temperature is generally 50 to 150°C, and the reaction time is generally 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 preferred.

[0216] After completion of the above reaction, when an organic solvent is used, it is removed under heating under reduced pressure. When a catalyst is used, if necessary, it is deactivated with a deactivator or the like and removed by washing with water or filtration operation, whereby the compound can be obtained.

[0217] To the compound having a hydroxyl group at the terminal thus obtained, glycidyloxyphenylmaleimide or the like is reacted. At this time, sodium hydroxide, potassium hydroxide, potassium carbonate or the like can be used as the catalyst, and as the solvent, toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide or the like may be used. The reaction temperature is from room temperature to 200°C, and the reaction time is from 1 to 24 hours. Then the catalyst is removed by filtration or the like, and the target compound can be obtained by extraction, solvent removal or the like. The Diels-Alder reaction with respect to this compound is as described above.

[0218] The aliphatic hydroxy compound is not particularly limited. For example, 1,4 - butanediol, 1,5 - pentanediol, 1,6 - hexanediol, 1,7 - heptanediol, 1,8 - octanediol, 1,9 - nonanediol, 1,10 - decanediol, 1,11 - undecanediol, 1,12 - dodecanediol, 1,13 - tridecanediol, 1,14 - tetradecanediol, 1,15 - pentadecanediol, 1,16 - hexadecanediol, 2 - methyl - 1,11 - undecanediol, 3 - methyl - 1,11 - undecanediol, 2,6,10 - trimethyl - 1,11 - undecanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, polyheptamethylene glycol diglycidyl ether, etc. may be mentioned. They may be used alone or in combination of two or more.

[0219] Among these, from the viewpoint of excellent balance between the flexibility and heat resistance of the obtained cured product, it is preferable to use a dihydroxy compound having a polyether structure or a linear alkylene chain with 12 to 14 carbon atoms. It is most preferable to use polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,12 - dodecanediol, 1,13 - tridecanediol, 1,14 - tetradecanediol.

[0220] The alkyl dihalide 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. They may be used alone or in combination of two or more.

[0221] The dihalogenated aralkyl compound is not particularly limited, and examples thereof include dichloroxylene, dichloromethylbiphenyl, dibromoxylene, dibromomethylbiphenyl, etc. It may be used alone or in combination of two or more.

[0222] The reaction ratio of the aromatic dihydroxy compound to the dialkyl halide compound or dihalogenated aralkyl compound is preferably in the range of the former / latter of 1 / 1.01 to 1 / 5.0 (molar ratio). From the viewpoint of well-balanced flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is 1 / 1.02 to 1 / 3.0 (molar ratio).

[0223] The reaction of the aromatic dihydroxy compound with the dialkyl halide compound or dihalogenated aralkyl compound 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, and alkali metal carbonates such as sodium carbonate, potassium carbonate. These may be used in combination of two or more catalysts. Among them, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferable 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 10 moles per 1 mole of the phenolic hydroxyl group of the aromatic hydroxy compound. The form of these catalysts is not particularly limited, and they may be used in the form of an aqueous solution or in a solid form.

[0224] The reaction between the aromatic dihydroxy compound and the dialkyl halide compound or diarylalkyl halide 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 types.

[0225] When carrying out the reaction, the reaction temperature 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.

[0226] The compound having an alkyl halide group at the terminal thus obtained is reacted with hydroxyphenylmaleimide or the like. At this time, sodium hydroxide, potassium hydroxide, potassium carbonate, or the like can be used as the catalyst, and toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide, or the like can be used as the solvent. The reaction temperature is room temperature to 200°C, and the reaction time is 1 to 24 hours. Then, the catalyst is removed by filtration or the like, and the target compound can be obtained by extraction, solvent removal, or the like. The Diels-Alder reaction of this compound is as described above.

[0227] The intermediate of the parent diene before carrying out the Diels-Alder reaction can be represented by the following general formula (4)'.

[0228]

Chemical formula

[0229] [Thermally expandable particles (D)]

[0230] The thermally expandable particles (D) contained in the epoxy resin composition of this embodiment may be made of an inorganic material or an organic material. Examples of the inorganic material include thermally expandable graphite provided in, for example, JP-A-2000-44219. Examples of those made of an organic material include those in which a thermoplastic polymer is used as an outer shell and a volatile expanding agent that becomes gaseous at a temperature below its softening point is microencapsulated to obtain thermally expandable microcapsules.

[0231] Among these, from the viewpoint of excellent uniform dispersibility when used as an epoxy resin composition, it is preferable to use thermally expandable microcapsules made of an organic material. Among these, from the viewpoint of the heat resistance and durability of the expandable particles, it is preferable to use thermally expandable graphite.

[0232] "Thermally expandable microcapsules" As a method for producing the thermally expandable microcapsules, although it was provided in JP-B-42-26524 in the past, from the viewpoint of thermally curing the epoxy resin in this embodiment, it is preferable to have heat resistance. Examples of production methods for heat-resistant thermally expandable microcapsules are provided in, for example, WO99 / 46320, WO99 / 43758, JP-A-2002-226620, etc.

[0233] That is, from the preferable viewpoint that during the thermal curing of the epoxy resin, the particles maintain their shape as they are without thermal expansion and expand thermally at a high temperature by thermal energy after use, it is preferable that the thermally expandable microcapsules have a polymer obtained by polymerizing a nitrile-based monomer and a monomer having a carboxyl group as essential components as an outer shell polymer.

[0234] In order to further impart heat resistance, it is also preferable to use a monomer having an amide group or a monomer having a cyclic structure in the side chain in combination.

[0235] As a method for obtaining the heat-resistant thermally expandable microcapsules, for example, the outer shell polymer is adjusted by appropriately blending a polymerization initiator with the above components. As the polymerization initiator, known polymerization initiators such as peroxides and azo compounds can be used. For example, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxide, 2,2'-azobis(2,4-dimethylvaleronitrile), etc. can be mentioned. Preferably, an oil-soluble polymerization initiator soluble in the polymerizable monomer to be used is used. The glass transition temperature (Tg) of the polymer constituting the outer shell of the thermally expandable microcapsules is desirably 120°C or higher. The Tg of the polymer can be calculated from the Tg of each homopolymer of the constituent monomers. It is also possible to measure it by differential scanning calorimetry (DSC) or the like.

[0236] The blowing agent contained in the microcapsules is a substance that becomes gaseous below the softening point of the outer shell polymer, and known substances are used. For example, propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, normal hexane, isohexane, heptane, octane, nonane, decane, petroleum ether, halogenated methane, low-boiling liquids such as tetraalkylsilane, and compounds such as AIBN that decompose thermally upon heating to become gaseous. It is selected as needed depending on the temperature range in which the capsules are to be foamed. The above blowing agents are used alone or in a mixture of two or more.

[0237] In addition, fluorine-based compounds such as HCF, HCFC, HFC, and HFE; examples include what are commonly referred to as Freons, fluorocarbons, fluoroethers, etc. However, due to concerns such as ozone layer depletion and global warming, it is better to avoid using these in the current social situation. In actual production, the conventional method for producing thermally expandable microcapsules is generally used. That is, as the dispersion stabilizer in an aqueous system, inorganic fine particles such as silica, magnesium hydroxide, calcium phosphate, and aluminum hydroxide are used. In addition, as the dispersion stability auxiliary agent, a condensation product of diethanolamine and aliphatic dicarboxylic acid, polyvinylpyrrolidone, methylcellulose, polyethylene oxide, polyvinyl alcohol, various emulsifiers, etc. are used.

[0238] The average particle diameter of the thermally expandable microcapsules is 1 to 500 μm, preferably 3 to 100 μm, and more preferably 5 to 50 μm. As a method for measuring the average particle diameter of the thermally expandable microcapsules, for example, a particle size distribution diameter measuring device (LA-950, manufactured by HORIBA) can be used to measure the volume average particle diameter.

[0239] "Thermally expandable graphite" As a method for producing the thermally expandable graphite, it is provided in, for example, JP-A-2000-44219 etc. However, from the viewpoint of thermally curing the epoxy resin in this embodiment, it is preferably heat-resistant. As a manufacturing method for heat-resistant thermally expandable graphite, it is provided in, for example, JP-A-2012-193053 etc.

[0240] Thermally expandable graphite can usually be obtained by treating graphite such as natural graphite, pyrolytic graphite, and kish graphite with a mixture of concentrated sulfuric acid and a strong oxidizing agent (hereinafter this treatment is referred to as acid treatment) to form an intercalation compound between the graphite layers, followed by washing with water, filtering, and drying. As the acid treatment method, those based on concentrated sulfuric acid such as concentrated sulfuric acid and nitric acid, concentrated sulfuric acid and potassium permanganate, concentrated sulfuric acid and perchloric acid, concentrated sulfuric acid and hydrogen peroxide, etc. are common. Also, a method using only fuming nitric acid is known.

[0241] The thermally expandable graphite is selected according to the range of the major axis of the particles. For this reason, commercially available expandable graphite is expressed in terms of particle size instead of being expressed by the major axis. Specifically, in commercially available expandable graphite, classification is performed using a sieve, and from the mesh number of the sieve, the characteristics of the expandable graphite product are expressed in terms of what percentage or more of the particles pass through a certain mesh.

[0242] As a preferable particle size grade of the thermally expandable graphite used as the thermally expandable particles (D) according to the present embodiment, it is 20 to 300 mesh, more preferably 30 to 200 mesh.

[0243] As the thermally expandable particles (D), they may be mixed with the epoxy resin (A) and the epoxy resin (B) as they are, or a masterbatch in which the thermally expandable particles (D) are dispersed at a high concentration in various resins may be used and mixed with the epoxy resin (A) and the epoxy resin (B).

[0244] As such thermally expandable particles (D), commercially available products can also be used. Examples of commercially available products include Microsphere manufactured by Matsumoto Yushi Seiyaku Co., Ltd. (trade names: F-20D, F-30D, F-40D, FN-100D, FN-100MD, FN-100SD, FN-100SSD, FN-180D, FN-180SD, FN-180SSD, F-190D, F-260D), Microsphere manufactured by Kureha Corporation (trade names: H850D, H880D, S2340D, S2640D), Expanded graphite manufactured by Fuji Kogyo Co., Ltd. (trade names: EXP-50S120K, EXP-50S150), Expanded graphite manufactured by Ito Graphite Co., Ltd. (trade names: 953240L, 9550250), Thermally expandable graphite manufactured by Air Water Inc. (trade names: 50LTE-U, MZ-260, CA-60, SS-3, SS-3LA), etc. It is preferable to appropriately select particles that do not thermally expand at the curing temperature of the epoxy resin composition and thermally expand at the heating temperature during disassembly.

[0245] As the use ratio of the thermally expandable particles (D), from the viewpoint of expressing the effect of sufficiently expanding during disassembly after use and reducing adhesiveness without impairing the adhesiveness when curing the epoxy resin composition of the present embodiment and the flexibility of the cured product, it is preferably used in the range of 3 to 40 parts by mass, particularly preferably in the range of 5 to 30 parts by mass, based on 100 parts by mass in total of the epoxy resin (A) and the epoxy resin (B).

[0246] [Compound (I)] The epoxy resin composition of the present embodiment preferably further contains a compound (I) having reactivity with the glycidyl ether group-containing compound (C). The glycidyl ether group-containing compound (C) according to the present embodiment can be made into an epoxy resin composition by using the compound (I) in combination. The epoxy resin composition can be suitably used for various electrical and electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulation materials.

[0247] Examples of the compound (I) having reactivity with the glycidyl ether group-containing 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. As the curing agent, it can be appropriately selected according to the physical properties of the intended cured product, but it is particularly preferable to use a hydroxyl group-containing compound or an amine group-containing compound from the viewpoints of mechanical strength and adhesion to the base material.

[0248] 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;

[0249] 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);

[0250] aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, picoline;

[0251] Examples of the modified amine compounds include epoxy compound-added polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, amine imides, boron trifluoride-piperidine complexes, boron trifluoride-monoethylamine complexes, and the like.

[0252] Examples of the acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

[0253] Examples of the phenolic hydroxyl group-containing compounds include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 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 phenol nuclei and alkoxy group-containing aromatic rings are linked by formaldehyde), and the like.

[0254] Examples of the amide compound include dicyandiamide and polyamide amine. The polyamide amine can be obtained, for example, by reacting an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, a carboxylic acid compound such as a fatty acid or dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain.

[0255] Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.

[0256] The thiol compound preferably contains two or more thiol groups in one molecule. Examples include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol and the like.

[0257] When using these curing agents, only one type of curing agent may be used, or two or more types 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, the amine-based compound, particularly dicyandiamide, is preferable from the viewpoints of workability, curability, and long-term stability. Further, in applications for semiconductor encapsulation materials, solid-type phenolic compounds are preferable from the viewpoint of the heat resistance of the cured product. In addition, in battery applications, aliphatic amines and thiol compounds are preferable from the viewpoint of low-temperature curing.

[0258] Also, from the viewpoint of further expressing the effects of the present invention more effectively, the compound (I) having reactivity with the glycidyl ether group-containing compound (C) is preferably a hydroxyl group-containing compound or an amino group-containing compound having a reversible bond.

[0259] Examples of the hydroxyl group-containing compound having a reversible bond include a hydroxyl group-containing compound in which a structural unit A' having one or more hydroxyl groups and a structural unit B' different from the A' are linked in the form of A'-B'-A', and the structural unit A' and the structural unit B' are bonded by a reversible bond.

[0260] Examples of the reversible bond include the same ones as the reversible bond in the glycidyl ether group-containing compound (C) in the present embodiment.

[0261] [Other epoxy resins] Furthermore, the epoxy resin composition of the present embodiment can be used in combination with other epoxy resins other than the epoxy resin (A), the epoxy resin (B), and the glycidyl ether group-containing compound (C) according to the present embodiment, as long as the effects of the present embodiment are not impaired. At this time, the total amount of the epoxy resin (A), the epoxy resin (B), and the glycidyl ether group-containing compound (C) in the epoxy resin composition of the present embodiment is preferably 30% by mass or more, particularly preferably 40% by mass or more, in all the epoxy resins.

[0262] Other epoxy resins that can be used in combination are not restricted in any way other than not belonging to epoxy resin (A), epoxy resin (B), or glycidyl ether group-containing compound (C). 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. They 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.

[0263] The concentration of the reversible bond in the epoxy resin composition of the present embodiment is preferably 0.10 mmol / g or more with respect to the total mass of the curable components in the epoxy resin composition. According to such a configuration, the easy disassembly property, repairability, and remoldability of the cured product obtained from the epoxy 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. Further, when the glycidyl ether group-containing compound (C) of the present embodiment has a plurality of reversible bonds, or when a hydroxyl group-containing compound having the aforementioned reversible bond is used alone or in combination with another curing agent as a curing agent, the concentration as the total of the reversible bonds is preferably 0.10 mmol / g or more with respect to the total mass of the curable components in the epoxy resin composition, 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 can be appropriately selected according to, for example, the glass transition temperature defined at the top of the tanδ peak 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 preferable range, sufficient repairability and remoldability 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 in the high concentration side of the preferable 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 glycidyl ether group-containing compound (C) is low, sufficient repairability and remoldability functions are likely to be exhibited. Therefore, for example, by appropriately adjusting the aging temperature for repair and the heating temperature for remolding in a timely manner, the expression effect of the repairability and remoldability 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.

[0264] Although the ratio of the total glycidyl ether groups in the epoxy resin composition of the present embodiment to the total active groups capable of reacting with the glycidyl ether groups is not particularly limited, from the viewpoint of good mechanical properties and the like of the resulting cured product, the amount of the active groups capable of reacting with the glycidyl ether groups is preferably 0.4 to 1.5 equivalents with respect to 1 equivalent of the total glycidyl ether groups in the resin composition.

[0265] [Curing accelerator] The epoxy resin composition of the present embodiment may contain a curing accelerator. Various curing accelerators can be used, and examples include urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, organic acid metal salts, Lewis acids, amine complex salts, etc. When used for adhesive applications, urea compounds, particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), are preferred from the viewpoints of excellent workability and low-temperature curability. When used for semiconductor encapsulation material applications, triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene is preferred among tertiary amines, from the viewpoints of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc.

[0266] 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.

[0267] 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.

[0268] Examples of the imidazoline compound include 2-methylimidazoline, 2-phenylimidazoline, and the like.

[0269] 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.

[0270] [Other thermosetting resins and thermoplastic resins] Moreover, the epoxy resin composition of the present embodiment may be used in combination with other thermosetting resins and thermoplastic resins as long as the effects of the present embodiment are not impaired.

[0271] Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, active ester resins, vinyl benzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, and the like. 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 embodiment are not impaired, but it is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the epoxy resin composition.

[0272] 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.

[0273] 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, and 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.

[0274] The resin having a benzoxazine structure is not particularly limited, and examples thereof include a reaction product of bisphenol F, formalin, and aniline (F-a type benzoxazine resin), a reaction product of diaminodiphenylmethane, formalin, and phenol (P-d type benzoxazine resin), a reaction product of bisphenol A, formalin, and aniline, a reaction product of dihydroxydiphenyl ether, formalin, and aniline, a reaction product of diaminodiphenyl ether, formalin, and phenol, a reaction product of dicyclopentadiene-phenol adduct type resin, formalin, and aniline, a reaction product of phenolphthalein, formalin, and aniline, a reaction product of diphenyl sulfide, formalin, and aniline, and the like. These may be used alone or in combination of two or more kinds.

[0275] The active ester resin is not particularly limited, but generally, compounds having two or more highly reactive ester groups such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. in one molecule 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 its halide. 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.

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

[0277] Furthermore, various novolak resins, alicyclic diene compounds such as dicyclopentadiene, addition polymerization resins of alicyclic diene compounds and phenol compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (zylok resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylol ethane resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and various vinyl polymers may be used in combination.

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

[0279] 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.

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

[0281] When using these other resins, the blending ratio of the glycidyl ether group-containing compound (C) of the present embodiment and the other resin can be arbitrarily set according to the application. However, from the viewpoint of not inhibiting the reparability and reshaping properties exhibited by the present invention, it is preferable that the other resin is in a proportion of 0.5 to 100 parts by mass with respect to 100 parts by mass of the glycidyl ether group-containing compound (C) of the present embodiment.

[0282] [Non-halogenated flame retardant] When used in applications where high flame retardancy is required for the epoxy resin composition of the present embodiment, a non-halogenated flame retardant that substantially does not contain halogen atoms may be blended.

[0283] The non-halogen flame retardant includes, for example, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. There are no restrictions on their use. It can be used alone, multiple flame retardants of the same type can be used, or flame retardants of different types can be combined and used.

[0284] As for the phosphorus flame retardant, either inorganic or organic ones can be used. Examples of inorganic compounds include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide.

[0285] Furthermore, it is preferable that the red phosphorus is surface-treated for the purpose of preventing hydrolysis, etc. 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 the film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc.

[0286] Examples of the organic phosphorus compound include, in addition to 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, cyclic organic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

[0287] The compounding quantity of these phosphorus-based flame retardants is appropriately selected according to the type of phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of a resin composition containing all of a non-halogen-based flame retardant and other fillers, additives, etc., when red phosphorus is used as the non-halogen-based flame retardant, it is preferably compounded in the range of 0.1 part by mass to 2.0 parts by mass. When 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 in the range of 0.5 part by mass to 6.0 parts by mass.

[0288] When using the phosphorus-based flame retardant, it may be used in combination with hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc.

[0289] 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.

[0290] 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 guanidylmelamine sulfate, melem sulfate, melam sulfate, etc., (2) condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, etc. with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine, 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.

[0291] Examples of the cyanuric acid compound include cyanuric acid, melamine cyanurate, etc.

[0292] The compounding amount of the nitrogen-based flame retardant is appropriately selected according to the type of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of a resin composition containing all of a non-halogen-based flame retardant and other fillers and additives, etc., it is preferably compounded in the range of 0.05 to 10 parts by mass, and more preferably compounded in the range of 0.1 part by mass to 5 parts by mass.

[0293] When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, etc. may be used in combination.

[0294] The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom. For example, silicone oil, silicone rubber, silicone resin, etc. can be mentioned. The compounding 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, in 100 parts by mass of a resin composition containing all of a non-halogen-based flame retardant and other fillers and additives, etc., it is preferably compounded in the range of 0.05 to 20 parts by mass. When using the silicone-based flame retardant, a molybdenum compound, alumina, etc. may be used in combination.

[0295] Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low-melting-point glasses, etc.

[0296] Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, etc.

[0297] 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.

[0298] 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.

[0299] Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc.

[0300] Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, borax, etc.

[0301] Examples of the low melting point glass include glassy compounds such as Seeply (manufactured by Boxui 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, lead borosilicate system, etc.

[0302] The compounding amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, it is preferably compounded in the range of 0.05 parts by mass to 20 parts by mass, and more preferably in the range of 0.5 parts by mass to 15 parts by mass, in 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives.

[0303] Examples of the organic metal salt-based flame retardant include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, a compound in which a metal atom and an aromatic compound or a heterocyclic compound are ionically bonded or coordinately bonded, etc.

[0304] The compounding amount of the organometallic salt-based flame retardant is appropriately selected according to the type of the organometallic salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, it is preferably compounded in the range of 0.005 parts by mass to 10 parts by mass in 100 parts by mass of the resin composition containing all of the non-halogen-based flame retardant and other fillers, additives, etc.

[0305] [Filler] The epoxy resin composition of the present embodiment may contain a filler that does not belong to the thermally expandable particles (D) according to the present embodiment. Examples of the filler include an inorganic filler and an organic filler. Examples of the inorganic filler include inorganic fine particles.

[0306] 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 heat conduction: boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.; for those with excellent conductivity: metallic fillers and / or metal-coated fillers using a simple metal or an alloy (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 showing 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 abrasion 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.

[0307] For example, when using silica as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdery silica and colloidal silica can be used. Examples of commercially available powdery silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildecks H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industries Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Chemical Ltd., SG Flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

[0308] Examples of commercially available colloidal silica include, for example, 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.

[0309] Silica fine particles with surface modification may also be used. For example, those obtained by surface-treating the silica fine particles with a reactive silane coupling agent having a hydrophobic group, or those modified with a compound having a (meth)acryloyl group can be mentioned. Examples of commercially available powdery 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.

[0310] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped ones can be used. The primary particle diameter is preferably in the range of 5 to 200 nm.

[0311] 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 heteroelements in the crystal structure of titanium oxide can also be used. As the elements 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 organic solvents or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., and ATM-100 manufactured by Tayca Corporation. Examples of commercially available slurry-type titanium oxide fine particles include TKD-701 manufactured by Tayca Corporation.

[0312] [Fibrous substrate] The epoxy resin composition of this embodiment may further contain a fibrous substrate. The fibrous substrate is not particularly limited, but those used in fiber-reinforced resins are preferable, and examples include inorganic fibers and organic fibers.

[0313] 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 (silicon carbide fibers), ceramic fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the above metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0314] 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, and polyarylate, natural fibers such as cellulose, pulp, cotton, wool, and silk, and regenerated fibers such as protein, polypeptide, and alginic acid.

[0315] Among them, carbon fiber and glass fiber are preferable because of their wide industrial application ranges. Only one of these may be used, or a plurality of types may be used simultaneously.

[0316] 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. Further, it may have a three-dimensional shape in which the aggregate of fibers has a thickness.

[0317] [Dispersion medium] The epoxy resin composition of the present embodiment may use a dispersion medium for the purpose of adjusting the solid content and viscosity of the resin composition. The dispersion medium may be any liquid medium that does not impair the effects of the present embodiment, and examples thereof include various organic solvents and liquid organic polymers.

[0318] 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 may be used alone or in combination, and among them, methyl ethyl ketone is preferable in terms of volatility during coating and solvent recovery.

[0319] The liquid organic polymer mentioned above is a liquid organic polymer that does not directly contribute to the curing reaction. Examples include acrylic polymers (Flowlen WK-20: Kyoeisha), amine salts of special modified phosphoric esters (HIPLAAD ED-251: Kusumoto Chemicals), modified acrylic block copolymers (DISPERBYK 2000; BYK-Chemie), etc.

[0320] [Other Formulations] The resin composition of this embodiment 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.

[0321] By curing the resin composition of this embodiment, a cured product can be obtained. When curing, curing can be carried out 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-stage heating process.

[0322] In addition, the epoxy resin composition of this embodiment 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.

[0323] 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.

[0324] [Preparation Method of Epoxy Resin Composition] The epoxy resin composition of this embodiment may be prepared by uniformly mixing the foregoing 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.

[0325] The epoxy resin composition of this embodiment contains the epoxy resin (A) of this embodiment described above, the epoxy resin (B) of this embodiment described above, the glycidyl ether group-containing compound (C) of this embodiment described above, the thermally expandable particles (D) of this embodiment described above, and, if necessary, a compound (I) reactive with the glycidyl ether group-containing compound (C), and further, if necessary, a curing agent, filler, fibrous substrate, dispersion medium, and resin other than the various compounds described above that can be used in combination, are dissolved in a dispersion medium such as the foregoing organic solvent. After dissolution, the solvent is distilled off, and the epoxy resin composition can be obtained by drying under reduced pressure using a vacuum oven or the like. Alternatively, the epoxy resin composition of this embodiment may be in a state where the foregoing constituent materials are uniformly mixed. At this time, it is preferably uniformly mixed using a mixer or the like. The blending ratio of each constituent material can be appropriately adjusted according to the properties of the desired cured product, such as mechanical strength, heat resistance, reparability, and remoldability. Also, in the production of the epoxy resin composition, the specific mixing order of the constituent materials is not particularly limited.

[0326] (Cured product) The cured product of this embodiment is obtained by curing a compound (I) reactive with the glycidyl ether group-containing compound with the glycidyl ether group-containing compound (C) of this embodiment. The curing method can be appropriately selected and adopted from known methods according to the properties of the compound (I) reactive with the glycidyl ether group-containing compound (C) used.

[0327] Since the cured product of this embodiment is cured by the glycidyl ether group-containing compound (C) of this embodiment as described above, it can maintain good mechanical strength by expressing an appropriate crosslinking density. Further, when mechanical energy such as scratches or external force is applied to the cured product of this embodiment, the reversible bond is broken, but since the equilibrium moves in the bonding direction, an adduct is formed again, and it is considered that the scratch can be repaired and the product can be remolded.

[0328] The structure of the obtained cured product can be confirmed by infrared absorption (IR) spectrometry using Fourier transform infrared spectroscopy (FT-IR), elemental analysis method, X-ray scattering method, etc.

[0329] The cured product which is one embodiment of this embodiment can be obtained by using the glycidyl ether group-containing compound (C) of this embodiment as a component of the epoxy resin composition as described above. However, the intermediate of the conjugated diene described above, which is an intermediate of the glycidyl ether group-containing compound (C), is used, and a compound capable of undergoing an addition reaction by the Diels-Alder reaction is used in combination, and in the process of curing, while forming the glycidyl ether group-containing compound (C) (while synthesizing in situ), it can also be made into a cured product.

[0330] For example, when a curing reaction is carried out using the compound represented by the formula (4)’, a furan having a glycidyl ether group, and a compound (I) reactive with the glycidyl ether group-containing compound (C) as essential raw materials, in the process of the curing reaction, the glycidyl ether group-containing compound (C) represented by the formula (4) can be obtained, and further, as the curing reaction proceeds, a cured product can be obtained. The maleimide having a glycidyl ether group that can be used at this time is the same as the above.

[0331] The epoxy resin composition of this embodiment and the cured product produced by the epoxy resin composition are excellent in both heat resistance and reparability, and have remoldability, and are useful for the following applications.

[0332] The cured product of the curable resin according to this embodiment 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. can be appropriately used according to the application, and it can also be in the form of the shape of the laminate, which can be a flat plate, sheet-like, or have a three-dimensional structure, and can also be three-dimensional. It can be in any shape according to the purpose, such as having curvature on the entire surface or a part thereof. Also, there are no restrictions on the hardness, thickness, etc. of the substrate. Further, it can also be a multi-layer laminate formed by laminating a first substrate, a layer made of the cured product of the epoxy resin composition of this embodiment, and a second substrate in this order. Since the epoxy resin composition of this embodiment has excellent 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 according to this embodiment can be used as a substrate, and the cured product of this embodiment can be further laminated.

[0333] Moreover, since the cured product of the curable resin according to this embodiment 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 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 this embodiment.

[0334] In a laminate formed by laminating the cured product of the present embodiment and a substrate, the layer containing the cured product may be formed directly on the substrate by coating or molding, or a pre-formed product 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 the 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 to the substrate. Also, the cured product of the present embodiment may be laminated by coating and curing a precursor that can be a substrate, or may be cured after adhering the precursor that can be a substrate or the composition of the present embodiment in an uncured or semi-cured state. The precursor that can be a substrate is not particularly limited, and examples include various epoxy resin compositions, etc.

[0335] The cured product obtained by using the epoxy resin composition of the present embodiment 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 is particularly excellent in adhesive force to iron, copper, and aluminum, it can be preferably used as an adhesive for iron, copper, and aluminum.

[0336] The epoxy resin composition of this embodiment can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering, electronics, aircraft, and the space industry. When used for bonding different materials such as between metal and non-metal, this adhesive can maintain high adhesiveness without being affected by changes in the temperature environment, and peeling and the like are unlikely 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 also 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, and an anisotropic conductive paste for mounting.

[0337] When the epoxy resin composition of this embodiment has a fibrous substrate and the fibrous substrate is a reinforcing fiber, the epoxy resin composition containing the fibrous substrate can be used as a fiber-reinforced resin. The method of adding the fibrous substrate to the composition is not particularly limited as long as the effects of this embodiment are not impaired. Examples of the method of compounding the fibrous substrate and the composition include kneading, coating, impregnation, injection, and pressure bonding, etc., and can be appropriately selected according to the form of the fiber and the use of the fiber-reinforced resin.

[0338] The method for molding the fiber-reinforced resin is not particularly limited. If a plate-like product is to be manufactured, the extrusion molding method is common, but it is also possible by 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-like 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, calender molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, coating molding, etc. can be mentioned. Also, in the case of a resin curable 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 used as 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.

[0339] Since the cured product using the epoxy resin composition of the present embodiment has both good heat resistance and restorability and has remoldability, it can be used as a molding material for large cases, motor housings, casting materials inside the case, gears, pulleys, etc. These may be cured products of resin alone or fiber-reinforced cured products such as glass chips.

[0340] The fiber-reinforced resin can form a state called uncured or semi-cured prepreg. After the product is distributed 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 adhered, 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.

[0341] The cured product of this embodiment has good 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 substrates, etc., as well as adhesives and resist materials. It can also be suitably used as the matrix resin of 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 in various applications, for example, industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., aerospace-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.

[0342] Among them, taking advantage of the excellent flexibility in 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 this embodiment 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 it is difficult for peeling or the like to occur. Also, in addition to structural member applications, the adhesive of this embodiment 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 optical component bonding, adhesives for bonding optical disks, adhesives for printed wiring board mounting, die bonding adhesives, semiconductor adhesives such as underfills, underfills for BGA reinforcement, anisotropic conductive films, anisotropic conductive pastes, and other mounting adhesives.

[0343] In addition, taking advantage of the excellent easy-disassembly property of the cured product of the present embodiment, an easy-disassembly adhesive material containing the epoxy resin composition of the present embodiment can be used. It is preferable that the easy-disassembly adhesive material is the epoxy resin composition of the present embodiment. The disassembly method using the easy-disassembly adhesive material of the present embodiment includes, for example, an adhering step of adhering the easy-disassembly adhesive material to the surface of an adherend and joining it to the adherend, a curing step of curing the easy-disassembly adhesive material to obtain a cured product, and a heat treatment step of performing heat treatment on the cured product to thermally dissociate the reversible bond contained in the general formula (4) derived from the glycidyl ether group-containing compound (C) and expand the thermally expandable particles (D), and a disassembly step of disassembling the adherend and the cured product. In addition, the disassembly method using the easy-disassembly adhesive material of the present embodiment may include, for example, an adhering step of adhering the easy-disassembly adhesive material to the surface of an adherend and joining it to the adherend, a curing step of curing the easy-disassembly adhesive material to obtain a cured product, a heat treatment step of performing heat treatment on the cured product to thermally dissociate the reversible bond contained in the general formula (4) derived from the glycidyl ether group-containing compound (C) and expand the thermally expandable particles (D), a cooling step of cooling the cured product after heat treatment to room temperature, and a disassembly step of disassembling the adherend and the cured product.

[0344] Hereinafter, examples will be given and described for representative products.

[0345] 1. Semiconductor encapsulation material As a method for obtaining a semiconductor encapsulant from the resin composition of the present embodiment, a method of sufficiently melt-mixing the resin composition, compounding agents such as a curing accelerator and an inorganic filler, etc., using an extruder, kneader, roll, etc. until it becomes uniform is mentioned. At that time, as the inorganic filler, fused silica is usually used, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, highly filled crystalline silica, alumina, silicon nitride, etc., having a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc. may be used. 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 epoxy resin composition. In particular, 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.

[0346] 2. Semiconductor device As the semiconductor package molding for obtaining a semiconductor device from the epoxy resin composition of the present embodiment, a method of molding the above semiconductor encapsulant using a casting, transfer molding machine, injection molding machine, etc., and further heating at 50 to 250 °C for 2 to 10 hours is mentioned.

[0347] 3. Printed circuit board As a method for obtaining a printed circuit board from the composition of the present embodiment, a method of laminating the above prepreg by a conventional method, appropriately laminating copper foil, and thermocompression bonding at 170 to 300 °C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa is mentioned.

[0348] 4. Flexible substrate As a method for manufacturing a flexible substrate from the crosslinkable resin composition of the present embodiment, 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 heater, volatilizing the solvent from the electrically insulating film, and B-staging the crosslinkable resin composition. The third step is a step of thermocompression bonding (the bonding pressure is preferably 2 to 200 N / cm and the bonding temperature is preferably 40 to 200 °C) a metal foil to the adhesive using a heating roll or the like on the electrically insulating film on which the crosslinkable resin composition has been B-staged. In addition, 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.

[0349] 5. Build-up substrate Examples of the method for obtaining a build-up substrate from the composition of the present embodiment 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 by a spray coating method, a curtain coating method, etc. and then curing it (step 1). After that, if necessary, after making holes such as a predetermined through-hole portion, treating with a roughening agent, forming unevenness by hot washing the surface, and plating a metal such as copper (step 2). Such operations are sequentially repeated as desired to form a build-up of a resin insulating layer and a conductor layer of a predetermined circuit pattern alternately (step 3). Note that the holes for the through-hole portion are made after the formation of the outermost resin insulating layer. Also, the build-up substrate of the present embodiment can be manufactured by heat-pressure bonding a copper foil with resin in which the resin composition is semi-cured on 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.

[0350] 6. Build-up Film As a method for obtaining a build-up film from the composition of this embodiment, the composition can be applied to the surface of a support film (Y) as a base material, and the organic solvent can be dried by further heating or blowing hot air, etc. to form a layer (X) of the composition.

[0351] 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 in a ratio such that the non-volatile content is 30 to 60% by mass.

[0352] 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 resin composition layer preferably has a thickness of 10 to 100 μm. In addition, the layer (X) of the composition in this embodiment may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the adhesion of dust and scratches to the surface of the resin composition layer.

[0353] 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, aluminum foil, and other metal foils. The support film and the protective film may be subjected to a mat treatment, a corona treatment, and a release treatment in addition to these. The thickness of the support film is not particularly limited, but it is usually 10 to 150 μm, preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0354] After the above-mentioned support film (Y) is laminated on the circuit board, or after an insulating layer is formed by heat curing, it is peeled off. If the support film (Y) is peeled off after the epoxy resin composition layer constituting the build-up film is heat cured, it is possible to prevent the adhesion of dust or the like during the curing process. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0355] 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 off, the layer (X) is laminated on one side 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 roll type. If necessary, the build-up film and the circuit board may be heated (preheated) as required before lamination. The lamination conditions preferably have a pressure bonding temperature (lamination temperature) of 70 to 140°C, a pressure bonding pressure of 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and preferably laminated under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0356] 7. Conductive paste As a method for obtaining a conductive paste from the epoxy resin composition of this embodiment, 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

[0357] 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.

[0358] 1 H and 13 C-NMR, FD-MS spectra, and GPC were measured under the following conditions.

[0359] 1 H-NMR: JEOL RESONANCE "JNM-ECA600" Magnetic field strength: 600 MHz Number of integrations: 32 times Solvent: DMSO-d 6 Sample concentration: 30 mass%

[0360] 13 C-NMR: JEOL RESONANCE "JNM-ECA600" Magnetic field strength: 150 MHz Number of integrations: 320 times Solvent: DMSO-d 6 Sample concentration: 30 mass%

[0361] FD-MS: JEOL Ltd. "JMS-T100GC AccuTOF" Measurement range: m / z = 50.00 to 2000.00 Rate of change: 25.6 mA / min Final current value: 40 mA Cathode voltage: -10 kV

[0362] GPC: Tosoh Corporation "HLC-8320GPC" Column: Tosoh Corporation "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Measurement conditions: 40 °C Mobile phase: tetrahydrofuran Flow rate: 1 ml / min Standard: Tosoh Corporation "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F"

[0363] 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.

[0364] Examples of the calculation method of the repeating unit number include calculation from various appropriate instrumental analysis results such as GPC molecular weight measurement, FD-MS, and NMR.

[0365] Synthesis Example 1 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthesis Co., Ltd.: epoxy equivalent 210 g / eq) and 240 g (2.1 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq) were charged into a flask equipped with a thermometer, a condenser, and a stirrer. After heating up to 140 °C over 30 minutes, 6.6 g of a 20% aqueous sodium hydroxide solution was charged. Then, it took 30 minutes to heat up to 150 °C, and further reacted at 150 °C for 16 hours. Then, sodium phosphate of the neutralization amount was added to obtain 646 g of a hydroxy compound (Ph-1). Since this hydroxy compound (Ph-1) gave a peak of M+ = 771 corresponding to the theoretical structure of m = 1 in the following structural formula (Ph-1) in the mass spectrum, it was confirmed that it contained the target hydroxy compound. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-1) was 2053 g / eq, and the average value of the repeating unit m was 6.9.

[0366]

Chemical Formula

[0367] Synthesis Example 2 In Synthesis Example 1, 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (epoxy equivalent weight: 210 g / eq) was changed to 472 g (2.0 equivalents) of diglycidyl ether of 1,15-pentadecanediol (epoxy equivalent weight: 236 g / eq), and the reaction was carried out in the same manner as in Synthesis Example 1 to obtain 697 g of hydroxy compound (Ph-2). Since a peak of M+ = 813 corresponding to the theoretical structure of m = 1 in the following structural formula (Ph-2) was obtained in the mass spectrum of this hydroxy compound (Ph-2), it was confirmed that the hydroxy compound as the target substance was contained. The hydroxyl equivalent weight calculated from the GPC of this hydroxy compound (Ph-2) was 2226 g / eq, and the average value of the repeating unit m was 6.8.

[0368] [Chemical Formula]

[0369] Synthesis Example 3 In Synthesis Example 1, 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (epoxy equivalent weight: 210 g / eq) was changed to 380 g (2.0 equivalents) of diglycidyl ether of 1,9-nonanediol (epoxy equivalent weight: 190 g / eq), and the reaction was carried out in the same manner as in Synthesis Example 1 to obtain 607 g of hydroxy compound (Ph-3). Since a peak of M+ = 729 corresponding to the theoretical structure of m = 1 in 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 as the target substance was contained. The hydroxyl equivalent weight calculated from the GPC of this hydroxy compound (Ph-3) was 1989 g / eq, and the average value of the repeating unit m was 7.2.

[0370] [Chemical Formula]

[0371] Synthesis Example 4 In Synthesis Example 1, except that 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthesis Co., Ltd.: epoxy equivalent 210 g / eq) and 240 g (2.1 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq) were changed to 962 g (2.0 equivalents) of diglycidyl ether of polypropylene glycol (“Denacol EX-931” manufactured by Nagase ChemteX Corporation: epoxy equivalent 481 g / eq) and 274 g (2.4 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq), the reaction was carried out in the same manner as in Synthesis Example 1, and 1211 g of a hydroxy compound (Ph-4) was obtained. Since a peak of M+ = 1226 corresponding to the theoretical structure with m = 1 and n2 = 11 in the following structural formula (Ph-4) was obtained in the mass spectrum of this hydroxy compound (Ph-4), it was confirmed that the target hydroxy compound was contained. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-4) was 1582 g / eq, and the average value of the repeating unit m was 3.3.

[0372] [Chemical Formula]

[0373] Synthesis Example 5 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei Co., Ltd.: epoxy equivalent 210 g / eq) and 240 g (2.1 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq) in Synthesis Example 1 were changed to 890 g (2.0 equivalents) of diglycidyl ether of polytetramethylene glycol (“Denacol EX-991L” manufactured by Nagase ChemteX Corporation: epoxy equivalent 445 g / eq) and 274 g (2.4 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq), and the reaction was carried out in the same manner as in Synthesis Example 1, and 1140 g of a hydroxy compound (Ph-5) was obtained. Since a peak of M+ = 1380 corresponding to the theoretical structure of m = 1 and n2 = 11 in the following structural formula (Ph-5) was obtained in the mass spectrum of this hydroxy compound (Ph-5), it was confirmed that it contained the target hydroxy compound. The hydroxyl equivalent calculated from GPC of this hydroxy compound (Ph-5) was 2520 g / eq, and the average value of the repeating unit m was 5.1.

[0374] [Chemical formula]

[0375] Synthesis Example 6 In Synthesis Example 1, except that 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthesis Co., Ltd.: epoxy equivalent 210 g / eq) and 240 g (2.1 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq) were changed to 126.2 g (0.39 mol) of diglycidyl ether of 1,6-hexanediol (“SR-16H” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.: epoxy equivalent 160 g / eq), 78.1 g (0.08 mol) of diglycidyl ether of polypropylene glycol (“Denacol EX-931” manufactured by Nagase ChemteX Corporation: epoxy equivalent 481 g / eq), and 114.6 g (0.50 mol) of bisphenol A (hydroxyl equivalent 114 g / eq), the reaction was carried out in the same manner as in Synthesis Example 1, and 317 g of a hydroxy compound (Ph-6) was obtained. Since a peak of M+=1684 corresponding to the theoretical structure of m1 = 1, m2 = 1, n2 = 11 in the following structural formula (Ph-6) was obtained in the mass spectrum of this hydroxy compound (Ph-6), it was confirmed that the target hydroxy compound was contained. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-6) was 1597 g / eq.

[0376]

Chemical Structure

[0377] Synthesis Example 7 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei Co., Ltd.: epoxy equivalent 210 g / eq) and 240 g (2.1 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq) in Synthesis Example 1 were changed to 136 g (0.43 mol) of diglycidyl ether of 1,6-hexanediol ("SR-16H" manufactured by Sakamoto Yakuhin: epoxy equivalent 160 g / eq), 66 g (0.07 mol) of diglycidyl ether of polytetramethylene glycol ("Denacol EX-991L" manufactured by Nagase ChemteX: epoxy equivalent 445 g / eq), and 119.7 g (0.53 mol) of bisphenol A (hydroxyl equivalent 114 g / eq). The reaction was carried out in the same manner as in Synthesis Example 1, and 318 g of a hydroxy compound (Ph-7) was obtained. From the mass spectrum of this hydroxy compound (Ph-7), a peak of M+ = 1839 corresponding to the theoretical structure of m1 = 1, m2 = 1, and n2 = 11 in the following structural formula (Ph-7) was obtained. Thus, it was confirmed that the obtained hydroxy compound contained the target hydroxy compound. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-7) was 1896 g / eq.

[0378]

Chemical Formula

[0379] Synthesis Example 8 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei Co., Ltd., epoxy equivalent 210 g / eq) and 456 g (4.0 equivalents) of bisphenol A (hydroxyl equivalent 114 g / eq) were charged into a flask equipped with a thermometer, a cooling tube, and a stirrer. After heating up to 140 °C over 30 minutes, 4.0 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, the neutralizing amount of sodium phosphate was added to obtain 858 g of a hydroxy compound (Ph-8). Since a peak of M+ = 771 corresponding to the theoretical structure of m = 1 in the following structural formula (Ph-8) was obtained in the mass spectrum of this hydroxy compound (Ph-8), it was confirmed that the target hydroxy compound was contained. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-8) was 388 g / eq.

[0380] [Chemical formula]

[0381] Synthesis Example 9 The reaction was carried out in the same manner as in Synthesis Example 8 except that 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (epoxy equivalent 210 g / eq) in Synthesis Example 8 was changed to 962 g (2.0 equivalents) of diglycidyl ether of polypropylene glycol (manufactured by Nagase ChemteX Corporation, "Denacol EX-931", epoxy equivalent 481 g / eq), and 1390 g of a hydroxy compound (Ph-9) was obtained. Since a peak of M+ = 1226 corresponding to the theoretical structure of m = 1 and n2 = 11 in the following structural formula (Ph-9) was obtained in the mass spectrum of this hydroxy compound (Ph-9), it was confirmed that the target hydroxy compound was contained. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-9) was 593 g / eq.

[0382] [Chemical formula]

[0383] Synthesis Example 10 In Synthesis Example 8, the reaction was carried out in the same manner as in Synthesis Example 8 except that 420 g (2.0 equivalents) of diglycidyl ether of 1,12-dodecanediol (epoxy equivalent 210 g / eq) was changed to 884 g (2.0 equivalents) of diglycidyl ether of polytetramethylene glycol (“Denacol EX-991L” manufactured by Nagase ChemteX: epoxy equivalent 442 g / eq), and 1313 g of hydroxy compound (Ph-10) was obtained. From the fact that a peak of M+ = 1380 corresponding to the theoretical structure of m = 1 and n2 = 11 in the following structural formula (Ph-10) was obtained in the mass spectrum of this hydroxy compound (Ph-10), it was confirmed that the target hydroxy compound was contained. The hydroxyl equivalent calculated from the GPC of this hydroxy compound (Ph-10) was 600 g / eq.

[0384]

Chemical formula

[0385] Synthesis Example 11 Into a flask equipped with a thermometer, a dropping funnel, a condenser tube, and a stirrer, while purging with nitrogen gas, 205.3 g of the hydroxy compound (Ph-1) obtained in Synthesis Example 1, 647.5 g (7.0 mol) of epichlorohydrin, and 150 g of n-butanol were added and dissolved. Then, after heating to 65 °C, the pressure was reduced to the pressure at which azeotropy occurs, and 10.6 g (0.13 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 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. Then, unreacted epichlorohydrin was distilled off by vacuum distillation. 200 g of methyl isobutyl ketone and 100 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 15.0 g of a 10% aqueous sodium hydroxide solution was added to this solution, and after reacting at 80 °C for 2 hours, washing with 100 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 fine filtration, the solvent was distilled off under reduced pressure to obtain 235 g of an epoxy resin (Ep-1). The epoxy equivalent of the obtained epoxy resin (Ep-1) was 2320 g / eq. The epoxy resin had a peak of M+ = 883 corresponding to the theoretical structure of m = 1, q = 1, p 1 = 0, p 2 = 0 in the following structural formula (Ep-1) in the mass spectrum, and it was confirmed that the epoxy resin (Ep-1) which was the target substance was contained.

[0386]

Chemical formula

[0387] Synthesis Example 12 In Synthesis Example 11, the reaction was carried out in the same manner as in Synthesis Example 11, except that 205.3 g of the hydroxy compound (Ph-1) was changed to 222.6 g of the hydroxy compound (Ph-2), and 251 g of an epoxy resin (Ep-2) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-2) was 2510 g / eq. Since a peak of M+ = 925 corresponding to the theoretical structure of m = 1, p1 = 0, p2 = 0, q = 1 in the following structural formula (Ep-2) was obtained in the mass spectrum, it was confirmed that the obtained epoxy resin contained the target epoxy resin (Ep-2).

[0388]

Chemical formula

[0389] Synthesis Example 13 In Synthesis Example 11, the reaction was carried out in the same manner as in Synthesis Example 11, except that 205.3 g of the hydroxy compound (Ph-1) was changed to 198.9 g of the hydroxy compound (Ph-3), and 229 g of an epoxy resin (Ep-3) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-3) was 2250 g / eq. Since a peak of M+ = 841 corresponding to the theoretical structure of m = 1, p1 = 0, p2 = 0, q = 1 in the following structural formula (Ep-3) was obtained in the mass spectrum, it was confirmed that the obtained epoxy resin contained the target epoxy resin (Ep-3).

[0390]

Chemical formula

[0391] Synthesis Example 14 In Synthesis Example 11, 205.3 g of the hydroxy compound (Ph-1) was used, and the reaction was carried out in the same manner as in Synthesis Example 11 except that it was changed to 158.2 g of the hydroxy compound (Ph-4), and 193 g of an epoxy resin (Ep-4) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-4) was 1802 g / eq. For this epoxy resin, a peak of M+ = 1336 corresponding to the theoretical structure of m = 1, n2 = 11, p1 = 0, p2 = 0, q = 1 in the following structural formula (Ep-4) was obtained by mass spectrometry, so it was confirmed that the target epoxy resin (Ep-4) was contained.

[0392] [Chemical formula]

[0393] Synthesis Example 15 In Synthesis Example 11, 205.3 g of the hydroxy compound (Ph-1) was used, and the reaction was carried out in the same manner as in Synthesis Example 11 except that it was changed to 252.0 g of the hydroxy compound (Ph-5), and 277 g of an epoxy resin (Ep-5) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-5) was 2834 g / eq. For this epoxy resin, a peak of M+ = 1492 corresponding to the theoretical structure of m = 1, n2 = 11, p1 = 0, p2 = 0, q = 1 in the following structural formula (Ep-5) was obtained by mass spectrometry, so it was confirmed that the target epoxy resin (Ep-5) was contained.

[0394] [Chemical formula]

[0395] Synthesis Example 16 In Synthesis Example 11, 205.3 g of the hydroxy compound (Ph-1) was reacted in the same manner as in Synthesis Example 11 except that it was changed to 198.4 g of the hydroxy compound (Ph-6), and 229 g of an epoxy resin (Ep-6) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-6) was 2244 g / eq. The epoxy resin gave a peak of M+ = 1796 corresponding to the theoretical structure of m1 = 1, m2 = 2, n2 = 11, p1 = 0, p2 = 0, q = 1 in the following structural formula (Ep-6) in the mass spectrum, and thus it was confirmed that the target epoxy resin (Ep-6) was contained.

[0396]

Chemical formula

[0397] Synthesis Example 17 In Synthesis Example 11, 205.3 g of the hydroxy compound (Ph-1) was reacted in the same manner as in Synthesis Example 11 except that it was changed to 191.4 g of the hydroxy compound (Ph-7), and 223 g of an epoxy resin (Ep-7) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-7) was 2167 g / eq. The epoxy resin gave a peak of M+ = 1951 corresponding to the theoretical structure of m1 = 1, m2 = 2, n2 = 11, p1 = 0, p2 = 0, q = 1 in the following structural formula (Ep-7) in the mass spectrum, and thus it was confirmed that the target epoxy resin (Ep-7) was contained.

[0398]

Chemical formula

[0399] Synthesis Example 18 In Synthesis Example 11, the reaction was carried out in the same manner as in Synthesis Example 11 except that 205.3 g of the hydroxy compound (Ph-1) was changed to 388 g of the hydroxy compound (Ph-8), and 399 g of an epoxy resin (Ep-8) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-8) was 488 g / eq. Since a peak of M+ = 883 corresponding to the theoretical structure with m = 1, p1 = 0, p2 = 0, and q = 1 in the following structural formula (Ep-8) was obtained in the mass spectrum, it was confirmed that the obtained epoxy resin contained the target epoxy resin (Ep-8).

[0400] [Chemical formula]

[0401] Synthesis Example 19 In Synthesis Example 11, the reaction was carried out in the same manner as in Synthesis Example 11 except that 205.3 g of the hydroxy compound (Ph-1) was changed to 593 g of the hydroxy compound (Ph-9), and 584 g of an epoxy resin (Ep-9) was obtained. The epoxy equivalent of the obtained epoxy resin (Ep-9) was 714 g / eq. Since a peak of M+ = 1336 corresponding to the theoretical structure with m = 1, p1 = 0, p2 = 0, and q = 1 in the following structural formula (Ep-9) was obtained in the mass spectrum, it was confirmed that the obtained epoxy resin contained the target epoxy resin (Ep-9).

[0402] [Chemical formula]

[0403] Synthesis Example 20 In Synthesis Example 11, the reaction was carried out in the same manner as in Synthesis Example 11, except that 205.3 g of the hydroxy compound (Ph-1) was changed to 600 g of the hydroxy compound (Ph-10), to obtain 591 g of an epoxy resin (Ep-10). The epoxy equivalent of the obtained epoxy resin (Ep-10) was 722 g / eq. In the mass spectrum of this epoxy resin, a peak of M+ = 1492 corresponding to the theoretical structure of m = 1, p1 = 0, p2 = 0, q = 1 in the following structural formula (Ep-10) was obtained, so it was confirmed that the epoxy resin (Ep-10) as the target substance was contained.

[0404]

Chemical formula

[0405] Synthesis Example 21 An epoxy compound (Ep-11) was synthesized according to the method described in the literature of J. Network Polym., Jpn., Vol. 29, 208; 2008. The epoxy equivalent of the obtained epoxy (compound Ep-11) was 450 g / eq.

[0406]

Chemical formula

[0407] Synthesis Example 22 To a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, while purging with nitrogen gas, 48.8 g (epoxy equivalent 488 g / eq) of the epoxy resin (EP-8) obtained in Synthesis Example 18 and 19.6 g (0.2 mol) of furfuryl alcohol were added and dissolved. Then, 0.7 g (0.007 mol) of triethylamine was added, the temperature was raised to 70 °C over 30 minutes, and the reaction was further carried out at 70 °C for 9 hours. Then, the temperature was raised to 150 °C, and excess furfuryl alcohol was distilled off under reduced pressure to obtain 53 g of a furan compound (F-1). The molecular weight of this furan compound (F-1) measured by GPC was Mn = 1600 and Mw = 4900. The molecular weight per mole of the furan structure calculated from 1H-NMR of this furan compound (F-1) was 575 g / eq.

[0408] [Chemical formula]

[0409] Synthesis Example 23 In a flask equipped with a thermometer, a stirrer, and a condenser, 29 g of the furan compound (F-1, furan equivalent 575 g / eq) obtained in Synthesis Example 22, 11.9 g of 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (BMI-THM manufactured by Daiwa Kasei Kogyo Co., Ltd.), and 50 g of toluene were charged. After substitution with nitrogen, the mixture was reacted at 60°C for 20 hours. Thereafter, toluene was distilled off under reduced pressure to obtain 41 g of the maleimide compound (M-1). The molecular weights measured by GPC were Mn = 2300 and Mw = 9000. Also, the molecular weight per mole of the maleimide structure calculated from 1H-NMR was 1627 g / eq.

[0410] [Chemical formula]

[0411] Synthesis Example 24 In a flask equipped with a thermometer, a stirrer, and a condenser, 40 g of the maleimide compound (M-1, maleimide equivalent 1627 g / eq) obtained in Synthesis Example 23, 3.9 g of furfuryl glycidyl ether (manufactured by Kanto Chemical), and 50 g of toluene were charged. After substitution with nitrogen, the mixture was reacted at 60°C for 12 hours. Thereafter, toluene was distilled off under reduced pressure to obtain 40 g of the glycidyl ether group-containing compound (D-1). The molecular weights measured by GPC were Mn = 2500 and Mw = 9400. Also, the epoxy equivalent was 1780 g / eq.

[0412] [Chemical formula]

[0413] Synthesis Example 25 In Synthesis Example 22, the reaction was carried out in the same manner as in Synthesis Example 22 except that 48.8 g of an epoxy resin (Ep-8) (epoxy equivalent 488 g / eq) was changed to 71.4 g of an epoxy resin (Ep-9) (epoxy equivalent 714 g / eq), and 74 g of a furan compound (F-2) was obtained. The molecular weight measured by GPC of this furan compound (F-2) was Mn = 1900 and Mw = 5100. The molecular weight per mole of the furan structure calculated from the 1H-NMR of this furan compound (F-2) was 796 g / eq.

[0414]

Chemical Structure

[0415] Synthesis Example 26 In Synthesis Example 23, the reaction was carried out in the same manner as in Synthesis Example 23 except that 29 g of a furan compound (F-1, furan equivalent 575 g / eq) was changed to 40 g of a furan compound (F-2, furan equivalent 796 g / eq), and 52 g of a maleimide compound (M-2) was obtained. The molecular weight measured by GPC was Mn = 3600 and Mw = 9900. Also, the molecular weight per mole of the maleimide structure calculated from 1H-NMR was 2069 g / eq.

[0416]

Chemical Structure

[0417] Synthesis Example 27 In Synthesis Example 24, the reaction was carried out in the same manner as in Synthesis Example 24 except that 40 g of a maleimide compound (M-1, maleimide equivalent 1627 g / eq) was changed to 51 g of a maleimide compound (M-2, maleimide equivalent 2069 g / eq), and 52 g of a glycidyl ether group-containing compound (D-2) was obtained. The molecular weight measured by GPC was Mn = 3900 and Mw = 10600. Also, the epoxy equivalent was 2223 g / eq.

[0418]

Chemical Structure

[0419] Synthesis Example 28 The reaction was carried out in the same manner as in Synthesis Example 22, except that 48.8 g (epoxy equivalent: 488 g / eq) of the epoxy resin (Ep-8) in Synthesis Example 22 was changed to 72.2 g (epoxy equivalent: 722 g / eq) of the epoxy resin (Ep-10), and 74 g of the furan compound (F-3) was obtained. The molecular weights measured by GPC of this furan compound (F-3) were Mn = 2400 and Mw = 8100. The molecular weight per mole of the furan structure calculated from the 1H-NMR of this furan compound (F-3) was 804 g / eq.

[0420]

Chemical Formula

[0421] Synthesis Example 29 The reaction was carried out in the same manner as in Synthesis Example 23, except that 29 g of the furan compound (F-1, furan equivalent: 575 g / eq) in Synthesis Example 23 was changed to 40 g of the furan compound (F-3, furan equivalent: 804 g / eq), and 53 g of the maleimide compound (M-3) was obtained. The molecular weights measured by GPC were Mn = 4200 and Mw = 13100. Also, the molecular weight per mole of the maleimide structure calculated from the 1H-NMR was 2085 g / eq.

[0422]

Chemical Formula

[0423] Synthesis Example 30 The reaction was carried out in the same manner as in Synthesis Example 24, except that 40 g of the maleimide compound (M-1, maleimide equivalent: 1627 g / eq) in Synthesis Example 24 was changed to 52 g of the maleimide compound (M-3, maleimide equivalent: 2085 g / eq), and 53 g of the glycidyl ether group-containing compound (D-3) was obtained. The molecular weights measured by GPC were Mn = 3100 and Mw = 13200. Also, the epoxy equivalent was 2239 g / eq.

[0424]

Chemical Formula

[0425] Synthesis Example 31 In Synthesis Example 22, 48.8 g of the epoxy resin (Ep-8) (epoxy equivalent: 488 g / eq) was changed to 21 g of the diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Gosei Co., Ltd.; epoxy equivalent: 210 g / eq), and the reaction was carried out in the same manner as in Synthesis Example 22 to obtain 29 g of the furan compound (F-4). Since the mass spectrum showed a peak of M+ = 510 corresponding to the theoretical structure of the following structural formula (F-4), it was confirmed that the obtained furan compound contained the target furan compound (F-4). The molecular weight of this furan compound (F-4) measured by GPC was Mn = 800 and Mw = 1300. The molecular weight per mole of the furan structure calculated from the 1H-NMR of this furan compound (F-4) was 302 g / eq.

[0426] [Chemical Formula]

[0427] Synthesis Example 32 In Synthesis Example 23, 29 g of the furan compound (F-1, furan equivalent: 575 g / eq) was changed to 15 g of the furan compound (F-4, furan equivalent: 302 g / eq), and the reaction was carried out in the same manner as in Synthesis Example 23 to obtain 27 g of the maleimide compound (M-4). The molecular weight measured by GPC was Mn = 2000 and Mw = 6400. Also, the molecular weight per mole of the maleimide structure calculated from the 1H-NMR was 1081 g / eq.

[0428] [Chemical Formula]

[0429] Synthesis Example 33 In Synthesis Example 24, the reaction was carried out in the same manner as in Synthesis Example 24 except that 40 g of the maleimide compound (M-1, maleimide equivalent 1627 g / eq) was changed to 27 g of the maleimide compound (M-4, maleimide equivalent 1081 g / eq), and 28 g of the glycidyl ether group-containing compound (D-4) was obtained. The molecular weights measured by GPC were Mn = 2800 and Mw = 7200. The epoxy equivalent was 1235 g / eq.

[0430]

Chemical Formula

[0431] Synthesis Example 34 In Synthesis Example 22, the reaction was carried out in the same manner as in Synthesis Example 22 except that 48.8 g (epoxy equivalent 488 g / eq) of the epoxy resin (Ep-8) was changed to 45.0 g (epoxy equivalent 450 g / eq) of the epoxy resin (Ep-11), and 49 g of the furan compound (F-5) was obtained. The molecular weights measured by GPC of this furan compound (F-5) were Mn = 1100 and Mw = 1900. The molecular weight per mole of the furan structure calculated from the 1H-NMR of this furan compound (F-5) was 537 g / eq.

[0432]

Chemical Formula

[0433] Synthesis Example 35 In Synthesis Example 23, the reaction was carried out in the same manner as in Synthesis Example 23 except that 29 g of the furan compound (F-1, furan equivalent 575 g / eq) was changed to 26 g of the furan compound (F-5, furan equivalent 537 g / eq), and 39 g of the maleimide compound (M-5) was obtained. The molecular weights measured by GPC were Mn = 3200 and Mw = 7100. The molecular weight per mole of the maleimide structure calculated from 1H-NMR was 1552 g / eq.

[0434]

Chemical Formula

[0435] Synthesis Example 36 The reaction was carried out in the same manner as in Synthesis Example 24, except that 40 g of the maleimide compound (M-1, maleimide equivalent: 1627 g / eq) in Synthesis Example 24 was changed to 39 g of the maleimide compound (M-5, maleimide equivalent: 1552 g / eq), and 40 g of the glycidyl ether group-containing compound (D-5) was obtained. The molecular weights measured by GPC were Mn = 3600 and Mw = 8000. Also, the epoxy equivalent was 1706 g / eq.

[0436]

Chemical formula

[0437] Preparation of Compositions and Cured Products of Examples 1 to 24 and Comparative Examples 1 to 6 Using each compound according to the formulations shown in Tables 1 to 2 (the numbers in the tables are based on mass), they were uniformly mixed using a mixer ("Avatori Rentarou ARV-200" manufactured by Shinchi 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.

[0438] <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 carried out in accordance with JIS K 7162-2 using a tensile tester ("Autograph AG-IS" manufactured by Shimadzu Corporation), and the elongation at the break point at a measurement environment of 23°C was evaluated (test speed: 2 mm / min).

[0439] <Adhesion and Disassembly Evaluation> Using each compound according to the formulations shown in Tables 1 to 2 (the numbers in the tables are based on mass), they were uniformly mixed using a mixer (ARV-200, manufactured by Shinki Co., Ltd.) to obtain a curable resin composition. This resin composition was applied to one of two cold-rolled steel sheets (SPCC-SD, 1.0 mm×25 mm×100 mm, manufactured by TP Giken Co., Ltd.), glass beads (J-80, manufactured by Potters Balotini Co., Ltd.) were added as spacers, and the other SPCC-SD was bonded thereto (bonding area: 25 mm×12.5 mm). This was heat-cured at the temperature according to Tables 1 to 2 to obtain a shear test piece. The adhesiveness was evaluated by performing a tensile shear test using the test piece. The test was conducted according to JIS K 6850, and the maximum point stress at a measurement environment of 23°C was compared. ·Initial adhesiveness: A shear test was performed on the prepared test piece without any special treatment. ·Adhesiveness after heating: The prepared test piece was heated at 200°C for 30 minutes using a heat dryer, and after further cooling the substrate to room temperature, a shear test was performed. ·Evaluation of disassemblability: The strength reduction rate was calculated by “(Initial adhesiveness−Adhesiveness after heating) / Initial adhesiveness×100”. ·Evaluation of reproducibility of disassemblability: The standard deviation of “Adhesiveness after heating” was evaluated and evaluated according to the following criteria. A: The standard deviation is less than 0.5 MPa (extremely good reproducibility) B: The standard deviation is 0.5 MPa or more and less than 1.5 MPa (good reproducibility) C: The standard deviation is 1.5 MPa or more (poor reproducibility) -: Since the strength reduction rate is less than 10%, the evaluation was not carried out (no disassembly function) The maximum point stress at a measurement environment of 23°C was compared.

[0440] <Structural periodicity> Cross-sections of the cured resin were prepared using an ultramicrotome, and the structural periodicity was observed. The observation method was carried out using a scanning electron microscope (SEM) so that the contrast of the morphology could be clearly discriminated.

[0441] SEM Model used: JSM-7800F manufactured by JEOL Ltd. Accelerating voltage: 5 kV

[0442]

Table 1

[0443]

Table 2

[0444] In addition, 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) DICY: Dicyandiamide (“DICY7” manufactured by Mitsubishi Chemical Corporation) DCMU: 3-(3,4-dichlorophenyl)-1,1-dimethylurea) (“B-605-IM” manufactured by DIC Corporation) DTA: Diethylenetriamine (manufactured by Kanto Chemical) F-260D, F-190D: Thermal expansion capsules (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) 953240L: Thermal expansion graphite (manufactured by Ito Graphite Industries) EXP 50S150: Thermal expansion graphite (manufactured by Fuji Graphite Industries)

[0445] In Examples 1 to 24, results showed good flexibility, initial adhesive strength, strength reduction rate during additional heating, and reproducibility of the disintegration function expression. In this system, when the expansion material expands during heating, it induces the destruction of the adhesive layer and the reduction of the adhesive area at the adhesive layer / substrate interface. Therefore, not only during the heating operation but also after returning to room temperature, easy disassembly is exhibited.

[0446] Furthermore, this system has a phase separation structure, suggesting that the reversible bonding units may be unevenly distributed in the adhesive layer. The uneven distribution of the reversible bonding structure in the soft sea phase further enhances the dissociation effect due to the Retro-Diels-Alder reaction during heating. As a result, it is speculated that the softening and embrittlement of the adhesive layer during heating are induced, the expansion effect of the expansion capsules is further promoted, and as a result, the reproducibility of easy disassembly is improved.

[0447] Comparative Examples 1 and 4 did not exhibit dismantling function because they did not contain an expansion material in the composition. When heated, reversible bonds are dissociated (Retro-Diels-Alder reaction), but the bonds are re-formed (Diels-Alder reaction) during the cooling process to room temperature, which is thought to be why dismantling ability was not exhibited under room temperature conditions.

[0448] In Comparative Examples 2 and 5, the adhesive strength varied greatly when the adherend was heated, and the dismantling function could not be reproduced. Comparative Examples 2 and 5 did not contain reversible bonds, and it is presumed that the function was not fully expressed by the effect of the expansive agent alone.

[0449] The flexibility of the cured product and the initial adhesive strength were very low in Comparative Examples 3 and 6. In the Examples, the phase-separated structure of the epoxy resin (A) and the epoxy resin (B) provided both flexibility and adhesiveness, but in Comparative Examples 3 and 6, the phase-separated structure did not appear, and it is believed that the flexibility and adhesiveness were not achieved.

Claims

1. A cured product obtained by curing an epoxy resin composition, The epoxy resin composition An epoxy resin (A) having an epoxy equivalent of 500 to 10,000 g / eq represented by the following general formula (1), Epoxy resin (B) with an epoxy equivalent of 100-300 g / eq, A glycidyl ether group-containing compound (C) represented by the following general formula (4) and having a molecular weight of 1000 or more, Thermally expandable particles (D), The compound contains a compound (I) that is reactive with the glycidyl ether group-containing compound (C), The hardened material includes a sea-island structure. A cured product characterized by the following features. 【Chemistry 1】 [In formula (1), each Ar independently has a structure that is either unsubstituted or has a substituted aromatic ring, X is a structural unit represented by the following general formula (2), and Y is a structural unit represented by the following general formula (3), 【Chemistry 2】 [In equations (2) and (3), Ar is the same as described above.] R １ , R ２ Each of these is independently a hydrogen atom, a methyl group, or an ethyl group. R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. R ３ , R ４ , R ７ , R ８ Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R ５ , R ６ , R ９ , R １０ each independently represent a hydrogen atom or a methyl group, n1 is an integer between 4 and 16. n² is the average value of the repeating units, ranging from 2 to 30. R １１ , R １２ Each of these is independently a glycidyl ether group or a 2-methylglycidyl ether group. R １３ , R １４ Each of these is independently a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group. R １５ , R １６ is a hydrogen atom or a methyl group, m1, m2, p1, p2, and q are repeated average values, m1 and m2 are independently between 0 and 25, and m1 + m2 ≥ 1. p1 and p2 are independently between 0 and 5. q is between 0.5 and 5. However, the bonding between X represented by general formula (2) and Y represented by general formula (3) may be random or blocky, and the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively. 【Transformation 3】 [The furan-derived structure in formula (4) may have a halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as substituents. n is the average value of the number of repetitions, from 0.5 to 10, and m is an integer from 1 to 4. Z １ This is given by the following equation (5), Z ２ is one of the structures represented by the following formulas (6A) and (6B), and Z ３ The structure is one of the structures represented by the following formulas (7-1) to (7-3), and each of the multiple structures in a single molecule may be identical or different. 【Chemistry 4】 In formula (5), the aromatic ring may be substituted or unsubstituted, and * represents a bond point. G is a glycidyl group or a 2-methylglycidyl group, and the -OG on the naphthalene ring in the formula may be bonded at any location. 【Chemistry 5-1】 【Chemistry 5-2】 [In formulas (6A) and (6B), Ar is independently a structure having an unsubstituted or substituted aromatic ring, R １ , R ２ Each of these is independently a hydrogen atom, a methyl group, or an ethyl group. R is a hydrogen atom or a methyl group. R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. n1 is an integer between 4 and 16, and n2 is the average value of the repeating units, between 2 and 30. k1 is the average number of repetitions and is in the range of 0.5 to 5. p1 and p2 are independently between 0 and 5. X is a structural unit represented by the following formula (6-1), and Y is a structural unit represented by the following formula (6-2), 【Transformation 6】 [In formula (6-1) (6-2), Ar, R, R １ , R ２ R', n1, and n2 are the same as described above. m1 and m2 are repeated average values, each independently ranging from 0 to 25, and m1 + m2 ≥ 1. However, the bonding between structural unit X represented by formula (6-1) and structural unit Y represented by formula (6-2) may be random or block-like, and the total number of each structural unit X and Y present in one molecule is m1 and m2, respectively. 【Transformation 7】 【Transformation 8】 【Chemistry 9】 [In formulas (7-1) to (7-3), n3 and n5 are the average values ​​of the number of repetitions, ranging from 0.5 to 10, respectively; n4 is an integer from 1 to 16; and R'' is independently a hydrogen atom, a methyl group, or an ethyl group.]

2. The cured product according to claim 1, wherein the compound (I) that is reactive with the glycidyl ether group-containing compound (C) is a hydroxyl group-containing compound or an amine group-containing compound.

3. The cured product according to claim 1 or 2, wherein the concentration of reversible bonds in the glycidyl ether group-containing compound (C) relative to the total mass of curable components in the epoxy resin composition is 0.10 mmol / g or more.

4. The cured product according to claim 1 or 2, wherein the mass ratio (A):(B) of the epoxy resin (A) to the epoxy resin (B) is 90:10 to 10:

90.

5. The cured product according to claim 1 or 2, wherein the thermally expandable particles (D) are at least one selected from the group consisting of thermally expandable microcapsules and expanded graphite.

6. The cured product according to claim 1 or 2, wherein the proportion of the thermally expandable particles (D) used is in the range of 3 to 40 parts by mass with respect to 100 parts by mass of the total of the epoxy resin (A) and the epoxy resin (B).

7. A laminate comprising a base material and a layer containing the cured product described in claim 1 or 2.

8. A heat-resistant member containing the cured product described in claim 1 or 2.

9. A method of dismantling using a dismantling adhesive material, The disassemblable adhesive material comprises the epoxy resin composition described in claim 1, A bonding step of attaching the disassemblable adhesive material to the surface of the adherend and joining it to the adherend, A curing step to cure the aforementioned disassemblable adhesive material and obtain a cured product, A heat treatment step is performed on the cured product to thermally dissociate the reversible bonds contained in the general formula (4) derived from the glycidyl ether group-containing compound (C) and to expand the thermally expandable particles (D), The process includes a dismantling step of separating the adherend and the cured material, The hardened material includes a sea-island structure. Disassembly method.

10. The demolition method according to claim 9, further comprising a cooling step of cooling the hardened material after heat treatment to room temperature, after the heat treatment step and before the demolition step.

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