Epoxy resin composition, its cured products and laminates

Abstract

This invention provides an epoxy resin composition, its cured form, and a laminate that possess flexibility, toughness, and adhesion while exhibiting heat-induced disintegration. The epoxy resin composition of this invention comprises an epoxy resin (A) with an epoxy equivalent of 500 g / eq to 10,000 g / eq, an epoxy resin (B) with an epoxy equivalent of 100 g / eq to 300 g / eq, and a compound (C) having an anthracene dimer backbone. The epoxy resin (A) is represented by the following general formula (1), and the compound (C) has two or more epoxy-containing groups or two or more curing-containing groups.

Description

Technical Field

[0001] This invention relates to an epoxy resin composition, its cured form, and its laminate. This application asserts priority based on Japanese Patent Application No. 2021-190532, filed on November 24, 2021, the contents of which are incorporated herein by reference. Prior Technology

[0002] From the perspective of reducing carbon dioxide emissions or improving fuel efficiency, lightweighting technologies for automobiles, aircraft, and other vehicles are expected to advance lightweighting, such as reducing the number of spot welds or using carbon fiber reinforced plastics (CFRP) in combination with metals. To achieve this, high-performance adhesives for structural materials are essential, especially in the heat bonding of aluminum and CFRP, where the large difference in thermal expansion leads to warping or fluctuations caused by interfacial stress due to expansion and contraction. Adhesives that can mitigate stress are required.

[0003] On the other hand, achieving high adhesion performance has also become a major reason for the production of products that are difficult to recycle, limiting their dismantling or reusability after use. Against the backdrop of recent increased environmental awareness, the development of adhesives that maintain high adhesion performance while being easy to peel off after use has also become important.

[0004] Against this backdrop, the development of easily disintegrating adhesives is gaining momentum. Generally, thermoplastic resins are often used for hot melting, but in recent years, technologies have also been proposed that reduce adhesion and facilitate peeling by pre-mixing thermally expanding materials or thermally decomposable compounds into thermosetting resins and then primarily imparting heat energy after use (see, for example, Patent Document 1 and Patent Document 2).

[0005] However, in the technology of Patent Document 1, a previously used epoxy resin composition is basically used as the adhesive. Foaming caused by thermally expanding materials within the cured material (adhesive layer) is difficult to fully manifest, resulting in insufficient peelability, or sometimes incomplete removal due to the brittleness of the adhesive layer. Furthermore, in the technology of Patent Document 2, because it pre-contains thermally decomposable compounds, there is a complexity in its use, requiring highly controlled heating temperatures during the curing reaction. Especially when using a highly thermally conductive metal substrate, it is undeniable that the adhesive may overheat in unpredictable locations, potentially causing adverse effects. [Existing Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2003-286464 [Patent Document 2] Japanese Patent Application Publication No. 2013-256557 Summary of the Invention

[0007] [The problem that the invention aims to solve]

[0008] In view of the above, the object of the present invention is to provide an epoxy resin composition that can be preferably used as a structural adhesive, etc., wherein the epoxy resin composition has excellent flexibility, toughness, adhesion to the substrate, and can be easily disassembled (peeled) after use. [Methods for solving problems]

[0009] The inventors conducted intensive research and discovered that by using an epoxy resin with a specific structure and incorporating compounds with an anthracene dimer skeleton into the resin composition, the aforementioned problem could be solved, thus completing the invention.

[0010] That is, in this invention, the content disclosed herein includes the following embodiments[1] to embodiments

[15] . [1] An epoxy resin composition, characterized in that it contains: Epoxy resins (A) with epoxy equivalents of 500 g / eq to 10,000 g / eq Epoxy resin (B) with an epoxy equivalent of 100 g / eq to 300 g / eq, and Compound (C) having an anthracene dimer skeleton The epoxy resin (A) is represented by the following general formula (1), The compound (C) has two or more epoxy groups or two or more hardening groups. [Chemistry 1] In formula (1), Ar represents an aromatic ring containing either an unsubstituted or substituent group, respectively. X is the structural unit represented by the following general formula (2), and Y is the structural unit represented by the following general formula (3). [Chemistry 2] In equations (2) and (3), Ar is the same as described above. R1 and R2 are independently hydrogen atoms, methyl atoms, or ethyl atoms, respectively. R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. R3, R4, R7, and R8 are independently hydroxyl, glycidyl ether, or 2-methylglycidyl ether, respectively. R5, R6, R9, and R10 are each independently a hydrogen atom or a methyl group. n is an integer from 4 to 16. n² is the average value of the repeating units and is between 2 and 30. R11 and R12 are independently glycidyl ether group or 2-methylglycidyl ether group, respectively. R13 and R14 are independently hydroxyl, glycidyl ether, or 2-methylglycidyl ether, respectively. R15 and R16 are hydrogen atoms or methyl groups. m1, m2, p1, p2, and q are the average values ​​of the repeating units. m1 and m2 are independently between 0 and 25, and m1 + m2 ≥ 1. p1 and p2 are independently 0~5, q is 0.5~5; wherein, the bond between X represented by the general formula (2) and Y represented by the general formula (3) can be random or block, and the total number of each structural unit X and Y existing in a molecule are m1 and m2 respectively. [2] The epoxy resin composition as described in [1], wherein Ar in general formulas (1) to (3) is independently represented by any of the following structural formulas (4): [Chemistry 3] [The aromatic ring in formula (4) may be substituted or unsubstituted, * indicates a bond node] [3] The epoxy resin composition as described in [1] or [2], wherein n1 in the general formula (2) is 6 to 12, R3 and R4 are hydroxyl groups, and R5 and R6 are hydrogen atoms. [4] An epoxy resin composition as described in any one of [1] to [3], wherein R' in the general formula (3) is a divalent hydrocarbon group with 2 to 6 carbon atoms, R7 and R8 are hydroxyl groups, and R9 and R10 are hydroxyl groups. [5] The epoxy resin composition as described in any one of [1] to [4], wherein the compound (C) having an anthracene dimer skeleton is a compound (C-i1) represented by the following general formula (I-1). [Chemistry 4] In general formula (I-1), Each of the multiple R 1a independently represents a hydrogen atom or a monovalent substituent, wherein at least one R 1a is an epoxy group. Each of the multiple R 2a independently represents a hydrogen atom or a monovalent substituent, wherein at least one R 2a is an epoxy group. [6] The epoxy resin composition as described in any one of [1] to [4], wherein the compound (C) having an anthracene dimer skeleton is a compound (C-i2) represented by the following general formula (I-2). [Chemistry 5] In general formula (I-2), Each R 11a independently represents a hydrogen atom or a monovalent substituent, wherein at least one R 11a is a group containing a hardening group. Each R 21a independently represents a hydrogen atom or a monovalent substituent, wherein at least one R 21a is a group containing a hardening group. [7] The epoxy resin composition as described in [6], wherein in the compound (C-i2) represented by the general formula (I-2), at least one R 11a and at least one R 21a are selected from the group consisting of amino groups, hydroxyl groups and carboxyl groups. [8] An epoxy resin composition as described in [6] or [7], wherein in the compound (C-i2) represented by the general formula (I-2), at least one R11a and at least one R21a are carboxyl groups. [9] The epoxy resin composition as described in any one of [1] to [8] further contains a hardener (D).

[10] The epoxy resin composition as described in any one of [1] to [9] is an adhesive.

[11] A cured epoxy resin composition, which is a cured epoxy resin composition as described in any one of [1] to

[10] .

[12] A cured epoxy resin composition as described in

[11] , wherein the cured epoxy resin composition has an island structure comprising a sea portion and an island portion. The average particle size of the sea-grown part is 10 nm to 100 μm.

[13] A laminate is formed by laminating a substrate with a hardener as described in

[11] or

[12] .

[14] A laminate is formed by laminating a first substrate, a layer containing a hardener as described in

[11] or

[12] , and a second substrate in that order.

[15] The laminate as described in

[14] , wherein the first substrate is a substrate containing metal or metal oxide, and the second substrate is a substrate containing plastic. [The effects of the invention]

[0011] According to the present invention, by using an epoxy resin having long-chain alkyl or polyether chains in one molecule, the stress-relieving ability of the cured product is excellent. By separating the cured phases comprising two specific epoxy resins, a flexible matrix phase and a rigid island phase are generated, achieving both flexibility and toughness. Furthermore, the cured product can possess both flexibility based on elastic deformation and high adhesion to substrates. Moreover, by utilizing the anthracene dimer framework with dissociation capabilities, heat-induced disintegration is achieved. As a result, it exhibits easy disintegration (peelability). Based on these, the epoxy resin composition of the present invention can be preferably used as a structural adhesive, etc. Simple Explanation of the Diagram

[0012] none Implementation

[0013] The present invention will now be described in more detail. Furthermore, the present invention is not limited to the embodiments shown below.

[0014] "~" refers to the value above the value before the "~" mark and below the value after the "~" mark.

[0015] In the description of the radical (atomic group) in this specification, the description of "unsubstituted or unsubstituted" includes both descriptions of having no substituent and descriptions of having a substituent. For example, the term "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Unless otherwise specified, the term "organic group" in this specification refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, "monovalent organic group" means an atomic group obtained by removing one hydrogen atom from any organic compound.

[0016] (Epoxy resin composition) The epoxy resin composition of this embodiment contains epoxy resin (A) with an epoxy equivalent of 500 g / eq to 10,000 g / eq, epoxy resin (B) with an epoxy equivalent of 100 g / eq to 300 g / eq, and compound (C) having an anthracene dimer backbone. Epoxy resin (A), epoxy resin (B), and compound (C) will then be described in detail.

[0017] In the epoxy resin composition of this embodiment, since the compound (C) has an anthracene dimer backbone and has groups containing epoxy groups or groups containing curing groups, the anthracene dimer backbone is introduced into the crosslinking structure of the epoxy resin composition curing body of this embodiment.

[0018] According to current research and inventors' insights, the unsubstituted anthracene dimer backbone decomposes upon heating to a thermal dissociation temperature of approximately 100°C to 220°C, thus becoming a monomeric structure (thermal dissociation). For example, by attaching the epoxy resin composition of this embodiment to the surface of the adherend and performing a first heat treatment at a temperature lower than the thermal dissociation temperature of the anthracene dimer backbone used, the epoxy resin reacts with the hardener to obtain a hardened body bonded to the adherend. Then, by performing a second heat treatment on the hardened body at a temperature above the thermal dissociation temperature, the anthracene dimer backbone in the hardened body thermally dissociates. This second heat treatment causes "decrosslinking," exhibiting disintegration. On the other hand, the hardened body obtained using the first heat treatment is generally stable at temperatures below 80°C. Therefore, good adhesion strength and easy disintegration can coexist. Furthermore, no heat is required other than thermal degradation to establish the anthracene dimer framework as a monolithic structure (for dissociation). This is a desirable property, for example, when followed by the dissociation of opaque / complex-shaped materials.

[0019] The epoxy resin composition of this embodiment will be described in more detail below. The epoxy resin composition of this embodiment contains epoxy resin (A) with an epoxy equivalent of 500 g / eq to 10,000 g / eq, epoxy resin (B) with an epoxy equivalent of 100 g / eq to 300 g / eq, and a compound (C) having an anthracene dimer backbone, said compound (C) having two or more epoxy-containing groups or two or more curing-containing groups. The epoxy resin (A) is represented by the following general formula (1).

[0020] [Chemistry 6]

[0021] In formula (1), Ar represents an aromatic ring containing either an unsubstituted or substituent group, respectively. X is the structural unit represented by the following general formula (2), and Y is the structural unit represented by the following general formula (3).

[0022] [Chemistry 7]

[0023] In equations (2) and (3), Ar is the same as described above. R1 and R2 are independently hydrogen atoms, methyl atoms, or ethyl atoms, respectively. R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. R3, R4, R7, and R8 are independently hydroxyl, glycidyl ether, or 2-methylglycidyl ether, respectively. R5, R6, R9, and R10 are each independently a hydrogen atom or a methyl group. n is an integer from 4 to 16. n² is the average value of the repeating units and is between 2 and 30. R11 and R12 are independently glycidyl ether group or 2-methylglycidyl ether group, respectively. R13 and R14 are independently hydroxyl, glycidyl ether, or 2-methylglycidyl ether, respectively. R15 and R16 are hydrogen atoms or methyl groups. m1, m2, p1, p2, and q are the average values ​​of the repeating units. m1 and m2 are independently between 0 and 25, and m1 + m2 ≥ 1. p1 and p2 are independently 0~5, q is 0.5~5; wherein, the bond between X represented by the general formula (2) and Y represented by the general formula (3) can be random or block, and the total number of each structural unit X and Y existing in a molecule are m1 and m2 respectively.

[0024] [Epoxy Resin (A)] The epoxy resin (A) of this embodiment contains structural units X represented by general formula (2) and / or structural units Y represented by general formula (3) in its structure. By the presence of alkyl groups or polyether groups in each structural unit, the cured material exhibits high flexibility. In particular, regarding the flexibility caused by the alkyl groups, it can follow the thermal expansion of the substrate when used as an adhesive. In addition, the polyether groups have the effect of reducing the viscosity of the epoxy resin (A) itself. In this respect, it can help improve the coatability and processability of the epoxy resin composition.

[0025] In the epoxy resin (A), structural unit X and structural unit Y can be present individually, or both structural unit X and structural unit Y can be present in one molecule. In this case, X and Y can be block bonds or random bonds, and the total number of structural units X and structural units Y contained in one molecule are m1 and m2, respectively.

[0026] Ar in general formula (1) representing epoxy resin (A), Ar in general formula (2) representing structural unit X, and Ar in general formula (3) representing structural unit Y are all structures containing an aromatic ring that is unsubstituted or has a substituent. However, there is no particular limitation on the aromatic ring. Examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring.

[0027] Of these, Ar is preferably any structure represented by the following structural formula (4).

[0028] [Chemistry 8]

[0029] [The aromatic ring in formula (4) may be substituted or unsubstituted, * indicates a bond node]

[0030] In addition, structures represented by formulas such as the following are also listed as Ar.

[0031] [Chemistry 9]

[0032] (In the formula, the aromatic ring may be substituted or unsubstituted, n3=1~4, * denotes a bond node)

[0033] The aromatic ring of Ar may be substituted or unsubstituted. When Ar has substituents, the substituents are preferably alkyl, halogen, glycidyl ether, 2-methylglycidyl ether, etc. Unsubstituted, or alkyl, glycidyl ether, or 2-methylglycidyl ether groups are preferred. The number of substituents is preferably two or less per aromatic ring, more preferably one or less, and especially preferably unsubstituted.

[0034] The structure of Ar is preferably the following. * indicates a bond node.

[0035] [Chemistry 10]

[0036] Regarding preferred structures for Ar with substituents, the following structures can be listed. * indicates a bond node.

[0037] [Chemistry 11]

[0038] In the structural unit X represented by the general formula (2), the repeating unit n1 is an integer from 4 to 16. By having n1 of 4 or more, the force is increased, and the deformation mode of the hardened material is elastic deformation. In addition, by having n1 of 16 or less, the decrease in crosslinking density can be suppressed. Preferably, it is 4 to 15, and more preferably 6 to 12.

[0039] In the structural unit X represented by the general formula (2), R1 and R2 are independently hydrogen atoms, methyl or ethyl, respectively; R3 and R4 are independently hydroxyl, glycidyl ether or 2-methylglycidyl ether, respectively; and R5 and R6 are independently hydrogen atoms or methyl.

[0040] Of these, R3 and R4 are preferably hydroxyl groups, and R5 and R6 are preferably hydrogen atoms.

[0041] 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. If it is within this range, it is preferable in terms of achieving a good balance between the viscosity of the epoxy resin (A) and the crosslinking density of the resulting cured product. Preferably, it is 2 to 25, and more preferably 4 to 20.

[0042] In the structural unit Y represented by the general formula (3), R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. If it is within this range, the adhesion force is increased, and the deformation mode of the hardened material is elastic deformation. Preferably, R' is a divalent hydrocarbon group with 2 to 6 carbon atoms.

[0043] The divalent hydrocarbon group is not particularly limited, and examples include: linear or branched alkyl groups, alkenyl groups, alkyne groups, cycloalkyl groups, aryl groups, and arylalkyl groups (divalent groups having alkyl and aryl groups), etc.

[0044] Examples of alkyl groups include: methylene, ethyl, propyl, butyl, pentyl, hexyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Examples of alkenyl groups include: vinyl, 1-methylvinyl, propenyl, butenyl, pentenyl, etc. Examples of ynyl groups include: ethynyl, propynyl, butynyl, pentynyl, hexynyl, etc. Examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Examples of aryl groups include: phenyl, methylphenyl, xylylene, naphthyl, etc.

[0045] Of these, from the viewpoint of balancing the ease of obtaining raw materials, the viscosity of the resulting epoxy resin (A), and the flexibility when making a cured product, ethyl, propyl, and tetramethylene are preferred.

[0046] In the structural unit Y represented by the general formula (3), R7 and R8 are independently hydroxyl, glycidyl ether, or 2-methylglycidyl ether, respectively, and R9 and R10 are independently hydrogen atoms or methyl groups, respectively. R7 and R8 are preferably hydroxyl groups, and R9 and R10 are preferably hydrogen atoms.

[0047] As described above, the epoxy resin (A) used in this embodiment is represented by the general formula (1). In the general formula (1), m1 and m2 are the average values ​​of the repetitions of the structural unit X and structural unit Y, respectively, and are independently 0~25, and m1+m2≧1.

[0048] Furthermore, in the general formula (1), R11 and R12 are independently glycidyl ether group or 2-methylglycidyl ether group, R13 and R14 are independently hydroxyl, glycidyl ether group or 2-methylglycidyl ether group, R15 and R16 are hydrogen atoms or methyl groups, p1, p2, and q are the average values ​​of repeating units, p1 and p2 are independently 0~5, and q is 0.5~5. Among these, R11 and R12 are preferably glycidyl ether group, R13 and R14 are preferably hydroxyl group, and R15 and R16 are preferably hydrogen atoms. In addition, p1 and p2 are preferably 0~2, and q is preferably 0.5~2.

[0049] Furthermore, the epoxy equivalent of the epoxy resin (A) used in this embodiment is 500 g / eq to 10,000 g / eq. Within this range, the resulting cured product exhibits an excellent balance between flexibility and crosslinking density. From the viewpoint of ease of handling and a further balance between flexibility and crosslinking density, a range of 600 g / eq to 8,000 g / eq is preferred, and more preferably, a range of 800 g / eq to 5,000 g / eq is preferred.

[0050] In the epoxy resin (A) of this embodiment, as a resin having both the structural unit X and the structural unit Y in one molecule, the following structural formulas can be listed as examples.

[0051] [Chemistry 12]

[0052] [Chemistry 13]

[0053] [Chemistry 14]

[0054] [Chemistry 15]

[0055] [Chemistry 16]

[0056] [Chemistry 17]

[0057] [Chemistry 18]

[0058] [Chemistry 19]

[0059] [Chemistry 20]

[0060] [Chemistry 21]

[0061] [Chemistry 22]

[0062] [Chemistry 23]

[0063] In the structural formulas (A-1) to (A-12), ran represents a random bond, G is a glycidyl group, R' represents a divalent hydrocarbon group with 2 to 12 carbon atoms, n1 is an integer from 4 to 16, n2 is the average value of the repeating unit and is 2 to 30, m1, m2, p1, p2, and q are the average values ​​of the repeating unit, m1 and m2 are independently 0.5 to 25, p1 and p2 are independently 0 to 5, and q is 0.5 to 5. The repeating units present in the repeating unit may be the same or different.

[0064] From the viewpoint that the resulting hardened material has a better balance of physical properties, the structure represented by the structure (A-1), (A-2), (A-3), (A-5), (A-7), (A-8), and (A-9) is preferred.

[0065] In the epoxy resin (A), the epoxy resin having the structural unit X can be, for example, the resin represented by the following structural formula.

[0066] [Chemistry 24]

[0067] [Chemistry 25]

[0068] [Chemistry 26]

[0069] [Chemistry 27]

[0070] [Chemistry 28]

[0071] [Chemistry 29]

[0072] [Chemistry 30]

[0073] [Chemistry 31]

[0074] [Chemistry 32]

[0075] [Chemistry 33]

[0076] [Chemistry 34]

[0077] [Chemistry 35]

[0078] In the 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 the average values ​​of the repeating units, m1 is 0.5 to 25, p1 and p2 are independently 0 to 5, and q is 0.5 to 5. The repeating units present in the repeating units may be the same or different.

[0079] Of the various structural formulas, those represented by the structural formulas (A-13), (A-14), (A-15), (A-17), (A-19), (A-20), and (A-21) are preferred in terms of providing a better balance of physical properties of the resulting hardened material.

[0080] In the epoxy resin (A), the epoxy resin having the structural unit Y can be, for example, the resin represented by the following structural formula.

[0081] [Chemistry 36]

[0082] [Chemistry 37]

[0083] [Chemistry 38]

[0084] [Chemistry 39]

[0085] [Chemistry 40]

[0086] [Chemistry 41]

[0087] [Chemistry 42]

[0088] [Chemistry 43]

[0089] [Chemistry 44]

[0090] [Chemistry 45]

[0091] [Chemistry 46]

[0092] [Chemistry 47]

[0093] In the structural formulas (A-25) to (A-36), G is a glycidyl group, R' is a divalent hydrocarbon group with 2 to 12 carbon atoms, n2 is the average value of the repeating unit and is 2 to 30, m2, p1, p2, and q are the average values ​​of the repeating units, m2 is 0.5 to 25, p1 and p2 are independently 0 to 5, and q is 0.5 to 5. The repeating units present in the repeating units may be the same or different.

[0094] Of the various structural formulas, the one represented by the structural formulas (A-25), (A-26), (A-27), (A-29), (A-31), (A-32), and (A-33) is preferred in terms of the superior physical property balance of the resulting hardened material.

[0095] The method for manufacturing the epoxy resin (A) used in this embodiment is not particularly limited. However, in terms of ease of obtaining raw materials or reaction, the following method is preferred: for example, reacting diglycidyl ether (a1) of a dihydroxy compound having an alkyl chain or a polyether chain with an aromatic hydroxy compound (a2) in a molar ratio (a1) / (a2) of 1 / 1.01 to 1 / 5.0, and then reacting the hydroxy compound (equivalent to a precursor or intermediate of epoxy resin (A)) with epihaloalcohol (a3).

[0096] In the reaction of diglycidyl ether (a1) of a dihydroxy compound having an alkyl chain or a polyether chain with an aromatic hydroxy compound (a2) to obtain a hydroxy compound, the product sometimes contains unreacted aromatic hydroxy compound (a2). In the synthesis of the epoxy resin (A) used in this embodiment, this unreacted aromatic hydroxy compound (a2) can be directly supplied as a next step in the reaction with epihaloalcohol (a3), or it can be removed. From the viewpoint of balancing the strength and flexibility of the cured product obtained from the epoxy resin composition of this embodiment containing the obtained epoxy resin (A), the presence rate of the unreacted aromatic hydroxy compound (a2) in the hydroxy compound supplied as a next step is preferably in the range of 0.1% to 30% by mass.

[0097] There are no particular limitations on the method for removing the unreacted aromatic hydroxyl compound (a2), and various methods can be used. Examples include column chromatography with different polarities, distillation with different boiling points, and extraction with alkaline solutions that have different solubilities in alkaline water. Among these, alkaline solution extraction is preferred in terms of efficiency because it does not involve thermal degradation. In this case, toluene or methyl isobutyl ketone, which are immiscible with water, can be used as the organic solvent for dissolving the target compound. From the viewpoint of solubility in the target compound, methyl isobutyl ketone is particularly preferred.

[0098] The diglycidyl ether (a1) that is a dihydroxy compound having an extended alkyl chain or a polyether chain is not particularly limited. Examples of diglycidyl ethers having an extended alkyl chain include: 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol diglycidyl ether, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl ether, 2,6,10-trimethyl-1,11-undecanediol diglycidyl ether, etc. In addition, examples of diglycidyl ethers having polyether chains include: polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polypentamethylene glycol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, and polyheptamethylene glycol diglycidyl ether. These may contain organochlorine impurities generated during the glycidyl etherification of hydroxyl compounds, or may contain organochlorine compounds such as 1-chloromethyl-2-glycidyl ether (chloromethyl group) as represented by the following structure. These diglycidyl ethers can be used alone or in combination of two or more.

[0099] [Chemistry 48]

[0100] Among these, the preferred materials for achieving an excellent balance between the resulting hardened material's flexibility and heat resistance are 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.

[0101] In addition, by reacting the diglycidyl ether having an alkyl chain and the diglycidyl ether having a polyether chain simultaneously with an aromatic hydroxyl compound (a2), a hydroxyl compound having both structural unit X and structural unit Y can be obtained. By further reacting it with epihalool (a3), an epoxy resin (A) having both structural unit X and structural unit Y can be obtained.

[0102] The aromatic hydroxyl compound (a2) is not particularly limited, and examples include: dihydroxybenzenes such as hydroquinone, resorcinol, and catechol; gallnutol; 1,2,4-trihydroxybenzene, 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; and dihydroxynaphthalenes. Tetrafunctional phenols such as 1,1'-methylenebis(2,7-naphthyldiol), 1,1'-binaphth-2,2',7,7'-tetraol, and 1,1'-oxobis(2,7-naphthyldiol), bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane and bis(4-hydroxyphenyl) benzo[a][b][c ...c][b][c][c][b][c][c][b][c][c][b][c][c][c][c][c][c][c][c][c][c][c][c][c 2,2'-Biphenyl, 4,4'-Biphenyl, (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 Biphenyl compounds such as '-diol and 4'-methyl-(1,1'-biphenyl)-3,4'-diol, addition polymers of phenol and dicyclopentadiene, and addition polymers of phenol and terpene compounds, naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane, and so-called xylok-type phenolic resins, which are products of the condensation reaction of phenol with phenyl dimethyl chloride or phenyl dimethyl chloride, can be used alone or in combination with two or more. Furthermore, compounds with structures formed by substituting the aromatic rings of the aforementioned compounds with methyl, tert-butyl, or halogen atoms as substituents can also be listed. Moreover, the phenols containing alicyclic structures or the xylok-type phenolic resins may contain not only difunctional components but also trifunctional or higher components. In this embodiment, they can be used directly, or they can be purified through column chromatography or other steps to extract only the difunctional components.

[0103] Among these, bisphenols are preferred in terms of their excellent balance between softness and toughness when the cured material is produced, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferred in terms of their significant contribution to toughness. Furthermore, when the curing properties or heat resistance of the cured material are important, dihydroxynaphthalenes are preferred, and 2,7-dihydroxynaphthalene is particularly preferred in terms of its significant contribution to rapid curing. Additionally, when the moisture resistance of the cured material is important, compounds containing alicyclic structures are preferred.

[0104] Regarding the reaction ratio of the diglycidyl ether (a1) of the dihydroxy compound having an alkyl chain or a polyether chain to the aromatic hydroxy compound (a2), from the viewpoint of reaction efficiency, it is preferred that (a1) / (a2) be 1 / 1.01 to 1 / 5.0 (molar ratio), and more preferably that (a1) / (a2) be 1 / 1.02 to 1 / 3.0 (molar ratio).

[0105] The reaction of the diglycidyl ether (a1) of the dihydroxy compound having an alkyl chain and a polyether chain with the aromatic hydroxy compound (a2) is preferably carried out in the presence of a catalyst. Various compounds can be used as catalysts, such as: alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; phosphorus compounds such as triphenylphosphine; chlorides such as DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, and benzyltributylammonium; bromides; iodides; quaternary ammonium salts such as tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, and benzyltributylphosphonium; triethylamine; N,N-dimethylbenzylamine; tertiary amines such as 1,8-diazabicyclo[5.4.0]undecene and 1,4-diazabicyclo[2.2.2]octane; and imidazoles such as 2-ethyl-4-methylimidazolium and 2-phenylimidazolium. Two or more catalysts can also be used in combination. Among these, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred for their ability to accelerate the reaction and reduce impurities. The amount of these catalysts used is not particularly limited, but it is preferred to use 0.0001 mol to 0.1 mol relative to 1 mol of the aromatic hydroxyl group in the aromatic hydroxyl compound (a2). The form of these catalysts is also not particularly limited; they can be used in aqueous solution or solid form.

[0106] Furthermore, the reaction between the diglycidyl ether (a1) of the dihydroxy compound having alkyl or polyether chains and the aromatic hydroxy compound (a2) can be carried out in the absence of a solvent or in the presence of an organic solvent. Examples of usable organic solvents include: methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propanol, butanol, etc. The amount of organic solvent used is typically 50% to 300% by mass relative to the total mass of the raw materials, preferably 100% to 250% by mass. These organic solvents can be used alone or in combination. For rapid reaction, solvent-free reaction is preferred; on the other hand, the use of dimethyl sulfoxide is preferred in order to reduce impurities in the final product.

[0107] The reaction temperature for carrying out the reaction is typically 50°C to 180°C, and the reaction time is typically 1 hour to 30 hours. To reduce impurities in the final product, the reaction temperature is preferably 100°C to 160°C. Furthermore, if the resulting compound exhibits significant coloration, an antioxidant or reducing agent may be added to suppress this. As an antioxidant, there are no particular limitations; examples include hindered phenolic compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, or phosphite compounds containing trivalent phosphorus atoms. As a reducing agent, there are no particular limitations; examples include hypophosphorous acid, phosphorous acid, thiosulfate, sulfurous acid, bisulfite, or salts thereof.

[0108] After the reaction is complete, neutralization or washing may be performed until the pH of the reaction mixture reaches 3-7, preferably 5-7. Neutralization or washing can be carried out according to standard methods. For example, when using an alkaline catalyst, acidic substances such as hydrochloric acid, sodium dihydrogen phosphate, p-toluenesulfonic acid, or oxalic acid can be used as neutralizing agents. After neutralization or washing, if necessary, the solvent can be removed by distillation under reduced pressure and heating to concentrate the product and obtain the hydroxyl compound.

[0109] By combining the glycidyl ether having an alkyl chain with a glycidyl ether having a polyether chain, a hydroxyl compound having both structural unit X and structural unit Y can be obtained. In this case, as a preferred structure, compounds represented by the following structural formulas can be listed, for example.

[0110] [Chemistry 49]

[0111] [Transformation 50]

[0112] [Chemistry 51]

[0113] [Chemistry 52]

[0114] [Chemistry 53]

[0115] [Chemistry 54]

[0116] [Chemistry 55]

[0117] [Chemistry 56]

[0118] [Chemistry 57]

[0119] [Chem.58]

[0120] [Chemistry 59]

[0121] [Transformation 60]

[0122] In each of the structural formulas, ran represents a random bond, R' is a divalent hydrocarbon group with 2 to 12 carbon atoms, n1 is an integer from 4 to 16, n2 is the average value of the repeating unit and is 2 to 30, and m1 and m2 are the average values ​​of the repeating units and are independently 0.5 to 25 respectively. The repeating units present in the repeating units may be the same or different.

[0123] In addition, by using the glycidyl ether having an alkyl chain as a raw material, a hydroxyl compound having the structural unit X can be obtained. In this case, as a preferred structure, for example, compounds represented by the following structural formulas can be listed.

[0124] [Chemistry 61]

[0125] [Chemistry 62]

[0126] [Chemistry 63]

[0127] [Chemistry 64]

[0128] [Chemistry 65]

[0129] [Chemistry 66]

[0130] [Chemistry 67]

[0131] [Chemistry 68]

[0132] [Chemistry 69]

[0133] [Chemistry 70]

[0134] [Chemistry 71]

[0135] [Chemistry 72]

[0136] In each of the above structural formulas, n1 is an integer from 4 to 16, and m1 is the average value of the repeating unit, which is from 0.5 to 25.

[0137] Furthermore, by using the glycidyl ether having the polyether chain as a raw material, a hydroxyl compound having the structural unit Y can be obtained. In this case, as a preferred structure, for example, compounds represented by the following structural formulas can be listed.

[0138] [Chemistry 73]

[0139] [Chemistry 74]

[0140] [Chemistry 75]

[0141] [Chemistry 76]

[0142] [Chemistry 77]

[0143] [Chemistry 78]

[0144] [Chemistry 79]

[0145] [Chemistry 80]

[0146] [Chemistry 81]

[0147] [Chemistry 82]

[0148] [Chemistry 83]

[0149] [Chemistry 84]

[0150] In each of the structural formulas, R' is a divalent hydrocarbon group with 2 to 12 carbon atoms, n2 is the average value of the repeating units and is 2 to 30, and m2 is the average value of the repeating units and is 0.5 to 25. The repeating units present in the repeating units may be the same or different.

[0151] [Manufacturing method of epoxy resin (A)] In the method for manufacturing the epoxy resin (A), the method for the glycidyl etherification reaction of the obtained precursor (intermediate) hydroxyl compound is not particularly limited. Examples include reacting phenolic hydroxyl groups with epihaloalcohols; or olefinizing the phenolic hydroxyl groups by oxidizing the carbon-carbon double bonds of the olefin with an oxidizing agent. Among these, the method using epihaloalcohols (a3) ​​is preferred in terms of ease of obtaining raw materials or reaction.

[0152] One method for using epihalool (a3) ​​is as follows: 0.3 to 100 mol of epihalool (a3) ​​is added to the mixture relative to 1 mol of the aromatic hydroxyl group of the obtained hydroxyl compound. Simultaneously, 0.9 to 2.0 mol of an alkaline catalyst is added at a temperature of 20°C to 120°C for 0.5 to 10 hours, either in a single addition or slowly. Regarding the amount of epihalool (a3) ​​added, the greater the excess of epihalool (a3), the closer the resulting epoxy resin is to its theoretical structure, and the formation of secondary hydroxyl groups generated in the reaction of unreacted aromatic hydroxyl groups with epoxy groups can be suppressed. From this perspective, the range of 2.5 to 100 equivalents is preferred. The alkaline catalyst can be a solid or its aqueous solution. When using an aqueous solution, it can be added continuously while water and epihalool (a3) ​​are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The water is then removed by separation, and the epihalool (a3) ​​is continuously returned to the reaction mixture.

[0153] Furthermore, in industrial production, the first batch of epoxy resin production uses entirely new epihaloalcohol (a3), but in subsequent batches, it is preferable to use epihaloalcohol (a3) ​​recovered from the crude reaction products, along with new epihaloalcohol (a3) ​​equivalent to the portions consumed and lost in the reaction. At this point, the epihaloalcohol (a3) ​​used is not particularly limited; examples include epichlorohydrin and epibromohydrin. Epichlorohydrin is preferred in terms of ease of acquisition.

[0154] Furthermore, there are no particular limitations on alkaline catalysts; examples include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferred for their excellent catalytic activity in epoxy resin synthesis reactions; examples include sodium hydroxide and potassium hydroxide. These alkali metal hydroxides can be used in the form of an aqueous solution of approximately 10% to 55% by mass, or in solid form.

[0155] Furthermore, the reaction rate in the synthesis of epoxy resins can be increased by using multiple organic solvents. There are no particular limitations on these organic solvents; examples include: ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, dibutanol, and terbutanol; cellosolves such as methyl and ethyl cellosolves; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide. These organic solvents can be used individually, or two or more can be used in combination to adjust polarity.

[0156] After washing the reactants from the glycidylation reaction with water, unreacted epihaloalcohols (a3) ​​or the combined organic solvents are removed by distillation under heating and reduced pressure. Alternatively, to further prepare epoxy resins with low hydrolytic halogen content, the obtained epoxy resin can be redissolved in organic solvents such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of alkali metal hydroxides such as sodium hydroxide or potassium hydroxide can be added for further reaction. In this case, phase transfer catalysts such as quaternary ammonium salts or crown ethers can be present to increase the reaction rate.

[0157] When using an interphase transfer catalyst, its usage is preferably in the range of 0.1% to 3.0% by mass relative to the epoxy resin used. After the reaction is complete, the generated salt is removed by filtration and washing with water, and the solvents such as toluene and methyl isobutyl ketone are further removed by distillation under heating and reduced pressure, thereby obtaining a high-purity epoxy resin.

[0158] In this embodiment, from the viewpoint of imparting further flexibility and readily exhibiting the disintegration caused by the compound (C) described later, the cured product obtained by curing the epoxy resin composition preferably has a phase-separated structure. From this viewpoint, it is characterized in that an epoxy resin (B) with an epoxy equivalent of 100 g / eq to 300 g / eq is used in the epoxy resin (A).

[0159] [Epoxy Compound B]

[0160] As for the epoxy resin (B) in this embodiment, it is acceptable as long as its epoxy equivalent is in the range of 100 g / eq to 300 g / eq, and its structure is not limited. Examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc. (liquid epoxy resin), brominated epoxy resin such as brominated phenolic varnish type epoxy resin, solid bisphenol A type epoxy resin, phenolic varnish type epoxy resin, cresolic phenolic varnish type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol Addition reaction epoxy resins, phenolic aralkyl epoxy resins, phenyl ether epoxy resins, naphthyl ether epoxy resins, naphthol phenolic varnish epoxy resins, naphthol aralkyl epoxy resins, naphthol-phenol cocondensed phenolic varnish epoxy resins, naphthol-cresol cocondensed phenolic varnish epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenolic resin epoxy resins, biphenyl modified phenolic varnish epoxy resins, etc., can be used alone or in combination of two or more. It is preferable to select various types according to the target application or the physical properties of the cured product.

[0161] Among these, it is preferable to use epoxy resins with an epoxy equivalent of 100 g / eq to 300 g / eq in 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. It is particularly preferred to use epoxy resins with an epoxy equivalent of 100 g / eq to 300 g / eq in bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD ​​type epoxy resin.

[0162] In this embodiment, the ratio of epoxy resin (A) to epoxy resin (B) is not particularly limited. From the viewpoint of easy phase separation in the cured material, the mass ratio (A):(B) of epoxy resin (A):(B) is 97:3 to 3:97, preferably 10:90 to 90:10, and most preferably 80:20 to 20:80. By achieving a sea-island structure through phase separation in the cured material, the cured material exhibits both good adhesion and stress relief capabilities, demonstrates high adhesion over a particularly wide temperature range, and reduces the molding shrinkage rate of the resin composition before and after heat curing.

[0163] Furthermore, in the case where the compound (C) having an anthracene dimer skeleton described later has an epoxy group, the epoxy resin (B) of this embodiment does not contain the compound (C) having an anthracene dimer skeleton.

[0164] [Compounds with an anthracene dimer skeleton (C)] Compound (C), which contains an anthracene dimer skeleton, may contain only one anthracene dimer skeleton in its molecule, or it may contain two or more (e.g., 2 to 4) anthracene dimer skeletons in its molecule. It is believed that compound (C) can achieve better disintegration properties due to the presence of two or more anthracene dimer skeletons in its molecule. Compound (C) has two or more epoxy groups or two or more hardening groups.

[0165] Examples of epoxy-containing groups include those represented by the general formula -LE (where L is a single bond or a divalent group, and E is an epoxy group). There is no particular limitation on the divalent group of L. L can be an alkyl group, a cycloalkyl group, an aryl group, an ether group, a carbonyl group, a carboxyl group (-COO or -OCO-), a sulfide group, or a divalent group formed by linking two or more groups selected from these groups. For example, L can be a divalent organic group having 1 to 10 carbon atoms.

[0166] As a group containing a hardening group, examples of substituents that can react with epoxy groups can be listed. The group containing a hardening group is preferably selected from at least one of the group consisting of amino groups, hydroxyl groups, carboxyl groups, acid anhydride groups, amide groups, amide-imino groups, thiol groups, ester groups, and maleimino groups, and more preferably amino groups, hydroxyl groups, or carboxyl groups.

[0167] The preferred forms and specific examples of the epoxy-containing group and the curing-containing group will be described in detail using the general formulas (I-1) and (I-2) described later.

[0168] (Compounds containing anthracene dimer skeleton (C-i1)) As the compound (C) containing an anthracene dimer skeleton, it is preferably the compound (C-i1) containing an anthracene dimer skeleton represented by the following general formula (I-1) (hereafter sometimes simply referred to as "compound (C-i1)").

[0169] [Chemistry 85]

[0170] In general formula (I-1), multiple R 1a independently represent hydrogen atoms or monovalent substituents, wherein at least one R 1a is an epoxy group, and multiple R 2a independently represent hydrogen atoms or monovalent substituents, wherein at least one R 2a is an epoxy group.

[0171] From the perspective of the coexistence of adhesion and easy disintegration, it is preferable that one to three of R1a are epoxy-containing groups, more preferably one to two of R1a are epoxy-containing groups, and even more preferably one of R1a is an epoxy-containing group. Similarly, it is preferable that one to three of R2a are epoxy-containing groups, more preferably one to two of R2a are epoxy-containing groups, and even more preferably one of R2a is an epoxy-containing group.

[0172] As epoxy-containing groups of R1a and R2a, examples include groups represented by the general formula -LE (L is a single bond or a divalent linked group, E is an epoxy group). There is no particular limitation on the divalent linked group of L. L can be an alkyl group, an cycloalkyl group, an aryl group, an ether group, a carbonyl group, a carboxyl group (-COO or -OCO-), a sulfide group, or a divalent group formed by linking two or more groups selected from these groups. L can be, for example, a divalent organic group having 1 to 10 carbon atoms. Multiple Ls can exist in the general formula (I-1), and these Ls can be the same or different from each other.

[0173] When R1a is not an epoxy-containing group, R1a is either a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include: alkyl, alkoxy, cycloalkyl, aryl, alkenyl, alkynyl, aryloxy, amino, alkylamino, arylamino, cyano, nitro, silylalkyl, and halogen (e.g., fluorine). From the viewpoint of ease of obtaining raw materials, R1a is preferably a hydrogen atom. When R2a is not an epoxy-containing group, the specific state of R2a is the same as that of R1a.

[0174] From the viewpoint of availability of raw materials or ease of synthesis, it is preferable that the epoxy-containing group is substituted at position 1, 2, or 9 of each anthracene structure above and below in general formula (I-1). Specifically, in general formula (I-1), it is preferable that R1a and R2a, surrounded by the following circles, are epoxy-containing groups. Among these, considering steric hindrance during dimerization, the first three substitution positions can be preferably listed. Furthermore, regarding further improving the adhesion strength before the disintegration treatment (before the second heat treatment), it is preferable that the epoxy-containing group is substituted at position 1 or 2 of each anthracene structure in general formula (I-1), more preferably at position 2. According to the inventors' understanding, when the epoxy-containing group is substituted at position 1 or 2 of each anthracene structure in general formula (I-1), compared to when the epoxy-containing group is substituted at position 9 of each anthracene structure in general formula (I-1), there is a tendency for the dimer decomposition temperature to be higher. Therefore, it is presumed that the decomposition of the anthracene dimer skeleton during adhesion (first heat treatment) is suppressed, resulting in a further improvement in adhesion strength.

[0175] [Chemistry 86]

[0176] [Chemistry 87]

[0177] [Chemistry 88]

[0178] [Chemistry 89]

[0179] In addition, the compound (C-i1) may also be a mixture of various compounds with different substitution positions of epoxy groups.

[0180] As specific examples of the compound (C-i1), the following anthracene monomers can be listed as dimers by photochemical reactions.

[0181] [Chemistry 90]

[0182] A1 represents a hydrogen atom or a methyl group.

[0183] In addition, the following compound described in Japanese Patent Application Publication No. 2010-270022 (which is a document concerning high refractive index materials, not a document concerning easily disintegrating bonding technology) can also be cited as a specific example of the compound (C-i1).

[0184] [Chemistry 91]

[0185] (Compounds containing anthracene dimer skeleton (C-i2)) As the compound (C) containing an anthracene dimer skeleton, it is preferably the compound (C-i2) containing an anthracene dimer skeleton represented by the following general formula (I-2) (hereafter sometimes simply referred to as "compound (C-i2)").

[0186] [Chemistry 92]

[0187] In general formula (I-2), each of the plurality of R 11a independently represents a hydrogen atom or a monovalent substituent, wherein at least one R 11a is a group containing a hardening group, and each of the plurality of R 21a independently represents a hydrogen atom or a monovalent substituent, wherein at least one R 21a is a group containing a hardening group. The group containing a hardening group is preferably selected from at least one of the group consisting of groups containing amino groups, groups containing hydroxyl groups, and groups containing carboxyl groups.

[0188] From the perspective of the coexistence of adhesion and disintegration, it is preferable that one to three of R 11a are bases containing a hardening group, more preferably one to two of R 11a are bases containing a hardening group, and even more preferably one of R 11a is a base containing a hardening group. Similarly, it is preferable that one to three of R 21a are bases containing a hardening group, more preferably one to two of R 21a are bases containing a hardening group, and even more preferably one of R 21a is a base containing a hardening group.

[0189] As groups containing a hardening group in R 11a and R 21a, examples include groups represented by the general formula -LE (L is a single bond or a divalent linker, Z is an amino group, hydroxyl group, or carboxyl group). There is no particular limitation on the divalent linker of L. L can be an alkyl group, a cycloalkyl group, an aryl group, an ether group, a carbonyl group, a carboxyl group (-COO or -OCO-), a sulfide group, or a divalent group formed by linking two or more groups selected from these groups. L can be, for example, a divalent organic group having 1 to 10 carbon atoms. Multiple Ls can exist in the general formula (I-2), and these Ls can be the same or different from each other.

[0190] When R 11a is not a group containing a hardening group, R 11a can be a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include: alkyl, alkoxy, cycloalkyl, aryl, alkenyl, alkynyl, aryloxy, amino, alkylamino, arylamino, cyano, nitro, silylalkyl, and halogen (e.g., fluoro). From the viewpoint of ease of obtaining raw materials, R 11a is preferably a hydrogen atom. When R21a is not a base containing a hardening group, the specific state of R2a is the same as that of R11a.

[0191] From the viewpoint of availability of raw materials or ease of synthesis, it is preferable that the group containing the hardening group is substituted at position 1, 2, or 9 of each anthracene structure above and below in general formula (I-2). Regarding the specific substitution positions, as illustrated by the circles in general formula (I-1) (R 1a is replaced with R 11a, and R 2a is replaced with R 21a). Furthermore, in terms of further improving the adhesion strength before disintegration treatment (before the second heating), it is preferable that the group containing the hardening group is substituted at position 1 or 2 of each anthracene structure above and below in general formula (I-1), more preferably at position 2. According to the inventors' understanding, when the hardening group is substituted at position 1 or 2 of each anthracene structure above and below in general formula (I-1), compared to when the hardening group is substituted at position 9 of each anthracene structure above and below in general formula (I-1), there is a tendency for the decomposition temperature of the dimer to be higher. Therefore, it is speculated that the decomposition of the anthracene dimer skeleton during the adhesion of the adherent (first heat treatment) was suppressed, resulting in a further increase in adhesion strength. For the sake of caution, it is described that the curing agent (b1) containing anthracene dimer skeleton may also be a mixture of various curing agents with different substitution positions of the curing groups.

[0192] As a specific example of a hardener (b1) containing an anthracene dimer backbone, the following examples can be listed: anthracene monomers obtained by dimerization via photochemical reaction.

[0193] [Chemistry 93]

[0194] [Chemistry 94]

[0195] [Chem. 95]

[0196] [Chemistry 96]

[0197] In the following examples, n is an integer from 6 to 12.

[0198] [Chemistry 97]

[0199] [Chem. 98]

[0200] [Chemistry 99]

[0201] In the epoxy resin composition of this embodiment, the amount of compound (C) used is such that the adhesion or flexibility of the epoxy resin composition during curing is not compromised, and that it expands sufficiently upon disassembly after use to reduce adhesion. Therefore, it is preferable to use a range of 3 to 40 parts by weight relative to a total of 100 parts by weight of epoxy resin (A) and epoxy resin (B), and more preferably a range of 5 to 30 parts by weight.

[0202] [Cure agent (D)] As an epoxy resin composition of this embodiment, it is preferred to further include a curing agent (D) that can react with ordinary epoxy resins.

[0203] The curing agent (D) is not particularly limited, and examples include: amine compounds, acid anhydrides, acetamine compounds, compounds containing phenolic hydroxyl groups, carboxylic acid compounds, or hydroxyl compounds that are precursors to the epoxy resin (A).

[0204] Examples of such amine compounds include: trimethylenediamine, triethylenediamine, N,N,N',N'-tetramethyltriethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, diethylenepropyldiamine, N,N,N',N'-tetramethyltriethylenepropyldiamine, tetramethyldiamine, pentaethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, and triethylenetetramine. Aliphatic amine compounds such as tetraethylpentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethyldiamine), polyoxyethylenediamine, polyoxypropyldiamine, bis(2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, and meta-xylenediamine;

[0205] Piperidine, piperazine, menthane diamine, isophorone diamine, methylmorpholine, ethylmorpholine, N,N',N''-tris(dimethylaminopropyl)hexahydro-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxospirocyclic (5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N'-dimethylpiperazine, 1,8-diazabicyclo-[5.4.0]undec-7-ene (1,8-diazabicyclo-[5.4.0]undec-7-ene, DBU) and other alicyclic and heterocyclic amine compounds;

[0206] Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, pyridine, methylpyridine, and α-methylbenzylmethylamine;

[0207] Modified amine compounds include epoxy addition polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-encapsulated polyamines, dicyandiamine, guanidine, organic acid acehydrazine, diaminomaleonitrile, aminoimines, boron trifluoride-piperidine complexes, boron trifluoride-monoethylamine complexes, and other modified amine compounds.

[0208] Examples of such acid anhydrides include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0209] Examples of compounds containing phenolic hydroxyl groups include: bisphenol compounds, phenol-formaldehyde varnish resins, cresol-formaldehyde varnish resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene-phenol addition-type resins, phenol-aralkyl resins (neophenolic resins), naphthol-aralkyl resins, trimethylolpropane resins, tetrahydroxyphenylethane resins, naphthol-formaldehyde varnish resins, naphthol-phenol cocondensed phenolic varnish resins, naphthol-cresol cocondensed phenolic varnish resins, and biphenyl-modified phenolic resins. Polyvalent phenol compounds include: (polyvalent phenol compounds formed by linking phenol nuclei with dimethylene groups), biphenyl-modified naphthol resin (polyvalent naphthol compounds formed by linking phenol nuclei with dimethylene groups), aminotriazine-modified phenol resin (polyvalent phenol compounds formed by linking phenol nuclei with melamine, benzoguanamine, etc.), or alkoxy-containing aromatic ring-modified phenolic varnish resin (polyvalent phenol compounds formed by linking phenol nuclei with formaldehyde and alkoxy-containing aromatic rings), etc. Examples of such bisphenol compounds include: bis(4-hydroxyphenyl)methane (bisphenol F), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 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)monazine (bisphenol S).

[0210] Examples of such amide compounds include dicyandiamine or polyamides. Polyamides can be obtained by reacting aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, and azelaic acid, or carboxylic acid compounds such as fatty acids and dimers, with aliphatic polyamines or polyamines having polyoxyalkylene chains.

[0211] Examples of carboxylic acid compounds include: carboxylic acid-terminated polyesters, polyacrylic acid, maleic acid-modified polypropylene glycol, and other carboxylic acid polymers.

[0212] When using these hardeners, only one type of hardener may be used, or two or more may be mixed. For example, amine compounds such as dicyandiamine may be mixed with compounds containing phenolic hydroxyl groups such as bisphenol F. Furthermore, in applications such as underfill materials or general coatings, amine compounds, carboxylic acid compounds, and / or anhydride compounds are preferred. In addition, in applications such as adhesives or flexible wiring substrates, amine compounds, especially dicyandiamine, are preferred in terms of workability, curing properties, and long-term stability. In addition, in applications such as semiconductor sealing materials, solid-type phenolic compounds are preferred in terms of the heat resistance of the cured material.

[0213] Furthermore, in the case where the compound (C) of this embodiment has an anthracene dimer skeleton has a group containing a curing group, the curing agent (D) of this embodiment does not contain the compound (C).

[0214] [Hardening Accelerator] Furthermore, the epoxy resin composition of this embodiment may also include a curing accelerator. Various substances can be used as the curing accelerator, such as: urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, organic acid metal salts, Lewis acids, amine salts, etc. When used as an adhesive, urea compounds, especially 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), are preferred in terms of workability and low-temperature curing properties. When used as a semiconductor sealing material, triphenylphosphine is preferred as a phosphorus compound in terms of excellent curing properties, heat resistance, electrical properties, and moisture resistance reliability, and 1,8-diazabicyclo-[5.4.0]-undecene is preferred as a tertiary amine.

[0215] Examples of such phosphorus compounds include: alkylphosphines such as ethylphosphine and butylphosphine, first phosphines such as phenylphosphine; dialkylphosphines such as dimethylphosphine and dipropylphosphine; second phosphines such as diphenylphosphine and methylethylphosphine; and third phosphines such as trimethylphosphine, triethylphosphine, and triphenylphosphine.

[0216] Examples of tertiary amines include: triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, 1,8-diazabicyclo[5.4.0]-undecene, 1,4-diazabicyclo[2.2.2]octane, and other tertiary amines.

[0217] Examples of imidazoles include: imidazole, 1-methylimidazolium, 2-methylimidazolium, 3-methylimidazolium, 4-methylimidazolium, 5-methylimidazolium, 1-ethylimidazolium, 2-ethylimidazolium, 3-ethylimidazolium, 4-ethylimidazolium, 5-ethylimidazolium, 1-n-propylimidazolium, 2-n-propylimidazolium, 1-isopropylimidazolium, 2-isopropylimidazolium, 1-n-butylimidazolium, 2-n-butylimidazolium, 1-isobutylimidazolium, 2-isobutylimidazolium, 2-undecyl-1H-imidazolium, 2-heptadecyl-1H-imidazolium, 1,2-dimethylimidazolium, 1,3-dimethylimidazolium, 2,4-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1-phenylimidazolium, 2-phenyl-1H-imidazolium, 4-methyl-2- Phenyl-1H-imidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 2-phenylimidazolium isocyanurate adduct, 2-methylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazolium, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazolium hydrochloride, etc.

[0218] Examples of such imidazoline compounds include 2-methylimidazoline and 2-phenylimidazoline.

[0219] Examples of the urea compounds mentioned above 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, etc.

[0220] Furthermore, even if the compound (C) of this embodiment, which has an anthracene dimer skeleton, functions as a curing accelerator, the curing accelerator of this embodiment does not contain the compound (C).

[0221] [Other ingredients] In the epoxy resin composition of this embodiment, in addition to the epoxy resin (A) and the epoxy resin (B), other epoxy resins may be used in combination without impairing the effects of this embodiment. In this case, the total amount of epoxy resin (A) and epoxy resin (B) in the epoxy resin composition of this embodiment is preferably 30% by mass or more, and more preferably 40% by mass or more, of the total epoxy resin.

[0222] As a type of epoxy resin that can be used in combination, there are no restrictions except that it does not belong to epoxy resin (A) or epoxy resin (B). Examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc. (liquid epoxy resin), brominated epoxy resin such as brominated phenolic varnish type epoxy resin, solid bisphenol A type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, triphenylmethane type epoxy resin, etc. Epoxy resins, including esters, tetraphenylethane type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, phenyl ether type epoxy resins, naphthyl ether type epoxy resins, naphthol phenolic varnish type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol cocondensed phenolic varnish type epoxy resins, naphthol-cresol cocondensed phenolic varnish type epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resins, and biphenyl modified phenolic varnish type epoxy resins, can be used alone or in combination of two or more. It is preferable to select from various options based on the target application or the physical properties of the cured product.

[0223] The amount of epoxy resin and hardener used in the epoxy resin composition of this embodiment is not particularly limited. In terms of the good mechanical properties of the obtained cured product, the amount of active groups (hardening groups) in the hardener is preferably 0.4 to 2.0 equivalents relative to the total amount of epoxy groups in the epoxy resin composition.

[0224] When the compound (C) contained in the epoxy resin composition of this embodiment has epoxy-containing groups, for example, in the embodiment containing compound (C-I1) in the epoxy resin composition of this embodiment, the amount of curing agent used is preferably 0.4 to 2.0 equivalents of the active groups in the curing agent, relative to the total amount of epoxy groups in the epoxy resin composition. The total amount of epoxy groups in the epoxy resin composition is the total amount of epoxy groups in epoxy resin A, epoxy resin B, compound (C-I1), and other arbitrarily blended epoxy resins other than these contained in the epoxy resin composition of this embodiment.

[0225] In the case where the compound (C) contained in the epoxy resin composition of this embodiment has a group containing a curing group, for example in the embodiment of the epoxy resin composition containing compound (C-I2), the amount of curing agent used is preferably 0.4 equivalents to 2.0 equivalents relative to the total amount of epoxy groups in the epoxy resin composition (1 equivalent).

[0226] Furthermore, when epoxy groups react with curing groups, new active groups such as hydroxyl groups are generated that can react with either epoxy groups or curing groups. Therefore, if either epoxy groups or curing groups are in excess in the resin composition, these groups will also react with the newly generated active groups. This reduces unreacted components associated with performance degradation.

[0227] The epoxy resin composition of this embodiment may further contain fillers that are not part of the compound (C). Examples of fillers include inorganic fillers and organic fillers. Examples of inorganic fillers include, for instance, inorganic microparticles.

[0228] As inorganic microparticles, those with excellent heat resistance include alumina, magnesium oxide, titanium dioxide, zirconium oxide, and silicon dioxide (quartz, smoked silicon dioxide, settled silicon dioxide, silicic anhydride, fused silicon dioxide, crystalline silicon dioxide, ultrafine amorphous silicon dioxide, etc.); those with excellent thermal conductivity include boron nitride, aluminum nitride, alumina, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, and diamond; those with excellent electrical conductivity are metal fillers and / or metal-coated fillers using metal monomers or alloys (such as iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); and those with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and bentonite, or titanate. Potassium, magnesium sulfate, sepiolite, vermiculite, aluminum borate, calcium carbonate, titanium dioxide, barium sulfate, zinc oxide, and magnesium hydroxide; those with high refractive index include barium titanate, zirconium oxide, and titanium dioxide; those exhibiting photocatalytic properties include titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, and other photocatalytic metals, their compounds, and their oxides; those with excellent wear resistance include silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide, and their compounds and oxides; those with excellent electrical conductivity include silver, copper, tin oxide, and indium oxide; those with excellent insulation properties include silicon dioxide; and those with excellent ultraviolet shielding properties include titanium dioxide and zinc oxide. These inorganic microparticles can be selected appropriately according to the application, and can be used alone or in combination. In addition to the properties listed in the examples, the inorganic microparticles also have various other properties, so they can be selected according to their intended use.

[0229] For example, when using silicon dioxide as inorganic microparticles, there are no particular limitations; known silicon dioxide microparticles such as powdered silicon dioxide or colloidal silicon dioxide can be used. Examples of commercially available powdered silicon dioxide microparticles include Aerosil 50 and 200 manufactured by Aerosil Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Ltd., E220A and E220 manufactured by Nippon Silicon Dioxide Industries Ltd., SYLYSIA 470 manufactured by Fuji-silysia Ltd., and SG Flack manufactured by Nippon Sheet Glass Ltd.

[0230] In addition, commercially available colloidal silica products include, for example, methanol silica gel, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL manufactured by Nissan Chemical Industries, Ltd.

[0231] Surface-modified silica microparticles can be used, for example, those surface-treated with a reactive silane coupling agent having a hydrophobic group, or those modified with a compound having a (meth)acrylic group. Examples of commercially available powdered silica modified with a compound having a (meth)acrylic group include Aerosil RM50 and R711 manufactured by Aerosil Corporation of Japan, and examples of commercially available colloidal silica modified with a compound having a (meth)acrylic group include MIBK-SD manufactured by Nissan Chemical Industries, Ltd.

[0232] The shape of the silicon dioxide microparticles is not particularly limited, and they can be spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregular in shape. Furthermore, the primary particle size is preferably in the range of 5 nm to 200 nm.

[0233] As titanium dioxide microparticles, not only extender pigments but also UV-responsive photocatalysts can be used, such as anatase titanium dioxide, rutile titanium dioxide, and brookite titanium dioxide. Furthermore, particles designed to respond to visible light by doping the crystalline structure of titanium dioxide with foreign elements can also be used. Anionic elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, or cationic elements such as chromium, iron, cobalt, and manganese, are preferred as dopants in titanium dioxide. In terms of form, they can be powders, sols or slurries dispersed in organic solvents or water. Examples of commercially available powdered titanium dioxide microparticles include Aerosil P 25 manufactured by Aerosil Ltd. and ATM 100 manufactured by Tayca Ltd. Examples of commercially available slurry-like titanium dioxide microparticles include Tayca Ltd. TKD-701.

[0234] The epoxy resin composition of this embodiment may further contain a fibrous matrix. The fibrous matrix is ​​not particularly limited, but is preferably a user of fiber-reinforced resins, including inorganic or organic fibers.

[0235] Inorganic fibers, besides carbon fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers, can include carbon fibers, activated carbon fibers, graphite fibers, tungsten carbide fibers, ceramic fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0236] Organic fibers can include synthetic fibers made from resins such as polybenzodiazepine, polyarylamide, polyp-phenylene benzo-oxazole (PBO), polyphenylene sulfide, polyester, acrylic acid, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as proteins, polypeptides, and alginic acid.

[0237] Carbon fiber and glass fiber are preferred due to their wide range of industrial applications. Only one type of fiber can be used, or multiple types can be used simultaneously.

[0238] The fibrous matrix can be an aggregate of fibers, whether continuous or discontinuous, and can be woven or non-woven. Alternatively, it can be a fiber bundle formed by arranging fibers in one direction, or a sheet formed by arranging fiber bundles side-by-side. Furthermore, the aggregate of fibers can have a three-dimensional shape with thickness.

[0239] [Dispersion medium] For the purpose of adjusting the solid content or viscosity of the resin composition, a dispersion medium can also be used in the epoxy resin composition of this embodiment. As a dispersion medium, any liquid medium that does not impair the effects of the present invention is acceptable, and various organic solvents, liquid organic polymers, etc., can be listed.

[0240] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatics such as toluene and xylene; alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These can be used alone or in combination. Among them, methyl ethyl ketone is preferred in terms of volatility during application or solvent recovery.

[0241] The liquid organic polymers mentioned are liquid organic polymers that do not directly contribute to the curing reaction. Examples include carboxyl-containing polymer modifiers (Flowlen G-900, NC-500: Kyoeisha), acrylic polymers (Flowlen WK-20: Kyoeisha), amine salts of specially modified phosphate esters (HIPLLAD ED-251: Kusunoki Kasei), and modified acrylic block copolymers (DISPERBYK 2000; BYK-Chemie), etc.

[0242] [Other Resins] Furthermore, the resin composition of this embodiment may also contain resins other than those described in this embodiment. As the resin, any commonly known resin may be used without compromising the effects of this embodiment; for example, a thermosetting resin or a thermoplastic resin may be used.

[0243] Thermosetting resins are resins that are substantially insoluble and can be transformed into infusible substances when hardened by heating, radiation, or catalysts. Specific examples include: phenolic resins, urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, silicone resins, carbamate resins, furan resins, ketone resins, xylene resins, thermosetting polyamine resins, benzoxazine resins, reactive ester resins, aniline resins, cyanate ester resins, styrene-maleic anhydride (SMA) resins, and maleimide resins. One or more of these thermosetting resins may be used in combination.

[0244] Thermoplastic resins are resins that can be melted and molded by heating. Specific examples include: polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile butadiene styrene (ABS) resin, and acrylonitrile styrene (ABS) resin. Styrene (AS) resins, including polymethyl methacrylate resins, acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyethylene terephthalate resins, vinyl alcohol resins, cellulose acetate resins, ionomer resins, polyacrylonitrile resins, polyamide resins, polyacetal resins, polybutylene terephthalate resins, polylactic acid resins, polyphenylene ether resins, modified polyphenylene ether resins, polycarbonate resins, polyurethane resins, polyphenylene sulfide resins, polyetherimide resins, polyetherurethane resins, polyacrylate resins, thermoplastic polyimide resins, polyamide-imide resins, polyetheretherketone resins, polyketide resins, liquid crystal polyester resins, fluoropolymers, syndiotactic polystyrene resins, and cyclic polyolefin resins. These thermoplastic resins can be used individually or in combination with two or more other resins.

[0245] [Other ingredients] The resin composition of this embodiment may also contain other formulations. Examples include: catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, reactive diluents, etc.

[0246] Curing methods for epoxy resin compositions By curing the resin composition of this embodiment, a cured product can be obtained. Curing can be performed at room temperature or by heating. In the case of heat curing, curing can be performed in a single heating step or through multiple heating stages. The curing temperature of the epoxy resin composition in this embodiment is preferably lower than the dissociation start temperature of the anthracene dimer backbone contained in the epoxy resin composition. The curing temperature of the epoxy resin composition in this embodiment is preferably 20 degrees lower than the dissociation start temperature of the anthracene dimer backbone. More preferably, it is 30 degrees lower than the dissociation start temperature of the anthracene dimer backbone. Regarding the dissociation onset temperature of the anthracene dimer skeleton, the behavior of estimating the dissociation onset temperature can be achieved by heating the substituted anthracene dimer compound or its solution at a specified temperature and then using analytical devices such as nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and gas chromatography to quantify the amount of substituted anthracene monomeric compounds generated due to thermal dissociation.

[0247] Furthermore, the epoxy resin composition of the present invention can also be cured using an active energy beam. In this case, a photocationic polymerization initiator can be used as the polymerization initiator. Visible light, ultraviolet light, X-rays, electron beams, etc., can be used as the active energy beam.

[0248] Examples of photocationic polymerization initiators include aryl-strontium salts and aryl-iodide salts, specifically arylstrontium hexafluorophosphate, arylstrontium hexafluoroantimonate, arylstrontium tetra(pentafluoro)borate, and tri(alkylphenyl)strontium hexafluorophosphate. Photocationic polymerization initiators can be used alone or in combination of two or more.

[0249] [Preparation method of epoxy resin composition] The epoxy resin composition of this embodiment can be prepared simply by uniformly mixing the various components, and there is no particular limitation on the method. For example, it can be prepared by uniformly mixing using a pot mill, ball mill, bead mill, roller mill, homogenizer, ultramill, homogenizing disperser, universal mixer, Bamboo mixer, kneader, etc.

[0250] [Hardened material] The cured material of this embodiment is obtained by curing the epoxy resin composition. Various curing conditions can be selected depending on the type of curing agent and curing accelerator. These curing conditions are the same as those for known epoxy resin compositions, requiring no special method. The resulting cured material can be laminated with a substrate to form a laminate. The substrate for the laminate can be any inorganic material such as metal or glass, or an organic material such as plastic or wood, depending on the application. The shape of the laminate can be flat, sheet-like, or even three-dimensional. It can also be any shape corresponding to the purpose, such as having curvature on the entire surface or a portion thereof. Furthermore, there are no limitations on the hardness or thickness of the substrate. Additionally, the cured material of this embodiment can be used as a substrate to further laminate other cured materials of this embodiment. The cured epoxy resin composition of this embodiment is preferably an island structure having a sea portion and an island portion, wherein the average particle size of the sea portion is 10 nm to 100 μm.

[0251] Alternatively, a multilayer laminate formed by sequentially stacking a first substrate, a layer containing a cured resin composition, and a second substrate can also be manufactured. The resin composition of this embodiment exhibits excellent adhesion, and therefore can be preferably used as an adhesive for bonding the first substrate and the second substrate.

[0252] The resin composition of this embodiment exhibits particularly high adhesion to metals and / or metal oxides, making it especially suitable for use as a primer for metals. Examples of metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and materials composed of these metals. Examples of metal oxides include single oxides and / or composite oxides of these metals. It exhibits particularly excellent adhesion to iron, copper, and aluminum, thus making it suitable for use as an adhesive for these materials.

[0253] Furthermore, the resin composition of this embodiment can alleviate stress, and therefore is particularly suitable for bonding dissimilar materials. For example, even in a laminate of dissimilar materials where the first substrate is a metal and / or metal oxide and the second substrate is a plastic layer, the adhesion can be maintained by the stress-relieving ability of the resin composition.

[0254] In the laminated body of this embodiment, the layer containing the hardened material can be formed by directly coating or molding the substrate, or by laminating a pre-formed material. In the case of direct coating, there are no particular limitations on the coating method, and examples include: spraying, spin coating, dip coating, roller coating, doctor blade coating, doctor blade coating, curtain coating, slot coating, screen printing, inkjet printing, etc. In the case of direct molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, compression molding, etc.

[0255] When laminating a molded resin composition, an uncured or semi-cured resin composition layer can be laminated and then cured, or a fully cured layer containing the cured material can be laminated relative to a substrate.

[0256] Furthermore, the cured material of this embodiment can be deposited by applying a precursor that can become a substrate and then curing it, or the precursor that can become a substrate or the composition of this embodiment can be bonded in an uncured or semi-cured state and then cured. There are no particular limitations on the precursor that can become a substrate, and various curable resin compositions can be listed.

[0257] The resin composition of this embodiment has a fibrous matrix. When the fibrous matrix is ​​a reinforcing fiber, the composition containing the fibrous matrix can be used as a fiber-reinforcing resin.

[0258] The method of making the composition contain a fibrous matrix is ​​not particularly limited if it does not impair the effect of this embodiment. Examples of methods include compounding the fibrous matrix with the composition by mixing, coating, impregnation, injection, and pressing. The appropriate method can be selected according to the morphology of the fiber and the application of the fiber-reinforcing resin.

[0259] There are no particular limitations on the method for molding the fiber-reinforced resin of this embodiment. If manufacturing a sheet-like product, extrusion molding is typically used, but planar pressing can also be employed. Other methods include extrusion molding, blow molding, compression molding, vacuum forming, and injection molding. Furthermore, if manufacturing a film-like product, solution casting can be used in addition to melt extrusion. When using melt molding methods, examples include: inflation film forming, casting, extrusion lamination, calendering, sheet forming, fiber forming, blow molding, injection molding, rotational molding, and coating molding. Additionally, in the case of resins that are cured using active energy lines, various curing methods utilizing active energy lines can be used to manufacture cured products. In particular, when thermosetting resin is used as the main component of the matrix resin, molding methods that involve pre-impregnating the molding material and then pressing or heating it under pressure in an autoclave can be listed. In addition, RTM (Resin Transfer Molding) molding, VaRTM (Vacuum Assisted Resin Transfer Molding) molding, lamination molding, and hand lay-up molding can also be listed.

[0260] The fiber-reinforced resin of this embodiment can be formed into a state known as an uncured or semi-cured prepreg. Alternatively, the article can be circulated in the prepreg state and then undergo final curing to form a cured product. In the case of forming a laminate, final curing is performed after the prepreg is formed and after the other layers are laminated, thereby forming a laminate with closely spaced layers, which is therefore preferable.

[0261] There is no particular limitation on the mass ratio of the components used to the fibrous matrix at this time, but it is generally preferred to prepare the prepreg with the resin component in the prepreg being 20% ​​to 60% by mass.

[0262] Regarding the resin composition of this embodiment, its cured form exhibits excellent adhesion to the substrate, making it particularly suitable for use in electronic components. It is especially suitable for use in semiconductor sealing materials, circuit boards, extension films, extension substrates, adhesives, or resist materials. Furthermore, it is also preferably used in fiber-reinforced resin matrix resins, and is particularly suitable as a prepreg with high heat resistance. Electronic components obtained in this manner can be preferably used for a variety of applications, including, but not limited to, industrial machinery parts, general machinery parts, automotive, railway, and vehicle parts, aerospace-related parts, electronic and electrical parts, building materials, container and packaging components, consumer goods, sports and leisure products, and wind power generation frame components.

[0263] This adhesive, by effectively utilizing the excellent flexibility of the hardened material, can be ideally used as an adhesive for structural components in the automotive, tram, civil engineering, electronics, aerospace, and space industries. For example, when bonding different materials such as metals and non-metals, this adhesive maintains high adhesion regardless of temperature variations and is less prone to peeling. Furthermore, besides its application in structural components, this adhesive can also be used for general office applications, medical applications, and for bonding carbon fiber, battery units, modules, or housings. Examples include adhesives for bonding optical components, bonding optical discs, mounting printed circuit boards, die bonding, semiconductor adhesives such as filler adhesives, filler adhesives for ball grid array (BGA) reinforcement, and adhesives for mounting anisotropic conductive films and anisotropic conductive pastes.

[0264] The following examples illustrate representative products.

[0265] [1] Semiconductor sealing materials As a method for obtaining a semiconductor sealing material from the resin composition of the present invention, the following method can be listed: The resin composition, curing accelerator, and inorganic filler are thoroughly melted and mixed until homogeneous using an extruder, kneader, roller, etc., as needed. At this time, fused silica is typically used as the inorganic filler. When used as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, highly filled materials such as crystalline silica, alumina, and silicon nitride, which have higher thermal conductivity than fused silica, can be used, or highly filled materials such as fused silica, crystalline silica, alumina, and silicon nitride can be used. Regarding the filling rate, it is preferable to use an inorganic filler in the range of 30% to 95% by mass relative to 100 parts by mass of the curable resin composition. More preferably, it is 70 parts by mass or more, and even more preferably 80 parts by mass or more, in order to improve flame retardancy, moisture resistance, soldering crack resistance, and reduce the coefficient of linear expansion.

[0266] [2] Semiconductor devices As a semiconductor encapsulation molding process for obtaining a semiconductor device from the curable resin composition of the present invention, the following methods can be used: the semiconductor sealing material is molded using a casting machine, a transfer molding machine, an injection molding machine, etc., and then heated at 50°C to 250°C for a period of 2 to 10 hours.

[0267] [3] Printed circuit board As a method for obtaining a printed circuit board from the composition of the present invention, the following method can be listed: the prepreg volume layer is appropriately stacked with copper foil by conventional method, and heated and pressed at 170°C to 300°C for 10 minutes to 3 hours under a pressure of 1 MPa to 10 MPa.

[0268] [4] Addition layer substrate A method for obtaining an augmentation substrate from the composition of the present invention can be illustrated by the following steps: First, the composition, incorporating rubber, fillers, etc., is applied to a circuit board on which circuits are formed using a spray coating method, curtain coating method, etc., and then cured (Step 1). Next, as needed, through holes are made, and the surface is treated with a roughening agent and washed with hot water to create an uneven surface, followed by plating with a metal such as copper (Step 2). This process is repeated sequentially as needed to form alternating layers of resin insulating layer and conductor layer with a specified circuit pattern (Step 3). Furthermore, the through holes are made after the outermost resin insulating layer is formed. Alternatively, regarding the augmentation substrate of the present invention, a resin-coated copper foil, formed by semi-curing the resin composition on a copper foil, can be heated to 170°C to 300°C and pressed onto a wiring board on which circuits are formed to form a roughened surface, thus omitting the plating process and producing the augmentation substrate.

[0269] [5] Extension membrane As a method for obtaining a thickened film from the composition of the present invention, it can be manufactured by coating the composition onto the surface of a support film (Y) serving as a substrate, and then drying the organic solvent by heating or blowing hot air to form a layer (X) of the composition.

[0270] The organic solvents used herein are preferably ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.; cellolytic agents, carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; and preferably, the non-volatile components are used in a proportion of 30% to 60% by mass.

[0271] The thickness of the formed layer (X) is typically set to be greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer in the circuit board is typically in the range of 5 μm to 70 μm; therefore, the thickness of the resin composition layer is preferably 10 μm to 100 μm. Furthermore, the composition layer (X) described in this invention can be protected by the protective film described later. By using the protective film, the adhesion or scratches of dust and other contaminants to the surface of the resin composition layer can be prevented.

[0272] The supporting film and protective film can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate; and polyimide. Furthermore, they can be made of release paper or metal foils such as copper foil and aluminum foil. In addition to matte treatment and corona treatment, the supporting film and protective film can also undergo release treatment. The thickness of the supporting film is not particularly limited, but it is typically 10 μm to 150 μm, preferably in the range of 25 μm to 50 μm. The thickness of the protective film is preferably set to 1 μm to 40 μm.

[0273] After the support film (Y) is laminated onto 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 curable resin composition layer constituting the laminated film has been heat-cured, it can prevent dust and other contaminants from adhering during the curing process. When peeling is performed after curing, the support film is usually demolded beforehand.

[0274] The build-up film obtained in the manner described above can be used to manufacture multilayer printed circuit boards. For example, when layer (X) is protected by a protective film, after peeling off the protective film, layer (X) is laminated on one or both sides of the circuit board by, for example, vacuum lamination, in a manner that allows the layer (X) to directly contact the circuit board. The lamination method can be batch lamination or continuous lamination using rollers. In addition, the build-up film and the circuit board can be heated (preheated) before lamination, as needed. Regarding the lamination conditions, it is preferred to set the pressing temperature (lamination temperature) to 70°C to 140°C, the pressing pressure to 1 kgf / cm² to 11 kgf / cm² (9.8 × 10⁴ N / m² to 107.9 × 10⁴ N / m²), and the lamination is preferably performed under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0275] [6] Conductive paste As a method for obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing conductive particles in the composition can be cited. The conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive according to the type of conductive particles used. [Examples]

[0276] Next, the present invention will be specifically described by way of examples and comparative examples. Unless otherwise specified in advance below, "parts" and "%" are based on mass. The present invention is not limited thereto.

[0277] 1H-nuclear magnetic resonance (1H-NMR), field desorption mass spectrometry (FD-MS) spectrum, and GPC were measured under the following conditions.

[0278] <1H-NMR> 1H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE Magnetic field strength: 600 MHz Accumulation times: 32 times Solvent: DMSO-d6 Sample concentration: 30% by mass

[0279] <FD-MS spectrum> FD-MS: "JMS-T100GC AccuTOF" manufactured by JEOL Ltd. Measurement range: m / z = 50.00~2000.00 Rate of change: 25.6 mA / min Final current value: 40 mA Cathode voltage: -10 kV

[0280] <gpc> GPC: "HLC-8320GPC" manufactured by Tosoh Corporation. Tube Columns: "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Measurement conditions: 40℃ Mobile phase: Tetrahydrofuran Flow rate: 1 ml / min Standard: PStQuick A, PStQuick B, PStQuick E, and PStQuick F manufactured by Tosoh Corporation.

[0281] <Epoxy Equivalent> The epoxy equivalent of the synthesized epoxy resin was determined according to Japanese Industrial Standards (JIS) K7236, and the epoxy equivalent (g / eq) was calculated.

[0282] <Number of repeating units> As a method for calculating the number of repeating units, examples include calculations based on GPC molecular weight determination or analysis results from various appropriate instruments such as FD-MS and NMR.

[0283] (Synthesis example 1) 210 g (0.5 moles) of 1,12-dodecanediol diglycidyl ether (manufactured by Yokkaichi Synthetic Co., Ltd.; epoxy equivalent 210 g / eq) and 119.7 g (0.53 moles) of bisphenol A (hydroxyl equivalent 114 g / eq) were added to a flask equipped with a thermometer and a stirrer. After heating to 140°C over 30 minutes, 3.2 g of 20% sodium hydroxide aqueous solution was added. Subsequently, the temperature was raised to 150°C over 30 minutes, and the reaction was carried out at 150°C for 16 hours. Then, a neutralization amount of sodium phosphate was added to obtain 320 g of hydroxyl compound (Ph-1). Based on the peak value of M+=771 obtained from the mass spectrometry, which corresponds to the theoretical structure of the following structural formula (Ph-1) with m 1=1 and n 1=12, it was confirmed that the hydroxyl compound (Ph-1) contains the hydroxyl compound as the target. The hydroxyl equivalent of the hydroxyl compound (Ph-1) calculated by GPC is 2000 g / eq.

[0284] [Chemistry 100]

[0285] (Synthesis example 2) Except for converting 210 g (0.5 mol) of 1,12-dodecanediol diglycidyl ether (epoxy equivalent 210 g / eq) in Synthesis Example 1 into 136 g (0.43 mol) of 1,6-hexanediol diglycidyl ether (SR-16H manufactured by Sakamoto Pharmaceutical: 160 g / eq) and 66 g (0.07 mol) of polytetramethylenediol diglycidyl ether (Denacol EX-991L manufactured by Nagase ChemteX: 445 g / eq) in Synthesis Example 1, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain 320 g of hydroxyl compound (Ph-2). Based on the peak value of M+=1839 obtained from mass spectrometry, corresponding to the theoretical structure (Ph-2) with n1=6, m1=1, n2=11, m2=1, the presence of a hydroxyl compound (Ph-2) as the target compound was confirmed. The hydroxyl equivalent of the hydroxyl compound (Ph-2) calculated by GPC was 1896 g / eq.

[0286] [Chemistry 101]

[0287] (Synthesis example 3) Except for converting 210 g (0.5 mol) of 1,12-dodecanediol diglycidyl ether (epoxy equivalent 210 g / eq) from Synthesis Example 1 into 481 g (0.5 mol) of polypropylene glycol diglycidyl ether (Denacol EX-931 manufactured by Nagase ChemteX: epoxy equivalent 481 g / eq), the reaction was carried out in the same manner as in Synthesis Example 1 to obtain 590 g of hydroxyl compound (Ph-3). Based on the peak value of M+=1226 obtained from mass spectrometry, corresponding to the theoretical structure of the following structural formula (Ph-3) with m=1 and n=11, it was confirmed that the hydroxyl compound (Ph-3) contains the hydroxyl compound as the target. The hydroxyl equivalent of the hydroxyl compound (Ph-3) calculated by GPC was 593 g / eq, and the average value of the repeating unit m was 0.8. [Chemistry 102]

[0288] (Synthesis Example 4) In a flask equipped with a thermometer, dropping funnel, cooling tube, and stirrer, 200 g of the hydroxyl compound (Ph-1) obtained in Synthesis Example 1, 437 g (4.72 moles) of epichlorohydrin, and 118 g of n-butanol were added and dissolved while being purged with nitrogen. After heating to 65°C, the pressure was reduced to the azeotropic pressure, and 6.66 g (0.08 moles) of 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. Stirring continued for 0.5 hours under the same conditions. During this time, the distillate obtained by azeotropic distillation was separated using a Dean-Stark trap; the water layer was removed, and the oil layer was returned to the reaction system for further reaction. Unreacted epichlorohydrin was then removed by vacuum distillation. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to the crude epoxy resin obtained at this point and dissolved. Then, 10 g of 10% sodium hydroxide aqueous solution was added to the solution and reacted at 80°C for 2 hours. The solution was then washed three times with 50 g of water until the pH of the washing solution was neutral. Subsequently, the system was dehydrated by azeotropic distillation, and after precision filtration, the solvent was removed by distillation under reduced pressure to obtain 190 g of epoxy resin (Ep-1). The epoxy equivalent of the obtained epoxy resin (Ep-1) was 2320 g / eq. Based on the peak value of M+=883 obtained from mass spectrometry, corresponding to the theoretical structure of the following structural formula (Ep-1) with m 1=1, n 1=12, p 1=0, p 2=0, q=1, it was confirmed that the epoxy resin (Ep-1) contained the target epoxy resin (Ep-1).

[0289] [Chemistry 103]

[0290] (Synthesis Example 5) Except that 200 g of the hydroxyl compound (Ph-1) obtained in Synthesis Example 1 was replaced with 200 g of the hydroxyl compound (Ph-2) obtained in Synthesis Example 2, the reaction was carried out in the same manner as in Synthesis Example 3 to obtain 190 g of epoxy resin (Ep-2). The epoxy equivalent of the obtained epoxy resin (Ep-2) was 2167 g / eq. Based on the peak value of M+=1951 obtained by mass spectrometry, which corresponds to the theoretical structure of the following structural formula (Ep-2) with m1=1, n1=6, m2=1, n2=11, q=1, p1=0, p2=0, it was confirmed that the epoxy resin (Ep-2) contains the structure of the target compound.

[0291] [Chemistry 104]

[0292] (Synthesis Example 6) Except that 200 g of the hydroxyl compound (Ph-1) obtained in Synthesis Example 1 was replaced with 200 g of the hydroxyl compound (Ph-3) obtained in Synthesis Example 3, the reaction was carried out in the same manner as in Synthesis Example 3 to obtain 191 g of epoxy resin (Ep-3). The epoxy equivalent of the obtained epoxy resin (Ep-3) was 2167 g / eq. Based on the peak value of M+=1492 obtained by mass spectrometry, which corresponds to the theoretical structure of the following structural formula (Ep-3) with m=1, n=11, q=1, p1=0, p2=0, it was confirmed that the epoxy resin (Ep-2) contained the structure of the target epoxy resin (Ep-3).

[0293] [Chemistry 105]

[0294] (Synthesis Example 7) According to a previous report ("Chemistry Letters" (2009), 38, (7), 726-727), a 2-anthracarboxylic acid dimer with the following structure (hereinafter also referred to as 2-AC dimer) was synthesized by photochemical reaction.

[0295] [Chemistry 106]

[0296] (Synthesis Example 8) According to a previous report (Journal of the American Chemical Society, 2018, 140, (34), 10820-10828), a 9-anthracarboxylic acid dimer with the following structure (hereinafter also referred to as 9-AC dimer) was synthesized by photochemical reaction.

[0297] [Chemistry 107]

[0298] (Synthesis Example 9) According to a previous report ("Scientific Reports" (2020), 10, (1), 20214), an anthracene compound containing a glycidyl ether group with the following structure was synthesized (A-1).

[0299] [Chemistry 108]

[0300] (Synthesis Example 10) 6.0 g of the anthracene compound (A-1) obtained in Synthesis Example 9 and 20 g of tetrahydrofuran were added to a flask and dissolved using a stirrer. The mixture was then irradiated with UV light (LC8, manufactured by Hamamatsu Photonics Co., Ltd.) at a intensity of 30 mW / cm² for 30 hours. The precipitate was then recovered by suction filtration, dried under reduced pressure overnight at room temperature, and then dried under reduced pressure at 70°C for 24 hours to obtain 4.9 g of anthracene dimer with the following structure (hereinafter also referred to as 9-AG dimer).

[0301] [Chemistry 109]

[0302] (Examples 1-9 and Comparative Examples 1-3) According to the formulation in Table 1, epoxy resin, substituted anthracene dimer compound, curing agent and curing accelerator were uniformly mixed using a mixer (Thinky Co., Ltd.'s "Defoaming Stirring Taro ARV-200") to obtain epoxy resin compositions EPC-1 to EPC-9 and epoxy resin compositions cEPC-1 to cEPC-3 of Examples 1 to 9 and Comparative Examples 1 to 3.

[0303] <Tension and Shear Test> The epoxy resin compositions EPC-1 to EPC-9 and cEPC-1 to cEPC-3 obtained in Examples 1 to 9 and Comparative Examples 1 to 3, respectively, were coated onto one of two cold-rolled steel sheets (SPCC-SD manufactured by TP Tech Co., Ltd., 1.0 mm × 25 mm × 100 mm). Glass beads (J-80 manufactured by Potters-Ballotini Co., Ltd.) were added as spacers, and the other SPCC-SD sheet (adhesion area: 25 mm × 12.5 mm) was bonded to it. The sheets were then heat-cured according to the temperatures specified in Table 1 to obtain test pieces. Tensile shear tests were performed on the test pieces to evaluate adhesion. The tests were conducted according to JIS K 6850, and the maximum point stress at the test environment of 23°C was compared.

[0304] Initial adhesion: Shear tests were conducted without any special treatment of the prepared test specimens. The results are shown in Table 1. Adhesion after heating: The prepared test pieces were heated using a heating dryer under the specified conditions of "additional heating" shown in Table 1, and then shear tests were performed. The results are shown in Table 1.

[0305] <Disintegration Evaluation> The strength reduction rate was calculated using the formula: (initial adhesion force - adhesion force after heating) / initial adhesion force × 100. The results are shown in Table 1.

[0306] <Structural Periodicity> For the resin composition prepared according to Table 1, silicon tubes were used as spacers, and the resin was held in place using an aluminum mirror panel (JIS H 4000 A1050P manufactured by Engineering Test Service Co., Ltd.) and heat-cured at the temperatures specified in Table 1 to obtain a resin hardened material with a thickness of 0.8 mm. The obtained resin hardened material was cross-sectioned using an ultramicrotome for periodic structural observation. The observation method used a scanning electron microscope (SEM) to clearly determine the morphology comparison. SEM observation confirmed the presence or absence of phase-separated structures in the hardened material. In cases where the hardened material exhibited phase-separated structures and these structures formed island structures, the particle size of the islands was measured. Furthermore, regarding the average particle size, 50 islands were randomly selected from a 200 μm × 260 μm field of view, and their particle sizes were measured to calculate the average particle size. The results are shown in Table 1.

[0307] <sem> Model used: JSM-7800F manufactured by Nippon Electronics Co., Ltd. Accelerating voltage: 5 kV

[0308] [Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 1 2 3 Epoxy resin composition EPC-1 EPC-2 EPC-3 EPC-4 EPC-5 EPC-6 EPC-7 EPC-8 EPC-9 cEPC-1 cEPC-2 cEPC-3 Epoxy compound (A) (parts by weight) Ep-1 50 50 50 50 50 55 55 91 Ep-2 55 Ep-3 45 45 Epoxy compounds (B) (parts by weight) E-850S 33 33 33 33 33 36 36 45 45 36 91 Substituted anthracene dimer compound (C) (parts by weight) 2-AC dimer 9 9 9 9 9 9 9 9 9-AC dimer 9 9 9-AG dimer 9 hardener (parts by weight) BPF 8 8 8 8 8 9 DICY 4.1 4.1 4.1 4.1 4.1 4.5 4.6 4.5 10.2 0.9 mXDA 8.9 8.9 hardening accelerator (parts by weight) DCMU 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 Hardening conditions Temperature (°C) 150 150 150 150 150 150 150 100 150 150 150 - time 30 min 3 h 3 h 3 h 3 h 3 h 3 h 3 h 3 h 30 min 3 h - Additional heating Temperature (°C) 200 200 170 200 200 200 200 200 200 30 min 3 h - time 3 h 3 h 3 h 30 min 3 h 3 h 3 h 3 h 3 h 30 min 3 h - Tensile shear test Maximum point stress (MPa) Initial value followed by force 22.8 23.3 23.3 23.3 28.8 19.5 22.4 6 9.05 21.3 12.1 - After heating, the force is applied. 3.9 4.9 5.74 4.07 23.4 12.3 15.7 3.82 4.08 21.8 12.2 - Strength reduction rate (%) 82.9 79.0 75.4 82.5 18.8 36.9 29.9 36.3 54.9 -2.3 -0.8 - Structural periodicity shape islands islands islands islands islands islands islands islands islands islands none - Particle size (μm) 1.1 1.1 1.1 1.1 1.0 1.0 1.0 0.4 0.5 1.1 - -

[0309] Furthermore, the ingredients shown in the table are described below. Epoxy Resin B: EPICLON 850S epoxy resin (bisphenol A type liquid epoxy resin, epoxy equivalent 188 g / eq) manufactured by DIC Corporation. Hardener: BPF-HG (Bisphenol F) manufactured by Chung Jung Chemical Industry. Hardener: Dicyandiamine (DICY7) manufactured by Mitsubishi Chemical Corporation Hardener: m-Xylenediamine (mXDA) manufactured by Kanto Chemical. Hardening accelerator: B-605-IM (3-(3,4-dichlorophenyl)-1,1-dimethylurea) manufactured by DIC Corporation. In addition, the meanings of "strength reduction rate: -2.3% and -0.8%" for Comparative Example 1 and Comparative Example 2 shown in the table are the meanings of "strength increase rate: 2.3% and 0.8%" respectively.

[0310] (Examples 10-15 and Comparative Example 4) Tensile Test For epoxy resin compositions EPC-1, EPC-2, EPC-5 to EPC-8, and cEPC-2 obtained in Examples 1, 2, 5-8, and Comparative Example 2, respectively, silicon tubes were used as spacers, and the resin was held in place using an aluminum mirror panel (JIS H 4000 A1050P manufactured by Engineering Test Service Co., Ltd.), and heat-cured at the temperatures specified in Table 2 to obtain a resin-cured material with a thickness of 0.8 mm. The obtained curing material was then stamped into a dumbbell shape (JIS K 7161-2-1BA) using a stamping die, and used as a test piece. Tensile tests were performed on the test pieces using a tensile testing machine (Automatic Graphing Machine AG-IS manufactured by Shimadzu Corporation) according to JIS K 7162-2, and the elongation at break at an ambient temperature of 23°C was evaluated (test speed: 2 mm / min). The results are shown in Table 2.

[0311] [Table 2] Example Comparative example 10 11 12 13 14 15 4 Epoxy resin composition EPC-1 EPC-2 EPC-5 EPC-6 EPC-7 EPC-8 cEPC-2 Hardening temperature (°C) 150 150 150 150 150 100 150 Hardening time 30 min 3 h 3 h 3 h 3 h 3 h 3 h Tensile test Elongation at break (%) 36.6 52.7 13.3 48.9 21.7 14.5 <1

[0312] (Inspection) In the cured epoxy composition of the present invention, by having a phase-separated structure, the low-elasticity phase (high flexibility) and the high-elasticity phase (adhesion strength) are independent, possessing both properties. It can be observed that the phase separation is caused by the difference in the "crosslinking rate" of the matrix resins that constitute the low-elasticity phase / high-elasticity phase respectively and the difference in the "compatibility" of the cured product after crosslinking. In addition, by using resins containing long-chain alkyl groups and polyethers in the main chain as a low-elasticity phase, it can be found that high flexibility can be imparted. Furthermore, since anthracene dimers possess curing groups that can react with epoxy groups, anthracene dimer backbones are incorporated into the cured network. By further heating the cured material, the thermal dissociation function of the anthracene dimer backbone can be observed, resulting in network cleavage and exhibiting easy disintegration.

[0313] As shown in Table 1, in Comparative Example 2, even when the anthracene dimer framework was introduced in the same manner as in Example 1, the dissociation function as in this invention was not exhibited when using a different type of epoxy resin than in Example 1. Based on the use of the two specific epoxy resins of this invention, it is presumed that the anthracene dimer framework is dispersed in a manner conducive to dissociation in the cured epoxy resin composition. In Comparative Example 1, since it does not contain anthracene dimer skeleton that performs dissociation, it does not exhibit easy disintegration. Furthermore, in Comparative Example 3, the resin composition is of high viscosity and therefore cannot be formulated, making evaluation impossible. Furthermore, in the case where the cured epoxy resin composition of one embodiment of the present invention has an island structure, it is presumed that the anthracene dimer skeleton is distributed in a way that facilitates dissociation function in both the sea portion and the island portion.

[0314] As shown in Table 2, in Examples 10 to 15, which used epoxy resin compositions EPC-1, EPC-2, and EPC-5 to EPC-8 obtained in Examples 1, 2, 5 to 8, even with the introduction of anthracene dimer backbone, the cured material exhibited high flexibility due to its island-like structure. However, in Comparative Example 4, which used epoxy resin composition cEPC-2 obtained in Comparative Example 2, high flexibility was not observed because the cured material did not have an island-like structure.

[0315] none< / sem> < / gpc>

Claims

1. An epoxy resin composition, characterized in that it comprises: an epoxy resin (A) with an epoxy equivalent of 500 g / eq to 10,000 g / eq, an epoxy resin (B) with an epoxy equivalent of 100 g / eq to 300 g / eq, a compound (C) having an anthracene dimer skeleton, and a curing agent (D), wherein the epoxy resin (A) is represented by the following general formula (1), and the compound (C) has two or more epoxy-containing groups or two or more curing groups; in formula (1), Ar is independently a structure containing an unsubstituted or substituted aromatic ring, X is a structural unit represented by the following general formula (2), Y is a structural unit represented by the following general formula (3), and in formulas (2) and (3), Ar is the same as described above, R1 and R2 are independently hydrogen atoms, methyl or ethyl, and R' is a divalent hydrocarbon group with 2 to 12 carbon atoms. R3, R4, R7, and R8 are independently hydroxyl, glycidyl ether, or 2-methylglycidyl ether groups, respectively; R5, R6, R9, and R10 are independently hydrogen atoms or methyl groups, respectively; n1 is an integer from 4 to 16; n2 is the average value of the repeating units and is from 2 to 30; R11 and R12 are independently glycidyl ether or 2-methylglycidyl ether groups, respectively; R13 and R14 are independently hydroxyl, glycidyl ether, or 2-methylglycidyl ether groups, respectively; R15 and R16 are hydrogen atoms or methyl groups; m1, m2, p1, p2, and q are the average values ​​of the repeating units; m1 and m2 are independently from 0 to 25, and m1 + m2 ≥ 1; p1 and p2 are independently from 0 to 5; q is from 0.5 to 5; where... The bond between X represented by the general formula (2) and Y represented by the general formula (3) can be random or block, indicating that the total number of each structural unit X and Y existing in a molecule is m1 and m2, respectively.

2. The epoxy resin composition as claimed in claim 1, wherein, Ar in general formulas (1) to (3) can be independently represented by any of the following structural formulas (4): The aromatic ring in formula (4) may be substituted or unsubstituted, and * indicates a bond node.

3. The epoxy resin composition as described in claim 1 or claim 2, wherein, In the general formula (2), n1 is 6 to 12, R3 and R4 are hydroxyl groups, and R5 and R6 are hydrogen atoms.

4. The epoxy resin composition as described in claim 1 or claim 2, wherein, In the general formula (3), R' is a divalent hydrocarbon group with 2 to 6 carbon atoms, R7 and R8 are hydroxyl groups, and R9 and R10 are hydroxyl groups.

5. The epoxy resin composition as described in claim 1 or claim 2, wherein, The compound (C) having an anthracene dimer skeleton is the compound (C-i1) represented by the following general formula (I-1); in general formula (I-1), a plurality of R1a independently represent hydrogen atoms or monovalent substituents, wherein at least one R1a is an epoxy group, and a plurality of R2a independently represent hydrogen atoms or monovalent substituents, wherein at least one R2a is an epoxy group.

6. The epoxy resin composition as described in claim 1 or claim 2, wherein, The compound (C) having an anthracene dimer skeleton is the compound (C-i2) represented by the following general formula (I-2); In general formula (I-2), a plurality of R11a independently represent hydrogen atoms or monovalent substituents, wherein at least one R11a is a group containing a hardening group, and a plurality of R21a independently represent hydrogen atoms or monovalent substituents, wherein at least one R21a is a group containing a hardening group.

7. The epoxy resin composition as claimed in claim 6, wherein, In the compound (C-i2) represented by the general formula (I-2), at least one R11a and at least one R21a are selected from the group consisting of amino-containing groups, hydroxyl-containing groups and carboxyl-containing groups.

8. The epoxy resin composition as claimed in claim 6, wherein, In the compound (C-i2) represented by the general formula (I-2), at least one R11a and at least one R21a are carboxyl groups.

9. The epoxy resin composition as described in claim 1 or claim 2 is an adhesive.

10. A cured epoxy resin composition, which is a cured epoxy resin composition as described in any one of claims 1 to 9.

11. A cured product of the epoxy resin composition as claimed in claim 10, wherein, The cured epoxy resin composition has an island structure comprising a sea portion and an island portion, wherein the average particle size of the sea portion is 10 nm to 100 μm.

12. A laminate formed by laminating a substrate with a hardened material as described in claim 10 or claim 11.

13. A laminate formed by laminating a first substrate, a layer comprising a hardener as described in claim 10, and a second substrate in that order.

14. The stack as described in claim 13, wherein, The first substrate is a substrate containing metal or metal oxide, and the second substrate is a substrate containing plastic.

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