JP2013056990A - Epoxy resin composition for reworking - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for reworking formable of a cured product having high crosslinking density on cationic polymerization, wherein when the functions of the cured product become unnecessary, the cured product is easily decomposed and solubilized on exposure to specific conditions, and to provide a cured product which is obtained by curing the epoxy resin composition for reworking, has high crosslinking density, and is easily decomposed and shows solubility in solvents on exposure to specific conditions.SOLUTION: The epoxy resin composition for reworking contains an epoxy compound (A) represented by formula (1), wherein R, Rand Rare the same or different and each represents an alicyclic epoxy group; and Rrepresents a group containing an alicyclic epoxy group, a hydrocarbon group or a hydrogen atom. It is preferable that the epoxy resin composition for reworking further contains a curing agent (B) and a curing accelerator (C) or a cationic polymerization initiator (D).

Description

  In the present invention, a cured product having a high crosslinking density can be formed by cationic polymerization, and when the function as a cured product becomes unnecessary, it is easily decomposed and solubilized by exposure to specific conditions. The present invention relates to an epoxy resin composition for rework.

  Thermal and / or photo-curable resins represented by epoxy resins are known to form a cured product having excellent electrical properties, moisture resistance, heat resistance, etc. and insoluble and infusible properties by cationic polymerization. For optical component materials, mechanical component materials, electrical / electronic component (for example, printed wiring board) materials (for example, sealing materials), automotive component materials, civil engineering and building materials, molding materials, coating materials, adhesives, etc. It is used.

  However, the “insoluble” or “infusible” property of the cured product can be problematic in some cases. For example, an electronic component or wiring circuit placed on a printed wiring board is sealed and protected with a curable resin, but when the electronic component or wiring circuit is repaired or discarded, the electronic component or wiring is removed from the printed wiring board. When collecting the circuit, it is necessary to remove the sealing resin without damaging these electronic components and wiring circuits.

  As a conventional method for removing a sealing resin, a method of decomposing and removing by a chemical reaction under severe conditions using a strong alkali or strong acid, or after swelling the sealing resin with an organic solvent, There is a method of removing by mechanical means. However, it has been extremely difficult to completely remove only the sealing resin without damaging the electronic components and the wiring circuit.

  Also in the field of adhesives, there is a need for a releasable adhesive that can be peeled off without destroying the adherend after it has been bonded once.

  Furthermore, in recent years, in the field of electric / electronic component materials, mounting of semiconductor elements on a substrate has been promoted in order to cope with the multi-function and light weight of electric / electronic components. As the solder becomes lead-free, a resin having reflow heat resistance applicable to lead-free solder mounting is required.

  From the above, it is possible to form a cured product having a function such as heat resistance by crosslinking and curing by polymerization, and when the function as a cured product is no longer necessary, it can be easily exposed to specific conditions. A curable resin that can be separated and recovered without being destroyed by decomposition and solubilization (= curable resin for rework) is a re-peelable adhesive, coating film, photoresist, electronic component and wiring circuit. Application in various applications such as a sealing material is expected.

  Conventionally, as a monomer component constituting the curable resin for rework, diepoxide in which two epoxy groups described in Patent Document 1 are connected by an acetal or ketal structure, or tannin derived from plant biomass described in Patent Document 2 Epoxy compounds described in Non-Patent Document 1 are known. These monomer components can be crosslinked and cured by polymerization to form a cured product having a specific function. When the function as a cured product is no longer necessary, it can be easily exposed by exposure to specific conditions. Although it can be decomposed and solubilized, it can form a cured product that has even better reworking capability, that is, a reflow heat resistance that has higher crosslink density than conventional and can be applied to lead-free solder mounting. When there is no need for the function as a cured product, there has been a demand for an epoxy resin for rework that can be easily decomposed and solubilized by exposure to specific conditions.

Japanese Patent Laid-Open No. 5-230335 JP 2010-241855 A

Polymer Papers Vol.65, No.2, pp.113-123 (Feb., 2008)

  Therefore, the object of the present invention is to form a cured product having a high crosslinking density by cationic polymerization, and when the function as a cured product is no longer necessary, it is easily decomposed by exposure to specific conditions. And a reworkable epoxy resin composition to be solubilized, and a cured product obtained by curing the reworkable epoxy resin composition, having a high cross-linking density, and easily decomposing when exposed to specific conditions. Is to provide.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have condensed an alcohol having a cyclohexene ring and an aldehyde having a cyclohexene ring to thereby form a cyclohexene via a [—C (—O—) ₂ —] moiety. It is possible to obtain an acetal compound in which three or more rings are bonded, and by oxidizing the acetal compound, an alicyclic epoxy group (alicyclic ring) is formed via a [—C (—O—) ₂ —] moiety. It has been found that a novel epoxy compound can be obtained in which three or more adjacent carbon atoms and a group consisting of two oxygen atoms and one oxygen atom are bonded. The novel epoxy compound has three or more alicyclic epoxy groups in one molecule and has many crosslinking points per monomer unit. Therefore, when polymerized, it has a three-dimensional crosslinked structure and has excellent heat resistance. Can form a cured product having heat resistance and toughness, and the [-C (-O-) _2- ] moiety in the molecule does not exhibit electrophilicity or nucleophilicity. Aldehydes, ketones, or diols that are not cleaved, but are easily cleaved by exposure to wet heat and / or acid, and exhibit solvent solubility, that is, the novel epoxy compounds have excellent reworking ability I found. In the present specification, the “rework ability” is crosslinked / cured by polymerization to form a cured product having a predetermined function, and when the function as the cured product becomes unnecessary, By being easily decomposed and solubilized by exposure to specific conditions, the adherend can be separated and recovered in a reusable state without destroying the adherend. The “rework resin” refers to a resin having the rework ability. The present invention has been completed based on these findings.

［式中、Ｒ¹、Ｒ²、Ｒ³は、同一又は異なって、脂環式エポキシ基を含む基を示し、Ｒ⁴は、脂環式エポキシ基を含む基、炭化水素基、又は水素原子の何れかを示す］
で表されるエポキシ化合物（Ａ）を含むことを特徴とするリワーク用エポキシ樹脂組成物を提供する。 That is, the present invention provides the following formula (1):

[Wherein R ¹ , R ² and R ³ are the same or different and each represents a group containing an alicyclic epoxy group, and R ⁴ represents a group containing an alicyclic epoxy group, a hydrocarbon group or a hydrogen atom. Indicate any]
The epoxy compound (A) represented by these is included, The epoxy resin composition for rework characterized by the above-mentioned is provided.

（式中、Ｒ⁵は、単結合又は２価の炭化水素基を示す）
で表される基が好ましい。 As a group containing the said alicyclic epoxy group, following formula (2)

(In the formula, R ⁵ represents a single bond or a divalent hydrocarbon group)
The group represented by these is preferable.

（式中、Ｒ^5-1、Ｒ^5-2、Ｒ^5-3は、同一又は異なって、単結合又は炭素数１〜２のアルキレン基を示す）
で表される脂環式トリエポキシ化合物が好ましい。 As said epoxy compound (A), following formula (3)

(Wherein R ^5-1 , R ^5-2 and R ^5-3 are the same or different and each represents a single bond or an alkylene group having 1 to 2 carbon atoms)
The alicyclic triepoxy compound represented by these is preferable.

  The epoxy resin composition for reworking of the present invention preferably further contains a curing agent (B) and a curing accelerator (C), or a cationic polymerization initiator (D).

  The present invention also provides a cured product obtained by curing the epoxy resin composition for rework.

  The present invention further provides a method for using the epoxy resin composition for rework including a step of cationic polymerization of the epoxy resin composition for rework to obtain a cured product, and a step of decomposing and solubilizing the obtained cured product. .

Since the epoxy resin composition for reworking according to the present invention contains an epoxy compound having three or more alicyclic epoxy groups in one molecule and having many crosslinking points, the crosslinking density is high by polymerization and extremely excellent heat resistance. It is possible to form a cured product having the properties (reflow heat resistance applicable to lead-free solder mounting) and toughness. In addition, since the epoxy compound contains a [—C (—O—) ₂ —] moiety in the molecule, an aldehyde, ketone, or diol that is rapidly cleaved and shows solvent solubility by exposure to wet heat conditions or acid. Can be formed. Therefore, it can be used as a cured product while a cured product having heat resistance and toughness is required. After the function as the cured product is no longer necessary, it can be exposed to wet heat conditions and / or exposure to acids. It decomposes rapidly and becomes a decomposition product that is soluble in the solvent, and can be easily removed from the adherend surface by dissolving in the solvent. The adherend can be collected and reworked without being damaged.

  In the present invention, the epoxy resin composition for rework includes optical component materials, mechanical component materials, electrical / electronic component materials (for example, sealing materials), automotive component materials, civil engineering and building materials, molding materials, coating materials, adhesives, and fibers. Reinforced plastics (FRP: fiber reinforced plastics, such as GFRP (glass fiber reinforced plastics), CFRP (carbon fiber reinforced plastics, etc.) materials, plastic forming materials, etc., especially semiconductor encapsulants, re-peelable adhesives, coating materials, Useful for photoresist.

  The epoxy resin composition for reworking of this invention contains the epoxy compound (A) represented by the said Formula (1), It is characterized by the above-mentioned.

[Epoxy compound (A)]
The epoxy compound (A) of the present invention is represented by the above formula (1). In the formula (1), R ¹ , R ² and R ³ are the same or different and represent a group containing an alicyclic epoxy group, and R ⁴ is a group containing a cycloaliphatic epoxy group, a hydrocarbon group, or Indicates any hydrogen atom. When R < ¹ > -R < ⁴ > shows group containing an alicyclic epoxy group, these may be the same and may differ.

The group containing the alicyclic epoxy group may be a group containing at least one alicyclic epoxy group, but in the present invention, the group represented by the above formula (2) is particularly preferable. . In formula (2), R ⁵ represents a single bond or a divalent hydrocarbon group.

  Examples of the divalent hydrocarbon group include divalent aromatic hydrocarbon groups such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, and biphenylene; Cycloalkylene groups such as den, 1,2-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene; 2-cyclohexene-1,4-diyl group, etc. A cycloalkenylene group; a divalent bridged cyclic group such as an adamantane-1,3-diyl group; a carbon such as a methylene, ethylene, trimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, tetramethylene group An alkylene group of about 1 to 6; an alkenylene group of about 2 to 6 carbon atoms such as a propenylene group; an alkynylene group of about 2 to 6 carbon atoms such as a propynylene group; It is below.

The group containing an alicyclic epoxy group in the present invention is represented by the above formula (2), and R ^{5 in} the formula is an alkylene group [in particular, R ^5-1 , R ^5-2 , or R ^{5 -3} is a C1-C2 alkylene group], which is preferable in that a cured product having a low molecular weight between cross-linking points and a higher cross-linking density can be formed.

Examples of the hydrocarbon group for R ⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these groups are bonded. Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. An alkyl group having about 10 and more preferably about 1 to 3); an alkenyl group having about 2 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 3) such as vinyl, allyl and 1-butenyl groups; Examples thereof include an alkynyl group having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as a propynyl group.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups; Cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as pentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4 4.0.1, ^2,5 . And a bridged cyclic hydrocarbon group such as 1 ^7,10 ] dodecan-3-yl group.

  Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl and naphthyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to 4 units). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

  The hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyls. It may have a group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), carbamoyl group, cyano group, nitro group, acyl group, amino group, sulfo group, heterocyclic group and the like. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

As the epoxy compound (A) represented by the formula (1) according to the present invention, among them, R ¹ , R ² , R ³ are the same or different and contain an alicyclic epoxy group (in particular, the above-mentioned A group represented by formula (2), wherein R ⁴ represents a hydrogen atom, and an alicyclic triepoxy compound represented by formula (3) is particularly preferred. In formula (3), R ^<5-1> , R ^<5-2> and R ^<5-3> are the same or different and each represents a single bond or an alkylene group having 1 to 2 carbon atoms. Specific examples of the alicyclic triepoxy compound represented by the formula (3) include the following compounds.

The epoxy compound (A) of the present invention is represented by the above formula (3) in that a cured product having a high oxirane oxygen concentration, a low molecular weight between cross-linking points, and a higher cross-linking density can be formed. A compound in which at least one of R ^5-1 , R ^5-2 , and R ^5-3 in the alicyclic triepoxy compound is a single bond is preferable, and in particular, a cured product having both high heat resistance and toughness. R ^5-1 and R ^5-2 are the same or different and are alkylene groups having 1 to 2 carbon atoms (particularly preferably, R ^5-1 and R ^5-2 are methylene groups) in that they can be formed. And a compound in which R ^5-3 is a single bond.

The epoxy compound (A) represented by the formula (1) can be produced, for example, by oxidizing an acetal compound represented by the following formula (4) using an oxidizing agent. In the formula (4), R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are the same or different and represent a group containing a cyclohexenyl group, and R ^{4 ′} is a group containing a cyclohexenyl group, a hydrocarbon group Or a hydrogen atom.

As the acetal compound represented by the above formula (4) in the present invention, R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are the same or different and each represents a group containing a cyclohexenyl group, and R ^{4 ′} Is preferably a compound showing a hydrogen atom, and particularly preferably an acetal compound represented by the following formula (5). In formula (5), R ^5-1 , R ^5-2 , and R ^5-3 are the same or different and each represents a single bond or an alkylene group having 1 to 2 carbon atoms, and R ⁵ in the above formula (3) ^-1 , R ^5-2 and R ^5-3 .

Specific examples of the acetal compound represented by the above formula (5) include the following compounds.

  Examples of the oxidizing agent used in the reaction for oxidizing the acetal compound represented by the above formula (4) (hereinafter sometimes referred to as “oxidation reaction”) include peracids (for example, formic acid, peracetic acid, trifluoroperoxide). Organic peracids such as acetic acid, perbenzoic acid, metachloroperbenzoic acid, monoperoxyphthalic acid; inorganic peracids such as permanganic acid) and peroxides (eg, hydrogen peroxide, peroxide, hydroperoxide, peroxoacid, Peroxo acid salts) and the like. In the present invention, it is particularly preferable to use a peracid in that an epoxy compound can be obtained efficiently without using a catalyst.

  The amount of the oxidant used is, for example, about 3.0 to 6.0 mol, preferably about 3.1 to 5.0 mol, particularly preferably with respect to 1 mol of the acetal compound represented by the above formula (4). Is about 3.2 to 4.0 moles. When the amount of the oxidizing agent used exceeds the above range, it becomes uneconomical and side reactions tend to increase. On the other hand, when the usage-amount of an oxidizing agent is less than the said range, there exists a tendency for the production | generation of a monoepoxide and / or diepoxide to increase.

  The oxidation reaction is performed in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; Halogenated hydrocarbons such as chloroform, methylene chloride and 1,2-dichloroethane; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide and the like Amides; Nitriles such as acetonitrile, propionitrile, and benzonitrile; Organic acids such as acetic acid, and the like. These solvents are used alone or in admixture of two or more.

  As the usage-amount of a solvent, it is about 3-20 weight times of the acetal compound represented by the said Formula (4), for example, Preferably it is about 8-15 weight times.

  The reaction temperature is, for example, about 0 to 90 ° C, preferably about 20 to 70 ° C. The reaction time is, for example, about 1 to 10 hours, preferably about 2 to 6 hours. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  The oxidation reaction can be terminated, for example, by adding sodium thiosulfate, sodium sulfite or the like.

  After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

Moreover, the acetal compound represented by the above formula (4) includes an alcohol compound represented by the following formula (6-1) and the following formula (6-2), and an aldehyde represented by the following formula (7) or It can be synthesized by condensing with a ketone compound. R ^{1 ′} , R ^{2 ′} , and R ^{3 ′} in the following formulas (6-1), (6-2), and (7) are the same or different and represent a group containing a cyclohexenyl group, and R ^{4 '} Represents any of a group containing a cyclohexenyl group, a hydrocarbon group, or a hydrogen atom. R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , and R ^{4 ′} in formulas (6-1), (6-2), and (7) are each an acetal compound represented by the above formula (4). It corresponds to R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} .
R ^{1 ′} —OH (6-1)
R ^{2 ′} —OH (6-2)
R ^{3 ′} — (C═O) —R ^{4 ′} (7)

In particular, the acetal compound represented by the above formula (5) includes an alcohol compound represented by the following formula (6-3) and the following formula (6-4), and an aldehyde represented by the following formula (7-1). It can be synthesized by condensing the compound. R ^5-1 , R ^5-2 , and R ^5-3 in the following formulas (6-3), (6-4), and (7-1) are the same or different and have a single bond or a carbon number of 1 to 2 corresponds to R ^5-1 , R ^5-2 , and R ^5-3 in the acetal compound represented by the above formula (5).

Examples of the alcohol compound represented by the above formula (6-3) and the above formula (6-4) include a compound represented by the following formula. The alcohol compound represented by the above formula (6-3) and the alcohol compound represented by the following formula (6-4) may be the same or different.

Moreover, as an aldehyde compound represented by the said Formula (7-1), the compound etc. which are represented by a following formula can be mentioned, for example.

  The use amount of the aldehyde or ketone compound represented by the above formula (7) is, for example, with respect to 1 mol of the total of the alcohol compounds represented by the above formula (6-1) and the above formula (6-2). For example, it is about 0.2 to 1.0 mol, preferably about 0.3 to 0.8 mol, particularly preferably about 0.4 to 0.6 mol. When the amount of the alcohol compound represented by the above formula (6-1) and the above formula (6-2) exceeds the above range, it tends to be uneconomical. On the other hand, when the usage-amount of the aldehyde or ketone compound represented by the said Formula (7) exceeds the said range, there exists a tendency for the hemiacetal body which is a reaction intermediate to increase, and for a by-product to increase.

  The condensation reaction is preferably performed in the presence of an acid catalyst in that the target product can be obtained in high yield and the production of by-products can be suppressed. Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and heteropoly acid; benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and sulfonic acid strongly acidic. Examples thereof include sulfonic acids such as ion exchange resins. You may use an acid catalyst individually or in combination of 2 or more types. The amount of the acid catalyst used is, for example, 0.01 to 10 parts by weight, preferably 100 parts by weight of the total of alcohol compounds represented by the above formula (6-1) and the above formula (6-2), preferably About 0.1 to 1.0 part by weight.

  The condensation reaction is performed in the presence or absence of a solvent. Examples of the solvent include water; alcohols such as methanol, ethanol, isopropyl alcohol, and ethylene glycol; aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; benzene, toluene, xylene, Aromatic hydrocarbons such as ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide (DMSO) and the like. These solvents are used alone or in admixture of two or more.

  The reaction temperature is, for example, about 0 to 100 ° C., preferably about 20 to 50 ° C. The reaction time is, for example, about 1 to 48 hours, preferably about 5 to 36 hours, and particularly preferably about 10 to 24 hours. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  Moreover, it is preferable that the said condensation reaction removes the water which arises during reaction from the point which can advance reaction efficiently. The water can be removed by, for example, distillation, azeotropic dehydration, addition of a dehydrating agent (for example, sodium sulfate, molecular sieves, etc.), and the like.

  After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

  According to the said manufacturing method, the epoxy compound (A) represented by the said Formula (1) is compoundable efficiently.

[Epoxy resin composition for rework]
The epoxy resin composition for reworking according to the present invention contains, for example, about 40 to 100% by weight of the monomer component (cation polymerizable monomer component) of the total amount (nonvolatile content) of the epoxy resin composition for reworking. And the epoxy resin composition for rework which concerns on this invention is characterized by including the epoxy compound (A) represented by the said Formula (1), As the content, for example, in the epoxy resin composition for rework It is about 10% by weight or more (preferably about 10 to 100% by weight, particularly preferably about 15 to 90% by weight) of the total monomer components to be contained. When the epoxy compound (A) represented by the above formula (1) having a large number of crosslinking points per monomer unit is contained in the above range, the cured product has a high crosslinking density by polymerization and is excellent in heat resistance and toughness. Is preferable in that it can be formed. On the other hand, when the content of the epoxy compound (A) represented by the above formula (1) is below the above range, the number of crosslinking points per monomer unit is decreased and the crosslinking density is lowered. There is a tendency for the strength and toughness to decrease.

  In addition to the epoxy compound (A) represented by the above formula (1), the epoxy resin composition for rework according to the present invention can be used together with the epoxy compound (A) represented by the above formula (1) as a monomer component. You may contain the other epoxy compound which can superpose | polymerize. Examples of other epoxy compounds include triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and modified bisphenol A. Type epoxy resin, modified bisphenol F type epoxy resin, biphenyl type epoxy resin, and phenoxy resin.

  In addition to the epoxy compound (A) represented by the above formula (1), the reworking epoxy resin composition according to the present invention further includes a curing agent (B) and a curing accelerator (C), or a curing catalyst ( D) is preferably contained.

Examples of the curing agent (B) include well-known and conventional compounds used as curing agents for epoxy compounds. For example, phthalic anhydride, 3 or 4-methyl-1,2,3,6-methyltetrahydro Phthalic anhydride, 3 or 4-methyl-hexahydrophthalic anhydride, methyl-3,6 endomethylene-1,2,3,6-tetrahydrophthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, Acid anhydrides such as hexahydrophthalic anhydride, nadic anhydride, methyl anhydride, glutaric anhydride, hydrogenated methyl nadic anhydride, hydrogenated nadic anhydride, 5-norbornene-2,3-carboxylic anhydride Chain aliphatic polyamines such as diethylenetriamine and triethylenetetramine, and cyclic aliphatic amines such as N-aminomethylpiperazine Meta-xylene diamine, meta-amines such as aromatic amines phenylenediamine; polyamide resin; 2- imidazoles methylimidazole; BF ₃ complex compound of an amine, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts and, Bronsted acid salts such as phosphonium salts; adipic acid; sebacic acid; terephthalic acid; trimellitic acid; polycarboxylic acids such as carboxyl group-containing polyesters.

  As the curing agent (B) in the present invention, use of an acid anhydride (particularly, 3 or 4-methyl-hexahydrophthalic anhydride, hydrogenated methylnadic acid anhydride) is low in workability. It is preferable in that an excellent epoxy resin composition for rework can be prepared, and a cured product having excellent heat resistance and transparency can be obtained by polymerization. Examples of the acid anhydride include trade names “Licacid MH-700”, “Licacid MH”, “Licacid HH”, “Licacid TH”, “Licacid MT-500”, “Licacid HNA-100” (and above, New Japan). Manufactured by Rika Co., Ltd.), trade names “HN-2200”, “HN-2000”, “HN-5000”, “MHAC-P”, “hymic acid anhydride” (manufactured by Hitachi Chemical Co., Ltd.), Commercial products such as trade name “Quinhard 200” (manufactured by Nippon Zeon Co., Ltd.) can be used.

  The amount of the curing agent (B) used is, for example, about 50 to 150% by weight, preferably about 70 to 120% by weight of the total monomer components contained in the rework epoxy resin composition.

  Examples of the curing accelerator (C) include phosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate and derivatives thereof; benzyldimethylamine, triethylenediamine, 1,8-diazabicyclo [5,4,0]. Tertiary amine compounds such as undecene-7 and derivatives thereof; quaternary ammonium compounds such as tetrabutylammonium bromide and tetrabenzylammonium bromide and derivatives thereof; 2-ethyl-4-methyl-imidazole, 2,3-dihydro- Examples thereof include imidazole compounds such as 1H-pyrrolo [1,2a] benzimidazole and 1-cyanoethyl-2-methyl-imidazole and derivatives thereof; organometallic salts and the like. In the present invention, it is particularly preferable to use a quaternary ammonium compound or a derivative thereof. For example, trade names “U-CAT SA-1”, “U-CAT SA-102”, “U-CAT SA” Commercial products such as “−5003”, “U-CAT SA-5002”, “U-CAT SA-603”, “U-CAT 18X” (manufactured by San Apro Co., Ltd.) can be used.

  The amount of the curing accelerator (C) used is about 0.05 to 5.0 parts by weight, preferably about 0.1 to 4.0 parts by weight with respect to 100 parts by weight of the curing agent.

  Examples of the curing catalyst (D) include polymerization initiators such as a photocationic polymerization initiator and a thermal cationic polymerization initiator.

  As the cationic photopolymerization initiator, known and commonly used cationic photopolymerization initiators can be used. For example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium. Salt (selenium ion and anion salt), ammonium salt (ammonium ion and anion salt), phosphonium salt (phosphonium ion and anion salt), transition metal complex ion and anion salt, etc. . These can be used alone or in combination of two or more.

  Examples of the sulfonium salt include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenyl. Sulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt , Triarylsulfonium salts such as 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt; diphenylphenacylsulfonium salt, diphenyl-4-nitrophenacylsulfonium salt, diphenylbenzyl Diarylsulfonium salts such as ruphonium salt and diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt and 4-methoxyphenylmethylbenzylsulfonium salt; dimethylphenacylsulfonium salt, phena Examples thereof include trialkylsulfonium salts such as a siltetrahydrothiophenium salt and a dimethylbenzylsulfonium salt.

  As the diphenyl [4- (phenylthio) phenyl] sulfonium salt, a trade name “CPI-101A” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate 50% propylene carbonate solution), Trade name “CPI-100P” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate 50% propylene carbonate solution), trade name “K1-S” (manufactured by San Apro Co., Ltd. Commercial products such as antimony triarylsulfonium salts) may be used.

  Examples of the iodonium salt include diphenyl iodonium salt, di-p-tolyl iodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt, and the like.

  Examples of the selenium salt include triaryl selenium such as triphenyl selenium salt, tri-p-tolyl selenium salt, tri-o-tolyl selenium salt, tris (4-methoxyphenyl) selenium salt, and 1-naphthyldiphenyl selenium salt. Diaryl selenium salts such as diphenylphenacyl selenium salt, diphenyl benzyl selenium salt, diphenyl methyl selenium salt; monoaryl selenium salts such as phenyl methyl benzyl selenium salt; trialkyl selenium salts such as dimethyl phenacyl selenium salt Can do.

  Examples of the ammonium salt include tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Pyrrolium salts such as alkyl ammonium salts; N, N-dimethylpyrrolidinium salts, N-ethyl-N-methylpyrrolidinium salts; N, N′-dimethylimidazolinium salts, N, N′-diethylimidazolinium salts, etc. Imidazolinium salts; tetrahydropyrimidinium salts such as N, N′-dimethyltetrahydropyrimidinium salt, N, N′-diethyltetrahydropyrimidinium salt; N, N-dimethylmorpholinium salt, N, N -Diethylmorpholini Morpholinium salts such as uranium salts; N, N-dimethylpiperidinium salts, N, N-diethylpiperidinium salts; pyridinium salts such as N-methylpyridinium salts and N-ethylpyridinium salts; N, N′-dimethylimidazo Imidazolium salts such as lithium salts; Quinolium salts such as N-methylquinolium salts; Isoquinolium salts such as N-methylisoquinolium salts; Thiazonium salts such as benzylbenzothiazonium salts; Acridium salts such as benzylacridium salts Etc.

  Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; Examples thereof include tetraalkylphosphonium salts such as benzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylphenacylphosphonium salt.

Examples of salts of the transition metal complex ions include salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ , (η5-cyclopentadienyl) (η6-xylene) Cr ⁺ ; Examples thereof include salts of iron complex cations such as η5-cyclopentadienyl) (η6-toluene) Fe ⁺ and (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ .

Examples of the anion (counter ion) for forming a salt with the cation include, for example, SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ³⁻ , (CF ₃ CF ₂ CF ₂ ). ^{_{3 PF 3-, (C 6 F}} 5) 4 B -, (C 6 F 5) 4 Ga -, a sulfonate anion (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonic acid anion, methane Sulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion), (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenate ion, halogenated sulfonate ion, sulfate ion , Carbonate ion, aluminate ion, hexafluorobismuth ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion It can be mentioned.

  Examples of the thermal cationic polymerization initiator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

  Examples of the arylsulfonium salts include hexafluoroantimonate salts. In the present invention, for example, trade names “SP-66”, “SP-77” (manufactured by ADEKA Corporation), trade names “Sun-Aid SI-60L”, “Sun-Aid SI-80L”, “Sun-Aid SI-” Commercially available products such as “100 L” (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate). Examples of the boron trifluoride amine complex include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, and boron trifluoride piperidine complex.

  The amount of the curing catalyst (D) used is, for example, about 0.1 to 3.0% by weight, preferably about 0.3 to 1.0% by weight, based on the total monomer components contained in the rework epoxy resin composition. is there.

  Furthermore, you may add another additive as needed to the epoxy resin composition for rework which concerns on this invention within the range which does not impair the effect of this invention. Examples of other additives include organic solvents, curing reaction modifiers, coupling agents, flame retardants, inorganic fillers, ion trappers, stress relieving agents (for example, silicone rubber powder), dyes, and colorants (for example, , Carbon black, etc.), leveling agents, antifoaming agents, and the like. The blending amount of these other additives (the total amount when used in combination of two or more) is, for example, about 5% by weight or less with respect to the total amount of the epoxy resin composition for rework (the total amount of nonvolatile components).

  Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as ethyl acetate, methoxybutyl acetate, and propylene glycol monomethyl ether acetate; propylene glycol monomethyl ether, Examples include ether solvents such as dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, and dipropylene glycol monopropyl ether. These can be used alone or in admixture of two or more. By adding an organic solvent, the viscosity of the epoxy resin composition for rework can be adjusted, and coatability can be improved.

  Examples of the curing reaction modifier include compounds having a hydroxyl group such as ethylene glycol, diethylene glycol, and glycerin. These can be used alone or in combination of two or more. The reaction can be allowed to proceed slowly by adding a curing reaction modifier.

  Examples of the coupling agent include epoxy silane, amino silane, ureido silane, vinyl silane, alkyl silane, organic titanate, and aluminum alkylate. These can be used alone or in combination of two or more.

  Examples of the flame retardant include red phosphorus, phosphoric acid, phosphoric acid ester, melamine, melamine derivatives, compounds having a triazine ring, cyanuric derivatives, isocyanuric derivatives, phosphorous nitrogen-containing compounds (for example, cyclophosphazenes), metal compounds (for example, Zinc oxide, iron oxide, molybdenum oxide, ferrocene, etc.), antimony oxide (for example, antimony trioxide, antimony tetroxide, antimony pentoxide, etc.), brominated epoxy resin, and the like. These can be used alone or in combination of two or more.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, Examples thereof include powders such as stearite, spirels, mullite, and titania, beads formed by spheroidizing these, and glass fibers. Furthermore, aluminum hydroxide, magnesium hydroxide, zinc silicate, zinc molybdate and the like can be used as an inorganic filler having a flame retardant effect. These can be used alone or in combination of two or more. By adding an inorganic filler, the hygroscopic property, thermal conductivity, and strength of the resulting cured product can be improved, and the thermal expansion coefficient can be reduced.

  Examples of the ion trapper agent include hydrotalcites; hydrous oxides of elements such as magnesium, aluminum, titanium, zirconium, and bismuth. These can be used alone or in combination of two or more. By adding an ion trapper agent, the moisture resistance and heat resistance of the resulting cured product can be improved.

  The epoxy resin composition for reworking of the present invention includes, for example, the epoxy compound (A) represented by the above formula (1), other monomer components copolymerizable as necessary, a curing agent (B), and a curing accelerator. (C) or a curing catalyst (D), other additives, etc. are blended, and the mixture is prepared by stirring and mixing while excluding bubbles under vacuum as necessary. The temperature at the time of stirring and mixing is, for example, about 10 to 60 ° C. The stirring / mixing may be performed by any means capable of uniformly dispersing and mixing the mixed components (materials). For example, a 2-roll mill, 3-roll mill, ball mill, sand mill, hensil A mixer, a planetary mixer, a pressure kneader, an extruder, an attritor, a high-speed mixer, a self-revolving stirrer, or the like can be used.

  The epoxy resin composition for rework prepared by the above method can be molded by, for example, a well-known conventional molding method, and then heat treatment is performed to promote cationic polymerization and form a cured product. As heating temperature, it is about 50-200 degreeC, for example, Preferably it is about 60-180 degreeC. The heating time is, for example, about 0.5 to 12 hours, preferably 1 to 10 hours. An oven etc. are mentioned as a heating means. Further post-baking may be performed after the heat treatment. The post-baking is performed, for example, by heating at about 50 to 200 ° C., preferably about 60 to 180 ° C., for about 0.5 to 12 hours, preferably about 1 to 10 hours.

  The polymerization reaction may be performed under normal pressure, or may be performed under reduced pressure or under pressure. The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

The cured product of the present invention thus obtained has a high crosslink density and is excellent in heat resistance and toughness. The temperature at which the storage elastic modulus (E ′) obtained by dynamic viscoelasticity measurement is 10 ⁹ Pa or less is an epoxy resin for rework comprising an epoxy compound (A), a curing agent (B), and a curing accelerator (C). In the case of a cured product of the composition, for example, it is 170 ° C. or higher, preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher. In the case of a cured product of the epoxy resin composition for rework consisting of the epoxy compound (A) and the curing catalyst (D), for example, it is 220 ° C. or higher, preferably 230 ° C. or higher.

  Further, the peak top temperature (= inflection point temperature: corresponding to the glass transition temperature) of the loss tangent (tan δ = E ″ / E ′) includes an epoxy compound (A), a curing agent (B), and a curing accelerator. In the case of the cured product of the epoxy resin composition for rework consisting of (C), for example, it is 210 ° C or higher, preferably 220 ° C or higher. In the case of a cured product of an epoxy resin composition for rework comprising an epoxy compound (A) and a curing catalyst (D), the temperature is, for example, 260 ° C or higher, preferably 270 ° C or higher.

In addition, the cured product of the present invention is easily solubilized by cleavage of the [—C (—O—) ₂ —] moiety by exposure to wet heat conditions and / or acid. Therefore, the temperature at which the storage elastic modulus (E ′) in the cured product after exposure to wet heat conditions and / or acids is 10 ⁹ Pa or less is, for example, 100 ° C. or less, preferably 90 ° C. or less (for example, 50 to 90 ° C., Preferably it is 60-90 degreeC, Most preferably, it is 70-90 degreeC. The peak top temperature (= inflection temperature: corresponding to the glass transition temperature) of the loss tangent (tan δ = E ″ / E ′) is, for example, 120 ° C. or less, preferably 90 ° C. or less.

Furthermore, it means that it has the outstanding rework ability, so that the difference of the temperature from which the storage elastic modulus (E ') of the hardened | cured material before and behind exposure to wet heat conditions and / or an acid becomes 10 < ⁹ > Pa or less is large. In the cured product of the present invention, the difference in temperature at which the storage elastic modulus (E ′) of the cured product before and after exposure to wet heat conditions and / or acid is 10 ⁹ Pa or less is, for example, 50 ° C. or more, preferably 100 ° C. or more. Particularly preferably, it is 110 ° C. or higher, and most preferably 130 ° C. or higher.

  The exposure to the wet heat condition is, for example, a temperature of 23 ° C. or higher (preferably about 60 to 90 ° C.), a humidity of 50% RH or higher (preferably about 60 to 90% RH), and about 100 to 500 hours (preferably For about 200 to 300 hours). The heating means is not particularly limited, and for example, an oven, a dryer, heating steam, an oil bath, a water bath, an infrared heating furnace, a high-frequency heating furnace, or the like can be used.

  The exposure to the acid is, for example, about 1 minute to 24 hours (preferably 1 to 20 hours) in a solution in which the acid is dissolved (for example, in a solution obtained by mixing an acid and water in an organic solvent). Degree) It is performed by dipping. Examples of the acid include organic acids (for example, carboxylic acids such as acetic acid, propionic acid, chloroacetic acid, and benzoic acid; sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid), inorganic acids ( For example, sulfuric acid, phosphoric acid, hydrochloric acid, etc.) and Lewis acid (for example, boron trifluoride etherate, aluminum chloride, stannic chloride, etc.) can be mentioned. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use an organic acid as the acid because the resin has excellent solubility. The acid content in the solution (the total amount when two or more are used in combination) is, for example, about 10 to 60% by weight, preferably about 20 to 40% by weight.

  The epoxy resin composition for rework according to the present invention can form a cured product having heat resistance and toughness by cationic polymerization as described above. In addition, when the cured product is no longer needed, it is easily decomposed by exposure to mild conditions such as wet heat and / or exposure to an acid, and is decomposed into a compound that is soluble in the solvent. It can be dissolved and removed.

  The epoxy resin composition for rework according to the present invention includes optical component materials, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, coating materials, adhesives, sealing materials, and fiber reinforced plastics. (FRP: fiber reinforced plastics, such as GFRP (glass fiber reinforced plastics), CFRP (carbon fiber reinforced plastics), etc.) materials, plastic forming materials, etc., especially semiconductor encapsulants, re-peelable adhesives, coating materials, photoresists Is preferably used.

  Examples of the optical component include an imaging lens, a spectacle lens, a filter, a diffraction grating, a prism, a light guide, and a light beam for a camera (vehicle camera, digital camera, PC camera, mobile phone camera, surveillance camera, etc.). Condenser lens, lens for light diffusion, cover glass for display device, photo sensor, photo switch, LED, light emitting element, optical waveguide, optical splitter, optical fiber adhesive, display element substrate, color filter substrate, touch panel substrate , A display protective film, a display backlight, a light guide plate, an antireflection film, and the like.

  Furthermore, since the cured product of the present invention is excellent in heat resistance as described above, it has reflow heat resistance applicable to lead-free solder mounting and is sealed with the rework epoxy resin composition according to the present invention. In the process of mounting on the substrate optical components made of the epoxy resin composition for rework according to the present invention on a substrate, mounting directly and very efficiently in the same solder reflow process as the surface mounting of other electronic components This makes it possible to produce highly efficient products.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. “Part” used in the examples means “part by weight” unless otherwise specified.

Synthesis Example 1 [1-bis (3-cyclohexenylmethoxy) methyl-3-cyclohexene: synthesis of compound (II)]
While stirring a mixture of 3-cyclohexene-1-methanol (44.9 g), p-toluenesulfonic acid (97.3 mg), and anhydrous sodium sulfate (9.02 g), the mixture was stirred at 25 ° C. at 25 ° C. Aldehyde (22.1 g) was added dropwise over 1 hour. After stirring at 20 ° C. for 20 hours, p-toluenesulfonic acid (97.5 mg), anhydrous magnesium sulfate (9.00 g) and hexane (12.0 g) were added, and the mixture was further stirred at 20 ° C. for 20 hours. After adding hexane (32.1 g), the insoluble matter was filtered, and the insoluble matter on the filter paper was rinsed with hexane (43.2 g). The obtained filtrates were combined, washed once with a 7 wt% aqueous sodium hydrogen carbonate solution (66.3 g) and three times with water (66.2 g), and then concentrated under reduced pressure. Obtained as a liquid. From the result of ¹ H-NMR measured by adding trans-stilbene as an internal standard substance, the purity of the compound (II) was 92.6%. The yield of compound (II) in the residue was 88.0% based on 3-cyclohexene-1-carboxaldehyde.
¹ H-NMR (500 MHz, CDCl ₃ , TMS standard) δ 5.72-5.63 (br m, 6H), 4.23 (d, 1H, J = 6.9 Hz), 3.58-3.46 (m, 2H), 3.35-3.27 (m , 2H), 2.19-1.69 (m, 18H), 1.38-1.23 (m, 3H)

Example 1 [3,4-Epoxy-1-bis (3,4-epoxycyclohexylmethoxy) methylcyclohexane: Synthesis of Compound (I)]
To a solution of compound (II) (1-bis (3-cyclohexenylmethoxy) methyl-3-cyclohexene, 58.6 g) obtained in Synthesis Example 1 in methylene chloride (775 g), water-containing metachloromethane at 30 ° C. After adding perbenzoic acid (170 g) over 87 minutes, the mixture was stirred at 30 ° C. for 4 hours. Thereafter, a 20% by weight aqueous sodium thiosulfate solution (214 g) was added dropwise at 30 ° C. over 18 minutes, followed by stirring for 30 minutes. After further adding a 7 wt% aqueous sodium hydrogen carbonate solution (814 g), the organic layer was washed once with a 7 wt% aqueous sodium hydrogen carbonate solution (816 g) and 3 times with water (597 g) and concentrated. The obtained concentrated residue was purified by silica gel column chromatography to obtain 40.7 g of Compound (I) as a colorless transparent viscous liquid. The yield based on the compound (II) was 64%. ¹ H-NMR confirmed the disappearance of a peak of δ5.72 to 5.63 ppm derived from the double bond of the raw material and the generation of a proton peak of δ3.23 to 3.05 ppm derived from the epoxy group.
¹ H-NMR (500 MHz, CDCl ₃ , TMS standard) δ 4.08-3.97 (m, 1H), 3.43-3.25 (m, 2H), 3.23-3.05 (m, 8H), 2.23-1.45 (m, 18H), 1.22-0.93 (m, 3H)

The oxirane oxygen concentration determined by titration with an acetic acid solution of hydrogen bromide was 12.85% by weight, which was 98% of the theoretical value (13.17% by weight).
The theoretical oxirane oxygen concentration obtained from the structural formula of the following compound is as follows.
Oxirane oxygen concentration of 3,4-epoxy-6-methylcyclohexanecarboxaldehyde bis (3,4-epoxycyclohexylmethyl) acetal: 11.81% by weight
Oxirane oxygen concentration of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (trade name “CEL 2021P”, manufactured by Daicel Chemical Industries, Ltd.): 12.68% by weight

Example 2
For 100 parts of the compound (I) obtained in Example 1, an arylsulfonium salt (trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd., hereinafter “SI-100L” as a thermal cationic polymerization initiator. The resin composition (1) was prepared by adding 0.6 parts. The obtained resin composition (1) was cured at 65 ° C. for 2 hours, and further cured at 150 ° C. for 1.5 hours to obtain a transparent cured product (1).

Comparative Example 1
3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (trade name “CEL 2021P”, manufactured by Daicel Chemical Industries, Ltd., represented by the following formula instead of compound (I), hereinafter “CEL 2021P” The resin composition (2) was prepared in the same manner as in Example 2 except that 100 parts were used, and a cured product (2) was obtained.

Example 3
3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name “HN2200”, manufactured by Hitachi Chemical Co., Ltd., hereinafter sometimes referred to as “HN2200”) with respect to 100 parts of compound (I) 107 parts, 2.14 parts of a quaternary ammonium compound (trade name “U-CAT 18X”, manufactured by San Apro Co., Ltd., hereinafter sometimes referred to as “U-CAT 18X”) as a curing accelerator, and ethylene glycol ( A resin composition (3) was prepared by adding 1.07 parts of a reagent (manufactured by Wako Pure Chemical Industries, Ltd.), cured at 110 ° C. for 3 hours, and further cured at 150 ° C. for 2 hours to obtain a cured product (3 )

Comparative Example 2
Example 3 A resin composition (4) was prepared by adding 130 parts of “HN2200”, 2.60 parts of “U-CAT 18X” and 1.30 parts of ethylene glycol to 100 parts of “CEL 2021P”. The cured product (4) was obtained by curing under the same conditions.

  For the cured products obtained in Examples 2 and 3 and Comparative Examples 1 and 2, the storage elastic modulus was measured by the following method, and the resin compositions obtained in Examples 2 and 3 and Comparative Examples 1 and 2 were measured. Rework ability was evaluated.

<Measurement of storage modulus>
Using the solid viscoelasticity measuring apparatus (trade name “RSA-III”, manufactured by TA Instruments), the cured products obtained in Examples 2 and 3 and Comparative Examples 1 and 2 were 10 ° C. to 350 ° C. in a nitrogen atmosphere. Measure the storage elastic modulus (E ′) at a tensile mode and a forced vibration frequency of 10 Hz while raising the temperature at 5 ° C./min until the temperature at which the storage elastic modulus (E ′) becomes 10 ⁹ Pa: T1 (° C.) Asked. The higher the temperature (T1) at which the storage elastic modulus becomes 10 ⁹ Pa, the higher the heat resistance.

In addition, the cured products obtained in Examples 2 and 3 and Comparative Examples 1 and 2 were measured using a wet heat tester (trade name “MTH-4400”, manufactured by Sanyo Electric Co., Ltd.) at a temperature of 85 ° C. Humidity: After maintaining at 85% RH for 250 hours, the storage elastic modulus (E ′) was measured by the method adopted for the heat resistance evaluation. About the hardened | cured material after wet-heat environment exposure, temperature: T2 (degreeC) from which storage elastic modulus (E ') will be 10 < ⁹ > Pa was calculated | required.

<Evaluation of rework ability>
The rework ability of the resin compositions obtained in Examples 2 and 3 and Comparative Examples 1 and 2 was evaluated according to the following criteria. In addition, it means that it is excellent in rework ability, so that the difference (T1-T2) of the temperature (degreeC) in which the storage elastic modulus of the hardened | cured material before and behind exposure to a humid heat environment becomes 10 < ⁹ > Pa is large.
Evaluation criteria T1 is 200 ° C. or higher, and T2 is 100 ° C. or lower: A
T1 is 170 ° C. or higher and lower than 200 ° C., and T2 is 100 ° C. or lower: ○
T2 exceeds 100 ° C .: ×

Claims (7)

Following formula (1)

[Wherein R ¹ , R ² and R ³ are the same or different and each represents a group containing an alicyclic epoxy group, and R ⁴ represents a group containing an alicyclic epoxy group, a hydrocarbon group or a hydrogen atom. Indicate any]
The epoxy resin composition for rework characterized by including the epoxy compound (A) represented by these. A group containing an alicyclic epoxy group is represented by the following formula (2):

(In the formula, R ⁵ represents a single bond or a divalent hydrocarbon group)
The epoxy resin composition for rework of Claim 1 which is group represented by these. The epoxy compound (A) is represented by the following formula (3)

(Wherein R ^5-1 , R ^5-2 and R ^5-3 are the same or different and each represents a single bond or an alkylene group having 1 to 2 carbon atoms)
The epoxy resin composition for rework according to claim 1, which is an alicyclic triepoxy compound represented by the formula:   The epoxy resin composition for rework according to any one of claims 1 to 3, further comprising a curing agent (B) and a curing accelerator (C).   The epoxy resin composition for rework according to any one of claims 1 to 3, further comprising a cationic polymerization initiator (D).   Hardened | cured material obtained by hardening | curing the epoxy resin composition for rework in any one of Claims 1-5.   A process for obtaining a cured product by cationic polymerization of the epoxy resin composition for rework according to any one of claims 1 to 5, and a process for decomposing and solubilizing the obtained cured product. How to use.