JPH048444B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a curable composition, particularly an epoxy resin composition suitable for paints, adhesives, printed circuit boards, sealants for semiconductor devices, coating materials, molding materials, and the like. Problems to be solved by conventional technology and invention Epoxy resin has excellent adhesive properties among thermosetting resins.
Due to its well-balanced dimensional stability, moisture resistance, water resistance, chemical resistance, and electrical and mechanical properties, it is used in a variety of applications such as paints, adhesives, printed circuit boards, semiconductor element encapsulants, coating materials, and molding materials. It is often used in various fields. Curing methods for epoxy resins include reactions with primary and secondary amines, reactions with polyfunctional carboxylic acids and phenolic resins, reactions with acid anhydrides, Lewis acids, and tertiary amines. Reactions by ring-opening polymerization of epoxy groups using quaternary onium salts and the like as catalysts are well known. Among these, cured products obtained by reactions with primary amines, secondary amines, polyfunctional carboxylic acids, phenolic resins, etc. have a relatively high crosslinking density, are hard, and have excellent mechanical strength. However, in such a system, since the epoxy group undergoes a ring-opening addition reaction, alcoholic hydroxyl groups are inevitably produced. When applied to adhesives and paints, the generated hydroxyl groups play a major role in improving adhesion, but on the other hand, these hydroxyl groups also affect the electrical properties of cured epoxy resins, especially the electrical properties of the resin after humidification tests. This has led to a significant decline in Such a phenomenon is very inconvenient when epoxy resin is used as a base material for printed circuits or as a sealing material for semiconductor devices. On the other hand, reactions with acid anhydrides and curing of epoxy resins with catalysts are due to ring-opening polymerization of epoxy rings, and hydroxyl groups are not produced except at the terminal where the reaction stops; The curable epoxy resin composition of this system has only a small amount of hydroxyl groups. Therefore, it seems that there is little deterioration in electrical properties due to hydroxyl groups. However, the cured epoxy resin produced by this curing system has a relatively low crosslinking density, and various properties are degraded due to this. Therefore, for these reasons, phenolic resins, particularly cresol novolak resins, are used as excellent curing agents for epoxy resins used as sealants for semiconductor devices. However, as mentioned above, in such a curing system, alcoholic hydroxyl groups are inevitably produced during the reaction. A similar problem is an important related compound of epoxy resins. It can also occur when the epoxy groups in the side chains of polyglycidyl methacrylate and its copolymers react with various crosslinking agents and reagents (alcohols, phenols, carboxylic acids, amines, and their polyfunctional compounds). Are known. Means for Solving the Problems The present inventors have conducted extensive studies to solve the above problems, and have found that the epoxy groups of the polymer side chains, in the presence or absence of a specific onium salt or related catalyst, We discovered that it undergoes addition reactions with various active esters without producing any hydroxyl groups, and that this reactivity varies greatly depending on the type of catalyst and ester, so the reaction can be easily controlled, leading to the present invention. This is what I did. That is, the present invention provides an epoxy resin with a polycarboxylic acid and a hydroxyl group selected from monovalent phenols, naphthols, and heterocyclic compounds having N, O, and/or S atoms in the presence or absence of a catalyst. or one or more esters with a mercapto group-containing compound, or esters of benzoic acid with a hydroxy group- or mercapto group-containing compound selected from aromatic hydroxy compounds, aromatic sulfur compounds hydroquinone, polyhydric alcohols, phenolic resins, and polyvinylphenols. The present invention relates to an epoxy resin curable composition. The epoxy resin used in the present invention can be any of the commonly used epoxy resins. Typical examples thereof include, for example, the reaction between bisphenol A and epichlorohydrin or methylepichlorohydrin. Bisphenol type epoxy resins obtained, bisphenol type epoxy resins such as epoxy resins having a halogen in a part of the aromatic group, epoxy resins with the same benzene nucleus as a cyclohexane ring, novolac type phenolic resins, cresol resins and epichlorohydrin. or phenolic resins and epoxy resins obtained by the reaction of methyl epichlorohydrin, phthalate ester type epoxy resins obtained by the reaction of phthalic acid or isophthalic acid with epichlorohydrin, ethylene glycol, 1,4-butanediol, propylene glycol, polyethylene glycol, Glycidyl ether type epoxy resin of aliphatic polyfunctional alcohol having a glycidyl ether group at the end, such as trimethylolpropane and glycerin;
Epoxidized polybutadiene, epoxy resins in which a nitrogen atom and glycidyl group are bonded such as N,N-diglycidylaniline, alicyclic epoxy resins such as vinylcyclohexene diepoxide, other glycidyl ester resins, glycidyl amine resins, heterocyclic resins, etc. Epoxy resin, etc. Furthermore, during the curing reaction of these epoxy resins, it is also possible to partially replace them with a monofunctional epoxy compound in order to modify their properties. Furthermore, among the esters in the present invention, polycarboxylic acids and monovalent phenols, naphthols,
Esters with hydroxy- or mercapto-containing compounds selected from heterocyclic compounds having N, O and/or S atoms include, for example, adipic acid, sebacic acid, malic acid, succinic acid, phthalic acid, isophthalic acid, trimellitic acid, p-nitrophenyl ester, 2,4-dinitrophenyl ester, 4- of polycarboxylic acids such as pyromellitic acid, itaconic acid, fumaric acid, benzophenonetetracarboxylic acid, cyclohexenedicarboxylic acid, nadic acid, etc.
Nitronaphthyl ester, 2,4-dinitronaphthyl ester, 4-chlorophenyl ester,
2,4-dichlorophenyl ester, phenylthioester, phenyl ester, 4-methylphenyl ester, ester of N-hydroxybenztriazole, thioester of 2-mercaptobenzthiazole, thioester of 2-mercaptobenzoxazole, 2- Examples include esters of mercaptobenzimidazole, but these are representative and are not limited to these. Examples of esters of benzoic acid and aromatic hydroxy or sulfur compounds (e.g. bisphenol A, bisphenol S), hydroquinone, polyhydric alcohols, phenolic resins, polyvinylphenols, etc. include benzoic acid, 4-nitrobenzoic acid, 4-nitrobenzoic acid, - Benzoic acids such as chlorobenzoic acid and 2,4-dinitrobenzoic acid, hydroquinone, bisphenol A, bisphenol S, 1,4-butanediol, ethylene glycol, bisphenol A
and ethylene oxide adducts, esters of trimethylolpropane, pentaerythritol, glycerin, sorbitol, resorcinol, etc., as well as phenol novolac, cresol novolac, benzoic acid, 4-nitrobenzoic acid, 4-chlorobenzoic acid, 2, Examples include esters such as 4-dinitrobenzoic acid. Among these esters, compounds having an electron-withdrawing nitro group or halogen on the phenoxy group or carboxylic acid group, thiophenoxide, 2-thiobenzthiazole group, 2-thiobenzoxazole group, 2-thiobenzimidazole group, Active esters containing benztriazole generally exhibit high reactivity and are excellent as curing agents. Furthermore, specific examples of these esters include, for example, adipic acid di(nitrophenyl) ester (NA) Adipic acid di(benzotriazyl) ester (BA) Adipic acid di(thiobenzothiazyl) ester (MA) Adipic acid di(thiophenyl) ester (TA) Sebacic acid di(nitrophenyl) ester (NS) Sebacic acid di(thiobenzothiazyl) ester (MS) Sebacic acid di(benzotriazyl) ester (BS) Sebacic acid di(thiophenyl) ester (TS) Isophthalic acid di(benzotriazyl) ester (DI) Isophthalic acid di(thiobenzothiazyl) ester (MI) Isophthalic acid di(thiophenyl) ester (TI) Isophthalic acid di(4-nitrophenyl) ester (NI) Trimellistate tri(4-nitrophenyl) ester, trimellitate tri(thiophenyl) ester, trimellitate tri(2-chlorophenyl) ester, trimellitate tri(2,4-dichlorophenyl) ester, trimellitate tri(2,4, 6-trichlorophenyl) ester,
Trimellitic acid esters such as trimellitic acid tri(phenyl) ester, trimellitic acid tri(thiobenzothiazyl) ester, trimellitic acid tri(thiobenzoxazyl) ester, etc.

[Formula] or

[Formula] Tetra(4-nitrophenyl) pyromellistate
esters, pyromellitic acid tetra(thiophenyl) ester, pyromellitic acid tetra(phenyl) ester, pyromellitic acid tetra(thiobenzothiazyl) ester, pyromellitic acid tetra(benzotriazyl) ester, pyromellitic acid tetra(2-chlorophenyl) ester, etc. Pyromellitic acid esters

[Formula] or

[Formula] Benzophenonetetracarboxylic acid tetra(2-
nitrophenyl) ester, benzophenonetetracarboxylic acid tetra(thiophenyl) ester,
Esters of benzophenonetetracarboxylic acid such as benzophenonetetracarboxylic acid tetra(phenyl) ester and benzophenonetetracarboxylic acid tetra(2-chloro-4-nitrophenyl) ester etc., where R is

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] represents. Furthermore, benzoic acid, 2-chlorobenzoic acid, 2,4
- Benzoic acids such as dichlorobenzoic acid, thiobenzoic acid, 4-nitrobenzoic acid, 2,4-dinitrobenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid and esters such as bisphenol A or bisphenol S are Triesters of phloroglucin, Esters of bisphenol S These are esters of bisphenol A, and esters with phenolic resins are, for example,

[Formula] or

【formula】

【formula】

[Formula] or

【formula】

[Formula] n≒8 etc., and ester with polyvinylphenol is or

【formula】

[Formula] or

【formula】

[Formula] etc. (In the above formula, R is

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] X represents NO ₂ , Cl, H). Further, the catalyst used in the present invention has the general formula (R) ₃ N, [(R)
₄ N]X and/or _[ (R) ₄ ^P ]X (wherein R is an aliphatic, aromatic ^or alicyclic hydrocarbon group ^, Various quaternary onium salts of other acid residues, N is a nitrogen atom and P is a phosphorus atom, tertiary amines are used. However, quaternary onium salts are better than tertiary amines in terms of catalytic activity. Furthermore, among these, as R, those having an alkyl chain in the range of _C2 to _C6 are preferred, and as X, Cl, Br, I, etc. are preferred. Further, in the formula, R can be the same or different, and a part or all of R can be a compound having an aryl group, an alkyl group, or an aralkyl group each having a different number of carbon atoms. Examples of tertiary amines are triethylamine (TEA), tripropylamine (TPA), trin
-butylamine (TBA), N,N-diethylaniline, N,N-dimethylaniline, diazabicycloundecene-7, etc. Quaternary ammonium salts include tetramethylammonium bromide (TMAB), tetraethylammonium bromide ( TEAB), tetra n-propylammonium bromide (TPAB), tetra n-butylammonium bromide (TBAB), tetrabutylammonium hydroxide (TBAHD), tetra n-
Pentylammonium bromide (TPEAB),
Tetra n-hexylammonium bromide (THAB), tetra n-octylammonium bromide (TOAB), tetramethylammonium chloride (TMAC), tetraethylammonium chloride (TEAC), tetra n-propylammonium chloride (TPAC), tetra n-
Butylammonium chloride (TBAC), tetra n-butylammonium iodide, tetra n
-Butylammonium hydrogen sulfate (TBAH), tetra n-butylammonium perchlorate (TBAP), tetra n-butylphosphonium bromide (TBPB), benzyltrimethylammonium chromide (BTMAC), cetyltrimethylammonium bromide, benzyltriethylammonium iodide , tetrapropylphosphonium chloride, tetraethylphosphonium iodide, benzyltrimethylphosphonium bromide, tetrabutylammonium hydroxide, and the like. Still other catalysts include 18-crown-
6 (CR6), 15-crown-5 (CR5), dicyclohexyl-18-crown-6 (DCHC), dibenzo-
Crown ethers such as 18-crown-6 (DBCR) and benzo-15-crown-5 (BCR5) are effective, and these crown ethers and
KBr, KSCN, CH ₃ COOK, CH ₃ COONa,

It has also been found that a mixture of inorganic and organic salts such as [Formula] exhibits high activity comparable to that of quaternary phonium salts. Although this catalytic mechanism is not fully clear, for example, in the case of 18-crown-6 and KBr, It is presumed that it forms active salts such as , and exhibits the same action as quaternary onium. The amount of catalyst to be added is preferably about 0.1 to 20 mol % based on the epoxy group, but from an industrial standpoint, 0.1 to 5 mol % is preferable. Effect In the present invention, esters of polyhydric carboxylic acids with phenol, naphthol, or heterocyclic compounds having N, S, and O, or benzoic acid and aromatic hydroxy compounds, aromatic sulfur compounds, hydroquinone, and polycarboxylic acids are added to the epoxy resin. By adding esters with alcohol, phenolic resin, and poly(vinylphenol), the cured product does not generate alcoholic hydroxyl groups and does not cause a decrease in electrical properties, making it particularly suitable for application to electrical materials. , and by selecting the type of tertiary amine, quaternary onium salt, crown ether di-salt, etc. and ester of the present invention,
It is possible to adjust the curing temperature and time, and the use of epoxy resin curing compositions is expanded. Examples Examples are shown below. The invention is not limited to these examples. Example 1 Bisphenol type epoxy resin: Epicote
828 [manufactured by Ciel Kagaku Co., Ltd., equivalent weight 186] 0.93 g (0.005 mol as an epoxy group) was mixed with various carboxylic acid esters (0.005 mol as an ester group) and catalyst 3.
% by mole and reacted under the conditions shown in Table 1. As is clear from this result, even in the presence of a catalyst (TBAB: tetrabutylammonium bromide), the mixture of Epicote 828 and adipate di(p-nitrophenyl) ester remains stable without curing for about 4 months at 30°C. Benzotriazole ester, 2-mercaptobenzotrithiazole ester, and thiophenyl ester of adipic acid cured in 20 days, 13 days, and 60 days, respectively. On the other hand, mixtures of Epicote 828 and these esters cured at 100° C. in 8 to 10 hours.
Furthermore, it cured within 1 hour at 150°C, and within 30 minutes at 180°C. It is clear from this that the epoxy-ester curing system is an extremely good curing system. The progress of the reaction is shown by the epoxy group at 910 cm ^-1 according to the IR spectrum.

This was confirmed by the disappearance of the absorption of [Formula] and the disappearance or shift of the C═O absorption of the carbonyl group of the active ester.

[Table] Example 2 Table 2 shows the results when a portion of MA was changed to adipic acid by curing Epicote 828 and adipic acid di(thiobenzthiazole) ester (MA). As is clear from this, the reactivity between ester and epoxy is comparable to or higher than the reactivity between adipic acid and epoxy.

[Table] Example 3 Aromatic amine glycidyl-based epoxy resin [manufactured by Nippon Kayaku Co., Ltd.: GAN] (epoxy equivalent: 121) 0.605 g
(0.005 mol as epoxy group) and various active esters are shown in Table 3. This system also showed a tendency to be slightly more reactive than the bisphenol type, which is probably due to the effect of the tertiary amine structure in the epoxy compound. The progress of the reaction was similarly confirmed by the decrease or disappearance of the absorption of the epoxy group at 910 cm ^-1 in the IR spectrum.

[Table] Example 4 Ethylene glycol diglycidyl ether: Epolite 40F [manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.] (epoxy equivalent: 132.4) 0.662 g (0.005 mol as an epoxy group) and each ester (as an ester group)
0.005 mol) and reacted under certain conditions. As a result, as shown in Table 4, Epolite
The system of 40F and adipic acid di(p-nitrophenyl) ester (NA), adipic acid di(benzotriazole ester) (BA) and adipic acid di(thiophenyl ester) (TA) is approximately 49
It remained stable without curing for days. On the other hand, adipic acid di(thiobenzotriazole) ester (MA)
It hardened in 20 days. All of these systems cured within 10 hours at 100°C. Furthermore, although these cured products are generally softer than the bisphenol type, the IR spectrum showed that the absorption of the epoxy group at 910 cm ^-1 disappeared, confirming that the reaction had progressed almost completely. .

[Table] Example 5 Polyethylene glycol diglycidyl ether [Epolite 200E (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.: epoxy equivalent weight 193] 0.968 g (0.005 as epoxy group)
moles) and various esters (as ester groups)
0.005 mol) was similarly mixed and cured. A mixture of Epolite 200E and NA and TA is 30
It remained stable without curing for 4 months at ℃. On the other hand, BA,
The MA mixtures were cured at 30°C in 90 and 60 days, respectively. Furthermore, at 100°C, all cured within 14 hours.
The progress of this reaction was confirmed by the disappearance of the 910 cm ^-1 epoxy group by IR, and all cured products were soft elastic bodies at room temperature.

【table】 \ / \ /
OO
The cured product of this system is a soft elastic body. Example 6 Trimethylolpropane triglycidyl ether [Epolite 100MF (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
Manufactured by: Epoxy equivalent 142.0] 0.71g (0.005 mol as epoxy group) and various active esters (0.005 mol as ester group) are reacted under specified conditions,
The results are shown in Table 6. At 30℃, mixtures of Epolite 100MF and BA and MA cured in 60 days and 11 days, respectively, but NA
The mixture of and TA was stable for about 3.5 months. However, both mixtures have 10
Hardened within hours.

【table】 \ /
O
Example 7 Glycerin diglycidyl ether [Epolite]
80MF (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.): Epoxy equivalent
150.5) 0.753g (0.005 mol as epoxy group) and various esters (as ester group)
0.005 mol) and the results are shown in Table 7. A mixture of Epolite 80MF and NA and TA is 30
It remained stable without curing for about 3.5 months at ℃. On the other hand, the mixture with BA and MA respectively at 30℃
It hardened in 60 days and 10 days. When the reaction temperature was 100°C, all cured within 8 hours. Further, when the reaction temperature was 150°C, it was cured within 1 hour, and when the reaction temperature was 180°C, it was cured within 30 minutes. All of the cured products became soft and rubbery, and the progress of the reaction was also confirmed by the disappearance of absorption of the epoxy group at 910 cm ^-1 by IR spectrum.

[Table] Example 8 Hydrogenated bisphenol A diglycidyl ether [Epolite 4000 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.: epoxy equivalent weight 239] 1.19 g (0.005 mol as epoxy group) and various esters (0.005 mol as ester group)
The reaction conditions and results are shown in Table 8. The mixture with NA and TA remained stable without curing for 3.5 months at 30°C. The mixture with BA and MA cured in 60 days and 10 days at 30°C, respectively. Furthermore, at 100°C, all mixtures were cured within 15 hours.

[Table] Example 9 p-nitrogen of cresol novolak synthesized from Epicote 828 [manufactured by Ciel Kagaku Co., Ltd.] 1.86 g (0.01 mol as epoxy group), cresol novolak with an average degree of polymerization of 8, and p-nitrobenzoic acid. 2.67 g of benzoic acid ester (0.01 mole as ester group) in THF10
Dissolved in ml. After adding TBAB (3 mol% based on the epoxy group) as a catalyst,
THF was removed at 50°C, and the mixture was reacted at 150°C for 1 hour. From the IR spectrum of the cured product, it was confirmed that the reaction had progressed because the absorption of the epoxy group at 910 cm ^-1 disappeared. The reaction proceeded well under the same conditions when GAN (an epoxy resin manufactured by Kyoeisha Yushi Co., Ltd.), Epolite 40E, and Epolite 100MF were used in place of Epicote 828. Example 10 1.86 g of Epicote 828 (manufactured by Ciel Chemical Co., Ltd.) and hydroquinone di(p-nitrophenyl ester) 4.08g (0.01 mol as ester group) and the catalyst benzyltriethylammonium bromide (5 mol%) were reacted at 180°C for 30 minutes. The IR spectrum of the cured product showed that the absorption of epoxy groups disappeared, confirming that the reaction was progressing. GAN, Epolite instead of Epicote 828
The reaction proceeded well under the same conditions when 200E and Epolite 4000 were used. Moreover, this curing reaction proceeded in 1 hour at 150°C. Example 11 1.86 g (0.01 mol) of Epicote 828 and 1.34 g (as ester group) of p-nitrophenylbenzoate of polyvinylphenol (average molecular weight = 1700)
After adding 0.01 mol) to 5 ml of THF, the THF was removed under reduced pressure at room temperature. After this, the reaction was carried out at 150°C for 1 hour. This cured product had excellent hardness and strength. Example 12 Bisphenol A type epoxy resin (Epicote
828, epoxy equivalent 186), add equimolar amount of MI,
5 mol% of catalyst was added to this and cured at 100°C for 6 hours. This reaction proceeded well within 6 hours and cured products were obtained. Furthermore, the IR spectrum is 910cm
Since the absorption of the epoxy group of ^-1 almost disappeared in all cases, it was found that all the compounds had a catalytic effect. Furthermore, under similar conditions, epoxy resins such as isophthalic acid diglycidyl ester, vinyl cyclohexene dioxide,
Other types of epoxy compounds such as triglycidyl isocyanurate (these epoxy compounds were synthesized or commercially available reagents were used) or mixtures of these compounds or a portion thereof, such as butyl glycidyl ether, phenyl glycidyl ether,
2,4-dibromophenyl glycidyl ether,
Even when a monofunctional epoxy compound such as styrene oxide was used instead, the curing reaction proceeded well.

【table】

[Table] Example 13 Good results were also obtained when curing Epicote 828 and dinitrophel isophthalate (NI) by replacing part of the NI with piperazine, a type of diamine. Ta.

[Table] Example 14 Table 11 shows the results when part of TI was replaced with phthalic anhydride during curing of GAN and thiophenolisophthalic acid (TI).

[Table] Example 15 Epicote 828 (1.86 g, 0.01 mol) and thiophenyl ester of trimellitic acid (1.92 g, 0.01 mol as ester group) were dissolved in 10 ml of THF,
1 mol % TEAC was added to this to make a homogeneous solution. After quickly removing THF at 30-50℃
When heated at 150°C for 1 hour, the reaction progressed and a hard cured product was obtained. Similarly, an excellent cured product was obtained by replacing the ester with phenyl ester of pyromellitic acid (1.40 g, 0.01 mol as ester) and curing under the same conditions. Effects of the Invention The present invention provides epoxy resin with phenol, naphthol or N of a polycarboxylic acid, in the presence or absence of a catalyst consisting of at least one of a tertiary amine, a quaternary onium salt, a crown ether, and a crown ether salt complex. Epoxy resin curable composition prepared by adding esters with heterocyclic compounds having S and O atoms, or esters of benzoic acid with aromatic hydroxy compounds, aromatic ionic compounds, hydroquinone, polyhydric alcohols, phenolic resins, or polyvinylphenols. is a very convenient curing system. In other words, (1) hydroxyl groups are not generated in the curing system of epoxy resins using esters, so it is possible to avoid deterioration in the properties of epoxy resins, especially electrical properties, caused by hydroxyl groups.
(2) By selecting the type of ester and the type of catalyst to be reacted with the epoxy resin, a one-component epoxy resin composition can be created that is stable at low temperatures such as room temperature and can be cured exceptionally well at high temperatures. (3)
Esters, especially active esters, used in this curing system can also react with alcohols and amines. Therefore, in a crosslinking system that uses an active ester of a polyfunctional carboxylic acid in combination with amines, there is not only a curing reaction with each epoxy resin, but also a curing reaction with each epoxy resin.
Reactions between amines and active esters also occur, making it possible to adjust the crosslinking density and the hardness and flexibility of the cured epoxy resin. (4) Furthermore, the cured epoxy resin requires alcoholic hydroxyl groups. When using amines (primary and secondary) as part of the esters,
In addition, it can be used as a co-curing system in place of carboxylic acids, phenolic resins, etc., and can be said to be a new curing system composition that has not existed before. Of course, it is suitable for paints, adhesives, printed circuit boards, semiconductor element encapsulants, coating materials, and molding materials.
It can be said to be an excellent invention that can be expected to be applied to new fields.

Claims (1)

[Claims] 1. In the presence or absence of a catalyst in an epoxy resin,
An ester of a polyhydric carboxylic acid and a hydroxy group- or mercapto group-containing compound selected from monovalent phenols, naphthols, heterocyclic compounds having N, O and/or S atoms, or benzoic acid and an aromatic hydroxy compound; An epoxy resin curable composition containing one or more esters with a hydroxy group- or mercapto group-containing compound selected from aromatic sulfur compounds, hydroquinone, polyhydric alcohols, phenolic resins, and polyvinylphenols. 2 The catalyst has the general formula (R) ₃ N, [(R) ₄ N]X and/
or [(R) ₄ P]X. The curable epoxy resin composition according to claim 1. (In the formula, R is an aliphatic, aromatic or alicyclic hydrocarbon group, X is a halogen or other acid residue, N is a nitrogen atom, and P is a phosphorus atom) 3 The catalyst is a crown ether 2. The curable epoxy resin composition according to claim 1, which is a complex of a compound or a crown ether and an inorganic or organic compound. 4 Diglycidyl ether type epoxy resin in which the epoxy resin is bisphenol A, phenol resin type epoxy resin, aliphatic ether type epoxy resin, alicyclic ether type epoxy resin, ester type epoxy resin, polyfunctional glycidyl amine type epoxy resin The curable epoxy resin composition according to claim 1, 2, or 3, which comprises an epoxy resin, an epoxy resin comprising a heterocyclic polyfunctional glycidyl compound, or a modified product thereof. 5 One or more polyfunctional carboxylic acids whose esters are isophthalic acid, terephthalic acid, adipic acid, sebacic acid, fumaric acid, succinic acid, trimellitic acid, and pyromellitic acid, and phenol, chlorophenol, nitrophenol, dinitrophenol, Monovalent phenols or thiophenols consisting of dichlorophenol, thiophenol, nitrochlorophenol, thiochlorophenol, and esters with mercaptobenzthiazole, mercaptobenzoxazole, and N-hydroxybenztriazole, or hydroquinone, resorcinol, Multifunctional phenols consisting of bisphenol A, bisphenol S, phloroglucin, polyvinylphenol, cresol novolak, benzoic acid, chlorobenzoic acid, folic acid, nitrobenzoic acid, dichlorobenzoic acid, chloronitrobenzoic acid, naphthalenecarboxylic acid Claims 1 and 2 are esters of aromatic carboxylic acids consisting of polyfunctional phenols consisting of
The epoxy resin curable composition according to item 1, 3 or 4.