JPH08301980A - Novel epoxy resin, intermediate and production method, epoxy resin composition using the same, and cured product thereof - Google Patents

Abstract

(57) [Summary] [Purpose] Epoxy resin that has excellent moisture resistance, heat resistance, and mechanical properties such as impact resistance, and is useful for applications such as lamination, molding, casting, and adhesion. And a manufacturing method thereof. Moreover, the polyhydric hydroxy resin used as an intermediate body of this epoxy resin and its manufacturing method are provided, and the epoxy resin composition using this epoxy resin and its hardened material are also provided. [Structure] The following general formula (1): (However, A represents a benzene ring or a naphthalene ring which may be substituted with an alkyl group having 1 to 6 carbon atoms, B represents an aromatic ring, R represents a hydrogen atom or a methyl group, and G represents a glycidyl group. And n is a number from 0 to 15). Further, it is an intermediate polyvalent hydroxy resin which gives such an epoxy resin, a method for producing the same, an epoxy resin composition using the epoxy resin and a cured product thereof.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyfunctional epoxy resin and an intermediate thereof, which gives a cured product excellent in mechanical strength such as moisture resistance, heat resistance and impact resistance, a method for producing the same, and further a method for producing the same. The present invention relates to an epoxy resin composition used and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, particularly with the advance of the field of advanced materials, there has been a demand for the development of higher performance base resins. For example, epoxy resins as composite material matrix resins used in the aerospace industry are strongly required to have higher heat resistance and moisture resistance. However, there is no known epoxy resin that has hitherto been known that satisfies these requirements. For example,
Well-known bisphenol-type epoxy resins are widely used because they are liquid at room temperature and have good workability and easy mixing with curing agents and additives. There is a problem with. Further, a phenol novolac type epoxy resin is known as one having improved heat resistance, but it has a problem in moisture resistance and impact resistance.

Therefore, an epoxy compound of phenol aralkyl resin has been proposed for the purpose of improving the moisture resistance and the impact resistance (Japanese Patent Laid-Open No. 238,122).
This epoxy compound is also insufficient in heat resistance. Also,
An epoxy compound of a divalent phenol aralkyl resin has been proposed for the purpose of high heat resistance (Japanese Patent Laid-Open No. 64-79,2).
No. 15). However, this epoxy compound is not sufficient in terms of moisture resistance. JP-B-47-13782 discloses that phenol, diphenyl ether and paraxylylene glycol dimethyl ether are reacted in the presence of an acid catalyst to obtain a solid resin, which is then epoxylated with epichlorohydrin. Although a method for producing an epoxidized phenolic resin that undergoes conversion is described, since there is a large difference in the reactivity between diphenyl ether and phenol in this method, both are alternately bonded via a cross-linking agent. A resin having such a structure cannot be obtained, and sufficient improvement in performance cannot be expected.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to have excellent performance in moisture resistance, heat resistance and mechanical properties such as impact resistance, and to perform lamination, molding, casting and bonding. An object of the present invention is to provide an epoxy resin useful for such uses and a method for producing the same. Another object of the present invention is to provide a polyvalent hydroxy resin which is an intermediate of this epoxy resin and a method for producing the same. Still another object is to provide an epoxy resin composition using them and a cured product thereof.

[0005]

That is, the present invention provides the following general formula (1):

[Chemical 4] (However, A represents a benzene ring or a naphthalene ring which may be substituted with an alkyl group having 1 to 6 carbon atoms, B represents an aromatic ring, R represents a hydrogen atom or a methyl group, and G represents a glycidyl group. And n is a number from 0 to 15). Further, the present invention provides the following general formula (2)

Embedded image (However, A represents a benzene ring or a naphthalene ring which may be substituted with an alkyl group having 1 to 6 carbon atoms, B represents an aromatic ring, R represents a hydrogen atom or a methyl group, and n represents 0 to 0.
It represents a polyvalent hydroxy resin). Further, the present invention is a method for producing a polyfunctional epoxy resin represented by the general formula (1), which comprises reacting a polyhydric hydroxy resin represented by the general formula (2) with epichlorohydrin. .

The present invention also provides 2 to 30 moles per 1 mole of an aromatic compound represented by the following general formula (3) H-B-H (3) (wherein B represents an aromatic ring). The following general formula (4)

[Chemical 6] (Wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) and at least one crosslinking agent selected from divinylbenzenes are reacted with each other, and then the following general formula ( 5) H-A-OH (5) (wherein A represents a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 6 carbon atoms), a phenol or naphthol represented by A method for producing a polyhydric hydroxy resin represented by the general formula (2), which comprises reacting.

Furthermore, the present invention provides an epoxy resin composition comprising an epoxy resin and a curing agent, which comprises a polyfunctional epoxy resin represented by the general formula (1) or a polyfunctional hydroxy resin represented by the general formula (2). An epoxy resin composition containing at least one of them as an essential component and a cured product obtained by curing the same.

The polyhydric hydroxy resin represented by the general formula (2) is a compound represented by the general formula (4) in an amount of 2 to 30 mol per 1 mol of the aromatic compound represented by the general formula (3). And at least one cross-linking agent selected from divinylbenzenes
It is obtained by reacting with a seed and then with a phenol or naphthol represented by the general formula (5).

As the aromatic compound represented by the general formula (3), there are aromatic compounds having at least two substitutable hydrogens, for example, tetramethylbenzenes such as xylenes, trimethylbenzenes and durene. , Diethylbenzenes, triethylbenzenes, tetraethylbenzenes, isopropylbenzene, diisopropylbenzenes, triisopropylbenzenes, naphthalene, methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene, biphenyl, diphenylether, acenaphthene, fluorene, dibenzofuran, anthracene,
Phenanthrene is mentioned, and these compounds are used individually or as a mixture. In some cases, petroleum-based or coal-based tar fractions containing these compounds can be used. Preferably, 1 to 3 ring aromatic hydrocarbons and the like can be mentioned.

Examples of the cross-linking agent include p-xylylene glycol, α, α'-dimethoxy-p-xylene,
α, α′-diethoxy-p-xylene, α, α′-diisopropyl-p-xylene, α, α′-dibutoxy-p
-Xylene, m-xylylene glycol, α, α'-dimethoxy-m-xylene, α, α'-diethoxy-m-
Xylene, α, α′-diisopropoxy-m-xylene, α, α′-dibutoxy-m-xylene, 1,4-di (2-hydroxy-2-ethyl) benzene, 1,4-di (2- Methoxy-2-ethyl) benzene, 1,4-di (2-hydroxy-2-ethyl) benzene, 1,4-di (2-ethoxy-2-ethyl) benzene, p-divinylbenzene, m-divinylbenzene or Examples thereof include a mixture of these, and xylylene glycol dialkyl ethers are preferable in order to suppress self-polymerization of the crosslinking agent during the reaction.

In the synthesis of the reaction intermediate of the aromatic compound and the crosslinking agent, an excess amount of the crosslinking agent with respect to the aromatic compound is used. The amount of the cross-linking agent used is usually in the range of 2 to 30 mol per mol of the aromatic compound, but preferably 3
Is in the range of up to 15 moles. If it is more than this, the effect of improving the resin performance such as moisture resistance and heat resistance derived from the aromatic group is small, and if it is less than this, the functional group density of the obtained resin becomes small and the heat resistance is lowered.

This zero reaction is carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid,
Organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride, or solids such as activated clay, silica-alumina and zeolite Acid etc. are mentioned.

The reaction is usually carried out at 10 to 250 ° C. for 1 to 20 hours. The end point of the reaction during the synthesis of the reaction intermediate is usually the time when the aromatic compound disappears, or when xylylene glycol or xylylene glycol dialkyl ether is used as a cross-linking agent, the condensation amount is twice the molar amount of the aromatic compound. The time when water or alcohol is produced. If the reaction rate is lower than this, unreacted aromatic compounds will remain, and there is a problem of bleed-out when molding as an epoxy resin composition. If the reaction rate is higher than this, gelation may occur. During the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as a solvent. .

The reaction intermediate obtained by the reaction of the aromatic compound and the crosslinking agent is then reacted with the phenol or naphthol represented by the general formula (5). Examples of the phenols and naphthols include phenol and o-
Cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tertiary butylphenols, phenylphenols, 2,6
-Xylenol, 2,6-diethylphenol, 1-naphthol, 2-naphthol and the like can be mentioned, and these phenolic compounds are used alone or as a mixture of two or more kinds. These phenolic compounds are usually used in excess with respect to the crosslinking agent used. The amount used is usually in the range of 1 to 15 mol, preferably 1.2 to 10 mol, per mol of the crosslinking agent. If it is less than this range, the softening point of the resin becomes high and the workability in molding is impaired. On the other hand, if the amount is larger than this, the amount of the excess phenolic compound removed after the reaction is finished becomes large, which is not industrially preferable. By this reaction, the polyvalent hydroxy resin represented by the above general formula (2) is produced. For this, purification is carried out by separating the catalyst, excess phenolic compound and the like, if necessary. The concentration of the polyvalent hydroxy resin represented by the general formula (2) in the solid content is preferably 50% by weight or more. In the general formulas (1) and (2), n means the average number of repetitions.

The polyfunctional epoxy resin of the present invention is produced by reacting the polyhydric hydroxy resin represented by the above general formula (2) with epichlorohydrin. This reaction can be performed in the same manner as a usual epoxidation reaction.
For example, after dissolving the polyhydric hydroxy resin represented by the general formula (2) in an excess of epichlorohydrin, it is heated at 50 to 150 ° C., preferably in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. , 60-120 ℃
The method of reacting in the range of 1 to 10 hours can be mentioned. At this time, the amount of the alkali metal hydroxide used is 0.8 to 2 mol, based on 1 mol of the hydroxyl group in the polyvalent hydroxy resin,
It is preferably in the range of 0.9 to 1.2 mol. Further, epichlorohydrin is used in excess with respect to the hydroxyl groups in the polyhydric hydroxy resin, but is usually in the range of 1.5 to 15 mol, preferably 2 to 8 mol, per 1 mol of the hydroxyl groups in the polyhydric hydroxy resin. Is. After completion of the reaction, excess epichlorohydrin was distilled off, the residue was dissolved in a solvent such as toluene and methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent was distilled off. An epoxy resin can be obtained. The concentration of the polyfunctional epoxy resin represented by the general formula (1) in the solid content is preferably 50% by weight or more.

The epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent,
The polyfunctional epoxy resin represented by the general formula (1) as the epoxy resin component, and the general formula (2) as the curing agent component
At least one of the polyhydric hydroxy resins represented by is blended as an essential component.

As the curing agent when the polyfunctional epoxy resin represented by the general formula (1) is used as an essential component, all curing agents generally known as curing agents for epoxy resins can be used. Examples include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines and the like. To give a concrete example, as the polyphenols,
For example, divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol, or tris- (4-hydroxy). Phenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, naphthol novolac, trivalent or more phenols represented by polyvinylphenol,
Furthermore, phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2 '
There are polyphenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, etc. of divalent phenols such as biphenol, hydroquinone, resorcin, naphthalenediol, etc. As the acid anhydride, there are phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, nadic acid anhydride, trimellitic anhydride and the like. . In addition, as amines, 4,
Aromatic amines such as 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-xylylenediamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, tri There are aliphatic amines such as ethylenetetramine, and polyvalent hydroxy resins represented by the above general formula (2). In the resin composition of the present invention, one kind or two or more kinds of these curing agents can be mixed and used, but the compounding amount of the epoxy resin according to the present invention is 5 to 100% by weight in the whole epoxy resin.
Range.

When the polyhydric hydroxy resin represented by the general formula (2) is an essential component, the epoxy resin is
Any ordinary epoxy resin having two or more epoxy groups in the molecule can be used. For example, bisphenol A, bisphenol S, fluorene bisphenol,
Divalent phenols such as 4,4′-biphenol, 2,2′-biphenol, hydroquinone and resorcin, or tris- (4-hydroxyphenyl) methane,
Glucidyl derived from trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac and o-cresol novolac, or halogenated bisphenols such as tetrabromobisphenol A Examples thereof include etherified products and polyfunctional epoxy resins represented by the above general formula (1). These epoxy resins can be used alone or in combination of two or more, and the compounding amount of the polyvalent hydroxy resin according to the present invention is in the range of 5 to 100% in the whole epoxy resin.

Further, in the composition of the present invention containing the polyfunctional epoxy resin represented by the general formula (1) or the polyhydric hydroxy resin represented by the general formula (2) as an essential component, polyester, Polyamide, polyimide, polyether,
Polyurethane, petroleum resin, indene coumarone resin, phenoxy resin, and other oligomers or polymer compounds may be blended appropriately, and inorganic fillers, pigments, retardants, thixotropic agents, coupling agents, fluidity improvement You may mix additives, such as an agent.

Examples of the inorganic filler include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. Pigments Examples thereof include organic or inorganic extender pigments and scaly pigments. As thixotropic agents, silicone-based, castor oil-based,
Aliphatic amide wax, oxidized polyethylene wax,
An organic bentonite type etc. can be mentioned. Furthermore, a conventionally known curing accelerator can be used if necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids and the like. As the addition amount,
Usually, 0.2 to 5 per 100 parts by weight of epoxy resin
The range is parts by weight. Further, if necessary, the resin composition of the present invention may include a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black, and A flame retardant such as antimony oxide, a stress reducing agent such as silicon oil, a lubricant such as calcium stearate, and the like can be added.

The cured product of the present invention can be formed by molding the above epoxy resin composition by a method such as casting, compression molding or transfer molding. The temperature during the production is usually in the range of 120 to 220 ° C.

[0022]

EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples. (Production of Polyhydric Hydroxyl Resin) Example 1 In a 500 ml four-necked flask, p-xylylene glycol dimethyl ether 166 g (1.0 mol), anthracene 44.5 g (0.25 mol), p-toluenesulfonic acid 8. Charge 4 g and stir under a nitrogen stream for 15
The reaction was performed at 0 ° C. During this period, the produced methanol was removed from the system. After about 2 hours, when 16 g of methanol was produced, 216 g (2 mol) of o-cresol was added, and the mixture was further reacted at 150 ° C. for 2 hours. During this time, the produced methanol was removed from the system. When the production of methanol was completed, the mixture was neutralized with sodium carbonate, and excess o-cresol was distilled off under reduced pressure to give a brown resin 2.
00g was obtained. The softening point of the obtained resin was 84 ° C., and the melt viscosity at 150 ° C. based on the ICI cone plate method was 4.4 p. The GPC chart of the obtained resin is shown in FIG. Here, the GPC measurement is performed by an apparatus: HLC
-82A (manufactured by Tosoh Corporation) and column: TSK-GE
L2000 × 3 and TSK-GEL 4000 × 1 (both manufactured by Tosoh Corporation) were used under the conditions of solvent: THF, flow rate: 1.0 ml / min, temperature: 38 ° C., detector: RI.

Example 2 A 500 ml four-necked flask was charged with 166 g (1.0 mol) of p-xylylene glycol dimethyl ether, 59.3 g (0.33 mol) of anthracene and 9.0 g of p-toluenesulfonic acid, and nitrogen. 15 under agitation while stirring
The reaction was performed at 0 ° C. During this period, the produced methanol was removed from the system. After about 2 hours, when 21 g of methanol was produced, 206 g (1.9 mol) of o-cresol was added, and the mixture was further reacted at 150 ° C. for 2 hours. During this time, the produced methanol was removed from the system. When the production of methanol was completed, the mixture was neutralized with sodium carbonate, and excess o-cresol was distilled off under reduced pressure to give a brown resin 2.
60 g was obtained. The softening point of the obtained resin was 97.4 ° C. The GPC chart of the obtained resin is shown in FIG.

Example 3 A 500 ml four-necked flask was charged with 166 g (1.0 mol) of p-xylylene glycol dimethyl ether, 56.7 g (0.33 mol) of diphenyl ether and 13.3 g of p-toluenesulfonic acid, and charged with nitrogen. The reaction was carried out at 150 ° C. under a stream of air with stirring. During this period, the produced methanol was removed from the system. After about 3 hours, when 21 g of methanol was produced, 180 g of o-cresol (1.67
Mol) was added, and the mixture was further reacted at 150 ° C. for 2 hours.
During this time, the produced methanol was removed from the system. When the production of methanol was completed, the mixture was neutralized with sodium carbonate, and excess o-cresol was distilled off under reduced pressure to obtain 216 g of a brown resin. The OH equivalent of the obtained resin is 28.
1.4, softening point 96 ℃, melt viscosity at 150 ℃ 14
It was p. The GPC chart of the obtained resin is shown in FIG.

Example 4 A 500-ml four-necked flask was charged with 166 g (1.0 mol) of p-xylylene glycol dimethyl ether, 42.5 g (0.25 mol) of diphenyl ether, and 12.5 g of p-toluenesulfonic acid, and charged with nitrogen. The reaction was carried out at 150 ° C. under a stream of air with stirring. During this period, the produced methanol was removed from the system. After about 3 hours, when 16 g of methanol was produced, 202.5 g of o-cresol (1.
88 mol) was added, and the mixture was further reacted at 150 ° C. for 2 hours. During this time, the produced methanol was removed from the system. When the production of methanol was completed, the mixture was neutralized with sodium carbonate, and excess o-cresol was distilled off under reduced pressure to obtain 237.5 g of a brown resin. O of the obtained resin
The H equivalent was 248.9, the softening point was 99.8 ° C, and the melt viscosity at 150 ° C was 19p. The GPC chart of the obtained resin is shown in FIG.

Example 5 A 500 ml four-necked flask was charged with 166 g (1.0 mol) of p-xylylene glycol dimethyl ether, 16.8 g (0.125 mol) of durene, and 7.5 g of p-toluenesulfonic acid and charged with nitrogen. 150 with stirring under air flow
The reaction was carried out at ° C. During this period, the produced methanol was removed from the system. After about 7 hours, when 10 g of methanol was produced, 157.5 g (1.46 mol) of o-cresol.
Was added, and the mixture was further reacted at 150 ° C. for 3 hours. During this time, the produced methanol was removed from the system. When the production of methanol was completed, the mixture was neutralized with sodium carbonate, and excess o-cresol was distilled off under reduced pressure to obtain 232.5 g of a brown resin. The OH equivalent of the obtained resin is 2
25, softening point is 92 ℃, melt viscosity at 150 ℃ is 11p
Met.

Example 6 A 500 ml four-necked flask was charged with 166 g (1.0 mol) of p-xylylene glycol dimethyl ether, 11.2 g (0.083 mol) of durene and 7 g of p-toluenesulfonic acid, and under a nitrogen stream. The reaction was carried out at 150 ° C. with stirring. During this period, the produced methanol was removed from the system. After about 18.5 hours, when 5.8 g of methanol was produced, 180 g (1.67 mol) of o-cresol.
Was added, and the mixture was further reacted at 150 ° C. for 6 hours. During this time, the produced methanol was removed from the system. When the production of methanol was completed, the mixture was neutralized with sodium carbonate, and excess o-cresol was distilled off under reduced pressure to obtain 224.5 g of a brown resin. The OH equivalent of the obtained resin is 2
25, the softening point was 86 ° C., and the melt viscosity at 150 ° C. was 8 p.

(Production of Polyfunctional Epoxy Resin) Example 7 100 g of the resin obtained in Example 1 was replaced with epichlorohydrin 60
It is dissolved in 0 g, 0.25 g of benzyltriethylammonium chloride is further added, and the mixture is decompressed (about 150 mmH
g), 48% aqueous sodium hydroxide solution at 70 ° C. 33.
1 g was added dropwise over 3.5 hours. During this time, the water produced was removed from the system by azeotropic distillation with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropping is completed,
Furthermore, the reaction was continued for 30 minutes. Then, the salt produced by filtration was removed, and after washing with water, epichlorohydrin was distilled off to obtain 106 g of an epoxy resin. The epoxy equivalent was 323.7 and the softening point was 61 ° C. The GPC chart of the obtained resin is shown in FIG.

Using this resin, a resin composition having the composition shown in Table 1 was formed and then molded (150 ° C., 3 minutes) to obtain a cured test piece. The test pieces were post-cured at 180 ° C. for 12 hours and then subjected to various physical property tests. The results are shown in Table 1.
The glass transition point and the coefficient of linear expansion were measured at a temperature rising rate of 7 ° C./min using a thermomechanical measuring device. Further, the water absorption rate, using an unsaturated pressure cooker device,
It was measured by absorbing moisture for 96 hours under the condition of 133 ° C. and 3 atm. Furthermore, fracture toughness is AF Yee, RA Pearson, Jour
nal of Materials Science, 21, 2462 (1986).

Example 8 Using 100 g of the resin obtained in Example 2 and 28.7 g of 48% aqueous sodium hydroxide solution, the same reaction as in Example 7 was carried out to obtain 120 g of epoxy resin. Epoxy equivalent is 44
1, and the softening point was 76.4 ° C. The GPC chart of the obtained resin is shown in FIG. Using this resin, various physical property tests were carried out in the same manner as in Example 7. The results are shown in Table 1.

Example 9 Using 100 g of the resin obtained in Example 3 and 31.9 g of 48% sodium hydroxide aqueous solution, the same reaction as in Example 7 was carried out to obtain 98 g of epoxy resin. Epoxy equivalent is 47
It was 1.4 and the softening point was 75.0 degreeC. The GPC chart of the obtained resin is shown in FIG. Using this resin, various physical property tests were carried out in the same manner as in Example 7. The results are shown in Table 1.

Example 10 100 g of the resin obtained in Example 4 and 32.8 g of a 48% aqueous sodium hydroxide solution were used for the same reaction as in Example 7 to obtain 96 g of an epoxy resin. Epoxy equivalent is 42
The softening point was 0.5 and the softening point was 78.5 ° C. The GPC chart of the obtained resin is shown in FIG. Using this resin, various physical property tests were carried out in the same manner as in Example 7. The results are shown in Table 1.

Example 11 100 g of the resin obtained in Example 5 and 36.2 g of a 48% aqueous sodium hydroxide solution were used for the same reaction as in Example 7 to obtain 102 g of an epoxy resin. Epoxy equivalent is 27
5, and the softening point was 70.5 ° C. Also, 150
The melt viscosity at 0 ° C. was 4.0 poise. The GPC chart of the obtained resin is shown in FIG. Using this resin, various physical property tests were carried out in the same manner as in Example 5. The results are shown in Table 1.

Example 12 Using 100 g of the resin obtained in Example 6 and 36.2 g of a 48% aqueous sodium hydroxide solution, the same reaction as in Example 7 was carried out to obtain 103 g of an epoxy resin. Epoxy equivalent is 27
7, and the softening point was 60.2 ° C. Also, 150
The melt viscosity at ° C was 2.0 poise. The GPC chart of the obtained resin is shown in FIG. Using this resin, various physical property tests were carried out in the same manner as in Example 7. The results are shown in Table 1.

Comparative Example 1 Using o-cresol novolac type epoxy resin, various physical property tests were carried out in the same manner as in Example 7. The results are shown in Table 1.

[0036]

[Table 1]

[0037]

The cured product obtained by curing the epoxy resin and polyhydric hydroxy resin of the present invention has excellent moisture resistance and heat resistance, and also has excellent mechanical properties such as impact resistance. However, it can be suitably used for applications such as lamination, molding, casting, and adhesion.

[Brief description of drawings]

FIG. 1 is a GPC chart of a resin (polyhydric hydroxy resin) obtained in Example 1 of the present invention.

FIG. 2 is a GPC chart of the resin (polyvalent hydroxy resin) obtained in Example 2 of the present invention.

FIG. 3 is a GPC chart of the resin (polyhydric resin) obtained in Example 3 of the present invention.

FIG. 4 is a GPC chart of the resin (polyvalent hydroxy resin) obtained in Example 4 of the present invention.

FIG. 5 is a GPC chart of the resin (polyfunctional epoxy resin) obtained in Example 7 of the present invention.

FIG. 6 is a GPC chart of the resin (polyfunctional epoxy resin) obtained in Example 8 of the present invention.

FIG. 7 is a GPC chart of the resin (polyfunctional epoxy resin) obtained in Example 9 of the present invention.

FIG. 8 is a GPC chart of the resin (polyfunctional epoxy resin) obtained in Example 10 of the present invention.

FIG. 9 is a GPC chart of the resin (polyfunctional epoxy resin) obtained in Example 11 of the present invention.

FIG. 10 is a GPC chart of the resin (polyfunctional epoxy resin) obtained in Example 12 of the present invention.

Claims (6)

[Claims] 1. The following general formula (1): (However, A represents a benzene ring or a naphthalene ring which may be substituted with an alkyl group having 1 to 6 carbon atoms, B represents an aromatic ring, R represents a hydrogen atom or a methyl group, and G represents a glycidyl group. And n is a number from 0 to 15). 2. The following general formula (2): (However, A represents a benzene ring or a naphthalene ring which may be substituted with an alkyl group having 1 to 6 carbon atoms, B represents an aromatic ring, R represents a hydrogen atom or a methyl group, and n represents 0 to 0.
A polyhydric hydroxy resin represented by the formula (denoting an integer of 15). 3. The method for producing a polyfunctional epoxy resin according to claim 1, wherein the polyhydric hydroxy resin according to claim 2 is reacted with epichlorohydrin. 4. The following general formula (3) H—B—H (3) (wherein B represents an aromatic ring), relative to 1 mol of the aromatic compound, 2 to 30 mol of the following general formula. (4) [Chemical Formula 3] (Wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) and at least one crosslinking agent selected from divinylbenzenes are reacted with each other, and then the following general formula ( 5) H-A-OH (5) (wherein A represents a benzene ring or a naphthalene ring which may be substituted by an alkyl group having 1 to 6 carbon atoms), a phenol or naphthol represented by The method for producing a polyhydric hydroxy resin according to claim 2, wherein the reaction is carried out. 5. An epoxy resin composition comprising an epoxy resin and a curing agent, which comprises at least one of the polyfunctional epoxy resin according to claim 1 and the polyvalent hydroxy resin according to claim 2 as an essential component. Epoxy resin composition. 6. A cured product obtained by curing the epoxy resin composition according to claim 5.