JPS59175480A - Polyepoxy compound, its preparation and use - Google Patents

Abstract

NEW MATERIAL:A polyepoxy compound consisting of a polyglycidyl ether of a polynuclear polyhydric phenol shown by the formula (R<1> and R<2> are H, or lower alkyl; R<3> is H, lower alkyl, or halogen; n is 0-5). USE:A curable composition of epoxy resin. Having improved heat-resistant characteristics such as glass transition point, heat distortion temperature, heat-resistant elasticity, etc., useful as an adhesive, coating compound, insulating material, laminate for printed circuit, sealing material, etc. PREPARATION:A polynuclear polyhydric phenol shown by the formula is reacted with an epihalohydrin in the presence of a catalyst (e.g., sodium hydroxide, propylamine, etc.) to give a halohydrin ether of polynuclear polyhydric phenol, and the halohydrin ether of the polynuclear polyhydric phenol is reacted with an alkali hydroxide, to give a polyepoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyglycidyl ether compound of polynuclear polyhydric phenols, a method for producing the same, and an epoxy resin curable composition having excellent heat resistance properties comprising the polyepoxy compound. More specifically, it is possible to form an epoxy resin curable composition with excellent heat resistance properties such as glass transition temperature, heat distortion temperature, and heat resistance elastic properties, and to produce an epoxy resin molding material with excellent heat resistance properties and a laminated layer for printed circuits. The present invention provides polyepoxy compounds that can be used as plates or advanced composite materials.

Conventionally, various compounds have been proposed as polyepoxy compounds used in epoxy resin curable compositions. Recently, in fields such as molding materials, varnishes, printed circuit laminates, and advanced composite materials (ACM), there has been a demand for epoxy resin curable compositions with excellent heat-resistant properties such as glass transition temperature, heat distortion temperature, and heat-resistant elastic properties. has been done. Conventionally, as polyepoxy compounds constituting heat-resistant epoxy resin curable compositions, epoxidized phenol novolak 'll resin, epoxidized ortho-cresol novolank resin, 1, 1, 2
．． Polyglycidyl ethers of polynuclear phenols such as tetraglycidyl ether of 2-tetrakis(p-hydroxyphenyl)ethane, tetraglycidylated products of xylylene diamine, hexaglycidylated products of R3,5-)lyaminomethylbenzene, and triglycidyl ethers of incyanuric acid. Polyglycidylated aromatic polyamines such as glycidylated compounds are widely used. However, epoxy resin curable compositions using these polyepoxy compounds do not have sufficient heat resistance properties as described above, and cannot be used in fields that require heat resistance properties. There is a need for the development of curable epoxy resin compositions.

Based on this recognition, the present inventors investigated the development of an epoxy resin curable composition with excellent heat resistance properties, and as a result, the present inventors developed a polyglycidyl ether of polynuclear polyhydric pheno-JVs having a specific structure. The inventors have discovered that an epoxy resin curable composition that achieves the above objectives can be obtained by using a polyepoxy compound, and have arrived at the present invention. According to the present invention, the polyepoxy compound composed of polyglycidyl ether of polynuclear polyhydric phenols of the present invention is a new compound, and the epoxy resin curable composition composed of the polyepoxy compound and a curing agent has a glass transition temperature, a temperature of It has particularly excellent heat resistance properties such as deformation temperature and thermoelastic properties, and is also characterized by improved mechanical properties such as bending strength, Izod impact strength, and Rockwell hardness.

To summarize the present invention, the present invention comprises the general formula [I] [wherein,
R1 and R2 represent a hydrogen atom or a lower alkyl group, R5 represents a hydrogen atom, a lower alkyl group or a halogen atom, and n represents an integer of 0 to 5. The gist of the invention is a polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols represented by the general formula [I] [wherein R1 and R2 represent a hydrogen atom or a lower alkyl group, and R5 represents It represents a hydrogen atom, a lower alkyl group or a halogen atom, and n represents an integer of 0 to 5.

] By reacting the polynuclear polyhydric phenol represented by the formula with epihalohydrin in the presence of a catalyst, a halohydrin ether of the polynuclear polyhydric phenol is produced, and then a halohydrin of the polynuclear polyhydric phenol is produced. The gist of the invention is a method for producing polyglycidyl ether of polynuclear polyhydric phenols represented by the general formula (1), which is characterized by reacting an ether with an alkali hydroxide;
and R2 represents a hydrogen atom or a lower alkyl group, R
3 represents a hydrogen atom, lower alkyl or halogen atom,
n represents an integer from 0 to 5. The gist of the invention is an epoxy resin curable composition comprising: a polyepoxy compound consisting of a polyglycidyl ether of a polynuclear polyhydric phenol represented by the following formula; and (b) a curing agent.

The polyepoxy compound of the present invention has the general formula [I] [wherein,
R1 and R2 represent a hydrogen atom or a lower alkyl group, R3 represents a hydrogen atom, a lower alkyl group or a halogen atom, and n represents an integer of O to 5. ] This is a polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols. The dihydroxyphenyl group constituting M of the polynuclear polyhydric phenol represented by the general formula CI) is 3,4-dihydroxyphenyl M, 2.
4-dihydroxyphenyl group or 2,5-dihydroxyphenyl group, dihydroxyphenylene group halo,
4-dihydroxy-1,6-phenylene group, 2,4-dihydroxy-1,5-phenylene group, or ci2.5-dihydroxy-1,3-phenylene group, all of which are catechol component units, resorcin component units, or hydroquinone Corresponds to a component unit. There is no problem even if two or more of these dihydroxyphenyl groups are contained in one molecule of polynuclear polyhydric phenol. In addition, the general formula (1)
R1 and (2) constituting the polynuclear polyhydric phenol represented by can each be a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.; Preferably, at least one of R and R is a hydrogen atom. Similarly, R6 is a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, fluorine, a fluorine group,
Examples include halogen atoms such as bromine, and R6 may be bonded to any of the ortho, meta, and rose positions relative to the hydroxyl group. In addition, in the polynuclear polyhydric phenols represented by the general formula (1), n is an integer representing O to 5, and it may be a mixture of two or more types of polynuclear polyhydric phenols representing these integers. .

More specifically, the polynuclear polyhydric phenols represented by the general formula [I] constituting the polyepoxy compound of the present invention include the polynuclear polyhydric phenols represented by the following general formulas [■] to [V]. -/I/ class can be exemplified.

The polyepoxy compound of the present invention is a polyglycidyl ether of a polynuclear polyhydric phenol represented by the general formula CI), and usually accounts for 80% or more, preferably 90% or more, particularly preferably 4j of 90% or more of the phenolic hydroxyl groups of the polynuclear polyhydric phenol. is a polyepoxy compound in which 95% or more is glycidyl etherified.

Here, glycidyl ether refers to glycidyl ether represented by the general formula (V') formed by the reaction of one molecule of shrimp halohydrin with one phenolic hydroxyl group of the polynuclear polyhydric phenol, as well as phenolic A glycidyl ether represented by the general formula (Vl) formed by the reaction of a -/cyanic hydroxyl group and the produced glycidyl ether may also be used. The molar ratio of all the 2-hydroxyoxy-1,3-propylene groups to all the glycidyl groups in the polyepoxy compound of the present invention is generally 0.5 or less, preferably 0.1 or less. The epoxy equivalent of the polyepoxy compound of the present invention is usually 122 to 50.
0 g/l equivalent, preferably in the range of 125 to 400 g/l equivalent, and the phenolic hydroxyl equivalent is usually in the range of 1220 g/l equivalent or more, preferably 2500 g/l equivalent or more.

The polyepoxy compound of the present invention is produced by reacting the polynuclear polyhydric phenol represented by the general formula (1) with epihalohydrin in the presence of a catalyst to produce a halohydrin ether of the polynuclear polyhydric phenol. After that, it is produced by reacting the halohydrin ether of the polynuclear polyvalent pheno-)V with an alkali hydroxide. Specific examples of the epihalohydrin used in the method of the present invention include epichlorohydrin, shrimp bromohydrin, shrimp iodohydrin, and the like. The proportion of epihalohydrin used is generally 2 to 15 mol, preferably 2 to 7 mol, per mxi mol of phenolic water of the polynuclear polyhydric phenol.

Examples of the catalyst used in the method of the present invention include bases and ammonium salt compounds.

Specifically, alkali hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; primary amines such as propylamine, butylamine, hexylamine, and octylamine; and tertiary amines such as diethylamine, dipropylamine, and dibutylamine. Amines, tertiary amines such as triethylamine, tripropylamine, tributylamine, tetramethylammonium chloride, tetramethylammonium iodide, tetraethylammonium chloride, tetracylic ammonium bromide, tetraethylammonium iodide, tetrapropylammonium chloride, chloride Amines such as tetrabutylammonium, penzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide ammonium salt, trimethylamine hydrochloride, triethylamine hydrochloride, dimethylamine bromide frozen salt, diethylamine hydrochloride, etc. Examples include salt. The proportion of these catalysts used is usually 0.005 to 5 mol, preferably 0.005 to 5 mol, per 1 mol equivalent of the polynuclear polyhydric phenol. [) It is in the range of 1 to 1 mole.

In the method of the present invention, this halohydrin etherification reaction is generally carried out at 5°C to 110°C, preferably at 7°C.

It is carried out at temperatures between 100°C and 100°C. In this halohydrin etherification reaction step, a method may be adopted in which the phenolic hydroxyl groups of the polynuclear polyhydric phenols are almost completely converted into halohydrin etherification, or a method may be adopted in which the phenolic hydroxyl groups of the polynuclear polyhydric phenols are almost completely converted into halohydrin etherification. A reaction mixture consisting of a halohydrin ether of a polynuclear polyhydric phenol and a raw material is obtained by partial, for example, halohydrin etherification to a range of usually 40 to 80%, preferably 50 to 70%, and the reaction mixture is It is also possible to adopt a method in which the halohydrin etherification reaction and the dehydrohalogenation reaction proceed simultaneously by reacting the mixture with an alkali hydroxide.

In the method of the present invention, the dehydrohalogenation reaction of the halohydrin ether is carried out in the presence of an alkali hydroxide. Specific examples of the alkali hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., but it is preferable to use IJium hydroxide. The proportion of alkali hydroxide used is usually 0680 to 1.2 mol, preferably 0.95 to 1 mol, per 1 molar equivalent of the phenolic hydroxyl group of the polynuclear polyhydric phenol as the raw material supplied to the halohydrin ethyl reaction step. .1 mole range. It is preferable that the dehydrohalogenation reaction of the halohydrin ether proceeds while removing the water produced in the reaction from the reaction system. An example of a method in which lohydrin is distilled out by azeotropic distillation, the distillate is separated into an aqueous phase and a shrimp halohydrin phase, the aqueous phase is removed, and the shrimp lohydrin phase is recycled to the reaction system. be able to. The dehydrohalogenation reaction of the halohydrin ether may be carried out in one step, or may be carried out in two or multiple steps. The dehydrohalogenation reaction is usually carried out in a shrimp halohydrin solvent, which is the raw material for the halohydrin etherification reaction step, but ketones such as methyl ethyl ketone and methyl isobutyl ketone, benzene, toluene, xylene, cumene, cymene, and ethylbenzene are used. It can also be carried out in aromatic hydrocarbon solvents such as. The proportion of these solvents used is usually 4 to 10 times, preferably 5 to 7 times, the weight ratio of the polynuclear polyhydric phenols in the raw materials. The dehydrohalogenation reaction is usually carried out at a temperature of 70 to 110"C, preferably 80 to 100°C. In the method of the present invention, the reaction mixture after the previous dehydrohalogenation reaction is The polyglycidyl ether of polynuclear polyhydric phenols can be prepared by a conventional method, for example, after neutralizing unreacted alkali hydroxide in the reaction mixture with an aqueous solution of phosphoric acid, alkali phosphate, acetic acid, etc. The polyglycidyl ether of the polynuclear polyhydric phenol is obtained by removing the salt by a treatment such as extraction, adsorption or filtration, and removing the solvent by gate distillation.

The polyepoxy compound of the present invention can be used as an epoxy resin curable composition by being blended with a curing agent. As the curing agent to be added to the epoxy resin curable composition of the present invention, any compound conventionally known as a curing agent for epoxy resins can be used. For example, specifically, chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylene diamine, and diethylaminoprobylamine, menthanediamine, N-aminoethylpiperazine, isophoronediamine, and L3-diaminocyclohexane. cycloaliphatic polyamines such as, aliphatic polyamine adducts such as adducts of diethylenetriamine and ethylene oxide or propylene oxide,
Ketoimines such as condensates of diethylenetriamine and acetone, modified aliphatic polyamines such as cyanoethylated diethylenetriamine, polyamide amines such as dimer acid/diethylenetriamine condensates, dimer acid/triethylenetetramine condensates, 4,4'-methylene dianiline , m-phenylenediamine, aromatic amines such as xylylenediamine, 4,4'-methylenedianiline,
Aromatic modified amines such as pheni-glycidyl ether adducts, mercaptan curing agents such as polysulfide resins, acid anhydride curing agents such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and phthalic anhydride;
Copolymers with acid anhydride groups such as ethylene/maleic anhydride copolymers, compounds with phenolic hydroxyl groups such as novolak or resol type pheno-)V resin initial condensates, dicyandiamide, aniline - Examples include formaldehyde resin, melamine resin, and urea resin. It is preferable to mix an appropriate one out of these depending on the purpose of use. The blending ratio of the curing agent is usually 1 to 200 parts by weight, preferably 6 to 100 parts by weight, per 100 parts by weight of the above-mentioned BoIJ epoxy compound.

In addition to the r3ij polyepoxy compound and the curing agent, the epoxy resin curable composition of the present invention may optionally contain a curing accelerator, an inorganic or organic filler/warming agent, a flame retardant, a heat stabilizer, and an antiseptic. Various additives such as oxidizing agents and lubricants are added. Furthermore, in addition to the polyepoxy compound of the present invention, conventionally known polyepoxy compounds can also be used in combination.

As the curing accelerator, conventionally known curing accelerators are used. Specifically, benzyldimethylamine, 2-(
dimethylaminomethyl)fer/-, 2,4.6-)
Lis(dimethylaminomethy)V)pheno-/', N
r N'-dimethylpiperazine, 2-ethyl-4-methylimidazole, etc. can be exemplified. The blending ratio of the curing accelerator is usually 0.1 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the polyepoxy compound.

Specifically, inorganic fillers include silica, silica/alumina, alumina, glass powder, glass beads, glass fiber, asbestos, mica, graphite, carbon fiber,
Titanium oxide, molybdenum disulfide, beryllium oxide, magnesium oxide, calcium oxide, magnesium hydroxide,
Examples include calcium hydroxide, Talelev, celite, metal powder, and metal fiber. Heat resistance and mechanical properties are improved no matter which of these inorganic fillers is blended. Among these inorganic fillers, heat resistance is further improved when glass fiber, carbon fiber, asbestos, etc. are blended, abrasion resistance is further improved when graphite, titanium oxide, molybdenum disulfide, etc. are blended, and mica, asbestos, etc. Arc resistance is further improved by blending with glass powder, etc., electrical properties such as conductivity are improved by blending with carbon black, metal fiber, metal powder, graphite, etc., and electrical properties such as conductivity are further improved by blending with carbon black, metal fiber, metal powder, graphite, etc. When blended, thermal conductivity is improved. The blending ratio of these inorganic light/protective agents varies greatly depending on the type of inorganic filler blended into the epoxy resin curable composition and the purpose of use of the epoxy resin curable composition. It is usually in the range of 10 to 250 parts by weight,
The amount is preferably from 60 to 200 parts by weight, particularly preferably from 60 to 150 parts by weight.

As the organic filler, various high molecular weight polymers, fibrous polymers, etc. are blended. Specifically, as a high molecular weight polymer,
Examples include fluorine-based polymers such as polytetrafluoroethylene.

Specifically, the organic fibrous filler includes polyterephthaloy/L/-I)-phenylenediamine, polyterephthaloyl inphthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, polyisophthaloyl)V-m -Fully aromatic polyamides such as phenylenediamine, 'nylon 66, nylon 10, nylon 12
Polyamide fiber, polyamideimide fiber, polybenzimidazole fiber, polyethylene terephthalate, etc.
Polycondensation type synthetic fibers such as polyester fibers such as poly-1,4-butylene terephthalate; Addition polymerization type synthetic fibers such as polyvinyl alcohol type synthetic fibers and acrylic fibers such as polyacrylonitrile; Cotton, hemp, flax, wool, raw silk Examples include natural fibers such as. Among the organic fibrous fillers, it is preferable to blend an organic synthetic fiber filler, and it is particularly preferable to blend a filler made of polycondensed synthetic fibers, and especially a fibrous filler made of wholly aromatic polyamide. It is preferable to do so. The organic fibrous filler can be used in any of the usual single fiber, strand, and cross shapes. The fiber thickness of these organic fibrous fillers is usually in the range of 2 to 20 microns, preferably 5 to 15 microns. In addition, these fibrous materials can be used in either short or long fibrous materials, and the length of the fibrous material can be selected as appropriate depending on the purpose of use. It is usually in the range of 0.1 to J, 2C1n, preferably Q, 3 to 0.6 cm. The blending ratio of the organic fibrous filler is usually 1 to 60 parts by weight per 100 parts by weight of the polyepoxy compound.
Parts by weight are preferably in the range from 5 to 40 parts by weight, particularly preferably from 10 to 30 parts by weight. When the inorganic or organic filler is a cloth-like or mat-like base material, the epoxy resin curable composition is dissolved in an organic solvent and impregnated into the base material to form a prepreg, and then this prepreg is prepared. A laminate made of the composition of the present invention can be obtained by stacking a plurality of sheets and press-gluing them as necessary. When the inorganic or organic filler is in the form of single fibers or strands,
They can be blended by conventionally known blending methods.

Specifically, flame retardants include halogenated aliphatic hydrocarbons,
Halogenated alicyclic hydrocarbons, halogenated aromatic hydrocarbons,... halogenated aromatic ethers,... halogenated phenols,... halogenated poly(dIi) phenols,...
Organic/logen compounds such as halogenated aromatic carboxylic acids or their acid anhydrides, halogenated novolac type phenol M fats, halogenated eboxyno 1ζ lac type phenol)v resins; boron compounds; inorganic phosphides, organic phosphorus compounds, etc. Phosphorus compounds; antimony compounds such as inorganic antimony compounds and organic antimony compounds; bismuth compounds:
Examples include arsenic compounds. The blending ratio of the flame retardant is usually 1 to 100 parts by weight, preferably 50 M parts to 100 parts by weight of the above-mentioned BoIJ epoxy compound.

The epoxy resin curable composition of the present invention has a glass transition point,
It has particularly excellent heat resistance properties such as heat distortion temperature and heat elasticity resistance, as well as excellent mechanical properties such as bending strength, Izot impact strength, and Rockwell hardness, so it can be used in a wide variety of applications. Available. Specifically, adhesives, adhesives, paints, insulating materials, prepregs, structural laminates, printed circuit laminates, switchboards, transistors, and ICs.
.

Examples include sealing materials for LSIs, molding materials for electrical appliances such as switches and connectors, and sliding materials such as washers and bearings.

Next, the present invention will be specifically explained using examples. The method for producing the polynuclear polyvalent phenols used in the Examples is specifically shown in Reference Examples.

Reference example Lusorcin 88g (0-8mo)v), 1,4-di(2-hydroxy-2-propy/L/)benzene 19.4g (0
-1 mol), benzene 100mβ, salt production fil IQ
l]mβ was placed in a reactor, and the reaction was carried out at 5°C for 15 hours with stirring.

After the reaction was completed, the organic layer was separated and neutralized with an aqueous sodium bicarbonate solution. After the neutralization was completed, unreacted resorcin contained in the organic layer was removed by washing with hot water, and the organic layer was cooled in an ice-water bath. A solid was precipitated by cooling, which was filtered and recrystallized with methanol to obtain white crystals with a melting point of 165-169°C.
Obtained with a yield of 0%.

From the IR spectrum, NMR spectrum, and elemental analysis of this compound, it was confirmed that it had the following structure.

Reference Example 2 Resorcinol 88g (0-8mo)v), 1.4-di(2-
155 g (0,8
mol), Ben 92,250 ml, and 1 ml of concentrated hydrochloric acid were placed in a reactor, and the reaction was carried out at 50'C for 2 hours with stirring, and then for 2 hours at reflux temperature. After the reaction was completed, benzene and water were distilled off to obtain a yellowish brown resin with a yield of 96%.

The melting point of this resin is 100 to 130°C, and the reaction was carried out in the same manner as in Reference Example 1 except that catechol was used instead of resorcinol in Reference Example 1. Ta. The product was recrystallized from benzene to give white crystals with a melting point of 193-197°C in a yield of 70%. IR spectrum of this compound,
NMR spectrum (Masbek)/and elemental analysis confirmed the following structure.

Reference Examples 4 to 6 In Reference Example 1, 1,4-di(2-hydroxy-2-
The same procedure as in Reference Example 1 was carried out except that propyl/I/)benzene was used as shown in Table 1. The obtained product was confirmed to have the structure shown in Table 1 from NMR spectrum, mass spectrum, and elemental analysis.

Example 1 529 g (i, 4 mol) of the compound shown in Reference Example 1, 4023 g (43-5 g) of epichlorohydrin, 57.2 g of a 50% aqueous solution of tetramethylammonium chloride (
0.26 mo/L/) and 64 g of water were placed in a reactor and reacted at 90"C for 4 hours with stirring. To this, 798 g (9.6 mo) v) of a 48% caustic soda aqueous solution was added for 1.5 hours. During this time, the condensed distillate was separated, the upper water layer was removed, and the lower epichlorohydrin layer was returned to the reactor, maintaining the water concentration of the reaction mixture at about 2%.After the reaction, the reaction mixture was added to 225 [i of water, thoroughly stirred to wash the organic layer, and then separated.
0e was added and thoroughly stirred, and the organic layer was washed. After separating the organic layer, 240 ml of 17% aqueous sodium phosphate solution was added to neutralize it.

The organic layer was dehydrated by heating and then filtered, and the P solution was further concentrated to obtain a polyepoxy compound with a yield of 90%. The number average molecular weight (stone n) of this polyepoxy compound determined by gel permeation chromatography is 900, the molecular weight distribution (w/M n ) is 1.68, and the epoxy equivalent determined by the hydrochloric acid/dioxane method is 180 g. /eq
Met. IR spectrum of this polyepoxy compound,
It was confirmed from the NMR spectrum and elemental analysis that the compound of Reference Example 1 had a glycidyl etherified structure.

Examples 2 to 6 Example 1 except that the compounds of Reference Example 2, Reference Example 6, Reference Example 4, Reference Example 5, and Reference Example B were used instead of the compound shown in Reference Example 1 in Example 1. I did the same thing. The characteristic values of the obtained polyepoxy compound were determined in the same manner as in Example 1, and are shown in Table 2.

In addition, the structures of these polyepoxy compounds were investigated by IR spectrum, NMR spectrum, and elemental analysis, and the compounds of Reference Example 2, Reference Example 6, Reference Example 4, Reference Example 5, and Reference Example B were found to be glycidyl ether Example 7, Comparative Example 1 180 g of the polyepoxy compound obtained by the method of Example 1 and 49-5 g of diaminodiphenylmethane were melted and mixed at 80°C, and cast molding was performed. This was cured by heating at 100°C for 2 hours and then at 150°C for 4 hours. The physical properties of the obtained molded product were measured and the results shown in Table 5 were obtained (Example 7).

In addition, commonly used bisphenol A type epoxy resin (manufactured by Mikata Petrochemical Epoxy Co., Ltd., EPOMIK R
-140) +90 was carried out in the same manner as in Example 7, and the physical properties of the molded product were measured.

The results are also shown in Table 3 (Comparative Example 1). □Table 6 Examples 8 to 12 The same procedure as Example 7 was carried out except that the polyepoxy compounds obtained by the methods of Examples 2 to B were used as shown in Table 4. The physical properties of the obtained molded products were measured and are shown in Table Comparative Examples 2 to 4. The same procedure as in Example 7 was conducted except that a commercially available heat-resistant epoxy resin was used as shown in Table 5. Obtained Example 1, Comparative Example 5 828 g of polyebogish compound obtained by the method of Example 1, 37 g of dicyandiamide, 2.1 g of benzyldimethylamine
g was dissolved in 673 g of dimethylformamide to prepare a varnish. This is glass cloth manufactured by Nittobo (WE-1).
8 was impregnated with -BZ2) and dried at 140''C for 4 minutes to prepare a prepreg.

Nine sheets of this prepreg were laminated with two sheets of copper foil on both sides, and press molding was performed at 170° C. for 1 hour. The physical properties of the obtained laminate are shown in Table 6 (Example 15).

In addition, bispheno-/L'A type epoxy resin (manufactured by Mikata Petrochemical Epoxy Co., Ltd., EPOMIK R-501) sog
.

Similarly, 20 g of (EPOMIK R-140) was dissolved in 20 g of methyl ethyl ketone, and a solution of 4 g of dicyandiamide and 15 g of dimethylformamide, 0.2 g of benzyldimethylamine, and 15 g of methylceron lube were mixed thereto to prepare a varnish. This varnish was impregnated into glass d, and the prepreg production conditions were set at 130°C1.
The same procedure as in Example 13 was carried out except that the time was 8 minutes. The physical properties of the obtained laminate are shown in Table 6 (Comparative Example 5).

Claims (3)

[Claims] (1) General formula (1) [In the formula, R1 and R2 represent a hydrogen atom or a lower alkyl group, and R3 represents a hydrogen atom, a lower alkyl group, or...
It represents a rogen atom, and n represents an integer of O to 5. ] A polyepoxy compound consisting of a polyglycidyl ether of polynuclear polyphenol/L/. (2) General formula (1) [wherein R1 and R2 represent a hydrogen atom or a lower argyl group, R6 represents a hydrogen atom, a lower alkyl group or a halogen atom, and n represents an integer of 0 to 5. ] By reacting the polynuclear polyvalent phenol represented by the formula with shrimp halohydrin in the presence of a catalyst, a halohydrin ether of the polynuclear polyvalent phenol Jv is produced, and then the polynuclear polyvalent phenol Jv is produced. A method for producing a polyepoxy compound comprising a polyglycidyl ether of a polynuclear polyhydric phenol represented by the general formula [I], which comprises reacting a rhohydrin ether with an alkali hydroxide. (3) (a) General formula [I] [In the formula, R1 and R2 represent a hydrogen atom or a lower alkyl group, and R3 represents a hydrogen atom, a lower alkyl p group, or]
It represents a rogen atom, and n represents an integer of 0 to 5. An epoxy resin curable composition comprising a polyepoxy compound comprising a polynuclear polyphenol/V-class polyglycidyl ether represented by the following formula, and (b) a curing agent.