JPH0428712B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyepoxy compound consisting of polyglycinedyl ether of polynuclear polyhydric phenols and a method for producing the same. More specifically, it is possible to form a cured epoxy resin composition with excellent heat resistance properties such as glass transition temperature, heat distortion temperature, and heat resistance elastic properties, and epoxy resin molding materials with excellent heat resistance properties, and laminates for printed circuits. It also provides epoxy compounds that can be used in advanced composite materials. Conventionally, various compounds have been proposed as polyepoxy compounds used in epoxy resin curable compositions. Recently, in the fields of molding materials, varnishes, printed circuit laminates, advanced composite materials (ACM), etc.
There is a demand for an epoxy resin curable composition that has excellent heat resistance properties such as glass transition temperature, heat distortion temperature, and heat elastic properties. Conventionally, polyepoxy compounds constituting heat-resistant epoxy resin cured compositions include:
Epoxidized phenol novolak resin, epoxidized orthocresol novolak resin, 1,1,
2,2-tetrakis (p-hydroxyphenyl)
Polyglycidyl ether of polynuclear phenols such as tetraglycidyl ether of ethane, diglycidylated product of xylylene diamine, 1,3,5-
Polyglycidylated aromatic polyamines such as hexaglycidylated triaminomethylbenzene and triglycidylated isocyanuric acid 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 composition consisting of polyglycindyl ether of polynuclear polyhydric phenols 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 comprising polyglycidyl ether of polynuclear polyhydric phenols of the present invention is a new compound, and the epoxy resin curable composition comprising the polyepoxy compound and a curing agent has a glass transition point,
It has particularly excellent heat resistance properties such as heat distortion temperature and heat elasticity resistance, and also has excellent mechanical properties such as bending strength, Izot impact strength, and Rockwell hardness. To summarize the present invention, the present invention has the general formula [I] [In the formula, R ¹ , R ³ and R ⁴ each represent a lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, R ⁵ and R ⁶ each represent a hydrogen atom,
Indicates a lower alkyl group or a halogen atom. The gist of the material invention is a polyepoxy compound consisting of a polyglycidyl ether of a polynuclear polyhydric phenol represented by the general formula [I] [In the formula, R ¹ , R ³ and R ⁴ each represent a lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, R ⁵ and R ⁶ each represent a hydrogen atom,
Indicates a lower alkyl group or a halogen atom. ] By reacting polynuclear polyhydric phenols represented by ] with epihalohydrin in the presence of a catalyst,
After producing the halohydrin ether of the polynuclear polyhydric phenol, the halohydrin ether of the polynuclear polyhydric phenol is reacted with an alkali hydroxide, which is represented by the general formula [I] above. The gist of the invention is a method for producing a polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols. The polyepoxy compound of the present invention has the general formula [I] [In the formula, R ¹ , R ³ and R ⁴ each represent a lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, R ⁵ and R ⁶ each represent a hydrogen atom,
Indicates a lower alkyl group or a halogen atom. ] This is a polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols.
The polynuclear polyhydric phenols represented by the general formula [I] can be obtained, for example, by reacting resorcinol or its nuclear substituted product with a ketone in the presence of an acidic catalyst. In the general formula [I], R ¹ , R ³ and R ⁴ each represent a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, and R ² represents a hydrogen atom or a methyl group, an ethyl group, or a propyl group. R ⁵ and R ⁶ are hydrogen atoms, respectively.
Indicates a lower alkyl group such as a methyl group, ethyl group, propyl group, butyl group, or a halogen atom such as fluorine, chlorine, bromine, or iodine. Specifically, the polynuclear polyhydric phenols represented by the general formula [I] include 2,4,4-trimethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman,
2,4,4-triethyl-3-methyl-2-(2,
4,4-dihydroxyphenyl)-7-hydroxychroman, 2,4,4-tri-n-propyl-3
-ethyl-2-(2,2-dihydroxyphenyl)
-7-hydroxychroman, 2,4,4-trimethyl-2-(6-methyl-2,4-dihydroxyphenyl)-7-hydroxychroman, 2,4,
4-trimethyl-2-(6-chloro-2,4-dihydroxyphenyl)-7-hydroxychroman,
2,4,4-trimethyl-2-(6-bromo-2,
Examples include 4-dihydroxyphenyl)-7-hydroxychroman. The polyepoxy compound of the present invention is a polyglycidyl ether of a polynuclear polyhydric phenol represented by the above general formula [I], and usually 80% or more, preferably 90% or more, of the phenolic hydroxyl groups of the polyhydric phenol, particularly Preferably, it is a polyepoxy compound in which 95% or more is glycidyl etherified. Here, glycidyl ether is a general formula formed by the reaction of one molecule of epihalohydrin with one phenolic hydroxyl group of the polynuclear polyhydric phenol [] In addition to the glycidyl ether represented by the general formula [] A mixture of glycidyl ethers represented by the formula 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 140 to 300 g/1 equivalent, preferably
The phenolic hydroxyl equivalent is usually in the range of 1400 g/1 equivalent; the phenolic hydroxyl equivalent is usually in the range 155 to 250 g/1 equivalent
The range is 1400 g/1 equivalent or more, preferably 2500 g/1 equivalent or more. The polyepoxy compound of the present invention is produced by reacting a polynuclear polyhydric phenol represented by the general formula [I] 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 polyhydric phenol with an alkali hydroxide. Specific examples of the epihalohydrin used in the method of the present invention include epichlorohydrin, epibromohydrin, and epiiodohydrin. The proportion of epihalohydrin used is generally 2 to 15 mol, preferably 3 to 7 mol, per 1 mol of the phenolic hydroxyl group of the polynuclear polyhydric phenol. Examples of the catalyst used in the method of the present invention include bases and ammonium salt compounds. Specifically, sodium hydroxide,
Alkali hydroxides such as potassium hydroxide and lithium hydroxide; primary amines such as propylamine, butylamine, hexylamine, and octylamine; secondary amines such as diethylamine, dipropylamine, and dibutylamine; Tertiary amines such as butylamine, tetramethylammonium chloride, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium chloride, tetrabutylammonium chloride,
Quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, choline chloride, amine salts such as trimethylamine hydrochloride, triethylamine hydrochloride, dimethylamine hydrobromide, diethylamine hydrochloride, etc. can be exemplified. The proportion of these catalysts used is generally 0.005 to 5 mol, preferably 0.01 to 1 mol, per 1 molar equivalent of the polynuclear polyhydric phenol. In the direction of the present invention, this halohydrin etherification reaction is generally carried out at 50 to 110°C, preferably at 70°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 partially, for example, usually 40 to 80%, preferably 50 to 70%, halohydrin etherification, 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 sodium hydroxide. The ratio of alkali hydroxide used is usually 0.80 to 1.2 mol, preferably 0.95 to 1.2 mol, per 1 molar equivalent of the phenolic hydroxyl group of the polynuclear polyhydric phenol as the raw material supplied to the halohydrin etherification reaction step.
It is in the range of 1.1 mol. It is preferable that the dehydrohalogenation reaction of the halohydrin ether proceeds while removing the water produced in the reaction from the reaction system.A method for removing water is to co-produce the produced water with the epahalohydrin in the reaction system. An example of a method is to perform distillation by boiling distillation, separate the distillate into an aqueous phase and an epahalohydrin phase, remove the aqueous phase, and circulate the epahalohydrin phase to the reaction system.
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 an epihalohydrin 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,
It can also be carried out in aromatic hydrocarbon solvents such as xylene, cumene, cymene, ethylbenzene. The proportion of these solvents used is usually 4 to 10 in terms of weight ratio to the polynuclear polyhydric phenols as raw materials.
times, preferably in the range of 5 to 7 times. 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 polyglycidyl ether of the polynuclear polyhydric phenol is separated from the reaction mixture after the dehydrohalogenation reaction. As a method, a conventional method can be used, for example, replacing unreacted alkali hydroxide in the reaction mixture with phosphoric acid,
After neutralization with an aqueous solution of alkali phosphate, acetic acid, etc., the salts are removed by extraction, adsorption, filtration, etc., and the solvent is removed by distillation, thereby converting the polynuclear polyhydric phenols into polyphenols. Glycidyl ether is obtained. 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, dipropylenediamine, diethylaminopropylamine, menthanediamine, N-
Aminoethylpiperazine, isophoronediamine,
Cycloaliphatic polyamines such as 1,3-diaminocyclohexane, aliphatic polyamine adducts such as adducts of diethylenetriamine and ethylene oxide or propylene oxide, ketoimines such as condensates of diethylenetriamine and acetone, diaminoethylated diethylenetriamine, etc. modified aliphatic polyamines, dimer acids,
Polyamide amines such as diethylenetriamine condensate, dimer acid/triethylenetetramine condensate, aromatic amines such as 4,4'-methylene dianiline, m-phenylene diamine, xylylene diamine, 4,4'-methylene dianiline・Aromatic modified amines such as phenyl glycidyl ether adduct, mercabutane curing agents such as polysulfide resins, acid anhydride curing agents such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and phthalic anhydride, ethylene/anhydride Copolymers with acid anhydride groups such as maleic acid, compounds with phenolic hydroxyl groups such as novolac type or resol type phenolic resin initial condensates, dicyandiamide, aniline/formaldehyde resins, melamine resins, urea resins, etc. I can give an example. It is preferable to select and blend an appropriate curing agent from among these curing agents depending on the purpose of use. The blending ratio of the curing agent is usually 1 to 200 parts by weight per 100 parts by weight of the polyepoxy compound,
The preferred range is 3 to 100 parts by weight. In addition to the polyepoxy compound and the curing agent, the epoxy resin curable composition using the polyepoxy compound of the present invention may optionally contain a curing accelerator, an inorganic or organic filler, a retardant, a heat resistant agent, etc. Various additives such as stabilizers, antioxidants, and lubricants are added. Further, as the polyepoxy compound, it is also possible to use conventionally known polyepoxy compounds in addition to the polyepoxy compound of the present invention. As the curing accelerator, conventionally known curing accelerators are used. Specifically, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N,N'-dimethylpiperazine,
Examples include 2-ethyl 4-methylimidazole. The blending ratio of the curing accelerator is usually 0.1 parts by weight per 100 parts by weight of the polyepoxy compound.
It ranges from 1 to 10 parts by weight, preferably from 1 to 5 parts by weight. 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, and oxide. Examples include calcium, magnesium hydroxide, calcium hydroxide, talc, 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 properties are further improved by blending glass fiber, carbon fiber, asbestos, etc., abrasion resistance is further improved by blending graphite, titanium oxide, molybdenum disulfide, etc., and mica,
Arc resistance is further improved by blending with asbestos, 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 alumina, titanium oxide, beryllium oxide, etc. When added, thermal conductivity is improved. The blending ratio of these inorganic fillers 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. The amount is generally 1 to 250 parts by weight, preferably 30 to 200 parts by weight, and particularly preferably 60 to 150 parts by weight. As the organic filler, various high molecular weight polymers, fibrous polymers, etc. are blended. Specific examples of the polymer include fluorine-based polymers such as polytetrafluoroethylene. Specifically, the organic fibrous fillers include polyterephthaloyl-p-phenylenediamine, polyterephthaloyl isophthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, and polyisophthaloyl-p-phenylenediamine. Fully aromatic polyamides such as yl-m-phenylenediamine, polyamide fibers such as nylon 66, nylon 6, nylon 10, and nylon 12, polyamideimide fibers, polybenzimidazole fibers, polyethylene terephthalate,
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;
Examples include natural fibers such as cotton, hemp, flax, wool, and raw silk. Among organic fibrous fillers, organic synthetic fibrous fillers are preferably blended, and fillers made of polycondensed synthetic fibers are particularly preferably blended, and fibrous fillers made of wholly aromatic polyamide are particularly preferably blended. It is preferable to mix them. The organic fibrous filler can be used in any of the usual single fiber, strand, and cross shapes. The thickness of these organic fibrous filler fibers is usually 3 to 20μ, preferably 5 to 20μ.
It is in the range of 15μ. In addition, these fibrous materials can be used either as short fibrous materials or long fibrous materials, and the length of the fibrous material can be selected as appropriate depending on the purpose of use, but the fiber length is usually It ranges from 0.1 to 1.2 cm, preferably from 0.3 to 0.6 cm. The blending ratio of the organic fibrous filler is usually 1 to 100 parts by weight of the polyepoxy compound.
It ranges from 60 parts by weight, preferably 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 base material is impregnated with the epoxy resin curable composition as a varnish dissolved in an organic solvent to form a prepreg, and the prepreg A laminate made of the composition of the present invention can be obtained by stacking and press-curing a plurality of sheets as necessary. When the inorganic or organic filler is in the form of a single fiber or a strand, it can be blended by a conventionally known blending method. Specifically, flame retardants include halogenated aliphatic hydrocarbons, halogenated alicyclic hydrocarbons, halogenated aromatic hydrocarbons, halogenated aromatic ethers, halogenated phenols, halogenated polynuclear polyhydric phenols, and halogenated organic halogen compounds such as halogenated aromatic carboxylic acids or their acid anhydrides, halogenated novolac type phenolic resins, and halogenated epoxy novolac type phenolic resins; boron compounds; phosphorus compounds such as inorganic phosphorus compounds and organic phosphorus compounds; inorganic antimony compounds , antimony compounds such as organic antimony compounds; bismuth compounds; and arsenic compounds. The blending ratio of the flame retardant is the same as that of the polyepoxy compound.
The amount is usually 1 to 100 parts by weight, preferably 3 to 50 parts by weight per 100 parts by weight. The curable epoxy resin composition formed by blending the polyepoxy compound of the present invention has particularly excellent heat resistance properties such as glass transition temperature, heat distortion temperature, and heat insulation properties, and has mechanical properties such as bending strength, Izod impact strength, and Rockwell hardness. Because it has excellent physical properties, it can be used in a wide variety of applications. Specifically, adhesives, varnishes, paints, insulating materials, laminates, printed circuit laminates, switchboards, sealing materials for transistors, ICs, LSIs, etc., molding materials for switches, connectors, washers, bearings, etc. Examples include sliding materials. Next, the present invention will be specifically explained using examples. Note that the method for producing polynuclear polyhydric phenols used in Examples and Comparative Examples is specifically shown in Reference Examples. Reference example 1 Resorcinol 1100g (10mol), 36% hydrochloric acid 100ml
(1.2 mol), methanol 800ml into the reactor, 50
heated to ℃. 232 g (4 mol) of acetone was added dropwise to this over 2 hours. The reaction was further carried out at 50°C for 3 hours. Thereafter, the reaction mixture was poured into 3 parts of water to precipitate a product, which was washed with 2 parts of water. After filtering the product, it was vacuum dried at 60° C. overnight to obtain 329 g of white powder. The melting point of this compound determined by microscopy is 235
The temperature was ~237°C, and the molecular weight was found to be 300 by spectrum measurement. The IR spectrum of this compound shows phenolic OH around 3500 cm ^-1 .
Characteristic absorptions of aromatic nuclei near 1600 and 1500 cm ^-1 and methyl groups near 1450 cm ^-1 were observed. Further, the following structure was confirmed from the ¹ H nuclear magnetic resonance spectrum measured by dissolving this compound in acetone- _d6 . NMR (in CD ₃ COCD ₃ ) δ (ppm, TMS standard) Attribution 0.80 (S, 3H) a 1.20 (S, 3H) b 1.65 (S, 3H) c 1.85 (d, Jd, e=13cps, 1H) d 2.95 (d, Je, d= 13cps, 1H) e 6.15 (doubly d, Jf, k=7cps Jf, g=3cps, 1H) f 6.30 (d, Jg, f=3cps, 1H) g 6.35 (d, Jk, j=7cps, 1H) h 6.40 (S, 1H) i 6.95 (d, Jj, f = 7cps, 1H) j 7.00 (d, Jk, f = 7cps, 1H) k 8.15 (S, 1H) l 8.18 (S, 1H) m 8.45 (S , 1H) n Reference Example 1 600g of the compound obtained by the method shown in Reference Example 1
(2 moles), 2775 g (30 moles) of epichlorohydrin,
Tetramethylammonium chloride 50% aqueous solution
39.4 ml (0.18 mol) and 47.8 g of water were placed in a reactor and reacted at 90° C. for 4 hours with stirring. Add 550g (6.6mol) of 48% caustic soda solution to this.
It was added dropwise over 1.5 hours. During this time, the condensed distillate was separated, the upper aqueous layer was removed, and the lower epichlorohydrin layer was returned to the reactor, reducing the water concentration of the reaction mixture to about 2%. After the reaction, the reaction mixture was poured into 2,400 ml of water, thoroughly stirred, and the organic layer was washed and separated. Further, 2,400 ml of water was added and thoroughly stirred to wash the organic layer. After separating the organic layer, 240 ml of 17% aqueous sodium phosphate solution was added to neutralize it. The organic layer was heated to dehydrate and filtered, and the liquid was further concentrated to obtain 960 g of epoxy resin. The number average molecular weight (n) of this resin determined by gel permeation chromatography is 870.
The molecular weight distribution (w/n) was 1.14, the melting point measured by microscopy was 39-44°C, and the epoxy equivalent determined by the hydrochloric acid/dioxane method was 163 g/eq. In the IR spectrum of this resin, in addition to the characteristic absorption of phenyl and methyl groups shown in Reference Example 1, the absorption of phenolic OH around 3500 cm ^-1 disappeared, and newly appeared around 840 cm ^-1 and 900 cm ^-1 . Characteristic absorption of epoxy groups was observed in , and it was confirmed that the phenolic hydroxyl groups were glycidyl etherified. Furthermore, the following structure was confirmed from the ¹ H nuclear magnetic resonance spectrum measured by dissolving this resin in _CDC3 .

[Table] Example 2, Comparative Example 1 163 g of the epoxy resin 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 heated to 100℃ for 2 hours.
Further, it was cured by heating at 150°C for 4 hours. The physical properties of the resulting molded product were measured and the results shown in Table 2 were obtained (Example 2). In addition, commonly used bisphenol A
Type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd.,
The same procedure as in Example 2 was conducted except that 190 g of EPOMIK R-140) was used, and the physical properties of the molded product were evaluated. The results are also shown in Table 2 (Comparative Example 1).

[Table] Comparative Examples 2 to 4 The same procedure as Example 2 was carried out except that a commercially available heat-resistant epoxy resin was used as shown in Table 3. The physical properties of the obtained molded product were measured and the results shown in Table 3 were obtained.

[Table] (1) Epoxidized phenol novolak
(2) Epoxidized orthocresol novolak
(3) N,N,N',N'-tetraglycidyl metaxylene diamine Example 3, Comparative Example 5 819 g of epoxy resin obtained by the method of Example 1, 65.1 g of dicyandiamide, benzyldimethylamine
A varnish was prepared by dissolving 3.6 g in 312 g of dimethylformamide. Glass cloth (WE-18K-BZ2 manufactured by Nittobo Co., Ltd.) was impregnated with this 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 heated at 170℃.
Press molding was performed for 1 hour. The physical properties of the obtained laminate are shown in Table 3 (Example 3). In addition, 80 g of bisphenol A type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., EPOMIK R-301)
Dissolve 20g of the same (EPOMIK R-140) in 20g of methyl ethyl ketone, add a solution of 4g of dicyandiamide, 15g of dimethylformamide, 0.2g of benzyldimethylamine, and methyl celeryl butane.
A varnish was prepared by mixing 15 g of the solution. A laminate was obtained in the same manner as in Example 3, except that glass cloth was impregnated with this varnish and the prepreg preparation conditions were 130° C. and 8 minutes. Its physical properties are shown in Table 4 (Comparative Example 5).

【table】

Claims (1)

[Claims] 1 General formula [I] [In the formula, R ¹ , R ³ and R ⁴ each represent a lower alkyl group, R ² represents a hydrogen atom or a lower alkyl group, R ⁵ and R ⁶ each represent a hydrogen atom,
[represents a lower alkyl group or a halogen atom]. A polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols represented by: 2 General formula [I] [In the formula, R ¹ , R ³ and R ⁴ each represent a lower alkyl group, R ² represents hydrogen or a lower alkyl group, and R ⁵ and R ⁶ each represent a hydrogen atom, a lower alkyl group or a halogen atom] . A halohydrin ether of the polynuclear polyvalent phenol is produced by reacting a polynuclear polyvalent phenol represented by the formula with epihalohydrin in the presence of a catalyst, and then a halohydrin ether of the polynuclear polyvalent phenol is produced. 1. 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 with an alkali hydroxide.