JPS59157113A - Polyepoxy compound, its manufacture and use - Google Patents

Abstract

NEW MATERIAL:A polyepoxy compound composed of polynuclear polyhydric phenol polyglycidyl ether of formula I (R<1>, R<3>, and R<4> are each lower alkyl; R<2> is H or lower alkyl; R<5> and R<6> are each H, lower alkyl or halogen). EXAMPLE:A compound of formula II. USE:Curing agent incorporation will result in an epoxy resin-curable composition of high heat resistance, which is used in the manufacture of laminates for printed circuit. PREPARATION:A polynuclear polyhydric phenol of formula I and an epihalohydrin are made to react in the presence of a catalyst (e.g., NaOH, propylamine) to form a halohydrin ether of said phenol followed by reaction of the ether with an alkali hydroxide, thus obtaining the objective polyepoxy compound.

Description

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

Conventionally, various compounds have been proposed as polyepoxy compounds used in epoxy resin curable compositions. Recently, in fields such as molding materials, festivals, printed circuit laminates, and advanced composite materials (ACM), there has been a demand for curable epoxy resin compositions with excellent heat-resistant properties such as glass transition temperature, heat distortion temperature, and heat-resistant elastic properties. has been done. Conventionally, polyepoxy compounds constituting heat-resistant epoxy resin cured compositions include epoxidized phenol novolac resins, epoxidized orthocresol novolak trakis(p-hydroxyphenyl)ethane tetraglycidyl ether, and other polynuclear phenolic polyesters. Polyglycidylated aromatic polyamines such as glycidyl ether, diglycidylated xylylene diamine, hexaglycidylated R3,5-triaminomethylbenzene, and triglycidylated -(socyanuric acid) are widely used. However, the curable epoxy resin 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 epoxy resin curable 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, developed a polyglycidyl 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 an epoxy compound, and have arrived at the present invention. According to the present invention, the polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols of the present invention is a new compound,
The epoxy resin curable composition comprising the polyepoxy compound and curing agent has particularly excellent heat resistance properties such as glass transition temperature, heat distortion temperature, and heat elastic properties, and has excellent mechanical properties such as bending strength, Izod impact strength, and Rockwell hardness. It also has the characteristics of being excellent.

To summarize the present invention, the present invention is based on the general formula (1)
5 and R6 each represent a hydrogen atom, a lower alkyl group or a halogen atom. The gist of the invention is a polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols represented by the general formula [1] [wherein R, R and R each represent a lower alkyl group, and R is It represents a hydrogen atom or a lower alkyl group, and R and R each represent a hydrogen atom, a lower alkyl group, or a halogen atom. ] 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 a polyepoxy compound consisting of a polyglycidyl ether of a polynuclear polyhydric phenol represented by the general formula [1], which is characterized by reacting an ether with an alkali hydroxide, and further, (a
) General formula [1] [In the formula, R1, R3 and R4 each represent a lower alkyl group, R represents a hydrogen atom or a lower alkyl group, and R and R each represent a hydrogen atom, a lower argyl group or a halogen atom . The gist of the invention is an epoxy resin curable composition comprising a polyethylene 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 general formula (1) [in the formula
R1, R6 and R4 each represent a lower alkyl group, R represents a hydrogen atom or a lower alkyl group, and R and R each represent a hydrogen atom, a lower alkyl group or a halogen atom. ] It is a polyepoxy compound consisting of polyglycidyl ether of polyhydric phenols. The polynuclear polyhydric phenol represented by the general formula [1] 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, R and R4 each represent a lower alkyl group such as a methyl group, an ethyl group-propyl group, or a butyl group, and R2 represents a hydrogen atom or a methyl group, an ethyl group, a propyl group, or a butyl group. R and R each represent a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a halogen atom such as fluorine, chlorine, bromine, or iodine. Specifically, the polynuclear polyhydric phenols represented by the general formula [1] include 2,4.4-)rimethyltV-2-(2,4-dihydroxyphenylated)v)-
7-Hydroxychroman, 2,4.4-)diethyl-
3-Methyl-2-(2,4,4-dihydroxyphenyl)-7-hydroxychroman, 2.4.4-)IJ
n-propyl-5-ethyl-2-(2,4-dihydroxyphenyl)-7-hydroxychroman, 2.4°4-
trimethy/L/-2-(6-methy)v-2,4-dihydroxypheni)V)-7-hydroxychroman, 2,
4.4-trimethy/I/-2-(6-chloro-2,4-
dihydroxyphenyl)-7-hydroxychroman, 2
Examples include 1414-trimethyl-2-(6-bromo-2,4-dihydroxyphenyl)-7-hydroxychroman.

The polyepoxy compound of the present invention is a polyglycidyl ether of a polynuclear polyhydric phenol represented by the general formula (1), and usually 80% or more, preferably 90% or more of the heptaenolic hydroxyl groups of the polyhydric phenol, Particularly preferred is a polyepoxy compound in which 95% or more of the compound is glycidyl etherified. Here, glycidyl ether refers to the glycidyl ether represented by the general formula (1), which is formed by the reaction of one molecule of shrimp halohydrin with one phenolic hydroxyl group of the polynuclear polyhydric phenol; It may be a mixture of glycidyl ethers represented by general formula (III) formed by further reaction of the hydroxyl group and the produced glycidyl ether. 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 14
0 to 300 g/l equivalent, preferably 155 to 2
The phenolic hydroxyl equivalent is usually in the range of 1400 g/l equivalent, and the phenolic hydroxyl equivalent is usually in the range of 1400 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 [I] with shrimp halohydrin 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 shrimp halohydrin used in the method of the present invention include epichlorohydrin, shrimp bromohydrin, shrimp bromohydrin, and the like.

The proportion of the shrimp halohydrin 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, 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. Tertiary amines such as amines, triethylamine, tripropylamine, tributylamine, tetramethylammonium chloride, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium chloride, tetrabutylammonium chloride Monium, benzyltrimethylammonium chloride,
Quaternary ammonium salts such as benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, choline chloride, amine salts such as trimethylamine [acid acid], lyethylamine hydrochloride, dimethylamine hydrobromide, diethylamine hydrochloride, etc. I can give an example. The usage ratio of these catalysts is as follows:
The amount is usually 0.005 to 5 mol, preferably 0.01 to 1 mol, based on the molar equivalent.

In the method of the present invention, this halohydrin etherification reaction is usually carried out at a temperature of 50 to 110°C, preferably 70 to 100"C. In this hydrin etherification reaction step, the polynuclear polyhydric phenol It is also possible to adopt a method in which the phenolic hydroxyl groups of the polyhydric phenols are almost completely converted into halohydroline ether, or the phenolic hydroxyl groups of the polynuclear polyhydric phenols are partially converted, for example, usually from 40 to 80%, preferably from 50 to 80%. 70
By etherification of halohydrin in the range of %
A reaction mixture consisting of a halohydrin ether of a polynuclear polyhydric phenol and a raw material is obtained, and the reaction mixture is reacted with an alkali hydroxide to simultaneously advance a halohydrin etherification reaction and a dehydrohalogenation reaction. method can also be adopted.

In the method of the present invention, the dehydrohalogenation reaction of the halohydrin ether is carried out in the presence of an alkali hydroxide. Specifically, as alkali hydroxide, hydroxide)
Examples include IJium, potassium hydroxide, lithium hydroxide, etc., and it is preferable to use IJium hydroxide. The ratio of alkali hydroxide used is usually 0.80 to 1.2 mol, preferably 1 mol equivalent of pheno-p hydroxyl group of the polynuclear polyhydric phenol as the raw material supplied to the halohydrin etherification reaction step. 0.95
The range is from 1 to 1.1 moles. The dehydrohalogenation reaction of the halohydrin ether is preferably carried out while removing the water produced in the reaction from the reaction system, and the method for removing water is to co-produce the produced water with the epihalohydrin 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 epihalohydrin phase, remove the aqueous phase, and circulate the epihalohydrin phase to the reaction system.

Part 2. The dehydrohalogenation reaction of hydrin ether can be carried out in one step, or can 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 helohydrin etherification reaction step, and 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 70 to 110°C, preferably 80 to 1
It is carried out at a temperature of 00"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.

The method includes conventional methods, such as converting unreacted alkali hydroxide in the reaction mixture into phosphoric acid, alkali phosphate,
After neutralization with an aqueous solution such as acetic acid, the subite salt is removed by extraction, adsorption or filtration, and the solvent is removed by distillation to obtain the polyglycidyl ether of the polynuclear polyhydric phenol.

The polyepoxy compound of the present invention can be used in epoxy resin curable compositions by blending it with a curing agent.Epoxy resins have conventionally been used as hardening agents to be blended into the epoxy resin curable composition of the present invention. Any compound known as a curing agent for resins can be used, for example, linear aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylene diamine, diethylaminopropylamine, etc. , menthanediamine, N-amine ethylpiperazine, isophoro/diamine, cycloaliphatic polyamines such as 1,3-diaminocyclohexane, and aliphatic polyamithiadact-diethylenetriamine such as adducts of diethylenetriamine and ethylene oxide or propylene oxide. Ketoimines such as condensates with acetone, modified aliphatic polyamines such as diaminoethylated diethylenetriamine, polyamide amines such as dimer acid/diethylenetriamine condensates, dimer acid/triethylenetetramine condensates, 4,4'-methylene dianiline, Aromatic amines such as m-phenylene diamine and xylylene diamine, aromatic modified amines such as 4,4'-methylene dianiline and phenylglycidyl-ether adducts, and mercapsilanes such as polyester resins. yXW inhibitor, anhydrous Hekizahydrophta!
phosphoric acid, methyltetrahydrophthalic anhydride, anhydrous lid) V
Acid anhydride curing agents such as acids, copolymers with acid anhydride groups such as ethylene/maleic anhydride, compounds with phenolic hydroxyl groups such as novolac type or resol type phenolic resin initial condensates, dicyandiamide , aniline formaldehyde resin, melamine resin, urea resin and the like.

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, preferably 1 to 100 parts by weight, per 100 parts by weight of the polyepoxy compound.

In addition to the polyepoxy compound 1 and the curing agent, the curable epoxy resin composition of the present invention includes, if necessary, a curing accelerator, an inorganic or organic filler, a heat retardant, a heat stabilizer,
Various additives such as 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-(
dimethylaminomethy)v) phenol, 2.4.6-
) Lis(dimethylaminomethyl)phenol, N, N
Examples include '-dimethylpiperazine, 2-ethylv4-methylimidazole, and the like.

The blending ratio of the curing accelerator is as follows:
It is usually in the range of o, i to 1Q parts by weight, preferably 1 to 5 parts by weight per 00 parts by weight.

Specifically, inorganic fillers include silica, silica a/remina, alumina, glass powder, glass beads, glass a
m, asbestos, mica, graphite, carbon fiber, titanium oxide, molybdenum disulfide, beryllium oxide, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, Ri/Lev, celite, metal powder,
Examples include metal fibers. When any of these inorganic fillers is blended, the heat resistance properties and mechanical properties are improved. Among these inorganic fillers, the heat resistance properties are further improved by adding glass fiber, carbon fiber, asbestos, etc., and graphite, titanium oxide,
Addition of molybdenum disulfide, etc. further improves wear resistance, addition of mica, asbestos, glass powder, etc. further improves arc resistance, and addition of carbon black, metal fiber, metal powder, graphite, etc. Electrical properties such as conductivity are improved, and when alumina, titanium oxide, beryllium oxide, etc. are 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 usually 1 to 250 parts by weight, preferably 30 to 200 parts by weight, and particularly preferably 6Q 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 fillers include polyterephthaloyl-p-phenylenediamine, polyterephthaloyl-p-phenylenediamine, polyterephthaloyl-p-phenylenediamine, polyterephthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, and polyisophthaloyl-p-phenylenediamine. Fully aromatic polyamides such as '-m-phenylenediamide 7, polyamide fibers such as nylon 66, nylon 6, nylon 10, and nylon 12, polyamideimide I
#iM, Polycondensation type synthetic fibers such as polyester fibers such as polybenzimidazole fibers, polyethylene terephthalate and poly-1,4-butylene terephthalate; Acrylic) L/based woven fibers such as polyvinyl alcohol type synthetic fibers and polyacrylonitrile. Addition polymerization type synthetic fibers; natural fibers such as cotton, hemp, flax, wool, and raw silk can be exemplified. 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 in the range of 2 to 20 microns, preferably 5 to 15 microns. 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 m, preferably from 0.6 to 0.6α. The blending ratio of the organic fibrous filler is generally 1 to 60 parts by weight, preferably 5 to 40 parts by weight, and particularly preferably 10 to 30 parts by weight, based on 100 parts by weight of the polyepoxy compound. 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. Form by stacking multiple sheets and pre-curing as necessary,
A laminate consisting of the composition of the present invention can be obtained. 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 IIi phenols, halogenated aromatic carboxylic acids or their acid anhydrides, halogenated novolac-type phenols Organic halogen compounds such as resins and halogenated epoxy novolak type phenolic resins; boron compounds; phosphorus compounds such as inorganic phosphorus compounds and organic phosphorus compounds; antimony compounds such as inorganic antimony compounds and organic antimony compounds; bismuth compounds; arsenic compounds, etc. can do. The blending ratio of the flame retardant is usually 1 to 1 part by weight per 100 parts by weight of the polyepoxy compound.
00 parts by weight, preferably in the range of 1 to 50 parts by weight.

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 insulation properties, and also has 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, varnishes, paints, insulating materials, laminates, printed circuit laminates, switchboards, sealing materials for transistors, ICs, LSIs, etc., molding materials for switches, connectors, washers, bearings, etc. There are many examples of sliding materials.

Next, the present invention will be specifically explained using examples. In addition, the manufacturing method of polynuclear polyvalent phenol/I/ used in Examples and Comparative Examples is specifically shown in Reference Examples.

Reference example Lusorcin 1100g (10mol), 36% hydrochloric acid 100ml
1 (L2 mol) and 800 ml of methanol were placed in a reactor and heated to 50°C. 232 g of acetone (4 mol/I/) was added dropwise to this over 2 hours.
An hr reaction was performed. Thereafter, the reaction mixture was poured into water 6e to precipitate a product, which was washed with water 24. After filtering the product, it was vacuum dried at 60° C. overnight to obtain 629 g of white powder.

The melting point of this compound determined by microscopy is 235-23
7”C, and the molecular weight is 300 according to spectrum measurement.
It turned out to be. In the IR spectrum of this compound, characteristic absorptions of 7 enolic OH near the 55DD fraction, an aromatic nucleus near 1600 and 1500 cIc1, and a methyl group near 1450 m-1 were observed. In addition, the following structure was confirmed from the 1H nuclear magnetic resonance spectra (1H nuclear magnetic resonance spectra) obtained by dissolving this compound in a7-d6.

NMR (CD3COCD, middle ■ point (ppm, TMS standard) Attribution 0.
80 (S, 3H) al, 20
(S, 3H) bl, 65 (S,
3H) 1.85 (d, Jd, o=13cps, IH),,
d2.95 ((1, Je, d”13cps, 1H)
e6.30 (d, Jg, f=3cp8.IH)
g6.35 ((L, Jk, J=7cps, IH)
h6.40 (S, IHJ
16.95 (d, Jj, h==7cps, IH)
j7.00 (d, Jk, f=7cps, IH)
k8, '15 (S, IH)
18.18 (S, IH)
, m8.45 (S, IH)
n Reference Example 1 600 g (2 moles) of the compound obtained by the method shown in Reference Example 1, 2775 g (30 moles) of epichlorohydrin,
Tetramethylammonium chloride 50% aqueous solution 39.
4mA! CD, 18% L) and 47.8 g of water were placed in a reactor and reacted at 90° C. for 4 hours with stirring.

Add to this 550 g (6.6 moles) of 48% caustic soda aqueous solution.
was added dropwise over 1.5 hours. During this time, the condensed vapor □,
At 11 (δ, F), the upper aqueous layer was removed, the lower layer was extracted, and the 1 rhydrin layer was returned to the reactor to reduce the water concentration of the reaction mixture to about 2%.

After the reaction, the reaction mixture was poured into 2,400 $ of water, thoroughly stirred, and the second layer was washed and separated. more water 2
4 [10e] was added and thoroughly stirred, and the organic layer was washed. After separating the organic J, it was neutralized by adding 24 [] mg of a 77% aqueous sodium phosphate solution.The organic layer was heated and dehydrated, then filtered, and the p solution was further concentrated to obtain Evo-A. 960g was obtained.

The number average molecule 11 (Mn) of this resin determined by gel permeation chromatography is 870, and the molecule it
The distribution (yw/un) was 1.14, the melting point measured by the Class 2 mirror method was 39-41 VQ, 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 groups and methyl groups shown in Reference Example 1, 35
Absorption of phenolic OH around 00oi disappears,
A characteristic absorption of epoxy groups was newly observed near 34QOI+ and 900 cm2, and it was confirmed that the phenolic hydroxyl groups were glycidyl etherified.

Also, use this resin as cpcA! 1 measured by dissolving in 6
H nuclear magnetism, gas resonance spectroscopy)/The following structure was confirmed.

■ ■ Table 1 Example 2, Comparative Example 1 166 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 cured by heating at 100°C for 2 hours and then 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 epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., EPOMIK R
-140) The physical properties of the molded product were evaluated in the same manner as in Example 2 except that 190 g was used. The results are also shown in Table 2 (Comparative Example 1).

Table 2 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 6 were obtained.

Example 6, Comparative Example 5 819 g of epoxy resin obtained by the method of Example 1.

A varnish was prepared by dissolving 65.1 g of dicyandiamide and 3.6 g of benzyldimethylamine in 312 g of dimethylformamide. Glass cloth (W manufactured by Nittobo Co., Ltd.)
A prepreg was prepared by impregnating E-18 with -BZ 2) and drying at 140"C for 4 minutes. This prepreg was
The laminate was then laminated with two copper foils on both sides and press-molded at 170"C for 1 hour. The physical properties of the resulting laminate are shown in Table 3 (Example 3).

In addition, 8 g of bisphenol/l/A type epoxy resin (manufactured by Mitsui Petrochemical Ephoxy Co., Ltd., EPOMIK R-301 and 20 g of the same (EpoMzx R-140) were dissolved in 20 g of methyl ethyl ketone, and 4 g of dicyandiamide was added to the solution. A varnish was prepared by mixing a solution of 15 g of formamide, 0.2 g of pencil dimethylamine, and 15 g of methyl celerol. Glass cloth was impregnated with this varnish, and prepreg preparation conditions were set to 16
A laminate was obtained in the same manner as in Example 6 except that the temperature was 0°C for 8 minutes. Its physical properties are shown in Table 4 (Comparative Example 5).

Table 4 Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (3)

[Claims] (1) General formula [1] H [In the formula, R1, R3 and R4 each represent a lower alkyl group, R2 represents a hydrogen atom or a lower alkyl group, and R5 and R6 each represent a hydrogen atom, a lower alkyl group or a halogen Indicates an atom. ] A polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols. (2) General formula (1) [In the formula, R1, R6 and R4 each represent a lower alkyl group, R represents hydrogen or a lower alkyl group, and R5
and R6 each represent a hydrogen atom, a lower alkyl group or a halogen atom. ] By reacting the polynuclear polyhydric phenol represented by the formula with epihalohydrin in the presence of a catalyst, the halohydrin ether of the polynuclear polyhydric phenol is produced, and then the halohydrin ether of the polynuclear polyhydric 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 the polyglycidyl ether with an alkali hydroxide. (3) (a) General formula [1] [In the formula, R1, R3 and R4 each represent a lower alkyl group, R represents a hydrogen atom or a lower alkyl group,
R5 and R6 each represent a hydrogen atom, a lower alkyl group or a halogen atom. An epoxy resin curable composition comprising a polyepoxy compound comprising a polyglycidyl ether of a polynuclear polyhydric phenol represented by the following formula, and (b) a curing agent.