JPH0468312B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols and a method for producing the same. 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 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, as polyepoxy compounds constituting heat-resistant epoxy resin curable compositions, epoxidized phenol novolak resins, epoxidized orthocresol novolak resins, 1,
Polyglycidyl ether of polynuclear phenols such as tetraglycidyl ether of 1,2,2-tetrakis(p-hydroxyphenyl)ethane, tetraglycidyl compound of xylylene diamine, 1,
Polyglycidylated aromatic polyamines such as hexaglycidylated 3,5-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.
It cannot be used in fields where heat resistance is required, and there is a demand for the development of an epoxy resin curable composition with even better heat resistance. 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 polyepoxy compound consisting of 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 the above methods, and have thus arrived at the present invention. According to the present invention, the polyepoxy compound of the present invention comprising polyglydyl ether of polynuclear polyhydric phenols 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 outline the present invention, the present invention is based on the general formula [] [In the formula, R ¹ and R ² represent a hydrogen atom, R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ]
The gist of the material invention is a polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols represented by the general formula [] [In the formula, R ¹ and R ² represent a hydrogen atom, R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ]
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. The gist of the invention is a method for producing a polyepoxy compound comprising a polyglycidyl ether of a polynuclear polyhydric phenol represented by the general formula [], which is characterized by reacting the compound with an alkali hydroxide. The polyepoxy compound of the present invention has the general formula [] [In the formula, R ¹ and R ² represent a hydrogen atom, R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ]
This is a polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols represented by: The dihydroxyphenyl group constituting the polynuclear polyhydric phenol represented by the general formula [] is
3,4-dihydroxyphenyl group, 2,4-dihydroxyphenyl group or 2,5-dihydroxyphenyl group, and dihydroxyphenylene group is 3,4-dihydroxy-1,6-phenylene group,
It is a 2,4-dihydroxy-1,5-phenylene group or a 2,5-dihydroxy-1,3-phenylene group, and each corresponds to a catechol component unit, a resorcin component unit, or a hydroquinone 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 []
Consists of polynuclear polyvalent phenols represented by
R ¹ and R ² are each a hydrogen atom, and R ³ is a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group. Examples include alkyl groups such as phenyl groups, tolyl groups, aryl groups such as chlorophenyl groups, and halogen atoms such as fluorine, chlorine, and bromine.
R ³ may be bonded to either the ortho or para position relative to the hydroxyl group. Further, in the polynuclear polyhydric phenols represented by the above general formula [], n is an integer from 0 to 10, and it may be a mixture of two or more types of polynuclear polyhydric phenols representing these integers. More specifically, as the polynuclear polyhydric phenols represented by the general formula [] constituting the polyepoxy compound of the present invention, polynuclear polyhydric phenols represented by the following general formula [] or general formula [] are exemplified. be able to. The polyepoxy compound of the present invention is a polyglycidyl ether of polynuclear polyhydric phenols represented by the above general formula [], and usually accounts for 80% or more, preferably 90% or more, of the phenolic hydroxyl groups of the polynuclear polyhydric phenols, and 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 122 to 500 g/1 equivalent, preferably
It is in the range of 125 to 400 g/1 equivalent, and the phenolic hydroxyl equivalent is usually in the range of 1220 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 [] 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 method of the present invention, this halohydrin etherification reaction is usually 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. Partially, for example usually 40 or
By etherifying halohydrin to 80%, preferably in the range of 50 to 70%, a reaction mixture consisting of halohydrin ether of polynuclear polyhydric phenols and raw materials is obtained, and the reaction mixture is reacted with alkali hydroxide. Accordingly, it is also possible to employ a method in which the halohydrin etherification reaction and the dehydrohalogenation reaction proceed simultaneously. 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. 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.
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, dipropylene diamine, diethylaminopropylamine, menthanediamine, n-
aminoethylpiperazine, isophorodiamine,
Modifications such as 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, and cyanoethylated diethylenetriamine. Polyamide amines such as aliphatic polyamines, dimer acid/diethyleneamine condensates, dimer acid/triethylenetetramine condensates,
Aromatic amines such as 4,4'-methylene dianiline, m-phenylene diamine, xylylene diamine, aromatic modified amines such as 4,4'-methylene dianiline/phenyl glycidyl ether adduct, polysulfide resins, etc. mercaptan curing agents, acid anhydride curing agents such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and phthalic anhydride, and copolymers with acid anhydride groups such as ethylene/maleic anhydride copolymers. Examples include compounds having a phenolic hydroxyl group, such as a phenolic resin initial condensate of a combination, novolak type, or resol type, dicyandiamide, aniline/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 as follows:
The amount is generally 1 to 200 parts by weight, preferably 3 to 100 parts by weight per 100 parts by weight. In addition to the polyepoxy compound and the curing agent, the curable epoxy resin composition of the present invention may optionally include a curing accelerator, an inorganic or organic filler, a flame retardant, a heat stabilizer, an antioxidant, Various additives such as 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)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N,N'-dimethylpiperazine,
Examples include 2-ethyl-4-methylimidazole. The blending ratio of the curing accelerator is
Normally per 100 parts by weight of the polyepoxy compound
It ranges from 0.1 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 dioxide, beryllium oxide, magnesium oxide, and calcium oxide. , magnesium hydroxide, calcium hydroxide, talc, celite, metal powder, metal fiber, and the like. When any of these inorganic fillers is blended, the heat resistance properties and mechanical properties are improved. Among these inorganic fillers, heat resistance properties are further improved when glass fiber, carbon fiber, asbestos, etc. are blended, and abrasion resistance is further improved when graphite, titanium oxide, molybdenum disulfide, etc. are blended.
Arc resistance is further improved by blending mica, asbestos, glass powder, etc., electrical properties such as conductivity are improved by blending carbon black, metal fiber, metal powder, graphite, etc., and alumina, titanium oxide, oxidation etc. Adding beryllium or the like improves thermal conductivity. 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. Usually ranges from 10 to 250 parts by weight,
The amount is preferably from 30 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. 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 phthaloyl-m-phenylenediamine, nylon 66,
Polyamide fibers such as nylon 10 and nylon 12,
Polyamideimide fiber, polybenzimidazole fiber, polyethylene terephthalate, poly-1,
Polycondensation synthetic fibers such as polyester fibers such as 4-butylene terephthalate; addition polymerization synthetic fibers such as polyvinyl alcohol synthetic fibers and acrylic fibers such as polyacrylonitrile; cotton, hemp,
Examples include natural fibers such as flax, wool, and raw silk. Among organic fibrous fillers, organic synthetic fiber fillers are preferably blended, and fillers made of polycondensed synthetic fibers are particularly preferably blended, and in particular, fibrous fillers made of wholly aromatic polyamide are 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 fiber thickness of these organic fibrous fillers is usually in the range of 3 to 20μ, preferably 5 to 15μ. 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. Usually 0.1 to 1.2cm,
Preferably it is in the range of 0.3 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.
Preferably 5 to 40 parts by weight, particularly preferably
It ranges 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 phosphides and organic phosphorus compounds; inorganic antimony compounds , antimony compounds such as 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 3 to 50 parts by weight, per 100 parts by weight of the polyepoxy compound. The curable epoxy resin composition of the present invention is said to be particularly excellent in heat resistance properties such as glass transition point, heat distortion temperature, and heat elastic properties, and also excellent in mechanical properties such as bending strength, Izot impact strength, and Rockwell hardness. Due to its unique characteristics, it can be used in a wide variety of applications. Specifically, adhesives, varnishes, paints, insulating materials, prepregs, structural laminates, printed circuit laminates, switchboards, transistors,
Examples include sealing materials for ICs and 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. Note that the method for producing polynuclear polyhydric phenols used in Examples and Comparative Examples is specifically shown in Reference Examples. Reference example 1 1980 g (18 mol) of resorcin, 504 g (3 mol) of 2,6-dimethylol-p-cresol, 9 g (0.05 mol) of p-toluenesulfonic acid, ethanol
4500g was put into a reactor and reacted under reflux for 4 hours. Then, the mixture was concentrated to remove ethanol under a reduced pressure of 300 mmHg, and the contents were poured into water 26 to precipitate the product. This is filtered, washed with water, dried and made into resin.
Obtained 740g. The melting point of this resin determined using a microscope is 128-135
℃, and the number average molecular weight Mn of this resin determined by gel permeation chromatography is
It was 360. The IR spectrum of this compound has
^Phenolic OH, 1600 and
A characteristic absorption of aromatic groups was observed near 1500 cm ^-1 and a characteristic absorption of methyl groups was observed near 1450 cm ^-1 . Table 1 also shows the results of ^H1 nuclear magnetic resonance spectra measured by dissolving this resin in dimethyl sulfoxide- _d6 .

[Table] From the above results, it was confirmed that this resin had the following structure. Reference Example 2 In Reference Example 1, 2,6-dimethylol-p-
2750 g of resin was obtained in the same manner as in Reference Example 1 except that 1512 g (9 mol) of cresol was used. The melting point of this resin determined by microscopy is 157-172°C, and the number average molecular weight ( Mn ) determined by gel permeation chromatography is:
900, degree of polymerization n is 2, molecular weight distribution ( M w / M n)
was 1.42. In the ^H1 nuclear magnetic resonance spectrum measured by dissolving this resin in dimethyl sulfoxide- _d6 , peaks were observed at the positions listed in Table 1, except that the line width of the peaks became broader. From these results, it was confirmed that this resin had the following structure. Reference Examples 3 to 4 The same procedure as in Reference Example 1 was performed except that hydroquinone and catechol were used instead of resorcinol in Reference Example 1, and the results shown in Table 2 were obtained. Further, structural analysis was performed in the same manner as in Reference Example 1, and it was confirmed that the structure was one in which hydroquinone or catechol and p-cresol skeleton were bonded through a methylene group.

[Table] Reference Examples 5 to 8 In Reference Example 2, 2,6-dimethylol-p-
2,6-dimethylo-p-tert instead of cresol
-butylphenol, 2,6-dimethylol-p
The results shown in Table 3 were obtained in the same manner as in Reference Example 2, except that -chlorophenol, 2,6-dimethylolphenol, and 2,6-dimethylol-p-phenylphenol were used as shown in Table 3. In addition, structural analysis was performed in the same manner as in Reference Example 2, and resorcin and p-tert-butylphenol skeletons,
It was confirmed that the p-chlorophenol skeleton or phenol skeleton was alternately bonded with methylene groups to form a linearly connected structure.

[Table] Reference Example 9 In Reference Example 2, 2,6-dimethylol-p-
2,6-di(1-chloropropyl)-4-methylphenol 2241g (9 moles) instead of cresol
The resin was prepared in the same manner as in Reference Example 2 except that
Obtained 3000g. The number average molecular weight ( Mn ) determined by gel permeation chromatography is
1000, degree of polymerization n is 2, distribution amount distribution ( M w / M n)
was 1.40. Further, structural analysis was performed in the same manner as in Reference Example 1, and it was confirmed that resorcinol and p-cresol were bonded through an isopropylidene group. Example 1 615g of resin obtained by the method shown in Reference Example 1
(1.7 mol), 4023 g (43.5 mol) of epichlorohydrin, 57.2 g (0.26 mol) of a 50% aqueous solution of tetramethylammonium chloride, and 64 g of water were placed in a reactor.
The reaction was carried out at 90° C. for 4 hours while stirring. To this was added dropwise 798 g (9.6 mol) of a 48% caustic soda aqueous solution 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, maintaining the water concentration in the reaction mixture at about 2%. After the reaction, the reaction mixture was poured into 2250 ml of water, thoroughly stirred, and the organic layer was washed and separated. Furthermore, 2250 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, filtered, and the liquid was further concentrated to obtain 960 g of epoxy resin. The number average molecular weight ( Mn ) of this resin determined by gel permeation chromatography is
1120, the molecular weight distribution ( Mw / Mn ) was 1.42, the melting point measured by microscopy was 53-58°C, and the epoxy equivalent determined by the hydrochloric acid/dioxane method was 150 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 new absorption around 840 cm ^-1 and 900 cm ^-1 was observed. Characteristic absorption of epoxy groups was observed in , confirming that the resin of Reference Example 1 was glycidyl etherified. In addition, this resin was dissolved in CDCl ₃ and measured.
The following structure was confirmed from H nuclear magnetic resonance spectrum.

[Table] Examples 2 to 6 The procedure was carried out in the same manner as in Example 1, except that the resins obtained by the methods of Reference Example 2, Reference Example 5, Reference Example 6, Reference Example 7, and Reference Example 8 were used as shown in Table 5. Ivy. The characteristic values of the obtained resin were measured in the same manner as in Example 1 and are shown in Table 5. In addition, the IR spectra of these resins and _the
From the H nuclear magnetic resonance spectrum, resorcinol and p-cresol, p-tert-butylphenol, p-chlorophenol, phenol, and p-phenylphenol skeletons are alternately bonded with methylene groups and connected, resulting in epoxidation. It was confirmed that the structure was

[Table] Examples 7-8 The same procedure as in Example 1 was carried out except that the resins obtained by the methods of Reference Examples 3 and 4 were used. Further, the characteristic values of the obtained resin were measured in the same manner as in Example 1, and are shown in Table 6. In addition, the IR spectra of these resins and _the
From H nuclear magnetic resonance spectroscopy, it was confirmed that the hydroquinone, catechol, and p-cresol skeletons were connected by methylene groups and had an epoxidized structure.

[Table] Example 9 The same procedure as Example 1 was carried out except that the resin obtained by the method of Reference Example 9 was used. In addition, the characteristic values of the obtained resin were measured in the same manner as in Example 1, and M n was
1300, Mw / Mn was 1.50, melting point was 80-85°C, and epoxy equivalent was 180. Example 10, Comparative Example 1 150 g of the 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, and then
It was cured by heating at 150°C for 4 hours. The physical properties of the obtained molded product were measured and the results shown in Table 7 were obtained (Example
Ten). In addition, commonly used bisphenol A
Type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd.,
The physical properties of the molded product were measured in the same manner as in Example 8 except that 190 g of EPOMIK R-140) was used. The results are also shown in Table 7 (Comparative Example 1).

[Table] Examples 11-18 The same procedure as Example 10 was carried out except that the resins obtained by the methods of Examples 2-9 were used as shown in Table 8. The physical properties of the obtained molded product were measured and the results shown in Table 8 were obtained.

[Table] Comparative Examples 2 to 4 The same procedure as in Example 10 was carried out except that a commercially available heat-resistant epoxy resin was used as shown in Table 9. The physical properties of the obtained molded product were measured and the results shown in Table 9 were obtained.

[Table] Example 19, Comparative Example 5 688 g of epoxy resin obtained by the method of Example 2, 37 g of dicyandiamide, benzyldimethylamine
A varnish was prepared by dissolving 2.1 g in 373 g of dimethylformamide. A 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 10 (Example 19). In addition, bisphenol A type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., EPOMIK R-301) 80
A varnish was prepared by dissolving 20 g of EPOMIK R-140 in 20 g of methyl ethyl ketone, and mixing with this a solution of 4 g of dicyandiamide and 15 g of dimethylformamide, and a solution of 0.2 g of benzyldimethylamine and 15 g of methyl cellosolve. The same procedure as in Example 10 was carried out except that glass cloth was impregnated with this varnish and the prepreg preparation conditions were 130° C. and 8 minutes. The physical properties of the obtained laminate are shown in Table 10 (Comparative Example 5).

【table】

Claims (1)

[Claims] 1. General formula [] [In the formula, R ¹ and R ² represent a hydrogen atom, R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ]
A polyepoxy compound consisting of polyglycidyl ether of polynuclear polyhydric phenols represented by: 2 General formula [] [In the formula, R ¹ and R ² represent a hydrogen atom, R ³ represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ]
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. A method for producing a polyepoxy compound comprising a polyglycidyl ether of a polynuclear polyhydric phenol represented by the general formula [], characterized by reacting the polyglycidyl ether of a polynuclear polyhydric phenol with an alkali hydroxide.