JPS6331493B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel epoxy resin composition with excellent heat resistance, water resistance, and weather resistance. The epoxy resin currently most widely used in industry is the epi-bis type epoxy resin, which is produced by the reaction of bisphenol A and epichlorohydrin. This resin can be used in a wide variety of products ranging from liquids to solids, and has the advantage that the epoxy group has high reactivity and can be cured with polyamines at room temperature. However, although the cured product has excellent water resistance and is strong, it has drawbacks such as poor weather resistance, poor electrical properties such as tracking resistance, and low heat distortion temperature. Especially recently, super LSI
Epoxy resin made by reacting phenol or novolac resin with epichlorohydrin is used as sealing resin, but the resin contains several hundred ppm of chlorine.
This has caused problems such as deterioration of the electrical characteristics of electronic components. Alicyclic epoxy resins are examples of epoxy resins that do not contain chlorine and have excellent electrical properties and heat resistance. These are produced by epoxidation reaction of compounds having a 5-membered or 6-membered cycloalkenyl skeleton. The epoxy groups of these resins are so-called internal epoxy groups, and are usually cured by heating with acid anhydrides, but cannot be cured at room temperature with polyamines because of their low reactivity. Therefore, the range of use of alicyclic epoxy resins is extremely narrow. As alicyclic epoxy resins, those having the structures () and () are industrially produced and used. () is used as a heat-resistant epoxy diluent because of its extremely low viscosity, but it is highly toxic.
There are problems such as severe skin irritation of workers. () contains few impurities and has a low hue, and its cured product has a high heat deformation temperature and has a problem of poor water resistance due to the ester bond. Furthermore, since both () and () are low-viscosity liquid epoxy resins, solid epoxy resin molding systems such as transfer molding cannot be applied. In view of these problems, the present inventors conducted intensive research to develop a new epoxy resin, and as a result, they found that it is an alicyclic type, can be in any state from liquid to solid, and has excellent water resistance and heat resistance. and found an epoxy resin composition having excellent reactivity,
The present invention has now been accomplished. That is, the present invention comprises an epoxy resin represented by the following general formula, a curing agent, and optionally a filler.
This invention relates to a novel epoxy resin composition characterized by containing a flame retardant and various other additives. However, R ₁ is a monovalent or higher alcohol having 1 active hydrogens or an unsaturated compound residue having a hydroxyl group. n ₁ , n ₂ . . . n _l is 0 or an integer of 1 to 100, and the sum thereof is 1 to 100. l represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent X, and is represented by the following formula. The substituent X is

【formula】

( _R2 is H, alkyl group, alkylcarbonyl group,
any one of the arylcarbonyl groups), but

The resin represented by () contains one or more of the following formulas: Next, the present invention will be explained in detail. In the novel epoxy resin represented by the formula () of the present invention, R ₁ is a monohydric or more alcohol having l active hydrogens or an unsaturated compound residue having a hydroxyl group, but the precursor active hydrogen is Examples of the organic substances include alcohols, phenols, carboxylic acids, amines, and thiols. The alcohol may be a monohydric alcohol or a polyhydric alcohol. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol,
Aliphatic alcohols such as octanol, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3
Butanediol, 1,4 butanediol, pentanediol, 1,6 hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, Examples include polyhydric alcohols such as pentaerythritol and dipentaerythritol. Further, the compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples include allyl alcohol, acrylic acid, and methacrylic acid. The unsaturated double bonds of these compounds may also have an epoxidized structure. n ₁ , n ₂ ... n _l in general formula () is 0 or 1
~100, and the sum thereof is 1 to 100, but if it exceeds 100, it becomes a resin with a high melting point and is difficult to handle, making it practically unusable. l is an integer from 1 to 100. Among the substituents X of A in formula (),

Must include at least one [formula] Although it is

The more [formula] there are, the better. On the contrary

[Formula] is preferably as small as possible. That is, in the present invention, the substituent X is

[Formula] is the main one. Specifically, the novel epoxy resin represented by the formula () of the present invention is a polyether resin obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide using an organic compound having active hydrogen as an initiator. That is, it can be produced by epoxidizing a polycyclohexene oxide polymer having a vinyl group side chain with an oxidizing agent such as a peracid. 4-Vinylcyclohexene-1-oxide can be obtained by partially epoxidizing vinylcyclohexene obtained by dimerization of butadiene with peracetic acid. It is preferable to use a catalyst when 4-vinylcyclohexene-1-oxide is polymerized in the presence of active hydrogen. Examples of catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine; organic bases such as pyridines and imidazoles; organic acids such as formic acid, acetic acid, and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; and sodium methylate. alcoholates of alkali metals, alkalis such as KOH and NaOH, Lewis acids such as BF ₃ , ZnCl ₂ , AlCl ₃ and SnCl ₄ or their complexes, and organometallic compounds such as triethylaluminum and diethylzinc. Can be done. These catalysts can be used in an amount of 0.01 to 10%, preferably 0.1 to 5%, based on the reactants. Reaction temperature is -70~200℃, preferably -30℃
~100℃. The reaction can also be carried out using a solvent. A solvent containing active hydrogen cannot be used. That is, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic solvents such as benzene, toluene, and xylene, as well as ethers, aliphatic hydrocarbons, esters, and the like can be used. Now, in order to epoxidize the polycyclohexene oxide polymer having vinyl group side chains synthesized in this way and to produce the new epoxy resin of the formula () of the present invention, either peracids or hydroperoxides are used. Can be used. As peracids, performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, etc. can be used. Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability. Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide,
Cumene peroxide etc. can be used. A catalyst can be used during epoxidation if necessary. For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxides, the catalytic effect can also be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. . The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, olefin bonds can be epoxidized and substituents in the raw materials can be

[Formula] and generated substituents

[Formula] causes a side reaction with an epoxidizing agent, etc., resulting in a modified substituent, which is included in the target compound. Substituent in target compound

[Formula] Substituent

[Formula] and the ratio of the three modified substituents are determined by the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the olefin bond, and the reaction conditions. For example, when the epoxidizing agent is peracetic acid, the modified substituent mainly has the structure shown below, and is generated from the generated epoxy group and by-produced acetic acid. The target compound can be taken out from the reaction crude solution by ordinary chemical industrial means such as concentration.
Furthermore, the epoxy resin used in the present invention can be mixed with other epoxy resins as long as the properties of the composition are not impaired. Here, other epoxy resins may be any commonly used epoxy resins, such as epibis epoxy, bisphenol F epoxy, novolac epoxy, alicyclic epoxy, and epoxy resins such as styrene oxide and butyl glycidyl ether. Contains diluent. As the curing agent used in the present invention, curing agents used in known epoxy resins can be used, including amines, polyamide resins, acid anhydrides, polymercaptan resins, novolac resins, dicyandiamide,
This includes amine complexes of boron trifluoride. Here, the amines include the following. Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, menzendiamine, metaxylylenediamine, bis(4-amino-3-methylcyclohexyl)methane, adducts of the aliphatic polyamines with known epoxy compounds, and reactions with acrylonitrile. substances, reactants with ketones. Aromatic polyamines such as metaphenylene diamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl sulfide, and adducts of the aromatic polyamines and known epoxy compounds. tris(dimethylaminomethyl)phenol,
Secondary and tertiary amines and salts thereof such as piperidine, imidazole and derivatives thereof. and mixtures of the aforementioned amines. Polyamide resins include reactants of fatty acids, such as fatty acids, dimer acids, trimer acids, and aliphatic polyamines. Acid anhydrides include the following: Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, Acid anhydrides such as succinic anhydride, dodecenylsuccinic anhydride, succinic anhydride, and mixtures of the above acid anhydrides. Novolac resins include low molecular weight resinous products made by the condensation of phenols or mixtures of phenols and cresols, dihydroxybenzenes, and formaldehyde. Amine complexes of boron trifluoride include complexes of boron trifluoride and low molecular weight amine compounds such as monoethylamine, piperidine, aniline, butylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, tributylamine, and triethanolamine. It will be done. In addition, other hardening agents include boron tetrafluoride,
There are salts such as diazonium salts, iodonium salts, bromonium salts, and sulfinium salts of super strong acids such as phosphorus hexafluoride and arsenic hexafluoride. Also, among these curing agents, aliphatic polyamines, aromatic polyamines,
Polyamide resins and polymercaptan resins can be used as a mixture in any proportion, and can be used alone or in combination with a curing accelerator for the purpose of adjusting the curing rate. Here, the aforementioned secondary and tertiary amines can be used as the curing accelerator. The acid anhydride can be used as it is, but a curing catalyst and a curing accelerator can also be used together for the purpose of adjusting the curing rate and improving the physical properties of the cured product.
Here, the curing catalysts are the aforementioned secondary and tertiary amines and tin octylate. Curing accelerators include water, alcohols such as ethanol, propanol, isopropanol, cyclohexanol, and ethylene glycol, carboxylic acids such as acetic acid, propionic acid, succinic acid, and hexahydrophthalic acid, and active hydrogen such as ethylenediamine and diethylenetriamine. They are amines. The novolak resin can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines. Dicyandiamide can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines. The amine complex of boron trifluoride can be used alone or in combination with a curing rate regulator for the purpose of adjusting the curing rate. Here, any curing rate regulator may be used as long as it can be used in conventional epoxy resins, but specific examples include carboxylic acids, amines, acetylacetone complexes of metals, metals such as titanium, tin, etc. These include organometallic compounds, glycols, organoboron compounds, etc. The filler used in the present invention may be anything as long as it can be used as a filler for resin, but specific examples include silica sand, silica, alumina,
These include diatomaceous earth, calcium carbonate, asbestos, glass, magnesium carbonate, kaolin, metal powder, etc. Various shapes can be used, such as fibrous, flake, etc. Any flame retardant may be used as long as it can be used as a flame retardant for resins, but specific examples include halides such as tetrabromobisphenol A, hexabromobenzene, tris(dibromopropyl) phosphate, and trischloro. Examples include phosphorus compounds such as ethyl phosphate, antimony trioxide, etc. Various other additives can be used in combination depending on the purpose, such as thixotropy imparting agents such as Aerosil and Olben, conductivity imparting agents such as carbon black, etc.
There are mold release agents, lubricants, dyes, pigments, coupling agents, flexibility agents, plasticizers, etc., and they can also be used after being diluted with a solvent. By molding and curing the resin composition obtained in this way, a cured product with excellent mechanical properties such as tensile strength and hardness, electrical properties such as tracking resistance and arc resistance, and heat distortion temperature and low corrosivity can be obtained. Encapsulants for electronic parts, encapsulants for light emitting diodes, insulating varnishes for motors, transformers, etc., fiber-reinforced plastics, adhesives, powder coatings, electrodeposition coatings, printed circuit boards, cast materials, moldings. It can be used for things etc. The present invention will be further explained in detail by giving examples below. Synthesis example 1 Allyl alcohol 116g (2 mol), 4-vinylcyclohexene-1-oxide 496g (4 mol)
and 3.1 g of BF ₃ etherate were mixed at 60° C. and reacted until the conversion of 4-vinylcyclohexene-1-oxide reached 98% or more as determined by gas chromatography analysis. Ethyl acetate was added to the resulting reaction crude liquid, washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid. In the infrared absorption spectrum of the product, the absorption due to epoxy groups at 810 and 850 cm ^-1 observed in the raw material has disappeared, and absorption due to ether bonds exists at 1080 and 1150 cm ^-1 , and gas chromatography analysis shows that Allyl alcohol in the product is a trace amount, but in the infrared absorption spectrum it is 3450cm
It was confirmed that this compound has the structure shown by the following formula from the absorption of OH group at ^-1 . 434 g of this compound was dissolved in ethyl acetate and charged into a reactor, to which 388 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours. During this time, the reaction temperature was maintained at 40°C. After the completion of peracetic acid preparation, 40
It was further aged for 6 hours at °C. Add ethyl acetate to the reaction crude solution and add sodium carbonate.
It was washed with alkaline water containing 416 g, followed by thorough washing with distilled water. The ethyl acetate layer was concentrated to obtain a viscous clear liquid. This compound has an oxirane oxygen content of 9.97%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, absorption due to residual vinyl groups is observed at 1640 cm ^-1 and 3450 cm ^-1
OH group, 1730 cm ^-1 ,

[Formula] Since absorption is observed by the group, this compound has the structure of the general formula () (R ₁ : glycidyl ether group or allyloxy group, n=2 on average, contains some groups in which acetic acid is added to the epoxy group) It was confirmed. Synthesis Example 2 58g of allyl alcohol in the same manner as Synthesis Example 1
(1 mol), 868 g (7 mol) of 4-vinylcyclohexene-1-oxide, and 4.7 g of BF ₃ etherate were reacted to obtain a viscous liquid product. In the infrared absorption spectrum of the product, the absorption by epoxy groups at 810 and 850 cm ^-1 observed in the raw material disappeared, and the presence of absorption due to ether bonds at 1080 and 1150 cm ^-1 , gas chromatography analysis showed that Allyl alcohol in the product is a trace amount, but in the infrared absorption spectrum it is 3450cm
It was confirmed that this compound had the structure shown by the following formula from the presence of absorption of OH group at ^-1 . Further, 49.2 g of this compound was reacted with 395 g of peracetic acid in the same manner as in Example 1 to obtain a viscous transparent liquid. This compound has an oxirane oxygen content of 9.27%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, 1640cm ^-1
Absorption due to residual vinyl groups is observed in 3450
OH group at cm ^-1 , 1730 cm ^-1

This compound has the structure of the general formula () (R ₁ : glycidyl ether group or allyloxy group, n=7 on average, some groups include acetic acid added to an epoxy group) because absorption by the [formula] group is observed. I confirmed that there is. Synthesis Example 3 Using the same procedure as Synthesis Example 1, 64 g of methanol, 4
-Vinylcyclohexene-1-oxide 744g
4.1 g of BF ₃ etherate was reacted to obtain a viscous liquid product. In the infrared absorption spectrum of the product, the absorption due to epoxy groups at 810 and 850 cm ^-1 observed in the raw material has disappeared, and absorption due to ether bonds exists at 1080 and 1150 cm ^-1 , and gas chromatography analysis shows that , the methanol in the product is a trace amount, but the infrared absorption spectrum shows it to be 3450 cm ^-1
The absorption of OH groups confirmed that this compound had the structure shown by the following formula. Further, 573 g of this compound and 387 g of peracetic acid were reacted in the same manner as in Synthesis Example 1 to obtain a viscous transparent liquid. This compound has an oxirane oxygen content of 9.03%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, 1640cm ^-1
Absorption due to residual vinyl groups is observed in 3450
OH group in cm, 1730 cm ^-1

Since absorption by the [Formula] group was observed, it was confirmed that this compound has the structure of the general formula () (R ₁ : methoxy group, n = average 3, contains some groups in which acetic acid is added to the epoxy group) . Reference Example The total amount of chlorine in the epoxy resins synthesized in Synthesis Examples 1, 2, and 3 was measured. The measurement was performed by weighing approximately 2 g of the sample and decomposing and burning it in an oxygen cylinder, and the results shown in Table 1 were obtained. Considering that ordinary epoxy resins using epichlorohydrin as a starting material usually contain about several hundred ppm of total chlorine, it can be seen that the total chlorine content of the resin of the present invention is extremely small.

[Table] Synthesis Example 4 32 g (1 mol) of methanol, 868 g (7 mol) of 4-vinylcyclohexene-1-oxide, and 9.2 g of BF ₃ etherate were mixed at 60°C, and 4-vinylcyclohexene-1 was determined by gas chromatography analysis. -The reaction was allowed to occur until the oxide conversion rate reached 98% or higher. Ethyl acetate was added to the obtained reaction crude liquid and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid. In the infrared absorption spectrum of the product, the absorption by epoxy groups at 810 and 850 cm ^-1 observed in the raw material disappeared, and the presence of absorption due to ether bonds at 1080 and 1150 cm ^-1 , and gas chromatography analysis revealed that , the amount of allyl alcohol in the product is only trace, but it is 3450 in the infrared absorption spectrum.
It was confirmed that this compound has the structure shown by the following formula from the absorption of OH group at cm ^-1 . 434 g of this compound was dissolved in ethyl acetate and charged into a reactor, to which 388 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours. During this time, the reaction temperature was maintained at 40°C. After the completion of peracetic acid preparation, 40
It was aged for an additional 6 hours at °C. Add ethyl acetate to the reaction crude solution and add sodium carbonate.
It was washed with alkaline water containing 416 g, followed by thorough washing with distilled water. The ethyl acetate layer was concentrated to obtain a solid resin at room temperature. This compound has an oxirane oxygen content of 9.97%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, 1640cm ^-1
Absorption due to residual vinyl groups is observed in 3450
OH group at cm ^-1 , 1730 cm ^-1

Since absorption by the [Formula] group is observed, this compound has the structure of the general formula () (R: glycidyl group or allyl group, n = average 2, contains a small amount of acetic acid added to an epoxy group). confirmed. Example 1 A curing agent was added to the products of Synthesis Examples 1, 2, and 3, and the gel time was measured to examine the curability of the epoxy resin. A novolak type phenol resin (PSF-4300 Gunei Chemical Industry Co., Ltd.) was used as a curing agent, and 2-undecylimidazole (Kyuazol C ₁₁ Z, Shikoku Kasei Kogyo Co., Ltd.) was used as a curing catalyst. or,
3,4-epoxycyclohexylmethyl, a typical alicyclic epoxy resin, was used as a comparison resin.
Using 3',4'-epoxycyclohexanecarboxylate (Celoxide 2021, Daicel Chemical Industries, Ltd.), blend it according to the following formulation, melt and mix at 120°C for about 1 minute, then cool and mix. Obtained.
The gel time of the obtained formulation at 120°C was measured according to JIS-C2104-7 (hot plate method), and the results shown in Table 2 were obtained. It can be seen that the resin of the present invention has higher curability than conventional alicyclic epoxy resins. Compounding formula Epoxy resin 1.0 equivalent PSF-4300 1.1 equivalent Kyuazol C ₁₁ Z (based on the compound) 0.7% by weight

[Table] Example 2 Using the compounds of Synthesis Examples 1, 2, and 3, physical properties of cured products were measured. Using the same curing agent and curing catalyst as in Example 1, the following formulation was mixed in the same manner as in Example 1 to obtain a mixture. The resulting mixture was pulverized and press-molded to obtain a test piece. Molding is 90
~30℃ from 60℃ to 170℃ under pressure of ~100Kgf/ ^cm2
After heating at 170℃ for 10 minutes under pressure,
Post-curing was carried out for 2 hours in an oven set at .degree. The obtained cured product was cut into test pieces, and the physical properties were measured according to JIS-K-6911.
The results shown in Table 3 were obtained. Compounding formula Epoxy resin 1.0 equivalent PSF-4300 0.9 equivalent Kyuazol C ₁₁ Z (based on the compound) 0.7% by weight

[Table] Example 3 4-Methylhexahydrophthalic anhydride (Rikacid MH-700,
Curing was performed using Shin Nippon Rika Co., Ltd.). In addition, 3,4-epoxycyclohexylmethyl-3', which is a typical alicyclic epoxy resin, was used as a comparison resin.
Using 4'-epoxycyclohexanecarboxylate (Celoxide 2021, Daicel Chemical Industries, Ltd.), mix the following formulation, melt and mix at 80℃ for about 5 minutes, degas under reduced pressure, and harden by casting. A cured product was obtained. Curing in oven at 160℃
Pre-curing was carried out at 180° C. for 1 hour, and post-curing was further carried out for 2 hours at 180°C. The obtained cured product was cut into test pieces, and the heat distortion temperature was measured according to JIS-K-6911, and the results shown in Table 4 were obtained. Compounding formula Epoxy resin 1.0 equivalent MH-700 0.8 equivalent

[Table] Example 4 4-Methylhexahydrophthalic anhydride (Rikacid MH) was added to the products of Synthesis Examples 1 and 2 as a curing agent.
-700, Shin Nippon Chemical Co., Ltd.) and benzyldimethylamine as a curing catalyst. or,
3,4-epoxycyclohexylmethyl, a typical alicyclic epoxy resin, was used as a comparison resin.
Using 3,4-epoxycyclohexanecarboxylate (Celoxide 2021, Daicel Chemical Industries, Ltd.), the following formulation was used to compound
After melting and mixing for a minute, the mixture was defoamed under reduced pressure and cured by casting to obtain a cured product. Curing in the oven
Pre-curing was carried out at 100°C for 1 hour, and post-curing was further carried out at 160°C for 2 hours. The obtained cured product was cut into test pieces, and the heat distortion temperature was measured according to JIS-K-6911, and the results shown in Table 5 were obtained. Mixing recipe Epoxy resin 1.0 equivalent MH-700 0.9 equivalent Benzyldimethylamine (based on the mixture) 0.5% by weight

[Table] Example 5 4-Methylhexahydrophthalic anhydride (Rikacid MH-700,
Curing was carried out using Shin Nippon Chemical Co., Ltd.) and benzyldimethylamine as a curing catalyst. In addition, as a comparative resin, 3,4-epoxycyclohexylmethyl-3', which is a typical alicyclic epoxy resin,
Using 4'-epoxycyclohexane carboxylate (Celoxide 2021, Daicel Chemical Industries, Ltd.) and bisphenol A diglycidyl ether (Epicote 828, Yuka Ciel Epoxy Co., Ltd.), a general epoxy resin, the following formulation was prepared. After mixing at 80° C. for about 5 minutes, the mixture was degassed under reduced pressure and cured by casting to obtain a cured product. For curing, pre-cure in an oven at 100℃ for 1 hour, then further cure at 160℃.
Post-curing was carried out for 2 hours at °C. The obtained cured product was cut into test pieces, and the physical properties were measured according to JIS-K-6911.
The results shown in Table 6 were obtained. As is clear from the table, the resin of the present invention has good heat resistance and excellent electrical properties. Compounding recipe Epoxy resin 1 equivalent MH-700 1 equivalent Benzyldimethylamine (based on the compound) 0.5%

[Table] Example 6 The product of Synthesis Example 4 was added with 4-methylhexahydrophthalic anhydride (Rikacid MH-700,
Curing was performed using Shin Nippon Rika Co., Ltd.). In addition, as in Example 5, Celoxide 2021 was used as a comparative resin.
and Epicote 828 were mixed according to the following formulation, mixed at 80°C for about 5 minutes, defoamed under reduced pressure, and cured by casting to obtain a cured product. Precuring was performed in an oven at 130°C for 1 hour.
Celloxide 2021 and Epicote 828 were still in liquid form at this stage, so they were heated at 130°C for an additional 2 hours (3 hours in total), but no gelation was observed, so they were heated at 140°C for an additional hour. Where I went,
Gelation was observed in Celloxide 2021. After pre-curing under the above conditions, post-curing was carried out at 180° C. for 2 hours, but no cured product could be obtained with Epikote 828. The obtained cured product was cut into a test piece, and its physical properties were measured according to JIS-K-6911.
The obtained cured product was cut into test pieces,
Physical properties were measured according to JIS-K-6911, and Table 7
I got the result. As is clear from the table, the resin of the present invention has good heat resistance and excellent electrical properties. Mixing prescription Epoxy resin 1 equivalent MH-700

[Table] Synthesis Example 5 134 g (1 mol) of trimethylolpropane and 1863 g (15 mol) of vinylcyclohexene monoepoxide were reacted in the same manner as in Example 1 to obtain a product. When the obtained product was analyzed by elemental analysis, IR, and NMR, it was confirmed that it had the structure shown by the formula (). In the IR analysis, 810, 850 and
The absorption of epoxy group at 1850cm ^-1 disappears and the absorption becomes 1080cm ^-1
The absorption of the ether bond was newly generated. Furthermore, absorptions of vinyl groups at 910 cm ^-1 and 1640 cm ^-1 remain. In NMR, a peak similar to that in Example 1 was confirmed. The elemental analysis values are shown below. C H Analytical value 76.05 9.65 Theoretical value 75.82 9.73 From the above results, the structure of formula () was confirmed. Example 7 Using the compound of Synthesis Example 5 and cresol novolac epoxy (Toto Kasei, YDCN-702), the physical properties of the cured product were measured. Using the same curing agent and curing catalyst as in Example 1, the following formulation was mixed in the same manner as in Example 1 to obtain a mixture. The resulting mixture was pulverized and press-molded to obtain a test piece. Molding is 90
~30℃ from 60℃ to 170℃ under pressure of ~100Kgf/ ^cm2
After heating at 170℃ for 10 minutes under pressure,
Post-curing was carried out for 2 hours in an open set at .degree. The obtained cured product was cut into test pieces, and the physical properties were measured according to JIS-K-6911.
The results shown in Table 8 were obtained. Compounding formula Epoxy resin 1.0 equivalent PSF-4300 1.0 equivalent Kyuazol C ₁₁ Z (based on the compound) 0.7% by weight

【table】

Claims (1)

[Claims] 1. A novel epoxy resin represented by the general formula (), a curing agent, and optionally a filler, a flame retardant,
An epoxy resin composition characterized by containing various other additives. However, R ₁ is a residue of an organic compound having l active hydrogens, and the organic compound is one or a mixture of two or more selected from monohydric or more alcohols or unsaturated compounds having a hydroxyl group. n1, n2...nl are each 0 or an integer between 1 and 100, and their sum is between 1 and 100. l represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent, and is represented by the following formula. X is [formula]-CH=CH ₂ R ₂ is H, an alkyl group, an alkylcarbonyl group,
Any one of the arylcarbonyl groups, The resin represented by the formula () contains at least one or more of the following.