JPS6214167B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to epoxy resin compositions. DISCLOSURE OF THE INVENTION More specifically, the present invention provides an epoxy resin composition containing an epoxy resin, a reactive flexibility-imparting agent, and a curing agent. [In the formula, -R- is -CH ₂ -CH=CH-(CH ₂ ) ₂ -CH
=CH− _CH2− ,

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【formula】

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[Formula] or

[Formula] is shown. here again R′ is the base

[Formula] is shown. ] It concerns on the epoxy resin composition characterized by using the polycarboxylic acid glycidyl ester represented by these. The polycarboxylic acid glycidyl ester represented by the above general formula () is a new compound that has not been described in any literature. Specific examples of the polycarboxylic acid glycidyl ester represented by the above general formula () include the compounds shown below. Γ7,11-octadecadiene-1,18-dicarboxylic acid diglycidyl ester (compound 1) Γ6-vinyl-9-hexadecene-1,16-dicarboxylic acid diglycidyl ester (compound 2) Γ7,12-dimethyl-7. 11-octadecadiene-1,18-dicarboxylic acid diglycidyl ester (compound 3) Γ7,8-diphenyl-tetradecane-1,14-
Dicarboxylic acid diglycidyl ester (compound 4) Γ7,8-diaminocarbonyl-tetradecane-
1,14-dicarboxylic acid diglycidyl ester (compound 5) Γ7,8-dicyano-tetradecane-1,14-dicarboxylic acid diglycidyl ester (compound 6) Γ(6,7), (8,9)-bispropanediyl −
6,8-tetradecadiene 1,14-dicarboxylic acid diglycidyl ester (compound 7) Γtetradecane-1,6,7,8,9,14-hexacarboxylic acid hexaglycidyl ester (compound 8) Γ7,8-dimethyl -tetradecane-1・7・
8,14-tetracarboxylic acid tetraglycidyl ester (compound 9) Γtetradecane-1,7,8,14-tetracarboxylic acid tetraglycidyl ester (compound 10) Γ7,8-diacetyloxy-tetradecane-
1,14-dicarboxylic acid diglycidyl ester (compound 11) Γ7,8-dihydroxy-tetradecane-1,14
-dicarboxylic acid diglycidyl ester (compound
12) The compound of the present invention represented by the above general formula () can be produced by various methods, and a preferred example thereof is a method of reacting a polycarboxylic acid represented by the following general formula () with epichlorohydrin. . [In the formula, −R″− is −CH ₂ −CH=CH−(CH ₂ ) ₂ −CH
=CH− _CH2− ,

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【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] or

[Formula] is shown. ] Specific examples of the polycarboxylic acid represented by the general formula () are as follows. Γ7,11-octadecadiene-1,18-dicarboxylic acid (compound 1a) Γ6-vinyl-9-hexadecene-1,16-dicarboxylic acid (compound 2a) Γ7,12-dimethyl-7,11-octadecadiene 1・18-dicarboxylic acid (compound 3a) Γ7,8-diphenyl-tetradecane-1,14-
Dicarboxylic acid (compound 4a) Γ7,8-diaminocarbonyl-tetradecane-
1,14-dicarboxylic acid (compound 5a) Γ7,8-dicyano-tetradecane-1,14-dicarboxylic acid (compound 6a) Γ(6,7), (8,9)-bispropanediyl-
6,8-tetradecadiene-1,14-dicarboxylic acid (compound 7a) Γtetradecane-1,6,7,8,9,14-hexacarboxylic acid (compound 8a) Γ7,8-dimethyl-tetradecane-1. 7.
8,14-tetracarboxylic acid (compound 9a) Γtetradecane-1,7,8,14-detracarboxylic acid (compound 10a) Γ7,8-diacetyloxy-tetradecane-
1,14-dicarboxylic acid (compound 11a) Γ7,8-dihydroxy-tetradecane-1,14
-Dicarboxylic acid (compound 12a) Among the polycarboxylic acids represented by the above general formula (), compounds 1a to 3a are known compounds, and compounds 4a to 12a are new compounds.
Among compounds 4a to 12a, compound 8a is produced, for example, as follows. That is, cyclohexanone and hydrogen peroxide are reacted in an alcohol solution in the presence of an acid catalyst, then a maleic acid ester is reacted with the alkoxycyclohexyl peroxide produced in the presence of a ferrous salt, and the reaction product is further hydrated. Produced by decomposition. In the reaction between cyclohexanone and hydrogen peroxide, the ratio of the two used is usually 0.5 to 2 times the molar amount of the latter relative to the former. Examples of the acid catalyst include sulfuric acid, phosphoric acid, hydrochloric acid, etc., and it is usually advisable to use about 0.5 to 10 parts of such acid catalysts per 100 parts by weight (hereinafter simply referred to as "parts") of cyclohexanone. Examples of alcohol include methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, etc.
It is usually best to use about 200 to 1000 parts. The reaction temperature of the reaction is generally 0 to 30°C,
Reaction time is 5-20 minutes. In the reaction between the alkoxycyclohexyl peroxide thus produced and the maleic ester, the ratio of the two used is usually 1 to 3 times the molar amount of the latter to the former. Examples of maleic esters include dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-n-butyl maleate, and di-tert-butyl maleate. Examples of ferrous salts include ferrous sulfate, ferrous chloride, ferrous acetate, and ferrous ammonium sulfate salts. It is preferable to use about 2 moles. The reaction temperature is usually -10 to 10°C and the reaction time is 0.5 to 1 hour. Compound 8a is thus produced in the form of an ester, and compound 8a is produced by hydrolyzing this in accordance with a conventional method. Compound 4a can be obtained by performing the same reaction as above using styrene instead of maleic ester, Compound 5a can be obtained by performing the same reaction as above using acrylamide instead of maleic ester, and Compound 6a can be obtained by performing maleic acid ester. By performing the same reaction as above using acrylonitrile instead of the acid ester, compound 7a can be obtained by performing the same reaction as above using cyclopentadiene instead of the maleic ester. Instead, methacrylic acid esters (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate,
By carrying out the same reaction as above using tert-butyl methacrylate, etc., Compound 10a can be obtained by using acrylic esters (methyl acrylate, ethyl acrylate, n-propyl acrylate, n-acrylic acid, etc.) instead of maleic ester. -butyl, tert-butyl acrylate, etc.), Compound 11a can be obtained by carrying out the same reaction as above using vinyl acetate instead of maleic acid ester, Compound 12a can be obtained by carrying out the same reaction as above using vinyl acetate instead of maleate. Each is produced by performing the same reaction as above using vinyl alcohol instead of maleic ester. In addition, compounds 1a and 2a can be obtained by carrying out the same reaction as above using butadiene instead of maleate ester, and compound 3a can be obtained by carrying out the same reaction as above using isoprene instead of maleate ester. manufactured respectively. The reaction between the polycarboxylic acid represented by the above general formula () and epichlorohydrin can be carried out by appropriately adopting the reaction conditions for the conventional reaction between carboxylic acid and epichlorohydrin. For example, polycarboxylic acid and epichlorohydrin may be reacted in the presence of a catalyst such as a tertiary amine or a quaternary ammonium salt. The ratio of polycarboxylic acid and epichlorohydrin used is usually 1 carboxyl group in the former.
3 to 20 mol of the latter based on equivalent, preferably 5 to 10 mol
It is better to use moles. The third used as a catalyst
Examples of quaternary amines include triethylamine, tri-n-propylamine, benzyldimethylamine, and triethanolamine, and examples of quaternary ammonium salts include tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltrimethyl. Examples include ammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium acetate, methyltriethylammonium chloride, and the like. The amount of the catalyst used is usually 0.02 to 1.0% by weight based on the total amount of polycarboxylic acid and epichlorohydrin.
The content is preferably 0.1 to 0.3% by weight. The reaction temperature in this reaction is usually 80 to 150°C, preferably 90 to 110°C, and the chlorohydrin esterification reaction is generally completed in about 0.5 to 1 hour. Next, the compound of the present invention represented by the above general formula () is produced by neutralization with alkali hydroxide and dehydrochlorination, and the compound is separated by conventional separation means such as filtration, solvent extraction, washing, distillation, recrystallization, etc. It is isolated and purified from the reaction mixture. A preferred embodiment in which the compound of the present invention is obtained by reacting the polycarboxylic acid and epichlorohydrin is as follows. That is, the general formula ()
A polycarboxylic acid represented by the formula is mixed with epichlorohydrin in an amount of 3 to 10 times the mole per carboxyl group of the polycarboxylic acid, and then a tertiary amine,
A catalyst such as a quaternary ammonium salt is added, and as a first step, an addition reaction is carried out at 80 to 110°C to produce the corresponding polycarboxylic acid chlorohydrin ester. The reaction was stopped when the neutralization value became 1 or less, and then immediately heated to 80 to 100℃ as the second step.
Dehydrochloric acid is removed by adding a concentrated aqueous alkali hydroxide solution (concentration 40 to 60%) in an amount of 5 to 30% in excess of the theoretical amount at a temperature of do. After dropping the alkali hydroxide, raise the temperature to 105℃ as soon as possible, stop the reaction, and quickly cool it to room temperature.
The precipitated sodium chloride is separated by filtration. Pichlorohydrin was recovered under reduced pressure, the product was dissolved in an inert organic solvent, the catalyst and traces of sodium chloride were then removed by washing with water, and the product was dissolved under reduced pressure.
The target compound of the present invention is obtained by heating to about 140°C and recovering the inert organic solvent. The compound of the present invention has the following usefulness. Compounds 1 to 12 all have a viscosity at room temperature.
It is a liquid substance of 200 cps or less, and can be advantageously used as a reactive flexibility-imparting agent for epoxy resins, as is clear from the usage examples below. That is, these compounds have good compatibility with epoxy resins and can be mixed with epoxy resins in any proportion, and the storage stability of the mixture at low temperatures is also very good. Even if stored for a long period of time, crystals will not precipitate or phase separation will occur. Furthermore, when an epoxy resin composition prepared by adding and mixing Compounds 1 to 12 with an epoxy resin is cured, shrinkage deformation does not occur during curing, and it has excellent impact resistance (especially thermal shock resistance) and heat resistance. It is possible to provide a cured product having chemical resistance, adhesive strength, mechanical strength, electrical properties, etc. Furthermore, glycidyl acrylate obtained by adding acrylic acid or methacrylic acid to Compounds 1 to 12 is extremely useful as an ultraviolet curing paint or ink. All compounds of the present invention are also useful as curing agents for urethane resins. The use of the compound of the present invention as a reactive flexibility imparting agent for epoxy resins will be described in detail below. There are no particular restrictions on the epoxy resin used, and a wide range of known epoxy resins can be used.A typical example is bisphenol A type resin (e.g. Epicoat).
828, trademark, manufactured by Ciel Corporation). The amount of the compound of the present invention added to the epoxy resin is not particularly limited and may be appropriately selected within a wide range, but is usually 5 to 400 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of the epoxy resin. It is better to If the amount of the compound of the present invention added is extremely small, the flexibility and low-temperature properties of the cured product will tend to be impaired, and if the amount of the compound of the present invention added is extremely large, the heat resistance of the cured product will tend to decrease. A curing agent can be added to such an epoxy resin composition. As the curing agent, any curing agent conventionally known in this field can be used. The amount of the curing agent to be used is not particularly limited and may be appropriately selected within a wide range, but generally it is approximately stoichiometrically equivalent to the sum of the epoxy equivalents of the epoxy resin and the compound of the present invention. is desirable. Furthermore, various additives such as a curing accelerator, an extender, and a plasticizer may be appropriately blended into the epoxy resin composition as required. There is no particular limitation in producing the epoxy resin composition, and conventionally known methods can be employed as they are.
Since the compound of the present invention is a liquid compound with an extremely low viscosity and a cloud point of -5° C. or lower, it can be sufficiently kneaded and easily defoamed simply by stirring at room temperature. The epoxy resin can be cured under the usual curing conditions for epoxy resins, and can be cured at temperatures ranging from room temperature to 200°C by appropriately selecting the type and amount of the curing agent depending on the application. can. The epoxy resin composition can be used in a wide range of applications, including adhesives, paints, molded products, cast products, coating agents,
It can be effectively used in fields such as lining agents, sealing agents, and potting agents. Examples The production example of the polycarboxylic acid of the general formula (), which is a raw material for synthesizing the compound of the present invention, is taken as a reference example, and the production example of the compound of the present invention is listed as an example,
Further usage examples are listed. In addition, in the following, we will simply refer to "part".
"parts by weight" means "parts by weight". Reference example: 1200 kg of anhydrous methanol, 100 kg of maleic anhydride, and 3 ml of concentrated sulfuric acid in a reaction vessel equipped with a stirrer and condenser.
Kg is added, and the methanol is refluxed at 68°C while stirring. After 8 hours of reaction, when the acid value of the reaction solution reached 4.0, 850 kg of methanol was collected, and 449.6 kg of methanol solution containing dimethyl maleate (acid value 18.8 including sulfuric acid, 146.9 kg of dimethyl maleate,
(containing 300Kg of methanol and 2.7Kg of sulfuric acid). Into the reaction vessel containing 449.6 kg of the dimethyl maleate-containing methanol solution obtained above, 80 kg of cyclohexanone, 80 kg of the 35% hydrogen peroxide aqueous solution, and 98%
Add 0.9 kg of sulfuric acid and react while stirring at 18-20°C for 30 minutes. While maintaining this reaction solution at -5°C, 240 kg of powdered ferrous sulfate (heptahydrate) was gradually added and reacted. After the reaction, add 18 kg of 60% sulfuric acid,
After stirring, the mixture is allowed to stand still and separated into an upper polycarboxylic acid ester layer and a lower ferric salt layer. The polycarboxylic acid ester layer is washed with dilute sulfuric acid and water and dehydrated to obtain 167 kg of polycarboxylic acid methyl ester. Yield 94.1% (based on raw material cyclohexanone,
(The same applies hereinafter) From the lower ferric salt layer, 280 kg of 99% methanol is recovered by rectification. The following hexabasic acid methyl ester and tetrabasic acid methyl ester are separated from the polycarboxylic acid methyl ester obtained above by gas chromatography. (1) Dimethyl 7,8,9,10-tetramethoxycarbonyl-1,16-hexadecanedioate ratio: 62% IR: 1750cm ^-1 (〓C=O) 1450cm ^-1

[Formula] NMR: τ6.4 (−OCH ₃ ) 7.7 to 8.6 (−CH ₂ −) 6.8 to 7.2

[Formula] (Hydrogen ratio 18:10:4) Mass: Molecular weight 546 Elemental analysis value (as C ₂₆ H ₄₂ O ₁₂ ) C H O Analysis value (%) 57.24 7.71 35.50 Calculated value (%) 57.15 7.69 35.16 (2) Dimethyl 7,8-dimethoxycarbonyl-
1,14-tetradecanedioate ratio: 21% IR: 1750cm ^-1 (〓C=O) 1450cm ^-1

[Formula] NMR: τ6.4 (−OCH ₃ ) 7.7 to 8.6 (−CH ₂ −) 6.8 to 7.2

[Formula] (Hydrogen ratio 12:10:2) Mass: Molecular weight 402 Elemental analysis value (as C ₂₆ H ₃₄ O ₈ ) C H O Analysis value (%) 59.84 8.40 31.76 Calculated value (%) 59.70 8.46 31.84 Thus The obtained hexabasic acid methyl ester and tetrabasic acid methyl ester are respectively hydrolyzed according to conventional methods to obtain hexabasic acid (i.e., tetradecane-1.
6, 7, 8, 9, 14-hexacarboxylic acid, compound
8a) and tetrabasic acids (i.e. dodecane-1, 6, 7,
12-tetracarboxylic acid) is obtained. Example 1 338 parts of 7,11-octadecadiene-1,18-dicarboxylic acid, 925 parts of epichlorohydrin, and benzyltriethylammonium chloride were placed in a four-neck flask equipped with a stirrer, a condenser with a water separator, a thermometer, and a separatory funnel. Add 2 parts, heat to 90-100°C, and carry out the esterification reaction for 30 minutes under stirring and reflux. Next, at the same temperature, add 60 parts of 50% sodium hydroxide aqueous solution to 208 parts.
The mixture was added dropwise in portions, and stirred and refluxed at the same temperature for an additional 15 minutes. Cool to room temperature, filter to remove salt, recover epichlorohydrin under reduced pressure, and dissolve the product by adding 1 part of toluene. After washing three times with 300 ml of water, toluene was completely recovered at 140°C under reduced pressure (1 mmHg) and 7,11-octadecadiene-1,18
-Dicarboxylic acid diglycidyl ester (Compound 1) is obtained. Yield 97%, epoxy equivalent 240, acid value 0.03, iodine value 108.8, saponification value 233.3, chlorine content 0.31%, color
G1, viscosity 83 cps (23°C) Example 2 6-vinyl-9-hexadecene-1,16 in the same manner as in Example 1 above, except that 338 parts of 6-vinyl-9-hexadecene-1,16-dicarboxylic acid was used.
-Dicarboxylic acid diglycidyl ester (compound 2) is obtained. Yield 96.1%, epoxy equivalent 243, acid value 0.03, iodine value 105.1, saponification value 230, chlorine content 0.35%, color
G1, viscosity 90 cps (23°C) Example 3 7,12-dimethyl 7,12-dimethyl -7・
11-octadecadiene-1,18-dicarboxylic acid diglycidyl ester (compound 3) is obtained. Yield 96.1%, epoxy equivalent 270, acid value 0.03, iodine value 98.7, saponification value 215, color G1, viscosity 70 cps (23
℃) Example 4 7,8-diphenyl-tetradecane-1,14-
Example 1 above except that 438 parts of dicarboxylic acid was used.
In the same manner as above, 7,8-diphenyl-tetradecane-1,14-dicarboxylic acid diglycidyl ester (Compound 4) is obtained. Yield 97%, epoxy equivalent 290, acid value 0.02, iodine value 0, saponification value 195, color G1, viscosity 250 cps (23°C) Example 5 7,8-diaminocarbonyl-tetradecane-
7,8-diaminocarbonyl-tetradecane-1,14-dicarboxylic acid diglycidyl ester (Compound 5) is obtained in the same manner as in Example 1 above, except that 372 parts of 1,14-dicarboxylic acid is used. Yield 98%, epoxy equivalent 260, acid value 0.02, iodine value 0, saponification value 215.7, color G1, viscosity 93 cps (23
℃) Example 6 7,8-dicyano-tetradecane- was prepared in the same manner as in Example 1 above except that 336 parts of 7,8-dicyano-tetradecane-1,14-dicarboxylic acid was used.
1,14-dicarboxylic acid diglycidyl ester (compound 6) is obtained. Yield 95%, epoxy equivalent 235, acid value 0.01, iodine value 0, saponification value 250.4, color G1, viscosity 160 cps (23
℃) Example 7 (6.7), (8.9)-bispropanediyl-
(6.7) and (8.9)-bispropanediyl-6.8-tetradecanediene- 1,14-dicarboxylic acid diglycidyl ester (compound 7) is obtained. Yield 95.7%, epoxy equivalent 260.1, acid value 0.02, iodine value 108, saponification value 215.7, color G1, viscosity 183cps
(23°C) Example 8 Example 1 above except that 462 parts of tetradecane-1,6,7,8,9,14-hexacarboxylic acid was used.
Similarly, tetradecane-1, 6, 7, 8,
9,14-hexacarboxylic acid hexaglycidyl ester (compound 8) is obtained. Yield 90.5%, epoxy equivalent 150.5, acid value 0.03, iodine value 0, saponification value 372, color G1, viscosity 230 cps (23
℃) Example 9 7,8-dimethyl-tetradecane-1,7.
7,8-dimethyl-tetradecane-1,7,8,14-tetracarboxylic acid tetraglycidyl ester (Compound 9) is obtained in the same manner as in Example 1 above, except that 462 parts of 8,14-tetracarboxylic acid is used. Yield 92%, epoxy equivalent 172, acid value 0.03, iodine value 0, saponification value 326.2, color G1, viscosity 226 cps (23
℃) Example 10 Tetradecane-1,7,8,14-tetracarboxylic acid tetraglycidyl ester (compound 10) get. Yield 92%, epoxy equivalent 140.5, acid value 0.03, iodine value 0, saponification value 399.3, color G2, viscosity 191 cps (23
℃) Example 11 7,8-diacetyloxy-tetradecane-
7,8-Diacetyloxy-tetradecane-1,14-dicarboxylic acid diglycidyl ester (Compound 11) is obtained in the same manner as in Example 1 above, except that 402 parts of 1,14-dicarboxylic acid is used. Yield 96%, epoxy equivalent 272, acid value 0.02, iodine value 0, saponification value 206.3, color G1, viscosity 156 cps (23
℃) Example 12 7,8-dihydroxy-tetradecane-1,14
7,8-dihydroxy-tetradecane-1,14-dicarboxylic acid diglycidyl ester (Compound 12) is obtained in the same manner as in Example 1 above, except that 318 parts of -dicarboxylic acid is used. Yield 95.3%, epoxy equivalent 235, acid value 0.02, iodine value 0, saponification value 238.7, color G1, viscosity 240 cps (23
℃) Usage example 1 Viscosity of epoxy resin composition Bisphenol A type resin [Trademark Epicoat
828, epoxy equivalent 190, manufactured by Ciel Corporation], the compound of the present invention is uniformly mixed and dissolved in various proportions, and the viscosity (cps) of the resulting resin composition at 25°C is measured using a B-type viscometer [Tokyo Keiki Co., Ltd.]. Co., Ltd.).
The results obtained are shown in Table 1 below. For comparison, phenyl glycyl ether (compound A), which is the most excellent conventional reactive diluent or reactive flexibility imparting agent, Epicoat 871 [trademark, diglycidyl ester of dimer acid, epoxy equivalent: 430]
manufactured by Ciel Corporation] (compound B) and SB-20G [trademark,
Table 1 also shows the results obtained using 6-ethylhexadecane-1,16-dicarboxylic acid diglycidyl ester, epoxy equivalent: 300, manufactured in-house] (compound C).

【table】

Table 1 shows that the compounds of the present invention exhibit superior dilution effects compared to the comparative compounds. Usage Example 2 Storage Stability of Epoxy Resin Composition An epoxy resin composition is prepared by uniformly dissolving Epicote 828 and the compound of the present invention at various mixing ratios. The epoxy resin composition is left at room temperature for 30 days, and the presence or absence of crystal formation and phase separation is examined.
The results are shown in Table 2. In addition, the presence or absence of crystal formation and phase separation when the epoxy resin composition is left at 0° C. for 7 days is also examined in the same manner. The results are shown in Table 3. The meanings of each symbol in Tables 2 and 3 are as follows. ○: Completely transparent △: Turbid ×: Solid in a phase-separated or turbid state Compositions marked with ○ and △ can be used as epoxy resin compositions.

【table】

[Table] From Tables 2 and 3, the epoxy resin composition containing the compound of the present invention exhibits extremely superior compatibility compared to the case of using the comparative compound, and has particularly excellent storage stability at low temperatures. You can see that Usage Example 3 (1) Production of cured product Epicoat 828, test compound (invention compound or comparative compound) and hexahydrophthalic anhydride (HHPA) were mixed in the proportions shown in Table 4 below, and heated at 80°C for 2 hours. 2 hours at 120℃, 150℃
to obtain a cured product. In addition, Epicote 828, a test compound (invention compound or comparative compound) and diaminodiphenylmethane (DDM) were mixed in the proportions shown in Table 5 below, and 80
2 hours at ℃, 2 hours at 100℃, 2 hours at 150℃
A cured product is obtained by heating for a period of time.

【table】

【table】

[Table] (2) Mechanical properties of cured product In accordance with JIS-K-6919, test pieces (80 x 25 x 3 mm) were prepared from the cured product obtained in (1) above.
Bending speed: 1mm/min, span: 50.8, load point:
Measuring device under R3.17mm, temperature: 20±2℃
Bending strength and bending elastic modulus are measured using TOM500 [manufactured by Shinko Tsushinsha]. In addition, test piece Tambell No. 1 was prepared, tensile speed: 5 m/min, temperature: 20
Tensile strength and elongation are measured using a measuring device TOM500 under the condition of ℃. In addition, the test piece (63.5×12.7×
12.7 mm) and measure the impact strength (Izot) using a UF impact tester (manufactured by Ueshima Seisakusho) with a V-notch and a temperature of 23 to 25°C. Furthermore, JIS-K-
Temperature according to 6919: Measuring machine under the conditions of 22-25℃
Barcol hardness is measured using Model 934-1.
These results are summarized in Table 6.

[Table] From Table 6, it can be seen that the epoxy resin composition containing the compound of the present invention has significantly superior mechanical properties in all respects compared to the case where the comparative compound is used. In particular, it can be seen that in the case of DDM curing, the mechanical strength is further improved compared to the so-called additive-free product that does not contain the compound of the present invention or the comparative compound. (3) Thermal shock resistance of the cured product The thermal shock resistance of the cured product was examined using the flat washer method. In other words, float a flat washer (20 mm) on kraft paper on an aluminum cup with a diameter of 50 mm.
50 g of the epoxy resin composition having the formulations shown in Tables 4 and 5 above was cast and cured under the same conditions as in (1) above. Five specimens are prepared in this way.
Thermal shock was applied in cycles as shown in Table 7 below, and the crack resistance index was calculated in accordance with the following. Crack resistance index = Σ (crack occurrence number) x number of cracks/total number of samples The results obtained are shown in Table 8 below.

【table】

Table 8 shows that when the epoxy resin composition containing the compound of the present invention is cured by HHPA and DDM, the thermal shock resistance of the epoxy resin (Epicote 828) can be greatly improved. (4) Chemical resistance Test piece (25 x 25
×3mm). The test piece was soaked in 20% sulfuric acid.
The samples were immersed in 20% sodium hydroxide for 6 days, in toluene for 6 days, or in boiling water for 4 hours, and the appearance was observed and the change in weight was determined. The results are shown in Table 9. The weight change is determined as follows. Weight change = Weight after test - Initial weight / Initial weight x 100 (
%)

Table 9 shows that the chemical resistance of the cured product of the epoxy resin composition containing the compound of the present invention is comparable to that of conventional compositions. (5) Electrical properties of cured product In accordance with JIS-K-6911, a test piece (80 x 25 x 3 mm) was prepared from the cured product obtained in (1) above.
Volume resistivity, surface resistivity, dielectric constant, dielectric loss factor, dielectric breakdown voltage, tracking resistance, and arc resistance are measured at room temperature (23°C). Tracking resistance was determined using the IEC method (electrolyte 0.1% NH ₄ Cl was used,
Check with brass electrode (600V). The results
Shown in Table 10.

【table】

[Table] The following can be seen from Table 10. That is, in general, when a reactive diluent or a reactive flexibility imparting agent is added to an epoxy resin, the electrical properties usually deteriorate, but when the compound of the present invention is added, the electrical properties of the epoxy resin are completely impaired. Rather, the dielectric constant and dielectric loss factor have been improved.
Furthermore, the arc resistance was improved compared to the case where a comparative compound was added.

Claims (1)

[Scope of Claims] 1. In an epoxy resin composition containing an epoxy resin, a reactive flexibility-imparting agent, and a curing agent, the reactive flexibility-imparting agent has the general formula [In the formula, -R- is -CH ₂ -CH=CH-(CH ₂ ) ₂ -CH
=CH− _CH2− ,
【formula】 [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] Indicates [Formula] or [Formula]. Moreover, R′ here represents a group [formula]. ] An epoxy resin composition characterized by using a polycarboxylic acid glycidyl ester represented by the following.