JPS6069156A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide an epoxy resin compsn. which has good storage stability, does not cause deformation due to shrinkage during curing and gives a cured article having excellent mechanical and electrical characteristics, by blending a specified glycidyl ester of a polycarboxylic acid as a reactive flexibilizer. CONSTITUTION:A glycidyl ester of a polycarboxylic acid of formula I (wherein R is a group of formula II, III or IV) such as diglycidyl 7,11-octadecadiene-1,18-dicarboxylate, diglycidyl 6-vinyl-8-hexadecene-1,16-dicarboxylate or diglycidyl 7,8- dihydroxytetradecane-1,14-dicarboxylate is used as a reactive flexibilizer. 5- 400pts.wt. said flexibilizer and a hardener such as hexahydrophthalic anhydride are blended with 100pts.wt. epoxy resin such as Epikote 828 (a product of shell chemicals).

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, wherein the reactive flexibility-imparting agent has a general formula [wherein -F- is- CH2-CH=CH-(CH2)2-
CH=, CH-CH2-1-CH-(CH2) 2-C
The present invention relates to an epoxy resin composition 4- characterized in that polycarboxylic acid glycidyl ester /L/ represented by H=CH-CH3-13-CONH2CN is used.

The polycarboxylic acid glycidyl ester represented by the above general formula (1) 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 (1) include the compounds shown below.

07.11-octadecadiene-1,18-dicarboxylic acid diglycidyl ester)v (compound 1) 06-viny1v
-9-hexadecene-1,16-di,carboxylic acid diglycidyl ester/I/(Compound 2) 07.12-dimethy/
L/-7,11-octadecadiene-1,18-dicarboxylic acid diglycidyl ester/L/ (compound 3) 07.8-diphenyl-tetradecane-1,14-dicarboxylic acid diglycidyl ester iv (compound 4) o7 ,8-diaminocarbonyl-tetradecane-1,1
4-dicarboxylic acid diglycidyl ester (compound 5) o7,8-dicyano-tetradecane-1,14-dicarboxylic acid diglycidyl ester/L' (compound 6) 0(6,
7), (8,9)-bispropanediyl-6,8-tetradecadiene-1,14-dicarboxylic acid diglycidyl ester (compound 7) 0tetradecane-1,6,7,8,
9,14-hexacarboxylic acid hexaglycidyl ente/
” (Compound 8) o7,8-dimethyl-tetradecane-1,7,8°14
-Tetracarboxylic acid tetraglycidyl ester)v (Compound 9) 0Tetradecane-1,7,8,14-tetracarboxylic acid tetraglycidyl ester (Compound 10) (Compound 11
) o7,8-dihydroxy-tetradecane-1,14-dicarboxylic acid diglycidyl ester (compound 12) The compound of the present invention represented by the above general formula (I) can be produced by various methods, and a preferred example thereof is as follows. A method of reacting a polycarboxylic acid represented by the general formula (n) with epichlorohydrin can be mentioned.

[In the formula -i-cn2-cn=ca-(cH2)2-
ca=cu-ca2-1 The polycarboxylic acid represented by the general formula (IT) is specifically shown below.

07.11-Octadecadiene-1,18-dicarboxylic acid (Compound 1a) 7- 06-Pinyl-9-hexadecene-1,16-dicarboxylic acid (Compound 2a) 07.12-Dimethyl-7,11-octadeca Dien 1
．． 18-dicarboxylic acid (compound 8a) o7,8-diphenyl-tetradecane-1,14-dicarboxylic acid (compound 4a) o7,8-diaminocarbonyl-tetradecane-1,1
4-dicarboxylic acid (compound 5a) o7,8-dicyano-
Tetradecane-1,14-dicarboxylic acid (compound 6a) 0(6,7),(8,9)-bispropanediyl-6,
8-tetradecadiene-1,14-dicarboxylic acid (compound 7a) o tetradecane-1,6,7,8,9,14-hexacarboxylic acid (compound 8a) o7,8-dimethyl-tetradecane-1,7, 8, 14
-tetracarboxylic acid (compound 9a) 0tetradecane-1,7,8,14-tetracarboxylic acid (compound 10a)
) 07.8-Diacetyloxy-tetradecane-1°14
-dicarboxylic acid (compound 11a) 8-7,8-dihydroxytetradecane-1,14-dicarboxylic acid (compound 12a) Of the polycarboxylic acids represented by the above general formula (Il), compounds 1a to 8a are known compounds and Compounds 4a to 12a are new compounds. Compound 4a
Among compounds 12a to 12a, compound 8a is produced, for example, as follows. That is, cyclohexanone and hydrogen peroxide are reacted in an alcoholic solution in the presence of an acid catalyst, and then the resulting alkoxycyclohexyl peroxide is reacted with a maleic acid ester in the presence of a ferrous salt.
It is further produced by hydrolyzing the reaction product.

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 to the former. Examples of acid catalysts include sulfuric acid, phosphoric acid, and hydrochloric acid.
Usually 0 parts by weight (hereinafter simply referred to as "parts")
It is recommended to use about 5 to 10 parts. Examples of alcohol include methanol, ethanol, propatool, impropatool, n-butanol, tert-butanol, etc.
It is usually good to use about 200 to 1000 parts per part. The reaction temperature of the reaction is generally 0 to 30°C, and the reaction time is 5 to 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. Maleic acid esters include dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-n-butyl maleate, and di-te maleate.
Examples include rt-butyl. Examples of ferrous salts include ferrous sulfate, ferrous chloride, ferrous acetate, and ferrous ammonium sulfate. It is usually best to use about 1 to 2 moles. The reaction temperature is usually -10~10℃,
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 according to a conventional method.

Compound 4a can be converted to compound 5a by carrying out the same reaction as above using styrene instead of maleic ester.
Compound 6a can be obtained by carrying out the same reaction as above using acrylamide instead of maleic ester, Compound 6a can be obtained by carrying out the same reaction as above using acrylonitrile instead of maleic ester, and Compound 7a can be obtained by carrying out the same reaction as above using acrylamide instead of maleic ester. By carrying out the same reaction as above using cyclopentadiene instead of n-butyl,
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.) to produce compound 1.
Compound 1a is produced by carrying out the same reaction as above using vinyl acetate instead of maleate ester, and compound 12a is produced by carrying out the same reaction as above using vinyl alcohol instead of maleate ester. Ru. 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.

12- The reaction between the polycarboxylic acid represented by the above general formula (II) 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,
The reaction may be carried out in the presence of a catalyst such as an 8th class amine or a quaternary ammonium salt. The ratio of polycarboxylic acid and epichlorohydrin used is usually 8 to 20 mol, preferably 5 to 10 mol of the latter per 1 equivalent of carboxyl group of the former.
It is better to use moles. Examples of tertiary amines used as catalysts include triethylamine, tri-n-propylamine, benzyldimethylamine, and triethanolamine, and examples of quaternary ammonium salts include tetramethylammonium hydroxide and benzyltrimethylwater. Ammonium oxide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, penzyltrimethylammonium acetate
and methyltriethylammonium chloride. The amount of the catalyst used is usually 0.02 to 1.0% by weight, preferably 0.1 to 0.3% by weight, based on the total amount of polycarboxylic acid and epichlorohydrin. The reaction temperature in this reaction is usually 8
The temperature is 0 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 (I) is produced by neutralization with an alkali hydroxide and dehydrochloric acid, and the compound can be separated by conventional separation means such as filtration, solvent extraction, washing, distillation, recrystallization, etc. It is isolated and purified from the reaction mixture by.

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, a polycarboxylic acid represented by the general formula (If) and epichlorohydrin in an amount of 3 to 10 times the mole per carboxyl group of the polycarboxylic acid are mixed, and then a catalyst such as a tertiary amine or a quaternary ammonium salt is added. In the first step, an addition reaction is carried out at 80 to 110° C. to produce the corresponding polycarboxylic acid chlorohydrin ester. The reaction is stopped when the neutralization value becomes 1 or less, and then immediately as a second step, a concentrated aqueous alkali hydroxide solution (concentration 40-60%) is added at a temperature of 80-100°C in an excess of 5-30% over the theoretical amount. It is added little by little to dehydrochloride, and the added water and the produced water are removed as an azeotrope with epichlorohydrin. After the alkali hydroxide was added dropwise, the temperature was raised to 105°C as soon as possible, the reaction was stopped, and the mixture was quickly cooled to room temperature, and the precipitated sodium chloride was separated by filtration. The epichlorohydrin is recovered under reduced pressure, the product is dissolved in an inert organic solvent, the catalyst and traces of sodium chloride are then removed by washing with water, and the inert organic solvent is recovered by heating to about 140° C. under reduced pressure. , the desired compound of the present invention 15- is obtained.

The compound of the present invention has the following usefulness.

Compounds 1 to 12 all have a viscosity of 200 at room temperature.
It is a liquid substance of less than cps, 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.

16-1 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 variety of known epoxy resins can be used, and a representative example thereof is bisphenol A type resin (e.g., Epicoat 828, trademark, manufactured by Shell Co., Ltd.). 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 visibility 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 are no particular limitations on the production of the epoxy resin composition; any conventionally known method may be used as is.

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 has a wide range of applications and can be effectively used in fields such as adhesives, paints, molded products, cast products, coating agents, lining agents, sealing agents, and botting agents.

Examples General formula (II
The production example of the polycarboxylic acid () is listed as a reference example, the production example of the compound of the present invention is listed as an example, and further usage examples are listed. In the following, the term "parts" simply means "parts by weight."

Reference example: Anhydrous methanol 12 in a reaction vessel with a stirrer and a condenser.
00~, 100 g of maleic anhydride and 3 g of concentrated sulfuric acid were added, and methanol was refluxed at 68° C. while stirring. After reacting for 8 hours, when the acid value of the reaction solution reached 4.0, methanol 850 ~ was recovered, and methanol solution containing dimethyl maleate = 19-449.6 kg (acid value 18.8 including sulfuric acid, dimethyl maleate). 146.9 (containing 800 KIi of methanol and 2.7 glaze of sulfuric acid) is obtained.

Into a reaction vessel containing 449.6 kg of the dimethyl maleate-containing methanol solution obtained above, 88 kg of cyclohexanone was added.
(1,85% hydrogen peroxide aqueous solution 80% and 98% sulfuric acid 0
．． 9 was added, and the mixture was kept at 18-20°C and allowed to react with stirring for 80 minutes. While maintaining this reaction solution at -5° C., 240 g of powdered ferrous sulfate (heptahydrate) was gradually added to react. After the reaction, 60% sulfuric acid 181CIi was added, and after stirring, the mixture was separated into an upper polycarboxylic acid ester layer and a lower ferric salt layer by standing and separating. The polycarboxylic acid ester layer is washed with dilute sulfuric acid and water and dehydrated to obtain polycarboxylic acid methyl ester 167.

Yield 94.1% (based on the raw material cyclohexanone, the same applies hereinafter) The lower ferric salt layer recovers 99% methano20-1280~ by rectification-0 Methyl polycarboxylate obtained above The following hexabasic acid methyl ester and tetrabasic acid methyl ester are separated from the ester by gas chromatography.

(1) Dimethyl 7.8,9.10-tetramethoxycarbonyl-1,16-hexadicanedioate ratio:
62% IR: 1750cm-1 (c=o) 1450cm-
1” (-C-O-) NMR: τ 6°4 (-0CH3) 7.7-8.6 (-CH2-) 6.8-7.2 (-C-) (Hydrogen ratio 18:10: 4) Mass: Molecular weight 546 Elemental analysis value (as C26H41012) CHO Analysis value N 57.24 7.71 85.50 ↓'M
r hk l/IA y # (1+ ------(2
) Dimethyl 7,8-dimethoxycarbonyl-1,1
4-tetradecanedioate ratio: 21% IR: 1750 Cm-" (N C=0) 1 1450 cm-1 (-6-8-) NMR: τ 6.4 (-0CHa) 7.7-8.6
(-CH2-) (Hydrogen ratio 12:10:2) Mass: Molecular weight 402 Elemental analysis value (as C20Ba40s) CHO analysis value ((Foundation) 59.84 8.40 81.76 Calculated value (review) 59.70 8. 46 81.84 The hexabasic acid methyl ester and the tetrabasic acid methyl ester thus obtained are each hydrolyzed according to a conventional method to obtain a hexabasic acid (i.e., tetradecane-1,6°, 7,8,9,14-hexane). A carboxylic acid, compound 8a) and a tetrabasic acid (ie dodecane-1,6,7,12-tetracarboxylic acid) are obtained.

Example 1 7,11-octadecadiene-1,18 in a four-eye flask equipped with a stirrer, a condenser with a water separator, a thermometer and a separatory funnel.
- Add 338 parts of dicarboxylic acid, 925 parts of epichlorohydrin, and 2 parts of benzyltriethylammonium chloride, heat to 90 to 100°C, and carry out an esterification reaction for 30 minutes under stirring and reflux. Next, at the same temperature, 208 parts of a 50% sodium hydroxide aqueous solution was added dropwise over 60 minutes.
Stir and reflux at the same temperature for a minute. Cool to room temperature, allow to remove common salt, recover epichlorohydrin under reduced pressure,
Toluene II in the product! Add and dissolve. water 800
ml! After washing 3 times with , under reduced pressure (1 city) T,! i'), 1
Toluene is completely recovered at 40°C to obtain 7,11-octadecadiene-1,18-dicarboxylic acid diglycidyl ester (Compound 1).

28- Yield 97%, epoxy equivalent 240, acid value 0.08, iodine value 108.8, saponification value 288.8, chlorine content 0.31%, color G1, viscosity 88 cps (28°C) Example 2 6 6 in the same manner as in Example 1 above, except that 888 parts of -pinyru-9-hexadecene-1,16-dicarboxylic acid was used.
-Pinyl-9-hexadecene-1°16-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 0.85
%, color G1, viscosity 90 cps (28°C) Example 3 7.12-Dimethyl-7,11-octadecadiene-1
, 18-dicarboxylic acid (366 parts) was used in the same manner as in Example 1 above to obtain 7,12-dimethyl-7゜24-11-octadecadiene-1,18-dicarboxylic acid diglycidyl ester (compound 3). .

Yield 96.1%, epoxy equivalent 270, acid value 0.08,
Iodine value 98.7, saponification value 215, color G1, viscosity 70C
1) S (28°C) Example 4 7,8-diphenyl-tetradecane-1,14- was prepared in the same manner as in Example 1 above, except that 488 parts of 7,8-diphenyl-tetradecane-1,14-dicarboxylic acid was used. 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 (28°C) Example 5 7.8-diaminocarbonyl-tetradecane-1,14
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 -dicarboxylic acid is used.

Yield 98%, epoxy equivalent 260, acid value 0.02, iodine value 0, saponification value 215.7, color Gl
, viscosity 91 Cp8 (28°C) Example 6 7,8-dicyano-tetradecane-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 160Cp8 (28°C) Example 7 (6,7), (8,9)-bispropanediyl-6,8
-Tetradecanediene-1,14-dicarboxylic acid 374
(6, 7) in the same manner as in Example 1 above except for using
, (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 0.0
2. Iodine number 108, saponification number 215.7, color G1, viscosity 188 cp8 (28°C) Example 8 The above procedure except that 462 parts of tetradecane-1,6,7,8,9,14-hexacarboxylic acid was used. Tetradecane-1,6,7,8,9,14-hexacarboxylic acid hexaglycidyl ester (compound 8) is obtained in the same manner as in Example 1.

Yield 90.5%, epoxy equivalent 150.5, acid value 0.0
3. Iodine value 0, saponification value 372, color G1, viscosity 280C
pSC2B°C) Example 9 7.8-dimethyl-tetradecane-1,7,8,14-
7,8-dimethyl-tetradecane-
1,7,8,14-tetracarboxylic acid tetraglycidyl ester (compound 9) is obtained.

Yield 92%, epoxy equivalent 172, acid value 0.03, iodine value 0, saponification value 826.2 Color G1,
Viscosity 226 cps (28°C) Example 10 Tetradecane-1,7,8,14-tetracarboxylic acid 8
Tetradecane-1,7,8,14-tetracarboxylic acid tetraglycidyl ester (Compound 10) is obtained in the same manner as in Example 1 above, except that 74 parts were used.

Yield 92%, epoxy equivalent 140.5, acid value 0.08,
Iodine value 0, saponification value 899.8, color G2, viscosity 191C
I) 8 (28°C) Example 11 7.8-Diacetyloxy-tetradecane-1,14-
7,8-diacetyloxyteto28-labcan-1,14-dicarboxylic acid diglycidyl ester (Compound 11) is obtained in the same manner as in Example 1 except that 402 parts of dicarboxylic acid is used.

Yield 96%, epoxy equivalent 272, acid value 0.02, iodine value 0, saponification value 206.8, color G1
, viscosity 156 Cp8 (28°C) Example 12 7,8-dihydroxy-tetradecane-1,14-
Dicarboxylic acid diglycidyl ester (compound 12) is obtained.

Yield 95.8%, epoxy equivalent 285, acid value 0.02,
Iodine value 0, saponification value 288.7, color G1, viscosity 240c
ps (28°C) Use example 1 Viscosity of epoxy resin composition Bisphenol A type resin [trademark Epicoat 828, epoxy equivalent 190, manufactured by Shell Co., Ltd., 3100 parts by uniformly mixing and dissolving the compound of the present invention in various proportions to obtain a resin The viscosity (cps) of the composition at 25°C is measured using a B-type viscometer (manufactured by Tokyo Keiki). The results obtained are shown in Table 1 below. For comparison, phenylglycyl 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, Shell Co., Ltd.] [Compound B] and 5B-20G [
Table 1 also shows the results obtained using Compound C] (Trademark, 6-ethylhexadecane-1,16-dicarboxylic acid diglycidyl ester, epoxy equivalent weight 300, manufactured in-house).

From Table 1, it can be seen that the compounds of the present invention exhibit superior dilution effects compared to the comparative compounds.

Use 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 81-. 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 8. 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 Δ can be used as epoxy resin compositions.

32- Table 2 Table 3 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, especially at low temperatures. It can be seen that it has excellent storage stability.

Use Example 3 Epikot 828, a test compound (the compound of the present invention or a comparative compound), and hexahydrophthalic anhydride (HHPA) were mixed in the proportions shown in Table 4 below, and the mixture was heated at 80°C for 2 hours for 1 hour.
A cured product is obtained by heating at 20°C for 2 hours and at 150°C for 4 hours. Also, Epicor) 828, test compound (invention compound or comparative compound) and diaminodiphenylmethane (
DDM) in the proportions shown in Table 5 below and heated at 80°C for 2 hours, 100°C for 2 hours, and 150°C for 2 hours to obtain a cured product.

Table 4 Table 5 85- (2) Mechanical properties of cured product In accordance with JIS-6919, a test piece (80 x 25 x 3 m +++) was prepared from the cured product obtained in (1) above, and the bending speed = 1 mm. /min, span: 50.8, load point: R
3.17 hours, temperature: 20±2℃ Measuring machine TOM5
00 [manufactured by Shinko Tsushinsha] to measure the bending strength and bending elastic modulus. In addition, a test piece Tambell No. 1 was prepared, and the measuring machine TOM5 was used under the conditions of tensile speed: 5 m/min and temperature = 20°C.
00 is used to measure tensile strength and elongation. In addition, a test piece (6B, 5X12.7X12.7mm) was prepared using a measuring device U with a notch and a temperature of 23 to 25℃.
Measure the impact strength (IZOT) using a F impact tester (manufactured by Jyuji Seisakusho). Furthermore, J I S-
-6919, Barcol hardness is measured using a measuring device model 984-1 at a temperature of 22 to 25°C. These results are summarized in Table 6.

86-Table 6 It can be seen from Table 6 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 by the flat washer method. That is, in an aluminum cup with a diameter of 50 mm, a flat washer (20 mm) was floated on kraft paper, and 50 g of the epoxy resin composition having the formulation shown in Tables 4 and 5 above was cast.
) and cure under the same conditions.

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 according to the following.

The results obtained are shown in Table 8 below.

Table 7 Table 8 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. I understand.

(4) Chemical resistance Test piece (25 x 25
8+u). The test piece was soaked in 20% sulfuric acid for 6 days.
The sample was immersed in 20% sodium hydroxide for 6 days, toluene for 6 days, or boiled water for 4 hours, and the appearance was observed and weight changes were noted. The results are shown in Table 9. The weight change is determined as follows.

Table 9 From Table 9, it can be seen 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 the conventional composition.

(5) Electrical properties of the cured product In accordance with JIS-6911, test pieces (80 x 25 x 8 mm) were prepared from the cured product obtained in (1) above, and were measured for volume resistivity, surface resistivity, dielectric constant, and dielectric loss. rate, dielectric breakdown voltage, tracking resistance and arc resistance at room temperature (23
Measured at ℃). The tracking resistance is examined by the IEC method (electrolyte 0.1% NH4C1!, brass electrode 600V). The results are shown in Table 10.

43- Table 10 44- 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.

(that's all)

Claims (1)

[Scope of Claims] ■ 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 [wherein -R- is -CH2-CH =CH-(CH2)2-
CH=CH-CH2-1-CH-(CH2)2-CH=
An epoxy resin composition characterized by using a polycarboxylic acid glycidyl ether represented by CH-CH2-1CH-CH2 OCOCH30H U .