JPH03275714A - Curing agent composition for epoxy resin and epoxy resin composition containing same composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful as coating compound, etc., having a long pot life at normal temperature, developing mechanical properties and heat resistance even in middle-temperature curing, comprising an epoxy adduct of an imidazole compound, primary amine-containing aliphatic amine compound etc. CONSTITUTION:The objective composition comprising (A) an epoxy adduct of an imidazole compound shown by the formula [R<1> is H, 1-3C alkyl or (substituted) phenyl; R<2> is H or 1-3C alkyl] and/or Michael adduct modified substance and (B) a compound containing two or more active hydrogens which is a primary amine-containing aliphatic amine and/or a primary amine containing alicyclic amine compound or an epoxy adduct thereof and/or a Michael adduct modified substance preferably in a ratio of the component A/B=(25/75)-(60/40) (weight ratio).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a curing agent for epoxy resin 11Fi5. which uses a specific modified imidazole and a specific amine curing agent together.
The invention relates to products and epoxy resin compositions containing the same, and in particular, the viscosity of the curing agent is low, the pot life of the epoxy resin curing agent formulation is long, and the temperature is 60 to 100°C.
A curing agent composition for epoxy resin, which has the characteristic of being able to exhibit practically required mechanical properties and heat resistance even when cured at a medium temperature curing temperature range, and which is useful mainly as an anti-corrosion coating material, and a curing agent composition using the same. The present invention relates to an epoxy resin composition containing the present invention.

[Conventional technology]

It has been more than 40 years since epoxy resin appeared in the world. During this time, many hardening systems have been proposed, and their excellent performance has led to them being widely used as anti-corrosion coating materials.

Types of curing agents suitable for various conditions have been developed, and curing agents in various forms, from liquid to powder, have been put into practical use. When curing systems using amine curing agents are roughly classified, one of the following two methods is usually used.

a) Curing using a basic polymerization catalyst such as 2-ethyl-4-methylimidazole, dimethylbenzylamine, or 1.3.5-tris(dimethylaminomethyl)phenol.

b)) Curing using a compound having active hydrogen such as lyethylenetetramine, metaxylene diamine and modified products thereof.

In the case of an epoxy resin and a compound having active hydrogen, the compounding ratio of these is 110.7 to 5 in equivalent ratio (number of epoxy groups/number of active hydrogen), and in the case of a basic polymerization catalyst, 0.5 to 100 parts by weight of epoxy resin
It is common to use about 5 parts by weight. Regarding curing temperature, there are various types of curing, including curing at extremely low temperatures, so-called room-temperature curing, which is curing in a general environment, and heat curing, which is forced curing by heating, etc. They are selected and adopted depending on their suitability for use up to high temperatures of 200°C or higher.

[Problem to be solved by the invention]

Considering the physical properties of the cured product, heat curing is most preferable in terms of complete curing, since the reaction rate remains at 50 to 60% when cured at room temperature or below.

However, as a practical problem, heat curing at temperatures of 1.50"C or higher requires a huge amount of equipment costs, energy consumption, etc., and also poses a risk to workability, so it is not preferable. , more outrageously 60~
It can be said that it is most preferable in terms of cost and work safety if curing is carried out at a medium temperature of 100° C. and a cured product with excellent physical properties can be obtained.

When applying the above-mentioned curing systems a) and b) using the current amine curing agent to such medium-temperature curing, a
) method increases the pot life of the compound and provides a cured product with high mechanical properties such as tensile strength and bending strength, as well as heat resistance, but at medium humidity curing is insufficient and the cured product is brittle. It has the following drawbacks.

In method b), the viscosity of the compound is low, the curing is sufficient even at medium humidity, and the flexibility of the cured product is moderate, but the pot life of the compound is short and curing is difficult. It also has the disadvantage of being inferior in mechanical properties such as tensile strength and opening strength, and in heat resistance.

As mentioned above, the viscosity of the curing agent itself is low, the polarity of the compound is long at room temperature, and the mechanical properties, heat resistance, and flexibility of the cured product obtained by curing at medium humidity meet practical requirements. It has been difficult to create a hardening agent that can conform to this pattern.

[Means for deciding issues]

Based on the above-mentioned prior art, the present inventors have conducted intensive studies and found that when a liquid curing agent composition consisting of a specific modified imidazole and a specific amine-based curing agent is combined with an epoxy resin, it has a low viscosity. The present invention was completed based on the discovery that an epoxy resin composition with a very long pot life at room temperature and a medium-temperature curing that meets the practical requirements of mechanical properties, heat resistance, and flexibility can be obtained. I ended up doing it.

That is, the present invention provides (A, ) -Momonen (I) (wherein R1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent, and R2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) An epoxy adduct and/or Michael adduct modified product of an imidazole compound represented by (B) an aliphatic and/or alicyclic compound containing a primary amine. A liquid curing agent composition for epoxy resin characterized by containing an amine compound, or a compound having two or more active hydrogens which is an epoxy adduct and/or Michael adduct modified product of these, and (A) General Formula (I) (wherein R1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent, and R2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) ) An epoxy adduct and/or Michael adduct modified product of an imidazole compound represented by (B) an aliphatic and/or alicyclic amine compound containing a primary amine, or an epoxy adduct and/or Michael The present invention provides a liquid epoxy resin composition characterized by containing an adduct-modified compound having two or more active hydrogen atoms and (C) an epoxy resin.

The epoxy adduct-modified product of the imidazole compound represented by the general formula (I) used in the present invention may be, for example, an epoxy compound, preferably a Examples include reaction products obtained by dropping an epoxy compound having less than two functional groups under stirring.

The ratio of the imidazole compound represented by general formula (I) to the epoxy compound is such that the number of epoxy groups in the epoxy compound is usually 0.1 to 1.5 per active hydrogen in the imidazole compound. within the range of 0
．． A range of 8 to 162 pieces is preferable.

Epoxy compounds used here include (1) Monofunctional epoxy compounds such as butyl glycidyl ether,
2-ethylhexyl glycidyl ether, 1 carbon atom
Alcohol ether-type monoglycidyl ethers such as glycidyl ethers of mixed alcohols having 2 to 13 carbon atoms, butanol, 2-ethylhexyl alcohol, monoglycidyl ethers of alkylene oxide adducts of alcohols such as mixed alcohols having 12 to 13 carbon atoms, linoleic acid , glycidyl esters of unsaturated fatty acids having 18 carbon atoms such as oleic acid and tertiary carboxylic acids having 15 to 17 carbon atoms (Yuka Shell Co., Ltd., trade name Cardura E-1)
Examples include monoglycidyl esters such as 0), alkylene oxide compounds such as ethylene oxide and propylene oxide; Examples include diglycidyl ether and diglycidyl ether of trimethylolpropane.

Among these epoxy compounds, monofunctional epoxy compounds are preferred, and butyl glycidyl ether is particularly preferred.

Further, as a Michael adduct modified product of the imidazole compound represented by the general formula (I), for example, a nitrile group, a carbonyl group, etc. can be added to the imidazole at 60 to 90°C, which is made into a liquid by dissolving it with a solvent as necessary. Examples include reaction products obtained by adding or dropping a compound containing a carbon-carbon double viscosity adjacent to a typical electron-withdrawing group under stirring.

Incidentally, an epoxy compound may be added dropwise at the same time to produce a modified epoxy adduct and a modified Michael adduct at the same time.

The ratio of the imidazole compound represented by the general formula (I) and the compound containing carbon-carbon double viscosity adjacent to the electron-withdrawing group is as follows: The number of carbon-carbon double viscosity in the compound containing double viscosity is usually in a range of 0.1 to 1.3, and preferably in a range of 0.8 to 1.2.

As for the compound containing a carbon-carbon double bond adjacent to the electron-withdrawing group used here, the carbon-carbon double bond is
(2) Compounds containing one carbon-carbon double bond include, for example, acrylonitrile and (meth)acrylic ester represented by the following general formula (II). , and (1) Examples of the compound containing two carbon-carbon double bonds include compounds represented by the following general formulas (III) and (IV).

and R5 is a hydrogen atom, an alkyl group, an allyl group, an alkenyl group, a benzyl group or an alkyl group-substituted benzyl group, or -CO-(CH2OH, n is an integer from 1 to 30. However, an alkyl group, The number of carbon atoms in the alkenyl group is .about.30, which represents an alkyl group having 1 to 3 carbon atoms. ] [In the formula, R3 is the same as above, R7 is + cH2
+-11i-1CH-C-COO-R4 [In the formula, R3 is a hydrogen atom or a methyl group, R4 is an alkyl group, allyl group, alkenyl group, (JH (However, R3 and n in R are the same as above) be.)
represents. ] (In the formula, R represents -CHCH or -CH20H823.) Among these compounds containing one or two carbon-carbon double bonds adjacent to the electron-withdrawing group, acrylonitrile and phenoxy Examples include polyethylene glycol (meth)acrylic acid ester.

The modified epoxy adduct and modified Michael adduct (A) listed above may be used alone or in combination of two or more.

Aliphatic and/or primary amine-containing aliphatic and/or
or alicyclic amine compounds, or epoxy adduct and/or Michael adduct modified products thereof having two or more active hydrogens, such as polyoxypropylene monoamine, polyoxypropylene diamine, polyoxypropylene triamine, etc. Aliphatic aminated complex of polyoxyalkylene L'=6H; bis(3
-methyl4-amino-cyclohexyl)methane (BAS
Fi: cyclohexyl ring-containing alicyclic amine compounds such as Laromine C260 (trade name), 3-aminomethyl-3,5,5,-1-riftylcyclohexylamine (Daisel Huls, trade name isophoronediamine),
and compounds that are epoxy adduct and/or Michael adduct modified products of these and have two or more active hydrogen atoms. Each of these! Use 11 types or a mixture of two or more types.

Here, the epoxy compound used for epoxy adduct formation and the compound having a carbon-carbon double bond adjacent to an electron-withdrawing group used for Michael adduct are of the general formula (
Any compound used for epoxy adduct and/or Michael adduct modification of the imidazole compound represented by I) can be used.

In this case, the epoxy adduct and/or Michael adduct modification depends on the number of active hydrogens in the amine compound to be modified, but there are at least 1 active hydrogen per molecule, preferably 3 to 4.
It is preferable to denature so as to leave active hydrogen atoms.

Preferred examples include polyoxypropylene diamine,
Bis(3-methyl-4-amino-cyclohexyl)methane and acrylonitrile modified products thereof.

The above-mentioned epoxy adduct and/or Michael adduct modified product of the imidazole compound represented by Monka (I) (
A) [Hereinafter, abbreviated as modified product (A). ] and an aliphatic and/or alicyclic amine compound containing an 11th amine,
Or a compound (B) which is an epoxy adduct and/or Michael adduct modified product of these and has two or more active hydrogens [hereinafter abbreviated as compound (B)]. ] The usage ratio (A)/(B) is usually 10/90 to 70/ by weight.
30, especially 25/75 to 6 in that it has a long pot life when blended with epoxy resin and can be cured at medium temperature to obtain a cured product with excellent mechanical properties, heat resistance, and flexibility.
0/40 is preferred.

Examples of the epoxy resin (C) used in the present invention include a mixture of an epoxy resin having two or more epoxy groups and, if necessary, a reactive diluent having one or more epoxy groups. Among them, epoxy resins that are liquid at room temperature are preferred, and diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol AD are particularly preferred. In the case of an epoxy resin that is solid at room temperature, it can be used after being liquefied at room temperature using a solvent or the like.

However, using a large amount of solvent is not preferable since it becomes necessary to evaporate the solvent before or during curing and further deteriorates the working environment.

From the viewpoint of workability, it is desirable that the epoxy resin (C) has a low viscosity, but it is preferable to use one with a reactive diluent added thereto as necessary to reduce the viscosity.

Examples of reactive diluents include aliphatic glycidyl ethers obtained from alcohol and epichlorohydrin;
Glycidyl esters obtained from organic carboxylic acid and epichlorohydrin, glycidyl ethers obtained from monofunctional phenol and epichlorohydrin, glycidyl ether esters obtained from epichlorohydrin and a compound having both a phenol group and a carboxylic acid group in the same molecule. etc. are preferred.

Examples of aliphatic glycidyl ethers include aliphatic monoglycidyl ethers having 4 to 20 carbon atoms such as butyl glycidyl ether; ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, and alkylene of bisphenol A. Diglycidyl ethers obtained from oxide-added alcohols and the like; polyglycidyl ethers obtained from polyhydric alcohols such as trimethylolpropane, and the like.

Examples of glycidyl esters include those having 4 to 2 carbon atoms.
0 glycidyl esters of aliphatic carboxylic acids; glycidyl esters of aromatic carboxylic acids such as phthalic acid; and the like. Examples of glycidyl ethers obtained from monofunctional phenol and epichlorohydrin include p-te
Glycidyl ether of rt-butylphenol, p-5
Examples include glycidyl ether of butylphenol, cresyl glycidyl ether, and the like. Examples of glycidyl ether esters formed from a compound having both a phenol group and a carboxylic acid group in the same molecule and epichlorohydrin include glycidyl ether ester of p-oxybenzoic acid.

The average epoxy equivalent of the epoxy resin (C) used in the present invention (including reactive diluents used as necessary, but excluding non-reactive components such as solvents) is usually 80 to 1000.
Among them, the crosslinking density of the cured product is appropriate and the mechanical properties are improved.
1 in that a cured product with excellent heat resistance and flexibility can be obtained.
60-500 is preferable.

The above epoxy resin (C), the above modified product (A) and the compound (
The usage ratio of B) is within a range where the total of (A) and (B) ((A) + (B)l is usually 5 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin (C), Among them, 15
A range of 50 parts by weight is preferred.

In the curing agent composition for epoxy resin and the epoxy resin composition of the present invention, a solvent, a plasticizer, a filler, a stabilizer, a coloring agent, etc. can be used in combination, depending on the case.

Examples of solvents include alcohol solvents such as methanol, ethanol, and butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbon solvents such as benzene, toluene, and xylene;
Examples include ester solvents such as ethyl acetate, ethyl formate, and cellosolve acetate; cellosolve solvents such as methyl cellosolve and ethyl cellosolve; and mixtures of two or more thereof.

Examples of plasticizers include phthalate esters such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, lauryl phthalate, and distearyl phthalate; adipate esters such as dioctyl adibate; sepatate esters such as dioctyl sebacate; Examples include ester type plasticizers such as phosphoric esters such as cresyl phosphate, and mixtures of two or more thereof.

Examples of the filler include inorganic fillers such as calcium carbonate, talc, diatomaceous earth, and kaolin; organic fillers such as cellulose powder, powdered rubber, and recycled rubber.

Examples of stabilizers include metal soaps such as calcium stearate and aluminum stearate, inorganic acid salts such as dibasic phosphites and dibasic sulfates, and organic metal compounds such as dibutyltin dilaurate and dibutyltin malate. It will be done.

In order to obtain the curing agent composition for epoxy resins of the present invention, it is sufficient to simply mix, for example, the above-mentioned modified product (A) and compound (B), and further, if necessary, other additives.

Further, in order to obtain the epoxy resin composition of the present invention, for example, the epoxy resin curing agent composition obtained as described above and the epoxy resin (C) are mixed with other additives, solvents, etc. as necessary. There is a method of mixing the modified product (A), the compound (B), the epoxy resin (C), and, if necessary, other additives, solvents, etc.

(Example) The present invention will be specifically explained by showing synthesis examples, examples, and comparative examples below. Note that parts in the examples are parts by weight.

Synthesis Example 1 [Synthesis of epoxy adduct-modified product of imidazole compound represented by Monka (I)] 2-ethyl-4
-Pour 100 parts of methylimidazole into a flask and
℃, turn off the heat source, and dissolve butyl glycidyl ether 1.
18 parts were added dropwise to cause an exothermic reaction. After the dropwise addition, the temperature was raised to 120°C to complete the reaction and maintained for 1 hour to form a reddish brown transparent liquid (butyl glycidyl ether adduct of 2-ethyl-4-methylimidazole) (S- 1) was obtained.

Synthesis Example 2 (Same as above) 100 parts of 2-ethyl-4-methylimidazole was placed in a flask, heated to 80°C, the heat source was turned off, and 142 parts of butyl glycidyl ether was added dropwise to cause an exothermic reaction. After the dropwise addition, the temperature was raised to 120°C to complete the reaction.
A reddish-brown transparent liquid (butyl glycidyl ether adduct of 2-ethyl-4-methylimidazole) (S-2) with a viscosity of 4500 cps/25° C. was obtained by holding for a certain period of time.

Synthesis Example 3 (Same as above) 54 parts of ethyl alcohol and 1.2 parts of 2-methylimidazole were placed in a flask. Add 0 parts of O and keep it sealed at 70℃.
-Methylimidazole was dissolved.

Then turn off the heat source and persatic acid glycidyl ester (manufactured by Yuka Shell Co., Ltd., trade name Cardura E-10) 3
05 parts were added dropwise to cause an exothermic reaction. After the dropwise addition was completed, the temperature was maintained at 70° C. for 1 hour to complete the reaction. After the reaction was completed, the temperature was raised to 100°C, and ethyl alcohol was removed by vacuum distillation (maximum vacuum 20 mm, 11 g).
A reddish-brown transparent liquid with a viscosity of 1.3000 cps/25°C (
A persatic acid glycidyl ester adduct of 2-methylimidazole (S-3) was obtained.

Synthesis Example 4 [-Synthesis of Michael adduct modified imidazole compound represented by Monna (I)] 100 parts of 2-methylimidazole and phenoxypolyethylene glycol acrylate [manufactured by Toagosei Chemical Industry Co., Ltd., trade name: Aronix M-1.011288 parts] into a flask and heat to 60℃
The temperature was gradually raised to a temperature of 100% to cause a dissolution reaction. After confirming that all 2-methylimidazole had dissolved and the heat generation had subsided, the reaction was heated at 60°C for 1 hour and then for 12 hours to complete the reaction.
The mixture was maintained at 0°C for 1 hour to obtain a yellow transparent liquid (phenoxypolyethylene glycol acrylate adduct of 2-methylimidazole) (S-4) with a viscosity of 150 cps/25°C.

Synthesis Example 5 (Same as above) Diacrylate of imidazole 00 parts and polyethylene glycol (molecular ff 1400)
320 parts of the product (trade name: Light Acrylate 14EG-A) were placed in a flask, and the temperature was gradually raised to 60°C to cause a melt angle q reaction. After confirming that all of the 2-methylimidazole had melted and the heat generation had subsided, the reaction was maintained at 60°C for 1 hour and then at 120°C for 1 hour, resulting in a yellow transparent product with a viscosity of 800 eps/25°C. Liquid (polyethylene glycol diacrylate adduct of imidazole) (S-
5) was obtained.

Synthesis Example 6 [Synthesis of Michael adduct modified aliphatic amine compound containing primary amine] 100 parts of copolyoxypropylene diamine (manufactured by Mitsuishi Texaco Chemical, trade name: Jeffamine D-4001, molecular weight approximately 400) was placed in a flask. The mixture was heated to 65° C., and 13 parts of acrylonitrile was added dropwise with the heat source turned 11 to cause an exothermic reaction. After the dropwise addition was completed, the temperature was raised to 120°C to complete the reaction and maintained for 1 hour to obtain a yellow transparent liquid (acrylonitrile adduct of polyoxypropylene diamine) (S-6) with a viscosity of 40 CpS/25°C.

Synthesis Example 7 [Acid-containing epoxy adduct modified product of alicyclic amine compound containing primary amine] bis(3-methyl-4
-aminocyclohexyl)methane (BASF Japan■
1.00 parts of Laromine C-260 (trade name) was placed in a flask, heated to 80°C, the heat source was turned off, and 45.5 parts of butyl glycidyl ether was added dropwise to cause an exothermic reaction.

After completion of the dropwise addition, the temperature was raised to 120'C for 2"h to complete the reaction, and maintained for 11 hours until the viscosity was 520 (lcps/25
A yellow transparent liquid [butyl glycidyl ether adduct of bis(3-methyl-4-aminocyclohexyl)methane] (S-7) was obtained.

Examples 1 to 7 and Comparative Examples 1 to 4 Compounds (S-1) to (S7), 2- obtained in Synthesis Examples 1 to 7
Ethyl-4-methylimidazole (F, hereinafter referred to as 2 parts 4MZ), DiJ-Pharmin T-403, Dipfirmin D-400, Laromin C-260 and triethylenetetramine in the amount ratio shown in Table 1. The curing agent composition for epoxy resin of the present invention was obtained by mixing at room temperature, #I
The viscosity at 25° C. was measured using a t-111 cylindrical rotary viscometer. Further used as a curing agent in a comparative example (S-1)
, (S-6), 2 parts 4MZ and triethylenetetramine were similarly determined to have a viscosity of 11111. The viscosity measurement results are shown in Table 1.

Next, the above-mentioned curing agent composition for epoxy resin or curing agent,
The amount ratio of Evicron 850, Evolite M-1230, Evicron 725, and Evicron 830 shown in Table 1 was 2.
The epoxy resin compositions of the present invention and those for comparison were prepared by stirring at 0°C. The pot life and physical properties (thermal distortion temperature, bending strength, tensile strength, and Izod impact strength) were measured as follows. The results are shown in Table-1.

Pot Life 2 After mixing the amounts shown in Table 1, 20℃
The viscosity at n! ! We tracked the changes and determined the amount of time required to reach a viscosity twice the initial viscosity (the viscosity of the included samurai).

Physical properties: After defoaming the epoxy resin 11III under reduced pressure, it was poured into a casting frame made of a glass plate and cured under the conditions shown in Table 1. After curing is completed, the cured product is demolded and cut according to JIS-K 691.1,
A test piece was obtained. Bending strength, tensile strength, and Izot impact strength were measured at 23-25°C.

Ebicuron 850; Diglycidyl ether of bisphenol A [Epoxy equivalent: 190, manufactured by Dai 11 Ink Kagaku Kogyo ■] B) Evolite M-1230; Monoglycidyl ether of C12-13 alcohol [Epoxy equivalent, manufactured by Kyoeisha Urashi ■, 300-340 ] *3) Ebikuron 725; Alcohol ether type diglycidyl ether [manufactured by Dainippon Ink Chemical Co., Ltd., epoxy equivalent 1i140] *4) Ebikuron 830; diglycidyl ether of bisphenol F [manufactured by Dainippon Ink Chemical Co., Ltd., epoxy equivalent 173] ] Zero 5) Diefermin T-403; Polyoxypropylene triamine [manufactured by Mitsuishi Texaco Chemical ■ Molecular weight approximately 4
00] It also has the characteristic of being able to exhibit practically required mechanical properties and heat resistance even when cured at a medium temperature of about 100°C.

Therefore, the curing agent composition for epoxy resin and the epoxy resin composition of the present invention can be used very suitably in cases where long working hours are required in various fields such as paints, civil engineering and architecture, and electricity.

Claims (1)

[Claims] 1. (A) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or Indicates a phenyl group that may have a substituent, R^
2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) An epoxy adduct and/or Michael adduct modified product of an imidazole compound represented by (B) an aliphatic and/or alicyclic amine compound containing a primary amine, or an epoxy adduct and/or Michael adduct modified product thereof A liquid curing agent composition for an epoxy resin, comprising a compound having two or more active hydrogen atoms. 2. The curing agent composition according to claim 1, wherein the weight ratio (A)/(B) of the modified product (A) and the compound (B) is 10/90 to 70/30. 3. The curing agent composition according to claim 1, wherein the weight ratio (A)/(B) of the modified product (A) and the compound (B) is from 25/75 to 60/40. 4. The modified product (A) is a combination of an imidazole compound represented by the general formula (I) and a difunctional or less epoxy compound and/or a compound containing a carbon-carbon double bond adjacent to a nitrile group or a carbonyl group. The curing agent composition according to claim 1, which is a reaction product. 5. The modified product (A) is adjacent to the epoxy group and/or nitrile group or carbonyl group in the epoxy compound having less than two functional groups per active hydrogen in the imidazole compound represented by the general formula (I) The number of carbon-carbon double bonds in the compound containing carbon-carbon double bonds is 0.8
5. The curing agent composition according to claim 4, wherein the curing agent composition is a reaction product formed by using at a ratio of 1.2 to 1.2 pieces. 6. A compound containing a carbon-carbon double bond adjacent to a monofunctional epoxy compound and/or a nitrile group or a carbonyl group is The curing agent composition according to claim 4, which is a compound containing one or two double bonds. 7. An epoxy adduct and/or Michael adduct modified product of an aliphatic and/or alicyclic amine compound containing a primary amine, which has two or more active hydrogens, is combined with the amine compound and a difunctional or less epoxy The curing agent composition according to claim 4, which is a reaction product with a compound and/or a compound having a carbon-carbon double bond adjacent to a nitrile group or a carbonyl group. 8. (A) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R^1 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a substituent. Indicates a good phenyl group, R^
2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) An epoxy adduct and/or Michael adduct modified product of an imidazole compound represented by (B) an aliphatic and/or alicyclic amine compound containing a primary amine, or an epoxy adduct and/or Michael adduct modified product thereof A liquid epoxy resin composition comprising: a compound having two or more active hydrogen atoms; and (C) an epoxy resin. 9. The resin composition according to claim 8, wherein the epoxy resin (C) is a room temperature liquid epoxy resin. 10. Weight ratio of modified product (A) and compound (B) (A)/(
The resin composition according to claim 9, wherein B) is 10/90 to 70/30. 11. The resin composition according to claim 10, which contains a total of 5 to 100 parts by weight of the modified product (A) and the compound (B) based on 100 parts by weight of the epoxy resin (C). 12. The resin composition according to claim 10, which contains a total of 15 to 50 parts by weight of the modified product (A) and the compound (B) based on 100 parts by weight of the epoxy resin (C). 13. The modified product (A) is a combination of an imidazole compound represented by the general formula (I) and a difunctional or less epoxy compound and/or a compound containing a carbon-carbon double bond adjacent to a nitrile group or a carbonyl group. The resin composition according to claim 9, which is a reaction product. 14. The modified product (A) is adjacent to an epoxy group and/or a nitrile group or a carbonyl group in a difunctional or less epoxy compound with respect to one active hydrogen in the imidazole compound represented by the general formula (I) The number of carbon-carbon double bonds in the compound containing carbon-carbon double bonds is 0.
14. The resin composition according to claim 13, which is a reaction product formed by using a proportion of 8 to 1.2 pieces. 15. An epoxy adduct and/or Michael adduct modified product of an aliphatic and/or alicyclic amine compound containing a primary amine, which has two or more active hydrogens, is a compound that contains the amine compound and an epoxy with less than two functional groups. The resin composition according to claim 13, which is a reaction product with a compound and/or a compound having a carbon-carbon double bond adjacent to a nitrile group or a carbonyl group.