TWI454499B - Epoxy resin hardener and epoxy resin composition - Google Patents

Description

Epoxy resin hardener and epoxy resin composition

The present invention relates to an epoxy resin hardener containing a reaction product of a specific structure of a polyamine compound and a diglycidyl compound, an epoxy resin composition containing the epoxy resin hardener, and the epoxy resin composition. Hardened epoxy hardener.

Various polyamine compounds are widely used as epoxy resin hardeners and raw material systems thereof. The epoxy resin composition for room temperature curing using these epoxy resin hardeners has been widely used in coating materials such as ships, bridges, and anti-corrosion coatings for iron and steel buildings on sea and land, and concrete structures. Substrate, reinforcement, maintenance, floor panels for buildings, substrates for water and sewage equipment, paving materials, adhesives, etc.

Among the polyamine compounds, an epoxy resin curing agent comprising a polyamine compound having mutually different adducts having a side chain group represented by the following formula (I) can impart a good epoxy resin. The physical properties of the cured coating film and the physical properties of the cured epoxy resin are good (see JP-A-2004-67895).

(R) ₂ N-H ₂ C-A-CH ₂ -NHR (I) (A is a phenylene group or a cyclohexylene group, and R is a hydrogen atom or a phenethyl group; the plural R groups may be the same Can also be different, at least one of R is phenethyl)

However, an epoxy resin cured product obtained by hardening an epoxy resin composition containing an epoxy resin hardener represented by the formula (I) is in a field requiring flexibility or requires chemical resistance. In the field of (especially, organic solvent resistance), etc., it is not necessarily sufficient.

(disclosure of the invention)

An object of the present invention is to provide an epoxy resin hardener using a polyamine compound, which can impart good epoxy resin hard coating film properties and hardening at a point of good hardenability, flexibility or organic solvent resistance. An epoxy resin curing agent for physical properties, an epoxy resin composition containing the epoxy resin curing agent, and an epoxy resin curing agent for curing the epoxy resin composition.

As a result of intensive research, the present inventors have found that an epoxy resin composition containing an epoxy resin hardener has excellent flexibility and chemical resistance (especially resistance to organic solvents), and the epoxy resin hardener is A polyamine compound composed of a compound represented by the formula (1) and a polyamine compound obtained by reacting a diglycidyl compound having a specific structure.

That is, the present invention relates to an epoxy resin hardener, an epoxy resin composition, and an epoxy resin cured product shown below.

An epoxy resin curing agent comprising a reaction product of a polyamine compound represented by the formula (I) and a diglycidyl compound having a carbon number of 3 or more and a glycidyl group.

(R) ₂ N-H ₂ C-A-CH ₂ -NHR (I) (A is a phenylene group or a cyclohexylene group, and R is a hydrogen atom or a phenethyl group; the plural R groups may be the same Can also be different, at least one of R is phenethyl)

2. The epoxy resin hardener according to claim 1, wherein the polyamine compound contains 80% by weight or more of the polyamine compound represented by the formula (II).

RHN-H ₂ C-A-CH ₂ -NHR (II) (A is a phenylene group or a cyclohexylene group, and R is a hydrogen atom or a phenethyl group; and a plurality of R groups may be the same or a phase Different, at least one of R is phenethyl)

3. The epoxy resin hardener according to claim 1 or 2, wherein the diglycidyl compound is a compound represented by the formula (IV).

In the formula (IV), R is a hydrogen atom or an alkyl group; a plurality of R groups may be the same or different, and n is an integer of 3 or more)

4. The epoxy resin hardener according to any one of claims 1 to 3, wherein the carbon number between the glycidyl groups of the diglycidyl compound is 12 or less.

5. The epoxy resin hardener according to any one of claims 1 to 4, wherein the diglycidyl compound is a linear diglycidyl compound.

6. The epoxy resin hardener according to claim 5, wherein the diglycidyl compound is 1,6-hexanediol diglycidyl ether.

7. The epoxy resin hardener according to claim 5, wherein the diglycidyl compound is 1,4-butanediol diglycidyl ether.

8. The epoxy resin hardener according to any one of claims 1 to 4, wherein the diglycidyl compound is a branched diglycidyl compound.

9. The epoxy resin hardener according to claim 8, wherein the branched diglycidyl compound is a compound represented by the following formula (V).

(In the formula (V), R is a hydrogen atom, a methyl group or an ethyl group; R may be the same or different in plural, and at least two of R are a methyl group and/or an ethyl group; and, n is 3 or more. Integer)

10. The epoxy resin hardener according to claim 8 or 9, wherein the branched diglycidyl compound is 2,2-dimethyl-1,3-propanediol diglycidyl ether.

The epoxy resin hardener according to any one of claims 1 to 10, wherein a reaction ratio (active hydrogen number/epoxy group number) of the polyamine compound to the diglycidyl compound is from 3 to 10.

An epoxy resin composition comprising the epoxy resin hardener according to any one of claims 1 to 11.

A cured epoxy resin which is obtained by hardening an epoxy resin composition as in claim 12 of the patent application.

The epoxy resin hardener of the present invention can impart good hardenability (specifically, dryness to the touch) and good epoxy resin hard coat film properties as well as hardened physical properties (especially, excellent flexibility and resistance to organic matter) Solvent based epoxy resin composition.

(Detailed description of the invention)

The present invention relates to an epoxy resin hardener which comprises a reaction product of a polyamine compound represented by the formula (I) and a diglycidyl compound.

(R) ₂ N-H ₂ C-A-CH ₂ -NHR (I) (A is a phenylene group or a cyclohexylene group, and R is a hydrogen atom or a phenethyl group; the plural R groups may be the same Can also be different, at least one of R is phenethyl)

The polyamine compound represented by the formula (I) used in the present invention is a reaction product obtained by the reaction of a diamine compound represented by the formula (III) with styrene.

H ₂ N-CH ₂ -A-CH ₂ -NH ₂ (III) (A is a phenylene group or a cyclohexylene group)

Examples of the diamine compound represented by the formula (III) include o-toluenediamine, m-toluenediamine, p-toluenediamine, 1,2-bis(aminomethyl)cyclohexane, and 1,3-double. (Aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane. Among them, toluene diamine and 1,3-bis(aminomethyl)cyclohexane are preferred. Especially good inter-toluene diamine.

The polyamine compound represented by the formula (I) is an adduct obtained by an addition reaction of an amine group of a diamine compound represented by the formula (III) with an olefin group of styrene, and is added by styrene. In the number, it is possible to produce various 1 adducts, 2 adducts, and 3 adducts shown below. Here, Ph represents a phenethyl group.

(a): (Ph)HN-H ₂ C-A-CH ₂ -NH ₂ (b): (Ph)HN-H ₂ C-A-CH ₂ -NH(Ph) (c): (Ph) ₂ N-H ₂ C-A-CH ₂ -NH ₂ (d): (Ph) ₂ N-H ₂ C-A-CH ₂ -NH(Ph)

The polyamine compound represented by the formula (I) of the present invention may be composed of a single one of an adduct, a _two adduct and a three adduct, or may be any mixture thereof.

In particular, the polyamine compound represented by the formula (I) used in the present invention preferably contains 80% by weight or more of the polyamine compound represented by the formula (II), and more preferably 90% by weight or more.

RHN-H ₂ C-A-CH ₂ -NHR (II) (A is a phenylene group or a cyclohexylene group, and R is a hydrogen atom or a phenethyl group; and a plurality of R groups may be the same or a phase Different, at least one of R is phenethyl)

The polyamine compound represented by the formula (II) corresponds to the one adduct (a) and the two adduct (b) among the adducts (a) to (d). Therefore, the total of the one adduct (a) and the adduct (b) contained in the polyamine compound represented by the formula (I) used in the present invention is 80% by weight or more, and further preferably 90%. More than weight%.

When the polyamine compound represented by the formula (II) contained in the polyamine compound represented by the formula (I) is less than 80% by weight, the epoxy resin hard coat film and the epoxy resin hardened material may be hydrophobic. Sex and crosslink density will decrease. As a result, the water resistance and the organic solvent resistance of the epoxy resin cured coating film and the cured epoxy resin are lowered, which is not preferable.

In order to obtain a polyamine compound represented by the formula (I) having a composition having such a characteristic, the reaction ratio of the diamine compound represented by the formula (III) to styrene (styrene/diamine compound) is 1.5 or more. More preferably, the reaction is carried out at 1.2 or less (mole ratio).

The diglycidyl compound (a compound having two glycidyl groups; hereinafter referred to as "diglycidyl compound") used in the present invention has a carbon number of 3 or more, preferably 4 or more. When the carbon number between the glycidyl groups is less than 3, the effect of imparting flexibility to the epoxy resin cured coating film and the cured epoxy resin is small. Further, the polyamine compound represented by the formula (I) has a high concentration of a hydroxyl group generated during the reaction, and the hydrophobicity is lowered, so that it is resistant to the acid and alkali aqueous solution of the epoxy resin cured coating film and the epoxy resin cured product. The drug will be reduced.

The upper limit of the carbon number between the glycidyl groups is not limited, but is preferably 12 or less, and particularly preferably 8 or less. When the carbon number between the glycidyl groups exceeds 12, the affinity for the organic solvent becomes high, and the organic solvent resistance of the epoxy resin cured coating film and the cured epoxy resin is lowered, which is not preferable.

The structure of the diglycidyl compound used in the present invention is not particularly limited, and specific examples thereof include a diglycidyl ether compound represented by the following formula (IV).

In the formula (IV), R is a hydrogen atom or an alkyl group; and a plurality of R groups may be the same or different. Further, n represents a carbon number between glycidyl groups, and is 3 or more, preferably 3 or more and 12 or less. More preferably, it is an integer of 4 or more and 8 or less).

Examples of such a glycidyl compound include a linear diglycidyl compound and a branched diglycidyl compound.

The linear diglycidyl compound is a compound in which the atomic group composed of two or more atoms on the side chain of the carbon chain (main chain) between the glycidyl groups is not bonded, and R in the above formula (IV) is All hydrogen atoms.

When it is desired to impart more flexibility to the epoxy resin cured coating film and the cured product, a linear diglycidyl compound is preferably used.

Specific examples of the preferred linear diglycidyl compound include, for example, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,5-pentanediol condensed water. Glyceryl ether, 1,6-hexanediol diglycidyl ether, 1,7-heptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol Diglycidyl ether, 1,10-nonanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether. Among them, preferred are 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether.

The branched diglycidyl compound is a compound in which a group of two or more atoms is bonded to a side chain of a carbon chain (main chain) between glycidyl groups, and at least R in the above formula (IV) One is an alkyl group. The alkyl group may, for example, be a methyl group, an ethyl group or a propyl group.

Among the branched diglycidyl compounds, at least two of R in the above formula (IV) are preferably a methyl group and/or an ethyl group, and specific examples thereof include the following (V). a compound of the formula.

In the formula (V), R is a hydrogen atom, a methyl group or an ethyl group. The plural R groups may be the same or different, and at least two of R are a methyl group and/or an ethyl group. n represents 3 or more. Good system 3 or more and 12 or less)

That is, the total number of methyl groups and/or ethyl groups present between the glycidyl groups is preferably 2 or more. When the total number of methyl groups and/or ethyl groups is 2 or more, the effect of increasing the hydrophobicity by the increase of the alkyl group is the hydrophobicity of the hydroxyl group generated when the polyamine compound represented by the formula (I) is added. Further, the chemical resistance of the acid and alkali aqueous solution of the epoxy resin cured coating film and the epoxy resin cured product is improved.

It is preferable to use a branched diglycidyl compound when it is desired to improve the chemical resistance of the epoxy resin hardened coating film and the cured product.

Specific examples of the preferred branched diglycidyl compound include, for example, 2,2-dimethyl-1,3-propanediol diglycidyl ether (neopentyl glycol diglycidyl ether), 2,5- Dimethyl-2,5-hexanediol diglycidyl ether, 2,5-hexanediol diglycidyl ether, 2,4-pentanediol diglycidyl ether, 2-methyl-2, 4-pentanediol diglycidyl ether or the like. Of these, 2,2-dimethyl-1,3-propanediol diglycidyl ether (neopentyl glycol diglycidyl ether) is preferred.

The epoxy resin hardener of the present invention contains a reaction product obtained by a reaction of a polyamine compound represented by the formula (I) and a diglycidyl compound. This reaction product is produced by a reaction of an amine group of a polyamine compound represented by the formula (I) with a glycidyl group of a diglycidyl compound.

The diglycidyl compound used in the reaction may be used singly or in combination of two or more kinds of diglycidyl compounds. When two or more kinds of diglycidyl compounds are used, two or more kinds may be mixed and reacted with the polyamine compound represented by the formula (I), or may be reacted one by one for each type.

The reaction ratio of the polyamine compound to the diglycidyl compound represented by the formula (I) (the active hydrogen number of the polyamine compound / the number of epoxy groups of the diglycidyl compound) is preferably from 3 to 10, more preferably 4 ~8. When the reaction ratio exceeds 10, the effect of imparting flexibility and resistance to organic solvents is insufficient, and if it is less than 3, the viscosity is remarkably high, which is not preferable.

A conventionally known method can be used to react the diglycidyl compound with the polyamine compound represented by the formula (I). For example, a method in which a polyamine compound in which the number of epoxy groups of the diglycidyl compound becomes an excessive amount of active hydrogen is added to the reaction apparatus, and the diglycidyl compound is dropped and heated. The reaction temperature and the reaction time in this case are not particularly limited. However, in one example, the temperature of the polyamine compound is raised to 80° C., the liquid temperature is maintained at 80 to 90° C., and the diglycidyl compound is dropped, and the temperature is raised to 100° C. after the completion of the dropwise addition. The reaction was carried out for 2 hours, and the disappearance of the glycidyl group was confirmed by IR spectroscopy to terminate the reaction.

The epoxy resin hardener of the present invention contains the above reaction product obtained by a reaction of a polyamine compound represented by the formula (I) and a diglycidyl compound, or may be composed of the reaction product alone or It is a mixture with other polyamine compounds. Other polyamine compounds which can be mixed include, for example, an aliphatic polyamine compound, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine. And hexaethylenediamine or the like; an aliphatic polyamine compound having an aromatic ring; for example, xylylenediamine; and the aliphatic polyamine compound; for example, decylamine, isophoronediamine, bis(amine) Methyl)cyclohexane, N-aminomethylpyrazine, etc.; the aromatic polyamine compound may, for example, be phenylenediamine, diaminodiphenylmethane or diaminodiphenylphosphonium; Other polyamine skeleton polyamine compounds, norbornane skeleton polyamine compounds, and the like. These other polyamine compounds may be mixed without being invariable, and may be modified by an amine group modified by a reaction with a compound having a carboxyl group and an addition reaction with an epoxy compound. The mixture is modified by Mannich modification or the like which is produced by the reaction of formaldehyde and phenol, and then mixed. The mixing ratio at this time is not particularly limited as long as it does not detract from the characteristics of the epoxy resin hardener of the present invention, but it is preferable to make the other polyamine compound about 100 by weight with respect to 100 parts by weight of the reaction mixture of the present invention. The following.

The epoxy resin composition of the present invention contains an epoxy resin of a main component and an epoxy resin hardener. The epoxy resin used in the epoxy resin composition of the present invention may be an epoxy resin having a glycidyl group reactive with an active hydrogen derived from an amine group contained in the epoxy resin curing agent of the present invention. There is no particular limitation. Such an epoxy resin may, for example, be a polyfunctional epoxy resin or a monofunctional epoxy resin. The polyfunctional epoxy resin may, for example, be a diglycidyl ether compound of a mononuclear divalent phenol compound such as resorcin or hydroquinone; 4,4'-isopropylidene diol (bisphenol A), a diglycidyl ether compound of a polynuclear divalent phenol such as 4,4'-methylene diphenol (bisphenol F); a condensed water of a glycol such as ethylene glycol, propylene glycol, butylene glycol or hexanediol Glyceryl ether compound; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, azelaic acid, citric acid, isophthalic acid, citric acid a glycidyl ester compound of an aliphatic, aromatic or alicyclic dibasic acid such as cyclohexanedicarboxylic acid; 1,3-bis(N,N-diglycidylaminomethyl)benzene; A glycidylamine compound such as 3-bis(N,N-diglycidylaminomethyl)cyclohexane or the like. Further, the monofunctional epoxy resin may, for example, be a glycidyl ether compound of an alcohol such as butanol or higher alcohol, or a shrinkage of a mononuclear monovalent phenol compound such as phenol, m-cresol, p-cresol or o-cresol. A glycidyl ester compound of a monovalent carboxylic acid such as a glyceryl ether compound or neodecanoic acid.

Among them, 4,4'-isopropylidene diphenol diglycidyl ether (bisphenol A type epoxy resin) and 4,4'-methylene diphenol diglycidyl ether (bisphenol F type) Epoxy resin), and mixtures of these as a main component.

Further, when a bisphenol A type epoxy resin and/or a bisphenol F type epoxy resin are used as a main component, a bisphenol A type epoxy resin and/or a bisphenol F type epoxy resin other than a glycidyl group ring may be used. As the oxygen resin, for example, a small amount of a diol diglycidyl ether compound or a monofunctional glycidyl compound may be used in combination as a reactive diluent.

Further, in the epoxy resin composition of the present invention, an epoxy resin hardener other than the above-mentioned epoxy resin hardener of the present invention, or a filler or a plasticizer may be used in accordance with the use without departing from the effects of the present invention. A component such as a flow-adjusting component such as a modified component, a non-reactive diluent, or a rheological property imparting agent, a pigment, an adhesion-imparting agent, or the like, or a bouncing agent, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a light stabilizer Additives such as agents, hardening accelerators, and the like.

The ratio of the epoxy resin to the epoxy resin hardener of the epoxy resin composition of the present invention is preferably that the ratio of the active hydrogen number of the epoxy resin hardener of the present invention to the epoxy group number of the epoxy resin is 0.7 to 1.2. range. If it is this range, it is preferable in terms of the degree of crosslinking of the cured product and the water resistance.

The epoxy resin composition of the present invention can be hardened by a known method to form an epoxy resin cured product. The hardening conditions are appropriately selected in accordance with the use without departing from the scope of the effects of the present invention.

Example

The invention will be specifically described below by way of examples. However, the invention is not limited by these examples. Further, the measurement of the content of the polyamine compound represented by the formula (I), the measurement of the content of the polyamine compound represented by the formula (II), and the performance of the epoxy resin cured coating film (epoxy resin cured product) The evaluation of performance) was carried out in the following manner.

<Measurement of the content of the compound represented by the formulas (1) and (2)>

The gas chromatographic analysis GC-14A (manufactured by Shimadzu Corporation) was measured under the following conditions.

Pipe column: UltraAlloy-l (15 m long, film thickness 1.5 μm, inner diameter 0.5 mm) manufactured by Frontier Lab Co., Ltd. Carrier gas: 氦 Flow rate: 5.3 ml/min Internal standard substance: α, α'-bis (4-amino group) Phenyl)-1,4 diisopropylbenzene solvent: methanol sample injection amount: 0.5 μl temperature condition: INJ, DET: 300 ° C COL: 250 ° C / 10 minutes → 20 ° C / min temperature → 300 ° C / 18.7

<Evaluation of performance of epoxy resin hard coating film>

The epoxy resin composition was subjected to 240 grit treatment at 23 ° C and 50% RH, and coated with a thickness of 200 μm through a xylene degreased cold-rolled steel sheet (SPCC-SB) (JIS-G-3141). .

Appearance: The appearance (gloss, transparency, smoothness) of the coating film after 7 days of coating was visually evaluated, and the drying property (after 16 hours of hardening, 1, 4, and 7 days later) was touched by the four stages (◎: excellent, ○ : Good, △: slightly bad, ×: bad).

Water resistance: After 16 hours of coating, water droplets were dropped on the coating film after 1, 4, and 7 days, and the film change after one day of storage was observed in four stages (◎: excellent, ○: good, △: slightly bad, X) : Bad) to evaluate.

Chemical resistance: The coated steel sheet after 7 days of coating was immersed in each drug at 23 ° C for 4 weeks, and the film change after 1 and 4 weeks was visually observed in 4 stages (◎: excellent, ○: good, △: slightly Bad, ×: Bad) Evaluation. Further, the salt spray test was carried out in accordance with JIS K5600.

Flexibility (cupping test): The film was evaluated for resistance to cupping after 7 days of coating (according to JIS-K-5600).

<Synthesis Example 1>

In a 0.5 liter inner separation flask equipped with a stirring device, a thermometer, a nitrogen gas introduction tube, a dropping funnel, and a cooling tube, a polyamine compound (trade name "G", which is an addition reaction product of m-xylenediamine and styrene, is fed. -240"; manufactured by Mitsubishi Gas Chemical Co., Ltd., active hydrogen equivalent (AHEW): 103 g/eq, the content of the compound represented by the formula (I): 99.8% by weight, and the compound represented by the formula (II) Content: 88.8 wt%) 206.0 g, and the temperature was raised to 80 ° C while stirring under a nitrogen stream.

While maintaining the temperature at 80 ° C, 56.0 g of neopentyl glycol diglycidyl ether (epoxy equivalent: 140 g/eq, hereinafter referred to as "NPG") was added dropwise for 1 hour. After the completion of the dropwise addition, the mixture was heated to 100 ° C and reacted for 2 hours to obtain 261.4 g of an NPG adduct (reaction product A) of G-240.

<Synthesis Example 2>

206.0 g of G-240 (manufactured by Mitsubishi Gas Chemical Co., Ltd., AHEW: 103 g/eq) was fed in a flask similar to the synthesis example 1, and the temperature was raised to 80 ° C while stirring under a nitrogen stream. While maintaining the temperature at 80 ° C, 62.4 g of 1,4-butanediol diglycidyl ether (manufactured by Merk Co., Ltd., epoxy equivalent: 156 g/eq, hereinafter referred to as 1,4-BD) was dropped for 1 hour. After the completion of the dropwise addition, the mixture was heated to 100 ° C to carry out a reaction for 2 hours to obtain 267.6 g of a G-240 1,4-BD adduct (reaction product B).

<Synthesis Example 3>

206.0 g of G-240 (manufactured by Mitsubishi Gas Chemical Co., Ltd., active hydrogen equivalent: 103 g/eq) was fed to the flask in the same manner as in Synthesis Example 1, and the temperature was raised to 80 ° C while stirring under a nitrogen stream. While maintaining the temperature at 80 ° C, 1,6-hexanediol diglycidyl ether was dropped for 1 hour (manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy equivalent: 156 g/eq, hereinafter referred to as 1,6-HD) 62.4 g. After the completion of the dropwise addition, the mixture was heated to 100 ° C to carry out a reaction for 2 hours to obtain 267.7 g of a 1,6-HD adduct (reaction product C) of G-240.

<Synthesis Example 4>

206.0 g of G-240 (manufactured by Mitsubishi Gas Chemical Co., Ltd., AHEW: 103 g/eq) was fed in a flask similar to the synthesis example 1, and the temperature was raised to 80 ° C while stirring under a nitrogen stream. While maintaining the temperature at 80 ° C, 53.6 g of 1,2-propanediol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy equivalent: 134 g/eq, hereinafter referred to as 1,2-PD) was dropped for 1 hour. After the completion of the dropwise addition, the mixture was heated to 100 ° C to carry out a reaction for 2 hours to obtain 258.8 g of a 1,2-PD adduct (reaction product D) of G-240.

<Example 1>

The reaction product A and the bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 828, epoxy equivalent: 186 g/eq) were blended at a ratio shown in Table 1, at 23 ° C 50 The epoxy resin hardened coating film was hardened under the condition of %RH to evaluate the performance. The results are shown in Table 1.

<Example 2>

The reaction product B and the bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 828, epoxy equivalent: 186 g/eq) were blended at a ratio shown in Table 1, at 23 ° C 50 The epoxy resin hardened coating film was hardened under the condition of %RH to evaluate the performance. The results are shown in Table 1.

<Example 3>

The reaction product C and the bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 828, epoxy equivalent: 186 g/eq) were blended at a ratio shown in Table 1, at 23 ° C 50 The epoxy resin hardened coating film was hardened under the condition of %RH to evaluate the performance. The results are shown in Table 1.

<Example 4>

The reaction product A and the bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 807, epoxy equivalent: 168 g/eq) were blended at a ratio shown in Table 2 at 23 ° C. The epoxy resin hardened coating film was hardened under the condition of %RH to evaluate the performance. The results are shown in Table 2.

<Example 5>

The reaction product C and the bisphenol F type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 807, epoxy equivalent: 168 g/eq) were blended at a ratio shown in Table 2 at 23 ° C. The epoxy resin hardened coating film was hardened under the condition of %RH to evaluate the performance. The results are shown in Table 2.

<Comparative Example 1>

The reaction product D and the bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 828, epoxy equivalent: 186 g/eq) were blended at a ratio shown in Table 3 at 23 ° C. The epoxy resin hardened coating film was hardened under the condition of %RH to evaluate the performance. The results are shown in Table 3.

<Comparative Example 2>

G-240 (manufactured by Mitsubishi Gas Chemical Co., Ltd., active hydrogen equivalent: 103 g/eq) and bisphenol A epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 828, epoxy equivalent: 186 g/eq) And 1,6-hexanediol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy equivalent: 156 g/eq, hereinafter referred to as 1,6-HD), and blended at the ratio shown in Table 3, The epoxy resin hardened coating film was hardened under the condition of 23 ° C under 50% RH, and performance evaluation was performed. The results are shown in Table 3.

<Comparative Example 3>

G-240 (manufactured by Mitsubishi Gas Chemical Co., Ltd., active hydrogen equivalent: 103 g/eq) and bisphenol A epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicote 828, epoxy equivalent: 186 g/eq) The ratios shown in Table 3 were adjusted, and they were hardened under the conditions of 23 ° C and 50% RH to prepare an epoxy resin hardened coating film, and performance evaluation was performed. The results are shown in Table 3.

Claims (12)

An epoxy resin hardener comprising a reaction product of a polyamine compound represented by the formula (I) and a diglycidyl compound represented by the formula (IV), (R) ₂ NH ₂ CA-CH _2- NHR (I) (A is a phenylene group or a cyclohexylene group, and R is a hydrogen atom or a phenethyl group; a plurality of R groups may be the same or different, and at least one of R is a phenethyl group) In the formula (IV), R is a hydrogen atom or an alkyl group; a plurality of R groups may be the same or different, and n is an integer of 3 or more). The epoxy resin hardener according to claim 1, wherein the polyamine compound contains 80% by weight or more of the polyamine compound represented by the formula (II), and RHN-H ₂ CA-CH ₂ -NHR... II) (A is a phenylene group or a cyclohexylene group, and R is a hydrogen atom or a phenethyl group; a plurality of R groups may be the same or different, and at least one of R is a phenethyl group). The epoxy resin hardener according to claim 1 or 2, wherein the carbon number between the glycidyl groups of the diglycidyl compound is 12 or less. The epoxy resin hardener according to claim 1 or 2, wherein the diglycidyl compound is a linear diglycidyl compound. An epoxy resin hardener according to claim 4, wherein the diglycidyl compound is 1,6-hexanediol diglycidyl ether. The epoxy resin hardener according to claim 4, wherein the diglycidyl compound is 1,4-butanediol diglycidyl ether. The epoxy resin hardener according to claim 1 or 2, wherein the diglycidyl compound is a branched diglycidyl compound. The epoxy resin hardener according to claim 7, wherein the branched diglycidyl compound is a compound represented by the following formula (V), (In the formula (V), R is a hydrogen atom, a methyl group or an ethyl group; R may be the same or different in plural, and at least two of R are a methyl group and/or an ethyl group; and, n is 3 or more. The integer). The epoxy resin hardener according to claim 7, wherein the branched diglycidyl compound is 2,2-dimethyl-1,3-propanediol diglycidyl ether. The epoxy resin hardener according to claim 1 or 2, wherein a reaction ratio (active hydrogen number/epoxy group number) of the polyamine compound to the diglycidyl compound is from 3 to 10. An epoxy resin composition containing the epoxy resin hardener according to any one of claims 1 to 10. An epoxy resin hardened article, as claimed in claim 11 The epoxy resin composition of the article hardens.