KR101082364B1 - Epoxy resin hardener - Google Patents

Abstract

The present invention is an epoxy resin curing agent obtained by addition reaction of an ethoxylate or propoxylate bisphenol A epoxy resin having a weight average molecular weight of 100 to 2,000 to any one of ethylenediamine resin, polyamide resin or phenalkaamine resin. The hardener is an epoxy resin hardener with low viscosity and low VOC (Volatile organic compound), excellent coating and chemical resistance, especially plasticity of the coating film is improved adhesion to the adherend to ship, heavy corrosion, building paints It can be usefully used as a coating agent in the field.

Ethylenediamine, Polyamide, Phenalkaamine, Bisphenol-A Epoxy, Ethoxylate, Propoxylate

Description

Epoxy resin hardener

The present invention adds an ethoxylate or propoxylate bisphenol A epoxy resin to any one selected from ethylenediamine resin, polyamide resin or phenalkaamine resin, and thus has a lower viscosity than the bisphenol A epoxy resin adduct. It relates to an epoxy resin curing agent having excellent physical properties of low VOC plasticity.

Currently, epoxy resins have been used for a long time to coat metals and cements for waterproofing, corrosion prevention and preservation. In the case of room temperature curing coatings, these cured products form a very good film after curing by unique bonding in a cured state and have corrosion resistance.

These coatings have been used as solvent type and water soluble epoxy coatings, and new air pollution regulations are rapidly stimulating new systems in recent years.

In general, epoxy resins are excellent in water resistance, chemical resistance, and adhesion, and thus are used as structural adhesives and coatings. Epoxy resin coating market tends to reduce VOC (Volatile organic compound), but typical epoxy resin composition contains 40-50% volume resin, which has been used to maintain high molecular weight in coating. It is true and because of its high molecular weight, it has a high viscosity and has been used in large amounts in consideration of workability.

The typical epoxy resin composition has to lower the amount of solvent used to remove environmental effects, but suffers from increased viscosity, lower plasticity of the cured product, and adhesion problems due to lower amount of solvent.

In addition, many models have been used to use low molecular weight compositions at low viscosity, but there are no epoxy resins and hardeners that can properly match the film properties such as specific physical properties such as pot life and curing rate, and chemical and mechanical properties.

An object of the present invention is to solve the shortcomings of the conventional epoxy resin curing agent according to the air pollution, the purpose of the low viscosity and low VOC of the epoxy resin curing agent, according to the required hardening properties and workability.

In order to achieve the above object,

The present invention is characterized in that an addition reaction of an ethoxylate or propoxylate bisphenol A epoxy resin having a weight average molecular weight of 100 to 2,000 to any one of ethylenediamine resin, polyamide resin or phenalkaamine resin. It provides an epoxy resin curing agent.

As the ethoxylate or propoxylate bisphenol A epoxy resin, one or two or more compounds represented by the following general formula (2) are used.

In Chemical Formula 1,

R is either CH ₃ or H, and n is an integer of 1 to 10.

The ethoxylate or propoxylate bisphenol A epoxy resin used in the present invention is preferably reacted with 0.5 to 1 mol of ethoxylate or propoxylate bisphenol A at a ratio of 1.1 to 1.5 mol of epichlorohydrin.

The ethylenediamine resin uses any one selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, metaxylenediamine and isophoronediamine. At this time, the curing agent is preferably added and reacted by adding an ethoxylate or propoxylate bisphenol A epoxy resin in an amount of 0.005 to 0.5 equivalents based on 1 equivalent of ethylenediamine resin.

The polyamide resin uses an amine number of 90 ~ 400mgKOH / g, a viscosity of 5,000 ~ 200,000cps / 25 ℃. At this time, the curing agent is added to the reaction by adding an ethoxylate or propoxylate bisphenol A epoxy resin in 3 to 50 parts by weight to 100 parts by weight of polyamide resin.

The penalcaamine has an amine number of 100 to 600 mgKOH / g, and a viscosity of 500 to 60,000 cps / 25 ° C. At this time, the curing agent is preferably added by adding ethoxylate or propoxylate bisphenol A epoxy resin at 5 to 60 parts by weight to phenalkaamine 100 parts by weight.

Hereinafter, the present invention will be described in more detail.

First, the ethoxylate or propoxylate bisphenol A epoxy resin used in the present invention is prepared by reacting 0.5-1 mol of ethoxylate or propoxylate bisphenol A at a ratio of 1.1-1.5 mol of epichlorohydrin.

In this case, the used ethoxylate or propoxylate bisphenol A is a compound represented by the formula (1), the polymerization degree n can be used 1-10 mol, and commercially available BP-11, BP-22, BP-33, BP-44, BE-11, BE-22, BE-33, BE-44 [products of Kunshan) can be applied.

In Formula 2, R is any one of CH ₃ or H, n is an integer of 1 to 10.

At this time, when the echlorohydrin is used in less than the content range, it is difficult to expect a suitable reaction, while if the content exceeds the content range, there is a problem that the recovery amount is increased, the yield is lowered.

After adding the catalyst, the dropping time of epichlorohydrin is preferably 5-7 hours, and the completion of the dropwise addition and the preliminary reaction proceeds, but the reaction temperature is preferably 80-110 ° C. After the preliminary reaction, the present reaction is required, and the reaction temperature is preferably 90 to 110 ° C.

After the completion of the reaction, desalting is performed, and in this case, toluene is injected in such a way that the nonvolatile content is 40-50% of the theoretical amount of resin, and a sufficient amount of water is added to remove the salt. Wash with water. Dehydration reaction temperature is preferably 100 ~ 120 ℃, and dehydration reaction is completed when the dehydration reaction is completed. The desolvent reaction temperature is preferably 130 to 140 ° C, and is preferably removed through vacuum decompression.

There are various types of catalysts used in the reaction, and bases and amines may be selected from sodium hydroxide, sodium hydrogen sulfate, tin chloride, zinc chloride, Lewis acid salt and quaternary ammonium salt, and the amount of catalyst used is ethoxy It is 0.01-0.1 weight part with respect to 100 weight part of latex or propoxylate bisphenol A.

Ethoxylate or propoxylate bisphenol A epoxy resin prepared by the above method is a compound represented by the formula (2), epoxy equivalent 250 ~ 1,000g / eq, viscosity of 100 ~ 5,000cps.

According to the present invention, an epoxy resin curing agent obtained by adding and reacting an ethoxylate or propoxylate bisphenol A epoxy resin in an amount of 0.005 to 0.5 equivalents to 1 equivalent of ethylenediamine is compared with the case where a bisphenol A epoxy resin is used. A non-solvent curing agent having a considerably lower viscosity at the same equivalence ratio can be obtained. The hardener thus prepared has the advantage of being rich in plasticity and improving adhesion.

At this time, the use of an ethoxylate or propoxylate bisphenol A-based epoxy resin in an excess of the above range in the ethylene diamine may cause gelation problem, the use of a small amount may cause a problem that can not reach the desired physical properties have.

In addition, according to the present invention, an ethoxylate having a weight average molecular weight of 100 to 2,000 in a polyamide resin having an active hydrogen having an amine number of 90 to 400 mgKOH / g and a viscosity of 5,000 to 200,000 cps / 25 ° C. Alternatively, in the case of addition reaction of propoxylate bisphenol A epoxy, 3 to 50 parts by weight of polyamide is reacted, and the viscosity is 2 to 3 times higher than that of addition reaction of bisphenol A epoxy having an epoxy equivalent of 200 to 700. About twice as low, the plasticity and adhesion of the coating film were improved.

In this case, the use of an ethoxylate or propoxylate bisphenol A-based epoxy resin in an excess of the above range in the polyamide resin may cause gelation problems, the use of a small amount may not reach the desired properties May be caused.

Further, according to the present invention, an ethoxylate having a weight average molecular weight of 100 to 2,000 in phenalcaamine having an amine number of 100 to 600 mgKOH / g and a viscosity of 500 to 60,000 cps / 25 ° C as a Mannich base, or The epoxy resin curing agent obtained by addition-reacting propoxylate bisphenol A epoxy to 5 parts by weight to 100 parts by weight of Mannich curing agent increases the plasticity as the amount of ethoxylate bisphenol A epoxy is increased. The conventional Mannich base obtained by the combination includes a phenolic benzene nucleus, so that the disadvantages of inferior plasticity and poor adhesion are also improved.

When adding ethoxylate or propoxylate bisphenol-A epoxy, a solvent can be used together in some cases, and a solvent generally uses xylene, toluene, normal butanol, isobutanol, and normal propyl which are used a lot in an epoxy curing agent. Alcohol, isopropyl alcohol, etc. can be used. Moreover, the content is possible up to 5-40 weight% with respect to the weight of resin solid content.

While the epoxy resin curing agent according to the present invention has a high solids content to avoid VOC regulation, it has a low viscosity, is rich in plasticity, can improve the low temperature curing property, and can be used by diluting a small amount of an organic solvent. The adhesion of can also be improved over conventional hardeners.

The epoxy resin curing agent according to the present invention has a low viscosity and low VOC, and is excellent in room temperature drying property, low temperature drying property and corrosion resistance required by general anticorrosive paints, and in particular, it is rich in plasticity so that flexibility and impact resistance are relatively superior and adhesion The performance is excellent and workability is satisfactory. In particular, the plasticity required in the coating film is greatly improved, and by adding ethoxylate or propoxylate bisphenol A epoxy resin, it contains more oxygen groups than the conventional bisphenol A epoxy added type. Significantly improved adhesion.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are presented to aid the understanding of the present invention, but the present invention is not limited thereto.

≪ Example 1 >

Put nitrogen gas into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, add 104 g of diethylenetriamine, and heat and stir at 60 to 70 ° C. to give 62 g of ethoxylate bisphenol epoxy having an average molecular weight of 640 for 30 minutes. After addition, the mixture was stirred for 20 minutes, and the temperature of the reaction solution was raised to 100 ± 10 ° C. and maintained for 1 hour. At this time, the prepared curing agent was 720mgKOH / g amine, 34g / eq active hydrogen equivalent weight was 700cps.

<Example 2>

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and then 94g of polyamide resin having active hydrogen having an amine value of 210 mgKOH / g and a viscosity of 60,000 cps / 40 ° C was added. After heating and stirring to ˜70 ° C., 30.6 g of xylene was added and stirred for 20 minutes to dissolve well. Then, 6 g of ethoxylate bisphenol A epoxy having an average molecular weight of 640 was gradually added, followed by stirring for 20 minutes to obtain the reaction solution. The temperature was raised to 100 ± 10 ° C. and then maintained for 2 hours. The mixture was cooled to 80 ° C., and 13 g of normal butanol was added thereto, followed by stirring for 20 minutes. At this time, the prepared curing agent had an amine value of 148 mgKOH / g, an active hydrogen equivalent weight of 280 g / eq, and a viscosity of 2,000 cps.

<Example 3>

159.8 g of phenol and 81 g of formalin were added at 30 ° C or lower while blowing nitrogen gas into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and then 248.5 g of triethylenetetramine at 30 ° C or lower for 1 hour. Was slowly added dropwise. After raising the temperature of the reaction solution to 100 ± 5 ℃ and maintained for 2 hours, and heated to 150 ℃ to extract 70g of the reaction condensation water, and reduced pressure to extract 21g of the reaction condensation water and then cooled to 90 ℃, After adding 57.3 g of normal butanol, 118 g of propoxylate bisphenol epoxy having an average molecular weight of 640 was slowly added, followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. In this case, the prepared curing agent had an amine value of 261 mgKOH / g, an active hydrogen equivalent weight of 65 g / eq, and a viscosity of 2,500 cps.

<Example 4>

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and 100g of penalcaamine having a amine value of 310 mgKOH / g and a viscosity of 30,000 cps / 25 ° C was added, and 43.3 g of normal butanol was added thereto. Thereafter, 30 g of propoxylate bisphenol epoxy having an average molecular weight of 640 was gradually added by heating and stirring to 80 ° C., followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. At this time, the prepared curing agent was an amine value of 168 mgKOH / g, an active hydrogen equivalent weight of 240 g / eq, and a viscosity of 2,000 cps.

Example 5

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and 100g of penalcaamine having an amine value of 500 mgKOH / g and a viscosity of 2,000 cps / 25 ° C was added, and 30 g of xylene was added. 20 g of propoxylate bisphenol epoxy having an average molecular weight of 640 was slowly added by heating and stirring to 80 ° C., followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. At this time, the prepared curing agent was an amine value of 285mgKOH / g, active hydrogen equivalent weight 130g / eq, the viscosity was 2,000cps.

<Example 6>

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and 100g of penalcaamine having an amine value of 310 mgKOH / g and a viscosity of 30,000 cps / 25 ° C was added, and 30 g of xylene was added. 20 g of propoxylate bisphenol epoxy having an average molecular weight of 900 was slowly added by heating and stirring to 80 ° C., followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. In this case, the prepared curing agent had an amine value of 173 mgKOH / g, an active hydrogen equivalent weight of 200 g / eq, and a viscosity of 2,100 cps.

Comparative Example 1

While nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, 104 g of diethylenetriamine was added thereto, and the mixture was heated and stirred at 60 to 70 ° C. to add 40 g of bisphenol epoxy having an average molecular weight of 700 over 30 minutes. Thereafter, the mixture was stirred for 20 minutes, and the temperature of the reaction solution was raised to 100 ± 10 ° C. and maintained for 1 hour. In this case, the prepared curing agent had an amine value of 760 mgKOH / g, an active hydrogen equivalent weight of 35 g / eq, and a viscosity of 8,000 cps.

Comparative Example 2

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and then 94g of polyamide resin having active hydrogen having an amine value of 210 mgKOH / g and a viscosity of 60,000 cps / 40 ° C was added. 30.6 g of xylene was heated and stirred at ˜70 ° C., stirred for 20 minutes to dissolve well. Then, 6 g of bisphenol epoxy having an average molecular weight of 400 was gradually added, followed by stirring for 20 minutes to adjust the temperature of the reaction solution to 100 ± 10. The temperature was raised to 캜 and held for 2 hours. The mixture was cooled to 80 ° C., and 13 g of normal butanol was added thereto, followed by stirring for 20 minutes. In this case, the prepared curing agent had an amine value of 148 mgKOH / g, an active hydrogen equivalent weight of 284 g / eq, and a viscosity of 5,000 cps.

Comparative Example 3

159.8 g of phenol and 81 g of formalin were added at 30 ° C or lower while blowing nitrogen gas into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and then 248.5 g of triethylenetetramine at 30 ° C or lower for 1 hour. Was slowly added dropwise. After raising the temperature of the reaction solution to 100 ± 5 ℃ and maintained for 2 hours, and heated to 150 ℃ to extract 70g of the reaction condensation water, and reduced pressure to extract 21g of the reaction condensation water and then cooled to 90 ℃, After adding 57.3 g of normal butanol, 78.6 g of bisphenol epoxy having an average molecular weight of 400 was slowly added, followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. At this time, the prepared curing agent was 275 mgKOH / g amine, 58 g / eq active hydrogen equivalent weight, 5,400 cps.

<Comparative Example 4>

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and 100g of penalcaamine having an amine value of 310 mgKOH / g and a viscosity of 30,000 cps / 25 ° C was added, and 30 g of xyleneol was added. 20 g of bisphenol epoxy having an average molecular weight of 400 was gradually added by heating and stirring to 80 ° C., followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. In this case, the prepared curing agent had an amine value of 201 mgKOH / g, an active hydrogen equivalent weight of 227 g / eq, and a viscosity of 6,300 cps.

Comparative Example 5

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and 100g of penalcaamine having an amine value of 500 mgKOH / g and a viscosity of 2,000 cps / 25 ° C was added, and 30 g of xylene was added. 20 g of bisphenol epoxy having an average molecular weight of 400 was gradually added by heating and stirring to 80 ° C., followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. In this case, the prepared curing agent had an amine value of 280 mgKOH / g, an active hydrogen equivalent weight of 130 g / eq, and a viscosity of 3,100 cps.

Comparative Example 6

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and 100g of penalcaamine having an amine value of 310 mgKOH / g and a viscosity of 30,000 cps / 25 ° C was added, and 30 g of xyleneol was added. 20 g of a fatty acid-modified bisphenol epoxy having an average molecular weight of 1200 was gradually added by heating and stirring to 80 ° C., followed by stirring for 20 minutes to raise the temperature of the reaction solution to 100 ± 10 ° C., and then maintained for 2 hours. In this case, the prepared curing agent had an amine value of 151 mgKOH / g, an active hydrogen equivalent weight of 205 g / eq, and a viscosity of 11,000 cps.

&Lt; Comparative Example 7 &

Nitrogen gas was blown into a reaction vessel equipped with a stirrer, a nitrogen injection tube, a thermometer, and a distillation capacitor, and 100g of penalcaamine having an amine value of 310 mgKOH / g and a viscosity of 30,000 cps / 25 ° C was added, and 30 g of xyleneol was added. 20 g of an aliphatic epoxy (Kokudo Chemical Co., Ltd. product name PG-207P polyether epoxy) having an average molecular weight of 600 g was gradually added by heating and stirring at 80 ° C., followed by stirring for 20 minutes to adjust the temperature of the reaction solution to 100 ± 10 ° C. The temperature was raised to and maintained for 2 hours. In this case, the prepared curing agent had an amine value of 173 mgKOH / g, an active hydrogen equivalent weight of 214 g / eq, and a viscosity of 2,500 cps.

<Experimental Examples 1 to 6 and Comparative Experimental Examples 1 to 7>

Using the curing agents prepared in Examples 1 to 6 and Comparative Examples 1 to 7, the anticorrosive coating was prepared by the composition and conventional method shown in Table 1 below.

division Experimental Example (g) Comparative Experiment Example (g) One 2 3 4 5 6 One 2 3 4 5 6 7 Hardener Example 1 10 - - - - - - - - - - - - Example 2 - 75 - - - - - - - - - - - Example 3 - - 18 - - - - - - - - - - Example 4 - - - 65 - - - - - - - - - Example 5 - - - - 36 - - - - - - - - Example 6 - - - - - 55 - - - - - - - Comparative Example 1 - - - - - - 10 - - - - - - Comparative Example 2 - - - - - - - 78 - - - - - Comparative Example 3 - - - - - - - - 16 - - - - Comparative Example 4 - - - - - - - - - 62 - - - Comparative Example 5 - - - - - - - - - - 35 - - Comparative Example 6 - - - - - - - - - - - 56 - Comparative Example 7 - - - - - - - - - - - - 58 Ancamine K-54 1 2 2 2 2 2 2 2 2 2 2 2 2 2 EPOKUKDO YD-128 2 100 100 100 100 100 100 100 100 100 100 100 100 100 TiO ₂ 20 20 20 20 20 20 20 20 20 20 20 20 20 Talc 60 60 60 60 60 60 60 60 60 60 60 60 60 Dispersant One One One One One One One One One One One One One Sedimentation inhibitors 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Xylene 6 6 6 6 6 6 6 6 6 6 6 6 6 Normal butanol 6 6 6 6 6 6 6 6 6 6 6 6 6 2.4.6-tri (dimethylaminoethyl) phenol (manufactured by Airproduct)
2. Bisphenol A liquid epoxy, epoxy equivalent 184 ～ 190g / eq (Kukdo Chemical)
3. Dispersant: BYK-203 (BYK)
4. Sedimentation inhibitor: BYK-410 (BYK company)

For the anticorrosive paint prepared above, room temperature dryness, low temperature hardenability, flexibility, impact, adhesiveness, and corrosion resistance were measured, and the results are shown in Tables 2 and 3.

1) Room temperature dryness

The paint was coated on an iron plate at 25 ° C. and a relative humidity of 50%, and the dry film thickness was coated at 100 to 200 μm to measure the time taken for curing and drying to evaluate room temperature dryness.

(◎: less than 3 hours; ○: less than 4 hours; ×: more than 4 hours)

2) Low Temperature Curability

After coating the paint on the iron plate at 25 ℃ and 50% RH, dry coating thickness is 100 ~ 200㎛ and stored in 5 ℃ constant temperature and humidity room within 1 minute to measure the time taken for curing drying Evaluated.

(◎: within 18 hours; ○: within 24 hours; ×: over 24 hours)

3) Flexibility test

After blasting the surface roughness to 25 ~ 75㎛ on the iron plate, remove rust, dust, moisture, oil and other contaminants with an appropriate solvent, and paint each paint prepared above on it, drying at room temperature for 7 days, and then drying at 25 ℃. It was measured using an Erichen instrument in a constant temperature and humidity room.

(◎: No influence; ○: Slightly cracked; ×: Severe cracking)

4) Impact test

After blasting the surface roughness to 25 ~ 75㎛ on the iron plate, remove rust, dust, moisture, oil and other contaminants with an appropriate solvent, and paint each paint prepared above on it, drying at room temperature for 7 days, and then drying at 25 ℃. Measurements were made using a Dupont instrument in a constant temperature and humidity room.

(◎: No influence; ○: Slightly cracked; ×: Severe cracking)

5) Adhesive Test

After blasting the surface roughness to 25 ~ 75㎛ on the iron plate, remove rust, dust, moisture, oil and other contaminants with an appropriate solvent, and paint each paint prepared above on it, drying at room temperature for 7 days, and then drying at 25 ℃. After cutting using a cross cuter, the adhesive tape was peeled off and visually confirmed.

6) Corrosion Resistance Test

After blasting the surface roughness to 25 ~ 75㎛ on the iron plate, remove rust, dust, moisture, oil and other contaminants with a suitable solvent and paint each paint prepared above on it and dry it for 7 days at room temperature After the surface of the cut was installed in a salt spray tester to evaluate the performance after 300 hours.

(◎: No effect; ○: Slightly rusted; ×: Severe rusting)

division Experimental Example Comparative Experimental Example One 2 3 One 2 3 Room temperature dryness ◎ ◎ ◎ ◎ ◎ ◎ Low temperature curing ◎ ○ ◎ ◎ ○ ○ Flexibility ○ ◎ ◎ ○ ◎ × Impact ◎ ◎ ◎ × ○ × Adhesive 70/100 100/100 100/100 30/100 80/100 60/100 Corrosion resistance ◎ ◎ ◎ × ◎ ○

division Experimental Example Comparative Experimental Example 4 5 6 4 5 6 7 Room temperature dryness ◎ ◎ ◎ ◎ ◎ ◎ ○ Low temperature curing ◎ ◎ ◎ ◎ ◎ ○ × Flexibility ◎ ◎ ◎ ○ × ◎ ◎ Impact ◎ ◎ ◎ × × ◎ ◎ Adhesive 100/100 100/100 100/100 65/100 50/100 90/100 90/100 Corrosion resistance ◎ ◎ ◎ ◎ ◎ ○ ×

Claims (9)

Epoxy resin curing agent characterized by addition reaction of an ethoxylate or propoxylate bisphenol A epoxy resin having a weight average molecular weight of 100 to 2,000 to any one of ethylenediamine resin, polyamide resin or phenalkaamine resin. . The epoxy resin curing agent according to claim 1, wherein the ethoxylate or propoxylate bisphenol A epoxy resin comprises one or two or more compounds represented by the following Chemical Formula 2: [Formula 2]

In Chemical Formula 2, R is either CH ₃ or H, and n is an integer from 1 to 10. 3. The ethoxylate or propoxylate bisphenol A epoxy resin is reacted with 0.5 to 1 mole of ethoxylate or propoxylate bisphenol A at a ratio of 1.1 to 1.5 moles of epichlorohydrin. Epoxy resin curing agent. The ethylenediamine resin according to any one of claims 1 to 3, wherein the ethylenediamine resin is any one selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, metaxylenediamine, and isophoronediamine. Epoxy resin curing agent, characterized in that. The epoxy resin curing agent according to claim 4, wherein the curing agent is added and reacted by adding an ethoxylate or propoxylate bisphenol A epoxy resin in an amount of 0.005 to 0.5 equivalents based on 1 equivalent of ethylenediamine resin. The epoxy resin curing agent according to any one of claims 1 to 3, wherein the polyamide resin has an amine value of 90 to 400 mgKOH / g and a viscosity of 5,000 to 200,000 cps / 25 ° C. 7. The epoxy resin curing agent according to claim 6, wherein the curing agent is added to 100 parts by weight of the polyamide resin and added to an ethoxylate or propoxylate bisphenol A epoxy resin at 3 to 50 parts by weight. The epoxy resin curing agent according to any one of claims 1 to 3, wherein the phenalcaamine has an amine value of 100 to 600 mgKOH / g and a viscosity of 500 to 60,000 cps / 25 ° C. The epoxy resin curing agent according to claim 8, wherein the curing agent is added and reacted by adding ethoxylate or propoxylate bisphenol A epoxy resin at 5 to 60 parts by weight to 100 parts by weight of phenalkaamine.