An amine curing agent and epoxy resin material

Abstract

The application discloses an amine curing agent and an epoxy resin material, the amine curing agent comprises the following components in mass fractions: 60-100 parts of 4,4'-methylenebis(2,6-diisopropylaniline), 10-20 parts of a phenylenediamine compound, and 1-10 parts of a tertiary amine compound; H on a benzene ring of the phenylenediamine compound is replaced by at least one of C1-C10 alkyl, C1-C10 alkylthio or C1-C10 alkoxy; the tertiary amine compound comprises a C7-C20 aralkyl tertiary amine compound and / or a C5-C30 heterocyclic tertiary amine compound. The amine curing agent is prepared by compounding 4,4'-methylenebis(2,6-diisopropylaniline) with specific phenylenediamine compounds and tertiary amine compounds in specific amounts, and after the amine curing agent is applied to an epoxy resin system, the gel time is long, the glass transition temperature is high, the operable time is long, and the cured product can maintain good structural strength at high temperatures.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and particularly relates to an amine curing agent and an epoxy resin material. Background Technology

[0002] Uncured epoxy resin has a thermoplastic linear structure and requires a curing agent to form a three-dimensional network structure through a cross-linking reaction, thereby obtaining excellent mechanical properties, chemical stability, and heat resistance. Among various curing agents, amine curing agents are the most widely used due to their good modifiability, rich structure, low price, and excellent performance. However, traditional amine curing agents are difficult to reconcile with the requirements of processing performance and high temperature resistance. Curing agents such as aliphatic amines, polyether amines, and cycloaliphatic amines are liquids at room temperature and have good workability, but after curing with epoxy resin, their glass transition temperature (Tg) is usually below 100°C. When the operating temperature approaches or exceeds Tg, the material will transition from a glassy state to a highly elastic state, resulting in changes in deformation and modulus. Volume, coefficient of thermal expansion, specific heat, and thermal conductivity will all change significantly, making it impossible to maintain the original structural strength and dimensional stability, and thus failing to meet the temperature resistance requirements of epoxy resin materials in the electronics, aerospace, automotive manufacturing, or petrochemical industries. Although aromatic amine curing agents (such as 4,4'-diaminodiphenylmethane, etc.) can reach a Tg of over 150°C after curing with epoxy resin, they are usually solid at room temperature and typically need to be heated to over 80°C to liquefy. This places high demands on the construction site, has a short working time, and results in significant material waste.

[0003] One study provides a method for preparing a phenolic amine curing agent. Through the reaction of cashew phenol with diethylenetriamine, m-phenylenediamine, etc., a high glass transition temperature epoxy curing agent is prepared. This method involves few synthesis steps, is simple to operate, and exhibits good temperature resistance and adhesion properties, making it applicable to heat-resistant adhesives, coatings, and other fields. However, the Tg after complete curing with epoxy resin is still below 130℃. While this meets conventional temperature resistance requirements, it still falls short for applications such as underground oil exploration, aerospace composite materials, high-voltage transformer potting, and new energy vehicle on-board potting.

[0004] Another study proposed a method to lower the melting point of aromatic amine curing agents through eutectic melting. This involves compounding 2-3 aromatic amine compounds to form a low-melting-point system, resulting in a low-melting-point mixture that can be mixed with resin at low temperatures, extending the resin's working time. However, the high-melting-point components in the formulation pose a risk of precipitation, as it contains m-phenylenediamine and 4,4'-phenylene oxide. Diaminodiphenylmethane is highly toxic, and the Tg of the cured product is below 150°C.

[0005] With the rapid development of fields such as electronics and electrical engineering, semiconductor packaging, aerospace, automotive manufacturing, and petrochemicals, the performance requirements for high-temperature resistant polymer materials are increasing. The aforementioned limitations severely restrict the application of epoxy resins and their amine curing agents in high-temperature environments. Therefore, upgrading the performance of epoxy resin systems with excellent processing properties and wide applications, and developing matching high-temperature resistant curing agents, has become an important development direction that is both economical and technically feasible. This has also made the research on operable, high-temperature resistant amine curing agents a continuous hot topic in the field of polymer materials. Summary of the Invention

[0006] In order to solve at least one of the problems existing in the prior art, one of the objectives of the present invention is to provide an amine curing agent that, by compounding specific amine components, can achieve the effect of long gel time and high glass transition temperature when applied to an epoxy resin system. The amine curing agent also has the characteristics of good workability and high temperature resistance.

[0007] The second objective of this invention is to provide an epoxy resin material.

[0008] The third objective of this invention is to provide an application of the above-mentioned amine curing agent or the above-mentioned epoxy resin material.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A first aspect of the present invention provides an amine curing agent comprising the following components in parts by weight: 60-100 parts of 4,4'-methylenebis(2,6-diisopropylaniline), 10-20 parts of a phenylenediamine compound, and 1-10 parts of a tertiary amine compound; wherein the H on the benzene ring of the phenylenediamine compound is replaced by at least one of C1-C10 alkyl, C1-C10 alkylthio, or C1-C10 alkyloxy groups; and the tertiary amine compound comprises a C7-C20 aralkyl tertiary amine compound and / or a C5-C30 heterocyclic tertiary amine compound.

[0010] The amine curing agent of the present invention is based on 4,4'-methylenebis(2,6-diisopropylaniline) and has a specific molecular design, especially the presence of an isopropyl functional group at the ortho position of the amino group. This functional group reduces the reactivity of the amino group and also reduces the intermolecular forces of the aromatic ring, which is beneficial to prolonging the gel time. On this basis, it can be combined with specific phenylenediamine compounds and tertiary amine compounds to obtain amine curing agents and epoxy resin materials with low viscosity, long working time, high glass transition temperature, excellent mechanical properties, good chemical resistance, and low toxicity.

[0011] In some embodiments of the present invention, the H on the benzene ring of the phenylenediamine compound is replaced by at least one of C1-C5 alkyl, C1-C5 alkylthio, or C1-C5 alkyloxy groups.

[0012] In some specific embodiments of the present invention, the H on the benzene ring of the phenylenediamine compound is replaced by C1~C5 alkyl and / or C1~C5 alkyl thio groups.

[0013] For example, a phenylenediamine compound in which the H on the benzene ring is replaced by a C1-C5 alkyl group can be diethyltoluenediamine; specifically, 3,5-diethyl-2,4-diaminotoluene or 3,5-diethyl-2,6-diaminotoluene.

[0014] For example, a phenylenediamine compound in which the H on the benzene ring is replaced by a C1-C5 alkyl group and a C1-C5 alkyl thio group can be dimethylthiotoluenediamine; more specifically, such as 2,4-dimethylthiotoluenediamine or 2,6-dimethylthiotoluenediamine.

[0015] In some specific embodiments of the present invention, the phenylenediamine compound includes diethyltoluenediamine, dimethylthiotoluenediamine, or a combination thereof.

[0016] In some embodiments of the present invention, the H on the benzene ring of the phenylenediamine compound is replaced by C1-C10 alkyl and C1-C10 alkyl thio groups; in some specific embodiments of the present invention, the H on the benzene ring of the phenylenediamine compound is replaced by C1-C5 alkyl and C1-C5 alkyl thio groups.

[0017] In some specific embodiments of the present invention, the phenylenediamine compound is selected from dimethylthiotoluenediamine; in some examples of the present invention, the phenylenediamine compound is selected from 2,4-dimethylthiotoluenediamine and / or 2,6-dimethylthiotoluenediamine.

[0018] In some specific embodiments of the present invention, the tertiary amine compound includes C10-C15 aralkyl tertiary amine compounds and / or C10-C20 heterocyclic tertiary amine compounds.

[0019] For example, the C10-C15 aralkyl tertiary amine compound may be 2,4,6-tris(dimethylaminomethyl)phenol or N,N-dimethylbenzylamine.

[0020] For example, the C10-C20 heterocyclic tertiary amine compound can be 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine.

[0021] In some embodiments of the present invention, the tertiary amine compound includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, or 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine.

[0022] In some embodiments of the present invention, the tertiary amine compound is selected from C5-C30 heterocyclic tertiary amine compounds; in some embodiments of the present invention, the tertiary amine compound is selected from C10-C20 heterocyclic tertiary amine compounds.

[0023] In some specific embodiments of the present invention, the tertiary amine compound is selected from 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine.

[0024] By selecting appropriate types of phenylenediamine compounds or tertiary amine compounds to combine with 4,4'-methylenebis(2,6-diisopropylaniline), a longer gel time and a higher glass transition temperature can be obtained, resulting in a longer workable time during construction and better high-temperature resistance of the cured product.

[0025] In some embodiments of the present invention, the amine curing agent comprises the following components in parts by weight: 60-100 parts of 4,4'-methylenebis(2,6-diisopropylaniline), 10-20 parts of dimethylthiotoluenediamine, and 1-10 parts of 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine.

[0026] In some embodiments of the present invention, the mass ratio of 4,4'-methylenebis(2,6-diisopropylaniline) to phenylenediamine compound is 100:(10~30); in some specific embodiments of the present invention, the mass ratio of 4,4'-methylenebis(2,6-diisopropylaniline) to phenylenediamine compound is 100:(15~20).

[0027] In some embodiments of the present invention, the mass ratio of 4,4'-methylenebis(2,6-diisopropylaniline) to the tertiary amine compound is 100:(1~15); in some specific embodiments of the present invention, the mass ratio of 4,4'-methylenebis(2,6-diisopropylaniline) to the tertiary amine compound is 100:(5~10).

[0028] In some embodiments of the present invention, the viscosity of the amine curing agent at 25°C is ≤900 cps; specifically, it can be 600~900 cps; for example, it can be any value or a range between any two of 600 cps, 650 cps, 700 cps, 750 cps, 800 cps, 850 cps or 900 cps; in some specific embodiments of the present invention, the viscosity of the amine curing agent at 25°C is 650~700 cps.

[0029] Amine curing agents have low viscosity and good flow properties, which can achieve better construction performance.

[0030] A second aspect of the present invention provides an epoxy resin material obtained by curing an epoxy resin and an amine curing agent as described in the first aspect of the present invention.

[0031] In some embodiments of the present invention, the mass ratio of the epoxy resin to the amine curing agent is 100:(15~40); for example, it can be any value or a range between any two of 100:15, 100:20, 100:25, 100:30, 100:35 or 100:40; in some specific embodiments of the present invention, the mass ratio of the epoxy resin to the amine curing agent is 100:(25~30).

[0032] In some embodiments of the present invention, the epoxy equivalent of the epoxy resin is 180~190 g / eq; for example, it can be any value or a range between 180 g / eq, 182 g / eq, 185 g / eq, 188 g / eq or 190 g / eq.

[0033] In some embodiments of the present invention, the curing temperature is 40~180°C; for example, it can be any value or a range between any two of 40°C, 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, 160°C, 170°C or 180°C.

[0034] In some embodiments of the present invention, the glass transition temperature of the epoxy resin material is ≥170°C; specifically, it can be 170~200°C; for example, it can be any value or a range between any two of 170°C, 175°C, 180°C, 185°C, 190°C, 195°C or 200°C; in some specific embodiments of the present invention, the glass transition temperature of the epoxy resin material is 185~190°C.

[0035] Specifically, when determining the glass transition temperature of the epoxy resin material, the epoxy resin material is obtained by curing epoxy resin and amine curing agent at 180°C for 1 hour.

[0036] In some embodiments of the present invention, the gel time required for the epoxy resin and amine curing agent to cure at 40°C is ≥13h; specifically, it can be 13~30h; for example, it can be any value or a range between any two of 13h, 15h, 17h, 20h, 22h, 24h, 26h, 28h or 30h; in some specific embodiments of the present invention, the gel time required for the epoxy resin and amine curing agent to cure at 40°C is 22~26h.

[0037] A third aspect of the present invention provides an amine curing agent as described in the first aspect of the present invention, or an epoxy resin material as described in the second aspect of the present invention, for use in the fields of electronic and electrical and semiconductor packaging, aerospace, automotive manufacturing, or petrochemicals.

[0038] For example, the amine curing agent and epoxy resin material of the present invention can be applied to fields such as composite materials, electronic potting, and oil exploration.

[0039] The beneficial effects of this invention are as follows: Based on 4,4'-methylenebis(2,6-diisopropylaniline), this invention is compounded with specific phenylenediamine compounds and tertiary amine compounds in specific amounts. The resulting amine curing agent, when applied to epoxy resin systems, can achieve a long gel time and a high glass transition temperature, effectively extending the workable time during construction. Moreover, the cured product can still maintain good structural strength and dimensional stability at high temperatures, exhibiting good high-temperature resistance, good chemical resistance, and low toxicity. Attached Figure Description

[0040] Figure 1 The differential scanning calorimetry curve of the epoxy resin material in Example 4 is shown. Detailed Implementation

[0041] The following specific embodiments further illustrate the content of the present invention in detail. It should also be understood that the following embodiments are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the principles described herein are all within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make selections within a suitable range based on the description herein, and are not intended to be limited to the specific data in the examples below. Unless otherwise specified, the raw materials, reagents, or apparatus used in the following embodiments and comparative examples can be obtained from conventional commercial sources or by existing known methods.

[0042] It should be noted that the 4,4'-methylenebis(2,6-diisopropylaniline) used in the embodiments and comparative examples of the present invention was synthesized by the following method: 150 g of distilled water was placed in a 500 mL three-necked flask equipped with a stirrer and nitrogen protection device. Stirring was started, and 88.5 g of weighed diisopropylaniline was slowly added. 50 g of weighed hydrochloric acid (31%) was added to the flask using a separatory funnel, and the mixture was heated to 50 °C. Then, 50 g of weighed formaldehyde solution (30%) was added dropwise to the flask to initiate a condensation reaction, which was completed in approximately 1 hour. The reaction was then carried out at 80 °C for 6 hours after the addition. After the reaction was complete, 30% NaOH solution was added to neutralize the solution. The mixture was allowed to stand, and then extracted three times with dichloromethane. After extraction, the solution was evaporated to dryness and purified by column chromatography to obtain 88 g of the product 4,4'-methylenebis(2,6-diisopropylaniline) (brownish-yellow liquid, yield 96%). The synthetic route is as follows: .

[0043] The 4,4'-methylenebis(2,6-diisopropylaniline) of the present invention has a specific molecular design, particularly with an isopropyl functional group at the ortho position of the amino group. This functional group reduces the reactivity of the amino group and also reduces the intermolecular forces of the aromatic ring, which is beneficial to prolonging the gel time. When compounded with specific phenylenediamine compounds and tertiary amine compounds in specific amounts, it has the characteristics of long gel time and high glass transition temperature when applied to epoxy resin systems.

[0044] In the following examples and comparative examples, room temperature refers to 25±5℃.

[0045] In the following examples and comparative examples, diethyltoluenediamine is 3,5-diethyl-2,4-diaminotoluene.

[0046] In the following examples and comparative examples, dimethylthiotoluenediamine is a mixture of 2,4-dimethylthiotoluenediamine and 2,6-dimethylthiotoluenediamine, a commercially available product.

[0047] Example 1 An amine-based curing agent, prepared by the following method: 80 g of 4,4'-methylenebis(2,6-diisopropylaniline), 15 g of diethyltoluenediamine, and 5 g of accelerator 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added to a 250 mL round-bottom flask and stirred at room temperature for 30 min to obtain an amine curing agent (yellow to dark brown liquid).

[0048] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent. The specific preparation method is as follows: An amine curing agent is mixed with bisphenol A type epoxy resin E51 with an epoxy equivalent of 180-190. The resin to curing agent ratio is 100:28 by mass. The mixture is then cured at 40-180℃ to obtain an epoxy resin material.

[0049] Example 2 An amine-based curing agent, prepared by the following method: 80 g of 4,4'-methylenebis(2,6-diisopropylaniline), 15 g of diethyltoluenediamine and 5 g of N,N-dimethylbenzylamine (BDMA) were added to a 250 mL round-bottom flask and stirred at room temperature for 30 min to obtain an amine curing agent (dark brown liquid).

[0050] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent, and the specific preparation method is the same as that in Example 1.

[0051] Example 3 An amine-based curing agent, prepared by the following method: 80 g of 4,4'-methylenebis(2,6-diisopropylaniline), 15 g of diethyltoluenediamine and 5 g of 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine were added to a 250 mL round-bottom flask and stirred at room temperature for 30 min to obtain an amine curing agent (dark brown liquid).

[0052] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent, and the specific preparation method is the same as that in Example 1.

[0053] Example 4 An amine-based curing agent, prepared by the following method: 80 g of 4,4'-methylenebis(2,6-diisopropylaniline), 15 g of dimethylthiotoluenediamine and 5 g of 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine were added to a 250 mL round-bottom flask and stirred at room temperature for 30 min to obtain an amine curing agent (dark brown liquid).

[0054] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent, and the specific preparation method is the same as that in Example 1.

[0055] Comparative Example 1 Commercially available curing agents are a mixture of methylene diphenylamine and directional amines, with diaminodiphenylmethane and polymethylene polyaniline with more than four functional groups as the main components.

[0056] An epoxy resin material is obtained by curing with the above-mentioned curing agent, and the specific preparation method is the same as that in Example 1.

[0057] Comparative Example 2 An amine-based curing agent, prepared by the following method: 95 g of 4,4'-methylenebis(2,6-diisopropylaniline), 5 g of diethyltoluenediamine, and 5 g of accelerator 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) were added to a 250 mL round-bottom flask and stirred at room temperature for 30 min to obtain an amine curing agent (dark brown liquid).

[0058] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent, and the specific preparation method is the same as that in Example 1.

[0059] Comparative Example 3 An amine-based curing agent, prepared by the following method: 90 g of 4,4'-methylenebis(2,6-diisopropylaniline) and 10 g of diethyltoluenediamine were added to a 250 mL round-bottom flask and stirred at room temperature for 30 min to obtain an amine curing agent (dark brown liquid).

[0060] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent, and the specific preparation method is the same as that in Example 1.

[0061] Comparative Example 4 An amine-based curing agent, prepared by the following method: 80 g of 4,4'-methylenebis(2,6-diisopropylaniline) and 20 g of diethyltoluenediamine were added to a 250 mL round-bottom flask and stirred at room temperature for 30 min to obtain an amine curing agent (dark brown liquid).

[0062] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent, and the specific preparation method is the same as that in Example 1.

[0063] Comparative Example 5 An amine-based curing agent, prepared by the following method: Add 50 g of 4,4'-methylenebis(2,6-diisopropylaniline) and 50 g of diethyltoluenediamine to a 250 mL round-bottom flask and stir at room temperature for 30 min to obtain an amine curing agent (dark brown liquid).

[0064] An epoxy resin material is obtained by curing with the above-mentioned amine curing agent, and the specific preparation method is the same as that in Example 1.

[0065] Performance testing 1) Test the viscosity of the curing agent at 25°C in each example and comparative example; set the curing conditions of the epoxy resin material in each example and comparative example to 100g / 40°C and determine its gel time; set the curing conditions of the epoxy resin material in each example and comparative example to 180°C / 1h and determine the glass transition temperature (Tg, DSC method) of the cured sample.

[0066] 2) Chemical resistance test: The epoxy resin materials in each example and comparative example were cured at 80℃ for 2 hours, then cured at 150℃ for 3 hours to obtain a 10×5×1mm cured block, and the mass m0 was recorded; the cured block was then immersed in different test reagents at 25℃ for 7 days, and the mass m was recorded. t Calculate the rate of change of mass Δm = (mt -m0) / m0×100%. The test reagents are water, toluene, acetic acid (25%), sulfuric acid (10%), sulfuric acid (30%) and sodium hydroxide (10%).

[0067] 3) Observe the appearance of the curing agent in each example and comparative example, and measure the color (Gardner), amine value (perchloric acid titration method), specific gravity (25℃), and active hydrogen equivalent (Ahew) of the curing agent; set the curing conditions of the epoxy resin material in each example and comparative example to 100g / 40℃, and measure the time for doubling the viscosity of the mixed adhesive, the time for reaching 10000cps, and the gel time during this process; set the curing conditions of the epoxy resin material in each example and comparative example to 100g / 60℃, and measure the time for doubling the viscosity of the mixed adhesive, the time for reaching 10000cps, and the gel time during this process; set the curing conditions of the epoxy resin material in each example and comparative example to 180℃ for 1h, and measure the tensile strength, flexural strength, and compressive strength of the cured sample according to standard GB / T 2567-2021.

[0068] The test results are shown in Tables 1-3.

[0069] Table 1. Viscosity, gel time, and Tg of each example and comparative example.

[0070] Table 2. Mass change rate of each example and comparative example in different test reagents.

[0071] Table 3 Performance of each embodiment and comparative example

[0072] As shown in Table 1, the curing agents in Examples 1-4 of this invention have low viscosity (≤820cps), long gel time during curing (≥13h), long workable time, and high glass transition temperature (≥170℃). Comparative Example 1 is a commercially available product, which has excessively high viscosity and a short gel time during curing, requiring high standards for the construction site. Comparative Example 2 uses too little phenylenediamine and tertiary amine compounds, resulting in excessively high viscosity and a significantly shortened gel time. Comparative Examples 3-5 did not have the tertiary amine compound, resulting in high viscosity and a shortened gel time.

[0073] Figure 1The image shows the differential scanning calorimetry (DSC) curve of the epoxy resin material in Example 4. The epoxy resin material was obtained by curing epoxy resin and an amine curing agent at 180°C for 1 hour, with a sample amount of 5.2 mg. The Tg value was determined by two heating cycles in a nitrogen atmosphere at a rate of 50 mL / min. The blue curve represents the first heating cycle, from 25°C to 250°C at a rate of 10°C / min. The red curve represents the cooling stage, where the temperature was held at 250°C for 3 minutes, then cooled to 25°C at a rate of -10°C / min. The black curve represents the second heating cycle, where the temperature was held at 25°C for 3 minutes, then heated to 250°C at a rate of 10°C / min. The Tg value measured during the second heating cycle was used as the final result. Figure 1 As can be seen, the Tg of the epoxy resin material in Example 4 is close to 188°C, which is an extremely high Tg value.

[0074] As can be seen from Table 2, the mass change rate of the epoxy resin material in the embodiments of the present invention is small in different test reagents, indicating that it has good chemical resistance.

[0075] As can be seen from Table 3, the curing agent in the embodiments of the present invention is liquid at room temperature. It can be cured at different temperatures and has the characteristics of long gel time and long working time. Moreover, the cured epoxy resin material has excellent mechanical properties, especially good tensile strength, flexural strength and compressive strength.

[0076] In summary, this invention, based on 4,4'-methylenebis(2,6-diisopropylaniline), is compounded with specific phenylenediamine and tertiary amine compounds in specific amounts. The resulting amine curing agent, when applied to epoxy resin systems, achieves a long gel time and a high glass transition temperature, effectively extending the workable time during construction. Furthermore, the cured product maintains good structural strength and dimensional stability at high temperatures, exhibiting excellent high-temperature resistance, good chemical resistance, and low toxicity. The amine curing agent and epoxy resin materials provided by this invention have wide applications in the fields of electronics and electrical engineering, semiconductor packaging, aerospace, automotive manufacturing, and petrochemicals.

Claims

1. An amine-based curing agent, characterized in that, The amine curing agent comprises the following components in parts by weight: 60-100 parts of 4,4'-methylenebis(2,6-diisopropylaniline), 10-20 parts of phenylenediamine compound, and 1-10 parts of tertiary amine compound; wherein the H on the benzene ring of the phenylenediamine compound is replaced by at least one of C1-C10 alkyl, C1-C10 alkylthio, or C1-C10 alkyloxy groups; and the tertiary amine compound comprises C7-C20 aralkyl tertiary amine compound and / or C5-C30 heterocyclic tertiary amine compound.

2. The amine curing agent according to claim 1, characterized in that, The hydrogen atoms on the benzene ring of the phenylenediamine compound are replaced by C1-C5 alkyl groups and C1-C5 alkyl thio groups.

3. The amine curing agent according to claim 1, characterized in that, The phenylenediamine compound includes diethyltoluenediamine, dimethylthiotoluenediamine, or combinations thereof.

4. The amine curing agent according to claim 1, characterized in that, The tertiary amine compound is selected from C10~C20 heterocyclic tertiary amine compounds.

5. The amine curing agent according to claim 1, characterized in that, The tertiary amine compound includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine, or 1,3,5-tris(dimethylaminopropyl)-1,3,5-hexahydrotriazine.

6. The amine curing agent according to any one of claims 1 to 5, characterized in that, The viscosity of the amine curing agent at 25°C is ≤900cps.

7. An epoxy resin material, characterized in that, The epoxy resin material is obtained by curing epoxy resin and an amine curing agent according to any one of claims 1 to 6; the mass ratio of epoxy resin to amine curing agent is 100:(15 to 40).

8. The epoxy resin material according to claim 7, characterized in that, The epoxy equivalent of the epoxy resin is 180~190 g / eq; And / or, the curing temperature is 40~180℃.

9. The epoxy resin material according to claim 7, characterized in that, The glass transition temperature of the epoxy resin material is ≥170℃; And / or, the gel time required for the epoxy resin and amine curing agent to cure at 40°C is ≥13h.

10. The application of an amine curing agent as described in any one of claims 1 to 6, or an epoxy resin material as described in any one of claims 7 to 9, in the fields of electronic and electrical and semiconductor packaging, aerospace, automotive manufacturing, or petrochemicals.

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