A method for preparing multi-loaded epoxy resin composite materials

Abstract

This application provides a method for preparing a multi-loaded epoxy resin composite material, belonging to the technical field of epoxy resin-containing compositions. Artemisia annua and bentonite are mixed evenly in ethanol, and after the reaction is complete, the mixture is cooled, centrifuged, and dried to obtain product one. Epoxy resin, curing agent, accelerator, and product one are mixed evenly, vacuum degassing is performed, and the resulting mixture is cured to obtain the finished composite material. The composite material prepared by the above method is used in high-end microelectronics packaging, aerospace, printing, biochemistry, and sensors, exhibiting advantages such as low nitriding rate, low water vapor permeability, and excellent antibacterial properties.

Description

Technical Field

[0001] This application relates to a method for preparing a multi-loaded epoxy resin composite material, belonging to the technical field of compositions containing epoxy resin. Background Technology

[0002] Microelectronics technology, as one of the fastest-growing and most important technologies in today's industrial information society, is the "heart" of the electronics and information industry. A key indicator of microelectronics technology is the rapid progress and development of semiconductor integrated circuit technology. Integrated circuit technology mainly includes circuit design, manufacturing processes, packaging, and testing. With the deepening development of the integrated circuit industry, manufacturing and packaging technologies have become crucial pillars of the microelectronics industry. Electronic packaging materials, used to carry electronic components and their interconnections, serve as the sealing and substrate materials for integrated circuits and are a key factor determining electronic packaging technology. They provide mechanical support, environmental protection through sealing, and heat dissipation from electronic components, requiring excellent electrical insulation.

[0003] Epoxy resins possess excellent mechanical, electrical, processing, adhesion, weather resistance, water resistance, and thermal stability. They also offer superior cost-effectiveness, low cost, low density, and flexible encapsulation processes, accounting for over 90% of polymer-based encapsulation materials. However, due to the inherent macromolecular structure of epoxy resins, they exhibit high hygroscopicity, making them highly sensitive to moisture. Moisture intrusion is a significant factor leading to device failure, causing reliability issues such as corrosion failure and popcorn failure. Therefore, this non-hermetic encapsulation characteristic is the most significant drawback of epoxy resins as an encapsulation material, limiting their application in high-reliability applications. Furthermore, the poor antibacterial properties of epoxy resins lead to bacterial growth, often shortening their lifespan and limiting their use in environments with high sterility requirements, such as hospitals and food hygiene.

[0004] To improve the water and oxygen barrier properties of epoxy resin, CN105131534A, CN110055021A, CN103602300A, and other studies have compounded and modified epoxy resin. Although the above studies have improved the barrier properties of epoxy resin, the composites have poor heat resistance. In particular, they have not addressed the low helium permeation rate required for high-end encapsulation epoxy resins, thus limiting their application.

[0005] The antibacterial properties of epoxy resins are typically improved by adding antibacterial agents. Commonly used antibacterial agents are generally divided into three categories: inorganic antibacterial agents, organic antibacterial agents, and natural antibacterial agents. Inorganic nano-antibacterial agents (such as CN106065162A) are used due to their high specific surface energy and long-term stability, such as silver, zinc oxide, and cuprous oxide nanoparticles. However, their use in medicine is limited due to the introduction of heavy metal ions. Organic antibacterial agents (such as CN105647453A) mainly contain functional groups such as quaternary ammonium salts, phenolic hydroxyl groups, or halogens. However, their application is limited by drawbacks such as poor heat resistance, difficulty in grafting small molecules with polymers, and certain toxicity. Natural antibacterial agents (such as CN104927538A, CN105368364A, and CN106065162A) are derived from natural plant components, are environmentally friendly, and can be sustainably developed. However, none of them address improving the airtightness of epoxy resins or reducing permeation rates, thus limiting their application. Summary of the Invention

[0006] In view of this, this application provides a method for preparing a multi-loaded epoxy resin composite material, which not only reduces the nitriding rate and water vapor permeability, but also endows the composite material with antibacterial properties.

[0007] Specifically, this application is implemented through the following scheme:

[0008] A method for preparing a multi-loaded epoxy resin composite material includes the following steps:

[0009] (1) Mix 40-70 parts by weight of Artemisia argyi and 30-60 parts by weight of bentonite in ethanol, then place the mixture in a high-pressure reactor and react at 80-130°C for 6-24 hours. After cooling, centrifuge and dry under vacuum at 60°C to obtain bentonite loaded with Artemisia argyi extract, denoted as bentonite H.

[0010] (2) Take 50-70 parts by weight of epoxy resin, 0.5-40 parts by weight of curing agent and 0.1-3 parts by weight of accelerator, and add bentonite H. Disperse and stir at high speed in a mixing tank until the mixture is uniform. Degas under vacuum. Pour the resulting mixture into a preheated mold and place it in an oven. Cure at 25-180℃ for 1-24 hours to obtain the finished composite material. The composite material is loaded with Artemisia argyi extract and bentonite. The amount of bentonite H added is 3-15% of the total mass of epoxy resin, curing agent and accelerator.

[0011] The above method first involves uniformly mixing Artemisia annua, bentonite, and ethanol. The resulting solution is then transferred to a high-pressure reactor and reacted in an oven at a specific temperature for a certain time. After the reactor is removed and allowed to cool naturally to room temperature, the solution is extracted, centrifuged, and dried to obtain bentonite loaded with Artemisia annua extract. This bentonite is then uniformly mixed with epoxy resin and a curing agent and cured at a specific temperature to obtain a low-permeability antibacterial bentonite / epoxy resin composite material loaded with Artemisia annua extract. Compared to pure epoxy resin, the composite material prepared by this invention exhibits a lower permeability, superior antibacterial properties, and higher flexural strength. It can be used in high-end microelectronics packaging as well as in aerospace, printing, biochemistry, and sensor applications where high airtightness is required.

[0012] Furthermore, as a preferred option:

[0013] In step (1),

[0014] The Artemisia argyi refers to the roots, stems, leaves, or a mixture thereof.

[0015] The bentonite has a particle size of 5 nanometers to 200 micrometers.

[0016] The ethanol is ethanol with a purity higher than 95%.

[0017] In step (2),

[0018] The epoxy resin is a hydroxymethyl bisphenol A type epoxy resin, an alicyclic epoxy resin, a phenolic epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a glycidylamine type epoxy resin.

[0019] The curing agent is an amine curing agent, an acid anhydride curing agent, or an imidazole curing agent. More preferably, the amine curing agent includes polyamides, aliphatic amines, aromatic amines, alicyclic amines, polyether amines, and dicyandiamides; the acid anhydride curing agent includes aromatic acid anhydrides, epoxetine acid anhydrides, long-chain aliphatic acid anhydrides, haloan anhydrides, and anhydride adducts; the imidazole curing agent includes imidazole, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, diphenylimidazolium, or mixtures thereof.

[0020] The accelerator is any one of tertiary amine accelerators, quaternary ammonium salt accelerators, fatty amine accelerators, 2,4,6-tris(dimethylaminomethyl)phenol, N-p-chlorophenyl-N,N'-dimethylurea, or thiourea.

[0021] The above scheme first loads Artemisia annua extract onto bentonite using a solvothermal method. The ultra-high adsorption capacity of bentonite is used to load the Artemisia annua extract, combining the extraction of Artemisia annua and the modification of bentonite into one. Then, it is compounded with epoxy resin to prepare an antibacterial material with low helium permeability and low water vapor permeability, giving the epoxy resin good airtightness while also giving it antibacterial properties.

[0022] Compared with the prior art, the beneficial effects of this application are as follows:

[0023] 1) Due to the ultra-high adsorption capacity of bentonite, combined with the corresponding preparation method in this case, the Artemisia annua extract is well loaded onto it. Furthermore, the good airtightness of bentonite and the high antibacterial properties of Artemisia annua endow the material with good airtightness and excellent antibacterial properties, reducing the nitriding rate to 8.2*10. -8 Below atm·cc / s, water vapor permeability can be reduced to 1.21*10. -6 g / m 2 • It can be used for less than 24 hours, with an antibacterial rate of over 98.2% against Escherichia coli and over 97.3% against Staphylococcus aureus.

[0024] 2) The organic components in Artemisia annua extract have a good interaction with epoxy resin. When loaded onto bentonite, it also solves the interface problem of epoxy resin and bentonite composite, which is conducive to obtaining high air tightness.

[0025] The above process is simple, easy to operate and controllable, environmentally friendly and pollution-free, and low in cost, which can effectively save resources and achieve sustainable development. Attached Figure Description

[0026] Figure 1 The image shows a scanning electron microscope (SEM) image of the multi-loaded epoxy resin composite material prepared in Example 1.

[0027] Figure 2 This serves as a control for the antibacterial experiment against Escherichia coli in Example 1.

[0028] a - Reference 1, b - Reference 2, c - Materials prepared in Example 1;

[0029] Figure 3 This serves as a control for the antibacterial experiment against Staphylococcus aureus in Example 1.

[0030] a - Reference 1, b - Reference 2, c - Materials prepared in Example 1;

[0031] Figure 4 This serves as a control for the antibacterial experiment against Escherichia coli in Example 2.

[0032] a - Reference 1, b - Reference 2, c - Materials prepared in Example 2;

[0033] Figure 5 This serves as a control for the antibacterial experiment against Staphylococcus aureus in Example 2.

[0034] a - Reference 1, b - Reference 2, c - Materials prepared in Example 2;

[0035] Figure 6This serves as a control for the antibacterial experiment against Escherichia coli in Example 3.

[0036] a - Reference 1, b - Reference 2, c - Materials prepared in Example 2;

[0037] Figure 7 This serves as a control for the antibacterial experiment against Staphylococcus aureus in Example 3.

[0038] a - Reference 1, b - Reference 2, c - Materials prepared in Example 2;

[0039] Figure 8 This serves as a control for the antibacterial experiment against Escherichia coli in Example 4.

[0040] a - Reference 1, b - Reference 2, c - Materials prepared in Example 2;

[0041] Figure 9 This serves as a control for the antibacterial experiment against Staphylococcus aureus in Example 4.

[0042] a - Reference 1, b - Reference 2, c - Materials prepared in Example 2. Detailed Implementation

[0043] The detection method in the following examples is as follows:

[0044] (1) Helium permeation rate: DIN EN 1330-8.

[0045] (2) Antibacterial properties: Escherichia coli GB4789.38; Staphylococcus aureus GB479.10.

[0046] (3) Water vapor transmission rate: ASTM1249M.

[0047] Example 1

[0048] Take 40.0g of Artemisia annua leaves and 60.0g of bentonite and put them into 97% ethanol. Mix them evenly and then put them into a high-pressure reactor and react at 80℃ for 24 hours. After removing them and cooling them to room temperature naturally, centrifuge them and dry them under vacuum at 60℃ to obtain bentonite H loaded with Artemisia annua extract.

[0049] Take 70.0g of bisphenol A type epoxy resin, 0.5g of imidazole and 0.1g of N-p-chlorophenyl-N,N'-dimethylurea, and add bentonite H prepared by the above method. The amount of bentonite H added is 3% (about 2.118g) of the total mass of bisphenol A type epoxy resin, imidazole and N-p-chlorophenyl-N,N'-dimethylurea. After stirring evenly, degas under vacuum, pour into a mold, and then put into an oven at 180℃ for 1 hour to obtain a bentonite / epoxy resin composite low permeability antibacterial material loaded with Artemisia annua extract.

[0050] The helium permeation rate of the bentonite / epoxy resin composite low-helium permeation antibacterial material loaded with Artemisia annua extract was tested to be 8.2*10. -8 atm·cc / s, water vapor permeability is 1.05*10 -6 g / m 2 • After 24 hours, the antibacterial rate against Escherichia coli reached 98.2%, and the antibacterial rate against Staphylococcus aureus reached 97.3%.

[0051] Comparative Example 1

[0052] Take 70.0g of bisphenol A type epoxy resin, 0.5g of imidazole and 0.1g of N-p-chlorophenyl-N,N'-dimethylurea, stir evenly, degas under vacuum, pour into a mold, and then put into an oven at 180℃ for 1 hour to obtain reference standard 1.

[0053] Comparative Example 2

[0054] Take 70.0g of bisphenol A type epoxy resin, 0.5g of imidazole and 0.1g of N-p-chlorophenyl-N,N'-dimethylurea, add 7.5g of bentonite, stir evenly, degas under vacuum, pour into a preheated mold, and then put into an oven at 180℃ for 1 hour to obtain reference standard 2.

[0055] The products obtained in Example 1, Comparative Example 1, and Comparative Example 2 were tested:

[0056] (1) Transmission electron microscopy test

[0057] Transmission electron microscopy test results as follows Figure 1 As shown, from Figure 1 It can be seen that the product prepared in Example 1 has the characteristics of uniform clay dispersion and a flaky distribution.

[0058] (2) Nitriding rate and air tightness test

[0059] The helium permeation rate of the multi-loaded epoxy resin composite material in this case is 8.2 × 10⁻⁶. -8 atm·cc / s, water vapor transmission rate is 1.05*10 -6 g / m 2 ·24h.

[0060] The helium permeation rate of reference standard 1 was 7.3 × 10⁻⁶. -7 atm·cc / s, water vapor transmission rate is 1.12*10 -2 g / m 2 ·24h.

[0061] The helium permeation rate of reference standard 2 was 5.3 × 10⁻⁶. -8 atm·cc / s, water vapor transmission rate is 1.03*10 -6 g / m 2 ·24h.

[0062] (3) Antibacterial test

[0063] Antibacterial results such as Figure 2 , Figure 3 As shown, the antibacterial rate against Escherichia coli reached 98.2%, and the antibacterial rate against Staphylococcus aureus reached 97.3%; while neither control 1 nor control 2 had antibacterial activity.

[0064] Example 2

[0065] Take 20.0g of Artemisia annua stem, 20.0g of Artemisia annua leaf, 20.0g of Artemisia annua root, and 40.0g of bentonite and put them into ethanol. Mix them evenly and then put them into a high-pressure reactor and react at 120℃ for 8 hours. After cooling, remove them, centrifuge them, and vacuum dry them at 60℃ to obtain bentonite loaded with Artemisia annua extract.

[0066] 60.0g of phenolic epoxy resin, 30.0g of dicyandiamide and 1.8g of thiourea were mixed with 15% of the above-mentioned bentonite loaded with Artemisia annua extract, stirred evenly, degassed under vacuum, poured into a mold, and then placed in an oven at 160℃ for 8 hours to obtain a low-permeability antibacterial material of bentonite / epoxy resin loaded with Artemisia annua extract.

[0067] The helium permeation rate of the multi-loaded epoxy resin composite material obtained in Example 2 is 4.6*10. -8 atm·cc / s, water vapor transmission rate is 1.18*10 -6 g / m 2 ·24h; combined Figure 3 , Figure 4 It has an antibacterial rate of 100% against Escherichia coli and 100% against Staphylococcus aureus.

[0068] Example 3

[0069] Take 70.0g of Artemisia annua stem and 30.0g of bentonite and put them into ethanol, mix them evenly, and then put them into a high-pressure reactor and react at 130℃ for 6 hours. After cooling, centrifuge and dry under vacuum at 60℃ to obtain bentonite loaded with Artemisia annua extract.

[0070] 50.0g of alicyclic epoxy resin, 40.0g of hexahydrophthalic anhydride and 3.0g of 2,4,6-tris(dimethylaminomethyl)phenol, and 10% of the above-mentioned bentonite loaded with Artemisia annua extract were added. The mixture was stirred evenly, degassed under vacuum, poured into a mold, and then placed in an oven at 120℃ for 10 hours to obtain a low-permeability antibacterial material of bentonite / epoxy resin loaded with Artemisia annua extract.

[0071] The multi-loaded epoxy resin composite material obtained in Example 3 was subjected to transmission electron microscopy (TEM) testing, and the results are as follows: Figure 7 As shown; the helium permeation rate is 6.7*10-8 atm·cc / s, water vapor transmission rate is 1.21*10 -6 g / m 2 • 24h; 100% antibacterial rate against Escherichia coli and 100% antibacterial rate against Staphylococcus aureus.

[0072] Example 4

[0073] Take 50.0g of Artemisia annua root and 50.0g of bentonite and put them into ethanol, mix them evenly, and then put them into a high-pressure reactor and react at 100℃ for 16 hours. After cooling, centrifuge and dry under vacuum at 60℃ to obtain bentonite loaded with Artemisia annua extract.

[0074] 65.0g of bisphenol F epoxy resin, 15.0g of ethylenediamine and 1.0g of quaternary ammonium salt accelerator were added, along with 8% of the above-mentioned bentonite loaded with Artemisia annua extract. The mixture was stirred evenly, degassed under vacuum, poured into a mold, and then reacted at 25°C for 24 hours to obtain a low-permeability antibacterial material of bentonite / epoxy resin loaded with Artemisia annua extract.

[0075] The multi-loaded epoxy resin composite material obtained in Example 4 was subjected to transmission electron microscopy (TEM) testing, and the results are as follows: Figure 8 As shown; the helium permeation rate is 4.6*10 -8 atm·cc / s, water vapor transmission rate is 0.97*10 -6 g / m 2 • 24h; 100% antibacterial rate against Escherichia coli and 100% antibacterial rate against Staphylococcus aureus.

[0076] Comparative Example 3

[0077] Example 2 of CN110038762A is used as Comparative Example 3. The differences between it and Example 1 are shown in Table 1.

[0078] Table 1: Comparison of this case with Comparative Example 1

[0079]

[0080]

[0081] The parameters such as water vapor transmission rate of Comparative Example 3 in the table are from the test results of the product prepared in the manner of Comparative Example 3, and the test method is the same as that in this case.

[0082] Comparative Example 4

[0083] Example 1 of CN110055021A is used as Comparative Example 4. The differences between it and Example 1 are shown in Table 2.

[0084] Table 2: Comparison of this case with Comparative Example 4

[0085]

[0086]

[0087] The parameters such as the nitriding rate in Comparative Example 4 are from the test results of the product prepared in the same manner as in this case.

Claims

1. A method for preparing a multi-loaded epoxy resin composite material, characterized in that, Includes the following steps: (1) Mix 40-70 parts by weight of Artemisia annua and 30-60 parts by weight of bentonite in ethanol, react at 80-130℃ for 6-24 hours, cool, centrifuge, and dry under vacuum at 60℃ to obtain product one; (2) Take 50-70 parts by weight of epoxy resin, 0.5-40 parts by weight of curing agent and 0.1-3 parts by weight of accelerator, add the product obtained in step (1), stir until uniformly mixed, degas under vacuum, and cure the mixture at 25-180℃ for 1-24 hours to obtain the finished composite material. The amount of product added is 3-15% of the total mass of epoxy resin, curing agent and accelerator. The term "Artemisia annua" refers to the roots, stems, leaves, or mixtures thereof. The particle size of the bentonite is 5 nanometers to 200 micrometers. The epoxy resin is a type of hydroxymethyl bisphenol A epoxy resin, an alicyclic epoxy resin, a phenolic epoxy resin, a type of bisphenol A epoxy resin, a type of bisphenol F epoxy resin, or a glycidylamine epoxy resin. The multi-load epoxy resin composite materials prepared by the above method are used in high-end microelectronic packaging, as well as aerospace, printing, biochemistry, and sensors.

2. The method for preparing a multi-loaded epoxy resin composite material according to claim 1, characterized in that: In step (1), the ethanol is ethanol with a purity of 95% or higher.

3. The method for preparing a multi-loaded epoxy resin composite material according to claim 1, characterized in that: In step (2), the curing agent is an amine curing agent, an acid anhydride curing agent, or an imidazole curing agent.

4. The method for preparing a multi-loaded epoxy resin composite material according to claim 3, characterized in that: The imidazole curing agent comprises any one or a mixture of imidazole, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, and diphenylimidazolium.

5. The method for preparing a multi-loaded epoxy resin composite material according to claim 3, characterized in that: The amine curing agent is any one or a mixture of polyamides, aliphatic amines, aromatic amines, alicyclic amines, polyether amines, and dicyandiamides.

6. The method for preparing a multi-loaded epoxy resin composite material according to claim 3, characterized in that: The anhydride curing agent is any one or a mixture of aromatic anhydrides, alicyclic anhydrides, long-chain aliphatic anhydrides, haloan anhydrides, and anhydride adducts.

7. The method for preparing a multi-loaded epoxy resin composite material according to claim 1, characterized in that: In step (2), the accelerator is a tertiary amine accelerator, a quaternary ammonium salt accelerator, a fatty amine accelerator, 2,4,6-tris(dimethylaminomethyl)phenol, N-p-chlorophenyl-N,N'-dimethylurea, or thiourea.

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