High-heat-dissipation high-strength epoxy resin-based copper-clad plate and preparation method thereof

Abstract

The application relates to the technical field of epoxy resins, in particular to a high-heat-dissipation high-strength epoxy resin-based copper-clad plate and a preparation method thereof. The preparation method comprises the following steps: step 1: modified carbon fibers, modified heat-dissipation inorganic fillers, modified epoxy resins and a curing agent are added into a solvent and mixed to obtain an epoxy resin glue solution; step 2: a glass fiber cloth is treated by being immersed in the epoxy resin glue solution, and then cured to obtain a semi-cured sheet; N semi-cured sheets are stacked, and a double-sided copper-clad sheet is obtained; and finally, the high-heat-dissipation high-strength epoxy resin-based copper-clad plate is obtained.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin technology, specifically to a high-heat-dissipation, high-strength epoxy resin-based copper clad laminate and its preparation method. Background Technology

[0002] With the rapid development of electronic technology, the miniaturization and integration of electronic products, and the continuous increase in the packaging density of electronic devices, higher requirements are being placed on the performance of copper-clad laminates (CCLs). As the substrate for processing printed circuit boards (PCBs), the heat dissipation performance, strength, and heat resistance of CCLs directly affect the overall performance and reliability of electronic products.

[0003] In existing technologies, the resin solutions used in copper-clad laminates are mostly epoxy resin-based resin compositions. However, traditional epoxy resin-based copper-clad laminates still have some problems in practical applications: due to the relatively poor thermal conductivity of epoxy resin, electronic products generate a large amount of heat when operating in high-power, high-density packaging environments. If the heat dissipation performance of the copper-clad laminate is poor, this heat cannot be dissipated in time, leading to an increase in the operating temperature of the electronic product, thereby affecting its performance and lifespan.

[0004] Furthermore, traditional epoxy resin copper-clad laminates are prone to cracking or fracture when subjected to external forces, which affects their overall structural strength and reliability. This is particularly true in applications with high strength requirements, such as high-end servers and communication equipment, where traditional epoxy resin copper-clad laminates often fall short.

[0005] In summary, the preparation of a high-heat-dissipation, high-strength epoxy resin-based copper clad laminate is of great significance. Summary of the Invention

[0006] The purpose of this invention is to provide a high-heat-dissipation, high-strength epoxy resin-based copper clad laminate and its preparation method, so as to solve the problems mentioned in the background art.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0008] A method for preparing a high-heat-dissipation, high-strength epoxy resin-based copper-clad laminate includes the following steps:

[0009] Step 1: Add modified carbon fiber, modified heat-dissipating inorganic filler, modified epoxy resin, and curing agent to a solvent and mix to obtain epoxy resin adhesive;

[0010] Step 2: Impregnate glass fiber cloth with epoxy resin solution and cure it to obtain a prepreg; stack N prepregs and coat them with copper sheets on both sides to obtain an epoxy resin-based copper clad laminate.

[0011] Furthermore, the solvent is acetone.

[0012] In a more optimized manner, the raw materials of the epoxy resin adhesive include the following components, by mass parts: 15-25 parts modified carbon fiber, 10-20 parts modified heat-dissipating inorganic filler, 60-80 parts modified epoxy resin, 5-10 parts curing agent, and 80-150 parts solvent.

[0013] A more optimized method for preparing the modified carbon fiber is as follows:

[0014] S1-1: Add carbon fiber to a dopamine / tris(hydroxymethyl)aminomethane hydrochloride buffer solution with a pH of 8.0-9.0, react at 20-30°C for 20-28 hours, wash and dry to obtain dopamine-coated carbon fiber;

[0015] S1-2: Add epoxy silane coupling agent and 4-aminoimidazole to toluene and react at 55-65℃ for 6-8 hours to obtain imidazole silane coupling agent;

[0016] S1-3: Add imidazole silane coupling agent and dopamine-coated carbon fiber to 40-50 wt% ethanol aqueous solution and stir at 45-55℃ for 7-8 hours to obtain modified carbon fiber.

[0017] In a more optimized manner, the mass ratio of carbon fiber to dopamine hydrochloride / tris(hydroxymethyl)aminomethane buffer solution in the raw material for dopamine-coated carbon fiber is 2-3:10-15;

[0018] In the raw materials of the imidazole-based silane coupling agent, the mass ratio of epoxy silane coupling agent to 4-aminoimidazole is 2-2.5:1;

[0019] In the raw materials of the modified carbon fiber, the mass ratio of imidazole silane coupling agent to dopamine-coated carbon fiber is 1-2:3-5.

[0020] In a more optimized manner, the preparation method of the modified heat-dissipating inorganic filler is as follows:

[0021] S2-1: After washing nano-silicon carbide with hydrochloric acid, an aminosilane coupling agent is added for modification to obtain modified silicon carbide; under ultraviolet light irradiation, nano-boron nitride and a photoinitiator are added to an 8wt%~12wt% aqueous solution of trifluoroethyl methacrylate, washed and dried to obtain modified boron nitride.

[0022] S2-2: Mix and grind modified silicon carbide and modified boron nitride for 1-2 hours to obtain modified heat dissipation inorganic filler.

[0023] In a further embodiment, the grinding is a ball milling process, using steel balls and milling at a speed of 100-300 r / min for 1-2 hours.

[0024] In a more optimized manner, the mass ratio of nano-silicon carbide to aminosilane coupling agent in the raw material of the modified silicon carbide is 2-3:1-2.

[0025] In the raw material of the modified boron nitride, the mass ratio of nano boron nitride to 8wt% to 12wt% trifluoroethyl methacrylate aqueous solution is 2:15 to 20.

[0026] In the raw materials of the modified heat-dissipating inorganic filler, the mass ratio of modified silicon carbide to modified boron nitride is 1:1 to 2.

[0027] A more optimized method for preparing the modified epoxy resin is as follows:

[0028] S3-1: Bisphenol A type epoxy resin, 4-amino-3-hydroxybenzoic acid, and 4-boron-L-phenylalanine are added to toluene and reacted at 55-65℃ for 6-8 hours to obtain modified epoxy resin A.

[0029] S3-2: Modified epoxy resin A, epichlorohydrin, and 5wt% to 15wt% potassium hydroxide aqueous solution are added to ethanol and reacted at 25 to 35°C for 6 to 12 hours to obtain modified epoxy resin.

[0030] In a more optimized manner, the raw materials of the modified epoxy resin include the following components, by mass parts: 5-6 parts of bisphenol A type epoxy resin, 1-2 parts of 4-amino-3-hydroxybenzoic acid, 2-3 parts of 4-boron-L-phenylalanine, 3-5 parts of epichlorohydrin, 0.2-0.5 parts of 5wt%-15wt% potassium hydroxide aqueous solution, and 40-50 parts of ethanol.

[0031] The proposed method uses modified carbon fiber, modified heat-dissipating inorganic filler, modified epoxy resin, and other materials to create an epoxy resin-based copper clad laminate. The multi-component synergistic modification results in high strength, high heat dissipation performance, good electrical insulation properties, and good chemical stability, making it suitable for the preparation of epoxy resin-based copper clad laminates.

[0032] To improve heat dissipation performance, silicon carbide and boron nitride are compounded in a fixed mass ratio. In addition, nitrogen, boron, and silicon elements are respectively matched with imidazole groups and silicon elements in modified carbon fiber, and boron elements in modified epoxy resin. After compounding, the surface has amino and vinyl groups, which can enhance the dispersibility among the three elements and improve the curing effect.

[0033] To improve the strength of epoxy resin-based copper clad laminates, this solution employs modified carbon fibers. Through dopamine coating, an inorganic-organic hybrid coating layer is formed, increasing the active sites on the carbon fiber surface and facilitating subsequent reactions with other components. After dopamine coating and modification with imidazole silane coupling agents, the carbon fibers are uniformly dispersed, constructing a thermal conductivity network, improving interfacial bonding, reducing thermal resistance, accelerating heat transfer, and further enhancing heat dissipation efficiency. Furthermore, the modified carbon fibers also strengthen the bond between the fiber and the matrix, effectively transferring stress, uniformly dispersing stress to avoid concentration, improving interfacial toughness, and reducing crack propagation.

[0034] In this process, multiple hydroxyl groups are introduced through an amino-epoxy reaction, followed by epoxidation to obtain a modified epoxy resin. Boron and fluorine elements are introduced to increase heat dissipation and heat resistance. Furthermore, more epoxy groups are obtained through epoxidation to form a three-dimensional network structure. This three-dimensional network structure can effectively resist the action of external forces, hinder crack propagation, and further improve strength and heat dissipation performance.

[0035] More preferably, the curing agent includes one or more of acid anhydride curing agents, amine curing agents, and imidazole curing agents.

[0036] Compared with the prior art, the beneficial effects of the present invention are:

[0037] This method modifies carbon fiber, heat-dissipating inorganic filler (silicon carbide and boron nitride composite), and epoxy resin, and then composites them to prepare epoxy resin-based copper clad laminates, achieving multi-component synergistic modification. In terms of heat dissipation, the composite of silicon carbide and boron nitride, along with the synergistic effect of the elements, forms an efficient heat conduction pathway; in terms of strength, the modified carbon fiber increases interfacial bonding, and the modified epoxy resin forms a three-dimensional network structure; simultaneously, the material also possesses good electrical insulation properties and chemical stability, making it suitable for the preparation of epoxy resin-based copper clad laminates. Detailed Implementation

[0038] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] It should be noted that the following parts are by weight. There are no special restrictions on the manufacturers of the raw materials involved in this invention. Exemplary examples include: In the following embodiments, the specification of nano-boron nitride is 50nm, model BN-BN-001-100, purchased from Xi'an Bona Materials Technology Co., Ltd.; the specification of nano-silicon carbide is 30nm, model AM-SiC-051-1, purchased from Zhejiang Yamei Nanotechnology Co., Ltd.; the item number of carbon fiber is A01108, purchased from Wuhan Jiyesheng Chemical Co., Ltd.; the item number of bisphenol A epoxy resin is XHL1920, purchased from Hubei Xinhongli Chemical Co., Ltd.; the CAS number of the photoinitiator is 606-28-0; the purity of dopamine hydrochloride is 99%, CAS number is 62-31-7; the purity of tris(hydroxymethyl)aminomethane is 99%, CAS number is 77-86-1; and the pH of the dopamine hydrochloride (0.1g) / tris(hydroxymethyl)aminomethane buffer solution is 8.5.

[0040] Example 1: A method for preparing a high-heat-dissipation, high-strength epoxy resin-based copper clad laminate, comprising the following steps:

[0041] Step 1: S1: Add carbon fiber to a dopamine hydrochloride / tris(hydroxymethyl)aminomethane buffer solution at a mass ratio of 2.5:12.5, react at 25°C for 24 hours, wash and dry to obtain dopamine-coated carbon fiber; S2: Add epoxy silane coupling agent KH-560 and 4-aminoimidazole to toluene at a mass ratio of 2.3:1, react at 60°C for 7 hours to obtain imidazole-based silane coupling agent; S3: Add imidazole-based silane coupling agent and dopamine-coated carbon fiber at a mass ratio of 1.5:4 to a 45wt% ethanol aqueous solution, stir at 50°C for 7.5 hours to obtain modified carbon fiber;

[0042] Step 2: S1: After washing nano-silicon carbide with hydrochloric acid at a mass ratio of 2.5:1.5, it is modified by adding an aminosilane coupling agent to obtain modified silicon carbide; under ultraviolet light irradiation, nano-boron nitride and photoinitiator are added to a 10wt% trifluoroethyl methacrylate aqueous solution, with a mass ratio of nano-boron nitride to 10wt% trifluoroethyl methacrylate aqueous solution of 2:17.5, washed and dried to obtain modified boron nitride; S2: Modified silicon carbide and modified boron nitride are mixed at a mass ratio of 1:1.5 and ball-milled at 200 r / min for 1.5 hours to obtain modified heat dissipation inorganic filler;

[0043] Step 3: S1: Add 5.5 parts of bisphenol A type epoxy resin, 1.5 parts of 4-amino-3-hydroxybenzoic acid, and 2.5 parts of 4-boron-L-phenylalanine to toluene and react at 60°C for 7 hours to obtain modified epoxy resin A; S2: Add modified epoxy resin A, 4 parts of epichlorohydrin, and 0.3 parts of 10wt% potassium hydroxide aqueous solution to 45 parts of ethanol and react at 30°C for 8 hours to obtain modified epoxy resin;

[0044] Step 4: Add 20 parts modified carbon fiber, 15 parts modified heat dissipation inorganic filler, 70 parts modified epoxy resin, 5 parts ethylenediamine, and 3 parts 2-methylimidazole to 120 parts acetone and mix to obtain epoxy resin solution; Step 2: Impregnate glass fiber cloth with epoxy resin solution for 15 minutes and cure at 130℃ for 45 minutes to obtain a prepreg; Stack 5 prepregs, set the pressure to 4Pa, and double-sided copper clad laminate at 200℃ for 3 hours to obtain epoxy resin-based copper clad laminate.

[0045] Example 2: A method for preparing a high-heat-dissipation, high-strength epoxy resin-based copper clad laminate, comprising the following steps:

[0046] Step 1: S1: Add carbon fiber to a dopamine hydrochloride / tris(hydroxymethyl)aminomethane buffer solution at a mass ratio of 2.5:12.5, react at 25°C for 24 hours, wash and dry to obtain dopamine-coated carbon fiber; S2: Add epoxy silane coupling agent KH-560 and 4-aminoimidazole to toluene at a mass ratio of 2.3:1, react at 60°C for 7 hours to obtain imidazole-based silane coupling agent; S3: Add imidazole-based silane coupling agent and dopamine-coated carbon fiber at a mass ratio of 1.5:4 to a 45wt% ethanol aqueous solution, stir at 50°C for 7.5 hours to obtain modified carbon fiber;

[0047] Step 2: S1: After washing nano-silicon carbide with hydrochloric acid at a mass ratio of 2.5:1.5, modify it with an aminosilane coupling agent to obtain modified silicon carbide; under ultraviolet light irradiation, add nano-boron nitride and photoinitiator to a 10wt% trifluoroethyl methacrylate aqueous solution, with a mass ratio of nano-boron nitride to 10wt% trifluoroethyl methacrylate aqueous solution of 2:17.5, wash and dry to obtain modified boron nitride; S2: Mix modified silicon carbide and modified boron nitride at a mass ratio of 1:1.5 with 200 Ball milling at a speed of r / min for 1.5 hours yields modified heat-dissipating inorganic filler; Step 3: S1: Add 5.5 parts of bisphenol A type epoxy resin, 1.5 parts of 4-amino-3-hydroxybenzoic acid, and 2.5 parts of 4-boron-L-phenylalanine to toluene and react at 60℃ for 7 hours to obtain modified epoxy resin A; S2: Add modified epoxy resin A, 4 parts of epichlorohydrin, and 0.3 parts of 10wt% potassium hydroxide aqueous solution to 45 parts of ethanol and react at 30℃ for 8 hours to obtain modified epoxy resin;

[0048] Step 4: Add 15 parts modified carbon fiber, 10 parts modified heat dissipation inorganic filler, 60 parts modified epoxy resin, 3 parts ethylenediamine, and 2 parts 2-methylimidazole to 80 parts acetone and mix to obtain epoxy resin solution; Step 2: Impregnate glass fiber cloth with epoxy resin solution for 15 minutes and cure at 130℃ for 45 minutes to obtain a prepreg; Stack 5 prepregs, set the pressure to 4Pa, and double-sided copper clad laminate at 200℃ for 3 hours to obtain epoxy resin-based copper clad laminate.

[0049] Example 3: A method for preparing a high-heat-dissipation, high-strength epoxy resin-based copper clad laminate, comprising the following steps:

[0050] Step 1: S1: Add carbon fiber to a dopamine hydrochloride / tris(hydroxymethyl)aminomethane buffer solution at a mass ratio of 2.5:12.5, react at 25°C for 24 hours, wash and dry to obtain dopamine-coated carbon fiber; S2: Add epoxy silane coupling agent KH-560 and 4-aminoimidazole to toluene at a mass ratio of 2.3:1, react at 60°C for 7 hours to obtain imidazole-based silane coupling agent; S3: Add imidazole-based silane coupling agent and dopamine-coated carbon fiber at a mass ratio of 1.5:4 to a 45wt% ethanol aqueous solution, stir at 50°C for 7.5 hours to obtain modified carbon fiber;

[0051] Step 2: S1: After washing nano-silicon carbide with hydrochloric acid at a mass ratio of 2.5:1.5, it is modified by adding an aminosilane coupling agent to obtain modified silicon carbide; under ultraviolet light irradiation, nano-boron nitride and photoinitiator are added to a 10wt% trifluoroethyl methacrylate aqueous solution, with a mass ratio of nano-boron nitride to 10wt% trifluoroethyl methacrylate aqueous solution of 2:17.5, washed and dried to obtain modified boron nitride; S2: Modified silicon carbide and modified boron nitride are mixed at a mass ratio of 1:1.5 and ball-milled at 200 r / min for 1.5 hours to obtain modified heat dissipation inorganic filler;

[0052] Step 3: S1: Add 5.5 parts of bisphenol A type epoxy resin, 1.5 parts of 4-amino-3-hydroxybenzoic acid, and 2.5 parts of 4-boron-L-phenylalanine to toluene and react at 60°C for 7 hours to obtain modified epoxy resin A; S2: Add modified epoxy resin A, 4 parts of epichlorohydrin, and 0.3 parts of 10wt% potassium hydroxide aqueous solution to 45 parts of ethanol and react at 30°C for 8 hours to obtain modified epoxy resin;

[0053] Step 4: Add 25 parts modified carbon fiber, 20 parts modified heat dissipation inorganic filler, 80 parts modified epoxy resin, 7 parts ethylenediamine, and 3 parts 2-methylimidazole to 150 parts acetone and mix to obtain epoxy resin solution; Step 2: Impregnate glass fiber cloth with epoxy resin solution for 15 minutes and cure at 130℃ for 45 minutes to obtain a prepreg; Stack 5 prepregs, set the pressure to 4Pa, and double-sided copper clad laminate at 200℃ for 3 hours to obtain epoxy resin-based copper clad laminate.

[0054] Comparative Example 1: Based on Example 1, the mass ratio of the modified heat-dissipating inorganic filler was changed, while the rest of the process remained the same, and it was replaced with:

[0055] Step 1: S1: Add carbon fiber to a dopamine hydrochloride / tris(hydroxymethyl)aminomethane buffer solution at a mass ratio of 2.5:12.5, react at 25°C for 24 hours, wash and dry to obtain dopamine-coated carbon fiber; S2: Add epoxy silane coupling agent KH-560 and 4-aminoimidazole to toluene at a mass ratio of 2.3:1, react at 60°C for 7 hours to obtain imidazole-based silane coupling agent; S3: Add imidazole-based silane coupling agent and dopamine-coated carbon fiber at a mass ratio of 1.5:4 to a 45wt% ethanol aqueous solution, stir at 50°C for 7.5 hours to obtain modified carbon fiber;

[0056] Step 2: S1: After washing with hydrochloric acid, nano-silicon carbide is modified with aminosilane coupling agent at a mass ratio of 2.5:1.5 to obtain modified silicon carbide; under ultraviolet light irradiation, nano-boron nitride and photoinitiator are added to a 10wt% trifluoroethyl methacrylate aqueous solution, with a mass ratio of nano-boron nitride to 10wt% trifluoroethyl methacrylate aqueous solution of 2:17.5. After washing and drying, modified boron nitride is obtained; S2: Modified silicon carbide and modified boron nitride are mixed at a mass ratio of 3:1 and ball-milled at 200 r / min for 1.5 hours to obtain modified heat dissipation inorganic filler;

[0057] Step 3: S1: Add 5.5 parts of bisphenol A type epoxy resin, 1.5 parts of 4-amino-3-hydroxybenzoic acid, and 2.5 parts of 4-boron-L-phenylalanine to toluene and react at 60°C for 7 hours to obtain modified epoxy resin A; S2: Add modified epoxy resin A, 4 parts of epichlorohydrin, and 0.3 parts of 10wt% potassium hydroxide aqueous solution to 45 parts of ethanol and react at 30°C for 8 hours to obtain modified epoxy resin;

[0058] Step 4: Add 20 parts modified carbon fiber, 15 parts modified heat dissipation inorganic filler, 70 parts modified epoxy resin, 5 parts ethylenediamine, and 3 parts 2-methylimidazole to 120 parts acetone and mix to obtain epoxy resin solution; Step 2: Impregnate glass fiber cloth with epoxy resin solution for 15 minutes and cure at 130℃ for 45 minutes to obtain a prepreg; Stack 5 prepregs, set the pressure to 4Pa, and double-sided copper clad laminate at 200℃ for 3 hours to obtain epoxy resin-based copper clad laminate.

[0059] Comparative Example 2: Based on Example 1, without dopamine coating treatment, the remaining processes remained unchanged, specifically:

[0060] Step 1: S1: Add epoxy silane coupling agent KH-560 and 4-aminoimidazole to toluene at a mass ratio of 2.3:1, and react at 60°C for 7 hours to obtain imidazole silane coupling agent; S2: Add imidazole silane coupling agent and dopamine-coated carbon fiber to 45wt% ethanol aqueous solution at a mass ratio of 1.5:3.5, and stir at 50°C for 7.5 hours to obtain modified carbon fiber;

[0061] Step 2: S1: After washing nano-silicon carbide with hydrochloric acid at a mass ratio of 2.5:1.5, modify it with an aminosilane coupling agent to obtain modified silicon carbide; under ultraviolet light irradiation, add nano-boron nitride and photoinitiator to a 10wt% trifluoroethyl methacrylate aqueous solution, with a mass ratio of nano-boron nitride to 10wt% trifluoroethyl methacrylate aqueous solution of 2:17.5, wash and dry to obtain modified boron nitride; S2: Mix modified silicon carbide and modified boron nitride at a mass ratio of 1:1.5 with 200 Ball milling at a speed of r / min for 1.5 hours yields modified heat-dissipating inorganic filler; Step 3: S1: Add 5.5 parts of bisphenol A type epoxy resin, 1.5 parts of 4-amino-3-hydroxybenzoic acid, and 2.5 parts of 4-boron-L-phenylalanine to toluene and react at 60℃ for 7 hours to obtain modified epoxy resin A; S2: Add modified epoxy resin A, 4 parts of epichlorohydrin, and 0.3 parts of 10wt% potassium hydroxide aqueous solution to 45 parts of ethanol and react at 30℃ for 8 hours to obtain modified epoxy resin;

[0062] Step 4: Add 20 parts modified carbon fiber, 15 parts modified heat dissipation inorganic filler, 70 parts modified epoxy resin, 5 parts ethylenediamine, and 3 parts 2-methylimidazole to 120 parts acetone and mix to obtain epoxy resin solution; Step 2: Impregnate glass fiber cloth with epoxy resin solution for 15 minutes and cure at 130℃ for 45 minutes to obtain a prepreg; Stack 5 prepregs, set the pressure to 4Pa, and double-sided copper clad laminate at 200℃ for 3 hours to obtain epoxy resin-based copper clad laminate.

[0063] Comparative Example 3: Based on Example 1, without the use of imidazole silane coupling agent modification, and with the remaining processes unchanged, specifically:

[0064] Step 1: S1: Add carbon fiber to dopamine hydrochloride / tris(hydroxymethyl)aminomethane buffer solution at a mass ratio of 2.5:12.5, react at 25°C for 24 hours, wash and dry to obtain modified carbon fiber;

[0065] Step 2: S1: After washing nano-silicon carbide with hydrochloric acid at a mass ratio of 2.5:1.5, modify it with an aminosilane coupling agent to obtain modified silicon carbide; under ultraviolet light irradiation, add nano-boron nitride and photoinitiator to a 10wt% trifluoroethyl methacrylate aqueous solution, with a mass ratio of nano-boron nitride to 10wt% trifluoroethyl methacrylate aqueous solution of 2:17.5, wash and dry to obtain modified boron nitride; S2: Mix modified silicon carbide and modified boron nitride at a mass ratio of 1:1.5 with 200 Ball milling at a speed of r / min for 1.5 hours yields modified heat-dissipating inorganic filler; Step 3: S1: Add 5.5 parts of bisphenol A type epoxy resin, 1.5 parts of 4-amino-3-hydroxybenzoic acid, and 2.5 parts of 4-boron-L-phenylalanine to toluene and react at 60℃ for 7 hours to obtain modified epoxy resin A; S2: Add modified epoxy resin A, 4 parts of epichlorohydrin, and 0.3 parts of 10wt% potassium hydroxide aqueous solution to 45 parts of ethanol and react at 30℃ for 8 hours to obtain modified epoxy resin;

[0066] Step 4: Add 20 parts modified carbon fiber, 15 parts modified heat dissipation inorganic filler, 70 parts modified epoxy resin, 5 parts ethylenediamine, and 3 parts 2-methylimidazole to 120 parts acetone and mix to obtain epoxy resin solution; Step 2: Impregnate glass fiber cloth with epoxy resin solution for 15 minutes and cure at 130℃ for 45 minutes to obtain a prepreg; Stack 5 prepregs, set the pressure to 4Pa, and double-sided copper clad laminate at 200℃ for 3 hours to obtain epoxy resin-based copper clad laminate.

[0067] Comparative Example 4: Based on Example 1, the epoxy resin was not modified, and the other processes remained unchanged, specifically:

[0068] Step 1: S1: Add carbon fiber to a dopamine hydrochloride / tris(hydroxymethyl)aminomethane buffer solution at a mass ratio of 2.5:12.5, react at 25°C for 24 hours, wash and dry to obtain dopamine-coated carbon fiber; S2: Add epoxy silane coupling agent KH-560 and 4-aminoimidazole to toluene at a mass ratio of 2.3:1, react at 60°C for 7 hours to obtain imidazole-based silane coupling agent; S3: Add imidazole-based silane coupling agent and dopamine-coated carbon fiber at a mass ratio of 1.5:4 to a 45wt% ethanol aqueous solution, stir at 50°C for 7.5 hours to obtain modified carbon fiber;

[0069] Step 2: S1: After washing nano-silicon carbide with hydrochloric acid at a mass ratio of 2.5:1.5, it is modified by adding an aminosilane coupling agent to obtain modified silicon carbide; under ultraviolet light irradiation, nano-boron nitride and photoinitiator are added to a 10wt% trifluoroethyl methacrylate aqueous solution, with a mass ratio of nano-boron nitride to 10wt% trifluoroethyl methacrylate aqueous solution of 2:17.5, washed and dried to obtain modified boron nitride; S2: Modified silicon carbide and modified boron nitride are mixed at a mass ratio of 1:1.5 and ball-milled at 200 r / min for 1.5 hours to obtain modified heat dissipation inorganic filler;

[0070] Step 3: Add 20 parts modified carbon fiber, 15 parts modified heat dissipation inorganic filler, 70 parts epoxy resin, 5 parts ethylenediamine, and 3 parts 2-methylimidazole to 120 parts acetone and mix to obtain epoxy resin solution; Step 2: Impregnate glass fiber cloth with epoxy resin solution for 15 minutes and cure at 130℃ for 45 minutes to obtain a prepreg; Stack 5 prepregs, set the pressure to 4Pa, and double-sided copper clad laminate at 200℃ for 3 hours to obtain epoxy resin-based copper clad laminate.

[0071] Test experiment: The high heat dissipation and high strength epoxy resin-based copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-4 were tested for their performance: (1) Bending strength test: The epoxy resin-based copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-4 were tested for mechanical properties in accordance with GB / T 9341-2008 to evaluate their influence on strength performance; the results are shown in Table 1; (2) Thermal conductivity test: The high epoxy resin-based copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-4 were tested for thermal conductivity in accordance with ASTM-5470; the results are shown in Table 1.

[0072]

[0073] Table 1

[0074] Results Analysis: Analysis of the data in Table 1 shows that this method modifies carbon fiber, heat-dissipating inorganic filler (silicon carbide and boron nitride composite), and epoxy resin, and then composites them to prepare epoxy resin-based copper clad laminates, achieving multi-component synergistic modification. In terms of heat dissipation, the composite of silicon carbide and boron nitride, along with the synergistic effect of the elements, forms an efficient heat conduction pathway. Regarding strength, the modified carbon fiber increases interfacial bonding in the form of an inorganic-organic hybrid coating layer, and the modified epoxy resin forms a three-dimensional network structure. Simultaneously, the material also possesses good electrical insulation properties and chemical stability, making it suitable for the preparation of epoxy resin-based copper clad laminates.

[0075] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A method for preparing a high-heat-dissipation, high-strength epoxy resin-based copper-clad laminate, characterized in that: The method comprises the following steps: Step 1: modified carbon fiber, modified heat-dissipating inorganic filler, modified epoxy resin and curing agent are added into a solvent to mix, so that an epoxy resin glue solution is obtained; Step 2: a glass fiber cloth is treated by impregnation in the epoxy resin glue solution, and then cured to obtain a semi-cured sheet; N semi-cured sheets are stacked and covered with copper sheets on both sides to obtain an epoxy resin-based copper-clad plate; The preparation method of the modified carbon fiber is as follows: S1-1: carbon fiber is added into a dopamine hydrochloride / tris-hydroxymethyl aminomethane buffer solution with a pH of 8.0-9.0, and reacted at 20-30 DEG C for 20-28 hours, washed and dried to obtain dopamine-coated carbon fiber; S1-2: epoxy silane coupling agent and 4-aminoimidazole are added into toluene, and reacted at 55-65 DEG C for 6-8 hours to obtain imidazole-based silane coupling agent; S1-3: the imidazole-based silane coupling agent and dopamine-coated carbon fiber are added into 40-50 wt% ethanol aqueous solution, and stirred at 45-55 DEG C for 7-8 hours to obtain modified carbon fiber; The raw material of the modified heat-dissipating inorganic filler comprises modified silicon carbide and modified boron nitride in a mass ratio of 1:1-2.

2. The preparation method of the high-heat-dissipation high-strength epoxy resin-based copper-clad plate according to claim 1, characterized in that: The raw material of the epoxy resin glue solution comprises the following components in parts by mass: 15-25 parts of modified carbon fiber, 10-20 parts of modified heat-dissipating inorganic filler, 60-80 parts of modified epoxy resin, 5-10 parts of curing agent and 80-150 parts of solvent.

3. The preparation method of the high-heat-dissipation high-strength epoxy resin-based copper-clad plate according to claim 1, characterized in that: The raw material of the dopamine-coated carbon fiber comprises carbon fiber and dopamine hydrochloride / tris-hydroxymethyl aminomethane buffer solution in a mass ratio of 2-3:10-15; The raw material of the imidazole-based silane coupling agent comprises epoxy silane coupling agent and 4-aminoimidazole in a mass ratio of 2-2.5:1; The raw material of the modified carbon fiber comprises imidazole-based silane coupling agent and dopamine-coated carbon fiber in a mass ratio of 1-2:3-5.

4. The preparation method of the high-heat-dissipation high-strength epoxy resin-based copper-clad plate according to claim 1, characterized in that: The preparation method of the modified heat-dissipating inorganic filler is as follows: S2-1: nano silicon carbide is washed with hydrochloric acid, and then modified with amino silane coupling agent to obtain modified silicon carbide; Under ultraviolet light, nano boron nitride and photoinitiator are added into 8 wt%-12 wt% trifluoroethyl methacrylate aqueous solution, washed and dried to obtain modified boron nitride; S2-2: the modified silicon carbide and the modified boron nitride are mixed and ground for 1-2 hours to obtain modified heat-dissipating inorganic filler.

5. The preparation method of the high-heat-dissipation high-strength epoxy resin-based copper-clad plate according to claim 4, characterized in that: The raw material of the modified silicon carbide comprises nano silicon carbide and amino silane coupling agent in a mass ratio of 2-3:1-2; The raw material of the modified boron nitride comprises nano boron nitride and 8 wt%-12 wt% trifluoroethyl methacrylate aqueous solution in a mass ratio of 2:15-20.

6. The preparation method of the high-heat-dissipation high-strength epoxy resin-based copper-clad plate according to claim 2, characterized in that: The preparation method of the modified epoxy resin is as follows: S3-1: bisphenol A type epoxy resin, 4-amino-3-hydroxybenzoic acid and 4-boron-L-phenylalanine are added into toluene, and reacted at 55-65 DEG C for 6-8 hours to obtain modified epoxy resin A; S3-2: the modified epoxy resin A, epichlorohydrin and 5 wt%-15 wt% potassium hydroxide aqueous solution are added into ethanol, and reacted at 25-35 DEG C for 6-12 hours to obtain modified epoxy resin.

7. The preparation method of the high-heat-dissipation high-strength epoxy resin-based copper-clad plate according to claim 6, characterized in that: The raw material of the modified epoxy resin comprises the following components by mass fraction: 5-6 parts of bisphenol A type epoxy resin, 1-2 parts of 4-amino-3-hydroxybenzoic acid, 2-3 parts of 4-boron-L-phenylalanine, 3-5 parts of epoxy chloropropane, 0.2-0.5 parts of 5wt%-15wt% potassium hydroxide aqueous solution, and 40-50 parts of ethanol.

8. The preparation method of the high-heat-dissipation high-strength epoxy resin-based copper-clad plate according to claim 2, characterized in that: The curing agent comprises one or more of an acid anhydride curing agent, an amine curing agent, and an imidazole curing agent.

9. A high-heat-dissipation high-strength epoxy resin-based copper-clad plate prepared by the method according to any one of claims 1-8.

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