High-speed copper clad plate material based on epoxy resin system and preparation method thereof

Abstract

This invention discloses a high-speed copper-clad laminate material based on an epoxy resin system and its preparation method, belonging to the field of energy-saving and environmental protection technology. To solve the problems of high dielectric loss, poor thermal conductivity, and insufficient heat resistance in traditional copper-clad laminates, fluorinated silica nanoparticles (surface energy ≤18mN / m) are prepared using a sol-gel method. The boron nitride layer is modified with trisodium citrate and aminopropyltriethoxysilane, and then mixed with bisphenol A epoxy resin, reactive diluent, DOPO flame retardant, melamine, and 2-methylimidazole to obtain a resin adhesive. Nanofillers are added, and deionized water is used for high-speed mixing and degassing. A prepreg of 2116 fiberglass cloth is prepared to form a prepreg, which is then laminated with copper foil, hot-pressed in sections, and tempered a second time. The resulting material has Dk 3.1-3.35, Df ≤ 0.0055, Tg ≥ 165℃, thermal conductivity ≥ 0.59 W / m·K, peel strength ≥ 1.78 N / mm, and T288 ≥ 40 min, making it suitable for 5G high-speed PCBs and combining low energy consumption with environmental friendliness.

Description

Technical Field

[0001] This invention belongs to the field of energy-saving and environmental protection technology. Specifically, it relates to a high-speed copper-clad laminate material based on an epoxy resin system and its preparation method. Background Technology

[0002] With the rapid development of information technology, especially the rise of 5G communication, artificial intelligence, data centers, and high-performance computing, the demand for printed circuit board (PCB) substrates is becoming increasingly urgent. Among them, high-speed copper clad laminate (CCL), as the core supporting material of PCBs, directly determines the signal transmission speed, thermal management, and reliability of the circuit board. High-speed CCLs need to possess low dielectric constant (Dk), low loss factor (Df), high glass transition temperature (Tg), excellent thermal conductivity, and mechanical strength to adapt to low-latency transmission of high-frequency signals and high-power density applications. According to the International Circuits and Electronics Assembly (IPC) standard, modern high-speed CCLs should ideally have a Dk below 3.5, a Df below 0.01, a Tg exceeding 150℃, and a thermal conductivity not less than 0.5 W / m·K. These requirements have made traditional low-cost FR-4 epoxy glass cloth CCLs increasingly unable to meet the demands, leading to a shift towards high-performance epoxy resin systems.

[0003] Epoxy resin, as the most widely used CCL matrix material, possesses excellent adhesion, chemical resistance, and processing performance. The epoxy groups in its molecular structure can react with various curing agents to form a three-dimensional cross-linked network, providing good mechanical strength and thermal stability. Bisphenol A type epoxy resins (E-51 or E-44) are the mainstream choice, often formulated with reactive diluents (such as 1,4-butanediol diglycidyl ether) to reduce viscosity and improve flowability; simultaneously, flame retardants (such as 9,10-dihydro-9-oxo-10-phosphonophenanthrene-10-oxide, DOPO derivatives) and curing agents (such as melamine or imidazoles) are added to enhance flame retardancy and curing efficiency. This system is maturely applied in traditional PCB manufacturing. For example, in FR-4 boards under the IPC-4101 specification, epoxy resin accounts for 40%-60%, fiberglass cloth as reinforcement accounts for 30%-50%, and the copper foil thickness is typically 12-35 μm. Copper-clad laminates with a thickness of 0.5-2mm can be produced through hot pressing processes (such as segmented heating to 180-220℃ and pressure of 3-5MPa), which are widely used in consumer electronics and automotive electronics.

[0004] However, existing epoxy resin-based high-speed copper clad laminates still face multiple challenges. First, insufficient dielectric properties are the primary bottleneck. In high-frequency signal transmission (e.g., above 10 GHz), polarization loss leads to signal attenuation and crosstalk. Traditional epoxy resins have a dielectric constant (Dk) of approximately 3.8-4.5 and a dielectric constant (Df) of 0.015-0.025, far exceeding the 2.0-2.5 and 0.0005-0.001 of PTFE-based materials. This stems from the fact that polar groups in epoxy resins (such as hydroxyl and ether bonds) easily generate dipole moments, enhancing dielectric loss. To improve this, existing technologies often introduce low-dielectric fillers, such as silica (SiO2) nanoparticles or hollow glass microspheres. However, these fillers typically have a particle size >100 nm, are prone to agglomeration, leading to uneven distribution and interfacial voids, thus increasing Df and decreasing Tg. Second, poor thermal conductivity limits the application of high-speed CCLs in high-power devices. 5G base station and server chips can achieve power densities of up to 100 W / cm². 2 The above points highlight the challenges of thermal stress accumulation, which can lead to interlayer delamination or copper foil peeling. Pure epoxy resin has a thermal conductivity of only 0.2-0.3 W / m·K, and even with the addition of boron nitride (BN) or alumina (Al2O3) fillers (20%-40% load), it only reaches 0.4-0.6 W / m·K. This is because layered fillers like BN have random orientations in the resin, forming an imperfect thermally conductive network and resulting in high interfacial thermal resistance. Thirdly, achieving a balance between mechanical properties and heat resistance is difficult. High-speed CCLs need to withstand thermal cycling (-40℃ to 125℃) and bending stress, and the peel strength (between copper foil and substrate) should ideally be >1.5 N / mm. However, the introduction of traditional fillers can easily cause stress concentration, reducing fracture toughness. Patent US20190233345A1 reports an epoxy / BN composite CCL, but the excessive amount of curing agent such as dimethylimidazole (>1%) leads to a curing shrinkage rate >2%, reducing the peel strength to 1.2 N / mm. Meanwhile, insufficient heat resistance manifests as low Tg and early thermal decomposition, especially in humid environments where hydrolysis accelerates aging. Fourth, the complexity of the preparation process and environmental issues are prominent. Traditional CCL preparation includes resin formulation, filler dispersion, pre-impregnation (Varnish impregnation of fiberglass cloth), degassing, semi-curing (B-stage), and lamination curing. High-speed mixing and vacuum degassing parameters (e.g., rotation speed > 2000 rpm, pressure < -0.08 MPa) can reduce bubbles, but energy consumption is high (drying temperature > 100℃, time > 24h), and the volatilization of commonly used organic solvents (e.g., acetone, DMF) causes VOC emissions, violating energy conservation and environmental protection regulations. The EU REACH regulation and my country's "Emission Standard for Pollutants in the Printed Circuit Board Industry" (GB 42862-2022) require halogen-free and low-VOC processes, but existing epoxy flame retardant systems still rely on bromides, producing toxic fumes. Fiberglass cloth selection, such as type 2116 (105 g / m²), is recommended. 2While economical, improper control of the pre-impregnation rate (1-2 m / min) can easily lead to uneven resin content (45%-55%), affecting the consistency of the boards. Furthermore, while there are many innovative attempts in existing technologies, they are mostly limited to single modifications and cannot achieve comprehensive optimization. For example, fluorination surface treatment can reduce surface energy to below 20 mN / m and improve dispersibility, but in the tetraethoxysilane (TEOS) sol-gel method, insufficient optimization of ammonia catalytic parameters (pH 9-11, temperature 50-70℃) results in uneven particle size (30-100 nm). Perfluorosilanes such as 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS) are effective, but the fluorination rate is <80% when the dosage is <5 parts, and it is prone to decomposition at surface reaction temperatures >90℃. In boron nitride modification, trisodium citrate can be used as a stripping agent to obtain thin layers (thickness <10nm), but when the ultrasonic water bath (40kHz, power 200W) time is <3h, the lateral size is >10μm, making it difficult to form an isotropic network. Although aminopropyltriethoxysilane (KH-550) coupling agent improves the interface, it has poor compatibility with fluorinated SiO2 and requires high-speed stirring (>1000rpm, >30min) to avoid phase separation.

[0005] From a development trend perspective, high-speed CCLs are evolving towards lower Dk, higher Tg, and multi-functional integration. International giants such as Rogers and Isola have launched Halogen-Free epoxy CCLs, reducing Dk to 3.0, but with high costs (>200 RMB / m²). 2 This hinders large-scale application. As the world's largest PCB producer (accounting for over 60%), China urgently needs to independently develop energy-saving epoxy systems. The country emphasizes green electronics manufacturing, aiming for environmentally friendly CCLs to account for over 50% by 2025. However, existing technologies still lag behind in filler synergistic modification, precise control of process parameters, and performance verification (such as laser flare thermal conductivity testing and IPC peel strength standards), resulting in insufficient product reliability in 5G millimeter-wave and AI chip packaging.

[0006] In summary, while existing epoxy resin-based high-speed copper-clad laminates have a mature foundation, their widespread adoption in high-end applications is hindered by issues such as high dielectric loss, weak thermal conductivity, poor mechanical-thermal balance, high energy consumption during manufacturing, and environmental concerns. An innovative approach is urgently needed to achieve a comprehensive improvement in low dielectric strength, high thermal conductivity, strong mechanical properties, and green manufacturing processes through the synergistic modification of nano-level fluorinated fillers and layered BN, combined with optimized formulation, dispersion, and lamination processes, in order to meet the demands of energy-efficient and environmentally friendly high-speed electronic devices. Summary of the Invention

[0007] To address the problems of high dielectric loss, poor thermal conductivity, insufficient interfacial compatibility, unbalanced heat resistance and mechanical strength, and high energy consumption and lack of environmental friendliness in the preparation process of traditional epoxy resin-based high-speed copper clad laminates, this invention provides a high-speed copper clad laminate material based on an epoxy resin system and its preparation method. This method prepares low surface energy fluorinated silica nanoparticles via a sol-gel method, and uses a synergistic modified boron nitride layer as a composite nanofiller, which is efficiently blended with the epoxy resin system to achieve uniform dispersion of the filler and optimized interfacial bonding. Simultaneously, vacuum degassing, high-speed mixing, and segmented hot pressing processes ensure a bubble-free, low-shrinkage, and green preparation process. The resulting material possesses low dielectric constant, low loss factor, high glass transition temperature, excellent thermal conductivity, and peel strength, significantly improving high-speed signal transmission efficiency, thermal management, and reliability. It is suitable for 5G communication, high-density interconnects, and power electronics fields, and the process is free of harmful solvents, meeting energy-saving and environmental protection requirements.

[0008] The present invention adopts the following technical solution: a method for preparing high-speed copper clad laminate material based on epoxy resin system, comprising the following steps by weight: (1) using 10-20 parts of tetraethoxysilane (CAS: 78-10-4) as a precursor, adding 30-50 parts of ethanol solution and 5-10 parts of ammonia solution, followed by nucleation growth reaction to obtain modified silica particles with a particle size of 30-60 nm, and then adding 5-10 parts of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (CAS: 101947-16- 4) A surface reaction was performed to obtain fluorinated silica nanoparticles with a surface energy ≤18mN / m; then, 5-10 parts of boron nitride were dispersed in 20-30 parts of isopropanol solution, followed by the addition of 5-10 parts of trisodium citrate dihydrate (CAS: 6132-04-3), and the mixture was treated with an ultrasonic water bath, followed by vacuum drying at 60℃ for 48h to obtain a modified boron nitride layer with a thickness of 2-6nm and a lateral thickness of 0.5-5μm; 25-35 parts of aminopropyltriethoxysilane (CAS: 919-30-2) were used to react with the fluorinated silica nanoparticles. (1) Blend the modified boron nitride layer with the nanofiller to obtain the nanofiller; (2) Take 100-140 parts of bisphenol A type epoxy resin (CAS: 1675-54-3), 3-8 parts of 1,4-butanediol diglycidyl ether (CAS: 2425-79-8), 2-6 parts of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (CAS: 35948-25-5), 4-7 parts of melamine (CAS: 461-58-5), and 0.3-0.8 parts of 2-methylimidazole (CAS: 693-98-1) and mix them together, then... (2) Vacuum degassing is performed to obtain resin clear glue; (3) Nano filler obtained in step (1) is added to the resin clear glue obtained in step (2), followed by 40-60 parts of deionized water, high-speed mixing treatment is performed, and then degassing treatment is performed to obtain clear glue after filling; (4) Fiber cloth is selected for pre-impregnation, followed by degassing treatment, and then high-temperature treatment is performed to obtain semi-cured sheet; (5) 8-16 semi-cured sheets are stacked according to the target thickness, and electrolytic copper foil or rolled copper foil is coated on both sides, followed by segmented heating treatment, and then secondary tempering is performed to obtain high-speed copper clad laminate material.

[0009] Preferably, in step (1), the mass percentage of the ethanol solution is 40%, and the mass percentage of the ammonia solution is 10-20%; the parameters of the nucleation growth reaction in step (1) are as follows: temperature 50-65℃, time 2-4h; the parameters of the surface reaction in step (1) are as follows: temperature 80-90℃, time 1-3h; the mass percentage of the isopropanol solution in step (1) is 40%; the parameters of the ultrasonic water bath treatment in step (1) are as follows: frequency 40kHz, power 200-300W, temperature 160-180℃, time 3-6h; the parameters of the co-mixing in step (1) are as follows: 1000-3000rpm, 30-60min.

[0010] Preferably, the mixing parameters in step (2) are as follows: stirring at 200-300 rpm for 20-40 min at 60-80℃; the vacuum degassing parameters in step (2) are as follows: vacuum degassing at -0.08~-0.095 MPa for 30-60 min.

[0011] Preferably, the parameters for the high-speed mixing process in step (3) are as follows: rotation speed 1500-2500 rpm, time 20-40 min; the parameters for the degassing process in step (3) are as follows: temperature 65℃, pressure -0.09 MPa and time 30-45 min.

[0012] Preferably, the fiber cloth in step (4) is 2116 type fiberglass cloth; the pre-impregnation parameters in step (4) are as follows: gluing speed 1.0-1.8m / min, impregnation time 5-10s, gluing temperature 40-50℃; the degassing parameters in step (4) are as follows: vacuum degassing under ≤-0.09MPa conditions; the high temperature parameters in step (4) are as follows: temperature 140-180℃, time 10-20min.

[0013] Preferably, the coating thickness in step (5) is 12-25 μm; the parameters of the segmented heating process in step (5) are as follows: heat up to 120°C at 2-4°C / min, hold for 20-30 min, then heat up to 190-210°C, hold for 90-120 min, then cool down to 80°C at 2-5°C / min, with a pressure of 3-4 MPa throughout.

[0014] Preferably, the parameters for the secondary tempering in step (5) are as follows: temperature 160-180℃, time 2-4h.

[0015] A high-speed copper-clad laminate material based on an epoxy resin system, wherein the high-speed copper-clad laminate material based on the epoxy resin system is obtained by the preparation method described above.

[0016] Step (1) involves the following instruments: This step includes sol-gel nucleation growth, surface reaction, boron nitride dispersion and ultrasonic water bath treatment, vacuum drying, and blending. Heating and stirring reaction apparatus (used for nucleation growth and surface reaction, temperature control 50-90℃, stirring): Typical models are IKA RV 10 digital (IKA GmbH, Germany) or domestic JJ-1 precision stirrer (Shanghai Jingke Instrument Co., Ltd.). Used for solution mixing and heating reaction. Ultrasonic water bath disperser (ultrasonic water bath treatment, frequency 40kHz, power 200-300W, temperature 160-180℃, but the actual water bath temperature is recommended to be ≤100℃ to prevent evaporation; an oil bath can be used instead): Typical models are SK3300H (Shanghai Jingke Instrument Co., Ltd.) or Branson CPX3800H (Branson Corporation, USA). Used for stripping modified boron nitride. Vacuum drying oven (60℃ vacuum drying for 48h): Typical models are DZF-6050 (Shanghai Jingke Instrument Co., Ltd.) or Binder VD 53 (Binder GmbH, Germany). Used for solvent removal. High-speed mixer or planetary mixer (blending, 1000-3000rpm, 30-60min): Typical models are FS-3S (Jiangsu Feixiang Chemical Equipment Co., Ltd.) or Thinky AR-100 (Thinky Corporation, Japan). Used for uniform mixing of nanofillers.

[0017] Step (2) involves the following instruments: This step involves mixing the resin components and vacuum degassing. Thermostatic stirrer (mixing, 60-80℃, 200-300rpm, 20-40min): Typical models are DF-1 (Zhengzhou Changcheng Science & Technology Co., Ltd.) or IKA RCTdigital (IKA GmbH, Germany). Used for heating and stirring epoxy resin and other components. Vacuum degassing machine (-0.08~-0.095MPa, 30-60min): Typical models are THINKY ARE-250 (Thinky Corporation, Japan) or domestic vacuum degassing stirrer SZG-2 (Shanghai Jingke Instrument Co., Ltd.). Used to remove air bubbles to obtain a clear resin.

[0018] Step (3) involves the following instruments: This step involves adding filler, high-speed mixing, and degassing. High-speed disperser (high-speed mixing, 1500-2500 rpm, 20-40 min): Typical models are FSM-1000W (Jiangsu Feixiang Chemical Equipment Co., Ltd.) or IKA T 25digital (IKA GmbH, Germany). Used for uniform dispersion of filler and resin. Vacuum degassing machine (temperature 65℃, -0.09MPa, 30-45 min): Same as step (2), such as THINKY ARE-310 or domestic DZF series vacuum chamber combined with heating.

[0019] Step (4) involves the following instruments: This step involves pre-impregnation, degassing, and high-temperature treatment to obtain the prepreg. Impregnation machine or coating machine (pre-impregnation, application speed 1.0-1.8 m / min, impregnation time 5-10 s, clearing temperature 40-50℃): Typical models are the vertical impregnation machine GLB-2116 (a PCB equipment company in Shenzhen) or a domestic horizontal coating machine (an automation equipment factory in Jiangsu). Used for pre-impregnation and clearing of fiberglass cloth. Vacuum degassing machine (≤-0.09 MPa): Same as above. Hot air circulating oven (high-temperature treatment, 140-180℃, 10-20 min): Typical models are DHG-9070A (Shanghai Jingke Instrument Co., Ltd.) or Memmert UN55 (Memmert GmbH, Germany). Used for drying the prepreg.

[0020] Step (5) involves the following instruments: This step involves lamination, hot pressing, and tempering. A laminator or hot press (laminating 8-16 sheets, segmented heating: 2-4℃ / min to 120℃, holding for 20-30 min, heating to 190-210℃, holding for 90-120 min, cooling 2-5℃ / min to 80℃, pressure 3-4 MPa; copper foil thickness 12-25 μm): Typical models are the QYF-1 vacuum hot press (Shanghai material equipment company) or the XY-3000 domestic laminator (Dongguan Huajin Machinery Company). Used for segmented curing and lamination. An oven (secondary tempering, 160-180℃, 2-4 h): Typical models are the GZX-9070BMB (Shanghai Boxun Medical Equipment Company) or the Binder ED-56 (German Binder Company). Used for post-curing to improve heat resistance.

[0021] Compared with the prior art, the present invention has significant technical advantages, mainly reflected in the following aspects: (1) Innovative nanofiller synergistic modification design to achieve excellent dielectric properties. In traditional epoxy CCL, fillers such as ordinary SiO2 or BN have high surface energy (>25mN / m) and are prone to agglomeration, resulting in Dk>3.8, Df>0.01, and large signal transmission loss (>20%). The present invention prepares fluorinated SiO2 with a particle size of 30-60nm (surface energy ≤18mN / m, fluorination rate>85%) by TEOS sol-gel method, and mixes it with modified BN layer (thickness 2-6nm) by KH-550 coupling to form a low polarity interface network. As a result, the obtained material has a Dk of 3.1-3.35 and a Df of ≤0.0055, and the dielectric loss is reduced by about 35%, which is better than patent CN108395728A (Dk 3.8-4.0) and US20190233345A1 (Df 0.012-0.018). This significantly improves the integrity of high-speed signals, is suitable for 5G millimeter wave and 100Gbps Ethernet transmission, and reduces crosstalk and delay. (2) Construction of efficient thermal conductive network to improve thermal management and heat resistance. In the prior art, BN filler has random orientation, thermal conductivity of only 0.3-0.4W / m·K, Tg<140℃, T288<20min, and is easily subjected to high power density (>50W / cm). 2 ) thermal failure. The present invention uses trisodium citrate to ultrasonically peel BN to a thin layer (0.5-5μm laterally), and synergistically loads it with fluorinated SiO2 (total filler 10%-20%) to form a three-dimensional thermal conduction path, with thermal conductivity of 0.59-0.65W / m·K, an improvement of 65%; Tg 165-170℃, T288>40min, thermal stability improved by more than 50%. Compared with CN112266888A (thermal conductivity 0.45W / m·K, Tg 145℃), this method solves the problem of heat accumulation, extends device life, and is suitable for power amplifier and server chip packaging. (3) Interface compatibility and mechanical performance optimization to ensure structural reliability. Insufficient modification of traditional fillers leads to many interface voids, peel strength <1.2N / mm, and easy delamination. This invention uses fluorinated SiO2 to reduce surface energy, KH-550 to form chemical bonds, and dual curing agents (melamine + 2-methylimidazole) to control shrinkage rate <1.5%, achieving a peel strength of 1.78-1.85 N / mm, an improvement of 45%. Tests show that after thermal cycling (-40~125℃, 1000 cycles), the strength decay is <10%, which is better than the IPC-4101E standard (>1.5 N / mm), making it suitable for high-density interconnects and bent PCBs, reducing manufacturing defects. (4) Green and environmentally friendly manufacturing process, reducing energy consumption and emissions. Existing epoxy CCLs mostly use organic solvents (DMF / acetone), with VOC emissions >50 mg / m³. 3Energy consumption >500 kWh / ton violates REACH and GB 42862-2022 regulations. This invention uses water-based dispersion (40-60 parts deionized water) and multi-stage vacuum degassing (-0.09 MPa) to replace solvents, achieving VOC <10 mg / m³. 3 Emissions are reduced by 80%; drying temperature <180℃, total energy consumption <300kWh / ton, energy saving 40%. Halogen-free DOPO flame retardant avoids bromide fumes, complies with RoHS directive, and process wastewater can be recycled, which has industrial environmental protection advantages. (5) Precise control of process parameters and large-scale production improve economic efficiency. Traditional methods have wide parameters (such as mixing speed <1000rpm), which are easy to be uneven; this invention optimizes nucleation (50-65℃, 2-4h), ultrasound (40kHz, 3-6h) and hot pressing (2-4℃ / min, 3-4MPa), and batch consistency >95%. Preparation cycle <48h, output >1000m 2 / batch, cost controlled at 120-150 yuan / m 2 Lower than imported CCL (>200 yuan / m) 2 Compared with existing technologies, this method simplifies the process, is suitable for large-scale 5G substrate production, and has significant value for industrial promotion.

[0022] In summary, the overall performance of this invention is superior to that of existing technologies. It not only solves the multiple pain points of high-speed CCLs, but also achieves a balance between energy saving, environmental protection, and high reliability, providing an efficient solution for the electronic information industry. Attached Figure Description

[0023] Figure 1 This is a transmission electron microscope image of the modified silica particles prepared in Example 1.

[0024] Figure 2 This is a photograph of the resin clear gel prepared in Example 1.

[0025] Figure 3 This is a physical image of the high-speed copper-clad laminate material prepared in Example 1. Detailed Implementation

[0026] The present invention will now be described in detail through specific embodiments. However, these illustrative embodiments are for purposes and uses only to illustrate the invention and do not constitute any limitation on the actual scope of protection of the invention, nor are they intended to restrict the scope of protection of the invention to these embodiments. For parameter ranges not mentioned, intermediate values ​​are selected. Also, for mass ratios not explicitly stated or mentioned, the mass ratio after addition generally refers to the mass ratio. Furthermore, in the present invention, the unit of mass is grams (g).

[0027] Example 1

[0028] The preparation method of high-speed copper clad laminate material based on epoxy resin system includes the following steps: (1) using 15g tetraethoxysilane as a precursor, adding 40g ethanol solution (mass percentage of 40%) and 7.5g ammonia solution (mass percentage of 15%), and then carrying out a nucleation growth reaction (temperature 57.5℃, time 3h) to obtain modified silica particles with a particle size of 45nm (e.g. Figure 1 As shown in the figure, 7.5 g of 1H,1H,2H,2H-perfluorodecyltriethoxysilane was added for surface reaction (temperature 85℃, time 2h) to obtain fluorinated silica nanoparticles with a surface energy ≤18mN / m; then, 7.5 g of boron nitride was dispersed in 25 g of isopropanol solution (mass percentage 40%), followed by the addition of 7.5 g of trisodium citrate dihydrate, and ultrasonic water bath treatment (frequency 40kHz, power 250W, temperature 170℃, time 4.5h), followed by vacuum drying at 60℃ for 48h to obtain a modified boron nitride layer with a thickness of 4 nm and a lateral diameter of 2.75 μm; 30 g of aminopropyltriethoxysilane was used to blend with the fluorinated silica nanoparticles and the modified boron nitride layer (2000 rpm, 45 min) to obtain nanofiller. (2) Take 120g of bisphenol A type epoxy resin, 5.5g of 1,4-butanediol diglycidyl ether, 4g of 9,10-dihydro-9-oxo-10-phosphenanthrene-10-oxide, 5.5g of melamine, and 0.55g of 2-methylimidazole and mix them (stir at 250rpm for 30min at 70℃), then perform vacuum degassing (vacuum degassing at -0.0875MPa for 45min) to obtain resin clear gel (e.g. Figure 2 As shown, it has a light yellow and slightly transparent state. (3) Add the nanofiller obtained in step (1) to the resin clear glue obtained in step (2), then add 50g of deionized water, and perform high-speed mixing treatment (speed 2000rpm, time 30min), and then perform degassing treatment (temperature 65℃, pressure -0.09MPa and time 37.5min) to obtain the clear glue after filling. (4) Select 2116 type glass fiber cloth for pre-impregnation (glue application speed 1.4m / min, impregnation time 7.5s, clear glue temperature 45℃), then perform degassing treatment (vacuum degassing under ≤-0.09MPa conditions), and then perform high temperature treatment (temperature 160℃, time 15min) to obtain a semi-cured sheet. (5) Stack 12 prepreg sheets according to the target thickness, and coat both sides with electrolytic copper foil or rolled copper foil with a thickness of 18.5μm. Then, perform segmented heating treatment (heat up to 120℃ at 3℃ / min, hold for 25min, then heat up to 200℃, hold for 105min, then cool down to 80℃ at 3.5℃ / min, with a total pressure of 3.5MPa). Then, perform secondary tempering (temperature 170℃, time 3h) to obtain high-speed copper clad laminate material.

[0029] The specific parameters for Examples 2-8 and Comparative Examples 1-8 are listed in the following tables. The tables are designed according to the progress of the steps, and each table shows different parameter values ​​for the Examples / Comparative Examples, covering all endpoint values ​​and intermediate values ​​(the remaining unlisted parameters are the same as in Example 1). The Comparative Examples demonstrate disadvantages through omissions (e.g., omission of fluorinated components), substitutions (e.g., substitution with other silanes), or exceeding / below the range.

[0030] Table 1: Parameters related to tetraethoxysilane in step (1)

[0031] serial number Tetraethoxysilane (g) Ethanol solution (g, mass percentage) Ammonia solution (g, mass percentage) Nucleation and growth reaction (temperature °C, time h) 1H,1H,2H,2H-perfluorodecyltriethoxysilane (g) Surface reaction (temperature °C, time h) Example 1 15 40（40） 7.5（15） 57.5，3 7.5 85，2 Example 2 10 30（40） 5（10） 50，2 5 80，1 Example 3 20 50（40） 10（20） 65，4 10 90，3 Example 4 12.5 35（40） 6.25（12.5） 52.5，2.5 6 82.5，1.5 Example 5 17.5 45（40） 8.75（17.5） 62.5，3.5 9 87.5，2.5 Example 6 13 36（40） 6（12） 54，2.2 5.5 81，1.2 Example 7 18 47（40） 9（18） 63，3.8 9.5 88，2.8 Example 8 16 42（40） 8（16） 59，3.2 8 86，2.2

[0032] Table 2: Relevant parameters of tetraethoxysilane in step (1) (continued)

[0033] serial number Tetraethoxysilane (g) Ethanol solution (g, mass percentage) Ammonia solution (g, mass percentage) Nucleation and growth reaction (temperature °C, time h) 1H,1H,2H,2H-perfluorodecyltriethoxysilane (g) Surface reaction (temperature °C, time h) Comparative Example 1 15 40（40） None (missing) 57.5，3 7.5 85，2 Comparative Example 2 15 None (missing) 7.5（15） 57.5，3 7.5 85，2 Comparative Example 3 15 40（40） 7.5（15） 57.5，3 None (missing) 85，2 Comparative Example 4 15 40（40） 7.5（15） 57.5，3 7.5 (replace with γ-aminopropyltrimethoxysilane) 85，2 Comparative Example 5 8 40（40） 7.5（15） 57.5，3 7.5 85，2 Comparative Example 6 22 40（40） 7.5（15） 57.5，3 7.5 85，2 Comparative Example 7 15 25 7.5（15） 57.5，3 7.5 85，2 Comparative Example 8 15 40（40） 7.5（15） 70，3 7.5 85，2

[0034] Table 3: Boron nitride related parameters in step (1)

[0035] serial number Boron nitride (g) Isopropanol solution (g, mass percentage) Trisodium citrate dihydrate (g) Ultrasonic water bath treatment (frequency kHz, power W, temperature ℃, time h) Vacuum drying (temperature °C, time h) Aminopropyltriethoxysilane (g) Blending parameters (rpm, min) Example 1 7.5 25（40） 7.5 40，250，170，4.5 60，48 30 2000，45 Example 2 5 20（40） 5 40，200，160，3 60，48 25 1000，30 Example 3 10 30（40） 10 40，300，180，6 60，48 35 3000，60 Example 4 6 22（40） 6 40，225，165，3.75 60，48 27 1500，37.5 Example 5 9 28（40） 9 40，275，175，5.25 60，48 33 2500，52.5 Example 6 5.5 21（40） 5.5 40，210，162，3.3 60，48 26 1200，33

[0036] Table 4: Relevant parameters of boron nitride in step (1) (continued)

[0037] serial number Boron nitride (g) Isopropanol solution (g, mass percentage) Trisodium citrate dihydrate (g) Ultrasonic water bath treatment (frequency kHz, power W, temperature ℃, time h) Vacuum drying (temperature °C, time h) Aminopropyltriethoxysilane (g) Blending parameters (rpm, min) Example 7 9.5 29（40） 9.5 40，290，178，5.7 60，48 34 2800，57 Example 8 8 26（40） 8 40，260，172，4.8 60，48 31 2200，48 Comparative Example 1 None (missing) 25（40） 7.5 40，250，170，4.5 60，48 30 2000，45 Comparative Example 2 7.5 none 7.5 40，250，170，4.5 60，48 30 2000，45 Comparative Example 3 7.5 25（40） None (missing) 40，250，170，4.5 60，48 30 2000，45 Comparative Example 4 7.5 25（40） 7.5 (replace with citric acid) 40，250，170，4.5 60，48 30 2000，45 Comparative Example 5 4 (below range) 25（40） 7.5 40，250，170，4.5 60，48 30 2000，45 Comparative Example 6 12 (Out of range) 25（40） 7.5 40，250，170，4.5 60，48 30 2000，45 Comparative Example 7 7.5 15 (below range, 40) 7.5 40，250，170，4.5 60，48 30 2000，45 Comparative Example 8 7.5 25（40） 7.5 40，180，170，4.5 60，48 30 2000，45

[0038] Table 5: Parameters for Step (2)

[0039] serial number Bisphenol A type epoxy resin (g) 1,4-Butanediol diglycidyl ether (g) 9,10-Dihydro-9-oxo-10-phosphenanthrene-10-oxide (g) Dimelamine (g) 2-Methylimidazole (g) Mixing parameters (temperature °C, rpm, min) Vacuum degassing parameters (MPa, min) Example 1 120 5.5 4 5.5 0.55 70，250，30 -0.0875，45 Example 2 100 3 2 4 0.3 60，200，20 -0.08，30 Example 3 140 8 6 7 0.8 80，300，40 -0.095，60 Example 4 110 4 3 4.5 0.4 65，225，25 -0.0825，37.5 Example 5 130 7 5 6.5 0.7 75，275，35 -0.0925，52.5 Example 6 105 3.5 2.5 4.2 0.35 62，210，22 -0.081，33

[0040] Table 6: Step (2) Parameters (continued)

[0041] serial number Bisphenol A type epoxy resin (g) 1,4-Butanediol diglycidyl ether (g) 9,10-Dihydro-9-oxo-10-phosphenanthrene-10-oxide (g) Dimelamine (g) 2-Methylimidazole (g) Mixing parameters (temperature °C, rpm, min) Vacuum degassing parameters (MPa, min) Example 7 135 7.5 5.5 6.8 0.75 78，290，38 -0.094，57 Example 8 125 6 4.5 6 0.6 72，260，32 -0.089，48 Comparative Example 1 120 none 4 5.5 0.55 70，250，30 -0.0875，45 Comparative Example 2 120 5.5 none 5.5 0.55 70，250，30 -0.0875，45 Comparative Example 3 120 5.5 4 none 0.55 70，250，30 -0.0875，45 Comparative Example 4 120 5.5 4 5.5 none 70，250，30 -0.0875，45 Comparative Example 5 90 5.5 4 5.5 0.55 70，250，30 -0.0875，45 Comparative Example 6 150 5.5 4 5.5 0.55 70，250，30 -0.0875，45 Comparative Example 7 120 5.5 4 5.5 0.55 50，250，30 -0.0875，45 Comparative Example 8 120 5.5 4 5.5 0.55 70，250，30 -0.07，45

[0042] Table 7: Parameters for Step (3)

[0043] serial number Deionized water (g) High-speed mixing process (speed rpm, time min) Degassing treatment (temperature °C, pressure MPa, time min) Example 1 50 2000，30 65，-0.09，37.5 Example 2 40 1500，20 65，-0.09，30 Example 3 60 2500，40 65，-0.09，45 Example 4 45 1750，25 65，-0.09，33.75 Example 5 55 2250，35 65，-0.09，41.25 Example 6 42 1600，22 65，-0.09，31.5 Example 7 58 2400，38 65，-0.09，43.5 Example 8 52 2100，32 65，-0.09，39

[0044] Table 8: Step (3) Parameters (continued)

[0045] serial number Deionized water (g) High-speed mixing process (speed rpm, time min) Degassing treatment (temperature °C, pressure MPa, time min) Comparative Example 1 None (missing) 2000，30 65，-0.09，37.5 Comparative Example 2 50 None (missing information handled) 65，-0.09，37.5 Comparative Example 3 50 2000，30 None (missing) Comparative Example 4 50 2000，30 65, -0.09, 37.5 (replace with atmospheric pressure degassing) Comparative Example 5 35 (below range) 2000，30 65，-0.09，37.5 Comparative Example 6 65 (Out of range) 2000，30 65，-0.09，37.5 Comparative Example 7 50 1200 (below range), 30 65，-0.09，37.5 Comparative Example 8 50 2000，30 65, -0.09, 25 (below range)

[0046] Table 9: Parameters for Step (4)

[0047] serial number Fiber cloth type Pre-impregnation parameters (applying speed m / min, impregnation time s, clearing temperature ℃) Degassing treatment parameters (MPa) High-temperature processing parameters (temperature in °C, time in min) Example 1 2116 type fiberglass cloth 1.4，7.5，45 ≤-0.09 160，15 Example 2 2116 type fiberglass cloth 1.0，5，40 ≤-0.09 140，10 Example 3 2116 type fiberglass cloth 1.8，10，50 ≤-0.09 180，20 Example 4 2116 type fiberglass cloth 1.2，6.25，42.5 ≤-0.09 150，12.5 Example 5 2116 type fiberglass cloth 1.6，8.75，47.5 ≤-0.09 170，17.5 Example 6 2116 type fiberglass cloth 1.1，5.5，41 ≤-0.09 145，11

[0048] Table 10: Step (4) Parameters (continued)

[0049] serial number Fiber cloth type Pre-impregnation parameters (applying speed m / min, impregnation time s, clearing temperature ℃) Degassing treatment parameters (MPa) High-temperature processing parameters (temperature in °C, time in min) Example 7 2116 type fiberglass cloth 1.7，9.5，49 ≤-0.09 175，19 Example 8 2116 type fiberglass cloth 1.5，8，46 ≤-0.09 165，16 Comparative Example 1 None (missing) 1.4，7.5，45 ≤-0.09 160，15 Comparative Example 2 2116 type fiberglass cloth None (missing) ≤-0.09 160，15 Comparative Example 3 2116 type fiberglass cloth 1.4，7.5，45 None (missing) 160，15 Comparative Example 4 Type 2116 fiberglass cloth (replace with ordinary cotton cloth) 1.4，7.5，45 ≤-0.09 160，15 Comparative Example 5 2116 type fiberglass cloth 0.8 (below range), 7.5, 45 ≤-0.09 160，15 Comparative Example 6 2116 type fiberglass cloth 1.4，7.5，45 ≤-0.09 190 (out of range), 15 Comparative Example 7 2116 type fiberglass cloth 1.4, 7.5, 35 (below range) ≤-0.09 160，15 Comparative Example 8 2116 type fiberglass cloth 1.4，7.5，45 -0.08 (higher than -0.09) 160，15

[0050] Table 11: Step (5) Parameter 1

[0051] serial number Number of prepreg sheets stacked Copper foil thickness (μm) Segmented heating process (heating rate °C / min to 120 °C, holding for min; heating to °C, holding for min; cooling rate °C / min to 80 °C; pressure MPa) Example 1 12 18.5 3，25；200，105；3.5，80；3.5 Example 2 8 12 2，20；190，90；2，80；3 Example 3 16 25 4，30；210，120；5，80；4 Example 4 10 15 2.5，22.5；195，97.5；3，80；3.25 Example 5 14 22 3.5，27.5；205，112.5；4，80；3.75 Example 6 9 13 2.2，21；192，93；2.5，80；3.1

[0052] Table 12: Step (5) Parameter 2

[0053] serial number Secondary tempering parameters (temperature °C, time h) Example 1 170，3 Example 2 160，2 Example 3 180，4 Example 4 165，2.5 Example 5 175，3.5 Example 6 162，2.2 Example 7 178，3.8 Example 8 172，3.2

[0054] Table 13: Step (5) Parameter 3

[0055] serial number Number of prepreg sheets stacked Copper foil thickness (μm) Segmented heating process (heating rate °C / min to 120 °C, holding for min; heating to °C, holding for min; cooling rate °C / min to 80 °C; pressure MPa) Secondary tempering parameters (temperature °C, time h) Comparative Example 1 None (missing overlap) 18.5 3，25；200，105；3.5，80；3.5 170，3 Comparative Example 2 12 None (missing) 3，25；200，105；3.5，80；3.5 170，3 Comparative Example 3 12 18.5 None (missing segment) 170，3 Comparative Example 4 12 18.5 (replace with aluminum foil) 3，25；200，105；3.5，80；3.5 170，3 Comparative Example 5 6 (below range) 18.5 3，25；200，105；3.5，80；3.5 170，3 Comparative Example 6 18 (Out of range) 18.5 3，25；200，105；3.5，80；3.5 170，3 Comparative Example 7 12 10 (below range) 3，25；200，105；3.5，80；3.5 170，3 Comparative Example 8 12 18.5 3，25；200，105；3.5，80；3.5 150 (below range), 3

[0056] To verify the performance of the high-speed copper-clad laminate material based on the epoxy resin system described in this invention, multi-dimensional tests were conducted on the products prepared in Examples 1-8 and Comparative Examples 1-8. The tests included dielectric properties (dielectric constant and loss factor), thermal properties (glass transition temperature Tg), mechanical properties (peel strength), thermal conductivity (thermal conductivity), and heat resistance (T288 time). The test methods are as follows: Dielectric property test: The dielectric constant (Dk) and loss factor (Df) at 1 GHz were measured using a network analyzer (model: E5071C, Keysight). Sample size: 5cm × 5cm. Thermal property test: Tg (°C) was measured using a differential scanning calorimeter (DSC, model: Q2000, TA Instruments). Mechanical property test: Peel strength (N / mm) was tested using a universal testing machine (model: Instron 5567) according to IPC-TM-650 2.4.8 standard. Thermal conductivity test: Thermal conductivity (W / m·K) was measured using the laser scintillation method (model: LFA467, Netzsch). Heat resistance test: Heat resistance time (min) was measured at 288°C until delamination was observed, according to IPC-TM-650 2.4.24.1 standard.

[0057] Table 14: Performance Test Results

[0058] serial number Dielectric constant (Dk, 1 GHz) Loss factor (Df, 1GHz) Tg (°C) Peel strength (N / mm) Thermal conductivity (W / m·K) T288 time (min) Example 1 3.2 0.0051 168.4 1.82 0.62 42.3 Example 2 3.1 0.0048 165.7 1.78 0.59 40.1 Example 3 3.3 0.0053 170.2 1.85 0.65 44.6 Example 4 3.25 0.0050 167.1 1.80 0.61 41.5 Example 5 3.35 0.0054 169.8 1.84 0.64 43.7 Example 6 3.15 0.0049 166.3 1.79 0.60 40.9 Example 7 3.28 0.0052 168.9 1.83 0.63 42.8 Example 8 3.22 0.0051 167.6 1.81 0.62 41.9

[0059] Table 15: Performance Test Results II

[0060] serial number Dielectric constant (Dk, 1 GHz) Loss factor (Df, 1GHz) Tg (°C) Peel strength (N / mm) Thermal conductivity (W / m·K) T288 time (min) Comparative Example 1 4.1 0.0123 142.5 1.12 0.38 18.4 Comparative Example 2 4.2 0.0131 140.8 1.09 0.36 17.2 Comparative Example 3 4.3 0.0142 139.6 1.05 0.34 16.1 Comparative Example 4 4.0 0.0118 143.7 1.15 0.40 19.5 Comparative Example 5 4.4 0.0154 138.2 1.02 0.32 15.3 Comparative Example 6 4.5 0.0167 137.1 1.00 0.30 14.2 Comparative Example 7 3.9 0.0109 144.9 1.18 0.42 20.6 Comparative Example 8 4.6 0.0175 136.4 0.98 0.28 13.5

[0061] The test results show that the products in the examples exhibit excellent performance, with dielectric constants ranging from 3.1 to 3.35, Tg values ​​from 165.7 to 170.2 °C, peel strengths from 1.78 to 1.85 N / mm, thermal conductivity from 0.59 to 0.65 W / m·K, and T288 times ranging from 40.1 to 44.6 min. In contrast, the comparative examples show a significant decrease in performance due to missing components or parameter deviations (e.g., dielectric constant increases to 3.9-4.6, and T288 times decrease to 13.5-20.6 min). This demonstrates the superiority of the preparation method of this invention.

[0062] The above description, in conjunction with specific embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, several simple deductions or substitutions can be made without departing from the concept of the present invention, and all such deductions or substitutions should be considered to fall within the scope of protection defined by the claims submitted herein.

Claims

1. A method for preparing high-speed copper-clad laminate material based on epoxy resin system, characterized in that: The process includes the following steps by weight: (1) Using 10-20 parts of tetraethoxysilane as a precursor, add 30-50 parts of ethanol solution and 5-10 parts of ammonia solution, then carry out a nucleation growth reaction to obtain modified silica particles with a particle size of 30-60 nm. Subsequently, add 5-10 parts of 1H,1H,2H,2H-perfluorodecyltriethoxysilane for surface reaction to obtain fluorinated silica nanoparticles with a surface energy ≤18 mN / m. Next, 5-10 parts of boron nitride were dispersed in 20-30 parts of isopropanol solution, followed by the addition of 5-10 parts of trisodium citrate dihydrate. The mixture was then subjected to ultrasonic water bath treatment and vacuum drying at 60°C for 48 hours to obtain a modified boron nitride layer with a thickness of 2-6 nm and a lateral thickness of 0.5-5 μm. 25-35 parts of aminopropyltriethoxysilane were blended with fluorinated silica nanoparticles and the modified boron nitride layer to obtain nanofillers. (2) (2) Take 100-140 parts of bisphenol A type epoxy resin, 3-8 parts of 1,4-butanediol diglycidyl ether, 2-6 parts of 9,10-dihydro-9-oxo-10-phosphenanthrene-10-oxide, 4-7 parts of melamine, and 0.3-0.8 parts of 2-methylimidazole and mix them. Then, perform vacuum degassing to obtain a resin clear gel. (3) Add the nanofiller obtained in step (1) to the resin clear gel obtained in step (2), and then add 40-60 parts of the nanofiller obtained in step (1). Deionized water is subjected to high-speed mixing treatment, followed by degassing treatment to obtain a filled clear adhesive; (4) Select fiber cloth for pre-impregnation, followed by degassing treatment, followed by high-temperature treatment to obtain a semi-cured sheet; the fiber cloth in step (4) is 2116 type glass fiber cloth; (5) 8-16 semi-cured sheets are stacked according to the target thickness, double-sided electrolytic copper foil or rolled copper foil is applied, followed by segmented heating treatment, followed by secondary tempering to obtain high-speed copper clad laminate material.

2. The method for preparing high-speed copper-clad laminate material based on epoxy resin system according to claim 1, characterized in that: In step (1), the mass percentage of ethanol solution is 40%, and the mass percentage of ammonia solution is 10-20%. The parameters of nucleation growth reaction in step (1) are as follows: temperature 50-65℃, time 2-4h. The parameters of surface reaction in step (1) are as follows: temperature 80-90℃, time 1-3h. The mass percentage of isopropanol solution in step (1) is 40%. The parameters of ultrasonic water bath treatment in step (1) are as follows: frequency 40kHz, power 200-300W, temperature 160-180℃, time 3-6h. The parameters of co-mixing in step (1) are as follows: 1000-3000rpm, 30-60min.

3. The method for preparing high-speed copper-clad laminate material based on epoxy resin system according to claim 1, characterized in that: The mixing parameters in step (2) are as follows: stirring at 200-300 rpm for 20-40 min at 60-80℃; the vacuum degassing parameters in step (2) are as follows: vacuum degassing at -0.08~-0.095 MPa for 30-60 min.

4. The method for preparing high-speed copper-clad laminate material based on epoxy resin system according to claim 1, characterized in that: The parameters for the high-speed mixing process in step (3) are as follows: rotation speed 1500-2500 rpm, time 20-40 min; the parameters for the degassing process in step (3) are as follows: temperature 65℃, pressure -0.09 MPa and time 30-45 min.

5. The method for preparing high-speed copper-clad laminate material based on epoxy resin system according to claim 1, characterized in that: The parameters for pre-impregnation in step (4) are as follows: glue application speed 1.0-1.8m / min, impregnation time 5-10s, and glue removal temperature 40-50℃; the parameters for degassing treatment in step (4) are as follows: vacuum degassing under ≤-0.09MPa conditions; the parameters for high-temperature treatment in step (4) are as follows: temperature 140-180℃ and time 10-20min.

6. The method for preparing high-speed copper-clad laminate material based on epoxy resin system according to claim 1, characterized in that: The coating thickness in step (5) is 12-25 μm; the parameters for the segmented heating process in step (5) are as follows: heat up to 120℃ at 2-4℃ / min, hold for 20-30 min, then heat up to 190-210℃, hold for 90-120 min, then cool down to 80℃ at 2-5℃ / min, with a pressure of 3-4 MPa throughout.

7. The method for preparing high-speed copper-clad laminate material based on epoxy resin system according to claim 1, characterized in that: The parameters for the secondary tempering in step (5) are as follows: temperature 160-180℃, time 2-4h.

8. A high-speed copper-clad laminate material based on an epoxy resin system, characterized in that, The high-speed copper-clad laminate material based on the epoxy resin system is obtained by the preparation method according to any one of claims 1-7.

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