Carrier plate copper-clad plate material based on high-heat-resistance thermosetting resin and preparation method of carrier plate copper-clad plate material

Abstract

The invention discloses a carrier plate copper-clad plate material based on high-heat-resistance thermosetting resin and a preparation method of the carrier plate copper-clad plate material, and belongs to the technical field of composite high polymer materials. The material is prepared by synergistically modifying an epoxy resin system through a three-stage nano filler. The preparation method comprises the following steps: firstly, synthesizing 40-50nm titanium-containing quantum dots from tetrabutyl titanate through a solvothermal reaction; modifying fumed silica with a silane coupling agent to obtain a dispersion stabilizer; meanwhile, boron nitride powder is subjected to a hydrothermal reaction to form the heat-conducting filler. The preparation method comprises the following steps: sequentially adding the filler into a high-heat-resistance resin matrix compounded by bisphenol A type epoxy resin and naphthalene diglycidyl ether, adding a reinforcing agent, stirring to form slurry, impregnating glass fiber cloth, pre-curing and hot-pressing curing to obtain a prepreg, and finally, carrying out copper foil-clad lamination molding. The monodisperse state of the nanofiller in the resin matrix is realized, and the obtained copper-clad plate material is suitable for the field of high-frequency and high-speed electronic support plates.

Description

Technical Field

[0001] This invention belongs to the field of composite polymer materials technology, specifically, it relates to a carrier copper clad laminate material based on a high heat-resistant thermosetting resin and its preparation method. Background Technology

[0002] Copper clad laminate (CCL) is a key basic material for electronic interconnect structures such as printed circuit boards (PCBs) and packaging substrates. Its dielectric, thermal, and mechanical properties directly affect signal integrity, thermal management reliability, and dimensional stability and interlayer bonding reliability after multiple thermal cycles. With the continuous development of applications such as 5G communication, data centers, high-speed servers, automotive radar, and high-performance chip packaging, high-frequency and high-speed signal transmission has placed more stringent requirements on the dielectric properties of substrates. Industry and academia are generally focused on achieving copper clad laminate material systems with lower dielectric loss, more stable dielectric constant, and higher heat resistance at higher frequency bands.

[0003] Existing copper-clad laminates (CCLs) are typically composed of copper foil and an insulating layer. The insulating layer is often a composite of resin systems and reinforcing materials such as fiberglass cloth, along with fillers, curing systems, and additives to meet requirements for flame retardancy, processing, and reliability. In high-frequency and high-speed applications, dielectric constant (Dk) and dielectric loss (Df) are considered key parameters determining signal propagation speed and transmission loss. Furthermore, increased dielectric loss at higher frequencies is detrimental to signal transmission and system power consumption control. Therefore, developing CCL materials with low Df and stable Dk values ​​has significant engineering value. On the other hand, advanced packaging substrates and high-density PCBs operate under conditions such as lead-free reflow soldering, multiple laminations, localized high-power devices, and high ambient temperatures. Materials must not only possess low dielectric loss but also higher glass transition temperatures (Tg), higher thermal decomposition temperatures (Td), and better resistance to thermal delamination and thermal aging stability to ensure long-term reliability and manufacturing yield.

[0004] From the perspective of industrial materials, traditional epoxy / phenolic systems such as FR-4 are widely used due to their cost and mature processes. However, in ultra-high frequency or more demanding high-speed interconnect environments, the dielectric performance and heat resistance of conventional epoxy or phenolic resins often cannot simultaneously meet the requirements. Therefore, high-frequency and high-speed copper-clad laminates are gradually developing towards modified epoxy, PPE, cyanate ester, hydrocarbon resin, siloxane hybrid, PTFE and its composite systems. For example, some commercially available "low-loss laminate / prepreg" products can provide typical indicators: Tg can reach about 215℃, Td about 360℃, and Df about 0.0031 and Dk about 3.45 (10GHz) can be achieved, providing a usable material baseline for high-frequency and high-speed circuits. However, in advanced packaging substrates and applications with higher reliability levels, there is still a general demand for higher heat resistance limits, lower water absorption, better interface bonding and higher thermal conductivity. In particular, as systems evolve towards higher layer counts, smaller linewidths and spacings, higher power densities and higher operating frequencies, the multi-objective constraints of materials’ “electro-thermal-mechanical” will be significantly aggravated.

[0005] Specifically, copper-clad laminates (CCLs) for high-density packaging require low dielectric constant (Dk) / low dielectric constant (Df) to reduce insertion loss and crosstalk. They also need to maintain low thermal expansion mismatch and high peel strength after multiple hot-pressing processes, drilling / laser microvias, electroplating, reflow soldering, and service thermal cycles to prevent interlayer cracking, copper foil warping, hole wall cracks, and conduction failure. Material moisture absorption is also a crucial indicator: moisture absorption can cause dielectric drift, glass fiber / resin interface degradation, and an increased risk of "board bursting / delamination," potentially accelerating reliability issues such as electrochemical migration. Simultaneously, with the increasing integration of power devices, RF front-ends, and high-speed SerDes links, heat is highly concentrated in localized areas. Insufficient thermal conductivity of the substrate can exacerbate hotspot temperature rise, further inducing a chain reaction of problems such as interface fatigue, solder joint creep, and dielectric performance deterioration due to temperature drift. Therefore, improving the thermal conductivity, heat resistance, and interface reliability of materials while maintaining low dielectric loss has become an important development direction for high-frequency, high-speed CCLs.

[0006] At the materials design level, improving thermal conductivity often involves introducing thermally conductive and insulating fillers such as boron nitride, aluminum nitride, and alumina to construct heat conduction channels. However, high filler content often leads to processing problems such as increased resin viscosity, impregnation difficulties, increased porosity, and poor lamination fluidity. It may also cause electrical performance side effects such as increased dielectric constant, increased dielectric loss, or increased high-frequency scattering loss. In particular, micro / nano fillers have a significant tendency to agglomerate in resins, and insufficient interfacial compatibility can create "stress concentration points" and "thermal resistance interfaces," which not only weaken the efficiency of thermal conductivity improvement but also reduce toughness and peel strength, affecting the reliability of drilling, electroplating, and thermal shock. To improve interfacial bonding, silane coupling agents, surface coating, in-situ growth, and core-shell structures are often used to activate the filler surface and achieve chemical / physical coupling with the resin. However, how to achieve stable dispersion and strong interfacial bonding without significantly increasing the system polarity or introducing too many loss sources remains a challenge in engineering implementation.

[0007] In terms of flame retardancy and environmental protection, copper-clad laminates typically need to meet flame retardancy ratings such as UL94. For a long time, halogenated flame retardants containing bromine and other compounds have been widely used due to their high flame retardancy efficiency. However, they may release toxic gases or smoke during combustion or thermal decomposition, posing environmental and health risks. Therefore, halogen-free flame retardant systems have gradually become an important direction for the industry. In recent years, halogen-free flame retardant systems such as phosphorus, nitrogen, and silicon have received attention. However, some flame retardant additives may lead to deterioration of dielectric loss due to high polarizability or insufficient compatibility with resins, which inherently contradicts the core objective of "low dielectric loss" for high-frequency and high-speed copper-clad laminates. Therefore, developing thermosetting resin systems that balance low loss, flame retardancy, and high heat resistance, along with matching low-loss interface modification and dispersion control technologies, remains a pressing need.

[0008] In summary, existing technologies for high-frequency, high-speed carrier copper-clad laminate materials still face multiple bottlenecks: First, while increasing crosslinking density or replacing with high-Tg resin can improve heat resistance, it often leads to increased brittleness, narrower processing window, and increased lamination stress, making it difficult to balance peel strength and thermal shock reliability. Second, the addition of high thermal conductivity fillers is limited by dispersion, interfacial thermal resistance, and process viscosity, making it difficult to simultaneously achieve improved thermal conductivity and controlled dielectric loss. Third, there is a conflict between halogen-free flame retardancy and low dielectric loss in terms of material polarity and loss mechanism, and flame retardant modification can easily cause an increase in dielectric loss (Df). Fourth, moisture absorption and interfacial reliability issues are amplified under high-frequency, high-speed, and advanced packaging conditions, requiring materials to balance low water absorption, CAF resistance, and long-term electrothermal coupling stability. Therefore, there is an urgent need for a novel carrier copper clad laminate material based on a high heat-resistant thermosetting resin and its industrially feasible preparation method. Through the synergistic design of multi-scale functional fillers and interfacial chemistry, while ensuring low Dk / low Df, it can achieve high Td, high Tg, high thermal conductivity, good copper foil bonding strength and low water absorption, thereby meeting the application requirements of the next generation of high-frequency and high-speed carriers and high-reliability electronic equipment. Summary of the Invention

[0009] To address the challenges in balancing heat resistance, thermal conductivity, dielectric properties, and interface reliability in existing high-frequency and high-speed carrier copper-clad laminate materials, as well as issues such as difficulties in dispersing high thermal conductivity fillers, insufficient interfacial compatibility, inherent contradictions between halogen-free flame retardancy and low dielectric loss, and long-term reliability risks due to high water absorption, this invention provides a carrier copper-clad laminate material based on a high-heat-resistant thermosetting resin and its preparation method. By coupling multi-scale nanofiller synergistic design with a gradient dispersion-segmented curing process, multi-objective synergistic optimization of the material system in terms of dielectric, thermal, mechanical, and moisture resistance is achieved, meeting the stringent requirements of next-generation high-density packaging carriers and high-frequency and high-speed PCBs for the substrate.

[0010] Specifically, the technical concept of this invention lies in constructing a three-level functionalized enhancement system of "quantum dot anchoring - nanoparticle dispersion - thermally conductive network construction," and embedding it into a resin matrix composed of high-heat-resistant epoxy resin and a high-efficiency curing agent. Through a stepwise reaction and layer-by-layer assembly preparation strategy, it ensures that fillers of various sizes achieve monodispersity in the resin matrix and form effective interfacial chemical bonds. This simultaneously improves the glass transition temperature, thermal decomposition temperature, thermal conductivity, copper foil peel strength, and moisture resistance of the material without significantly increasing dielectric loss. The core innovations of this technical solution are reflected in the following four aspects: First, the in-situ synthesis and interfacial bridging mechanism of titanium-containing quantum dots. This invention uses tetrabutyl titanate as a precursor, and generates titanium-containing quantum dots with a particle size of 40-50 nm through a solvothermal reaction (180-220℃, 0.5-3MPa, 24h) in a high-pressure reactor. Subsequently, surface amino functionalization is achieved through triethylamine post-treatment. These quantum dots not only serve as the first-level nano-reinforcing phase, but more importantly, they can chemically bond with the epoxy and hydroxyl groups on the epoxy resin molecular chains during resin curing, forming a "quantum dot-resin" interfacial bridging structure. Compared to traditional silica or alumina nanoparticles, titanium quantum dots have higher dielectric constants and polarizabilities, but their nanoscale effects and surface engineering allow them to exist in a monodisperse state in the matrix, avoiding the dielectric loss concentration effect of micron-sized fillers. Simultaneously, the introduction of titanium can form stable Ti-OC bonds in the polymer network, effectively improving crosslinking density and thermal stability, thereby enabling the material's thermal decomposition temperature (Td) to exceed 400℃ and its glass transition temperature (Tg) to reach above 200℃. This quantum dot synthesis process uses an ethanol-water mixed solvent system, with mild and controllable reaction conditions, narrow particle size distribution, and high surface functionalization, laying a molecular-level foundation for subsequent compatibility with the resin matrix. Secondly, the surface modification strategy and dispersion stabilization effect of fumed silica are also discussed. To address the issues of high thermal conductivity boron nitride filler agglomeration and poor interfacial compatibility with epoxy resin, this invention introduces a second-level nanofunctional phase—fumed silica modified with 3-glycidyl etheroxypropyltrimethoxysilane (KH-560). This modification process is carried out under acidic conditions of pH 3-5, and ultrasonic dispersion (20kHz, 750W, 40min) ensures complete deagglomeration of silica particles, allowing the silane coupling agent to form covalently bonded epoxy functional groups on the particle surface. The modified silica not only exhibits good dispersion stability in the resin, but more importantly, its surface epoxy groups can synergistically react with the resin matrix and the surface functional groups of titanium quantum dots, forming a multi-level network structure of "quantum dot-silica-resin". This structure spatially hinders the aggregation tendency of boron nitride filler, achieving a "nano-segmentation" effect for the third-level thermally conductive filler, thus macroscopically exhibiting the monodisperse characteristics of the filler.Furthermore, the introduction of silica can adjust the rheological properties of the resin system, improve the impregnation performance of the slurry on the glass fiber cloth, reduce porosity, and enhance the density and dielectric consistency of the laminate. Third, the hydrothermal functionalization and network construction of boron nitride thermally conductive filler. This invention uses hexagonal boron nitride powder as the main thermally conductive phase, and grafts KH-550 silane coupling agent, 2-methylimidazole (curing accelerator), and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) onto the boron nitride surface through a hydrothermal reaction (80-90℃, 1.5-2h). This one-step hydrothermal process achieves multifunctional treatment of the boron nitride surface: the silane coupling agent provides chemical bonding sites with the resin, 2-methylimidazole can participate in the curing reaction of the epoxy resin and accelerate crosslinking, and the antioxidant inhibits oxidative degradation during high-temperature processing. Functionalized boron nitride in the resin matrix not only enhances thermal conductivity to over 1.2 W / (m·K) through phonon conduction, but more importantly, it forms a "chemical-physical" bicontinuous interface with the resin matrix, effectively reducing interfacial thermal resistance. Compared with traditional physical blending, this functionalization strategy improves thermal conductivity efficiency by over 30% while avoiding increased dielectric loss due to interfacial defects. The amount of boron nitride added is optimized to ensure thermal conductivity while maintaining the insulating properties and low dielectric loss of the material through the synergistic dispersion effect of the aforementioned two-stage nanophases. Fourth, the molecular design and compounding optimization of the high heat-resistant resin matrix. This invention uses bisphenol A type epoxy resin (CAS: 25068-38-6) and 1,6-bis(2,3-epoxypropoxy)naphthalene (naphthalenediol diglycidyl ether, CAS: 27610-48-6) in a mass ratio of 0.5-2:1 to form the resin matrix. Bisphenol A type epoxy resin provides basic mechanical strength and processability, while the introduction of the naphthalene ring structure significantly improves segment rigidity, reduces dielectric loss, and endows the material with higher thermal stability and glass transition temperature. This compound system achieves a Tg exceeding 200℃ and a Td exceeding 400℃. Furthermore, due to the conjugation effect and low polarizability of the naphthalene ring, the dielectric constant can be controlled below 3.5 at 10GHz, and the dielectric loss is below 0.005. The curing agent is polyetheramine (CAS: 9046-10-0), whose flexible segments alleviate the brittleness caused by high crosslinking density, improving the peel strength to above 1.2 N / mm. The synergistic curing reaction of the resin matrix and tertiary nanofillers is completed under a gradient temperature program of premixing at 60-80℃ and hot-pressing at 180-220℃, ensuring complete curing and minimizing internal stress.Through the coupling of the above four technological innovations, the copper-clad laminate material prepared by this invention achieves multi-dimensional breakthroughs in performance: thermal decomposition temperature Td≥400℃, glass transition temperature Tg≥200℃, thermal conductivity≥1.2W / (m·K), dielectric constant Dk≤3.5 at 10GHz, dielectric loss Df≤0.005, peel strength≥1.2N / mm, and water absorption ≤0.5%. These performance indicators not only meet the requirements of low dielectric loss for high-frequency and high-speed signal transmission, but also meet the stringent standards of high heat resistance, high thermal conductivity, and high reliability for advanced packaging substrates. Compared with existing technologies, this invention effectively solves the problems of difficult dispersion and insufficient interfacial compatibility of high thermal conductivity fillers through quantum dot bridging and multi-level nano-synergistic mechanisms, avoiding the drawbacks of sacrificing processability and dielectric properties by simply increasing filler content. Through the molecular design of naphthalene ring-structured epoxy resin, it achieves a balance between low dielectric loss and high heat resistance under the premise of halogen-free flame retardancy. Gradient dispersion and segmented curing processes ensure the process feasibility and batch stability of the material system. Therefore, this invention provides a high-performance, high-reliability carrier copper-clad laminate material solution for next-generation communication equipment, data centers, automotive electronics, and aerospace electronic systems, possessing significant engineering application value and industrialization prospects.

[0011] The present invention adopts the following technical solution: a method for preparing a carrier copper clad laminate material based on a high heat-resistant thermosetting resin, comprising the following steps by weight: (1) mixing 2-6 parts of tetrabutyl titanate (CAS No.: 5593-70-4), 4-8 parts of anhydrous ethanol, 6-10 parts of octadecylamine (CAS No.: 124-30-1) and 5-15 parts of oleic acid (CAS No.: 112-80-1), adding 40 parts of an aqueous ethanol solution and reacting at high temperature to obtain titanium-containing quantum dots, then adding an equal volume of 50% ethanol solution by mass and mixing, adding 1-5 parts of triethylamine (CAS No.: 121-44-8), heating and reacting, and after washing, centrifugation and drying, obtaining doped powder with a particle size of 40-50 nm; (2) mixing 1-5 parts of fumed silica (CAS No.: 7631-86-9, specific surface area 200-400 m²) with ... 2 / g) dispersed in 50 parts by mass percentage of 50% ethanol solution, adjusted pH to 3-5, ultrasonically dispersed, and then 0.1-0.5 parts of 3-glycidyl etheroxypropyltrimethoxysilane (CAS No.: 2530-83-8) were added and reacted at 40-60℃ for 12-24h. After drying at 80℃, modified nanoparticles were obtained; (3) 10-20 parts of boron nitride powder, 0.5-2 parts of KH-550 (CAS No.: 919-30-2), 1-5 parts of 2-methylimidazole (CAS No.: 693-98-1), 2-6 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (CAS No. 6683-19-8) and 40 -60 parts of deionized water, hydrothermal reaction to obtain thermally conductive filler; (4) 200 parts of high heat-resistant epoxy resin and 20-40 parts of polyetheramine (CAS No.: 9046-10-0) are mixed at 60-80℃ to obtain resin matrix; (5) the doped powder obtained in step (1), the modified nanoparticles obtained in step (2) and the thermally conductive filler obtained in step (3) are added to the resin matrix obtained in step (4) in sequence, 10-30 parts of reinforcing agent are added, and the mixture is stirred to obtain slurry; (6) glass fiber cloth is impregnated in the slurry obtained in step (5), pre-cured and then hot-pressed to obtain a semi-cured sheet; (7) electrolytic copper foil is covered on both the upper and lower sides of the semi-cured sheet obtained in step (6), and laminated to obtain a carrier copper-clad laminate material.

[0012] Preferably, the mass percentage of the ethanol-water solution in step (1) is 80%; the equipment for the high-temperature reaction in step (1) is a high-pressure reactor; the pressure of the high-temperature reaction in step (1) is 0.5-3MPa, the temperature of the high-temperature reaction is 180-220℃, the rotation speed of the high-temperature reaction is 200-300rpm, and the reaction time is 24h.

[0013] Preferably, in step (1), the heating reaction temperature is 140-180℃ and the heating reaction time is 12-24h; in step (1), the washing is performed 3 times, the washing solution is anhydrous ethanol, the centrifugation speed is 4000rpm, the centrifugation time is 15min, the drying temperature is 80℃, and the drying time is 6h.

[0014] Preferably, the reagent used to adjust the pH in step (2) is hydrochloric acid; the parameters for ultrasonic dispersion in step (2) are as follows: 20 kHz, 750 W and 40 min.

[0015] Preferably, the parameters of the hydrothermal reaction in step (3) are as follows: 80-90℃, 1.5-2h.

[0016] Preferably, the high heat-resistant epoxy resin in step (4) is composed of bisphenol A type epoxy resin (CAS No.: 25068-38-6) and 1,6-bis(2,3-epoxypropoxy)naphthalene (naphthalene diglycidyl ether) (CAS No.: 27610-48-6) in a mass ratio of (0.5-2):1.

[0017] Preferably, in step (5), the reinforcing agent is a mixture of DISPER985 (CAS No.: 149213-65-0) and propylene glycol methyl ether acetate (CAS No.: 108-65-6) in a mass ratio of (5-10): (10-20); in step (5), the stirring speed is 1000 rpm and the stirring time is 35 min.

[0018] Preferably, the thickness of the glass fiber cloth in step (6) is 0.05-0.2 mm; the impregnation parameters in step (6) are as follows: the impregnation vacuum degree is 0.02 MPa, the impregnation temperature is 60℃, and the impregnation time is 25 min; the pre-curing parameters in step (6) are as follows: curing at 120-160℃ for 10 min; the hot-press curing parameters in step (6) are as follows: curing at 180-220℃ and pressure of 1.5-3 MPa for 120 min.

[0019] Preferably, the thickness of the electrolytic copper foil in step (7) is 30 μm; the lamination parameters in step (7) are as follows: 180-220℃ and 1-2.5MPa pressure for 60-90 min;

[0020] A copper-clad laminate material based on a high-heat-resistant thermosetting resin is provided, wherein the copper-clad laminate material based on the high-heat-resistant thermosetting resin is obtained by the preparation method described above.

[0021] Compared to existing technologies, this invention achieves a systematic breakthrough in the dielectric properties, thermal characteristics, thermal conductivity, interface reliability, and process economy of copper-clad laminate materials by introducing a multi-scale nanofiller synergistic enhancement mechanism and a high-heat-resistant resin molecule design strategy. The specific technical effects are reflected in the following seven dimensions: First, a significant improvement in dielectric performance and optimization of frequency response stability. This invention achieves excellent performance at 10GHz high frequencies with dielectric constant Dk≤3.5 and dielectric loss Df≤0.005 through the interface bridging of titanium quantum dots and the low polarizability design of naphthalene ring structure epoxy resin, reducing dielectric loss by more than 40% compared to traditional epoxy systems (Dk>4.0, Df>0.008). The nanoscale effect of titanium quantum dots avoids the concentration of interface polarization loss caused by micron-sized fillers, while the conjugated rigid structure of naphthalene diglycidyl ether reduces the segment dipole reversal polarizability, enabling the material to maintain stable dielectric properties over a wide temperature range (-55℃~200℃) and a wide frequency range (1-20GHz). Test data from the examples show that Example 1 (Dk=3.2, Df=0.004) is significantly better than Comparative Example 1 (Dk=4.2, Df=0.008), meeting the stringent requirements for signal integrity in 5G millimeter wave and high-speed SerDes links. Secondly, the heat resistance level is significantly improved, and the thermomechanical stability is enhanced. This invention, through the synergistic effect of the chemical bonding network of the three-level nanofiller and the high cross-linking density resin matrix, achieves a material thermal decomposition temperature Td≥400℃ and a glass transition temperature Tg≥200℃, an improvement of over 20% compared to traditional FR-4 materials (Td approximately 300-350℃, Tg approximately 150-180℃). The Ti-OC bonds on the surface of the titanium quantum dots form cross-linking anchors with the epoxy resin, and the 2-methylimidazole grafted onto the boron nitride surface participates in the curing reaction, constructing a continuous cross-linking network of "resin-quantum dot-boron nitride," effectively inhibiting chain segment slippage and thermo-oxidative degradation at high temperatures. Thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) showed that Example 3 achieved a Td of 418.9℃ and a Tg of 215.2℃, while the comparative example, due to component deficiency, had a Td of only 362.7℃ and a Tg of only 180.4℃, confirming the decisive contribution of multi-scale synergistic enhancement to heat resistance. Third, the invention achieved a significant improvement in thermal conductivity and a breakthrough in thermal management capabilities. Through the dispersion and stabilization effects of hydrothermally functionalized boron nitride and fumed silica, the thermal conductivity was increased to ≥1.2 W / (m·K) under controllable filler loading, which is 2-3 times higher than that of traditional epoxy copper clad laminates (thermal conductivity approximately 0.3-0.5 W / (m·K)). After surface modification with KH-550 and 2-methylimidazole, the interfacial thermal resistance between boron nitride and the resin matrix was reduced by more than 40%, significantly improving phonon conduction efficiency. Fumed silica, acting as a "nanospacer," prevented boron nitride agglomeration, forming a more effective thermal conductivity network.Laser flare analysis (LFA) testing showed that Example 8 achieved a thermal conductivity of 1.48 W / (m·K), while the comparative example, due to interface defects and agglomeration, had a thermal conductivity of only 0.84-0.95 W / (m·K). This level of thermal conductivity can effectively alleviate local hotspot problems in power devices and RF modules, reducing the risk of thermal failure of the carrier board. Fourth, comprehensive improvement in interfacial bonding strength and mechanical reliability. This invention, through the chemical anchoring of titanium quantum dots and the surface epoxy functionalization of silica, improves the copper foil peel strength to ≥1.2 N / mm and reduces the water absorption rate to ≤0.5%, which is more than 50% higher and 40% lower than traditional materials (peel strength approximately 0.8 N / mm, water absorption rate approximately 0.8-1.0%), respectively. Quantum dots form a nanoscale pinning effect at the resin-copper foil interface, enhancing the synergistic effect of van der Waals forces and chemical bonding; at the same time, the low water absorption rate is attributed to the filling effect of nanofillers on the free volume of resin and the surface hydrophobic treatment, reducing the penetration path of water at the glass fiber / resin interface. IPC-TM-650 standard testing shows that Example 1 has a peel strength of 1.4 N / mm and a water absorption rate of only 0.3%, while Comparative Example 1 has only 0.8 N / mm and 0.9% respectively, significantly improving the material's CAF (conductive anode wire) resistance, thermal shock reliability, and long-term service life under humid and hot environments. Fifth, significant optimization of process feasibility and adaptability to large-scale production. This invention adopts gradient dispersion (ultrasonic assistance) and segmented curing (pre-curing + hot-pressing curing) processes. The slurry viscosity is stable within the impregnation range (viscosity of about 800-1200 mPa·s at 25℃). The impregnation vacuum degree of the fiberglass cloth is only 0.02 MPa, the time is 25 min, the lamination temperature is 180-220℃, and the pressure is 1-2.5 MPa. It is compatible with the process parameters of traditional epoxy copper clad laminates and requires no special equipment modification. The rheological regulation effect of fumed silica avoids the common problems of "network blockage" and "insufficient resin flow" in high-filler systems; the solvothermal synthesis of titanium quantum dots uses an ethanol-water solution system, which has readily available raw materials, controllable reaction conditions, and good batch repeatability. Comparative analysis shows that when the process parameters deviate from the scope of this invention (such as lack of vacuum impregnation or excessively low curing temperature), the porosity of the material increases and the performance dispersion increases, verifying the rationality of the process window of this invention and its feasibility for industrial scale-up. Sixth, the synergistic achievement of environmental protection and halogen-free flame retardancy. This invention does not use halogenated flame retardants such as bromine-based ones, but achieves UL94V-0 flame retardancy through the network structure effect of nanofillers and the intrinsic flame retardancy of boron nitride. Titanium quantum dots and boron nitride form a dense ceramicized carbon layer at high temperature, which inhibits the release of combustible gases and heat transfer; at the same time, the aromatic skeleton of the naphthalene ring structure epoxy resin improves the char formation rate. Compared to traditional bromine-containing systems, this invention offers significant advantages in terms of combustion product toxicity, flue gas density, and environmental compliance (meeting RoHS, REACH, and other regulations). It also avoids the negative impact of halogens on dielectric loss, achieving a harmonious balance between low loss and halogen-free flame retardancy. Seventh, it offers excellent overall cost-effectiveness and adaptability to various application scenarios.This invention, while meeting high-performance requirements, utilizes main raw materials (bisphenol A type epoxy resin, boron nitride, and fumed silica) that are all industrially mature products. Although tetrabutyl titanate and diglycidyl ether of naphthalene are relatively expensive, through optimized dosage (the mass ratio of bisphenol A to naphthalene ring epoxy is adjustable from 0.5 to 2:1) and performance premium, the overall material cost increase is controlled within 30%. The added value brought by performance improvement (such as improved yield, extended reliability, and expanded design margin) can completely cover the cost increase. The material system can be flexibly adapted to different application scenarios by adjusting the filler ratio and resin ratio: for example, increasing the boron nitride content can prepare a high thermal conductivity version (thermal conductivity ≥ 1.5 W / (m·K)) for power module carrier boards; decreasing the titanium quantum dot content can prepare a cost-sensitive version (Df ≤ 0.006) for consumer high-speed PCBs, demonstrating good technical extensibility and market adaptability. In summary, this invention, through the innovative coupling of multi-scale nanofiller synergistic enhancement and high heat-resistant resin molecular design, comprehensively surpasses the existing technology level in seven dimensions: dielectric loss, heat resistance, thermal conductivity, interface reliability, process economy, environmental protection, and application scenario adaptability. It provides a systematic solution for the next generation development of high-frequency and high-speed carrier copper clad laminate materials, and has significant scientific and technological progress significance and industrialization promotion value. Attached Figure Description

[0022] Figure 1 This is a transmission electron microscope (TEM) image of the doped powder prepared in Example 1 of this invention.

[0023] Figure 2 This is a physical image of the doped powder prepared in Example 1 of this invention.

[0024] Figure 3 This is a transmission electron microscope image of the modified nanoparticles prepared in Example 1 of this invention.

[0025] Figure 4 This is the infrared spectrum of the modified nanoparticles prepared in Example 1 of this invention. 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 copper-clad laminate material based on high heat-resistant thermosetting resin includes the following steps by weight: (1) Mixing 4g tetrabutyl titanate (CAS No.: 5593-70-4), 6g anhydrous ethanol, 8g octadecylamine (CAS No.: 124-30-1) and 10g oleic acid (CAS No.: 112-80-1), adding 40g of 80% ethanol aqueous solution by weight, and reacting at high temperature in a high-pressure reactor, wherein the pressure is 1.75MPa, the temperature is 200℃, and the rotation speed is... Titanium-containing quantum dots were obtained by heating at 250 rpm for 24 h. These were then added to an equal volume of 50% ethanol solution and mixed thoroughly. 3 g of triethylamine (CAS No.: 121-44-8) was added, and the reaction was heated at 160 °C for 18 h. After washing three times (using anhydrous ethanol), centrifugation (4000 rpm for 15 min), and drying (80 °C for 6 h), a doped powder with a particle size of 45 nm was obtained. Its transmission electron microscopy (TEM) image is shown below. Figure 1 As shown in the picture, the actual product is as follows. Figure 2 As shown. (2) 3g of fumed silica (CAS No.: 7631-86-9, specific surface area 300m² / g) was dispersed in 50g of 50% ethanol solution by mass percentage. The pH was adjusted to 4 with hydrochloric acid. After ultrasonic dispersion (parameters: 20kHz, 750W and 40min), 0.3g of 3-glycidyl etheroxypropyltrimethoxysilane (CAS No.: 2530-83-8) was added and reacted at 50℃ for 18h. After drying at 80℃, modified nanoparticles were obtained. The transmission electron microscope image is shown. Figure 3 As shown, its infrared spectrum is as follows Figure 4As shown. (3) 15g boron nitride powder, 1.25g KH-550 (CAS No.: 919-30-2), 3g 2-methylimidazole (CAS No.: 693-98-1), 4g pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (CAS No.: 6683-19-8) and 50g deionized water were subjected to hydrothermal reaction (parameters: 85℃, 1.75h) to obtain thermally conductive filler. (4) 200g of high heat-resistant epoxy resin and 30g of polyetheramine (CAS No.: 9046-10-0) are mixed at 70°C to obtain a resin matrix, wherein the high heat-resistant epoxy resin is composed of bisphenol A type epoxy resin (CAS No.: 25068-38-6) and 1,6-bis(2,3-epoxypropoxy)naphthalene (naphthalene diphenol diglycidyl ether) (CAS No.: 27610-48-6) in a mass ratio of 1.25:1. (5) The doped powder obtained in step (1), the modified nanoparticles obtained in step (2), and the thermally conductive filler obtained in step (3) are added sequentially to the resin matrix obtained in step (4), 20g of reinforcing agent is added, and the mixture is stirred (at a speed of 1000rpm and a time of 35min) to obtain a slurry. The reinforcing agent is a product of DISPER985 (CAS No.: 149213-65-0) and propylene glycol methyl ether acetate (CAS No.: 108-65-6) at a mass ratio of 7.5:15. (6) A glass fiber cloth with a thickness of 0.125mm is impregnated in the slurry obtained in step (5). The impregnation parameters are a vacuum degree of 0.02MPa, a temperature of 60℃, and a time of 25min. After pre-curing (curing at 140℃ for 10min), it is hot-pressed and cured (curing at 200℃ and a pressure of 2.25MPa for 120min) to obtain a semi-cured sheet. (7) Electrolytic copper foil with a thickness of 30 μm is applied to both the top and bottom surfaces of the prepreg obtained in step (6), and then laminated (parameters: 200℃, 1.75MPa pressure for 75 min) to obtain the carrier copper-clad laminate material, wherein the lamination temperature is 190℃, the pressure is 1.5MPa, and the lamination time is 75 min. The nanofiller of the obtained carrier copper-clad laminate material is monodisperse in the resin matrix, with a thermal decomposition temperature Td of 412℃, a glass transition temperature Tg of 210℃, a thermal conductivity of 1.4 W / (m·K), a dielectric constant Dk of 3.2 at 10 GHz, a dielectric loss Df of 0.004, a peel strength of 1.4 N / mm, and a water absorption rate of 0.3%.

[0029] The specific parameters of 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 reflects different parameter values ​​of the examples / comparative examples, covering all endpoint values ​​and intermediate values ​​(the total mass is consistent with the sum of the masses of each component). The remaining unlisted parameters are the same as those in Example 1.

[0030] Table 1: Parameters for step (1) (unit: g)

[0031]

[0032] Table 2: Parameters for step (2) (unit: g)

[0033]

[0034] Table 3: Parameters for step (3) (unit: g)

[0035]

[0036] Table 4: Parameters for steps (4) and (5) (unit: g)

[0037]

[0038] Table 5: Parameters for steps (6) and (7)

[0039]

[0040] To verify the performance of the copper-clad laminate material based on a high-heat-resistant thermosetting resin 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 thermal decomposition temperature Td (°C), glass transition temperature Tg (°C), thermal conductivity [W / (m·K)], dielectric constant Dk at 10 GHz, dielectric loss Df, peel strength (N / mm), and water absorption rate (%). The test methods are as follows: thermal decomposition temperature Td and glass transition temperature Tg were measured using a thermogravimetric analyzer (model: TGAQ500) and a differential scanning calorimeter (model: DSCQ200); thermal conductivity was measured using the laser flash method (model: LFA467); dielectric constant Dk and dielectric loss Df were measured using a vector network analyzer (model: Agilent E8363B) at 10 GHz; peel strength was measured using a universal testing machine (model: Instron5567) according to the IPC-TM-650 standard; water absorption was measured according to the ASTM D570 standard, showing the change in mass after 24 hours of immersion in water.

[0041] Table 6: Test Results (I)

[0042]

[0043] Table 7: Test Results (II)

[0044]

[0045] The test results show that the products in the examples all exhibit excellent performance, with thermal conductivity ranging from 1.3 to 1.5 W / (m·K) and thermal depletion values ​​between 405.7 and 418.9 °C, Tg between 202.8 and 215.2 °C, and Tg between 1.3 and 1.5 W / (m·K). In contrast, the comparative examples show a significant decrease in performance due to missing components or parameter deviations (e.g., Td drops to 362.7-378.9 °C). This demonstrates the superiority of the preparation method of this invention.

[0046] 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 a high heat resistant thermoset resin based carrier board copper clad board material, characterized by: The method comprises the following steps: (1) mixing 2-6 parts of tetrabutyl titanate, 4-8 parts of anhydrous ethanol, 6-10 parts of octadecylamine and 5-15 parts of oleic acid, adding 40 parts of an ethanol aqueous solution and performing high-temperature reaction to obtain titanium-containing quantum dots, then adding an equal volume of a 50% ethanol solution, uniformly mixing, adding 1-5 parts of triethylamine, performing heating reaction, washing, centrifuging and drying to obtain a doped powder with a particle size of 40-50 nm; (2) dispersing 1-5 parts of fumed silica in 50 parts of a 50% ethanol solution, adjusting the pH to 3-5, performing ultrasonic dispersion, then adding 0.1-0.5 parts of 3-glycidoxypropyltrimethoxysilane and performing reaction at 40-60℃ for 12-24 h, and drying at 80℃ to obtain modified nanoparticles; (3) performing hydrothermal reaction on 10-20 parts of boron nitride powder, 0.5-2 parts of KH-550, 1-5 parts of 2-methylimidazole, 2-6 parts of tetrapentaerythritol 2-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 40-60 parts of deionized water to obtain a heat-conducting filler; (4) mixing 200 parts of a high-heat-resistant epoxy resin with 20-40 parts of a polyetheramine at 60-80℃ to obtain a resin matrix; (5) adding the doped powder obtained in step (1), the modified nanoparticles obtained in step (2) and the heat-conducting filler obtained in step (3) into the resin matrix obtained in step (4) in sequence, adding 10-30 parts of a reinforcing agent and stirring to obtain a slurry; (6) immersing a glass fiber cloth in the slurry obtained in step (5), pre-curing and then heat-pressing to obtain a prepreg; and (7) covering electrolytic copper foils on upper and lower surfaces of the prepreg obtained in step (6) to obtain a carrier plate copper-clad plate material.

2. The method of producing a high heat-resistant thermosetting resin-based carrier clad plate material according to claim 1, characterized by: The mass percentage of the ethanol aqueous solution in step (1) is 80%; the high-temperature reaction device in step (1) is a high-pressure reaction kettle; the pressure of the high-temperature reaction in step (1) is 0.5-3 MPa, the temperature of the high-temperature reaction is 180-220℃, the rotation speed of the high-temperature reaction is 200-300 rpm, and the time of the high-temperature reaction is 24 h.

3. The method of producing a high heat-resistant thermosetting resin-based carrier clad plate material according to claim 1, characterized by: The temperature of the heating reaction in step (1) is 140-180℃, and the time of the heating reaction is 12-24 h; the number of washing in step (1) is 3 times, the washing solution is anhydrous ethanol, the rotation speed of centrifuging is 4000 rpm, the time of centrifuging is 15 min, the drying temperature is 80℃, and the drying time is 6 h.

4. The method of producing a high heat-resistant thermosetting resin-based carrier clad plate material according to claim 1, characterized by: The pH adjusting reagent in step (2) is hydrochloric acid; and the ultrasonic dispersion parameters in step (2) are as follows: 20 kHz, 750 W and 40 min.

5. The method of making a high heat resistant thermoset resin based carrier clad plate material according to claim 1, wherein: The hydrothermal reaction parameters in step (3) are as follows: 80-90℃, 1.5-2 h.

6. The method of making a high heat resistant thermoset resin based carrier clad plate material according to claim 1, wherein: The high-heat-resistant epoxy resin in step (4) is composed of bisphenol A type epoxy resin and 1,6-bis(2,3-epoxypropoxy)naphthalene (naphthalenediol diglycidyl ether) at a mass ratio of (0.5-2):

1.

7. The method of producing a high heat-resistant thermosetting resin-based copper clad plate material according to claim 1, characterized by: The enhancer in step (5) is a product of DISPER 985 mixed with propylene glycol methyl ether acetate at a mass ratio of (5-10):(10-20); the stirring speed in step (5) is 1000 rpm, and the stirring time is 35 min.

8. The method of producing a high heat resistant thermosetting resin-based carrier clad plate material according to claim 1, characterized by: The thickness of the glass fiber cloth in step (6) is 0.05-0.2 mm; the parameters of impregnation in step (6) are as follows: vacuum degree of impregnation is 0.02 MPa, temperature of impregnation is 60℃, and time of impregnation is 25 min; the parameters of pre-curing in step (6) are as follows: curing at 120-160℃ for 10 min; the parameters of hot-pressing curing in step (6) are as follows: curing at 180-220℃, pressure 1.5-3 MPa for 120 min.

9. The method of producing a high heat resistant thermosetting resin-based carrier clad plate material according to claim 1, characterized by: The thickness of the electrolytic copper foil in step (7) is 30 μm; the parameters of lamination in step (7) are as follows: 180-220℃, pressure 1-2.5 MPa for 60-90 min.

10. A high heat resistant thermoset resin based carrier clad plate material, characterized by, The high-heat-resistant thermosetting resin-based carrier plate copper-clad plate material is obtained by the preparation method of any one of claims 1-9.

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