High-thermal-conductivity epoxy resin composition for copper-clad plate and preparation method of high-thermal-conductivity epoxy resin composition

Abstract

According to the high-thermal-conductivity epoxy resin composition for the copper-clad plate and the preparation method of the high-thermal-conductivity epoxy resin composition, provided by the invention, the modified silane compound is firstly prepared, and then the modified silane compound is used for modifying the thermal-conductive filler, so that not only is the dispersity of the thermal-conductive filler in an epoxy resin system improved, but also the flame retardance of the system is improved. The aluminum-based copper-clad plate prepared from the epoxy resin composition is excellent in bending surface peel strength, heat resistance, breakdown voltage resistance and the like.

Description

Technical Field

[0001] The invention relates to a high thermal conductivity epoxy resin composition for copper-clad laminates and a preparation method thereof, in particular to a high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminates and a preparation method thereof. Background Art

[0002] With the continuous development of electronic technology, electronic products are gradually developing towards light, thin, small, high-density and multifunctional. Various electronic products have increasingly prominent requirements for high performance, light weight, small size and other aspects. Ultra-thinness and high density have become the mainstream development trend of flexible circuit boards. However, as circuit boards become thinner and thinner, the heat generated per unit area during operation is increasing. If the heat cannot be dissipated in time, the reliability and service life of electronic products will decrease. Therefore, the heat dissipation problem of circuit boards has attracted more and more attention. However, the thermal conductivity of traditional FR-4 copper clad laminates is low, only 0.15-0.30W / (mK), which cannot meet the requirements of rapid heat dissipation of terminal products. Aluminum-based copper clad laminates have excellent heat dissipation and electrical properties and have been widely used in integrated circuits, automobiles, motorcycles, office automation, high-power electrical equipment, power supply equipment and other fields.

[0003] Aluminum-based copper-clad laminates are composed of aluminum plates, thermally conductive insulating layers and copper foil. In addition to the general properties of copper-clad laminates, aluminum-based copper-clad laminates also have excellent heat dissipation performance, excellent dimensional stability, good processing performance and electromagnetic shielding performance. The thermally conductive insulating layer mainly plays a role in heat conduction and insulation. It is the core technology of aluminum-based copper-clad laminates. It directly affects the comprehensive performance of aluminum-based copper-clad laminates and is a research hotspot for high thermal conductivity aluminum substrates.

[0004] CN104610707A discloses a metal-based copper-clad laminate for high-power LEDs manufactured by high-performance RCC. The resin composition of the metal-based copper-clad laminate is a completely halogen-free and phosphorus-free resin, rubber and other components. The flame retardant purpose is achieved by high filling amounts of thermally conductive and flame-retardant fillers and resins. The laminate has good thermal conductivity and flame retardant properties, high heat resistance, high moisture resistance and low expansion coefficient. The thermally conductive insulating layer will not decompose during use, and will not produce toxic and harmful gases containing halogen or phosphorus due to combustion, which will not cause harm to people's health. The laminate is environmentally friendly and can be widely used in metal substrates, flexible boards, multilayer boards and the like with heat dissipation requirements. The thermally conductive insulating layer of the metal-based copper-clad laminate prepared by the resin composition is thin and has a fine pore size, which provides good thermal conductivity and flame retardant guarantees for the thin, light, short and integrated development of electronic products, and can achieve high-density wiring.

[0005] CN105623198A discloses a high thermal conductivity resin composition and its application. The patent adds thermal conductive fillers to the bismaleimide-modified epoxy and flexible epoxy resin system to prepare a thermally conductive metal substrate. Although the board has excellent heat dissipation and heat resistance and improved flexibility, the maximum peel strength of the board is only 1.4N / mm, and it will still crack after bending, and the insulating layer has no flame retardant function.

[0006] CN107502253A discloses a glue for high thermal conductivity copper-clad aluminum substrate and its preparation method, and the thermal conductivity and flame retardancy of the prepared product are very stable. The invention adds a large proportion of bisphenol A epoxy resin modified by inactive metal oxides, thereby greatly improving the heat resistance temperature of the product; using DDS as the main curing agent, which belongs to the sulfone class, the cured product has a more compact molecular structure, which can improve the cross-linking density of the product, increase the heat resistance and thermal conductivity of the material; the filler ratio is large, and aluminum oxide and / or aluminum nitride are used as fillers to improve the thermal conductivity of the material; high-purity aluminum oxide of different particle sizes is reasonably matched to improve the stacking degree of aluminum oxide and improve the thermal conductivity of the material.

[0007] The thermally conductive insulating layer is prepared by adding thermally conductive fillers to a thermosetting resin matrix. Although thermosetting resins represented by epoxy have excellent comprehensive performance, their thermal conductivity is very low and cannot meet the heat dissipation needs. In order to improve the thermal conductivity of the insulating dielectric layer, inorganic fillers with good thermal conductivity must be added. At present, thermally conductive particles such as aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, and silicon nitride are widely used. However, the above-mentioned thermally conductive particles have the problem of uneven dispersion in the resin matrix, which in turn affects the thermal conductivity of the insulating dielectric layer. Moreover, epoxy resin is a flammable material. When the heat dissipation performance is not good, heat and combustion will occur, which brings great challenges to the application. Summary of the invention

[0008] In order to solve the above technical problems, the present invention provides a high thermal conductivity epoxy resin composition for aluminum-based copper clad laminates and a preparation method thereof. The method first prepares a modified silane compound, and then uses the modified silane compound to modify the thermal conductive filler, thereby improving the dispersibility of the thermal conductive filler in the epoxy resin system and improving the flame retardancy of the system.

[0009] In order to achieve the above object, the present invention adopts the following technical solutions: A high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminates, wherein the composition is prepared from the following components in parts by mass: Epoxy resin 100 parts Thermoplastic rubber 10-20 parts Modified thermal conductive filler 120-160 parts Curing agent 5-20 parts 1-3 parts of curing accelerator Solvent 10-30 parts The epoxy resin is one or a combination of bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, and alicyclic epoxy resin; The thermoplastic rubber is a combination of one or more of carboxyl-terminated nitrile rubber, butyl rubber, hydrogenated nitrile rubber, nitrile rubber, and hydroxy-terminated nitrile rubber; The curing agent is a combination of one or more of dicyandiamide, diaminodiphenylmethane, amino resin, and anhydride curing agents; The curing accelerator is a combination of one or more of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-phenylimidazole; The solvent is a combination of one or more of toluene, acetone, xylene, methyl isobutyl ketone, methyl butyl ketone, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether; The preparation process of the modified thermally conductive filler is as follows: Step 1: Add phosphorus oxychloride and pentaerythritol to anhydrous acetonitrile and stir evenly. Under nitrogen protection, heat to 50-60°C and stir for 0.5-1h. Add aluminum chloride and continue to heat to 80-90°C and stir for 1-2h. Distill to remove the solvent, wash and dry to obtain intermediate 1. The mass of phosphorus oxychloride, pentaerythritol and aluminum chloride is: 3-5:1-2:0.03-0.1. The amount of anhydrous acetonitrile is 300-500ml. Step 2: Add intermediate 1, triethylamine and toluene into a flask, and dropwise add a toluene solution of p-hydroxybenzaldehyde into the flask, control the temperature during the dropping process to be between -5°C and 0°C, raise the temperature to 65-80°C after the dropping is completed, and keep the temperature for reaction for 3-5h. After the reaction is completed, cool and filter, and remove toluene and triethylamine from the filtrate by vacuum distillation to obtain intermediate 2; the molar ratio of intermediate 1, triethylamine and p-hydroxybenzaldehyde is 1:0.2:2; Step 3: The intermediate 2 and anhydrous methanol are placed in a flask, and an anhydrous methanol solution of 3-aminopropyltrimethoxysilane is added dropwise while stirring under nitrogen protection. After the addition is completed, the reaction is stirred at 60-70° C. for 5-8 hours. After the reaction is completed, the reaction product is poured into ice water, filtered, and dried to obtain a modified silane compound; The molar ratio of the intermediate 2 to the 3-aminopropyltrimethoxysilane is 1:2; Step 4: The mixture of aluminum oxide and silicon carbide is added to 200-300 ml of a sodium hydroxide aqueous solution with a mass fraction of 10 wt%, and reacted in a water bath at 70-80° C. for 3-5 hours with stirring. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with water, and dried at 60° C. for 10-12 hours to obtain a surface hydroxylated aluminum oxide and silicon carbide mixture 1; The mass ratio of aluminum oxide to silicon carbide is 2-3:1; Step 5: The modified silane compound and γ-glycidyloxypropyltrimethoxysilane are added to 300-500 ml of 90 wt% ethanol aqueous solution for hydrolysis to obtain a hydrolysis solution, and the surface hydroxylated aluminum oxide and silicon carbide mixture 1 is added to the above hydrolysis solution; reflux reaction is carried out under stirring conditions for 2-3 hours at a reaction temperature of 60-70°C, and the modified thermal conductive filler is obtained by filtering, washing and drying.

[0010] The mass ratio of the modified silane compound, γ-glycidyloxypropyltrimethoxysilane, surface hydroxylated aluminum oxide and silicon carbide mixture 1 is 4-5:1-2:20-30.

[0011] The preparation method of the high thermal conductive epoxy resin composition comprises the following steps: According to the formula, epoxy resin and thermoplastic rubber are weighed and added to the solvent, and stirred evenly. The modified thermal conductive filler is slowly added while stirring, and dispersed evenly using a high-speed shearing machine. Then, the curing agent and curing accelerator are added in sequence and stirred evenly to obtain a high thermal conductive epoxy resin composition.

[0012] The preparation method of the aluminum-based copper-clad laminate comprises the following steps: Step 1: Apply the high thermal conductivity epoxy resin composition to the rough surface of the copper foil. Step 2: baking the copper foil coated with the high thermal conductivity epoxy resin composition to form a semi-solid coated copper foil; Step 3: Lay the semi-solidified coated copper foil on the aluminum substrate, heat and pressurize to form the aluminum-based copper clad laminate, wherein the heating temperature is 160°C-210°C and the pressurizing pressure is 25-40kg / cm 2 , hot pressing time is 60-120min.

[0013] Compared with the prior art, the present invention has the following beneficial effects: The present invention firstly uses phosphorus oxychloride and pentaerythritol to prepare spirocyclic chlorinated bisphosphate under the action of a catalyst, then reacts the spirocyclic chlorinated bisphosphate with p-hydroxybenzaldehyde, introduces aldehyde groups at both ends of the spirocyclic chlorinated bisphosphate, obtains an intermediate II, then reacts the intermediate II with 3-aminopropyltrimethoxysilane, obtains a modified silane compound, the modified silane compound has a flame retardant structure spirocyclic chlorinated bisphosphate, can improve the flame retardancy of the system, uses the modified silane compound to modify a mixture of aluminum oxide and silicon carbide, obtains a modified filler, and can improve the dispersibility of the filler in the resin system. At the same time, the γ-glycidyl ether oxypropyl trimethoxy silane added in the filler modification process can introduce epoxy groups into the modified filler, and in the epoxy resin system curing process, the epoxy groups introduced by the modified filler participate in the curing crosslinking reaction, and can further improve the mechanical properties of the cured epoxy resin composition. DETAILED DESCRIPTION

[0014] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be appreciated by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work, all belong to the scope of protection of the present invention. If specific conditions are not indicated in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0015] Preparation Example 1 The preparation process of the modified thermally conductive filler is as follows: Step 1: 30.6 g of phosphorus oxychloride and 13.6 g of pentaerythritol were added to 400 ml of anhydrous acetonitrile and stirred evenly. Under nitrogen protection, the temperature was raised to 60°C and stirred for 1 hour. After adding 0.5 g of anhydrous aluminum chloride, the temperature was further raised to 80°C and stirred for 2 hours. After distilling off the solvent, the mixture was washed and dried to obtain intermediate 1. Step 2: 0.1 mol of intermediate 1, 0.2 mol of triethylamine and 450 ml of toluene were added into a flask, and 50 ml of toluene solution containing 0.2 mol of p-hydroxybenzaldehyde was added dropwise into the flask. The temperature during the addition process was controlled at -5°C. After the addition was completed, the temperature was raised to 70°C and kept for reaction for 3 hours. After the reaction was completed, the mixture was cooled and filtered, and the filtrate was distilled under reduced pressure to remove toluene and triethylamine to obtain intermediate 2. Step 3: 0.1 mol of intermediate 2 and 400 ml of anhydrous methanol were added into a flask, and 50 ml of anhydrous methanol solution of 0.2 mol of 3-aminopropyltrimethoxysilane was added dropwise while stirring under nitrogen protection. After the addition was completed, the mixture was stirred at 70°C for 6 hours. After the reaction was completed, the reaction product was poured into ice water, filtered, and dried to obtain a modified silane compound; Step 4: 20 g of aluminum oxide and 10 g of silicon carbide were added to 300 ml of a 10 wt% sodium hydroxide aqueous solution, stirred in a water bath at 70° C. for 3 h, cooled to room temperature after the reaction, filtered, washed with water, and dried at 60° C. for 12 h to obtain a surface hydroxylated aluminum oxide and silicon carbide mixture 1; Step 5: 5 g of modified silane compound and 2 g of γ-glycidyloxypropyltrimethoxysilane are added to 300 ml of 90 wt % ethanol aqueous solution for hydrolysis to obtain a hydrolysis solution, and 30 g of a surface hydroxylated aluminum oxide and silicon carbide mixture 1 is added to the above hydrolysis solution; reflux reaction is carried out under stirring conditions for 3 h at a reaction temperature of 70° C., and the modified thermal conductive filler 1 is obtained by filtering, washing and drying.

[0016] Preparation Example 2 The preparation process of the modified thermally conductive filler is as follows: Step 1: 30.6 g of phosphorus oxychloride and 13.6 g of pentaerythritol were added to 400 ml of anhydrous acetonitrile and stirred evenly. Under nitrogen protection, the temperature was raised to 60°C and stirred for 1 hour. After adding 0.5 g of aluminum chloride, the temperature was further raised to 80°C and stirred for 2 hours. After distilling off the solvent, the mixture was washed and dried to obtain intermediate 1. Step 2: 0.1 mol of intermediate 1, 0.2 mol of triethylamine and 450 ml of toluene were added into a flask, and 50 ml of toluene solution containing 0.2 mol of p-hydroxybenzaldehyde was added dropwise into the flask. The temperature during the addition process was controlled at -5°C. After the addition was completed, the temperature was raised to 70°C and kept for reaction for 3 hours. After the reaction was completed, the mixture was cooled and filtered, and the filtrate was distilled under reduced pressure to remove toluene and triethylamine to obtain intermediate 2. Step 3: 0.1 mol of intermediate 2 and 400 ml of anhydrous methanol were added into a flask, and 50 ml of anhydrous methanol solution of 0.2 mol of 3-aminopropyltrimethoxysilane was added dropwise while stirring under nitrogen protection. After the addition was completed, the mixture was stirred at 70°C for 6 hours. After the reaction was completed, the reaction product was poured into ice water, filtered, and dried to obtain a modified silane compound; Step 4: 20 g of aluminum oxide and 10 g of silicon carbide were added to 300 ml of a 10 wt% sodium hydroxide aqueous solution, stirred in a water bath at 70° C. for 3 h, cooled to room temperature after the reaction, filtered, washed with water, and dried at 60° C. for 12 h to obtain a surface hydroxylated aluminum oxide and silicon carbide mixture 1; Step 5: 7 g of the modified silane compound was added to 300 ml of an ethanol aqueous solution with a mass fraction of 90 wt % for hydrolysis to obtain a hydrolysis solution, and 30 g of a surface hydroxylated aluminum oxide and silicon carbide mixture 1 was added to the above hydrolysis solution; the mixture was refluxed for 3 h under stirring at a reaction temperature of 70° C., and the modified thermal conductive filler 1 was obtained by filtering, washing and drying.

[0017] Preparation Example 3 The preparation process of the modified thermally conductive filler is as follows: 7 g of γ-glycidyloxypropyltrimethoxysilane was added to 300 ml of 90 wt % ethanol aqueous solution for hydrolysis to obtain a hydrolysis solution, and 30 g of a surface hydroxylated aluminum oxide and silicon carbide mixture 1 was added to the above hydrolysis solution; the reaction was refluxed for 3 h under stirring at a reaction temperature of 70° C., and the modified thermal conductive filler 1 was obtained by filtering, washing and drying.

[0018] Example 1 Preparation of high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminate: According to the formula, 100 parts of epoxy resin E51 and 10 parts of terminal carboxyl nitrile rubber were weighed and added to 20 parts of toluene, and stirred evenly. 120 parts of modified thermal conductive filler 1 obtained in Preparation Example 1 were slowly added while stirring, and dispersed evenly using a high-speed shearing machine with a speed of 1200r / min and a dispersion time of 30min. Then, 15 parts of dicyandiamide and 2 parts of 2-methylimidazole were added in sequence and stirred evenly to obtain a high thermal conductive epoxy resin composition.

[0019] Example 2 Preparation of high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminate: According to the formula, 100 parts of epoxy resin E51 and 15 parts of terminal hydroxyl nitrile rubber were weighed and added to 30 parts of toluene, and stirred evenly. 140 parts of modified thermal conductive filler 1 obtained in Preparation Example 1 were slowly added while stirring, and dispersed evenly using a high-speed shearing machine with a speed of 1000 r / min and a dispersion time of 30 min. Then, 15 parts of diaminodiphenylmethane and 1.5 parts of 2-ethylimidazole were added in sequence and stirred evenly to obtain a high thermal conductive epoxy resin composition.

[0020] Example 3 Preparation of high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminate: According to the formula, 100 parts of bisphenol F epoxy resin and 18 parts of hydrogenated nitrile rubber were weighed and added to 30 parts of xylene, and stirred evenly. 160 parts of the modified thermal conductive filler 1 obtained in Preparation Example 1 were slowly added while stirring, and dispersed evenly using a high-speed shearing machine with a speed of 1500r / min and a dispersion time of 30min. Then, 12 parts of dicyandiamide and 3 parts of 2-phenylimidazole were added in sequence and stirred evenly to obtain a high thermal conductive epoxy resin composition.

[0021] Comparative Example 1 Preparation of high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminate: According to the formula, 100 parts of epoxy resin E51 and 10 parts of terminal carboxyl nitrile rubber were weighed and added to 20 parts of toluene, and stirred evenly. 120 parts of modified thermal conductive filler 2 obtained in Preparation Example 2 were slowly added while stirring, and dispersed evenly using a high-speed shearing machine with a speed of 1200r / min and a dispersion time of 30min. Then, 15 parts of dicyandiamide and 2 parts of 2-methylimidazole were added in sequence and stirred evenly to obtain a high thermal conductive epoxy resin composition.

[0022] Comparative Example 2 Preparation of high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminate: According to the formula, 100 parts of epoxy resin E51 and 10 parts of terminal carboxyl nitrile rubber were weighed and added to 20 parts of toluene, and stirred evenly. 120 parts of modified thermal conductive filler 3 obtained in Preparation Example 3 were slowly added while stirring, and dispersed evenly using a high-speed shearing machine with a speed of 1200r / min and a dispersion time of 30min. Then, 15 parts of dicyandiamide and 2 parts of 2-methylimidazole were added in sequence and stirred evenly to obtain a high thermal conductive epoxy resin composition.

[0023] Comparative Example 3 Preparation of high thermal conductivity epoxy resin composition for aluminum-based copper-clad laminate: According to the formula, 100 parts of epoxy resin E51 and 10 parts of terminal carboxyl nitrile rubber were weighed and added to 20 parts of toluene, and stirred evenly. 80 parts of aluminum oxide and 40 parts of silicon carbide were slowly added while stirring. A high-speed shearing machine was used to disperse the mixture evenly at a speed of 1200 r / min and a dispersion time of 30 min. Then, 15 parts of dicyandiamide and 2 parts of 2-methylimidazole were added in sequence and stirred evenly to obtain a high thermal conductivity epoxy resin composition.

[0024] Application Examples The high thermal conductivity epoxy resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were used to prepare aluminum-based copper-clad laminates: The preparation method of the aluminum-based copper-clad laminate comprises the following steps: Step 1: Apply the high thermal conductivity epoxy resin composition to the rough surface of the copper foil. Step 2: baking the copper foil coated with the high thermal conductivity epoxy resin composition to form a semi-solid coated copper foil; Step 3: Lay the semi-solidified glue-coated copper foil on the aluminum substrate, heat and press to form the aluminum-based copper-clad laminate, wherein the hot pressing temperature is 180°C and the pressure is 35kg / cm 2 , the hot pressing time is 100 minutes, and the thickness of the thermal conductive insulation layer is 100 microns.

[0025] Performance Testing The performance of the thermally conductive insulating layers prepared in Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention was tested and compared, wherein the tensile strength of the thermally conductive insulating layer was tested according to GB1042-1979 standard, and the thermal conductivity of the thermally conductive insulating layer was tested according to ASTM D5470-2006 method.

[0026] The results are shown in Table 1.

[0027] Table 1 Performance comparison of different thermal insulation layers

[0028] From the experimental results in Table 1, it can be seen that the epoxy resin composition of the present invention has high thermal conductivity, tensile strength and flame retardancy. The modified filler of the present application has a certain degree of improvement in thermal conductivity, tensile strength and flame retardancy compared to the unmodified filler and the filler modified by γ-glycidyloxypropyltrimethoxysilane alone.

[0029] The performance of the aluminum-based copper-clad laminates prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 3 was tested and compared, and the performance testing methods were as follows: (1) Bending surface peel strength: The copper foil is etched into a circuit with a width of 3 mm, and the circuit is fixed after being bent using a bending mold. The adhesion between the copper foil and the insulation layer is tested using a peel strength tester. The test conditions are: 288°C, 10s after thermal stress.

[0030] (2) Thermal stress: Cut the sample to be tested into three 50×50 mm samples. After bending them using a bending mold, immerse the 50×50 mm sample in a tin furnace at 288°C and observe the stratification and blistering time of the sample. The longer the time, the better the heat resistance.

[0031] (3) Baking plate: Cut the sample to be tested into three pieces of 100 × 100 mm and bake them in an oven at 288 °C for 2 h. Observe the stratification and bubbling of the samples.

[0032] (4) Breakdown voltage: According to the IEC60243-1 method, test the breakdown voltage of the thermal insulation layer and take the average value of 5 points.

[0033] The results are shown in Table 2.

[0034] Table 2 Performance comparison of different aluminum-based copper clad laminates

[0035] From the experimental results in Table 2, it can be seen that the aluminum-based copper-clad laminate prepared by using the epoxy resin composition of the present application has excellent bending surface peeling strength, heat resistance and breakdown voltage resistance. And compared with the unmodified filler and the filler modified by γ-glycidyloxypropyltrimethoxysilane alone, the peeling, heat resistance and breakdown voltage resistance are improved to a certain extent.

[0036] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the defined scope, they should all fall within the protection scope of the present invention.

Claims

1. A high thermal conductivity epoxy resin composition for copper clad laminates, characterized in that: The composition is prepared from the following components by weight: Epoxy resin 100 parts Thermoplastic rubber 10-20 parts Modified thermal conductive filler 120-160 parts Curing agent 5-20 parts 1-3 parts of curing accelerator 10-30 parts of solvent.

2. The high thermal conductivity epoxy resin composition for copper clad laminate according to claim 1, characterized in that: The preparation process of the modified thermally conductive filler is as follows: Step 1: Add phosphorus oxychloride and pentaerythritol to anhydrous acetonitrile and stir evenly. Under nitrogen protection, heat to 50-60°C, stir for 0.5-1h, add anhydrous aluminum chloride, continue to heat to 80-90°C, stir for 1-2h, distill to remove the solvent, wash, and dry to obtain intermediate 1; the mass of phosphorus oxychloride, pentaerythritol, and anhydrous aluminum chloride is: 3-5:1-2:0.03-0.1; the amount of anhydrous acetonitrile is 300-500ml; Step 2: Add intermediate 1, triethylamine and toluene into a flask, and dropwise add a toluene solution of p-hydroxybenzaldehyde into the flask, control the temperature during the dropwise addition process to be between -5°C and 0°C, raise the temperature to 65-80°C after the dropwise addition is completed, and keep the temperature for reaction for 3-5h. After the reaction is completed, cool and filter, and decompress the filtrate to distill out toluene and triethylamine to obtain intermediate 2; the molar ratio of intermediate 1, triethylamine and p-hydroxybenzaldehyde is 1:0.2:2; Step 3: The intermediate 2 and anhydrous methanol are placed in a flask, and an anhydrous methanol solution of 3-aminopropyltrimethoxysilane is added dropwise while stirring under nitrogen protection. After the addition is completed, the reaction is stirred at 60-70° C. for 5-8 hours. After the reaction is completed, the reaction product is poured into ice water, filtered, and dried to obtain a modified silane compound; The molar ratio of the intermediate 2 to the 3-aminopropyltrimethoxysilane is 1:2; Step 4: The mixture of aluminum oxide and silicon carbide is added to 200-300 ml of a sodium hydroxide aqueous solution with a mass fraction of 10 wt%, and reacted in a water bath at 70-80° C. for 3-5 hours with stirring. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed with water, and dried at 60° C. for 10-12 hours to obtain a surface hydroxylated aluminum oxide and silicon carbide mixture 1; The mass ratio of aluminum oxide to silicon carbide is 2-3:1; Step 5: The modified silane compound and γ-glycidyloxypropyltrimethoxysilane are added to 300-500 ml of 90 wt% ethanol aqueous solution for hydrolysis to obtain a hydrolysis solution, and the surface hydroxylated aluminum oxide and silicon carbide mixture 1 is added to the above hydrolysis solution; Reflux reaction for 2-3 hours under stirring conditions at a reaction temperature of 60-70° C., filtering, washing, and drying to obtain a modified thermal conductive filler; The mass ratio of the modified silane compound, γ-glycidyloxypropyltrimethoxysilane, surface hydroxylated aluminum oxide and silicon carbide mixture 1 is 4-5:1-2:20-30.

3. The high thermal conductivity epoxy resin composition for copper clad laminate according to claim 1, characterized in that: The epoxy resin is one or a combination of bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, and alicyclic epoxy resin.

4. The high thermal conductivity epoxy resin composition for copper clad laminate according to claim 1, characterized in that: The thermoplastic rubber is a combination of one or more of carboxyl-terminated nitrile rubber, butyl rubber, hydrogenated nitrile rubber, nitrile rubber, and hydroxyl-terminated nitrile rubber.

5. The high thermal conductivity epoxy resin composition for copper clad laminate according to claim 1, characterized in that: The curing agent is a combination of one or more of dicyandiamide, diaminodiphenylmethane, amino resin and anhydride curing agents.

6. The high thermal conductivity epoxy resin composition for copper clad laminate according to claim 1, characterized in that: The curing accelerator is a combination of one or more of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-phenylimidazole.

7. The high thermal conductivity epoxy resin composition for copper clad laminate according to claim 1, characterized in that: The solvent is a combination of one or more of toluene, acetone, xylene, methyl isobutyl ketone, methyl butyl ketone, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether.

8. A method for preparing a high thermal conductivity epoxy resin composition for copper clad laminates according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: according to the formula, epoxy resin and thermoplastic rubber are weighed, added into a solvent, stirred evenly, modified thermal conductive filler is slowly added while stirring, dispersed evenly by a high-speed shearing machine, and then a curing agent and a curing accelerator are added in sequence, stirred evenly, so as to obtain a high thermal conductive epoxy resin composition.

9. A method for preparing an aluminum-based copper-clad laminate, characterized in that: The steps include: Step 1: applying the high thermal conductivity epoxy resin composition as described in any one of claims 1 to 7 to the rough surface of the copper foil; Step 2: baking the copper foil coated with the high thermal conductivity epoxy resin composition to form a semi-solid coated copper foil; Step three: Lay the semi-solidified glue-coated copper foil on the aluminum substrate, and heat and pressurize to form the aluminum-based copper-clad laminate.

10. The method for preparing an aluminum-based copper-clad laminate according to claim 9, characterized in that: In step 3, the heating temperature is 160°C-210°C and the pressurization pressure is 25-40kg / cm 2 , hot pressing time is 60-120min.

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