Resin composition for high-modulus and high-thermal-conductivity copper-clad plate and application of resin composition

Abstract

The invention belongs to the technical field of electronic materials, and relates to a resin composition for a high-modulus and high-thermal-conductivity copper-clad plate and application of the resin composition. The invention discloses a resin composition for a high-modulus and high-thermal-conductivity copper-clad plate. The resin composition is prepared from the following raw materials: nitrile resin and composite thermal-conductive fibers, the composite heat-conducting fiber comprises carboxylated inorganic fiber, amino modified boron nitride, amino modified ceramic powder and a cross-linking agent. The boron nitride and the ceramic powder are subjected to amination treatment through a filler surface modification technology, the compatibility and dispersity of the boron nitride and the ceramic powder in resin are improved, the addition amount of the boron nitride is increased, the heat resistance and peel strength of the prepared laminated board are not affected, the peel strength of the copper foil reaches 1.0 N / mm or above, and the service life of the copper foil is prolonged. And the heat conductivity coefficient reaches over 1.5 W / (m.K).

Description

Technical Field

[0001] The present invention belongs to the technical field of electronic materials, and relates to a resin composition for a high-modulus and high-thermal-conductivity copper clad laminate and its application. Background Art

[0002] The encapsulation substrate is an important material for connecting chips and PCBs, providing functions such as protection, fixed support, and heat dissipation for the chips. The copper clad laminate is the core material for substrate manufacturing. As integrated circuits continue to develop towards being lighter, thinner, and smaller, higher requirements are put forward for the inherent properties of substrate materials in terms of heat, force, etc. The focus of the development of substrate materials is mainly to increase the modulus, reduce the coefficient of thermal expansion, and increase the thermal conductivity.

[0003] Nitrile resin is a high-performance resin with a high glass transition temperature, high heat resistance, high modulus, and low coefficient of thermal expansion, and can be used as a material for encapsulation substrates. However, as a plastic encapsulation material, it also has the problem of low thermal conductivity.

[0004] Adding high-thermal-conductivity fillers to the resin is a simple and fast method for preparing high-thermal-conductivity materials. Hexagonal boron nitride has very high thermal conductivity and electrical insulation properties, and is widely used in the preparation of high-thermal-conductivity and electrically insulating composites. However, it has poor compatibility with the resin and is difficult to disperse. A large amount of addition will lead to insufficient bonding force between the resin and the copper foil and poor heat resistance. Patent CN114539770B provides a high-thermal-conductivity and insulating phthalonitrile composite material, its preparation method and application. This composite material is prepared from a phthalonitrile-based core-shell composite material. The core-shell composite material has a core-shell structure, the inner core is a phthalonitrile-based microsphere, and the thermal-conductivity filler layer is coated on the surface of the inner core. A thermal-conductivity network is constructed through the core-shell composite material, and good thermal-conductivity performance is exhibited at a low content of thermal-conductivity fillers. However, the thermal-conductivity fillers in this method are not surface-treated, and the bonding force with the nitrile resin is insufficient, and it is easy to crack and delaminate under thermal shock. Summary of the Invention

[0005] The purpose of the present invention is to provide a resin composition, prepreg, copper clad laminate and application, by adding composite thermal-conductivity fibers to the nitrile resin to construct an effective thermal-conductivity network, solve the problem of insufficient thermal-conductivity performance of the nitrile resin, and at the same time solve the compatibility and dispersibility problems between boron nitride and the resin, so that the copper clad laminate made thereof has the advantages of high thermal conductivity, high modulus, low coefficient of thermal expansion, high peel strength, etc.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions: A resin composition for a high-modulus and high-thermal-conductivity copper clad laminate, comprising the following raw materials: nitrile resin, composite thermal-conductivity fibers; the composite thermal-conductivity fibers include carboxylated inorganic fibers, amino-modified boron nitride, amino-modified ceramic powder, and crosslinking agent composite.

[0007] Preferably, the weight ratio of the nitrile resin to the composite heat-conducting fiber is 20-50:50-80.

[0008] Preferably, in the composite heat-conducting fiber, the weight ratio of the carboxylated inorganic fiber, the amino-modified boron nitride, and the amino-modified ceramic powder is 30-50:20-30:20-40.

[0009] Preferably, the preparation of the composite heat-conducting fiber comprises the following steps: A. Reacting the inorganic fiber with an amino-silane coupling agent, an acid anhydride, and deionized water to obtain the carboxylated inorganic fiber; during the reaction, the acid anhydride first reacts with the amino-silane coupling agent to form a terminal carboxyl silane coupling agent. Immediately afterwards, the terminal carboxyl silane coupling agent undergoes hydrolysis and simultaneously condenses with the hydroxyl groups on the surface of the inorganic fiber to graft carboxyl groups onto the surface of the inorganic fiber, obtaining the carboxylated inorganic fiber.

[0010] B. Reacting boron nitride with an amino-silane coupling agent to obtain the amino-modified boron nitride; C. Reacting the ceramic powder with an amino-silane coupling agent to obtain the amino-modified ceramic powder; D. Mixing the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and the crosslinking agent, and performing a hydrothermal reaction to obtain the composite heat-conducting fiber.

[0011] Preferably, step A comprises: A1. Cleaning and drying the inorganic fiber to obtain a pretreated inorganic fiber; A2. Dissolving the amino-silane coupling agent and the acid anhydride in N,N-dimethylformamide, dispersing them evenly, then adding the pretreated inorganic fiber and deionized water, heating and reacting, and then taking out to obtain a crude inorganic fiber product; A3. Washing and drying the crude inorganic fiber product to obtain the carboxylated inorganic fiber; Step B comprises: B1. Performing surface plasma treatment on the boron nitride to obtain pretreated boron nitride; B2. After dispersing the pretreated boron nitride, adding the amino-silane coupling agent, heating and reacting, and then taking out to obtain a crude boron nitride product; B3. Washing and drying the crude boron nitride product to obtain the amino-modified boron nitride; Step C comprises: C1. Treating the ceramic powder in an acid agent, and then washing and drying to obtain a pretreated ceramic powder; C2. After dispersing the pretreated ceramic powder, add an amino-silane coupling agent, heat and react, and then take it out to obtain a crude ceramic powder product; C3. Wash and dry the crude ceramic powder product to obtain the amino-modified ceramic powder; Step D includes: dispersing the carboxylated inorganic fiber in deionized water, then adding the amino-modified boron nitride, the amino-modified ceramic powder, and the cross-linking agent, dispersing evenly, and then performing a hydrothermal reaction to obtain the composite heat-conducting fiber.

[0012] Preferably, step A includes: A1. Immerse the inorganic fiber in ethanol or deionized water, ultrasonically clean for 20 - 30 minutes, then filter and dry to obtain the pretreated inorganic fiber; A2. Dissolve the amino-silane coupling agent and the anhydride in N,N-dimethylformamide, disperse evenly, then add the pretreated inorganic fiber and deionized water, heat and react at 40 - 60 °C for 3 - 6 hours, and then centrifuge and take it out to obtain a crude inorganic fiber product; the weight ratio of the amino-silane coupling agent, the anhydride, N,N-dimethylformamide, the inorganic fiber, and deionized water is 5 - 10:1 - 1.2:50 - 100:10:10 - 30; A3. Wash the crude inorganic fiber product with ethanol or deionized water, and vacuum dry at 60 - 80 °C to obtain the carboxylated inorganic fiber.

[0013] Step B includes: B1. Perform surface plasma treatment on the boron nitride in an oxygen or argon environment for 10 - 30 minutes to obtain the pretreated boron nitride; B2. Disperse the pretreated boron nitride in an ethanol / water solution, ultrasonically disperse for 20 - 40 minutes, then add an amino-silane coupling agent, heat and stir and react at 60 - 80 °C for 4 - 12 hours, and take it out after the reaction is completed to obtain a crude boron nitride product; the weight ratio of the amino-silane coupling agent to the pretreated boron nitride is 0.5 - 5:100; B3. Filter the crude boron nitride product, wash it with ethanol or deionized water, and vacuum dry at 60 - 80 °C to obtain the amino-modified boron nitride; Step C includes: C1. Immerse the ceramic powder in a dilute nitric acid solution with a mass fraction of 10 - 12%, ultrasonically treat for 30 - 60 minutes, and then filter, wash, and dry to obtain the pretreated ceramic powder; C2. Disperse the pretreated ceramic powder in an ethanol / water solution, ultrasonically disperse for 20 - 40 minutes, then add an amino-silane coupling agent, and heat and stir to react at 60 - 80 °C for 12 - 24 hours. After the reaction is completed, take it out to obtain a crude ceramic powder product; the weight ratio of the amino-silane coupling agent to the pretreated ceramic powder is 0.5 - 5:100; C3. Filter the crude ceramic powder product, wash it with ethanol or deionized water, and vacuum dry it at 60 - 80 °C to obtain the amino-modified ceramic powder; Step D includes: dispersing the carboxylated inorganic fiber in deionized water, then adding the amino-modified boron nitride, the amino-modified ceramic powder, and the crosslinking agent. After dispersing evenly, perform a hydrothermal reaction to obtain the composite heat-conducting fiber.

[0014] Preferably, the inorganic fiber includes one or more of glass fiber, basalt fiber, quartz fiber, alumina fiber, aluminum nitride fiber, silicon carbide fiber, and diamond fiber; the diameter of the inorganic fiber is 0.2 - 10 μm; the length of the inorganic fiber is 100 - 500 μm; the amino-silane coupling agent includes one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminoethylaminopropyltrimethoxysilane; the acid anhydride includes one or more of succinic anhydride and maleic anhydride; the boron nitride includes hexagonal boron nitride; the diameter of the boron nitride is 0.05 - 10 μm; the ceramic powder includes one or more of silicon dioxide, alumina, magnesia, zinc oxide, and titanium dioxide; the particle size of the ceramic powder is 0.3 - 10 μm; the crosslinking agent includes epichlorohydrin; in step D, the weight ratio of the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and the crosslinking agent is 30 - 50:20 - 30:20 - 40:20 - 40.

[0015] More preferably, the ceramic powder is alumina.

[0016] Preferably, in step D, the weight ratio of the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and epichlorohydrin is 30 - 50:20 - 30:20 - 40:20 - 40.

[0017] As a crosslinking agent for carboxyl and amino groups, epichlorohydrin can carry out chemical reactions using the carboxyl groups in the carboxylated inorganic fiber and the amino groups in the amino-modified boron nitride and amino-modified ceramic powder, graft the amino-modified boron nitride and amino-modified ceramic powder onto the inorganic fiber, which is beneficial to reducing the interfacial thermal resistance between the fiber and the filler, constructing an effective heat-conducting path, and increasing the thermal conductivity of the resin composition.

[0018] Preferably, the hydrothermal reaction temperature is 90~120°C, and the reaction time is 2~3 hours.

[0019] An application of the resin composition for a high modulus and high thermal conductivity copper clad laminate as described above, which is used for one or more of prepregs and copper clad laminates.

[0020] A prepreg or copper clad laminate obtained by the above application.

[0021] Preferably, the prepreg includes a reinforcing substrate and the resin composition attached thereto by impregnation and drying.

[0022] Preferably, the copper clad laminate includes a laminate and metal foils laminated on one or both sides of the laminate, and the laminate includes one or several sheets of prepregs laminated together.

[0023] A copper clad laminate obtained by the above application.

[0024] A method for preparing a copper clad laminate as described above, which includes the following steps: Impregnate the glass fiber cloth with the resin composition, and bake it in an oven at 150~180°C for 1~15 minutes to obtain a prepreg. The method for manufacturing a copper clad laminate using the above prepreg includes the following steps: Stack 10 pieces of the prepregs prepared above, cover one copper foil with a thickness of 35 microns on each of the upper and lower sides, place them in a vacuum hot press for lamination, and laminate them at a temperature of 200~250°C for 1~5 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0025] Implementing the present invention has the following beneficial effects: 1. By using the filler surface modification technology, the present invention performs amination treatment on boron nitride and ceramic powder, improves the compatibility and dispersibility of boron nitride and ceramic powder in the resin, not only increases the addition amount of boron nitride, but also does not affect the heat resistance and peel strength of the prepared laminate. The peel strength of the copper foil reaches more than 1.0 N / mm.

[0026] 2. By using the surface modification grafting technology, with inorganic fibers as the basic framework, boron nitride and ceramic powder are grafted, an effective heat conduction path is established, the thermal conductivity of the resin composition is improved, the thermal conductivity of the prepared copper clad laminate reaches more than 1.5 W / (m·K), and at the same time, the bending modulus, bending strength of the copper clad laminate are improved, and the thermal expansion coefficient of the copper clad laminate is reduced, etc. Specific Embodiments

[0027] To make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments.

[0028] The raw materials used in the following examples and comparative examples are as described below: Glass fiber: chopped glass fiber (Nanjing Fiberglass Research & Design Institute Co., Ltd.) Aluminum nitride fiber: aluminum nitride fiber (Xiamen Juchi Technology Co., Ltd.) Boron nitride: NA50 (average particle size is 0.05μm, Dandong Chemical Research Institute Co., Ltd.) NA400 (average particle size is 0.4μm, Dandong Chemical Research Institute Co., Ltd.) HFLI (average particle size is 7μm, Dandong Chemical Research Institute Co., Ltd.) Aluminum oxide: E-HJA-005S (D50 is 0.3μm, Anhui Yestone Materials Technology Co., Ltd.) SLA-1 (D50 is 1.2μm, Anhui Yestone Materials Technology Co., Ltd.) SLA10 (D50 is 10μm, Anhui Yestone Materials Technology Co., Ltd.) Nitrile resin: phthalonitrile resin (Chengdu Keyi Polymer Technology Co., Ltd.) Glass fiber cloth: 2116 cloth (Henan Guangyuan New Materials Co., Ltd.) Example 1: Step 1: Immerse the glass fiber (with a diameter of 1μm and a length of 100μm) in ethanol, ultrasonically clean for 20 minutes, then filter and dry the glass fiber to obtain pretreated glass fiber; dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse evenly, then add the pretreated glass fiber and deionized water, heat and react at 60°C for 4 hours, then centrifuge and take out, wash with ethanol, and vacuum dry at 80°C to obtain carboxylated glass fiber.

[0029] Step 2: Perform surface plasma treatment on boron nitride (average particle size is 0.4μm) in an oxygen or argon environment for 30 minutes to obtain pretreated boron nitride; disperse the pretreated boron nitride in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino silane coupling agent thereto, heat and stir and react at 80°C for 10 hours, after the reaction is completed, filter, wash and dry the reaction product to obtain amino-modified boron nitride.

[0030] Step 3: Immerse aluminum oxide (average particle size is 0.3μm) in a 10% by mass dilute nitric acid solution, ultrasonically treat for 30 minutes, filter, wash and dry to obtain pretreated aluminum oxide; disperse the pretreated aluminum oxide in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino silane coupling agent thereto, heat and stir and react at 80°C for 15 hours, after the reaction is completed, filter, wash and dry the reaction product to obtain amino-modified aluminum oxide.

[0031] Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina and epichlorohydrin, disperse evenly, then carry out hydrothermal reaction. After the reaction is completed, filter, wash and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 50% glass fiber, 30% boron nitride, and 20% alumina.

[0032] Step 5: A resin composition, which includes by mass percentage: 35% nitrile resin and 65% composite heat-conducting fiber. Add the above resin composition into DMF solvent, stir evenly, then impregnate 2116 glass fiber cloth with it, and bake it in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0033] Step 6: Stack 10 pieces of the prepregs prepared above, cover one metal copper foil with a thickness of 35 microns on each of the upper and lower sides, place them in a vacuum hot press for lamination, and laminate at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0034] Example 2 A preparation method of a resin composition, prepreg and copper clad laminate, compared with Example 1, the difference is only in Step 4, which is specifically as follows: Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina and epichlorohydrin, disperse evenly, then carry out hydrothermal reaction. After the reaction is completed, filter, wash and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 40% glass fiber, 20% boron nitride, and 40% alumina.

[0035] Example 3 Step 1: Immerse glass fibers (with a diameter of 10 μm and a length of 500 μm) in ethanol, ultrasonically clean for 30 minutes, then filter and dry the glass fibers to obtain pretreated glass fibers; dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse evenly, add the pretreated glass fibers and deionized water, heat and react at 60 °C for 4 hours, then centrifuge and take out, wash with ethanol, and vacuum dry at 80 °C to obtain carboxylated glass fibers. Step 2: Carry out surface plasma treatment on boron nitride (with an average particle size of 0.05 μm) in an oxygen or argon environment for 30 minutes to obtain pretreated boron nitride; disperse the pretreated boron nitride in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino silane coupling agent thereto, heat and stir and react at 80 °C for 10 hours. After the reaction is completed, filter, wash and dry the reaction product to obtain amino-modified boron nitride.

[0036] Step 3: Immerse alumina (average particle size of 1.2 μm) in a 10% by mass dilute nitric acid solution, perform ultrasonic treatment for 30 minutes, filter, wash, and dry to obtain pretreated alumina; disperse the pretreated alumina in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino silane coupling agent thereto, heat and stir the reaction at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0037] Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, and then perform a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 50% glass fiber, 30% boron nitride, and 20% alumina.

[0038] Step 5: A resin composition, comprising by mass percentage: 20% nitrile resin and 80% composite heat-conducting fiber. Add the above resin composition to a DMF solvent, stir evenly, and then impregnate a 2116 glass fiber cloth therewith, and bake it in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0039] Step 6: Stack 10 pieces of the prepregs prepared above, cover each with a 35-micron-thick copper foil on the top and bottom, place them in a vacuum hot press for lamination, and laminate at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0040] Example 4 Step 1: Immerse glass fibers (diameter of 0.2 μm and length of 200 μm) in ethanol, perform ultrasonic cleaning for 30 minutes, then filter and dry the glass fibers to obtain pretreated glass fibers; dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse evenly, add the pretreated glass fibers and deionized water thereto, heat and react at 60 °C for 4 hours, then centrifuge and take out, wash with ethanol, and dry in vacuum at 80 °C to obtain carboxylated glass fibers. Step 2: Perform surface plasma treatment on boron nitride (average particle size of 0.05 μm) in an oxygen or argon environment for 30 minutes to obtain pretreated boron nitride; disperse the pretreated boron nitride in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino silane coupling agent thereto, heat and stir the reaction at 80 °C for 10 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified boron nitride.

[0041] Step 3: Immerse alumina (with an average particle size of 10 μm) in a 10% by mass dilute nitric acid solution, perform ultrasonic treatment for 30 minutes, filter, wash, and dry to obtain pretreated alumina; disperse the pretreated alumina in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino silane coupling agent thereto, heat and stir the reaction at 80 °C for 15 hours, after the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0042] Step 4: Disperse carboxylated glass fiber in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, and then perform a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 50% glass fiber, 30% boron nitride, and 20% alumina.

[0043] Step 5: A resin composition, by mass percentage, includes: 50% nitrile resin and 50% composite heat-conducting fiber. Add the above resin composition to DMF solvent, stir evenly, then impregnate 2116 glass fiber cloth therewith, and bake in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0044] Step 6: Stack 10 pieces of the prepregs prepared above, cover each with a 35-μm-thick copper foil on the top and bottom, place them in a vacuum hot press for lamination, and laminate at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0045] Example 5 Step 1: Immerse aluminum nitride fiber (with a diameter of 3 μm and a length of 350 μm) in ethanol, perform ultrasonic cleaning for 20 minutes, then filter and dry the aluminum nitride fiber to obtain pretreated aluminum nitride fiber; dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse evenly, add the pretreated aluminum nitride fiber and deionized water thereto, heat and react at 60 °C for 4 hours, then centrifuge and take out, wash with ethanol, and vacuum dry at 80 °C to obtain carboxylated aluminum nitride fiber.

[0046] Step 2: Perform surface plasma treatment on boron nitride (with an average particle size of 7 μm) in an oxygen or argon environment for 30 minutes to obtain pretreated boron nitride; disperse the pretreated boron nitride in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino silane coupling agent thereto, heat and stir the reaction at 80 °C for 10 hours, after the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified boron nitride.

[0047] Step 3: Immerse alumina (with an average particle size of 0.3 μm) in a 10% by mass dilute nitric acid solution, perform ultrasonic treatment for 30 minutes, filter, wash, and dry to obtain pretreated alumina; disperse the pretreated alumina in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino-silane coupling agent thereto, heat and stir the reaction at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0048] Step 4: Disperse carboxylated aluminum nitride fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, and then perform a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of aluminum nitride fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 50% aluminum nitride fiber, 25% boron nitride, and 25% alumina.

[0049] Step 5: A resin composition, by mass percentage, includes: 40% nitrile resin and 60% composite heat-conducting fiber. Add the above resin composition to a DMF solvent, stir evenly, and then impregnate a 2116 glass fiber cloth therewith, and bake it in an oven at 170 °C for 10 min to obtain a prepreg.

[0050] Step 6: Stack 10 pieces of the prepregs prepared above, cover each of the upper and lower sides with a 35-μm-thick copper foil, place them in a vacuum hot press for lamination, and laminate at a temperature of 230 °C for 2 hours to obtain a copper-clad laminate with a thickness of 1.0 mm.

[0051] Example 6 Step 1: Immerse aluminum nitride fibers (with a diameter of 0.2 μm and a length of 250 μm) in ethanol, perform ultrasonic cleaning for 20 minutes, then filter and dry the aluminum nitride fibers to obtain pretreated aluminum nitride fibers; dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse evenly, add the pretreated aluminum nitride fibers and deionized water thereto, heat and react at 60 °C for 4 hours, then centrifuge and take out, wash with ethanol, and vacuum dry at 80 °C to obtain carboxylated aluminum nitride fibers. Step 2: Perform surface plasma treatment on boron nitride (with an average particle size of 0.05 μm) in an oxygen or argon environment for 30 minutes to obtain pretreated boron nitride; disperse the pretreated boron nitride in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino-silane coupling agent thereto, heat and stir the reaction at 80 °C for 10 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified boron nitride.

[0052] Step 3: Immerse alumina (with an average particle size of 1.2 μm) in a 10% by mass dilute nitric acid solution, perform ultrasonic treatment for 30 minutes, filter, wash, and dry to obtain pretreated alumina; disperse the pretreated alumina in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino silane coupling agent thereto, heat and stir at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0053] Step 4: Disperse carboxylated aluminum nitride fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, and then perform a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of aluminum nitride fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 40% aluminum nitride fiber, 30% boron nitride, and 30% alumina.

[0054] Step 5: A resin composition, by mass percentage, includes: 50% nitrile resin and 50% composite heat-conducting fiber. Add the above resin composition to DMF solvent, stir evenly, and then impregnate 2116 fiberglass cloth therewith, and bake in an oven at 170 °C for 10 min to obtain a prepreg.

[0055] Step 6: Stack 10 pieces of the prepregs prepared above, cover each with a 35-μm-thick copper foil on the top and bottom, place them in a vacuum hot press for lamination, and laminate at 230 °C for 2 hours to obtain a copper-clad laminate with a thickness of 1.0 mm.

[0056] Comparative Example 1 Compared with Examples 1 to 4, the difference in Comparative Example 1 is that it does not contain any fillers, specifically as follows: Impregnate 2116 fiberglass cloth with nitrile resin, and bake in an oven at 170 °C for 10 min to obtain a prepreg. Stack 10 pieces of the prepregs prepared above, cover each with a 35-μm-thick copper foil on the top and bottom, place them in a vacuum hot press for lamination, and laminate at 230 °C for 2 hours to obtain a copper-clad laminate with a thickness of 1.0 mm.

[0057] Comparative Example 2 A preparation method of a resin composition, prepreg, and copper-clad laminate, compared with Example 1, the difference is that the inorganic fiber is not subjected to modification treatment, specifically as follows: Step 1: Subject boron nitride (with an average particle size of 0.4 μm) to surface plasma treatment for 30 minutes in an oxygen or argon environment to obtain pretreated boron nitride; disperse the pretreated boron nitride in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino-silane coupling agent thereto, heat and stir the reaction at 80 °C for 10 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified boron nitride.

[0058] Step 2: Immerse alumina (with an average particle size of 0.3 μm) in a 10% by mass dilute nitric acid solution, ultrasonically treat for 30 minutes, filter, wash, and dry to obtain pretreated alumina; disperse the pretreated alumina in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino-silane coupling agent thereto, heat and stir the reaction at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0059] Step 3: Disperse glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, filter, wash, and dry the product to obtain fiber / ceramic powder. By mass percentage, the component ratio in the prepared fiber / ceramic powder is: 50% glass fiber, 30% boron nitride, and 20% alumina.

[0060] Step 4: A resin composition, which includes, by mass percentage: 35% nitrile resin and 65% fiber / ceramic powder. Add the above resin composition to DMF solvent, stir evenly, then impregnate 2116 glass fiber cloth with it, and bake in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0061] Step 5: Stack 10 pieces of the prepregs prepared above, cover one piece of 35-micron-thick copper foil on each of the upper and lower sides, place them in a vacuum hot press for lamination, and laminate at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0062] Comparative Example 3 A method for preparing a resin composition, prepreg, and copper clad laminate, which is different from Example 1 in that boron nitride is not subjected to modification treatment, and is specifically as follows: Step 1: Immerse glass fibers (with a diameter of 1 μm and a length of 100 μm) in ethanol and ultrasonically clean for 20 minutes. Then filter and dry the glass fibers to obtain pretreated glass fibers. Dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse evenly, add the pretreated glass fibers and deionized water, and heat and react at 60 °C for 4 hours. After that, centrifuge and take out, wash with ethanol, and vacuum dry at 80 °C to obtain carboxylated glass fibers. Step 2: Immerse alumina (with an average particle size of 0.3 μm) in a 10% by mass dilute nitric acid solution and ultrasonically treat for 30 minutes. Filter, wash, and dry to obtain pretreated alumina. Disperse the pretreated alumina in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino silane coupling agent, and heat and stir to react at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0063] Step 3: Disperse the carboxylated glass fibers in deionized water, add boron nitride (with an average particle size of 0.4 um), amino-modified alumina, and epichlorohydrin, disperse evenly, and then carry out a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain fiber / ceramic powder. By mass percentage, the component ratio in the prepared fiber / ceramic powder is: 50% glass fiber, 30% boron nitride, and 20% alumina.

[0064] Step 4: A resin composition, by mass percentage, includes: 35% nitrile resin and 65% fiber / ceramic powder. Add the above resin composition to DMF solvent, stir evenly, and then impregnate a 2116 glass fiber cloth with it, and bake in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0065] Step 5: Stack 10 pieces of the prepregs prepared above, cover each with a 35-micron-thick copper foil on the top and bottom, place them in a vacuum hot press for lamination, and laminate at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0066] Comparative Example 4 A method for preparing a resin composition, prepreg, and copper clad laminate, compared with Example 1, is different in that the alumina is not modified, specifically as follows: Step 1: Immerse glass fibers (with a diameter of 1 μm and a length of 100 μm) in ethanol and ultrasonically clean them for 20 minutes. Subsequently, filter and dry the glass fibers to obtain pretreated glass fibers. Dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse them evenly, then add the pretreated glass fibers and deionized water, and heat and react at 60 °C for 4 hours. After that, centrifuge and take out, wash with ethanol, and vacuum dry at 80 °C to obtain carboxylated glass fibers. Step 2: Perform surface plasma treatment on boron nitride (with an average particle size of 0.4 μm) in an oxygen or argon environment for 30 minutes to obtain pretreated boron nitride. Disperse the pretreated boron nitride in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino silane coupling agent thereto, and heat and stir and react at 80 °C for 10 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified boron nitride.

[0067] Step 3: Disperse the carboxylated glass fibers in deionized water, add amino-modified boron nitride, alumina (with an average particle size of 0.3 μm), and epichlorohydrin, disperse them evenly, and then carry out a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain fiber / ceramic powder. By mass percentage, the component ratio in the prepared fiber / ceramic powder is: 50% glass fiber, 30% boron nitride, and 20% alumina.

[0068] Step 4: A resin composition, which includes, by mass percentage: 35% nitrile resin and 65% fiber / ceramic powder. Add the above resin composition to DMF solvent, stir evenly, and then impregnate 2116 glass fiber cloth with it, and bake in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0069] Step 5: Stack 10 pieces of the prepregs prepared above, cover one sheet of 35-micron-thick copper foil on each of the upper and lower sides, place them in a vacuum hot press for lamination, and laminate at 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0070] Comparative Example 5 A preparation method of a resin composition, prepreg, and copper clad laminate, compared with Example 1, is different in that it does not contain inorganic fibers, specifically as follows: Step 1: Perform surface plasma treatment on boron nitride (with an average particle size of 0.4 μm) in an oxygen or argon environment for 30 minutes to obtain pretreated boron nitride. Disperse the pretreated boron nitride in an ethanol / water solution, ultrasonically disperse for 20 minutes, add an amino silane coupling agent thereto, and heat and stir and react at 80 °C for 10 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified boron nitride.

[0071] Step 2: Immerse alumina (with an average particle size of 0.3 μm) in a 10% by mass dilute nitric acid solution, perform ultrasonic treatment for 30 minutes, filter, wash, and dry to obtain pretreated alumina; disperse the pretreated alumina in an ethanol / water solution, perform ultrasonic dispersion for 20 minutes, add an amino-silane coupling agent thereto, heat and stir the reaction at 80 °C for 15 hours, and after the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0072] Step 3: A resin composition, by mass percentage, includes: 35% of nitrile resin, 30% of amino-functionalized boron nitride, and 35% of amino-functionalized alumina. Add the above resin composition to a DMF solvent, stir evenly, and then impregnate a 2116 glass fiber cloth therewith, and bake it in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0073] Step 4: Stack 10 pieces of the prepregs prepared above, cover each with a 35-μm-thick copper foil on the top and bottom, place them in a vacuum hot press for lamination, and laminate at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0074] Comparative Example 6 A method for preparing a resin composition, prepreg, and copper clad laminate, compared with Example 1, the difference is only in Step 4, specifically as follows: Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, and then perform a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in preparing the composite heat-conducting fiber is: 20% of glass fiber, 30% of boron nitride, and 50% of alumina.

[0075] Comparative Example 7 A method for preparing a resin composition, prepreg, and copper clad laminate, compared with Example 1, the difference is only in Step 4, specifically as follows: Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, and then perform a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in preparing the composite heat-conducting fiber is: 60% of glass fiber, 20% of boron nitride, and 20% of alumina.

[0076] Comparative Example 8 A method for preparing a resin composition, a prepreg, and a copper clad laminate, which is different from Example 1 in that Step 4 is different, specifically as follows: Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, then carry out a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 50% glass fiber, 10% boron nitride, and 40% alumina.

[0077] Comparative Example 9 A method for preparing a resin composition, a prepreg, and a copper clad laminate, which is different from Example 1 in that Step 4 is different, specifically as follows: Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina, and epichlorohydrin, disperse evenly, then carry out a hydrothermal reaction. After the reaction is completed, filter, wash, and dry the reaction product to obtain a composite heat-conducting fiber of glass fiber grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fiber is: 50% glass fiber, 40% boron nitride, and 10% alumina.

[0078] Effect Example 1 Tables 1 to 3 show the ratios of the components in the formulations of Examples 1 to 6 and Comparative Examples 1 to 6.

[0079] Table 1

[0080] Table 2

[0081] Table 3

[0082] Effect Example 2 Test the properties of the copper clad laminates prepared in Examples 1 to 6 and Comparative Examples 1 to 9.

[0083] The performance test method is as follows: (1) Thermal conductivity: Test according to the method of ASTM D5470-2017 (2) Flexural modulus: Test by the DMA method and according to the method of IPC-TM-650 2.4.24.4

[0084] (3) Peel strength: Test according to the method of IPC-TM-650 2.4.8

[0085] (4) Thermal stress: Float the copper-containing sample in a 288 °C tin furnace and record the delamination time of the board explosion. If the board does not explode after 60 minutes of heating, record it as ">60 minutes".

[0086] (5) Coefficient of thermal expansion CTE: Test according to the method of IPC-TM-650 2.4.24 The test results are shown in Table 4.

[0087] Table 4

[0088] The performance of Table 4 shows that the present invention prepares composite heat-conducting fibers by surface-modifying and grafting inorganic fibers, boron nitride, and ceramic powder. It not only solves the compatibility and dispersion problems of boron nitride and ceramic powder in the resin matrix, increases the interaction force between the filler and the resin, reduces the scattering degree of phonons at the interface, reduces the thermal resistance, and improves the peel strength of the copper-clad laminate. At the same time, taking inorganic fibers as a bridge, high heat-conducting boron nitride and ceramic powder are surface-grafted to construct an effective heat-conducting path, significantly improving the thermal conductivity of the copper-clad laminate. Through the design and optimization of different components, the flexural modulus of the copper-clad laminate is significantly improved, and its coefficient of thermal expansion is reduced. In Examples 1-6, the thermal conductivity of the copper-clad laminate is greater than 1.5 W / (m·K), the peel strength reaches 1.14-1.45 N / mm, the flexural modulus is 28-34 GPa, the thermal shock is greater than 60 minutes, the coefficients of thermal expansion in the X and Y directions are 9.3-14.8 ppm / °C, and the coefficient of thermal expansion in the Z direction is 23.8-26.6 ppm / °C.

[0089] From the comparison of the performance data of Example 1 and Comparative Example 1, it can be seen that the nitrile resin itself has a low thermal conductivity and a relatively large coefficient of thermal expansion. After adding the composite heat-conducting fiber, the thermal conductivity is significantly improved, and the coefficient of thermal expansion is significantly reduced.

[0090] From the comparison of the performance data of Example 1 and Comparative Examples 2, 3, and 4, it can be seen that the unmodified fibers and ceramic powder have no binding force with each other, and the formed heat-conducting path is insufficient, resulting in a low thermal conductivity and a low peel strength of the copper-clad laminate.

[0091] For the addition ratio of inorganic fibers, from the comparison of Example 1 and Comparative Examples 5, 6, and 7, it can be seen that when the addition ratio of inorganic fibers is too low or too high, the thermal conductivity, flexural modulus, and peel strength of the copper-clad laminate all decrease significantly, and the coefficient of thermal expansion also increases.

[0092] Regarding the addition ratios of boron nitride and ceramic powder, it can be seen from the comparison between Example 1 and Comparative Example 8 and Comparative Example 9 that when the addition ratio of boron nitride is too low and the addition ratio of ceramic powder is too high, the thermal conductivity of the copper clad laminate decreases significantly; when the addition ratio of boron nitride is too high and the addition ratio of ceramic powder is too low, the peel strength and thermal shock of the copper clad laminate decrease significantly.

[0093] The above are only the preferred embodiments of the present invention, and do not impose any limitations on the technical scope of the present invention. Therefore, any minor modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A resin composition for high modulus and high thermal conductivity copper-clad laminate, characterized in that: The invention comprises the following raw materials: nitrile-based resin and composite thermal conductive fiber; the composite thermal conductive fiber comprises carboxylated inorganic fiber, amino-modified boron nitride, amino-modified ceramic powder and a cross-linking agent.

2. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 1, characterized in that: The weight ratio of the nitrile-based resin to the composite thermally conductive fiber is 20-50:50-80.

3. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 1, characterized in that: In the composite thermally conductive fiber, the weight ratio of the carboxylated inorganic fiber, the amino-modified boron nitride, and the amino-modified ceramic powder is 30-50:20-30:20-40.

4. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 1, characterized in that: The preparation of the composite thermally conductive fiber comprises the following steps: A. reacting inorganic fiber with aminosilane coupling agent, acid anhydride and deionized water to obtain the carboxylated inorganic fiber; B. reacting boron nitride with an aminosilane coupling agent to obtain the amino-modified boron nitride; C. reacting the ceramic powder with an aminosilane coupling agent to obtain the amino-modified ceramic powder; D. Mixing the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and the cross-linking agent, and performing a hydrothermal reaction to obtain the composite thermally conductive fiber.

5. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 4, characterized in that: Step A includes: A1. Washing and drying the inorganic fibers to obtain pretreated inorganic fibers; A2, dissolving the aminosilane coupling agent and the acid anhydride in N,N-dimethylformamide, dispersing them evenly, then adding the pretreated inorganic fiber and deionized water, heating for reaction, and then taking out to obtain a crude inorganic fiber product; A3, washing and drying the crude inorganic fiber product to obtain the carboxylated inorganic fiber; Step B includes: B1, subjecting the boron nitride to surface plasma treatment to obtain pretreated boron nitride; B2, after dispersing the pretreated boron nitride, adding an aminosilane coupling agent, heating for reaction, and then taking out to obtain a crude boron nitride product; B3, washing and drying the crude boron nitride product to obtain the amino-modified boron nitride; Step C includes: C1. treating the ceramic powder in an acid agent, and then washing and drying to obtain pretreated ceramic powder; C2, after dispersing the pretreated ceramic powder, adding an aminosilane coupling agent, heating for reaction, and then taking out to obtain a crude ceramic powder product; C3, washing and drying the crude ceramic powder product to obtain the amino-modified ceramic powder; Step D comprises: dispersing the carboxylated inorganic fiber in deionized water, adding the amino-modified boron nitride, the amino-modified ceramic powder and the cross-linking agent, and after uniform dispersion, performing a hydrothermal reaction to obtain the composite thermally conductive fiber.

6. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 4, characterized in that: Step A includes: A1, soaking the inorganic fiber in ethanol or deionized water, ultrasonically cleaning for 20-30 minutes, then filtering and drying to obtain pretreated inorganic fiber; A2, dissolving the aminosilane coupling agent and the acid anhydride in N, N-dimethylformamide, dispersing them uniformly, then adding the pretreated inorganic fiber and deionized water, heating and reacting at 40-60° C. for 3-6 hours, then centrifuging and taking out to obtain a crude inorganic fiber product; the weight ratio of the aminosilane coupling agent, the acid anhydride, the N, N-dimethylformamide, the inorganic fiber, and the deionized water is 5-10:1-1.2:50-100:10:10-30; A3, washing the crude inorganic fiber product with ethanol or deionized water, and vacuum drying at 60-80° C. to obtain the carboxylated inorganic fiber; Step B includes: B1, subjecting the boron nitride to surface plasma treatment in an oxygen or argon environment for 10 to 30 minutes to obtain pretreated boron nitride; B2, dispersing the pretreated boron nitride in an ethanol / water solution, ultrasonically dispersing for 20 to 40 minutes, adding an aminosilane coupling agent, heating and stirring at 60 to 80° C. for 4 to 12 hours, and taking out after the reaction is completed to obtain a crude boron nitride product; the weight ratio of the aminosilane coupling agent to the pretreated boron nitride is 0.5 to 5:100; B3, filtering the crude boron nitride product, washing with ethanol or deionized water, and vacuum drying at 60-80° C. to obtain the amino-modified boron nitride; Step C includes: C1. Soaking the ceramic powder in a dilute nitric acid solution with a mass fraction of 10-12%, ultrasonically treating for 30-60 minutes, and then filtering, washing and drying to obtain a pretreated ceramic powder; C2, dispersing the pretreated ceramic powder in an ethanol / water solution, ultrasonically dispersing for 20 to 40 minutes, adding an aminosilane coupling agent, heating and stirring at 60 to 80° C. for 12 to 24 hours, and taking out after the reaction is completed to obtain a crude ceramic powder product; the weight ratio of the aminosilane coupling agent to the pretreated ceramic powder is 0.5 to 5:100; C3, filtering the crude ceramic powder product, washing with ethanol or deionized water, and vacuum drying at 60-80° C. to obtain the amino-modified ceramic powder; Step D comprises: dispersing the carboxylated inorganic fiber in deionized water, adding the amino-modified boron nitride, the amino-modified ceramic powder, and the cross-linking agent, and after uniform dispersion, performing a hydrothermal reaction at 90-120° C. for 2-3 hours to obtain the composite thermally conductive fiber.

7. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 4, characterized in that: The inorganic fiber includes one or more of glass fiber, basalt fiber, quartz fiber, alumina fiber, aluminum nitride fiber, silicon carbide fiber, and diamond fiber; the diameter of the inorganic fiber includes 0.2-10 μm; the length of the inorganic fiber includes 100-500 μm; the aminosilane coupling agent includes one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminoethylaminopropyltrimethoxysilane; the acid anhydride includes one or more of succinic anhydride and maleic anhydride ; The boron nitride includes hexagonal boron nitride; the diameter of the boron nitride includes 0.05~10μm; the ceramic powder includes one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, and titanium dioxide; the particle size of the ceramic powder includes 0.3~10μm; the cross-linking agent includes epichlorohydrin; in step D, the weight ratio of the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and the cross-linking agent includes 30~50:20~30:20~40:20~40.

8. An application of the resin composition for high modulus and high thermal conductivity copper-clad laminate according to claim 1, characterized in that: Used for one or more of prepreg and copper clad laminate.

9. A prepreg obtained according to the use of claim 8.

10. A copper clad laminate obtained according to claim 8.

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