A resin composition for high modulus and high thermal conductivity copper clad laminates and its application

Abstract

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. The present invention discloses a resin composition for a high-modulus and high-thermal-conductivity copper clad laminate, which comprises the following raw materials: nitrile resin, composite thermal conductive fiber; the composite thermal conductive fiber comprises carboxylated inorganic fiber, amino-modified boron nitride, amino-modified ceramic powder, and crosslinker composite. The present invention performs amination treatment on boron nitride and ceramic powder through a filler surface modification technology to improve the compatibility and dispersion problems of boron nitride and ceramic powder in the resin, which 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, and the thermal conductivity reaches more than 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 high-modulus and high-thermal-conductivity copper clad laminates and its application. Background Art

[0002] Encapsulation substrates are important materials for connecting chips and PCBs, providing functions such as protecting, fixing, supporting, and dissipating heat for chips. Copper clad laminates are the core materials 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 key points in the development of substrate materials are 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 resins 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 resins 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 shown 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, a prepreg, a copper clad laminate and their applications. By adding composite thermal-conductivity fibers to the nitrile resin to construct an effective thermal-conductivity network, the problem of insufficient thermal-conductivity performance of the nitrile resin is solved. At the same time, the compatibility and dispersibility problems between boron nitride and the resin are solved, 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:

[0007] A resin composition for high-modulus and high-thermal-conductivity copper clad laminates, 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.

[0008] Preferably, the weight ratio of the nitrile resin to the composite heat-conducting fiber is 20-50:50-80.

[0009] 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.

[0010] Preferably, the preparation of the composite heat-conducting fiber includes the following steps:

[0011] A. React 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.

[0012] B. React boron nitride with an amino-silane coupling agent to obtain the amino-modified boron nitride;

[0013] C. React the ceramic powder with an amino-silane coupling agent to obtain the amino-modified ceramic powder;

[0014] D. Mix the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and the crosslinking agent, and carry out a hydrothermal reaction to obtain the composite heat-conducting fiber.

[0015] Preferably, step A includes:

[0016] A1. Clean and dry the inorganic fiber to obtain a pretreated inorganic fiber;

[0017] A2. Dissolve the amino-silane coupling agent and the acid anhydride in N,N-dimethylformamide, disperse them evenly, then add the pretreated inorganic fiber and deionized water, heat and react, and then take it out to obtain a crude inorganic fiber product;

[0018] A3. Wash and dry the crude inorganic fiber product to obtain the carboxylated inorganic fiber;

[0019] Step B includes:

[0020] B1. Perform surface plasma treatment on the boron nitride to obtain pretreated boron nitride;

[0021] B2. After dispersing the pretreated boron nitride, add an amino-silane coupling agent, heat and react, and then take it out to obtain a crude boron nitride product;

[0022] B3. Wash and dry the crude boron nitride product to obtain the amino-modified boron nitride;

[0023] Step C includes:

[0024] C1. Treat the ceramic powder in an acid agent, then wash and dry it to obtain a pretreated ceramic powder;

[0025] C2. Disperse the pretreated ceramic powder, then add an amino-silane coupling agent and heat for reaction. After that, take it out to obtain a crude ceramic powder product;

[0026] C3. Wash and dry the crude ceramic powder product to obtain the amino-modified ceramic powder;

[0027] Step D includes: Disperse the carboxylated inorganic fiber in deionized water, then add the amino-modified boron nitride, the amino-modified ceramic powder, and the crosslinking agent. After dispersing evenly, carry out a hydrothermal reaction to obtain the composite thermal conductive fiber.

[0028] Preferably, step A includes:

[0029] A1. Immerse the inorganic fiber in ethanol or deionized water, ultrasonically clean for 20 - 30 minutes, then filter and dry to obtain a pretreated inorganic fiber;

[0030] A2. Dissolve the amino-silane coupling agent and the acid anhydride in N,N-dimethylformamide, disperse evenly, then add the pretreated inorganic fiber and deionized water, and heat for reaction at 40 - 60 °C for 3 - 6 hours. After that, centrifuge and take it out to obtain a crude inorganic fiber product; the weight ratio of the amino-silane coupling agent, the acid anhydride, N,N-dimethylformamide, the inorganic fiber, and deionized water is 5 - 10:1 - 1.2:50 - 100:10:10 - 30;

[0031] 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.

[0032] Step B includes:

[0033] B1. Carry out surface plasma treatment on the boron nitride in an oxygen or argon environment for 10 - 30 minutes to obtain a pretreated boron nitride;

[0034] B2. Disperse the pretreated boron nitride in an ethanol / water solution, ultrasonically disperse for 20 - 40 minutes, then add an amino-silane coupling agent, and heat and stir for reaction at 60 - 80 °C for 4 - 12 hours. After the reaction is completed, take it out 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;

[0035] B3. Filter the crude boron nitride product, wash it with ethanol or deionized water, and vacuum dry it at 60 - 80 °C to obtain the amino-modified boron nitride;

[0036] Step C includes:

[0037] C1. Immerse the ceramic powder in a dilute nitric acid solution with a mass fraction of 10 - 12%, perform ultrasonic treatment for 30 - 60 minutes, then filter, wash, and dry to obtain the pretreated ceramic powder;

[0038] C2. Disperse the pretreated ceramic powder in an ethanol / water solution, perform ultrasonic dispersion 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 the crude ceramic powder product; the weight ratio of the amino-silane coupling agent to the pretreated ceramic powder is 0.5 - 5:100;

[0039] 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;

[0040] Step D includes: Disperse the carboxylated inorganic fiber in deionized water, then add 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.

[0041] Preferably, the inorganic fiber includes one or more of glass fiber, basalt fiber, quartz fiber, alumina fiber, aluminum nitride fiber, silicon carbide fiber, 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, 3-aminoethylaminopropyltrimethoxysilane; the acid anhydride includes one or more of succinic anhydride, 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 silica, alumina, magnesia, zinc oxide, 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.

[0042] More preferably, the ceramic powder is alumina.

[0043] Preferably, the weight ratio of the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and the epichlorohydrin in step D is 30-50:20-30:20-40:20-40.

[0044] As a cross-linking agent for carboxyl and amino groups, epichlorohydrin can utilize the carboxyl groups in the carboxylated inorganic fiber and the amino groups in the amino-modified boron nitride and amino-modified ceramic powder to carry out chemical reactions, 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 conduction path, and improving the thermal conductivity of the resin composition.

[0045] Preferably, the hydrothermal reaction temperature is 90-120 °C, and the reaction time is 2-3 hours.

[0046] An application of the resin composition for the high modulus and high thermal conductivity copper clad laminate described above, which is used for one or more of prepregs and copper clad laminates.

[0047] A prepreg or copper clad laminate obtained by the above application.

[0048] Preferably, the prepreg includes a reinforcing substrate and the resin composition attached thereto by impregnation and drying.

[0049] 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 layers of prepregs stacked together.

[0050] A copper clad laminate obtained by the above application.

[0051] A preparation method of the copper clad laminate as described above, which includes the following steps:

[0052] 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 manufacturing method of the 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.

[0053] Implementing the present invention has the following beneficial effects:

[0054] 1. By using the filler surface modification technology to amino-functionalize boron nitride and ceramic powder, the present invention improves the compatibility and dispersibility of boron nitride and ceramic powder in the resin, increases the addition amount of boron nitride without affecting the heat resistance and peel strength of the prepared laminate, and the peel strength of the copper foil reaches more than 1.0 N / mm.

[0055] 2. The present invention uses a surface modification grafting technique to graft boron nitride and ceramic powder onto an inorganic fiber as the basic framework, establishing an effective heat conduction path, enhancing the thermal conductivity of the resin composition, and achieving a thermal conductivity of the prepared copper clad laminate of over 1.5 W / (m·K). At the same time, the bending modulus and bending strength of the copper clad laminate are also improved, and the thermal expansion coefficient of the copper clad laminate is reduced, etc. Detailed Embodiments

[0056] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the specific embodiments.

[0057] The raw materials used in the following examples and comparative examples are described as follows:

[0058] Glass fiber: chopped glass fiber (Nanjing Fiberglass Research and Design Institute Co., Ltd.)

[0059] Aluminum nitride fiber: aluminum nitride fiber (Xiamen Juchi Technology Co., Ltd.)

[0060] Boron nitride: NA50 (average particle size of 0.05 μm, Dandong Chemical Research Institute Co., Ltd.)

[0061] NA400 (average particle size of 0.4 μm, Dandong Chemical Research Institute Co., Ltd.)

[0062] HFLI (average particle size of 7 μm, Dandong Chemical Research Institute Co., Ltd.)

[0063] Aluminum oxide: E-HJA-005S (D50 of 0.3 μm, Anhui Yestone Materials Technology Co., Ltd.)

[0064] SLA-1 (D50 of 1.2 μm, Anhui Yestone Materials Technology Co., Ltd.)

[0065] SLA10 (D50 of 10 μm, Anhui Yestone Materials Technology Co., Ltd.)

[0066] Nitrile resin: phthalonitrile resin (Chengdu Keyi High Polymer Technology Co., Ltd.)

[0067] Glass fiber cloth: 2116 cloth (Henan Guangyuan New Materials Co., Ltd.)

[0068] Example 1:

[0069] Step 1: Immerse the glass fiber (with a diameter of 1 μm and a length of 100 μm) in ethanol and ultrasonically clean it for 20 minutes. Then filter and dry the glass fiber to obtain the pretreated glass fiber. Dissolve 3-aminopropyltrimethoxysilane and succinic anhydride in N,N-dimethylformamide, disperse them evenly, add the pretreated glass fiber 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 fiber.

[0070] 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 it for 20 minutes, add an amino silane coupling agent, 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 3: Immerse alumina (with an average particle size of 0.3 μm) in a 10% by mass dilute nitric acid solution, ultrasonically treat it for 30 minutes, filter, wash, and dry to obtain pretreated alumina. Disperse the pretreated alumina in an ethanol / water solution, ultrasonically disperse it for 20 minutes, add an amino silane coupling agent, and 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 alumina.

[0072] Step 4: Disperse the carboxylated glass fiber in deionized water, add amino-modified boron nitride, amino-modified alumina, 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 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.

[0073] Step 5: A resin composition, including by mass percentage: 35% nitrile resin and 65% composite heat-conducting fiber. Add the above resin composition to DMF solvent, stir evenly, and then impregnate 2116 glass fiber cloth with it, and bake it in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0074] Step 6: Stack 10 pieces of the prepregs prepared above, cover one thickness of 35-micron copper foil on the top and bottom respectively, 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.

[0075] Example 2

[0076] A method for preparing a resin composition, a prepreg, and a copper clad laminate, which is different from Example 1 only in that step 4 is different, specifically as follows:

[0077] 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: 40% glass fiber, 20% boron nitride, and 40% alumina.

[0078] Example 3

[0079] 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: 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, 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.

[0080] Step 3: Immerse alumina (with an average particle size of 1.2 μm) in a 10% by mass fraction 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 and react at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0081] 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, 30% boron nitride, and 20% alumina.

[0082] Step 5: A resin composition, by mass percentage, includes: 20% of nitrile resin and 80% of composite heat-conducting fibers. Add the above resin composition into DMF solvent, stir evenly, then impregnate 2116 fiberglass cloth with it, and bake in an oven at 170 °C for 5 minutes to obtain a prepreg sheet.

[0083] Step 6: Stack 10 pieces of the prepreg sheets prepared above, cover one sheet of 35-micron-thick metallic copper foil on each of the upper and lower sides, place them in a vacuum hot press for lamination, laminate at a temperature of 230 °C for 2 hours to obtain a copper-clad laminate with a thickness of 1.0 mm.

[0084] Example 4

[0085] Step 1: Immerse glass fibers (with a diameter of 0.2 μm and a length of 200 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, then add the pretreated glass fibers and deionized water, heat and react at 60 °C for 4 hours, then take out by centrifugation, 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 0.05 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.

[0086] Step 3: Immerse alumina (with an average particle size of 10 μm) in a 10% by mass fraction 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 and react at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0087] Step 4: Disperse the 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% of glass fiber, 30% of boron nitride, and 20% of alumina.

[0088] Step 5: A resin composition, comprising by mass percentage: 50% of nitrile resin and 50% of composite heat-conducting fibers. Add the above resin composition into DMF solvent, stir evenly, then impregnate 2116 fiberglass cloth therewith, and bake in an oven at 170 °C for 5 minutes to obtain a prepreg sheet.

[0089] Step 6: Stack 10 pieces of the prepreg sheets 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, laminate at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0090] Example 5

[0091] Step 1: Immerse aluminum nitride fibers (with a diameter of 3 μm and a length of 350 μm) in ethanol, ultrasonically clean 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, then add the pretreated aluminum nitride 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 aluminum nitride fibers.

[0092] 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, ultrasonically disperse for 20 minutes, add an amino silane coupling agent thereto, heat and stir at 80 °C for 10 hours, after the reaction is completed, filter, wash and dry the reaction product to obtain amino-modified boron nitride.

[0093] Step 3: 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 at 80 °C for 15 hours, after the reaction is completed, filter, wash and dry the reaction product to obtain amino-modified alumina.

[0094] Step 4: Disperse the carboxylated aluminum nitride 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 composite heat-conducting fibers of aluminum nitride fibers grafted with boron nitride / alumina. By mass percentage, the component ratio in the preparation of the composite heat-conducting fibers is: 50% of aluminum nitride fibers, 25% of boron nitride, and 25% of alumina.

[0095] Step 5: A resin composition, by mass percentage, includes: 40% of nitrile resin and 60% of composite heat-conducting fibers. Add the above resin composition into DMF solvent, stir evenly, then impregnate 2116 fiberglass cloth with it, and bake it in an oven at 170 °C for 10 min to obtain a prepreg sheet.

[0096] Step 6:

[0097] Stack 10 pieces of the prepreg sheets prepared above, cover one sheet on 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.

[0098] Example 6

[0099] Step 1: Immerse aluminum nitride fibers (with a diameter of 0.2 μm and a length of 250 μm) in ethanol, ultrasonically clean 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, then add the pretreated aluminum nitride fibers and deionized water, heat and react at 60 °C for 4 hours, then take out by centrifugation, 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, 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.

[0100] Step 3: Immerse alumina (with an average particle size of 1.2 μm) in a 10% by mass fraction 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 and react at 80 °C for 15 hours, after the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0101] Step 4: Disperse the carboxylated aluminum nitride fibers in deionized water, add the 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 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% of aluminum nitride fibers, 30% of boron nitride, and 30% of alumina.

[0102] Step 5: A resin composition, by mass percentage, includes: 50% of nitrile resin and 50% of composite heat-conducting fibers. Add the above resin composition into DMF solvent, stir evenly, then impregnate 2116 fiberglass cloth with it, and bake it in an oven at 170 °C for 10 min to obtain a prepreg.

[0103] Step 6: 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, laminate at 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0104] Comparative Example 1

[0105] Compared with Examples 1 to 4, the difference in Comparative Example 1 is that it does not contain any fillers, specifically as follows:

[0106] Impregnate 2116 fiberglass cloth with nitrile resin, and bake it in an oven at 170 °C for 10 min to obtain a prepreg. 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, laminate at 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0107] Comparative Example 2

[0108] A preparation method of a resin composition, prepreg and copper clad laminate, compared with Example 1, the difference is that the inorganic fibers are not subjected to modification treatment, specifically as follows:

[0109] Step 1: Perform surface plasma treatment on boron nitride (average particle size is 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, heat and stir at 80 °C for 10 hours. After the reaction is completed, filter, wash and dry the reaction product to obtain amino-modified boron nitride.

[0110] Step 2: Immerse alumina (average particle size is 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 at 80 °C for 15 hours. After the reaction is completed, filter, wash and dry the reaction product to obtain amino-modified alumina.

[0111] Step 3: Disperse glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina and epichlorohydrin, and 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.

[0112] Step 4: A resin composition, by mass percentage, includes: 35% nitrile resin and 65% fiber / ceramic powder. Add the above resin composition into 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.

[0113] Step 5: 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.

[0114] Comparative Example 3

[0115] A preparation method of a resin composition, prepreg and copper clad laminate, compared with Example 1, the difference is that boron nitride is not subjected to modification treatment, specifically as follows:

[0116] Step 1: Immerse glass fibers (with a diameter of 1 μm and a length of 100 μm) in ethanol, 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, then 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: Immerse alumina (with an average particle size of 0.3 μm) in a 10% 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 to it, 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 alumina.

[0117] Step 3: Disperse 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, then carry out 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.

[0118] Step 4: A resin composition, by mass percentage, includes: 35% of nitrile resin and 65% of fiber / ceramic powder. Add the above resin composition into DMF solvent, stir evenly, then impregnate 2116 fiberglass cloth with it, and bake it in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0119] Step 5: Stack 10 pieces of the prepregs prepared above, cover each of the upper and lower sides with a copper foil with a thickness of 35 microns, place them in a vacuum hot press for lamination, and laminate them at a temperature of 230 °C for 2 hours to obtain a copper clad laminate with a thickness of 1.0 mm.

[0120] Comparative Example 4

[0121] A method for preparing a resin composition, prepreg, and copper clad laminate, compared with Example 1, the difference is that alumina is not subjected to modification treatment, specifically as follows:

[0122] Step 1: Immerse glass fibers (with a diameter of 1 μm and a length of 100 μm) in ethanol, 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, then 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: 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, 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.

[0123] Step 3: Disperse the carboxylated glass fibers in deionized water, add amino-modified boron nitride, alumina (with an average particle size of 0.3 um), and epichlorohydrin, disperse evenly, then carry out 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% of glass fibers, 30% of boron nitride, and 20% of alumina.

[0124] Step 4: A resin composition, by mass percentage, includes: 35% of nitrile resin and 65% of fiber / ceramic powder. Add the above resin composition into DMF solvent, stir evenly, then impregnate 2116 fiberglass cloth with it, and bake it in an oven at 170 °C for 5 minutes to obtain a prepreg.

[0125] Step 5: Stack 10 pieces of the above-prepared prepregs, cover each with a 35-micron-thick metallic copper foil on the top and bottom, place them in a vacuum hot press for lamination, laminate at 230 °C for 2 hours to obtain a copper-clad laminate with a thickness of 1.0 mm.

[0126] Comparative Example 5

[0127] A resin composition, prepreg, and method for preparing a copper-clad laminate, compared with Example 1, are different in that inorganic fibers are not included, specifically as follows:

[0128] Step 1: Perform surface plasma treatment on boron nitride (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, heat and stir at 80 °C for 10 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified boron nitride.

[0129] Step 2: Immerse alumina (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 at 80 °C for 15 hours. After the reaction is completed, filter, wash, and dry the reaction product to obtain amino-modified alumina.

[0130] Step 3: A resin composition, by mass percentage, includes: 35% nitrile resin, 30% amino-functionalized boron nitride, and 35% amino-functionalized alumina. 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.

[0131] Step 4: Stack 10 pieces of the above-prepared prepregs, cover each with a 35-micron-thick metallic copper foil on the top and bottom, place them in a vacuum hot press for lamination, laminate at 230 °C for 2 hours to obtain a copper-clad laminate with a thickness of 1.0 mm.

[0132] Comparative Example 6

[0133] A resin composition, prepreg, and method for preparing a copper-clad laminate, compared with Example 1, are different only in Step 4, specifically as follows:

[0134] 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: 20% glass fiber, 30% boron nitride, and 50% alumina.

[0135] Comparative Example 7

[0136] A method for preparing a resin composition, a prepreg and a copper clad laminate, compared with Example 1, the difference lies only in that Step 4 is different, specifically as follows:

[0137] 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: 60% glass fiber, 20% boron nitride, and 20% alumina.

[0138] Comparative Example 8

[0139] A method for preparing a resin composition, a prepreg and a copper clad laminate, compared with Example 1, the difference lies in that Step 4 is different, specifically as follows:

[0140] 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, 10% boron nitride, and 40% alumina.

[0141] Comparative Example 9

[0142] A method for preparing a resin composition, a prepreg and a copper clad laminate, compared with Example 1, the difference lies in that Step 4 is different, specifically as follows:

[0143] Step 4: Disperse carboxylated glass fibers in deionized water, add amino-modified boron nitride, amino-modified alumina and epichlorohydrin, disperse evenly, and 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, 40% boron nitride, and 10% alumina.

[0144] Effect Example 1

[0145] Tables 1 to 3 show the ratios of the components in the formulations of Examples 1 to 6 and Comparative Examples 1 to 6.

[0146] Table 1

[0147]

[0148] Table 2

[0149]

[0150] Table 3

[0151]

[0152] Effect Example 2

[0153] Test the properties of the copper-clad laminates prepared in Examples 1 to 6 and Comparative Examples 1 to 9.

[0154] The performance test method is as follows:

[0155] (1) Thermal conductivity: Test according to the method of ASTM D5470-2017

[0156] (2) Flexural modulus: Test by the DMA method and according to the method of IPC-TM-650 2.4.24.4.

[0157] (3) Peel strength: Test according to the method of IPC-TM-650 2.4.8.

[0158] (4) Thermal stress: Float the copper-containing sample in a 288 °C tin furnace, record the time of board explosion and delamination. If there is no board explosion after 60 minutes of heating, record it as ">60 minutes".

[0159] (5) Coefficient of thermal expansion CTE: Test according to the method of IPC-TM-650 2.4.24

[0160] The test results are shown in Table 4.

[0161] Table 4

[0162]

[0163] The performance in Table 4 shows that the present invention prepares composite heat-conducting fibers by surface-modifying and grafting inorganic fibers, boron nitride, and ceramic powders. This not only solves the problems of compatibility and dispersibility of boron nitride and ceramic powders in the resin matrix, increases the interaction force between the filler and the resin, reduces the phonon scattering degree at the interface, reduces the thermal resistance, and improves the peel strength of the copper-clad laminate. At the same time, with inorganic fibers as the bridge, high heat-conducting boron nitride and ceramic powders 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 bending modulus of the copper-clad laminate is significantly increased, and its coefficient of thermal expansion is reduced. In Examples 1 to 6, the thermal conductivity of the copper-clad laminate is greater than 1.5 W / (m·K), the peel strength reaches 1.14 to 1.45 N / mm, the bending modulus is between 28 and 34 GPa, the thermal shock is greater than 60 minutes, the coefficients of thermal expansion in the X and Y directions are 9.3 to 14.8 ppm / °C, and the coefficient of thermal expansion in the Z direction is 23.8 to 26.6 ppm / °C.

[0164] 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 fibers, the thermal conductivity is significantly improved, and the coefficient of thermal expansion is significantly reduced.

[0165] From the comparison of the performance data of Example 1 and Comparative Examples 2, 3, and 4, it can be seen that for the fibers and ceramic powders without surface modification, there is no binding force between them, the formed heat-conducting path is insufficient, and the copper-clad laminate has a low thermal conductivity and a low peel strength.

[0166] Regarding the addition ratio of inorganic fibers, from the comparison of Example 1 and Comparative Examples 5, 6, and 7, it can be seen that if the addition ratio of inorganic fibers is too low or too high, the thermal conductivity, bending modulus, and peel strength of the copper-clad laminate all decrease significantly, and the coefficient of thermal expansion will also increase.

[0167] Regarding the addition ratio of boron nitride and ceramic powders, from the comparison of Example 1 and Comparative Examples 8 and 9, it can be seen that if the addition ratio of boron nitride is too low and the addition ratio of ceramic powders is too high, the thermal conductivity of the copper-clad laminate decreases significantly; if the addition ratio of boron nitride is too high and the addition ratio of ceramic powders is too low, the peel strength and thermal shock of the copper-clad laminate decrease significantly.

[0168] The above are only the preferred embodiments of the present invention, and do not limit the technical scope of the present invention. Therefore, any minor modifications, equivalent changes, and decorations 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 a high modulus and high thermal conductivity copper clad laminate, characterized in that, It includes the following raw materials: nitrile resin, composite heat-conducting fiber; the composite heat-conducting fiber is composed of carboxylated inorganic fiber, amino-modified boron nitride, amino-modified ceramic powder, and cross-linking agent; 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; the ceramic powder includes one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, and titanium dioxide.

2. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 1, wherein The weight ratio of the nitrile resin to the composite heat-conducting fiber is 20-50:50-80.

3. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 1, wherein The preparation of the composite heat-conducting fiber includes the following steps: A. React the inorganic fiber with an amino-silane coupling agent, an acid anhydride, and deionized water to obtain the carboxylated inorganic fiber; B. React boron nitride with an amino-silane coupling agent to obtain the amino-modified boron nitride; C. React the ceramic powder with an amino-silane coupling agent to obtain the amino-modified ceramic powder; D. Mix the carboxylated inorganic fiber, the amino-modified boron nitride, the amino-modified ceramic powder, and the cross-linking agent, and carry out a hydrothermal reaction to obtain the composite heat-conducting fiber.

4. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 3, characterized in that, Step A includes: A1. Wash and dry the inorganic fiber to obtain pretreated inorganic fiber; A2. Dissolve the amino-silane coupling agent and the acid anhydride in N,N-dimethylformamide, disperse evenly, then add the pretreated inorganic fiber and deionized water, heat and react, and then take out to obtain a crude inorganic fiber product; A3. Wash and dry the crude inorganic fiber product to obtain the carboxylated inorganic fiber; Step B includes: B1. Carry out surface plasma treatment on the boron nitride to obtain pretreated boron nitride; B2. After dispersing the pretreated boron nitride, add an amino-silane coupling agent, heat and react, and then take out to obtain a crude boron nitride product; B3. Wash and dry the crude boron nitride product to obtain the amino-modified boron nitride; Step C includes: C1. Treat the ceramic powder in an acid agent, then wash and dry to obtain pretreated ceramic powder; C2. After dispersing the pretreated ceramic powder, add an amino-silane coupling agent, heat and react, and then take 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: Disperse the carboxylated inorganic fiber in deionized water, then add the amino-modified boron nitride, the amino-modified ceramic powder, and the cross-linking agent, disperse evenly, and carry out a hydrothermal reaction to obtain the composite heat-conducting fiber.

5. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 3, characterized in that, 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 pretreated inorganic fiber; A2. Dissolve the amino-silane coupling agent and the acid anhydride in N,N-dimethylformamide, disperse them evenly, then add the pretreated inorganic fiber and deionized water, and heat and react at 40 - 60 °C for 3 - 6 hours. After that, take it out by centrifugation to obtain the crude inorganic fiber product; the weight ratio of the amino-silane coupling agent, the acid anhydride, the 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 it at 60 - 80 °C to obtain the carboxylated inorganic fiber; 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 it for 20 - 40 minutes, then add the amino-silane coupling agent, and heat and stir to react at 60 - 80 °C for 4 - 12 hours. After the reaction is completed, take it out to obtain the 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 it 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 it for 30 - 60 minutes, and then filter, wash, and dry it to obtain the pretreated ceramic powder; C2. Disperse the pretreated ceramic powder in an ethanol / water solution, ultrasonically disperse it for 20 - 40 minutes, then add the 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 the 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: Disperse the carboxylated inorganic fiber in deionized water, then add the amino-modified boron nitride, the amino-modified ceramic powder, and the crosslinking agent, disperse them evenly, and perform hydrothermal reaction at 90 - 120 °C for 2 - 3 hours to obtain the composite thermal conductive fiber.

6. The resin composition for high modulus and high thermal conductivity copper clad laminate according to claim 3, wherein The inorganic fibers include one or more of glass fibers, basalt fibers, quartz fibers, alumina fibers, aluminum nitride fibers, silicon carbide fibers, and diamond fibers; the diameter of the inorganic fibers is 0.2 to 10 μm; the length of the inorganic fibers is 100 to 500 μm; the aminosilane coupling agent includes one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminoethylaminopropyltrimethoxysilane; the 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 to 10 μm; the ceramic powder includes one or more of silica, alumina, magnesia, zinc oxide, and titanium dioxide; the particle size of the ceramic powder is 0.3 to 10 μm; the crosslinking agent includes epichlorohydrin; in step D, the weight ratio of the carboxylated inorganic fibers, the amino-modified boron nitride, the amino-modified ceramic powder, and the crosslinking agent is 30 to 50: 20 to 30: 20 to 40: 20 to 40.

7. An application of the resin composition for high modulus and high thermal conductivity copper clad laminates according to claim 1, characterized in that, One or more of prepregs and copper clad laminates.

8. A prepreg obtained by the application according to claim 7.

9. A copper clad laminate obtained by the application according to claim 7.

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