Silicon nitride toughened hydrocarbon resin for copper-clad plate and preparation method thereof

Abstract

According to the silicon nitride toughened hydrocarbon resin for the copper-clad plate and the preparation method of the silicon nitride toughened hydrocarbon resin, the heat conductivity coefficient of a prepreg can be effectively improved, so that when the hydrocarbon resin is used in the copper-clad plate, the heat conductivity of the copper-clad plate can be effectively improved, and heat of the copper-clad plate can be quickly diffused out; damage caused by local heating of the surface of the copper-clad plate can be effectively avoided; silicon powder in the modified filler is subjected to protein foaming and in-situ sintering treatment to generate a silicon nitride three-dimensional network skeleton, the three-dimensional network skeleton and a continuous heat conduction path are constructed in hydrocarbon resin, heat conduction is accelerated, a complex of 2-ethyl-4-methylimidazole and silver acetate is deposited on the surfaces of boron nitride and the silicon nitride three-dimensional network skeleton, and the heat conduction efficiency is improved. A network structure formed by the boron nitride and silicon nitride three-dimensional network skeleton and the nano-silver fibers can play roles in transferring stress and preventing crack expansion, so that the heat-conducting property of the hydrocarbon resin can be effectively improved, and the toughening effect of the hydrocarbon resin is ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrocarbon resins, and more specifically, to a silicon nitride toughened hydrocarbon resin for copper clad laminates and a preparation method thereof. Background Art

[0002] The development of 5G communications has led to the rapid popularization of 5G communication equipment and the rapid development of the high-frequency PCB industry. Most 5G devices work in harsh environments such as high temperature, high radiation, and high cold. Therefore, the circuit boards used in 5G devices are different from ordinary circuit boards. The circuit boards used in 5G devices must operate stably in these harsh environments to meet the needs of the equipment. The performance of high-frequency copper clad laminate materials is mainly measured by two indicators: dielectric constant (Dk) and dielectric loss factor (Df). The smaller the Dk and Df, the more stable they are, and the better the performance of the high-frequency and high-speed substrate.

[0003] Common high-frequency and high-speed circuit board materials are as follows: hydrocarbon resin, LCP liquid crystal polymer, PTFE, PPE / PPO, etc.; hydrocarbon resin refers to polyolefin homopolymer or copolymer, including butadiene styrene copolymer, styrene homopolymer, butadiene homopolymer, styrene / divinylbenzene copolymer, styrene-butadiene-divinylbenzene copolymer, etc. Most hydrocarbon resins have excellent dielectric properties, high heat resistance, and good chemical resistance.

[0004] Currently, when hydrocarbon resin is applied to copper clad laminates, the thermal conductivity of hydrocarbon resin is poor, resulting in poor heat dissipation performance of the copper clad laminates. The heat of the copper clad laminates cannot be quickly diffused away, causing the surface of the copper clad laminates to be easily locally heated, causing serious damage to the copper clad laminates. Summary of the invention

[0005] In order to overcome the above-mentioned defects of the prior art, an embodiment of the present invention provides a silicon nitride toughened hydrocarbon resin for copper clad laminates and a preparation method thereof.

[0006] A silicon nitride toughened hydrocarbon resin for copper clad laminate comprises, by weight percentage, 28-32% of epoxy resin, 1.3-1.7% of curing agent, 18-22% of modified filler, and the rest of hydrocarbon resin.

[0007] Furthermore, the raw materials of the modified filler are calculated by weight percentage as follows: 5.1-5.9% of 2-ethyl-4-methylimidazole, 3.6-4.6% of silver acetate, 30.0-33.0% of silicon powder, 0.9-1.0% of dispersant, 2.1-2.7% of foaming agent, 1.2-1.8% of sintering aid, 30.0-33.0% of deionized water, and the rest is boron nitride.

[0008] Further, a silicon nitride toughened hydrocarbon resin for a copper clad laminate, calculated by weight percentage: 30-32% of epoxy resin, 1.5-1.7% of curing agent, 20-22% of modified filler, and the rest is hydrocarbon resin; the raw materials of the modified filler are calculated by weight percentage: 5.5-5.9% of 2-ethyl-4-methylimidazole, 4.1-4.6% of silver acetate, 31.5-33.0% of silicon powder, 0.95-1.0% of dispersant, 2.4-2.7% of foaming agent, 1.5-1.8% of sintering aid, 31.5-33.0% of deionized water, and the rest is boron nitride.

[0009] Further, a silicon nitride toughened hydrocarbon resin for a copper clad laminate, calculated by weight percentage: 30% of epoxy resin, 1.5% of curing agent, 20% of modified filler, and the rest is hydrocarbon resin; the raw materials of the modified filler are calculated by weight percentage: 5.5% of 2-ethyl-4-methylimidazole, 4.1% of silver acetate, 31.5% of silicon powder, 0.95% of dispersant, 2.4% of foaming agent, 1.5% of sintering aid, 31.5% of deionized water, and the rest is boron nitride.

[0010] Further, for a silicon nitride toughened hydrocarbon resin for a copper clad laminate, the curing agent is one or a combination of hexamethylenediamine, diethylenetriamine, triethylenetetramine, and diethylaminopropylamine; the dispersant is citric acid; the foaming agent is protein powder; the sintering aid is prepared by mixing alumina and yttrium fluoride in a weight ratio of 2:1.

[0011] A preparation method of a silicon nitride toughened hydrocarbon resin for a copper clad laminate, the specific preparation steps are as follows:

[0012] Step 1: Weigh the epoxy resin, curing agent, hydrocarbon resin, 2-ethyl-4-methylimidazole, silver acetate, silicon powder, dispersant, foaming agent, sintering aid, deionized water, and boron nitride in the raw materials of the modified filler.

[0013] Step 2: Add the silicon powder, dispersant, and sintering aid to deionized water, and perform ultrasonic treatment for 20-40 minutes to obtain a suspension. Add the foaming agent to the suspension and perform ultrasonic treatment for 20-40 minutes to obtain a slurry; perform water bath curing treatment on the slurry to obtain a silicon-containing three-dimensional skeleton, let it stand, dry, take it out after demolding, and perform in-situ reaction sintering in a nitrogen atmosphere for 1-3 hours to obtain a silicon nitride three-dimensional network skeleton.

[0014] Step 3: Add 2-ethyl-4-methylimidazole and silver acetate to an organic solvent, perform ultrasonic treatment for 10-20 minutes to obtain a treatment solution, then add boron nitride and the silicon nitride three-dimensional network skeleton to the treatment solution, perform ultrasonic treatment for 40-60 minutes, and then age at room temperature for 24h and vacuum dry for 24h to obtain a modified filler.

[0015] Step 4: Heat the epoxy resin and the hydrocarbon resin, blend and stir for 20 to 30 minutes, add the modified filler, continue to heat and blend and stir for 40 to 60 minutes, add the curing agent, continue to heat and stir for 40 to 60 minutes, and obtain the silicon nitride toughened hydrocarbon resin for copper clad laminate.

[0016] Furthermore, in step 2, the ultrasonic frequency is 40-60 KHz, the ultrasonic power is 400-600 W, the water bath curing temperature is 65-75° C., and the sintering treatment is performed at a temperature of 1500-1600° C.

[0017] Furthermore, in step three, the weight ratio of the total weight of 2-ethyl-4-methylimidazole and silver acetate to the organic solvent is 1:45-55, the ultrasonic frequency is 1.2-1.6 MHz, the ultrasonic power is 400-600 W, and the vacuum drying temperature is higher than the boiling point of the organic solvent.

[0018] Furthermore, in step 4, the heating temperature is 55-65° C., and the stirring speed is 240-480 r / min.

[0019] Furthermore, in step 2, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; the water bath curing temperature is 70°C, and the sintering treatment is performed at a temperature of 1550°C; in step 3, the weight ratio of the total weight of 2-ethyl-4-methylimidazole and silver acetate to the organic solvent is 1:50, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 500W, and the vacuum drying temperature is higher than the boiling point of the organic solvent; in step 4, the heating temperature is 60°C, and the stirring speed is 360r / min.

[0020] Technical effects and advantages of the present invention:

[0021] 1. The silicon nitride toughened hydrocarbon resin for copper clad laminate prepared by the raw material formula of the present invention can effectively improve the thermal conductivity of the prepreg, so that the hydrocarbon resin can effectively improve the thermal conductivity of the copper clad laminate when used in the copper clad laminate, thereby improving the heat dissipation performance of the copper clad laminate, and can quickly diffuse the heat of the copper clad laminate, and can effectively avoid local heat damage to the surface of the copper clad laminate; the modified filler can effectively perform filler modification treatment on the hydrocarbon resin, and can effectively enhance the thermal conductivity and toughening modification effect of the hydrocarbon resin; the silicon powder in the modified filler is uniformly dispersed in deionized water under the action of a dispersant, and is uniformly blended with a sintering aid, and then foamed under the action of a foaming agent protein powder, and then in-situ sintered to generate Si 3 N 4The three-dimensional network skeleton makes the modified filler present a three-dimensional distribution, constructs a three-dimensional network skeleton and a continuous heat conduction path, helps to accelerate the conduction of heat, improves the overall thermal conductivity, can effectively reduce the contact thermal resistance between the filler and the epoxy resin and the hydrocarbon resin, can effectively improve the thermal conductivity of the hydrocarbon resin, and ensure the toughening effect of the hydrocarbon resin; the modified filler contains a complex of 2-ethyl-4-methylimidazole and silver acetate, and the complex of 2-ethyl-4-methylimidazole and silver acetate is deposited on the surface of the three-dimensional network skeleton of boron nitride and silicon nitride. The network structure formed by the three-dimensional network skeleton of boron nitride and silicon nitride and the nano-silver fiber can play a role in transferring stress and preventing crack expansion, which can effectively improve the thermal conductivity and toughening effect of the hydrocarbon resin;

[0022] 2. In the present invention, the silicon powder, dispersant and sintering aid are ultrasonically treated in deionized water, which can effectively enhance the uniform dispersion of silicon powder in deionized water, and ensure the rapid and uniform contact of silicon powder, dispersant and sintering aid; the suspension is added to the foaming agent for ultrasonic treatment, and a silicon-containing three-dimensional skeleton is obtained after water bath curing treatment; the silicon-containing three-dimensional skeleton is in-situ sintered to form a silicon nitride three-dimensional network skeleton; 2-ethyl-4-methylimidazole and silver acetate are added to an organic solvent for ultrasonic treatment to prepare a complex of 2-ethyl-4-methylimidazole and silver acetate; the boron nitride and silicon nitride three-dimensional network skeleton and the complex of 2-ethyl-4-methylimidazole and silver acetate are immersed in ultrasonic treatment, and then aged and vacuum treated. After drying, a complex of 2-ethyl-4-methylimidazole and silver acetate can be effectively deposited on the surface of the three-dimensional network skeleton of boron nitride and silicon nitride, and the organic solvent can be removed; the epoxy resin and the hydrocarbon resin are heated and blended, and the modified filler is added and then heated, blended and stirred to effectively decompose the complex deposited on the surface of the three-dimensional network skeleton of boron nitride and silicon nitride to produce 2-ethyl-4-methylimidazole, triggering a curing reaction of the epoxy resin, and the silver ions are reduced to nano silver, which are melt-sintered and interconnected with the three-dimensional network skeleton of boron nitride and silicon nitride to form a heat conduction path, thereby ensuring the rapid synthesis of the hydrocarbon resin, and forming a support frame inside the hydrocarbon resin, thereby effectively ensuring the thermal conductivity and toughening performance of the hydrocarbon resin. DETAILED DESCRIPTION

[0023] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] Embodiment 1:

[0025] The invention provides a silicon nitride toughened hydrocarbon resin for a copper clad laminate, comprising 280 g of epoxy resin, 13 g of diethylenetriamine, 180 g of modified filler and 527 g of hydrocarbon resin; raw materials of the modified filler are: 9.18 g of 2-ethyl-4-methylimidazole, 6.48 g of silver acetate, 54 g of silicon powder, 1.62 g of citric acid, 3.78 g of protein powder, 1.44 g of aluminum oxide, 0.72 g of yttrium fluoride, 54 g of deionized water and 48.78 g of boron nitride;

[0026] Epoxy resin was purchased from Jinan Shanhai Chemical Technology Co., Ltd. Phoenix brand epoxy E51; diethylenetriamine was purchased from Jinan Chuangshi Chemical Co., Ltd., item number: HG001; hydrocarbon resin was purchased from Foshan Ruisheng Plastic Co., Ltd., model: R1125; 2-ethyl-4-methylimidazole was purchased from Sinopharm Chemical Reagent Co., Ltd., national medicine code: XW010110; silver acetate was purchased from Sinopharm Chemical Reagent Co., Ltd., national medicine code: L01166001; silicon powder was purchased from Sinopharm Chemical Reagent Co., Ltd. Co., Ltd., National Medicine Code: 81012160; citric acid was purchased from Sinopharm Chemical Reagent Co., Ltd., National Medicine Code: 10007108; protein powder was purchased from soy protein isolate from Hebei Tuohai Biotechnology Co., Ltd.; alumina was purchased from Sinopharm Chemical Reagent Co., Ltd., National Medicine Code: 10000928; yttrium fluoride was purchased from Sinopharm Chemical Reagent Co., Ltd., National Medicine Code: XW1370949402; boron nitride was purchased from Yumu (Ningbo) New Materials Co., Ltd., item number: SD055-66;

[0027] The preparation method of silicon nitride toughened hydrocarbon resin for copper clad laminates, the specific preparation steps are as follows:

[0028] Step 1: weigh epoxy resin, diethylenetriamine, hydrocarbon resin in the raw materials, 2-ethyl-4-methylimidazole, silver acetate, silicon powder, citric acid, protein powder, alumina, yttrium fluoride, deionized water, and boron nitride in the modified filler raw materials;

[0029] Step 2: Add silicon powder, citric acid, aluminum oxide, and yttrium fluoride to deionized water, and ultrasonically treat for 30 minutes to obtain a suspension, add protein powder to the suspension, and ultrasonically treat for 30 minutes to obtain a slurry; subject the slurry to water bath curing to obtain a silicon-containing three-dimensional skeleton, let it stand, dry, remove it from the mold, and sinter it in situ for 2 hours in a nitrogen atmosphere to obtain a silicon nitride three-dimensional network skeleton;

[0030] Step 3: Add 2-ethyl-4-methylimidazole and silver acetate to dichloromethane, perform ultrasonic treatment for 15 minutes to obtain a treatment solution, then add boron nitride and silicon nitride three-dimensional network skeleton to the treatment solution, perform ultrasonic treatment for 50 minutes, and then age at room temperature for 24 hours, and then vacuum dry for 24 hours to obtain a modified filler;

[0031] Step 4: Heat the epoxy resin and the hydrocarbon resin, blend and stir for 25 minutes, add the modified filler, continue to heat and blend and stir for 50 minutes, add diethylenetriamine, continue to heat and stir for 50 minutes, and obtain silicon nitride toughened hydrocarbon resin for copper clad laminate.

[0032] In step 2, the ultrasonic frequency is 40KHz, the ultrasonic power is 400W; the water bath curing temperature is 65°C, and the sintering treatment is performed at a temperature of 1500°C; in step 3, the weight ratio of the total weight of 2-ethyl-4-methylimidazole and silver acetate to dichloromethane is 1:45, the ultrasonic frequency is 1.2MHz, the ultrasonic power is 400W, and the vacuum drying temperature is 60°C; in step 4, the heating temperature is 55°C, and the stirring speed is 240r / min.

[0033] Embodiment 2:

[0034] Different from Example 1, the copper clad laminate uses silicon nitride to toughen the hydrocarbon resin, and weighs 320g of epoxy resin, 17g of diethylenetriamine, 220g of modified filler, and 443g of hydrocarbon resin; the raw materials of the modified filler are: 12.98g of 2-ethyl-4-methylimidazole, 10.12g of silver acetate, 72.6g of silicon powder, 2.2g of citric acid, 5.94g of protein powder, 2.64g of aluminum oxide, 1.32g of yttrium fluoride, 72.6g of deionized water, and 39.6g of boron nitride.

[0035] Embodiment 3:

[0036] Different from Examples 1-2, the copper clad laminate uses silicon nitride to toughen hydrocarbon resin, and weighs 300g of epoxy resin, 15g of diethylenetriamine, 200g of modified filler, and 485g of hydrocarbon resin; the raw materials of the modified filler are: 11.0g of 2-ethyl-4-methylimidazole, 8.2g of silver acetate, 63.0g of silicon powder, 1.9g of citric acid, 4.8g of protein powder, 2.0g of aluminum oxide, 1.0g of yttrium fluoride, 63.0g of deionized water, and 45.1g of boron nitride.

[0037] Embodiment 4:

[0038] The difference from Example 3 is that in step 2, the ultrasonic frequency is 50KHz and the ultrasonic power is 500W; the water bath curing temperature is 70°C, and the sintering treatment is carried out at 1550°C; in step 3, the weight ratio of the total weight of 2-ethyl-4-methylimidazole and silver acetate to the organic solvent is 1:50, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 500W, and the vacuum drying temperature is higher than the boiling point of the organic solvent; in step 4, the heating temperature is 60°C and the stirring speed is 360r / min.

[0039] Comparative Example 1:

[0040] The difference from Example 4 is that: the copper clad laminate uses silicon nitride to toughen hydrocarbon resin, weigh 300g of epoxy resin, 15g of diethylenetriamine, 45.1g of filler, and 485g of hydrocarbon resin; the raw material of the filler is: 45.1g of boron nitride;

[0041] The preparation method of silicon nitride toughened hydrocarbon resin for copper clad laminates, the specific preparation steps are as follows:

[0042] Step 1: Weigh the epoxy resin, diethylenetriamine, hydrocarbon resin in the raw materials, and boron nitride in the filler raw materials;

[0043] Step 2: Heat and blend the epoxy resin and the hydrocarbon resin for 25 minutes, add the filler-boron nitride, continue to heat and blend for 50 minutes, add diethylenetriamine, continue to heat and blend for 50 minutes, and obtain silicon nitride toughened hydrocarbon resin for copper clad laminate;

[0044] In step 2, the heating temperature is 60° C. and the stirring speed is 360 r / min.

[0045] Comparative Example 2:

[0046] The difference from Example 4 is that the copper clad laminate uses silicon nitride to toughen hydrocarbon resin, weigh 300g of epoxy resin, 15g of diethylenetriamine, 132.7g of modified filler, and 485g of hydrocarbon resin; the raw materials of the modified filler are: 63.0g of silicon powder, 1.9g of citric acid, 4.8g of protein powder, and 63.0g of deionized water;

[0047] The preparation method of silicon nitride toughened hydrocarbon resin for copper clad laminates, the specific preparation steps are as follows:

[0048] Step 1: Weigh the epoxy resin, diethylenetriamine, hydrocarbon resin in the raw materials, silicon powder, citric acid, protein powder and deionized water in the modified filler raw materials;

[0049] Step 2: Add silicon powder, citric acid, aluminum oxide, and yttrium fluoride to deionized water, and ultrasonically treat for 30 minutes to obtain a suspension, add protein powder to the suspension, and ultrasonically treat for 30 minutes to obtain a slurry; subject the slurry to water bath curing to obtain a silicon-containing three-dimensional skeleton, let it stand, dry, remove it from the mold, and sinter it in situ for 2 hours in a nitrogen atmosphere to obtain a silicon nitride three-dimensional network skeleton;

[0050] Step 3: heat and blend the epoxy resin and the hydrocarbon resin for 25 minutes, add the silicon nitride three-dimensional network skeleton, continue to heat and blend for 50 minutes, add diethylenetriamine, continue to heat and blend for 50 minutes, and obtain the silicon nitride toughened hydrocarbon resin for copper clad laminate;

[0051] In step 2, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; the water bath curing temperature is 70°C, and the sintering treatment is performed at a temperature of 1550°C; in step 3, the heating temperature is 60°C, and the stirring speed is 360r / min.

[0052] Comparative Example 3:

[0053] The difference from Example 4 is that:

[0054] Silicon nitride toughened hydrocarbon resin for copper clad laminate, weigh 300g of epoxy resin, 15g of diethylenetriamine, 108.1g of modified filler, 485g of hydrocarbon resin; the raw materials of the modified filler are: 63.0g of silicon nitride, 45.1g of boron nitride;

[0055] The preparation method of silicon nitride toughened hydrocarbon resin for copper clad laminates, the specific preparation steps are as follows:

[0056] Step 1: Weigh the epoxy resin, diethylenetriamine, hydrocarbon resin in the raw materials, and the silicon nitride and boron nitride in the modified filler raw materials;

[0057] Step 2: heat and blend the epoxy resin and the hydrocarbon resin for 25 minutes, add silicon nitride and boron nitride, continue to heat and blend for 50 minutes, add diethylenetriamine, continue to heat and blend for 50 minutes, and obtain silicon nitride toughened hydrocarbon resin for copper clad laminate;

[0058] In step 2, the heating temperature is 60° C. and the stirring speed is 360 r / min.

[0059] The silicon nitride toughened hydrocarbon resin for copper clad laminates in the comparative examples and embodiments of the present invention was tested and treated:

[0060] First, electronic glass fiber cloth was impregnated in silicon nitride toughened hydrocarbon resin for copper clad laminate for 10 minutes, and then baked at 150°C for 5 minutes to obtain a prepreg, and the performance of the prepreg was tested;

[0061] GB / T1040.1-2018 is used to test the tensile strength of the prepreg;

[0062] The thermal conductivity of the prepreg was tested at room temperature using the TC3000E thermal conductivity meter hot wire method produced by Xi'an Xiaxi Electronic Technology Co., Ltd.

[0063] The results are shown in Table 1:

[0064] Table 1:

[0065]

[0066] It can be seen from the above table that the silicon nitride toughened hydrocarbon resin for the copper clad laminate of the present invention can effectively improve the thermal conductivity of the prepreg, so that when the hydrocarbon resin is used in the copper clad laminate, it can effectively improve the thermal conductivity of the copper clad laminate, thereby improving the heat dissipation performance of the copper clad laminate, and can quickly diffuse the heat of the copper clad laminate, which can effectively avoid local heat damage to the surface of the copper clad laminate.

[0067] The modified filler in the present invention can effectively perform filler modification treatment on hydrocarbon resin, and can effectively enhance the thermal conductivity and toughening modification effect of hydrocarbon resin; the silicon powder in the modified filler is uniformly dispersed in deionized water under the action of a dispersant, and is uniformly blended with a sintering aid, and then foamed under the action of a foaming agent protein powder, and then in-situ sintered to generate Si 3 N 4The three-dimensional network skeleton makes the modified filler present a three-dimensional distribution, constructs a three-dimensional network skeleton and a continuous heat conduction path, helps to accelerate the conduction of heat, improves the overall thermal conductivity, can effectively reduce the contact thermal resistance between the filler and the epoxy resin and the hydrocarbon resin, can effectively improve the thermal conductivity of the hydrocarbon resin, and ensure the toughening effect of the hydrocarbon resin; in the modified filler, 2-ethyl-4-methylimidazole and silver acetate are jointly formed in dichloromethane to form a complex of 2-ethyl-4-methylimidazole and silver acetate, after adding boron nitride and silicon nitride three-dimensional network skeletons thereto, the complex of 2-ethyl-4-methylimidazole and silver acetate is deposited on the surface of the boron nitride and silicon nitride three-dimensional network skeletons, and under heating conditions, the complex is deposited on the boron nitride and silicon nitride three-dimensional network skeletons. The complex of 2-ethyl-4-methylimidazole and silver acetate on the surface of the frame decomposes to produce 2-ethyl-4-methylimidazole, which triggers the curing reaction of the epoxy resin. At the same time, the Ag+ ions are reduced to nanosilver, which are melt-sintered and interconnected with the three-dimensional network skeleton of boron nitride and silicon nitride to form a heat conduction path. The network structure formed by the three-dimensional network skeleton of boron nitride and silicon nitride and the nanosilver fibers can transfer stress and prevent crack expansion, which can effectively improve the thermal conductivity and toughening effect of hydrocarbon resin. In step 2, the silicon powder, dispersant, and sintering aid are ultrasonically treated in deionized water, which can effectively enhance the uniform dispersion of silicon powder in deionized water, and at the same time ensure the rapid and uniform contact of silicon powder, dispersant and sintering aid, which is convenient for subsequent treatment. , adding a foaming agent to the suspension for ultrasonic treatment, so that the foaming agent protein powder foams the silicon powder, and a silicon-containing three-dimensional skeleton is obtained after water bath curing treatment, and the silicon-containing three-dimensional skeleton is in-situ sintered to form a silicon nitride three-dimensional network skeleton; in step three, 2-ethyl-4-methylimidazole and silver acetate are added to an organic solvent for ultrasonic treatment, which can effectively produce a complex of 2-ethyl-4-methylimidazole and silver acetate, which is convenient for subsequent surface deposition treatment of the complex with boron nitride and silicon nitride three-dimensional network skeleton, and the boron nitride and silicon nitride three-dimensional network skeleton and the complex of 2-ethyl-4-methylimidazole and silver acetate are immersed in ultrasonic treatment, and then after aging and vacuum drying, the surface of the boron nitride and silicon nitride three-dimensional network skeleton can be effectively deposited. The complex of 2-ethyl-4-methylimidazole and silver acetate can effectively remove the organic solvent during the vacuum drying process; in step 4, the epoxy resin and the hydrocarbon resin are heated and blended, which can effectively ensure the rapid compounding of the epoxy resin and the hydrocarbon resin, and the modified filler is added and then continued to be heated, blended and stirred, which can effectively decompose the complex deposited on the surface of the three-dimensional network skeleton of boron nitride and silicon nitride to produce 2-ethyl-4-methylimidazole, triggering the curing reaction of the epoxy resin, and the silver ions are reduced to nanosilver, which are melt-sintered and interconnected with the three-dimensional network skeleton of boron nitride and silicon nitride to form a heat conduction path, ensuring the rapid synthesis of the hydrocarbon resin, and at the same time forming a supporting framework inside the hydrocarbon resin, which can effectively ensure the thermal conductivity and toughening performance of the hydrocarbon resin.

[0068] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A silicon nitride toughened hydrocarbon resin for copper clad laminate, characterized in that: The composition is calculated by weight percentage as follows: 28-32% epoxy resin, 1.3-1.7% curing agent, 18-22% modified filler, and the rest is hydrocarbon resin.

2. The silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 1, characterized in that: The raw materials of the modified filler are calculated by weight percentage as follows: 5.1-5.9% 2-ethyl-4-methylimidazole, 3.6-4.6% silver acetate, 30.0-33.0% silicon powder, 0.9-1.0% dispersant, 2.1-2.7% foaming agent, 1.2-1.8% sintering aid, 30.0-33.0% deionized water, and the rest is boron nitride.

3. The silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 2, characterized in that: The composition is calculated by weight as follows: 30-32% epoxy resin, 1.5-1.7% curing agent, 20-22% modified filler, and the rest is hydrocarbon resin; the raw materials of the modified filler are calculated by weight as follows: 5.5-5.9% 2-ethyl-4-methylimidazole, 4.1-4.6% silver acetate, 31.5-33.0% silicon powder, 0.95-1.0% dispersant, 2.4-2.7% foaming agent, 1.5-1.8% sintering aid, 31.5-33.0% deionized water, and the rest is boron nitride.

4. The silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 2, characterized in that: The weight percentage is: 30% epoxy resin, 1.5% curing agent, 20% modified filler, and the rest is hydrocarbon resin; the raw materials of the modified filler are calculated by weight percentage: 5.5% 2-ethyl-4-methylimidazole, 4.1% silver acetate, 31.5% silicon powder, 0.95% dispersant, 2.4% foaming agent, 1.5% sintering aid, 31.5% deionized water, and the rest is boron nitride.

5. The silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 2, characterized in that: The curing agent is one or more of hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine; the dispersant is citric acid; the foaming agent is protein powder; and the sintering aid is alumina and yttrium fluoride compounded in a weight ratio of 2:

1.

6. A method for preparing silicon nitride toughened hydrocarbon resin for copper clad laminate, characterized in that: The specific preparation steps are as follows: Step 1: weigh the epoxy resin, curing agent, hydrocarbon resin in the raw materials, 2-ethyl-4-methylimidazole, silver acetate, silicon powder, dispersant, foaming agent, sintering aid, deionized water, and boron nitride in the modified filler raw materials; Step 2: Add silicon powder, dispersant and sintering aid to deionized water, ultrasonically treat for 20 to 40 minutes to obtain a suspension, add a foaming agent to the suspension, and ultrasonically treat for 20 to 40 minutes to obtain a slurry; subject the slurry to water bath curing to obtain a silicon-containing three-dimensional skeleton, let it stand, dry, take it out after demolding, and sinter it in situ in a nitrogen atmosphere for 1 to 3 hours to obtain a silicon nitride three-dimensional network skeleton; Step 3: adding 2-ethyl-4-methylimidazole and silver acetate to an organic solvent, ultrasonically treating for 10 to 20 minutes to obtain a treatment solution, then adding boron nitride and silicon nitride three-dimensional network skeleton to the treatment solution, ultrasonically treating for 40 to 60 minutes, aging at room temperature for 24 hours, and vacuum drying for 24 hours to obtain a modified filler; Step 4: Heat the epoxy resin and the hydrocarbon resin, blend and stir for 20 to 30 minutes, add the modified filler, continue to heat and blend and stir for 40 to 60 minutes, add the curing agent, continue to heat and stir for 40 to 60 minutes, and obtain the silicon nitride toughened hydrocarbon resin for copper clad laminate.

7. The method for preparing a silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 6, characterized in that: In step 2, the ultrasonic frequency is 40-60 KHz, the ultrasonic power is 400-600 W, the water bath curing temperature is 65-75° C., and the sintering treatment is performed at a temperature of 1500-1600° C.

8. The method for preparing a silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 7, characterized in that: In step three, the weight ratio of the total weight of 2-ethyl-4-methylimidazole and silver acetate to the organic solvent is 1:45-55, the ultrasonic frequency is 1.2-1.6 MHz, the ultrasonic power is 400-600 W, and the vacuum drying temperature is higher than the boiling point of the organic solvent.

9. The method for preparing a silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 8, characterized in that: In step 4, the heating temperature is 55-65° C., and the stirring speed is 240-480 r / min.

10. The method for preparing a silicon nitride toughened hydrocarbon resin for copper clad laminate according to claim 9, characterized in that: In step 2, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; the water bath curing temperature is 70°C, and the sintering treatment is performed at a temperature of 1550°C; in step 3, the weight ratio of the total weight of 2-ethyl-4-methylimidazole and silver acetate to the organic solvent is 1:50, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 500W, and the vacuum drying temperature is higher than the boiling point of the organic solvent; in step 4, the heating temperature is 60°C, and the stirring speed is 360r / min.

Images