Silicon dioxide toughened modified BT resin-based copper-clad plate and preparation method thereof

Abstract

According to the silicon dioxide toughened and modified BT resin-based copper-clad plate and the preparation method thereof, the toughening and modifying treatment effect of the BT resin-based copper-clad plate can be effectively improved, and meanwhile, the thermo-oxidative aging resistance of the BT resin-based copper-clad plate is improved; hydrogenated resin and hydrocarbon resin are added in the synthesis process of BT resin to promote the cross-linking curing reaction of cyanate ester, and meanwhile, the hydrocarbon resin is subjected to self-polymerization reaction to increase the cross-linking density, so that excellent thermo-oxidative aging resistance is kept; due to the synergistic effect of the modified nano silicon dioxide and the multi-walled carbon nanotubes, the agglomeration phenomenon is reduced, and the dispersion treatment effect of the nano silicon dioxide and the multi-walled carbon nanotubes in the BT resin-based material can be effectively improved, so that the toughness and other mechanical properties of the BT resin-based copper-clad plate are effectively improved; the BT resin is modified by hydroxyl-terminated polybutadiene and nano silicon dioxide together, so that a good synergistic reinforcing and toughening effect is achieved, and meanwhile, the dielectric loss of the BT resin-based copper-clad plate is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of copper clad laminates, and more specifically, to a silicon dioxide toughened and modified BT resin-based copper clad laminate and a preparation method thereof. Background Art

[0002] Copper clad laminate is a plate material made by impregnating electronic glass fiber cloth or other reinforcing materials with resin, covering one or both sides with copper foil and hot pressing. It is referred to as copper clad laminate for short. The quality, performance, manufacturing cost, preparation, manufacturing level and long-term reliability and stability of printed circuit boards mainly depend on copper clad laminate.

[0003] BT resin is a thermosetting resin formed by adding bismaleimide (BMI) and triazine as the main resin components, and epoxy resin, polyphenylene ether resin (PPE) or allyl compounds as modified components. The cured BT resin has the following characteristics: excellent heat resistance, low dielectric constant, low dielectric loss, high resistance to metal ion migration, excellent mechanical properties, radiation resistance, chemical resistance, wear resistance and dimensional stability; therefore, BT resin is often used in the production and processing of copper clad laminates. In the process of applying BT resin to copper clad laminates, it is toughened and modified by using silica.

[0004] However, when BT resin is applied to copper clad laminates, with the popularization of electronic equipment and the improvement of its functions, circuits are faced with more and more high-temperature environments, and the performance requirements for copper clad laminates are becoming higher and higher. At the same time, the requirements for BT resin in copper clad laminates are also higher. 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 silica-toughened and modified BT resin-based copper clad laminate and a preparation method thereof.

[0006] A silicon dioxide toughened modified BT resin-based copper clad laminate comprises a prepreg and copper foil, wherein the copper foil is hot-pressed and laminated on the upper and lower surfaces of the prepreg; the prepreg is prepared by impregnating and curing an electronic glass fiber cloth in a modified BT resin solution; the raw materials of the modified BT resin solution are calculated by weight percentage as follows: 10.5-12.5% ​​of bismaleimide resin, 15.0-17.0% of hydrocarbon resin, 0.010-0.020% of cobalt acetylacetonate, 15.0-17.0% of terminal hydroxyl polybutadiene, 6.0-6.8% of modified silicon dioxide, and the rest is cyanate monomer.

[0007] Furthermore, the cyanate monomer is a bisphenol M type cyanate monomer; the hydrocarbon resin is one or a combination of hydrogenated styrene butadiene block copolymer, butadiene styrene copolymer, styrene homopolymer, butadiene homopolymer, styrene / divinylbenzene copolymer, styrene-butadiene-divinylbenzene copolymer.

[0008] Furthermore, the raw materials of the modified silicon dioxide are calculated by weight percentage as follows: 4.2-5.2% of multi-walled carbon nanotubes, 4.2-5.2% of silane coupling agent KH550, and the rest is nano silicon dioxide.

[0009] Furthermore, the raw materials of the modified BT resin liquid are calculated by weight percentage as follows: 11.0-12.0% of bismaleimide resin, 15.5-16.5% of hydrocarbon resin, 0.013-0.017% of cobalt acetylacetonate, 15.5-16.5% of terminal hydroxyl polybutadiene, 6.2-6.6% of modified silica, and the rest are cyanate monomers; the raw materials of the modified silica are calculated by weight percentage as follows: 4.5-4.9% of multi-walled carbon nanotubes, 4.5-4.9% of silane coupling agent KH550, and the rest are nano-silica.

[0010] Furthermore, the raw materials of the modified BT resin liquid are calculated by weight percentage as follows: 11.5% of bismaleimide resin, 16.0% of hydrocarbon resin, 0.015% of cobalt acetylacetonate, 16.0% of terminal hydroxyl polybutadiene, 6.4% of modified silica, and the rest are cyanate monomers; the raw materials of the modified silica are calculated by weight percentage as follows: 4.7% of multi-walled carbon nanotubes, 4.7% of silane coupling agent KH550, and the rest are nano-silica.

[0011] A method for preparing a BT resin-based copper-clad laminate toughened and modified by silica, the specific preparation steps are as follows:

[0012] Step 1: Weigh the bismaleimide resin, hydrocarbon resin, cobalt acetylacetonate, hydroxy-terminated polybutadiene, cyanate monomer in the modified BT resin liquid raw material, and the multi-walled carbon nanotubes, silane coupling agent KH550, and nano-silica in the modified silica raw material;

[0013] Step 2: adding half of the weight of multi-walled carbon nanotubes and half of the weight of silane coupling agent KH550 to deionized water, and performing water bath ultrasonic treatment for 40 to 60 minutes to obtain a mixture;

[0014] Step 3: Add nano-silica and the remaining multi-walled carbon nanotubes and silane coupling agent KH550 to the mixture, continue water bath ultrasonic treatment for 40 to 60 minutes, centrifuge, wash, and dry to obtain modified silica;

[0015] Step 4: Blending one-half part by weight of modified silica and one-half part by weight of hydroxyl-terminated polybutadiene and ultrasonically treating for 40 to 60 minutes to obtain a premix;

[0016] Step 5: adding bismaleimide resin, hydrocarbon resin, cobalt acetylacetonate, cyanate monomer, premix and remaining modified silica, and hydroxy-terminated polybutadiene to an organic solvent in sequence, heating and stirring for 2 to 3 hours to obtain a modified BT resin solution;

[0017] Step 6: Immerse the electronic glass fiber cloth in the modified BT resin solution for 10 to 20 minutes, cure it for 10 to 20 minutes, and cool it to room temperature after curing to obtain a semi-cured sheet;

[0018] Step 7: stack 4 to 6 prepregs between two copper foils, and then send them into a hot press for hot pressing. After the hot pressing, a silica-reinforced BT resin-based copper clad laminate is obtained.

[0019] Furthermore, in step 2, the weight ratio of the total weight of multi-walled carbon nanotubes and silane coupling agent KH550 to deionized water is 1:200-240, the water bath temperature is 50-60°C, the ultrasonic frequency is 40-60KHz, and the ultrasonic power is 400-600W; in step 3, the water bath temperature is 50-60°C, the ultrasonic frequency is 1.2-1.6MHz, the ultrasonic power is 200-400W, and the centrifugal speed is 8000-10000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the mixture is dried in a vacuum drying oven at 70-80°C.

[0020] Furthermore, in step 4, the ultrasonic frequency is 40-60KHz, and the ultrasonic power is 400-600W; in step 5, the weight ratio of bismaleimide resin to organic solvent is 1:2.5-3.5, the heating temperature is 60-70°C, the rotation speed during the first hour of stirring treatment is 240-360r / min, and the rotation speed of subsequent stirring treatment is 800-1000r / min, and the organic solvent is one of dichloromethane, butanone, and ethanol.

[0021] Furthermore, in step six, the curing temperature is 170-180°C; in step seven, the hot pressing curing process is: hot pressing treatment at 30-36MPa pressure and 135-145°C for 1h, then hot pressing treatment at 50-56MPa and 170-180°C for 1h, and finally hot pressing treatment at 30-36MPa and 190-200°C for 1h, and the heating rate is 2°C / min.

[0022] Further, in step 2, the weight ratio of the total weight of the multi-walled carbon nanotubes and the silane coupling agent KH550 to the weight of deionized water is 1:220, the water bath temperature is 55°C, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; in step 3, the water bath temperature is 55°C, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 300W, and the centrifugal speed is 9000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the mixture is dried in a vacuum drying oven at 75°C; in step 4, the ultrasonic frequency is 50KHz, the ultrasonic power is 500W; in step In step 5, the weight ratio of bismaleimide resin to organic solvent is 1:3.0, the heating temperature is 65°C, the rotation speed during the first hour of stirring treatment is 300r / min, and the rotation speed of subsequent stirring treatment is 900r / min, and the organic solvent is one of dichloromethane, butanone, and anhydrous ethanol; in step 6, the curing temperature is 175°C; in step 7, the hot pressing curing process is: hot pressing treatment at 33MPa pressure and 140°C for 1h, then hot pressing treatment at 53MPa and 175°C for h, and finally hot pressing treatment at 33MPa and 196°C for 1h, and the heating rate is 2°C / min.

[0023] Technical effects and advantages of the present invention:

[0024] 1. A silica-toughened and modified BT resin-based copper-clad laminate prepared by the raw material formula of the present invention can effectively improve the toughening and modification treatment effect of the BT resin-based copper-clad laminate, and at the same time improve the heat-oxidation aging resistance of the BT resin-based copper-clad laminate; bismaleimide resin and cyanate monomer react under the catalytic treatment of cobalt acetylacetone to prepare BT resin, and hydrogenated resin and hydrocarbon resin are added during the synthesis of BT resin to promote the curing reaction of BT resin and reduce the reaction temperature; hydrocarbon resin promotes the cross-linking curing reaction of cyanate, and at the same time, the polymerization reaction of hydrocarbon resin itself increases the cross-linking density, thereby maintaining excellent heat-oxidation aging resistance; the silane coupling agent KH550 in the modified silica has a certain effect on the curing reaction of BT resin. The multi-walled carbon nanotubes and nano-silica are subjected to surface grafting modification treatment. The synergistic effect of the modified nano-silica and multi-walled carbon nanotubes reduces the agglomeration phenomenon, which can effectively improve the dispersion treatment effect of nano-silica and multi-walled carbon nanotubes in BT resin-based materials, thereby effectively improving the toughness and other mechanical properties of BT resin-based copper-clad laminates; the terminal hydroxyl groups of hydroxyl-terminated polybutadiene and the silanol groups on the surface of nano-silica can react with the groups of the resin matrix to form a good interface bond; the BT resin is modified by using terminal hydroxyl polybutadiene and nano-silica together, which has a good synergistic strengthening and toughening effect, which can effectively improve the toughness of BT resin-based materials and reduce the dielectric loss of BT resin-based copper-clad laminates;

[0025] 2. In the present invention, part of the multi-walled carbon nanotubes and the silane coupling agent KH550 are first subjected to water bath ultrasonic treatment in deionized water, which can effectively perform surface grafting modification pretreatment on the multi-walled carbon nanotubes by the silane coupling agent KH550, effectively ensure the integrity of the grafting reaction of the silane coupling agent KH550 on the surface of the multi-walled carbon nanotubes, and effectively avoid the silane coupling agent KH550 only modifying the surface of the nano-silicon dioxide, resulting in too low a grafting amount on the surface of the multi-walled carbon nanotubes; nano-silicon dioxide and the remaining multi-walled carbon nanotubes and the silane coupling agent KH550 are added to the mixture and the water bath ultrasonic treatment is continued, and the mixture is centrifuged. , washing, and drying can effectively obtain modified silica for surface modification of nano-silica and multi-walled carbon nanotubes; a part of the modified silica is blended with a part of the terminal hydroxyl polybutadiene and subjected to ultrasonic treatment, and the modified silica and the terminal hydroxyl polybutadiene can be premixed in advance, which can effectively ensure the subsequent synergistic treatment effect of the modified silica and the terminal hydroxyl polybutadiene on the BT resin; bismaleimide resin, hydrocarbon resin, cobalt acetylacetonate, cyanate monomer, premix and the remaining modified silica and terminal hydroxyl polybutadiene are added to the organic solvent in sequence, heated and stirred to obtain a modified BT resin solution. DETAILED DESCRIPTION

[0026] 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.

[0027] Embodiment 1:

[0028] The invention provides a silicon dioxide toughened modified BT resin-based copper clad laminate, comprising a prepreg and a copper foil, wherein the copper foil is hot-pressed and laminated on the upper and lower surfaces of the prepreg; the prepreg is prepared by impregnating and curing an electronic glass fiber cloth in a modified BT resin solution; the raw materials of the modified BT resin solution are: 1050g of bismaleimide resin, 1500g of hydrogenated styrene butadiene block copolymer, 1.0g of cobalt acetylacetonate, 1500g of terminal hydroxyl polybutadiene, 600g of modified silicon dioxide, and 5349g of bisphenol M type cyanate monomer; the raw materials of the modified silicon dioxide are: 25.2g of multi-walled carbon nanotubes, 25.2g of silane coupling agent KH550, and 549.6g of nano silicon dioxide;

[0029] The present invention also provides a method for preparing a silica toughened and modified BT resin-based copper clad laminate, and the specific preparation steps are as follows:

[0030] Step 1: weighing bismaleimide resin, hydrogenated styrene butadiene block copolymer, cobalt acetylacetonate, terminal hydroxyl polybutadiene, bisphenol M type cyanate monomer in the modified BT resin liquid raw material, multi-walled carbon nanotubes, silane coupling agent KH550, and nano-silica in the modified silica raw material;

[0031] Step 2: adding half of the weight of multi-walled carbon nanotubes and half of the weight of silane coupling agent KH550 to deionized water, and performing water bath ultrasonic treatment for 50 minutes to obtain a mixture;

[0032] Step 3: Add nano-silica and the remaining multi-walled carbon nanotubes and silane coupling agent KH550 to the mixture, continue water bath ultrasonic treatment for 50 minutes, centrifuge, wash and dry to obtain modified silica;

[0033] Step 4: Blending one-half part by weight of modified silica and one-half part by weight of hydroxyl-terminated polybutadiene and ultrasonically treating for 50 minutes to obtain a premix;

[0034] Step 5: adding bismaleimide resin, hydrogenated styrene butadiene block copolymer, cobalt acetylacetonate, bisphenol M type cyanate monomer, premix and remaining modified silica, and hydroxyl-terminated polybutadiene to anhydrous ethanol in sequence, heating and stirring for 2.5 hours to obtain a modified BT resin solution;

[0035] Step 6: Immerse the electronic glass fiber cloth in the modified BT resin solution for 15 minutes, cure it for 15 minutes, and cool it to room temperature after curing to obtain a semi-cured sheet;

[0036] Step 7: stack 5 prepregs between two copper foils, and then send them into a hot press for hot pressing. After hot pressing, a silica-reinforced BT resin-based copper clad laminate is obtained.

[0037] In step 2, the weight ratio of the total weight of the multi-walled carbon nanotubes and the silane coupling agent KH550 to the weight of deionized water is 1:200, the water bath temperature is 50°C, the ultrasonic frequency is 40KHz, and the ultrasonic power is 400W; in step 3, the water bath temperature is 50°C, the ultrasonic frequency is 1.2MHz, the ultrasonic power is 200W, and the centrifugal speed is 8000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the mixture is dried at 70°C in a vacuum drying oven; in step 4, the ultrasonic frequency is 40KHz, the ultrasonic power is is 400W; in step 5, the weight ratio of bismaleimide resin to anhydrous ethanol is 1:2.5, the heating temperature is 60°C, the rotation speed is 240r / min for the first hour of stirring treatment, and the rotation speed of subsequent stirring treatment is 800r / min; in step 6, the curing temperature is 170°C; in step 7, the hot pressing curing process is: hot pressing treatment at 30MPa pressure and 135°C for 1h, then hot pressing treatment at 50MPa and 170°C for h, and finally hot pressing treatment at 30MPa and 190°C for 1h, and the heating rate is 2°C / min;

[0038] Bismaleimide resin was purchased from Hubei Xinyuhong Biomedical Technology Co., Ltd., item number: xyh001; hydrogenated styrene butadiene block copolymer was purchased from SEBS hydrogenated styrene-butadiene block copolymer 503T of Dongguan Longsheng Engineering Plastics Co., Ltd.; cobalt acetylacetonate was purchased from Hubei Xinghengye Technology Co., Ltd., brand: Hengye Brand; terminal hydroxyl polybutadiene was purchased from Hubei Xinghengye Technology Co., Ltd., brand: Hengye Brand; bisphenol M type cyanate monomer was purchased from Hubei Jiahui Xingcheng Biotechnology Co., Ltd., brand: Jiahui Xingcheng; multi-walled carbon nanotubes were purchased from Shanghai Gaibang Industrial Co., Ltd.; silane coupling agent KH550 was purchased from Shandong Yuanjin New Materials Co., Ltd.; nano-silica was purchased from Shanghai Zhenlishi Network Technology Co., Ltd., nano-grade fumed silica AEROSILR972.

[0039] Embodiment 2:

[0040] Different from Example 1, the raw materials of the modified BT resin liquid are: 1250g of bismaleimide resin, 1700g of hydrogenated styrene butadiene block copolymer, 2.0g of cobalt acetylacetonate, 1700g of terminal hydroxyl polybutadiene, 680g of modified silica, and 4668g of bisphenol M type cyanate monomer; the raw materials of the modified silica are: 35.36g of multi-walled carbon nanotubes, 35.36g of silane coupling agent KH550, and 609.28g of nano silica.

[0041] Embodiment 3:

[0042] Different from Examples 1-2, the raw materials of the modified BT resin liquid are: 1150g of bismaleimide resin, 1600g of hydrogenated styrene butadiene block copolymer, 1.5g of cobalt acetylacetonate, 1600g of terminal hydroxyl polybutadiene, 640g of modified silica, and 5008.5g of bisphenol M type cyanate monomer; the raw materials of the modified silica are: 30.08g of multi-walled carbon nanotubes, 30.08g of silane coupling agent KH550, and 579.84g of nano silica.

[0043] Embodiment 4:

[0044] The difference from Example 3 is that in step 2, the weight ratio of the total weight of multi-walled carbon nanotubes and silane coupling agent KH550 to deionized water is 1:220, the water bath temperature is 55°C, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; in step 3, the water bath temperature is 55°C, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 300W, and the centrifugal speed is 9000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the mixture is dried at 75°C in a vacuum drying oven; in step 4, the ultrasonic frequency is 50KHz , the ultrasonic power is 500W; in step five, the weight ratio of bismaleimide resin to anhydrous ethanol is 1:3.0, the heating temperature is 65°C, the rotation speed during the first hour of stirring treatment is 300r / min, and the rotation speed of subsequent stirring treatment is 900r / min; in step six, the curing temperature is 175°C; in step seven, the hot pressing curing process is: hot pressing treatment at 33MPa pressure and 140°C for 1h, then hot pressing treatment at 53MPa and 175°C for h, and finally hot pressing treatment at 33MPa and 196°C for 1h, and the heating rate is 2°C / min.

[0045] Comparative Example 1:

[0046] The difference from Example 4 is that the raw materials of the modified BT resin solution are: 1150g of bismaleimide resin, 1.5g of cobalt acetylacetonate, 1600g of terminal hydroxyl polybutadiene, 640g of modified silica, and 5008.5g of bisphenol M type cyanate monomer; the raw materials of the modified silica are: 30.08g of multi-walled carbon nanotubes, 30.08g of silane coupling agent KH550, and 579.84g of nano silica;

[0047] The preparation method of the silica toughened and modified BT resin-based copper clad laminate is as follows:

[0048] Step 1: weighing bismaleimide resin, cobalt acetylacetonate, terminal hydroxyl polybutadiene, bisphenol M type cyanate monomer in the modified BT resin liquid raw material, multi-walled carbon nanotubes, silane coupling agent KH550, and nano-silica in the modified silica raw material;

[0049] Step 2: adding half of the weight of multi-walled carbon nanotubes and half of the weight of silane coupling agent KH550 to deionized water, and performing water bath ultrasonic treatment for 50 minutes to obtain a mixture;

[0050] Step 3: Add nano-silica and the remaining multi-walled carbon nanotubes and silane coupling agent KH550 to the mixture, continue water bath ultrasonic treatment for 50 minutes, centrifuge, wash and dry to obtain modified silica;

[0051] Step 4: Blending one-half part by weight of modified silica and one-half part by weight of hydroxyl-terminated polybutadiene and ultrasonically treating for 50 minutes to obtain a premix;

[0052] Step 5: adding bismaleimide resin, cobalt acetylacetonate, bisphenol M type cyanate monomer, premix, remaining modified silica, and hydroxy-terminated polybutadiene to anhydrous ethanol in sequence, heating and stirring for 2.5 hours to obtain a modified BT resin solution;

[0053] Step 6: Immerse the electronic glass fiber cloth in the modified BT resin solution for 15 minutes, cure it for 15 minutes, and cool it to room temperature after curing to obtain a semi-cured sheet;

[0054] Step 7: stack 5 prepregs between two copper foils, and then send them into a hot press for hot pressing. After hot pressing, a silica-reinforced BT resin-based copper clad laminate is obtained.

[0055] Comparative Example 2:

[0056] The difference from Example 4 is that the raw materials of the modified BT resin solution are: 1150g of bismaleimide resin, 1600g of hydrogenated styrene butadiene block copolymer, 1.5g of cobalt acetylacetonate, 640g of modified silica, 5008.5g of bisphenol M type cyanate monomer; the raw materials of the modified silica are: 30.08g of multi-walled carbon nanotubes, 30.08g of silane coupling agent KH550, 579.84g of nano silica;

[0057] The preparation method of the silica toughened and modified BT resin-based copper clad laminate is as follows:

[0058] Step 1: weighing bismaleimide resin, hydrogenated styrene butadiene block copolymer, cobalt acetylacetonate, bisphenol M type cyanate monomer in the modified BT resin liquid raw material, multi-walled carbon nanotubes, silane coupling agent KH550, and nano-silica in the modified silica raw material;

[0059] Step 2: adding half of the weight of multi-walled carbon nanotubes and half of the weight of silane coupling agent KH550 to deionized water, and performing water bath ultrasonic treatment for 50 minutes to obtain a mixture;

[0060] Step 3: Add nano-silica and the remaining multi-walled carbon nanotubes and silane coupling agent KH550 to the mixture, continue water bath ultrasonic treatment for 50 minutes, centrifuge, wash and dry to obtain modified silica;

[0061] Step 4: adding bismaleimide resin, hydrogenated styrene butadiene block copolymer, cobalt acetylacetonate, bisphenol M type cyanate monomer, and modified silica to anhydrous ethanol in sequence, heating and stirring for 2.5 hours to obtain a modified BT resin solution;

[0062] Step 5: Immerse the electronic glass fiber cloth in the modified BT resin solution for 15 minutes, cure it for 15 minutes, and cool it to room temperature after curing to obtain a semi-cured sheet;

[0063] Step 6: stack 5 prepregs between two copper foils, and then send them into a hot press for hot pressing. After the hot pressing, a silica-reinforced BT resin-based copper clad laminate is obtained;

[0064] In step 2, the weight ratio of the total weight of multi-walled carbon nanotubes and silane coupling agent KH550 to deionized water is 1:220, the water bath temperature is 55°C, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; in step 3, the water bath temperature is 55°C, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 300W, and the centrifugal speed is 9000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the mixture is dried at 75°C in a vacuum drying oven; in step 4, the double-horse The weight ratio of imide resin to anhydrous ethanol is 1:3.0, the heating temperature is 65°C, the rotation speed during the first hour of stirring treatment is 300r / min, and the rotation speed during the subsequent stirring treatment is 900r / min; in step five, the curing temperature is 175°C; in step six, the hot pressing curing process is: hot pressing treatment at 33MPa pressure and 140°C for 1h, then hot pressing treatment at 53MPa and 175°C for 1h, and finally hot pressing treatment at 33MPa and 196°C for 1h, and the heating rate is 2°C / min.

[0065] Comparative Example 3:

[0066] The difference from Example 4 is that the raw materials of the modified BT resin solution are: 1150g of bismaleimide resin, 1600g of hydrogenated styrene butadiene block copolymer, 1.5g of cobalt acetylacetonate, 1600g of terminal hydroxyl polybutadiene, 609.92g of modified silica, 5008.5g of bisphenol M type cyanate monomer; the raw materials of the modified silica are: 30.08g of multi-walled carbon nanotubes, 579.84g of nano silica;

[0067] The preparation method of the silica toughened and modified BT resin-based copper clad laminate is as follows:

[0068] Step 1: weighing bismaleimide resin, hydrogenated styrene butadiene block copolymer, cobalt acetylacetonate, terminal hydroxyl polybutadiene, bisphenol M type cyanate monomer in the modified BT resin liquid raw material, and multi-walled carbon nanotubes and nano-silica in the modified silica raw material;

[0069] Step 2: adding nano-silica and multi-walled carbon nanotubes into deionized water, performing water bath ultrasonic treatment for 50 minutes, centrifuging, washing, and drying to obtain modified silica;

[0070] Step 3: Blending one-half part by weight of modified silica and one-half part by weight of hydroxyl-terminated polybutadiene and ultrasonically treating for 50 minutes to obtain a premix;

[0071] Step 4: adding bismaleimide resin, hydrogenated styrene butadiene block copolymer, cobalt acetylacetonate, bisphenol M type cyanate monomer, premix and remaining modified silica, and hydroxyl-terminated polybutadiene to anhydrous ethanol in sequence, heating and stirring for 2.5 hours to obtain a modified BT resin solution;

[0072] Step 5: Immerse the electronic glass fiber cloth in the modified BT resin solution for 15 minutes, cure it for 15 minutes, and cool it to room temperature after curing to obtain a semi-cured sheet;

[0073] Step 6: stack 5 prepregs between two copper foils, and then send them into a hot press for hot pressing. After the hot pressing, a silica-reinforced BT resin-based copper clad laminate is obtained;

[0074] In step 2, the water bath temperature is 55°C, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 300W, and the centrifugal speed is 9000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the mixture is dried at 75°C inside a vacuum drying oven; in step 3, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; in step 4, the weight ratio of bismaleimide resin to anhydrous ethanol is 1:3.0, the heating temperature is 65°C, the speed for the first hour of stirring treatment is 300r / min, and the speed for subsequent stirring treatment is 900r / min; in step 5, the curing temperature is 175°C; in step 6, the hot pressing curing process is: hot pressing treatment at 33MPa pressure and 140°C for 1h, then hot pressing treatment at 53MPa and 175°C for h, and finally hot pressing treatment at 33MPa and 196°C for 1h, and the heating rate is 2°C / min.

[0075] The prepreg and copper clad laminate in the silica toughened and modified BT resin-based copper clad laminate in the comparative example and the embodiment of the present invention were tested and processed:

[0076] Prepreg tensile strength test: tensile properties test according to GB / T528-2009;

[0077] Thermal oxidation aging performance test of copper clad laminate: After etching the copper clad laminate, prepare a sample with a size of 80mm×80mm. After testing the results of the initial stage of aging, heat oxidation treatment was carried out in a 155℃ blast oven. After being taken out, it was treated at 23℃ and 50% relative humidity for 24h. According to IEC61189-2-721-2015 (SPDR), the dielectric loss (D f )value;

[0078] The results are shown in Table 1:

[0079] Table 1:

[0080]

[0081]

[0082] It can be seen from the above table that the silica toughened and modified BT resin-based copper clad laminate of the present invention can effectively improve the toughening and modification treatment effect of the BT resin-based copper clad laminate, and at the same time improve the heat-oxidative aging resistance of the BT resin-based copper clad laminate.

[0083] In the present invention, bismaleimide resin and cyanate monomer react under the catalytic treatment of cobalt acetylacetonate to prepare BT resin, hydrogenated resin is added in the synthesis process of BT resin, and under the same reaction conditions, hydrocarbon resin promotes the curing reaction of BT resin and reduces the reaction temperature; hydrocarbon resin is introduced into cyanate ester-bismaleimide (BT) resin system to prepare cyanate ester-bismaleimide-hydrocarbon (BT-CH) composite resin system; hydrocarbon resin promotes the cross-linking curing reaction of cyanate ester, and at the same time, the hydrocarbon resin itself polymerizes to increase the cross-linking density, thereby maintaining excellent heat-oxidative aging resistance; silane coupling agent KH550 in modified silica performs surface grafting modification on multi-walled carbon nanotubes and nano-silica. The modified silica has a better contact and bonding effect with the resin-based material, and the modified silica has a better modification effect on the BT resin-based material; the multi-walled carbon nanotubes and nano-silicon dioxide in the modified silica are doped into the BT resin-based material, and the synergistic effect of nano-silicon dioxide and multi-walled carbon nanotubes reduces the agglomeration phenomenon, which can effectively improve the dispersion treatment effect of nano-silicon dioxide and multi-walled carbon nanotubes in the BT resin-based material, reduce agglomeration, and effectively improve the toughness and other mechanical properties of the BT resin-based copper clad laminate; terminal hydroxyl polybutadiene can significantly improve the toughness of BT resin, but the heat resistance is poor, and nano-silicon dioxide can play a reinforcing and toughening role , and it also has good thermal stability. The terminal hydroxyl groups of terminal hydroxyl polybutadiene and the silanol groups on the surface of nano-silica can react with the groups of the resin matrix to form a good interface bond; the use of terminal hydroxyl polybutadiene and nano-silica to modify BT resin has a good synergistic strengthening and toughening effect, which can effectively improve the toughness of BT resin-based materials and reduce the dielectric loss of BT resin-based copper-clad laminates; in step 2, firstly, a part of multi-walled carbon nanotubes and silane coupling agent KH550 are subjected to water bath ultrasonic treatment in deionized water, which can effectively carry out surface grafting modification pretreatment of multi-walled carbon nanotubes by silane coupling agent KH550, which can effectively ensure that the silane coupling agent KH550 is grafted on the surface of multi-walled carbon nanotubes The integrity of the reaction can effectively avoid the silane coupling agent KH550 only modifying the surface of nano-silica, resulting in too low a grafting amount on the surface of multi-walled carbon nanotubes; in step three, nano-silica and the remaining multi-walled carbon nanotubes and silane coupling agent KH550 are added to the mixture, and then the mixture is subjected to water bath ultrasonic treatment, centrifugation, washing, and drying, so that modified silica that modifies the surface of nano-silica and multi-walled carbon nanotubes can be effectively obtained; in step four, part of the modified silica is blended with part of the terminal hydroxyl polybutadiene for ultrasonic treatment, and the modified silica and the terminal hydroxyl polybutadiene can be pre-mixed in advance, which can effectively ensure the subsequent synergistic treatment effect of the modified silica and the terminal hydroxyl polybutadiene on the BT resin;In step five, bismaleimide resin, hydrocarbon resin, cobalt acetylacetonate, cyanate ester monomer, premix, and the remaining modified silica and hydroxyl-terminated polybutadiene are successively added into an organic solvent, and subjected to heating and stirring treatment to obtain a modified BT resin solution; in step six, an electronic glass fabric is impregnated and cured in the modified BT resin solution to obtain a prepreg; in step seven, a plurality of prepregs are stacked between two copper foils, and after hot pressing treatment, a silica toughened and modified BT resin-based copper clad laminate is obtained.

[0084] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A silica toughened and modified BT resin-based copper clad laminate, characterized in that: The invention comprises a prepreg and copper foil, wherein the copper foil is hot-pressed and laminated on the upper and lower surfaces of the prepreg; the prepreg is prepared by impregnating and curing an electronic glass fiber cloth in a modified BT resin solution; the raw materials of the modified BT resin solution are calculated by weight percentage as follows: 10.5-12.5% ​​of bismaleimide resin, 15.0-17.0% of hydrocarbon resin, 0.010-0.020% of cobalt acetylacetonate, 15.0-17.0% of terminal hydroxyl polybutadiene, 6.0-6.8% of modified silicon dioxide, and the rest is cyanate monomer.

2. A silica toughened and modified BT resin-based copper clad laminate according to claim 1, characterized in that: The cyanate monomer is a bisphenol M type cyanate monomer; the hydrocarbon resin is one or a combination of hydrogenated styrene butadiene block copolymer, butadiene styrene copolymer, styrene homopolymer, butadiene homopolymer, styrene / divinylbenzene copolymer, styrene-butadiene-divinylbenzene copolymer.

3. The silica toughened and modified BT resin-based copper clad laminate according to claim 1, characterized in that: The raw materials of the modified silicon dioxide are calculated by weight percentage as follows: 4.2-5.2% of multi-walled carbon nanotubes, 4.2-5.2% of silane coupling agent KH550, and the rest is nano silicon dioxide.

4. The silica toughened and modified BT resin-based copper clad laminate according to claim 3, characterized in that: The raw materials of the modified BT resin liquid are calculated by weight percentage as follows: 11.0-12.0% of bismaleimide resin, 15.5-16.5% of hydrocarbon resin, 0.013-0.017% of cobalt acetylacetonate, 15.5-16.5% of terminal hydroxyl polybutadiene, 6.2-6.6% of modified silicon dioxide, and the rest is cyanate monomer; the raw materials of the modified silicon dioxide are calculated by weight percentage as follows: 4.5-4.9% of multi-walled carbon nanotubes, 4.5-4.9% of silane coupling agent KH550, and the rest is nano silicon dioxide.

5. The silica toughened and modified BT resin-based copper clad laminate according to claim 3, characterized in that: The raw materials of the modified BT resin solution are calculated by weight percentage as follows: 11.5% of bismaleimide resin, 16.0% of hydrocarbon resin, 0.015% of cobalt acetylacetonate, 16.0% of terminal hydroxyl polybutadiene, 6.4% of modified silicon dioxide, and the rest is cyanate monomer; the raw materials of the modified silicon dioxide are calculated by weight percentage as follows: 4.7% multi-walled carbon nanotubes, 4.7% silane coupling agent KH550, and the rest is nano-silicon dioxide.

6. A method for preparing a silica toughened and modified BT resin-based copper clad laminate, characterized in that: The specific preparation steps are as follows: Step 1: Weigh the bismaleimide resin, hydrocarbon resin, cobalt acetylacetonate, hydroxy-terminated polybutadiene, cyanate monomer in the modified BT resin liquid raw material, and the multi-walled carbon nanotubes, silane coupling agent KH550, and nano-silica in the modified silica raw material; Step 2: adding half of the weight of multi-walled carbon nanotubes and half of the weight of silane coupling agent KH550 to deionized water, and performing water bath ultrasonic treatment for 40 to 60 minutes to obtain a mixture; Step 3: Add nano-silica and the remaining multi-walled carbon nanotubes and silane coupling agent KH550 to the mixture, continue water bath ultrasonic treatment for 40 to 60 minutes, centrifuge, wash, and dry to obtain modified silica; Step 4: Blending one-half part by weight of modified silica and one-half part by weight of hydroxyl-terminated polybutadiene and ultrasonically treating for 40 to 60 minutes to obtain a premix; Step 5: adding bismaleimide resin, hydrocarbon resin, cobalt acetylacetonate, cyanate monomer, premix and remaining modified silica, and hydroxy-terminated polybutadiene to an organic solvent in sequence, heating and stirring for 2 to 3 hours to obtain a modified BT resin solution; Step 6: Immerse the electronic glass fiber cloth in the modified BT resin solution for 10 to 20 minutes, cure it for 10 to 20 minutes, and cool it to room temperature after curing to obtain a semi-cured sheet; Step 7: stack 4 to 6 prepregs between two copper foils, and then send them into a hot press for hot pressing. After the hot pressing, a silica-reinforced BT resin-based copper clad laminate is obtained.

7. The method for preparing a silica toughened and modified BT resin-based copper clad laminate according to claim 6, characterized in that: In step 2, the weight ratio of the total weight of multi-walled carbon nanotubes and silane coupling agent KH550 to deionized water is 1:200-240, the water bath temperature is 50-60°C, the ultrasonic frequency is 40-60KHz, and the ultrasonic power is 400-600W; in step 3, the water bath temperature is 50-60°C, the ultrasonic frequency is 1.2-1.6MHz, the ultrasonic power is 200-400W, and the centrifugal speed is 8000-10000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the product is dried in a vacuum drying oven at 70-80°C.

8. The method for preparing a silica toughened and modified BT resin-based copper clad laminate according to claim 7, characterized in that: In step 4, the ultrasonic frequency is 40-60KHz, and the ultrasonic power is 400-600W; in step 5, the weight ratio of bismaleimide resin to organic solvent is 1:2.5-3.5, the heating temperature is 60-70°C, the rotation speed during the first hour of stirring treatment is 240-360r / min, and the rotation speed of subsequent stirring treatment is 800-1000r / min, and the organic solvent is one of dichloromethane, butanone, and ethanol.

9. A method for preparing a silica toughened and modified BT resin-based copper clad laminate according to claim 8, characterized in that: In step six, the curing temperature is 170-180°C; in step seven, the hot pressing curing process is: hot pressing treatment at 30-36MPa pressure and 135-145°C for 1h, then hot pressing treatment at 50-56MPa and 170-180°C for 1h, and finally hot pressing treatment at 30-36MPa and 190-200°C for 1h, and the heating rate is 2°C / min.

10. The method for preparing a silica toughened and modified BT resin-based copper clad laminate according to claim 9, characterized in that: In step 2, the weight ratio of the total weight of multi-walled carbon nanotubes and silane coupling agent KH550 to deionized water is 1:220, the water bath temperature is 55°C, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; in step 3, the water bath temperature is 55°C, the ultrasonic frequency is 1.4MHz, the ultrasonic power is 300W, and the centrifugal speed is 9000r / min; deionized water and anhydrous ethanol are used for repeated alternating washing treatment, and the mixture is dried in a vacuum drying oven at 75°C; in step 4, the ultrasonic frequency is 50KHz, and the ultrasonic power is 500W; in step 5 , the weight ratio of bismaleimide resin to organic solvent is 1:3.0, the heating temperature is 65°C, the rotation speed during the first hour of stirring treatment is 300r / min, and the rotation speed of subsequent stirring treatment is 900r / min, and the organic solvent is one of dichloromethane, butanone, and anhydrous ethanol; in step six, the curing temperature is 175°C; in step seven, the hot pressing curing process is: hot pressing treatment at 33MPa pressure and 140°C for 1h, then hot pressing treatment at 53MPa and 175°C for h, and finally hot pressing treatment at 33MPa and 196°C for 1h, and the heating rate is 2°C / min.

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