A high-speed copper clad laminate prepared using functional plastics

Abstract

The present invention relates to the technical field of copper clad laminates, and specifically discloses a high-speed copper clad laminate prepared using functional plastics. The high-speed copper clad laminate is formed by hot pressing and curing several functional plastic-modified epoxy-based prepregs; the functional plastic-modified epoxy-based prepregs are made of electronic-grade glass cloth and functional plastic-modified epoxy resin; the functional plastic-modified epoxy resin includes 5-20 parts by weight of functional plastics, 100 parts by mass of epoxy resin, 8-25 parts by mass of a curing agent composition, 5-25 parts by mass of a functional filler composition, 60-150 parts by mass of an organic solvent, and 1-5 parts by mass of a functional additive; the functional plastic is PEEK micropowder; the mass ratio of the total mass of the functional plastic and the functional filler composition to the mass of the epoxy resin is (15-25):100. The high-speed copper clad laminate in the present invention has low dielectric loss and excellent heat resistance, meeting the dielectric performance requirements of 5G high-frequency PCB substrates.

Description

Technical Field

[0001] The present invention relates to the technical field of copper clad laminates, and particularly to a high-speed copper clad laminate prepared using functional plastics. Background Art

[0002] With the rapid development of 5G technology, there are increasingly high requirements for the high-frequency, lightweight, and dielectric loss performance of electronic components. As an important part of electronic components, high-speed copper clad laminates determine the industrial technology level of electronic components.

[0003] The existing preparation process of high-speed copper clad laminates is as follows: An epoxy resin binder is coated on the upper and lower surfaces of an electronic-grade glass cloth and thermally cured into a prepreg for copper clad laminates. Multiple prepregs are stacked on top of each other to form a copper clad laminate substrate, and then copper foil is coated on one or both sides of the copper clad laminate substrate and hot-pressed to form a high-speed copper clad laminate.

[0004] Currently, the dielectric constant D k (3.5 - 5.5) and dielectric loss factor D f (>0.010) of copper clad laminates prepared using conventional epoxy resin binders are relatively high. Copper clad laminates made of epoxy resin binders are suitable for conventional circuit substrates, but cannot meet the requirements of today's high-frequency circuit substrate copper clad laminate composites.

[0005] The material performance requirements for 5G high-frequency copper clad laminates are as follows: The dielectric constant D k is lower than 4, and the dielectric loss factor D f is lower than 0.008.

[0006] In order to meet the material performance requirements of 5G high-frequency copper clad laminates, in the prior art, copper clad laminates are made using polytetrafluoroethylene resin with a low dielectric loss factor in combination with high-dielectric-performance fillers. Although the material performance requirements of 5G high-frequency copper clad laminates are met, industrial mass production cannot be achieved. The specific problems of the above prior art are as follows: Polytetrafluoroethylene-based copper clad laminates need to be hot-pressed and formed at a high temperature of 380 - 400 °C, requiring high equipment and complex processes, resulting in a relatively high overall production cost. Therefore, the applicant provides a high-speed copper clad laminate prepared using functional plastics with low dielectric loss and low dielectric constant. Summary of the Invention

[0007] The problem to be solved by the present invention is: to provide a high-speed copper clad laminate prepared using functional plastics, and the high-speed copper clad laminate prepared using functional plastics has the advantage of low dielectric loss D f , which can meet the requirements of today's market and the future development of copper clad laminate materials. The dielectric constant D k is lower than 4, and the dielectric loss factor D f is lower than 0.008.

[0008] A high-speed copper clad laminate prepared using functional plastics is achieved through the following technical solutions:

[0009] A high-speed copper clad laminate prepared using functional plastics is formed by hot pressing and curing several functional plastic-modified epoxy-based prepregs; the functional plastic-modified epoxy-based prepregs are made of electronic-grade glass cloth and functional plastic-modified epoxy resin; the functional plastic-modified epoxy resin includes 5-20 parts by weight of functional plastic microparticles, 100 parts by mass of epoxy resin, 8-25 parts by mass of a curing agent composition, 5-25 parts by mass of a functional filler composition, 60-150 parts by mass of an organic solvent, and 1-5 parts by mass of a functional additive;

[0010] The functional plastic microparticles are PEEK micropowder, and the particle size of the PEEK micropowder is less than 25 microns;

[0011] The mass ratio of the total mass of the functional plastic and the functional filler composition to the mass of the epoxy resin is (15-25):100;

[0012] The functional filler composition includes at least one of nano-scale boron nitride, titanium nitride, silicon dioxide, and sub-micron-scale hollow glass microspheres; the organic solvent is at least one of toluene, xylene, acetone, butanone, N,N-dimethylformamide, DMF, and propylene glycol monomethyl ether; the functional additive includes at least one of a defoaming agent, a leveling agent, and an anti-aging agent.

[0013] The epoxy resin reacts with PEEK micropowder with surface carboxyl activation to form a functional plastic-modified epoxy-based prepreg with a sea-island structure. The PEEK micropowder has good heat resistance stability and low dielectric loss performance, thereby endowing the prepared high-speed copper clad laminate with good heat resistance and dielectric properties. At the same time, the specific functional filler composition is used to improve the overall insulation and heat dissipation of the high-speed copper clad laminate, which can meet the dielectric property requirements, dimensional stability requirements, and anti-creep property requirements of 5G high-frequency PCB substrates. In summary, the high-speed copper clad laminate in the present invention has low dielectric loss and excellent heat resistance, meeting the dielectric property requirements of 5G high-frequency PCB boards.

[0014] Preferably, the functional filler composition is nano-scale boron nitride, titanium nitride, silicon dioxide, and sub-micron-scale hollow glass microspheres.

[0015] With the addition of the main filler - nano - boron nitride, the copper - clad laminate (CCL) in this application endows the application with good low - dielectric - loss factor and low - dielectric - constant performance. In addition, nano - boron nitride has a low coefficient of thermal expansion, high thermal conductivity and insulation, as well as good thermal stability and chemical resistance. Furthermore, it endows the application with good heat - resistant use performance, chemical - corrosion - resistant performance, good processing performance and relatively good insulation and heat - dissipation performance. The good insulation and heat - dissipation performance can assist the heat - resistant use performance, avoid the aging failure of the copper - clad laminate CCL under long - term high - temperature load, and is conducive to the improvement of the overall service life and use stability of the copper - clad laminate CCL.

[0016] Adding a small amount of auxiliary filler - nano - titanium nitride particles in this application can block the gaps between resin molecular chains, thereby improving the density, barrier performance, wear - resistance performance and impact - resistance performance of the copper - clad laminate. The high - density copper - clad laminate CCL structure is conducive to further improving the dielectric constant and dielectric - loss factor. Nano - titanium nitride can thus assist in enhancing the dielectric performance of the copper - clad laminate CCL.

[0017] Adding a small amount of auxiliary filler - nano - silica in this application has a large number of unsaturated residual bonds and hydroxyl groups in different bonding states on its surface, which has a high compatibility with the epoxy resin composition and is easy to cross - link with its polymer chain segments, thereby improving the density of the copper - clad laminate CCL and improving the dielectric constant and dielectric - loss factor. In addition, the copper - clad laminate CCL prepared by adding nano - silica has good weather - resistance performance, mainly because the reflectivity of nano - silica to ultraviolet short - wave 200 - 280nm reaches 70% - 80%; the reflectivity to ultraviolet medium - long - wave 280 - 400nm reaches 80% - 85%; the reflectivity to visible light 400 - 800nm is above 85%; and the reflectivity to near - infrared rays in the 800 - 1350 band also reaches above 70%.

[0018] Adding auxiliary filler - hollow glass microspheres in this application can reduce the total mass of the copper - clad laminate CCL to achieve the purpose of light weight. The main component of hollow glass microspheres is silica, which has more unsaturated residual bonds and hydroxyl groups in different bonding states on its surface, has a high compatibility with the special fluorosilicon - modified epoxy resin and is easy to cross - link with its polymer chain segments, thereby improving the density of the copper - clad laminate CCL, improving the dielectric constant and dielectric - loss factor, and also having good ultraviolet, visible light and infrared light reflection performance, which can improve the overall weather - resistance performance.

[0019] Preferably, the preparation method of the functional plastic particles is as follows:

[0020] Step 1: Freeze the PEEK resin pellets with liquid nitrogen and then place them in a low - temperature crusher for pre - crushing treatment. The particle size of the obtained pre - crushed material is less than 1mm, and the obtained pre - crushed material is input into a disk - type air - flow mill for air - flow grinding to obtain PEEK crushed material;

[0021] Step 2: Transfer the PEEK crushed materials obtained in Step 1 to a fine classifier for particle size screening to obtain PEEK fine crushed materials with a particle size less than 25 microns.

[0022] Step 3: Perform low-temperature plasma treatment on the PEEK fine crushed materials obtained in Step 2. The treatment atmosphere is an O2 / O3 mixed gas, and the volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:(0.5 - 2). The treatment temperature is 0 - 4°C, and the low-temperature plasma treatment is carried out for 300 - 500 s to obtain the finished PEEK crushed materials with surface activation of active functional groups, that is, the target product functional plastic particles.

[0023] Preferably, in Step 3, the obtained finished PEEK crushed materials are subjected to low-temperature plasma treatment. The treatment atmosphere is an O2 / O3 mixed gas, and the volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:2. The treatment temperature is 0°C, and the low-temperature plasma treatment is carried out for 8 minutes to obtain the finished PEEK crushed materials with surface activation of active functional groups, that is, the target product functional plastic particles.

[0024] Active carboxyl functional groups are formed on the surface of the above-mentioned finished PEEK crushed materials, which can react with epoxy resin, solve the problem of the precipitation of the finished PEEK crushed materials caused by the compatibility between the finished PEEK crushed materials and epoxy resin, and effectively improve the service life of high-speed copper clad laminates.

[0025] Preferably, in Step 2, the PEEK crushed materials obtained in Step 1 are transferred to a fine classifier for particle size screening to obtain PEEK fine crushed materials with a particle size less than 25 microns. The obtained PEEK fine crushed materials with a particle size less than 25 microns and an ethanol aqueous solution are put into a planetary ball mill at a mass ratio of 1:(5 - 10). The volume ratio of deionized water to ethanol in the ethanol aqueous solution is 1:(0.2 - 1.0). Using zirconia as the grinding beads, wet ball milling is carried out at 400 - 600 rpm for 15 - 30 minutes to obtain PEEK fine crushed materials.

[0026] After the finished PEEK crushed materials are treated by high-speed ball milling, the particle size is smaller, which can play a nano effect, further improve the dielectric properties, mechanical strength, and impact toughness of high-speed copper clad laminates, and is beneficial to enhancing the market competitiveness of the product high-speed copper clad laminates.

[0027] Preferably, the epoxy resin includes at least fluorosilicon-modified epoxy resin and bisphenol A-type epoxy resin. The fluorosilicon-modified epoxy resin is made of pentafluorophenyl methacrylate, methacryloxy silane KH570, and naphthalene ring-type epoxy resin.

[0028] Preferably, the curing agent composition is composed of pentafluoropropionic anhydride combined with at least one of phthalic anhydride, polyamide resin, and bis-NCO-terminated polyurethane prepolymer.

[0029] Preferably, the polyamide resin in the curing agent composition is at least one of tri-arm polyethylene glycol valerate (amide bond), tri-arm polyethylene glycol succinimidyl carbonate, and bi-arm polyethylene glycol succinimidyl carbonate.

[0030] Preferably, the isocyanate used for capping in the bis-NCO-terminated polyurethane prepolymer includes 1,3,5-tris(3-isocyanato-4-methylphenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0031] The fluorine and silicon elements introduced into the epoxy resin can effectively reduce the dielectric properties, high-temperature resistance, and chemical corrosion resistance of the matrix resin itself. Adjusting the benzene ring content (i.e., the content of π-π conjugated double bonds) in the epoxy resin composition has a positive effect on the dielectric properties of the cured product of the matrix resin. However, it will inevitably lead to a decrease in the impact strength and toughness of the cured product of the matrix resin, which is not conducive to the processing and use of high-speed copper clad laminates. Therefore, the finished PEEK crushed material needs to be processed by high-speed ball milling to refine it. Through the nano-effect of refined PEEK micropowder, the overall impact strength and toughness can be improved. Or a nano-level main filler - nano-level boron nitride is used in combination with an auxiliary filler for toughening and strengthening treatment to prepare a high-speed copper clad laminate with good dielectric properties, processing properties, high-temperature resistance, chemical corrosion resistance, and relatively excellent impact toughness.

[0032] Regarding the impact strength and toughness of high-speed copper clad laminates, the curing agent composition is compounded with a polyamide resin. As an elastomer molecular chain segment, it is used in combination with inorganic fillers to effectively improve the impact strength and toughness of the cured product of the matrix resin, and can also play an auxiliary role in improving the temperature stability and dielectric properties.

[0033] The bis-NCO-terminated polyurethane prepolymer in the curing agent composition endows the copper clad laminate with low-temperature resistance performance, adapts to extreme weather application sites, improves the overall safety factor of the copper clad laminate CCL, and enhances the market competitiveness of the product.

[0034] The introduction of the fluorine-containing curing agent in the composite curing agent is mainly to adjust the fluorine content in the cured product of the matrix resin to ensure the dielectric properties and chemical corrosion resistance of the prepared copper clad laminate CCL.

[0035] In summary, the copper clad laminate prepared in this application has the advantages of low dielectric loss, low dielectric constant, and lightweight.

[0036] Preferably, the preparation method of the high-speed copper clad laminate prepared using functional plastics is as follows:

[0037] Step A, preparation of functional plastic microparticles;

[0038] Step B: After the batching kettle is purged with nitrogen, accurately metered functional plastic particles, epoxy resin, curing agent composition, functional filler composition, organic solvent, and functional additives are put into the batching kettle for defoaming and mixing treatment. Defoaming and mixing are carried out at a kettle temperature of 0 - 10°C, a kettle pressure of 0.06 - 0.08 MPa, and at 200 - 400 rpm for 3 - 5 minutes. Then, the kettle pressure is adjusted to 0.04 - 0.05 MPa, and defoaming and mixing are carried out at 200 - 400 rpm for 10 - 15 minutes. The kettle pressure is maintained at 0.04 - 0.05 MPa, and defoaming and mixing are carried out at 500 - 600 rpm for 5 - 10 minutes to obtain a functional plastic-modified epoxy resin with a solid content of 40 - 60 wt%.

[0039] Step C: Preparation of the functional plastic-modified epoxy-based semi-cured sheet: The functional plastic-modified epoxy resin prepared in Step B is coated on the surface of an electronic-grade glass cloth and baked at 140 - 160°C for 10 - 15 minutes.

[0040] Step D: Preparation of the high-speed copper clad laminate: Take 4 - 12 sheets of the functional plastic-modified epoxy-based semi-cured sheet prepared in Step C, stack the functional plastic-modified epoxy-based semi-cured sheets on top of each other to form a high-speed copper clad laminate substrate, attach an HVLP copper foil to each side of the high-speed copper clad laminate substrate, and then carry out hot pressing and curing molding treatment. After natural cooling, the finished high-speed copper clad laminate is obtained.

[0041] Preferably, in Step D, for the preparation of the high-speed copper clad laminate: Take 4 - 12 sheets of the functional plastic-modified epoxy-based semi-cured sheet prepared in Step C, stack the functional plastic-modified epoxy-based semi-cured sheets on top of each other to form a high-speed copper clad laminate substrate, attach an HVLP copper foil to each side of the high-speed copper clad laminate substrate, and then carry out hot pressing and curing molding treatment. The process parameters for the hot pressing and curing molding are as follows: The initial pressure is 1.5 - 1.8 MPa, the hot plate temperature is 175 - 190°C, and the hot pressing time is 15 - 30 minutes; the middle pressure is 2.4 - 2.6 MPa, the hot plate temperature is 200 - 220°C, and the hot pressing time is 60 - 120 minutes; the final pressure is 3.2 - 3.5 MPa, the hot plate temperature is 220 - 235°C, and the hot pressing time is 15 - 30 minutes; after the final hot pressing treatment, adjust the hot pressing pressure to 0.1 - 0.2 MPa, the hot plate temperature to 120 - 125°C, and the hot pressing time to 30 - 60 minutes. After taking it out and natural cooling to room temperature, the finished high-speed copper clad laminate can be obtained.

[0042] The manufacturing method provided by the present invention is highly similar to the production equipment used in the existing process for manufacturing copper clad laminates with epoxy resin adhesives. That is, the production of high-speed copper clad laminates in the present invention can be satisfied by using a conventional production line for circuit substrates. The manufacturing method of the present invention is relatively simple for polytetrafluoroethylene-based copper clad laminates. The implementation operation difficulty is similar to that of the existing CCL process for manufacturing copper clad laminates with epoxy resin adhesives. The overall production difficulty is relatively low, which is convenient for realizing industrial mass production, reducing the overall production cost of copper clad laminates, and facilitating the popularization and application of high-quality copper clad laminates.

[0043] In summary, the present invention has the following advantages:

[0044] 1. The high-speed copper clad laminate in the invention has low dielectric loss and excellent heat resistance, meeting the dielectric performance requirements of 5G high-frequency substrates.

[0045] 2. The manufacturing method provided by the present invention has relatively low overall production difficulty, which is convenient for realizing industrial mass production, reducing the overall production cost of copper clad laminates, and facilitating the popularization and application of high-quality copper clad laminates. Specific Embodiments

[0046] To further understand the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with examples and comparative examples.

[0047] A high-speed copper clad laminate prepared using functional plastics is formed by hot pressing and curing several functional plastic-modified epoxy-based prepregs. The functional plastic-modified epoxy-based prepregs are made of electronic-grade glass cloth and functional plastic-modified epoxy resin.

[0048] The functional plastic-modified epoxy resin is composed of 5-20 parts by weight of functional plastic particles, 100 parts by mass of epoxy resin, 8-25 parts by mass of a curing agent composition, 5-25 parts by mass of a functional filler composition, 60-150 parts by mass of an organic solvent, and 1-5 parts by mass of a functional additive.

[0049] The epoxy resin includes at least fluorosilicon-modified epoxy resin and bisphenol A-type epoxy resin. The fluorosilicon-modified epoxy resin is made of pentafluorophenyl methacrylate, methacryloxy silane KH570, and naphthalene ring-type epoxy resin.

[0050] The curing agent composition is composed of pentafluoropropionic anhydride in combination with at least one of phthalic anhydride, polyamide resin, and bis-NCO-terminated polyurethane prepolymer.

[0051] Preferably, the curing agent composition is pentafluoropropionic anhydride in combination with phthalic anhydride, polyamide resin, and bis-NCO-terminated polyurethane prepolymer.

[0052] The polyamide resin in the curing agent composition is at least one of tribranched polyethylene glycol valerate (amide bond), tribranched polyethylene glycol succinimidyl carbonate, and dibranched polyethylene glycol succinimidyl carbonate.

[0053] The isocyanate used for capping in the bis-NCO-terminated polyurethane prepolymer includes 1,3,5-tris(3-isocyanato-4-methylphenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0054] The mass ratio of the total mass of the functional plastic and the functional filler composition to the mass of the epoxy resin is (15 - 25):100.

[0055] The functional filler composition includes at least one of nanoscale boron nitride, titanium nitride, silica, and submicron hollow glass microspheres. Preferably, the functional filler composition is nanoscale boron nitride, titanium nitride, silica, and submicron hollow glass microspheres.

[0056] The organic solvent is at least one of toluene, xylene, acetone, methyl ethyl ketone, N,N-dimethylformamide, DMF, and propylene glycol monomethyl ether.

[0057] The functional additives at least include at least one of defoamers, leveling agents, and anti-aging agents.

[0058] Preferably, the functional additives are composed of defoamers, leveling agents, and anti-aging agents.

[0059] The functional plastic particles are PEEK fine powder. Preferably, the particle size of the PEEK fine powder is less than 25 microns.

[0060] The preparation method of the functional plastic particles is as follows:

[0061] Step 1: The PEEK resin pellets are frozen with liquid nitrogen and then placed in a low-temperature crusher for pre-crushing treatment. The particle size of the obtained pre-crushed material is less than 1 mm, and the obtained pre-crushed material is input into a disk-type air jet mill for air jet grinding to obtain PEEK crushed material;

[0062] Step 2: The PEEK crushed material obtained in Step 1 is transferred to a fine classifier for particle size screening treatment to obtain PEEK fine crushed material with a particle size less than 25 microns;

[0063] Step 3: The PEEK fine crushed material with a particle size less than 25 microns obtained in Step 2 is subjected to low-temperature plasma treatment. The treatment atmosphere is an O2 / O3 mixed gas, and the volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:(0.5 - 2). The treatment temperature is 0 - 4 °C, and the low-temperature plasma treatment is carried out for 300 - 500 s to obtain the finished PEEK crushed material with surface activation of active functional groups, that is, functional plastic particles.

[0064] Preferably, in step three, the obtained finished PEEK crushed material is subjected to low-temperature plasma treatment. The treatment atmosphere is a mixed gas of O2 / O3, and the volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:2. The treatment temperature is 0 °C, and the low-temperature plasma treatment is carried out for 8 minutes, then the finished PEEK crushed material with surface activation of active functional groups, that is, the target product functional plastic particles, can be obtained.

[0065] Further preferably, in step two, the PEEK fine crushed material with a particle size less than 25 microns obtained in step two is transferred to a fine classifier for particle size screening treatment to obtain a PEEK fine crushed material with a particle size less than 25 microns. The PEEK fine crushed material with a particle size less than 25 microns and an ethanol aqueous solution are put into a planetary ball mill at a mass ratio of 1:(5 - 10). The volume ratio of deionized water to ethanol in the ethanol aqueous solution is 1:(0.2 - 1.0). Using zirconia as the grinding beads, wet ball milling is carried out at 400 - 600 rpm for 15 - 30 minutes to obtain the PEEK fine crushed material.

[0066] The preparation method of a high-speed copper clad laminate using a functional plastic is as follows:

[0067] Step A, preparation of functional plastic particles;

[0068] In step B, after the batching kettle is purged with nitrogen, accurately metered functional plastic particles, epoxy resin, curing agent composition, functional filler composition, organic solvent, and functional additives are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 0 - 10 °C and a kettle pressure of 0.06 - 0.08 MPa, defoaming and mixing are carried out at 200 - 400 rpm for 3 - 5 minutes, then the kettle pressure is adjusted to 0.04 - 0.05 MPa and defoaming and mixing are carried out at 200 - 400 rpm for 10 - 15 minutes, and the kettle pressure is maintained at 0.04 - 0.05 MPa and defoaming and mixing are carried out at 500 - 600 rpm for 5 - 10 minutes, then the functional plastic-modified epoxy resin with a solid content of 40 - 60 wt% can be prepared.

[0069] Step C, preparation of functional plastic-modified epoxy-based prepreg: The functional plastic-modified epoxy resin prepared in step B is coated on the surface of an electronic-grade glass cloth and baked at 140 - 160 °C for 10 - 15 minutes.

[0070] Step D, preparation of high-speed copper clad laminate: Take 4 - 12 sheets of the functional plastic-modified epoxy-based prepreg prepared in step C, stack the functional plastic-modified epoxy-based prepregs together to form a high-speed copper clad laminate substrate, attach a HVLP copper foil to each side of the high-speed copper clad laminate substrate, and then carry out hot pressing and curing molding treatment, and naturally cool to obtain the finished high-speed copper clad laminate.

[0071] Preferably, in step D, preparation of the high-speed copper clad laminate: Take 4 - 12 functional plastic-modified epoxy-based prepreg sheets prepared in step C, stack the functional plastic-modified epoxy-based prepreg sheets on top of each other to form a high-speed copper clad laminate substrate, attach an HVLP copper foil to each side of the high-speed copper clad laminate substrate, and then perform hot pressing and curing forming treatment. The process parameters for hot pressing and curing forming are as follows: the initial pressure is 1.5 - 1.8 MPa, the hot press plate temperature is 175 - 190 °C, and the hot pressing time is 15 - 30 min; the middle pressure is 2.4 - 2.6 MPa, the hot press plate temperature is 200 - 220 °C, and the hot pressing time is 60 - 120 min; the final pressure is 3.2 - 3.5 MPa, the hot press plate temperature is 220 - 235 °C, and the hot pressing time is 15 - 30 min; after completing the final hot pressing treatment, adjust the hot pressing pressure to 0.1 - 0.2 MPa, the hot press plate temperature is 120 - 125 °C, and the hot pressing time is 30 - 60 min. After taking it out and naturally cooling to room temperature, the finished high-speed copper clad laminate can be obtained.

[0072] Example 1

[0073] A preparation method of a high-speed copper clad laminate prepared using a functional plastic in this example includes the following steps:

[0074] Step 1, preparation of functional plastic-modified epoxy resin;

[0075] S1.1, preparation of fluorosilicon-modified epoxy resin: Add 0.1 mol of γ-methacryloxypropyltrimethoxysilane (KH570), 0.1 mol of pentafluorophenyl methacrylate (CAS NO.: 13642 - 97 - 2), and 80 g of xylene to a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping funnel. Heat to 80 °C and keep it warm for 10 min. Add 0.25 g of AIBN catalyst to the reaction system through the dropping funnel every 30 min. Keep the reaction temperature at 85 °C and react for 100 min under nitrogen protection. Then cool to 30 °C to obtain a fluorosilicon intermediate; Mix the obtained fluorosilicon intermediate with 320 g of EBA-65 series naphthalene ring-type epoxy resin (CAS: 27610 - 48 - 6), 240 g of toluene, and 150 g of butanone evenly at 180 rpm. Then add 1.0 g of DMP-30 catalyst to the four-necked flask, heat to 108 °C and carry out ring-opening reaction for 30 min, and cool to room temperature to obtain fluorosilicon-modified epoxy resin (fluorosilicon-modified EBA-65 series naphthalene ring-type epoxy resin);

[0076] Simultaneously prepare an isocyanate-terminated polyurethane prepolymer: First, prepare the polyol: Charge 1 mol of 2,6-diamino-3,5-difluoropyridine (CAS NO.: 247069-27-8), 1 mol of terephthalic acid, and 2.061 mol of 3-methyl-1,5-pentanediol into the reaction kettle. Stir and mix evenly at 240 rpm, then heat up to 135 °C at a rate of 0.6 °C / min and hold for 3 h. Then, heat up to 230 °C at a uniform rate of 0.5 °C / min and hold for 200 min. Then, control the temperature at the top of the distillation column to be 102 ± 0.5 °C. As the reaction proceeds, sample and measure the acid value. When the measured acid value reaches 30 ± 2 mgKOH / g, add 120 ppm of tetrabutyl titanate and evacuate the vacuum, that is, the mass of tetrabutyl titanate is 12×10 -3 wt% of the total mass of 2,6-diamino-3,5-difluoropyridine, terephthalic acid, and 3-methyl-1,5-pentanediol. Gradually evacuate the pressure in the kettle from atmospheric pressure to a relative vacuum of -0.098 MPa (25 torr, the set vacuum degree of the vacuum pump equipment) within 4 h, and then take samples for detection. When the hydroxyl value of the product in the kettle reaches 112 ± 3 mgKOH / g, the product is qualified. Break the vacuum in the reaction kettle with nitrogen and cool down to 110 °C, unload and package to obtain a fluorinated polyol with a number average molecular weight of 1000; Then, add 0.2 mol of the fluorinated polyol prepared in S1.1, 0.3 mol of polytetrahydrofuran ether diol with a molecular weight of 2000 (BASF PolyTHF 2000), 1.2 mol of dicyclohexylmethane diisocyanate HMDI (Yantai Wanhua), 0.05 mol of 4-(hexafluoro-2-hydroxyisopropyl)aniline (CAS NO.: 722-92-9), 0.85 mol of 1,4-butanediol, and 0.1 mol of 1,4-butenediol (CAS No.: 110-64-5) into the reaction kettle, mix evenly, heat to 80 °C and react until the measured viscosity of the liquid material in the kettle reaches between 5000 and 10000 mPa·s / 25 °C. The measured viscosity of the liquid material is 6540 Pa·s / 25 °C. Add 0.6 mol of 1,3,5-tris(3-isocyanato-4-methylphenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (CAS.: 20649-91-6) for end-capping reaction for 10 min, and mix evenly to obtain a polyurethane prepolymer end-capped with 1,3,5-tris(3-isocyanato-4-methylphenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione;

[0077] The boron nitride nanosheets, boron nitride whiskers, nano titanium nitride, nano silicon dioxide, and hollow glass microspheres were all subjected to wet ball milling treatment with KH570 coupling agent for 1 h, and the mass ratio of KH570 coupling agent to the above inorganic fillers (boron nitride nanosheets, boron nitride whiskers, nano titanium nitride, nano silicon dioxide, hollow glass microspheres) was controlled at 1:19;

[0078] At the same time, the preparation of functional plastic microparticles was carried out, and the specific method was as follows:

[0079] First, the PEEK resin pellets (PEEK Junhua 5600G) were frozen with liquid nitrogen and then placed in a low-temperature crusher for pre-crushing treatment. The obtained pre-crushed material was screened with a 1 mm mesh sieve, and the particle size of the obtained pre-crushed material was less than 1 mm. The obtained pre-crushed material was fed into a disk-type air classifier for air milling to obtain PEEK crushed material; then it was transferred to a fine classifier for particle size screening treatment to obtain PEEK fine crushed material with a particle size less than 25 microns; finally, the obtained PEEK fine crushed material was subjected to low-temperature plasma treatment. The treatment atmosphere was a mixed gas of O2 / O3, and the volume ratio of O2 to O3 in the O2 / O3 mixed gas was 1:1. The treatment temperature was 0 °C, and the low-temperature plasma treatment was carried out for 480 s to obtain the finished PEEK crushed material with surface activation of active functional groups, that is, the target product functional plastic microparticles;

[0080] S1.2 After the batching kettle is purged with nitrogen, weigh 60 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin (DIC, CAS: 2386-87-0, epoxy equivalent: 128-140, viscosity: 200 mPas), 35 parts of bisphenol A epoxy resin E20 (Baleng Petrochemical E20 epoxy resin cyd011, CAS: 38891-59-7), 5 parts of the fluorosilicon-modified EBA-65 series naphthalene ring-type epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil (CAS NO.: 54-20-6), 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1 (i.e., the polyurethane prepolymer terminated with 1,3,5-tris(3-isocyanato-4-methylphenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), 2 parts of triblock polyethylene glycol pentanoate (amide bond) with a peak molecular weight Mp of 2000 (3-arm PEG-SGA, Xiamen Sunrobang), 3 parts of boron nitride nanosheets (hBN-500nm boron nitride nanosheets, Yamei Nano Technology), 1 part of boron nitride whiskers (Beijing Decodaojin Technology, diameter: 1um, length: 10-20um), 1 part of nano titanium nitride (Wuhan Huaxiang Kejie Biotechnology, average particle size 700nm), 2 parts of nano silica (CAS No. 68611-44-9, AEROSIL R972), 5 parts of hollow glass microspheres (US 3M hollow glass microspheres S15), 8 parts of the finished PEEK broken material with surface activation of active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoamer - BASF Efka PB 2001, 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a kettle temperature of 4 ± 0.5 °C and a kettle pressure of 0.08 MPa, defoaming and mixing are carried out at 200 rpm for 5 min. Then the kettle pressure is adjusted to 0.05 MPa and defoaming and mixing are carried out at 400 rpm for 15 min. The kettle pressure is maintained at 0.04 MPa and defoaming and mixing are carried out at 600 rpm for 10 min to obtain the functional plastic-modified epoxy resin;

[0081] Step 2, Preparation of the functional plastic-modified epoxy-based semi-cured sheet: Coat the above-mentioned functional plastic-modified epoxy resin on the surface of 2116-type electronic-grade glass cloth and bake it at 150 °C for 10 min to obtain the semi-cured sheet;

[0082] Step 3, Preparation of high-speed copper clad laminate: Take 8 sheets of the above-mentioned functional plastic-modified epoxy-based prepreg, stack the functional plastic-modified epoxy-based prepregs together to form a high-speed copper clad laminate substrate, attach a sheet of HVLP copper foil to each side of the high-speed copper clad laminate substrate, and then carry out hot pressing and curing molding treatment. The process parameters of the hot pressing and curing molding are as follows: the initial pressure is 1.6 MPa, the hot platen temperature is 180 °C, and the hot pressing time is 30 min; the middle pressure is 2.5 MPa, the hot platen temperature is 215 °C, and the hot pressing time is 100 min; the end pressure is 3.25 MPa, the hot platen temperature is 225 °C, and the hot pressing time is 20 min; after completing the end hot pressing treatment, adjust the hot pressing pressure to 0.15 MPa, the hot platen temperature is 120 °C, and the hot pressing time is 60 min, and naturally cool to obtain the finished high-speed copper clad laminate.

[0083] Example 2

[0084] This example is basically the same as Example 1, the difference is: S1.2, after the batching kettle is replaced with nitrogen, weigh 60 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin, 30 parts of bisphenol A epoxy resin E20, 10 parts of the fluorosilicon-modified EBA-65 series naphthalene ring epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil, 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1, 2 parts of triblock polyethylene glycol valerate with a peak molecular weight Mp of 2000, 3 parts of boron nitride nanosheets, 1 part of boron nitride whiskers, 1 part of nano titanium nitride, 2 parts of nano silica, 5 parts of hollow glass microspheres S15, 8 parts of the finished PEEK broken material with surface activation of active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoaming agent - BASF Efka PB 2001, 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa and defoaming and mixing at 200 rpm for 5 min, adjust the kettle pressure to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and maintain the kettle pressure at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min to obtain the functional plastic-modified epoxy resin.

[0085] Example 3

[0086] This example is basically the same as Example 1, with the differences being as follows: S1.2, after the batching kettle is purged with nitrogen, weigh 55 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin, 25 parts of bisphenol A epoxy resin E20, 20 parts of the fluorosilicon-modified EBA-65 series naphthalene ring epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil, 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1, 2 parts of triblock polyethylene glycol valerate with a peak molecular weight Mp of 2000, 3 parts of boron nitride nanosheets, 1 part of boron nitride whiskers, 1 part of nanometer titanium nitride, 2 parts of nanometer silicon dioxide, 5 parts of hollow glass microspheres S15, 8 parts of the surface-activated finished PEEK crushed material with active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoamer - BASF Efka PB 2001, 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa, and defoaming and mixing at 200 rpm for 5 min, adjust the kettle pressure to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and maintain the kettle pressure at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min, then the functional plastic-modified epoxy resin can be prepared.

[0087] Example Four

[0088] This example is basically the same as Example 2, with the differences being as follows: S1.2, after the batching kettle is purged with nitrogen, weigh 60 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin, 30 parts of bisphenol A epoxy resin E20, 10 parts of the fluorosilicon-modified EBA-65 series naphthalene ring epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil, 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1, 2 parts of triblock polyethylene glycol valerate with a peak molecular weight Mp of 2000, 3 parts of boron nitride nanosheets, 1 part of boron nitride whiskers, 1 part of nanometer titanium nitride, 2 parts of nanometer silicon dioxide, 5 parts of hollow glass microspheres S15, 5 parts of the surface-activated finished PEEK crushed material with active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoamer - BASF Efka PB 2001, 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa, and defoaming and mixing at 200 rpm for 5 min, adjust the kettle pressure to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and maintain the kettle pressure at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min, then the functional plastic-modified epoxy resin can be prepared.

[0089] Example Five

[0090] This example is basically the same as Example 2, with the differences being: S1.2, after the batching kettle is purged with nitrogen, weigh 60 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin, 30 parts of bisphenol A epoxy resin E20, 10 parts of the fluorosilicon-modified EBA-65 series naphthalene ring epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil, 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1, 2 parts of the three-arm polyethylene glycol valerate with a peak molecular weight Mp of 2000, 3 parts of boron nitride nanosheets, 1 part of boron nitride whiskers, 1 part of nano titanium nitride, 2 parts of nano silica, 5 parts of hollow glass microspheres S15, 12 parts of the surface-activated finished PEEK broken material with active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoamer - BASF Efka PB 2001, 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa and defoaming and mixing at 200 rpm for 5 min, adjust the kettle pressure to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and maintain the kettle pressure at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min, then the functional plastic-modified epoxy resin can be prepared.

[0091] Example Six

[0092] This example is basically the same as Example 2, with the differences being: S1.2, after the batching kettle is purged with nitrogen, weigh 60 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin, 30 parts of bisphenol A epoxy resin E20, 10 parts of the fluorosilicon-modified EBA-65 series naphthalene ring epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil, 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1, 2 parts of the three-arm polyethylene glycol valerate with a peak molecular weight Mp of 2000, 1 part of boron nitride nanosheets, 1 part of boron nitride whiskers, 1 part of nano titanium nitride, 1 part of nano silica, 11 parts of hollow glass microspheres S15, 10 parts of the surface-activated finished PEEK broken material with active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoamer - BASF Efka PB 2001, 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa and defoaming and mixing at 200 rpm for 5 min, adjust the kettle pressure to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and maintain the kettle pressure at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min, then the functional plastic-modified epoxy resin can be prepared.

[0093] Example VII

[0094] This example is basically the same as Example II, except that: the preparation of functional plastic microparticles is as follows:

[0095] First, the PEEK resin pellets (PEEK Junhua 5600G) are frozen with liquid nitrogen and then placed in a low-temperature crusher for pre-crushing treatment. The obtained pre-crushed material is screened with a 1mm mesh sieve. The particle size of the obtained pre-crushed material is less than 1mm. The obtained pre-crushed material is fed into a disc-type air classifier for air grinding to obtain PEEK crushed material; then it is transferred to a fine classifier for particle size screening treatment to obtain PEEK fine crushed material with a particle size less than 25 microns; finally, the obtained PEEK fine crushed material is subjected to low-temperature plasma treatment. The treatment atmosphere is an O2 / O3 mixed gas. The volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:2. The treatment temperature is 0°C. After 480s of low-temperature plasma treatment, the finished PEEK crushed material with surface activation of active functional groups, that is, the target product functional plastic microparticles, is obtained.

[0096] Example VIII

[0097] This example is basically the same as Example II, except that: the preparation of functional plastic microparticles is as follows:

[0098] First, the PEEK resin pellets (PEEK Junhua 5600G) are frozen with liquid nitrogen and then placed in a low-temperature crusher for pre-crushing treatment. The obtained pre-crushed material is screened with a 1mm mesh sieve. The particle size of the obtained pre-crushed material is less than 1mm. The obtained pre-crushed material is fed into a disc-type air classifier for air grinding to obtain PEEK crushed material; then it is transferred to a fine classifier for particle size screening treatment to obtain PEEK fine crushed material with a particle size less than 25 microns. The PEEK fine crushed material and the ethanol aqueous solution are put into a planetary ball mill at a mass ratio of 1:(5 - 10). The volume ratio of deionized water to ethanol in the ethanol aqueous solution is 1:0.4. Using zirconia as the grinding beads, wet ball milling is carried out at 480rpm for 20min to obtain the PEEK fine crushed material; finally, the obtained PEEK fine crushed material is subjected to low-temperature plasma treatment. The treatment atmosphere is an O2 / O3 mixed gas. The volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:2. The treatment temperature is 0°C. After 480s of low-temperature plasma treatment, the finished PEEK crushed material with surface activation of active functional groups, that is, the target product functional plastic microparticles, is obtained.

[0099] Comparative Example I:

[0100] This comparative example is basically the same as the preparation of functional plastic modified epoxy resin in Example I, except that: the difference in Step 1, and the rest are the same.

[0101] Step 1, Preparation of the binder resin composition: After the batching kettle is purged with nitrogen, weigh 60 parts by mass of HP-7200H dicyclopentadiene phenol epoxy resin, 40 parts by mass of bisphenol A epoxy resin E20, 4 parts by mass of dicyandiamide (CAS No. 461-58-5), 6 parts by mass of 2-ethyl-4-methylimidazole (CAS.No: 931-36-2), 12 parts by mass of aluminum hydroxide (HT-205 ultrafine aluminum hydroxide, CAS.No: 21645-51-2, Shandong Taixing New Materials), 8 parts by mass of magnesium hydroxide with 800 mesh (CAS.No: 1309-42-8), 20 parts by mass of acetone, 80 parts by mass of xylene, 12 parts by mass of methyl ethyl ketone, 2 parts by mass of defoamer - BASF Efka PB 2001, 3 parts by mass of leveling agent - BYK RHEOBYK R 605 into the batching kettle for defoaming and mixing treatment. At a kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa and defoaming and mixing at 200 rpm for 5 min, adjust the kettle pressure to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and maintain the kettle pressure at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min to obtain the functional plastic modified epoxy resin.

[0102] Comparative Example 2:

[0103] This comparative example is basically the same as Comparative Example 1, and the difference lies in: Step 1, Preparation of the binder resin composition: After the batching kettle is purged with nitrogen, weigh 60 parts by mass of HP-7200H dicyclopentadiene phenol epoxy resin, 40 parts by mass of bisphenol A epoxy resin E20, 4 parts by mass of dicyandiamide (CAS No. 461-58-5), 6 parts by mass of 2-ethyl-4-methylimidazole (CAS.No: 931-36-2), 20 parts of the finished PEEK crushed material surface-activated by the active functional groups in S1.1, 20 parts by mass of acetone, 80 parts by mass of xylene, 12 parts by mass of methyl ethyl ketone, 2 parts by mass of defoamer - BASF Efka PB 2001, 3 parts by mass of leveling agent - BYK RHEOBYK R 605 into the batching kettle for defoaming and mixing treatment. At a kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa and defoaming and mixing at 200 rpm for 5 min, adjust the kettle pressure to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and maintain the kettle pressure at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min to obtain the functional plastic modified epoxy resin.

[0104] Comparative Example 3:

[0105] This comparative example is basically the same as the preparation of the binder resin composition in Example 1, except that: Step 1, preparation of the binder resin composition: After the batching kettle is purged with nitrogen, 60 parts by mass of HP-7200H dicyclopentadiene phenol epoxy resin, 40 parts by mass of bisphenol A epoxy resin E20, 4 parts by mass of dicyandiamide (CAS No. 461-58-5), 6 parts by mass of 2-ethyl-4-methylimidazole (CAS.No: 931-36-2), 6 parts of boron nitride nanosheets, 2 parts of boron nitride whiskers, 2 parts of nano titanium nitride, 2 parts of nano silica, 8 parts of hollow glass microspheres S15, 20 parts by mass of acetone, 80 parts by mass of xylene, 12 parts by mass of methyl ethyl ketone, 2 parts of defoaming agent - BASF Efka PB 2001, and 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa, and defoaming and mixing at 200 rpm for 5 min, the kettle pressure is adjusted to 0.05 MPa and defoaming and mixing is carried out at 400 rpm for 15 min, and the kettle pressure is maintained at 0.04 MPa and defoaming and mixing is carried out at 600 rpm for 10 min to obtain the functional plastic modified epoxy resin.

[0106] Comparative Example 4:

[0107] This comparative example is basically the same as Comparative Example 1, except that: S1.2, after the batching kettle is purged with nitrogen, 60 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin, 30 parts of bisphenol A epoxy resin E20, 10 parts of the fluorosilicon-modified EBA-65 series naphthalene ring type epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil, 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1, 2 parts of triblock polyethylene glycol valerate with a peak molecular weight Mp of 2000, 2 parts of boron nitride nanosheets, 1 part of boron nitride whiskers, 1 part of nano titanium nitride, 1 part of nano silica, 1 part of hollow glass microspheres S15, 5 parts of the surface-activated finished PEEK crushed material with active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoaming agent - BASF Efka PB 2001, and 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa, and defoaming and mixing at 200 rpm for 5 min, the kettle pressure is adjusted to 0.05 MPa and defoaming and mixing is carried out at 400 rpm for 15 min, and the kettle pressure is maintained at 0.04 MPa and defoaming and mixing is carried out at 600 rpm for 10 min to obtain the functional plastic modified epoxy resin.

[0108] Comparative Example 5:

[0109] This comparative example is basically the same as the preparation of the binder resin composition in Example 1, except that: S1.2, after the batching kettle is purged with nitrogen, 60 parts by weight of HP-7200H dicyclopentadiene phenol epoxy resin, 30 parts of bisphenol A epoxy resin E20, 10 parts of the fluorosilicon-modified EBA-65 series naphthalene ring type epoxy resin prepared in S1.1, 0.5 part of 5-trifluoromethyluracil, 7.5 parts of the isocyanate-terminated polyurethane prepolymer prepared in S1.1, 2 parts of triblock polyethylene glycol valerate with a peak molecular weight Mp of 2000, 3 parts of boron nitride nanosheets, 1 part of boron nitride whiskers, 1 part of nano titanium nitride, 1 part of nano silica, 4 parts of hollow glass microspheres S15, 20 parts of the surface-activated finished PEEK crushed material with active functional groups in S1.1, 20 parts of acetone, 80 parts of xylene, 12 parts of methyl ethyl ketone, 2 parts of defoamer - BASF Efka PB 2001, and 3 parts of leveling agent - BYK RHEOBYK R 605 are put into the batching kettle for defoaming and mixing treatment. At a batching kettle temperature of 4 ± 0.5 °C, a kettle pressure of 0.08 MPa, and defoaming and mixing at 200 rpm for 5 min, the kettle pressure is adjusted to 0.05 MPa and defoaming and mixing at 400 rpm for 15 min, and the kettle pressure is maintained at 0.04 MPa and defoaming and mixing at 600 rpm for 10 min to obtain the functional plastic-modified epoxy resin. Although the prepared copper clad laminate has excellent dielectric properties, its production cost is high and its toughness is relatively poor.

[0110] Comparative Example 6:

[0111] This comparative example is basically the same as the preparation of the binder resin composition in Example 1, except that: Step 3, preparation of high-speed copper clad laminate: Take 8 sheets of the functional plastic-modified epoxy-based prepreg prepared in Step 3, stack the functional plastic-modified epoxy-based prepregs on top of each other to form a high-speed copper clad laminate substrate, attach a HVLP copper foil to each side of the high-speed copper clad laminate substrate, and then perform hot pressing and curing treatment at a pressure of 2.4 MPa, a hot press plate temperature of 200 °C, and a hot pressing time of 180 min, and naturally cool to obtain the finished high-speed copper clad laminate.

[0112] Comparative Example 7:

[0113] This comparative example is basically the same as the preparation of the binder resin composition in Example 1, except that: the preparation of functional plastic microparticles, the specific method is as follows: First, freeze the PEEK resin pellets (PEEK Junhua 5600G) with liquid nitrogen and then place them in a low-temperature crusher for pre-crushing treatment. The obtained pre-crushed material is screened with a 1 mm mesh sieve, and the particle size of the obtained pre-crushed material is less than 1 mm. The obtained pre-crushed material is input into a disk-type air classifier for air grinding to obtain PEEK crushed material; finally, it is transferred to a fine classifier for particle size screening treatment to obtain PEEK fine crushed material with a particle size less than 25 microns.

[0114] Comparative Example 8:

[0115] This comparative example is basically the same as the preparation of the binder resin composition in Example 1, except that: the preparation of functional plastic microparticles is as follows: First, the PEEK resin pellets (PEEK Junhua 5600G) are frozen with liquid nitrogen and then placed in a low-temperature crusher for pre-crushing treatment. The obtained pre-crushed material is screened with a 1mm mesh sieve, and the particle size of the obtained pre-crushed material is less than 1mm. The obtained pre-crushed material is fed into a disk-type air jet mill for air jet grinding to obtain PEEK crushed material; finally, it is transferred to a fine classifier for particle size screening treatment to obtain PEEK fine crushed material with a particle size of 30-40 microns; finally, the obtained PEEK fine crushed material is subjected to low-temperature plasma treatment. The treatment atmosphere is an O2 / O3 mixed gas, and the volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:1. The treatment temperature is 0 °C, and the low-temperature plasma treatment is carried out for 480 s to obtain the finished PEEK crushed material with surface activation of active functional groups, that is, the target product functional plastic microparticles.

[0116] The high-speed copper clad laminates obtained in the above examples and comparative examples were subjected to performance tests. The results are shown in Table 1.

[0117] Table 1: Test parameter table of copper clad laminate

[0118]

[0119]

[0120] Remarks: Performance detection test: 1. Tg test method: Determined according to IPC TM—650 2.4.25 (DSC). 2. Dielectric constant and dielectric loss factor test method: Determined according to IPC TM—650 2.5.5.5 (10 GHz) method, and the test conditions are C-24 / 23 / 50. 3. Thermal expansion coefficient test method: Determined according to IPC TM—650 2.4.24 method. 4. Peel strength test method: Determined according to IPC TM—650 2.4.8 method, and the test conditions are 288 °C / 10 s.

[0121] Combining Examples 1 to 8 and Comparative Examples 1 to 8 and Table 1, it can be seen that comparing Examples 1 to 3 with Comparative Example 1, the copper clad laminates prepared from the epoxy resin composition formed by dicyclopentadiene-type epoxy resin, bisphenol A-type epoxy resin, and the prepared fluorosilicon-modified epoxy resin have relatively better comprehensive performance.

[0122] Combined with Examples 1 to 8 and Comparative Examples 1 to 8 and in conjunction with Table 1, it can be seen that when compared with Comparative Example 1, for Examples 1 to 3, the composite curing agent composed of pentafluoropropionic anhydride, isocyanate-capped polyurethane prepolymer, and polyamide resin has relatively better comprehensive properties for the prepared copper clad laminate.

[0123] In addition, the IZOD notched impact strength in Example 1 is 16.95 J / M, the IZOD notched impact strength in Example 2 is 18.38 J / M, while the IZOD notched impact strength in Comparative Example 1 is 13.51 J / M, and the IZOD notched impact strength in Comparative Example 2 is 9.07 J / M. From this, it can be known that the copper clad laminate prepared under the combination of the formula in this application and the specific preparation process has relatively good impact toughness, which is convenient for the overall processing and production. And the ball milling and nanosizing treatment of PEEK micropowder is beneficial to the improvement of the mechanical strength and impact toughness of the high-speed copper clad laminate.

[0124] Combined with Examples 1 to 8 and Comparative Examples 1 to 8 and in conjunction with Table 1, it can be seen that the copper clad laminate prepared with a functional filler composition composed of nanoscale boron nitride, titanium nitride, silicon dioxide, and submicron hollow glass microspheres has relatively better comprehensive properties.

[0125] Combined with Examples 1 to 8 and Comparative Examples 1 to 8 and in conjunction with Table 1, it can be seen that when the mass ratio of the total mass of the functional plastic and the functional filler composition to the mass of the epoxy resin is (15 - 25):100, the copper clad laminate prepared has relatively better comprehensive properties.

[0126] Combined with Examples 1 to 8 and Comparative Examples 1 to 8 and in conjunction with Table 1, it can be seen that the surface activation of the finished PEEK broken material can effectively improve the physical and chemical properties of the copper clad laminate, that is, the necessity of surface activation of the PEEK broken material. The surface forms active carboxyl functional groups that can react with the epoxy resin, solving the problem of the precipitation of the finished PEEK broken material caused by the incompatibility between the finished PEEK broken material and the epoxy resin, and effectively improving the service life of the high-speed copper clad laminate.

[0127] Combined with Examples 1 to 8 and Comparative Examples 1 to 8 and in conjunction with Table 1, it can be seen that the copper clad laminate prepared by using the three-stage hot pressing method provided in the present invention has relatively better comprehensive properties.

[0128] Combined with Examples 1 to 8 and Comparative Examples 1 to 8 and in conjunction with Table 1, it can be seen that the copper clad laminate prepared with PEEK micropowder having a particle size less than 25 microns has relatively better comprehensive properties.

Claims

1. A high-speed copper-clad laminate made of functional plastic, characterized in that: The high-speed copper-clad laminate prepared using functional plastic is formed by hot-pressing and curing a plurality of functional plastic-modified epoxy-based prepregs; The functional plastic modified epoxy-based prepreg is made of electronic grade glass cloth and functional plastic modified epoxy resin; The functional plastic modified epoxy resin comprises 5-20 parts by weight of functional plastic particles, 100 parts by weight of epoxy resin, 8-25 parts by weight of a curing agent composition, 5-25 parts by weight of a functional filler composition, 60-150 parts by weight of an organic solvent, and 1-5 parts by weight of a functional additive; The functional plastic particles are PEEK powders, and the particle size of the PEEK powders is less than 25 microns; The mass ratio of the total mass of the functional plastic particles and the functional filler composition to the mass ratio of the epoxy resin (15-25): 100; The functional filler composition includes at least one of nano-sized boron nitride, titanium nitride, silicon dioxide, and submicron-sized hollow glass microspheres; the organic solvent is at least one of toluene, xylene, acetone, butanone, N,N-dimethylformamide, and propylene glycol monomethyl ether; the functional additive includes at least one of a defoamer, a leveling agent, and an anti-aging agent; The preparation method of the functional plastic particles is as follows: Step 1: freeze the PEEK resin pellets with liquid nitrogen and place them in a low-temperature pulverizer for pre-crushing. The particle size of the obtained pre-crushed material is less than 1 mm. The obtained pre-crushed material is input into a disc-type air flow mill for air flow grinding to obtain PEEK crushed material; Step 2: The PEEK crushed material obtained in step 1 is transferred to a fine classifier for classification and particle size screening to obtain a PEEK fine crushed material with a particle size of less than 25 microns; Step three, the PEEK fine crushed material with a particle size of less than 25 microns obtained in step two is subjected to low-temperature plasma treatment, the treatment atmosphere is an O2 / O3 mixed gas, the volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:(0.5-2), the treatment temperature is 0-4°C, and the low-temperature plasma treatment is performed for 300-500s to obtain a finished PEEK crushed material with surface activation of active functional groups, that is, functional plastic particles.

2. The high-speed copper-clad laminate made of functional plastic according to claim 1, characterized in that: In step three, the PEEK finely crushed material is subjected to low-temperature plasma treatment. The treatment atmosphere is an O2 / O3 mixed gas. The volume ratio of O2 to O3 in the O2 / O3 mixed gas is 1:

2. The treatment temperature is 0°C. The low-temperature plasma treatment is performed for 8 minutes to obtain the finished PEEK crushed material with active functional groups activated on the surface, that is, functional plastic particles.

3. The high-speed copper-clad laminate made of functional plastic according to claim 2, characterized in that: Step 2: The PEEK crushed material obtained in step 1 is transferred to a micro-classifier for classification and particle size screening to obtain a PEEK fine crushed material with a particle size of less than 25 microns. The obtained PEEK fine crushed material with a particle size of less than 25 microns and an ethanol aqueous solution are put into a planetary ball mill at a mass ratio of 1: (5-10), the volume ratio of deionized water to ethanol in the ethanol aqueous solution is 1: (0.2-1.0), zirconium oxide is used as a grinding bead, and wet ball milling is performed at 400-600rpm for 15-30min to obtain the PEEK fine crushed material.

4. The high-speed copper-clad laminate made of functional plastic according to claim 1, characterized in that: The epoxy resin at least includes fluorine-silicon modified epoxy resin and bisphenol A type epoxy resin, and the fluorine-silicon modified epoxy resin is made of pentafluorophenyl methacrylate, methacryloxysilane KH570 and naphthalene ring type epoxy resin.

5. The high-speed copper-clad laminate made of functional plastic according to claim 1, characterized in that: The curing agent composition is composed of at least one of pentafluoropropionic anhydride, phthalic anhydride, polyamide resin, and double NCO-terminated polyurethane prepolymer.

6. The high-speed copper-clad laminate made of functional plastic according to claim 5, characterized in that: The polyamide resin in the curing agent composition is at least one of three-arm polyethylene glycol valerate (amide bond), three-arm polyethylene glycol succinimide carbonate, and two-arm polyethylene glycol succinimide carbonate.

7. The high-speed copper-clad laminate made of functional plastic according to claim 5, characterized in that: The end-blocking isocyanate in the double NCO-terminated polyurethane prepolymer includes 1,3,5-tris(3-isocyanato-4-methylphenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

8. The high-speed copper-clad laminate made of functional plastic according to claim 1, characterized in that: The preparation method of the high-speed copper-clad laminate prepared using functional plastic is as follows: Step A, preparation of functional plastic particles; Step B, after the batching kettle is replaced with nitrogen, the accurately measured functional plastic particles, epoxy resin, curing agent composition, functional filler composition, organic solvent, and functional additive are put into the batching kettle for defoaming and mixing treatment, and the batching kettle temperature is 0-10°C, the kettle pressure is 0.06-0.08MPa, and the defoaming and mixing are carried out at 200-400rpm for 3-5min, the kettle pressure is adjusted to 0.04-0.05MPa, and the defoaming and mixing are carried out at 200-400rpm for 10-15min, the kettle pressure is maintained at 0.04-0.05MPa, and the defoaming and mixing are carried out at 500-600rpm for 5-10min, and the functional plastic modified epoxy resin with a solid content of 40-60wt% can be obtained; Step C, preparation of functional plastic modified epoxy prepreg: coating the functional plastic modified epoxy resin prepared in step B on the upper surface of electronic grade glass cloth, and baking at 140-160° C. for 10-15 minutes; Step D, preparation of high-speed copper clad laminate: take 4-12 functional plastic modified epoxy prepregs prepared in step C, stack the functional plastic modified epoxy prepregs on each other to form a high-speed copper clad laminate substrate, attach a HVLP copper foil on both sides of the high-speed copper clad laminate substrate, then perform hot pressing curing and molding treatment, and naturally cool to obtain a finished high-speed copper clad laminate.

9. The high-speed copper-clad laminate made of functional plastic according to claim 8, characterized in that: The step D, preparation of high-speed copper clad laminate: take 4-12 functional plastic modified epoxy prepregs prepared in step C, stack the functional plastic modified epoxy prepregs together to form a high-speed copper clad laminate substrate, attach a HVLP copper foil on both sides of the high-speed copper clad laminate substrate, and then perform hot pressing curing and molding. The hot pressing curing and molding process parameters are as follows: the head end pressure is 1.5-1.8MPa, the hot pressing plate temperature is 175-190°C, and the hot pressing time is 15-30min The middle end pressure is 2.4-2.6MPa, the hot pressing plate temperature is 200-220℃, and the hot pressing time is 60-120min; the terminal pressure is 3.2-3.5MPa, the hot pressing plate temperature is 220-235℃, and the hot pressing time is 15-30min; after completing the terminal hot pressing treatment, the hot pressing pressure is adjusted to 0.1-0.2MPa, the hot pressing plate temperature is 120-125℃, and the hot pressing time is 30-60min. After taking it out and cooling it naturally to room temperature, the finished high-speed copper clad laminate can be obtained.

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