CN114889273B - Glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate and preparation method thereof - Google Patents
Glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate and preparation method thereof Download PDFInfo
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Abstract
The invention provides a glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate and a preparation method thereof, which belong to the technical field of copper-clad plates and comprise, by weight, 5-15 parts of polybutadiene, 2-6 parts of a styrene-butadiene copolymer, 3-9 parts of ethylene propylene diene monomer, 0.2-1.5 parts of an initiator and 70-90 parts of ceramic powder, wherein the raw materials are sequentially added into a solvent to obtain a glue solution, the glue solution is scraped on the surface of a PTFE film, and a prepreg is obtained after low-temperature drying, so that the microwave dielectric substrate is prepared. The microwave dielectric substrate with wide dielectric constant coverage can be prepared without glass cloth, and the microwave dielectric substrate with adjustable dielectric constant and composite substrate temperature coefficient can be prepared by adopting ceramic powder formulas with different dielectric constants, so that the microwave dielectric substrate has wide application, simple and controllable preparation process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate and a preparation method thereof.
Background
With the rapid development of modern information technology industry, society has entered a highly informationized era. In order to process the rapidly growing data, electronic communication devices are gradually coming into the trend of high frequency and miniaturization. Therefore, the high-frequency microwave substrate technology has higher requirements, and not only needs to meet the requirements of miniaturization and high integration, but also needs to develop towards low power consumption, high reliability and low cost.
For a pure microwave dielectric ceramic substrate, although the substrate has excellent dielectric property in a microwave frequency band, the substrate has the defects of brittleness, poor mechanical property and high processing difficulty. Although the organic resin substrate has good dielectric properties, it has disadvantages such as a high thermal expansion coefficient and poor thermal stability. Therefore, the composite dielectric substrate material should be produced, and the polymer resin and the inorganic material are compounded, so that the excellent performance of the polymer resin and the inorganic material is ensured, and the defects of the polymer resin and the inorganic material are overcome.
The polyolefin resin has rich resources, low price, stable dielectric property and excellent processing property, and is an ideal matrix for preparing high-frequency substrate materials. By regulating and controlling the types of ceramic fillers and the proportion of the compound ceramic, the compound dielectric substrate with dielectric constant changing within the range of 3.2-16.6, low dielectric loss and near zero temperature coefficient can be prepared by compounding the compound dielectric substrate with polyolefin resin, and the compound dielectric substrate has important significance for the development of the electronic industry. The substrate material with low dielectric constant can meet the requirements of high speed and reduced wiring pattern delay of IC (integrated circuit) chips, and the substrate material with high dielectric constant is favorable for high miniaturization and integration of microwave communication devices.
The Chinese patent invention discloses a composite substrate which is prepared by using glass cloth as a reinforcing material, soaking the glass cloth in glue solution obtained by mixing and stirring raw materials, drying and laminating the glass cloth. The composite substrate prepared by the method can obtain adjustable dielectric constant, but has higher dielectric loss, and the temperature coefficient of the dielectric constant of the substrate is not given. For high frequency microwave substrates and devices, the temperature coefficient of dielectric constant is a very important indicator, and when the temperature changes, the change in dielectric constant causes a shift in the resonant frequency. The larger value of the temperature coefficient of the dielectric constant greatly limits the practical application of the microwave substrate and the device manufactured by the microwave substrate, so that the temperature coefficient of the dielectric constant should be as smaller as possible in order to ensure the temperature stability of the substrate in the use process. Meanwhile, the glass fiber cloth reinforced material has difference of warp and weft knitting densities, and the obtained bonding sheet can influence the consistency and stability of high-frequency circuit signal transmission.
The Chinese patent application No. 202110617260.3 discloses a hydrocarbon resin-based composite substrate obtained by casting and molding at a curing temperature of 125 ℃ for 2-6 hours, wherein the hydrocarbon resin is easily oxidized at a higher temperature and time, and the composite substrate with lower dielectric loss is not prepared.
The Chinese patent of invention (application No. 2015114531. X) discloses a preparation process of a microwave composite dielectric substrate based on barium titanate ceramic powder, which is characterized in that the composite substrate is obtained by stirring, evaporating, die pressing or calendaring raw materials, and finally hot-pressing and sintering, and the substrate has an adjustable dielectric constant (6.5-13.5), but the patent does not give dielectric loss and dielectric constant temperature coefficient of the substrate. Compared to the die-pressing or calendaring method, the thickness of the film produced by knife coating is much smaller, and the thinner film is more favorable for the venting of air holes during hot pressing. This is advantageous for obtaining a substrate with a larger dielectric constant and smaller dielectric loss due to the small dielectric constant of air. Therefore, the invention provides a hydrocarbon resin ceramic composite material capable of producing a membrane by a knife coating method.
Disclosure of Invention
Aiming at the problems in the background technology, the invention provides the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate and the preparation method thereof, and the microwave dielectric substrate manufactured by taking the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as the resin matrix has lower dielectric constant and dielectric loss, simple manufacturing process and low price, and can be applied to the high-frequency and high-speed field.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the ceramic/hydrocarbon resin-based microwave dielectric substrate without glass fiber is characterized by comprising the following components in parts by weight, calculated according to the weight of solids:
further, the number average molecular weight of the resin prepolymer of the polybutadiene and the styrene-butadiene copolymer ranges from 8000 to 150000, the vinyl content is 20 to 80 percent, and the dielectric constant is less than 2.6.
Further, the third monomer introduced by the ethylene propylene diene monomer is ethylidene norbornene.
Further, the initiator is one or more of dicumyl peroxide, di-tert-butyl cumene peroxide, dibenzoyl peroxide or tert-butyl hydroperoxide.
Further, the ceramic powder is silicon dioxide, titanium dioxide and BaTi 4 O 9 Or BaTi 9 O 20 One or more of the following.
Further, the ceramic powder is modified by a silane coupling agent, wherein the silane coupling agent is one or more of vinyl trimethoxy silane (A171), gamma- (methacryloyloxy) propyl trimethoxy silane (KH 570), vinyl tri (b-methoxyethoxy) silane (KH-A172), vinyl triethoxy silane (A151) or gamma-methacryloyloxy propyl oxy silane (Z6030), and the content of the silane coupling agent is 1-5 wt% of the mass of the ceramic powder.
The invention also provides a preparation method of the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, which is characterized by comprising the following steps:
step 1: polybutadiene, a styrene-butadiene copolymer and ethylene propylene diene monomer rubber are prepared according to the following proportion of (5-15): (2-6): adding the mass ratio of (3-9) into a solvent, sequentially adding ceramic powder modified by a silane coupling agent and an initiator after dissolution, and uniformly stirring to obtain ceramic/hydrocarbon resin composite glue solution;
step 2: uniformly spreading the ceramic/hydrocarbon resin composite material glue solution on the surface of a Polytetrafluoroethylene (PTFE) film, and drying at a step temperature of not higher than 60 ℃ to obtain a prepreg;
step 3: laminating a plurality of prepregs, covering copper foils on the upper and lower bottom surfaces after lamination, and hot-pressing to prepare a copper-clad plate;
step 4: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded.
Further, the solvent in the step 1 is one or more of acetone, butanone, methanol, methyl ether, ethylene glycol methyl ether, benzene, toluene or xylene.
Further, the method for modifying the ceramic powder by the silane coupling agent in the step 1 specifically comprises the following steps: absolute ethyl alcohol and deionized water are mixed according to the following steps (1-9): the mass ratio of (1-9) is that a mixed solution is prepared, and then ceramic powder and the mixed solution are mixed according to the following weight ratio of 2:1, adding a silane coupling agent accounting for 1 to 5 weight percent of the mass of the ceramic powder, and drying the ceramic powder in an ultrasonic water bath at 120 ℃ to obtain the ceramic powder modified by the silane coupling agent.
Further, the thickness of the glue solution which is coated on the surface of the PTFE film in the step 2 is 0.2-1.5 mm.
Further, the temperature rising rate of the step temperature rising in the step 2 is 5-10 ℃/min, and the drying time is not less than 8h.
Further, the hot pressing conditions in the step 3 are as follows: under the pressure of 2-4 MPa, the temperature is kept at 180-200 ℃ for 0.5-4 h, and then kept at 200-300 ℃ for 0.5-4 h.
The beneficial effects of the invention are as follows:
1. the invention provides a glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, which is free of glass cloth, and can be used for preparing ultrathin prepregs by blade coating and low-temperature drying, so that the microwave dielectric substrate with wide dielectric constant coverage range (3.2-16.6) is prepared, and the low-temperature drying can reduce the possibility that a diaphragm is oxidized in the semi-curing stage, thereby effectively reducing the dielectric loss of the obtained microwave dielectric substrate;
2. the ethylene propylene diene monomer adopted by the invention has a very flexible methylene chain region in a main molecular chain, has very high flexibility at very low temperature, has no polar substituent group in ethylene propylene diene monomer molecules, has low intermolecular cohesive energy, and has enough internal energy for restoring the original state under the action of external stress, wherein the molecular chain of the copolymer is in a stretching state; by adding ethylene propylene diene monomer into the polybutadiene and styrene-butadiene copolymer system, a regular network structure is more easily generated during the crosslinking reaction, thereby being beneficial to improving the overall tensile strength;
3. the microwave dielectric substrate with adjustable dielectric constant and temperature coefficient of the composite substrate is prepared by adopting the ceramic powder formulas with different dielectric constants, the application is wide, the preparation process is simple and controllable, the cost is low, and the microwave dielectric substrate is suitable for industrial production.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1
The embodiment prepares the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, which specifically comprises the following steps:
step 1:9 parts of polybutadiene, 5.4 parts of a styrene-butadiene copolymer and 3.6 parts of ethylene propylene diene monomer with a third monomer of ethylidene norbornene are taken and fully dissolved by 36 parts of toluene solvent to obtain a mixed solution A.
Step 2: modification of ceramic powder SiO by silane coupling agent 2 And TiO 2 The method specifically comprises the following steps: absolute ethanol and deionized water were mixed according to 1:9, preparing a mixed solution B according to a mass ratio, and respectively mixing ceramic powder SiO 2 And TiO 2 Mixing with the mixed solution B according to the following 2:1 mass ratio to obtain SiO 2 Mixing solution C with TiO 2 Mixing the solution D; in SiO 2 Adding the mixed solution C into the ceramic powder SiO 2 1.5wt% of silane coupling agent A171 in TiO 2 Adding the mixed solution D into ceramic powder TiO 2 2wt% of a silane coupling agent A171; respectively through ultrasonic water bathsAnd drying at 120 ℃ to obtain ceramic powder SiO modified by the silane coupling agent 2 And TiO 2 。
Step 3: taking 80 parts of modified ceramic powder SiO 2 2 parts of modified ceramic powder TiO 2 And 0.36 part of di-tert-butyl peroxide (serving as an initiator) are sequentially added into the mixed solution A, and the hydrocarbon resin ceramic composite glue solution is obtained after uniform stirring.
Step 4: uniformly scraping the hydrocarbon resin ceramic composite material glue solution on the surface of the PTFE film, heating to 50 ℃ in a vacuum oven at a heating rate of 5-10 ℃/min, and drying for 8 hours to obtain the prepreg.
Step 5: laminating 3 prepregs together, covering copper foils on the upper bottom surface and the lower bottom surface, and hot-pressing to obtain a copper-clad plate, wherein the hot-pressing process comprises the following steps: maintaining at 180deg.C and 2.0Mpa for 90min, and maintaining at 220deg.C and 2.0Mpa for 130min.
Step 6: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded. The test results are shown in Table 1.
Example 2
The embodiment prepares the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, which specifically comprises the following steps:
step 1:9 parts of polybutadiene, 5.4 parts of a styrene-butadiene copolymer and 3.6 parts of ethylene propylene diene monomer with a third monomer of ethylidene norbornene are taken and fully dissolved by 36 parts of toluene solvent to obtain a mixed solution A.
Step 2: ceramic powder BaTi modified by silane coupling agent 4 O 9 、SiO 2 And TiO 2 The method specifically comprises the following steps: absolute ethanol and deionized water were mixed according to 1:9, preparing a mixed solution B, and respectively mixing ceramic powder BaTi 4 O 9 、SiO 2 And TiO 2 Mixing with the mixed solution B according to the following 2:1 to obtain BaTi 4 O 9 Mixed solution C, siO 2 Mixing solution D with TiO 2 Mixing the solution E; in BaTi 4 O 9 Adding the mixed solution C into the ceramicPowder BaTi 4 O 9 2wt% of silane coupling agent A171 in SiO 2 Adding the mixed solution D into the ceramic powder SiO 2 1.5wt% of silane coupling agent A171 in TiO 2 Adding the mixed solution E into ceramic powder TiO 2 2wt% of a silane coupling agent A171; respectively drying in ultrasonic water bath at 120 ℃ to obtain ceramic powder BaTi modified by a silane coupling agent 4 O 9 、SiO 2 And TiO 2 。
Step 3: 60 parts of modified ceramic powder BaTi is taken 4 O 9 5 parts of modified ceramic powder SiO 2 17 parts of modified ceramic powder TiO 2 And 0.36 part of di-tert-butyl peroxide is sequentially added into the mixed solution A, and the hydrocarbon resin ceramic composite glue solution is obtained after uniform stirring.
Step 4: uniformly scraping the hydrocarbon resin ceramic composite material glue solution on the surface of the PTFE film, heating to 50 ℃ in a vacuum oven at a heating rate of 5-10 ℃/min, and drying for 8 hours to obtain the prepreg.
Step 5: laminating 3 prepregs together, covering copper foils on the upper bottom surface and the lower bottom surface, and hot-pressing to obtain a copper-clad plate, wherein the hot-pressing process comprises the following steps: maintaining at 190 deg.C and 2.0MPa for 150min, and then maintaining at 250 deg.C and 2.0MPa for 150min.
Step 6: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded. The test results are shown in Table 1.
Example 3
The embodiment prepares the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, which specifically comprises the following steps:
step 1: 10 parts of polybutadiene, 6 parts of styrene-butadiene copolymer and 4 parts of ethylene propylene diene monomer with a third monomer of ethylidene norbornene are taken and fully dissolved by 40 parts of toluene solvent to obtain a mixed solution A.
Step 2: modification of ceramic powder SiO by silane coupling agent 2 And BaTi 9 O 20 The method specifically comprises the following steps: removing the absolute ethanolIonized water was prepared according to 1:9, preparing a mixed solution B, and respectively mixing ceramic powder SiO 2 And BaTi 9 O 20 Mixing with the mixed solution B according to the following 2:1 mass ratio to obtain SiO 2 Mixing solution C and BaTi 9 O 20 Mixing the solution D; in SiO 2 Adding the mixed solution C into the ceramic powder SiO 2 1.5wt% of silane coupling agent A171 in BaTi 9 O 20 Adding ceramic powder BaTi into the mixed solution D 9 O 20 2wt% of a silane coupling agent A171; respectively drying in ultrasonic water bath at 120 ℃ to obtain ceramic powder SiO modified by the silane coupling agent 2 And BaTi 9 O 20 。
Step 3: taking 30 parts of modified ceramic powder SiO 2 50 parts of modified ceramic powder BaTi 9 O 20 And 0.4 part of di-tert-butyl peroxide is sequentially added into the mixed solution A, and the hydrocarbon resin ceramic composite glue solution is obtained after uniform stirring.
Step 4: uniformly scraping the hydrocarbon resin ceramic composite material glue solution on the surface of the PTFE film, heating to 50 ℃ in a vacuum oven at a heating rate of 5-10 ℃/min, and drying for 8 hours to obtain the prepreg.
Step 5: laminating 3 prepregs together, covering copper foils on the upper bottom surface and the lower bottom surface, and hot-pressing to obtain a copper-clad plate, wherein the hot-pressing process comprises the following steps: maintaining at 190 deg.C and 2.0MPa for 150min, and then maintaining at 250 deg.C and 2.0MPa for 150min.
Step 6: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded. The test results are shown in Table 1.
Example 4
The embodiment prepares the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, which specifically comprises the following steps:
step 1: 10 parts of polybutadiene, 6 parts of styrene-butadiene copolymer and 4 parts of ethylene propylene diene monomer with a third monomer of ethylidene norbornene are taken and fully dissolved by 40 parts of toluene solvent to obtain a mixed solution A.
Step 2: modification of ceramic powder SiO by silane coupling agent 2 And BaTi 4 O 9 The method specifically comprises the following steps: absolute ethanol and deionized water were mixed according to 1:9, preparing a mixed solution B, and respectively mixing ceramic powder SiO 2 And BaTi 4 O 9 Mixing with the mixed solution B according to the following 2:1 mass ratio to obtain SiO 2 Mixing solution C and BaTi 4 O 9 Mixing the solution D; in SiO 2 Adding the mixed solution C into the ceramic powder SiO 2 1.5wt% of silane coupling agent A171 in BaTi 4 O 9 Adding ceramic powder BaTi into the mixed solution D 4 O 9 2wt% of a silane coupling agent A171; respectively drying in ultrasonic water bath at 120 ℃ to obtain ceramic powder SiO modified by the silane coupling agent 2 And BaTi 4 O 9 。
Step 3: 60 parts of modified ceramic powder SiO is taken 2 20 parts of modified ceramic powder BaTi 4 O 9 And 0.4 part of di-tert-butyl peroxide is sequentially added into the mixed solution A, and the hydrocarbon resin ceramic composite glue solution is obtained after uniform stirring.
Step 4: uniformly scraping the hydrocarbon resin ceramic composite material glue solution on the surface of the PTFE film, heating to 50 ℃ in a vacuum oven at a heating rate of 5-10 ℃/min, and drying for 8 hours to obtain the prepreg.
Step 5: laminating 3 prepregs together, covering copper foils on the upper bottom surface and the lower bottom surface, and hot-pressing to obtain a copper-clad plate, wherein the hot-pressing process comprises the following steps: maintaining at 190 deg.C and 2.0MPa for 150min, and then maintaining at 250 deg.C and 2.0MPa for 150min.
Step 6: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded. The test results are shown in Table 1.
Example 5
The embodiment prepares the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, which specifically comprises the following steps:
step 1:9 parts of polybutadiene, 5.4 parts of a styrene-butadiene copolymer and 3.6 parts of ethylene propylene diene monomer with a third monomer of ethylidene norbornene are taken and fully dissolved by 36 parts of toluene solvent to obtain a mixed solution A.
Step 2: ceramic powder TiO modified by silane coupling agent 2 And BaTi 4 O 9 The method specifically comprises the following steps: absolute ethanol and deionized water were mixed according to 1:9, preparing a mixed solution B, and respectively mixing ceramic powder TiO 2 And BaTi 4 O 9 Mixing with the mixed solution B according to the following 2:1 mass ratio to obtain TiO 2 Mixing solution C and BaTi 4 O 9 Mixing the solution D; in TiO 2 Adding the mixed solution C into ceramic powder TiO 2 2wt% of silane coupling agent A171 in BaTi 4 O 9 Adding ceramic powder BaTi into the mixed solution D 4 O 9 2wt% of a silane coupling agent A171; respectively drying in ultrasonic water bath at 120 ℃ to obtain ceramic powder TiO modified by a silane coupling agent 2 And BaTi 4 O 9 。
Step 3: taking 50 parts of modified ceramic powder TiO 2 32 parts of modified ceramic powder BaTi 4 O 9 And 0.36 part of di-tert-butyl peroxide is sequentially added into the mixed solution A, and the hydrocarbon resin ceramic composite glue solution is obtained after uniform stirring.
Step 4: uniformly scraping the hydrocarbon resin ceramic composite material glue solution on the surface of the PTFE film, heating to 50 ℃ in a vacuum oven at a heating rate of 5-10 ℃/min, and drying for 8 hours to obtain the prepreg.
Step 5: laminating 3 prepregs together, covering copper foils on the upper bottom surface and the lower bottom surface, and hot-pressing to obtain a copper-clad plate, wherein the hot-pressing process comprises the following steps: maintaining at 190 deg.C and 2.0MPa for 150min, and then maintaining at 250 deg.C and 2.0MPa for 150min.
Step 6: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded. The test results are shown in Table 1.
Comparative example 1
The comparative example prepares a microwave dielectric substrate, which specifically comprises the following steps:
step 1: 6.7 parts of polybutadiene and 13.3 parts of a styrene-butadiene copolymer were taken and sufficiently dissolved with 40 parts of a toluene solvent to obtain a mixed solution A.
Step 2: modification of ceramic powder SiO by silane coupling agent 2 、TiO 2 And BaTi 4 O 9 The method specifically comprises the following steps: absolute ethanol and deionized water were mixed according to 1:9, preparing a mixed solution B, and respectively mixing ceramic powder SiO 2 、TiO 2 And BaTi 4 O 9 Mixing with the mixed solution B according to the following 2:1 mass ratio to obtain SiO 2 Mixed solution C, tiO 2 Mixed solution D and BaTi 4 O 9 Mixing the solution E; in SiO 2 Adding the mixed solution C into the ceramic powder SiO 2 1.5wt% of silane coupling agent A171 in TiO 2 Adding the mixed solution D into ceramic powder TiO 2 2wt% of silane coupling agent A171 in BaTi 4 O 9 Adding ceramic powder BaTi into the mixed solution E 4 O 9 2wt% of a silane coupling agent A171; respectively drying in ultrasonic water bath at 120 ℃ to obtain ceramic powder SiO modified by the silane coupling agent 2 、TiO 2 And BaTi 4 O 9 。
Step 3: taking 30 parts of modified ceramic powder SiO 2 40 parts of modified ceramic powder BaTi 4 O 9 10 parts of modified ceramic powder TiO 2 And 0.4 part of di-tert-butyl peroxide is sequentially added into the mixed solution A, and the hydrocarbon resin ceramic composite glue solution is obtained after uniform stirring.
Step 4: uniformly scraping the hydrocarbon resin ceramic composite material glue solution on the surface of the PTFE film, heating to 50 ℃ in a vacuum oven at a heating rate of 5-10 ℃/min, and drying for 8 hours to obtain the prepreg.
Step 5: laminating 3 prepregs together, covering copper foils on the upper bottom surface and the lower bottom surface, and hot-pressing to obtain a copper-clad plate, wherein the hot-pressing process comprises the following steps: maintaining at 190 deg.C and 2.0MPa for 150min, and then maintaining at 250 deg.C and 2.0MPa for 150min.
Step 6: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded. The test results are shown in Table 1.
Comparative example 2
The comparative example prepares a microwave dielectric substrate, which specifically comprises the following steps:
step 1: 10 parts of polybutadiene, 6 parts of styrene-butadiene copolymer and 4 parts of ethylene propylene diene monomer with a third monomer of ethylidene norbornene are taken and fully dissolved by 40 parts of toluene solvent to obtain a mixed solution A.
Step 2: modification of ceramic powder SiO by silane coupling agent 2 And BaTi 4 O 9 The method specifically comprises the following steps: absolute ethanol and deionized water were mixed according to 1:9, preparing a mixed solution B, and respectively mixing ceramic powder SiO 2 And BaTi 4 O 9 Mixing with the mixed solution B according to the following 2:1 mass ratio to obtain SiO 2 Mixing solution C and BaTi 4 O 9 Mixing the solution D; in SiO 2 Adding the mixed solution C into the ceramic powder SiO 2 1.5wt% of silane coupling agent A171 in BaTi 4 O 9 Adding ceramic powder BaTi into the mixed solution D 4 O 9 2wt% of a silane coupling agent A171; respectively drying in ultrasonic water bath at 120 ℃ to obtain ceramic powder SiO modified by the silane coupling agent 2 And BaTi 4 O 9 。
Step 3: taking 30 parts of modified ceramic powder SiO 2 50 parts of modified ceramic powder BaTi 4 O 9 And 10 parts of di-tert-butyl peroxide are sequentially added into the mixed solution A, and the hydrocarbon resin ceramic composite glue solution is obtained after uniform stirring.
Step 4: and (3) dipping the glass fiber cloth into the hydrocarbon resin ceramic composite glue solution, placing the glass fiber cloth in a baking oven at 50 ℃ for 24 hours, and removing the solvent to obtain the prepreg.
Step 5: laminating 3 prepregs together, covering copper foils on the upper bottom surface and the lower bottom surface, and hot-pressing to obtain a copper-clad plate, wherein the hot-pressing process comprises the following steps: maintaining at 190 deg.C and 2.0MPa for 150min, and then maintaining at 250 deg.C and 2.0MPa for 150min.
Step 6: and (3) placing the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to a mass ratio of 1:1, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate after the copper foil is completely corroded. The test results are shown in Table 1.
TABLE 1 microwave dielectric substrate Performance test results
The invention adopts a microwave dielectric material strip line resonator method to measure the dielectric properties of the copper-clad plates obtained in examples 1-5 and comparative examples 1-2 at 10GHz according to IPCTM-650.5.5.5, including dielectric constants (D) k ) Dielectric loss (D) f ) And a temperature drift (TCR), the results are shown in table 1.
Compared with the process for preparing the prepreg by dipping the glass fiber cloth, the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate prepared by the method provided by the invention has obviously reduced dielectric loss; meanwhile, the temperature drift of the microwave dielectric substrate is very low within the dielectric constant range of 3.2-9.2 and is more close to 0 ppm/DEG C, and the temperature drift of the microwave dielectric substrate is as small as possible within the high dielectric constant range of 9.2-16.6, and meanwhile, the excellent dielectric property is maintained.
In the above embodiment, a specific preparation process of the prepreg is provided only for convenience of description, and it should be noted that, when the copper-clad plate is prepared, the hot pressing process is as follows: the copper-clad plate can be prepared by keeping the temperature of 180-300 ℃ for 60-300 min under 2-10 Mpa and then keeping the temperature of 180-300 ℃ for 60-300 min under 2-10 Mpa.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (6)
1. The ceramic/hydrocarbon resin-based microwave dielectric substrate without glass fiber is characterized by comprising the following components in parts by weight, calculated according to the weight of solids:
the ceramic powder is silicon dioxide, titanium dioxide and BaTi 4 O 9 Or BaTi 9 O 20 One or more of (a) and modified by a silane coupling agent; the silane coupling agent is one or more of vinyl trimethoxy silane, gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl tri (b-methoxyethoxy) silane, vinyl triethoxy silane or gamma-methacryloyloxy propyl oxy silane, and the content of the silane coupling agent is 1-5 wt% of the mass of the ceramic powder;
the preparation method of the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate comprises the following steps:
step 1: polybutadiene, a styrene-butadiene copolymer and ethylene propylene diene monomer rubber are prepared according to the following proportion of (5-15): (2-6): adding the mass ratio of (3-9) into a solvent, sequentially adding ceramic powder modified by a silane coupling agent and an initiator after dissolution, and uniformly stirring to obtain ceramic/hydrocarbon resin composite glue solution;
step 2: uniformly spreading the ceramic/hydrocarbon resin composite material glue solution on the surface of a polytetrafluoroethylene film, and drying at a step temperature of not higher than 60 ℃ to obtain a prepreg; wherein the temperature rising rate of the step temperature rising is 5-10 ℃/min, and the drying time is not less than 8h;
step 3: laminating a plurality of prepregs, covering copper foils on the upper and lower bottom surfaces after lamination, and hot-pressing to prepare a copper-clad plate;
step 4: and (3) placing the copper-clad plate into corrosive liquid, and finally preparing the ceramic/hydrocarbon resin-based microwave dielectric substrate without glass fiber after the copper foil is completely corroded.
2. The glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate according to claim 1, wherein the number average molecular weight of the resin prepolymer of polybutadiene and styrene-butadiene copolymer is 8000-150000, the vinyl content is 20-80%, and the dielectric constant is less than 2.6.
3. The glass fiber-free ceramic/hydrocarbon resin based microwave dielectric substrate of claim 1, wherein the initiator is one or more of dicumyl peroxide, di-t-butylcumene peroxide, dibenzoyl peroxide, or t-butyl hydroperoxide.
4. The glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate according to claim 1, wherein the solvent in step 1 is one or more of acetone, butanone, methanol, methyl ether, ethylene glycol methyl ether, benzene, toluene, or xylene.
5. The glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate according to claim 1, wherein the thickness of the glue solution scraped on the surface of the polytetrafluoroethylene film in the step 2 is 0.2-1.5 mm.
6. The glass fiber-free ceramic/hydrocarbon resin based microwave dielectric substrate according to claim 1, wherein the hot pressing conditions in step 3 are: under the pressure of 2-4 MPa, the temperature is kept at 180-200 ℃ for 0.5-4 h, and then kept at 200-300 ℃ for 0.5-4 h.
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