CN114889273A - Glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate and preparation method thereof - Google Patents
Glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate and preparation method thereof Download PDFInfo
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B38/00—Ancillary operations in connection with laminating processes
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
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Abstract
The invention provides a glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate and a preparation method thereof, belonging to the technical field of copper-clad plates. 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 temperature coefficient of the composite substrate is prepared by adopting ceramic powder formulas with different dielectric constants.
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 medium substrate and a preparation method thereof.
Background
With the rapid development of the modern information technology industry, the society enters a highly information-oriented era. In order to process rapidly increasing data, electronic communication devices are gradually coming up with the development trend of high frequency and miniaturization. Therefore, there is a high demand for high-frequency microwave substrate technology, and not only the miniaturization and high integration requirements are satisfied, but also the low power consumption, high reliability and low cost are developed.
The pure microwave dielectric ceramic substrate has excellent dielectric property in a microwave frequency band, but has the defects of easy brittleness, poor mechanical property and large processing difficulty. Although the organic resin-based substrate has good dielectric properties, it also has disadvantages such as a high thermal expansion coefficient and poor thermal stability. Therefore, the composite dielectric substrate material is produced, and the polymer resin and the inorganic material are compounded, so that the excellent performances of the polymer resin and the inorganic material are ensured, and the mutual defects are also made up.
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 the type of the ceramic filler and the proportion of the compound ceramic and compounding the ceramic filler with the polyolefin resin, the composite dielectric substrate with the dielectric constant varying within the range of 3.2-16.6, low dielectric loss and nearly zero temperature coefficient can be prepared, and the method has important significance for the development of the electronic industry. The substrate material with low dielectric constant can meet the requirements of high-speed IC (integrated circuit) chips and reduction of wiring pattern delay, and the substrate material with high dielectric constant is favorable for high miniaturization and integration of microwave communication devices.
The Chinese invention patent of resin composition, prepreg, laminated sheet, preparation method of prepreg, preparation method of laminated sheet and application thereof (application No. 202010612509.7) discloses a composite substrate obtained 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 composite substrate prepared by the method can obtain adjustable dielectric constant, but has higher dielectric loss, and does not give the temperature coefficient of the dielectric constant of the substrate. 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 of dielectric constant will cause the shift of resonant frequency. The large value of the temperature coefficient of dielectric constant greatly limits the practical application of the microwave substrate and the device made of the microwave substrate, so that the temperature coefficient of dielectric constant should be as small as possible in order to ensure the temperature stability of the substrate in the using process. Meanwhile, the glass fiber cloth reinforced material has difference of warp and weft weaving density, and the obtained bonding sheet can influence the consistency and stability of high-frequency circuit signal transmission.
The invention patent of China (application number 202110617260.3) discloses a hydrocarbon resin-based composite substrate formed by tape casting at a curing temperature of 125 ℃ for 2-6 hours, wherein the hydrocarbon resin is easily oxidized at higher temperature and time, and the composite substrate with lower dielectric loss is not easy to prepare.
In the invention patent of china, the preparation technology of a microwave composite dielectric substrate based on barium titanate ceramic powder (application number 201510414531.X), a composite substrate is disclosed, which is obtained by stirring, evaporating, molding or calendaring raw materials, and finally carrying out hot-pressing sintering, wherein the substrate has an adjustable dielectric constant (6.5-13.5), but the patent does not give out the dielectric loss and the temperature coefficient of the dielectric constant of the substrate. Compared with the die pressing or rolling method, the thickness of the membrane produced by the knife coating method is much smaller, and the thinner membrane is more beneficial to air hole discharge in the hot pressing process. Since the dielectric constant of air is small, it is advantageous to obtain a substrate with a larger dielectric constant and a smaller dielectric loss. The invention therefore proposes a hydrocarbon resin ceramic composite material which can be used to produce membranes by means of a doctor blade process.
Disclosure of Invention
The invention provides a glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate and a preparation method thereof aiming at the problems in the background art, the microwave dielectric substrate prepared by taking the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as a 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 realize the purpose, the technical scheme adopted by the invention is as follows:
the glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate is characterized by comprising the following components in parts by weight based on solid weight:
further, the number average molecular weight of the resin prepolymer of the polybutadiene and the styrene-butadiene copolymer is 8000-150000, the vinyl content is 20% -80%, and the dielectric constant is less than 2.6.
Further, a third monomer introduced by the ethylene propylene diene monomer is ethylidene norbornene.
Further, the initiator is one or more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene, 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 (a).
Further, the ceramic powder is modified by a silane coupling agent, the silane coupling agent is one or more of vinyl trimethoxy silane (A171), gamma- (methacryloyloxy) propyl trimethoxy silane (KH570), vinyl tri (b-methoxyethoxy) silane (KH-A172), vinyl triethoxy silane (A151) or gamma-methacryloxypropyl 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 medium substrate, which is characterized by comprising the following steps of:
step 1: polybutadiene, a styrene-butadiene copolymer and ethylene propylene diene monomer are mixed according to the weight ratio of (5-15): (2-6): (3-9), after dissolving, sequentially adding ceramic powder modified by a silane coupling agent and an initiator, and uniformly stirring to obtain a ceramic/hydrocarbon resin composite glue solution;
step 2: uniformly coating the ceramic/hydrocarbon resin composite material glue solution on the surface of a Polytetrafluoroethylene (PTFE) film in a scraping way, and carrying out stepped heating drying at the temperature of not higher than 60 ℃ to obtain a prepreg;
and step 3: overlapping a plurality of prepregs, covering copper foils on the upper and lower bottom surfaces after overlapping, and performing hot pressing to obtain a copper-clad plate;
and 4, step 4: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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, in the step 1, the solvent 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: anhydrous ethanol and deionized water are added according to the ratio of (1-9): (1-9) preparing a mixed solution, and mixing the ceramic powder and the mixed solution according to a mass ratio of 2: 1, adding a silane coupling agent accounting for 1-5 wt% of the mass of the ceramic powder, and drying 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 coated on the surface of the PTFE membrane in the step 2 is 0.2-1.5 mm.
Further, in the step 2, the temperature rise rate of the step temperature rise is 5-10 ℃/min, and the drying time is not less than 8 h.
Further, the hot pressing conditions in step 3 are as follows: keeping the temperature of 180-200 ℃ for 0.5-4 h under the pressure of 2-4 MPa, and keeping the temperature of 200-300 ℃ for 0.5-4 h.
The invention has the beneficial effects that:
1. the invention provides a glass-fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate, an ultrathin prepreg can be prepared only by blade coating and low-temperature drying without glass cloth, so that the microwave dielectric substrate with a wide dielectric constant coverage range (3.2-16.6) is prepared, and the low-temperature drying can reduce the possibility that a membrane is oxidized in a prepreg stage, so that the dielectric loss of the obtained microwave dielectric substrate is effectively reduced;
2. The ethylene propylene diene monomer adopted by the invention has a very soft methine chain region in the main molecular chain, still has very high flexibility at very low temperature, and the ethylene propylene diene monomer has no polar substituent group in the molecule, so that the intermolecular cohesive energy is low, and under the action of external stress, the molecular chain of the copolymer is in a stretching state and has enough internal energy for recovering the original state; by adding the ethylene propylene diene monomer into a polybutadiene and styrene-butadiene copolymer system, a regular network structure is more easily generated during a crosslinking reaction, and the improvement of the integral tensile strength is facilitated;
3. the microwave dielectric substrate with adjustable dielectric constant and temperature coefficient of the composite substrate is prepared by adopting ceramic powder formulas with different dielectric constants, has wide application, simple and controllable preparation process and low cost, and is suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments.
Example 1
The embodiment prepares the glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate, and 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 ethylidene norbornene as a third monomer are fully dissolved by 36 parts of a 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: mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 9, preparing a mixed solution B, and respectively mixing the ceramic powder SiO 2 And TiO 2 Mixing the mixed solution B according to the proportion of 2: 1 to obtain SiO 2 Mixed solution C and TiO 2 Mixing the solution D; in SiO 2 Adding ceramic powder SiO into the mixed solution C 2 1.5 wt% of silane coupling agent A171 in TiO 2 Adding ceramic powder TiO into the mixed solution D 2 2% by mass of a silane coupling agent A171; respectively treated by ultrasonic water bath and drying at 120 ℃ to obtain ceramic powder SiO modified by silane coupling agent 2 And TiO 2 。
And step 3: 80 portions of modified ceramic powder SiO are taken 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 mixture is uniformly stirred to obtain the glue solution of the hydrocarbon resin ceramic composite material.
And 4, step 4: uniformly scraping the glue solution of the hydrocarbon resin ceramic composite material on the surface of the PTFE film, heating to 50 ℃ at a heating rate of 5-10 ℃/min in a vacuum oven, and drying for 8h to obtain a prepreg.
And 5: laminating 3 prepregs together, covering copper foils on the upper and lower bottom surfaces, and performing hot pressing to obtain the copper-clad plate, wherein the hot pressing process comprises the following steps: maintaining at 180 deg.C and 2.0Mpa for 90min, and maintaining at 220 deg.C and 2.0Mpa for 130 min.
And 6: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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 medium substrate, and 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 ethylidene norbornene as a third monomer are fully dissolved by 36 parts of a toluene solvent to obtain a mixed solution A.
Step 2: modification of ceramic powder BaTi by silane coupling agent 4 O 9 、SiO 2 And TiO 2 The method specifically comprises the following steps: mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 9 preparing mixed solution B, and respectively mixing ceramic powder BaTi 4 O 9 、SiO 2 And TiO 2 Mixing the mixed solution B according to the proportion of 2: 1 to obtain BaTi 4 O 9 Mixed solution C, SiO 2 Mixing solution D and TiO 2 Mixing the solution E; in BaTi 4 O 9 Ceramic powder BaTi is added into the mixed solution C 4 O 9 2% by mass of a silane coupling agent A171 in SiO 2 Adding ceramic powder SiO into the mixed solution D 2 1.5 wt% of silane coupling agent A171 in TiO 2 Adding ceramic powder TiO into the mixed solution E 2 2% by mass of a silane coupling agent A171; respectively treated by ultrasonic water bath and drying at 120 ℃ to obtain ceramic powder BaTi modified by silane coupling agent 4 O 9 、SiO 2 And TiO 2 。
And step 3: 60 parts of modified ceramic powder BaTi 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 are sequentially added into the mixed solution A and uniformly stirred to obtain the glue solution of the hydrocarbon resin ceramic composite material.
And 4, step 4: uniformly scraping the glue solution of the hydrocarbon resin ceramic composite material on the surface of the PTFE film, heating to 50 ℃ at a heating rate of 5-10 ℃/min in a vacuum oven, and drying for 8h to obtain a prepreg.
And 5: laminating 3 prepregs together, covering copper foils on the upper and lower bottom surfaces, and performing hot pressing to obtain the copper-clad plate, wherein the hot pressing process comprises the following steps: maintaining at 190 deg.C and 2.0Mpa for 150min, and maintaining at 250 deg.C and 2.0Mpa for 150 min.
Step 6: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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 medium substrate, and specifically comprises the following steps:
Step 1: and (3) fully dissolving 10 parts of polybutadiene, 6 parts of a styrene-butadiene copolymer and 4 parts of ethylene propylene diene monomer with ethylidene norbornene as a third monomer by using 40 parts of a toluene solvent to obtain a mixed solution A.
And 2, step: modification of ceramic powder SiO by silane coupling agent 2 And BaTi 9 O 20 The method specifically comprises the following steps: mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 9, preparing a mixed solution B, and respectively mixing the ceramic powder SiO 2 And BaTi 9 O 20 Mixing the mixed solution B according to the proportion of 2: 1 to obtain SiO 2 Mixing solution C and BaTi 9 O 20 Mixing the solution D; in SiO 2 Adding ceramic powder SiO into the mixed solution C 2 1.5 wt% of silane coupling agent A171 in BaTi 9 O 20 Ceramic powder BaTi is added into the mixed solution D 9 O 20 2% by mass of a silane coupling agent A171; respectively treated by ultrasonic water bath and drying at 120 ℃ to obtain ceramic powder SiO modified by silane coupling agent 2 And BaTi 9 O 20 。
And 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 are sequentially added into the mixed solution A, and the mixture is uniformly stirred to obtain the glue solution of the hydrocarbon resin ceramic composite material.
And 4, step 4: uniformly scraping the glue solution of the hydrocarbon resin ceramic composite material on the surface of the PTFE film, heating to 50 ℃ at a heating rate of 5-10 ℃/min in a vacuum oven, and drying for 8h to obtain a prepreg.
And 5: laminating 3 prepregs together, covering copper foils on the upper and lower bottom surfaces, and performing hot pressing to obtain the copper-clad plate, wherein the hot pressing process comprises the following steps: maintaining at 190 deg.C and 2.0Mpa for 150min, and maintaining at 250 deg.C and 2.0Mpa for 150 min.
And 6: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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 medium substrate, and specifically comprises the following steps:
step 1: and (3) fully dissolving 10 parts of polybutadiene, 6 parts of a styrene-butadiene copolymer and 4 parts of ethylene propylene diene monomer with ethylidene norbornene as a third monomer by using 40 parts of a 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: mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 9, preparing a mixed solution B, and respectively mixing the ceramic powder SiO 2 And BaTi 4 O 9 Mixing the mixed solution B according to the proportion of 2: 1 to obtain SiO 2 Mixing solution C and BaTi 4 O 9 Mixing the solution D; in SiO 2 Adding ceramic powder SiO into the mixed solution C 2 1.5 wt% of silane coupling agent A171 in BaTi 4 O 9 Ceramic powder BaTi is added into the mixed solution D 4 O 9 2% by mass of a silane coupling agent A171; respectively treated by ultrasonic water bath and drying at 120 ℃ to obtain ceramic powder SiO modified by silane coupling agent 2 And BaTi 4 O 9 。
And step 3: taking 60 parts of modified ceramic powder SiO 2 20 portions of modified ceramic powder BaTi 4 O 9 And 0.4 part of di-tert-butyl peroxide are sequentially added into the mixed solution A, and the mixture is uniformly stirred to obtain the glue solution of the hydrocarbon resin ceramic composite material.
And 4, step 4: uniformly scraping the glue solution of the hydrocarbon resin ceramic composite material on the surface of the PTFE film, heating to 50 ℃ at a heating rate of 5-10 ℃/min in a vacuum oven, and drying for 8h to obtain a prepreg.
And 5: laminating 3 prepregs together, covering copper foils on the upper and lower bottom surfaces, and performing hot pressing to obtain the copper-clad plate, wherein the hot pressing process comprises the following steps: maintaining at 190 deg.C and 2.0Mpa for 150min, and maintaining at 250 deg.C and 2.0Mpa for 150 min.
Step 6: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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 medium substrate, and 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 ethylidene norbornene as a third monomer are fully dissolved by 36 parts of a toluene solvent to obtain a mixed solution A.
Step 2: modification of ceramic powder TiO by silane coupling agent 2 And BaTi 4 O 9 The method specifically comprises the following steps: mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 9 preparing a mixed solution B, and respectively preparing ceramic powder TiO 2 And BaTi 4 O 9 Mixing the mixed solution B according to the proportion of 2: 1 to obtain TiO 2 Mixing solution C and BaTi 4 O 9 Mixing the solution D; in TiO 2 Adding ceramic powder TiO into the mixed solution C 2 2% by mass of a silane coupling agent A171 in BaTi 4 O 9 Ceramic powder BaTi is added into the mixed solution D 4 O 9 2% by mass of a silane coupling agent A171; respectively treated by ultrasonic water bath and drying at 120 ℃ to obtain ceramic powder TiO modified by silane coupling agent 2 And BaTi 4 O 9 。
And 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 are sequentially added into the mixed solution A and uniformly stirred to obtain the hydrocarbon resin ceramic composite material And (6) glue solution.
And 4, step 4: uniformly scraping the glue solution of the hydrocarbon resin ceramic composite material on the surface of the PTFE film, heating to 50 ℃ at a heating rate of 5-10 ℃/min in a vacuum oven, and drying for 8h to obtain a prepreg.
And 5: laminating 3 prepregs together, covering copper foils on the upper and lower bottom surfaces, and performing hot pressing to obtain the copper-clad plate, wherein the hot pressing process comprises the following steps: maintaining at 190 deg.C and 2.0Mpa for 150min, and maintaining at 250 deg.C and 2.0Mpa for 150 min.
Step 6: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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, and 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 in 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: mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 9, preparing a mixed solution B, and respectively mixing the ceramic powder SiO 2 、TiO 2 And BaTi 4 O 9 Mixing the mixed solution B according to the proportion of 2: 1 to obtain SiO 2 Mixed solution C, TiO 2 Mixing solution D and BaTi 4 O 9 Mixing the solution E; in SiO 2 Adding ceramic powder SiO into the mixed solution C 2 1.5 wt% of silane coupling agent A171 in TiO 2 Adding ceramic powder TiO into the mixed solution D 2 2% by mass of a silane coupling agent A171 in BaTi 4 O 9 Ceramic powder BaTi is added into the mixed solution E 4 O 9 2% by mass of a silane coupling agent A171; respectively treated by ultrasonic water bath and drying at 120 ℃ to obtain ceramic powder SiO modified by silane coupling agent 2 、TiO 2 And BaTi 4 O 9 。
And step 3: taking 30 parts of modified ceramic powder SiO 2 40 parts of modified ceramic powder BaTi 4 O 9 10 portions of modified ceramic powder TiO 2 And 0.4 part of di-tert-butyl peroxide are sequentially added into the mixed solution A, and the mixture is uniformly stirred to obtain the glue solution of the hydrocarbon resin ceramic composite material.
And 4, step 4: uniformly scraping the glue solution of the hydrocarbon resin ceramic composite material on the surface of the PTFE film, heating to 50 ℃ at a heating rate of 5-10 ℃/min in a vacuum oven, and drying for 8h to obtain a prepreg.
And 5: laminating 3 prepregs together, covering copper foils on the upper and lower bottom surfaces, and performing hot pressing to obtain the copper-clad plate, wherein the hot pressing process comprises the following steps: maintaining at 190 deg.C and 2.0Mpa for 150min, and maintaining at 250 deg.C and 2.0Mpa for 150 min.
Step 6: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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, and specifically comprises the following steps:
step 1: and (3) fully dissolving 10 parts of polybutadiene, 6 parts of a styrene-butadiene copolymer and 4 parts of ethylene propylene diene monomer with ethylidene norbornene as a third monomer by using 40 parts of a 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: mixing absolute ethyl alcohol and deionized water according to the weight ratio of 1: 9, preparing a mixed solution B, and respectively mixing the ceramic powder SiO 2 And BaTi 4 O 9 Mixing the mixed solution B according to the proportion of 2: 1 to obtain SiO 2 Mixing solution C and BaTi 4 O 9 Mixing the solution D; in SiO 2 Adding ceramic powder SiO into the mixed solution C 2 1.5 wt% of silane coupling agent A171 in BaTi 4 O 9 Ceramic powder BaTi is added into the mixed solution D 4 O 9 2% by mass of a silane coupling agentA171; respectively treated by ultrasonic water bath and drying at 120 ℃ to obtain ceramic powder SiO modified by silane coupling agent 2 And BaTi 4 O 9 。
And 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 mixture is uniformly stirred to obtain the glue solution of the hydrocarbon resin ceramic composite material.
And 4, step 4: and (3) soaking the glass fiber cloth in the hydrocarbon resin ceramic composite glue solution, placing the glass fiber cloth in a 50 ℃ oven for 24 hours, and removing the solvent to obtain the prepreg.
And 5: laminating 3 prepregs together, covering copper foils on the upper and lower bottom surfaces, and performing hot pressing to obtain the copper-clad plate, wherein the hot pressing process comprises the following steps: maintaining at 190 deg.C and 2.0Mpa for 150min, and maintaining at 250 deg.C and 2.0Mpa for 150 min.
Step 6: and putting the copper-clad plate into corrosive liquid prepared by hydrogen peroxide and concentrated hydrochloric acid according to the 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 dielectric properties, including dielectric constant (D), of the copper-clad plates obtained in examples 1-5 and comparative examples 1-2 at 10GHz are measured by a microwave dielectric material stripline resonator method according to IPCTM-6502.5.5.5 k ) Dielectric loss (D) f ) And temperature drift (TCR), results are shown in table 1.
Compared with the process of 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 the advantages that the dielectric loss of the microwave dielectric substrate is obviously reduced; meanwhile, the temperature drift of the microwave dielectric substrate is very low and is closer to 0 ppm/DEG C within the dielectric constant range of 3.2-9.2, and is as small as possible within the high dielectric constant range of 9.2-16.6, and meanwhile, the excellent dielectric property is kept.
The above embodiment provides a specific preparation process of a prepreg for convenience of description, and it should be noted that, when preparing a copper-clad plate, the hot-pressing process is as follows: keeping the temperature of 180-300 ℃ and 2-10 Mpa for 60-300 min, and then keeping the temperature of 180-300 ℃ and 2-10 Mpa for 60-300 min, so that the copper-clad plate can be prepared.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate is characterized by comprising the following components in parts by weight based on solid weight:
2. the glass-fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as claimed in claim 1, wherein the resin prepolymer of polybutadiene and styrene-butadiene copolymer has a number average molecular weight in the range of 8000-150000, a vinyl content in the range of 20-80%, and a dielectric constant of 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-butylperoxyisopropyl benzene, dibenzoyl peroxide or t-butyl hydroperoxide.
4. The glass-fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as claimed in claim 1, wherein the ceramic powder is silica, titania, BaTi 4 O 9 Or BaTi 9 O 20 One or more of (a).
5. The glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as claimed in claim 1, wherein the ceramic powder is modified by a silane coupling agent, the silane coupling agent is one or more of vinyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, vinyltris (b-methoxyethoxy) silane, vinyltriethoxysilane or gamma-methacryloxypropyloxysilane, and the silane coupling agent content is 1 wt% to 5 wt% of the mass of the ceramic powder.
6. The preparation method of the glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate is characterized by comprising the following steps of:
step 1: polybutadiene, a styrene-butadiene copolymer and ethylene propylene diene monomer are mixed according to the weight ratio of (5-15): (2-6): (3-9), after dissolving, sequentially adding ceramic powder modified by a silane coupling agent and an initiator, and uniformly stirring to obtain a ceramic/hydrocarbon resin composite glue solution;
and 2, step: uniformly coating the glue solution of the ceramic/hydrocarbon resin composite material on the surface of a polytetrafluoroethylene film in a scraping way, and carrying out stepped heating drying at the temperature of not higher than 60 ℃ to obtain a prepreg;
and step 3: overlapping a plurality of prepregs, covering copper foils on the upper and lower bottom surfaces after overlapping, and performing hot pressing to obtain a copper-clad plate;
and 4, step 4: and (3) putting the copper-clad plate into the corrosive liquid, and finally preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate after the copper foil is completely corroded.
7. The method for preparing the glass-fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as claimed in claim 6, wherein the solvent in step 1 is one or more of acetone, butanone, methanol, methyl ether, ethylene glycol methyl ether, benzene, toluene or xylene.
8. The preparation method of the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as claimed in claim 6, wherein the thickness of the glue solution coated on the surface of the polytetrafluoroethylene film in step 2 is 0.2-1.5 mm.
9. The preparation method of the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as claimed in claim 6, wherein the step heating rate in step 2 is 5-10 ℃/min, and the drying time is not less than 8 h.
10. The method for preparing the glass fiber-free ceramic/hydrocarbon resin-based microwave dielectric substrate as claimed in claim 6, wherein the hot pressing conditions in step 3 are as follows: keeping the temperature of 180-200 ℃ for 0.5-4 h under the pressure of 2-4 MPa, and keeping the temperature of 200-300 ℃ for 0.5-4 h.
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