CN114437479A - High-frequency prepreg, high-frequency copper-clad plate and preparation method thereof - Google Patents
High-frequency prepreg, high-frequency copper-clad plate and preparation method thereof Download PDFInfo
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- CN114437479A CN114437479A CN202011192044.0A CN202011192044A CN114437479A CN 114437479 A CN114437479 A CN 114437479A CN 202011192044 A CN202011192044 A CN 202011192044A CN 114437479 A CN114437479 A CN 114437479A
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- coupling agent
- aerogel
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- internal hydrophobic
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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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
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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Abstract
The invention belongs to the field of copper-clad plates for printed circuit boards, and particularly relates to a high-frequency prepreg, a high-frequency copper-clad plate and a preparation method thereof. The high-frequency prepreg comprises a resin matrix, wherein glass fiber cloth is compounded or not compounded in the resin matrix, coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel are uniformly filled in the resin matrix, the sum of the mass percentages of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel accounts for 75-98.9%, the mass percentages of the coupling agent modified internal hydrophobic aerogel accounts for 0.1-10%, and the mass percentages of the coupling agent modified chopped fibers account for 1-15%. According to the invention, the spherical silicon dioxide aerogel has the characteristics of good fluidity and isotropy, a uniform filling structure with good isotropy is conveniently constructed, and the consistency of dielectric properties is improved while the dielectric constant and dielectric loss of the prepreg are reduced.
Description
Technical Field
The invention belongs to the field of copper-clad plates for printed circuit boards, and particularly relates to a high-frequency prepreg, a high-frequency copper-clad plate and a preparation method thereof.
Background
The copper-clad plate is a substrate material in the manufacture of the printed circuit board, plays roles of interconnection, conduction, insulation and support in the printed circuit board, and has great influence on the transmission speed, energy loss and characteristic impedance of signals in the circuit. The copper-clad plate is mainly a plate-shaped material which is prepared by dipping electronic glass fiber cloth or other reinforced materials with resin, covering one side or two sides with copper foil and hot-pressing.
With the development of microwave technology, various electronic communication devices are beginning to develop in high frequency, and high-speed transmission and processing of large-capacity information in high frequency band with low loss is required. Generally, the characteristic impedance is inversely proportional to the dielectric constant, and for a high-power and high-load high-frequency substrate, the smaller the dielectric constant, the better; on the other hand, since the smaller the dielectric loss, the less the loss representing signal transmission, the better the transmission quality can be provided by a material with a smaller dielectric loss.
The high-frequency high-speed copper-clad plate and the printed circuit board have become the mainstream of the modern 5G and the future 6G times, and SiO is used2The particles are used as fillers to manufacture copper clad laminates and printed circuit boards, and are researched by many enterprises or scientific research institutions. Due to the conventional SiO2The particles have high dielectric constant and dielectric loss, in terms of SiO2The copper clad laminate with particles as the filling material can not match the requirements of the high-frequency high-speed copper clad laminate in the present and future.
The Chinese invention patent application with the application publication number of CN107793515A discloses a tetrafluoroethylene-vinyl alcohol copolymer and a prepreg and a copper-clad plate prepared by modifying the copolymer, wherein the prepreg comprises the following raw material components in percentage by weight: 15-47 wt% of tetrafluoroethylene-vinyl alcohol copolymer, 15-47 wt% of epoxy resin, 25-33 wt% of propylene glycol monomethyl ether, 0-25 wt% of silicon dioxide aerogel and 0-0.05 wt% of imidazole accelerator.
The application publication number CN103030927A of the Chinese invention discloses a preparation method of a dielectric substrate and a metamaterial, which is mainly used for preparing a substrate with low dielectric constant and low dielectric loss by compounding silica aerogel powder and a thermosetting resin system.
The silica aerogel has the characteristics of low dielectric constant (1.2-3.0 (10GHz, SPDR)) and low dielectric loss (0.002-0.020 (10GHz, SPDR)), which is the reason that the silica aerogel can adjust the dielectric constant, but the direct use of the silica aerogel as a filling material has the following problems:
1) the nanoporous structure of the silica aerogel is easily damaged by solvent penetration (especially, low molecular weight solvents such as water and ethanol);
2) the porous structure of the aerogel can reduce the mechanical properties of the material;
3) the uniform filling of the aerogel with irregular morphology is difficult to realize.
4) The aerogel has extremely low density and is easy to delaminate in the dispersion process.
Disclosure of Invention
The invention aims to provide a high-frequency prepreg, which can realize effective filling and uniform filling of silicon dioxide aerogel in a resin material, and simultaneously reduce the dielectric constant and dielectric loss of a dielectric layer while ensuring the mechanical property.
The second purpose of the invention is to provide a high-frequency copper-clad plate.
The invention also provides a preparation method of the high-frequency copper-clad plate, which solves the problem that the silicon dioxide aerogel is not easy to disperse uniformly.
In order to achieve the purpose, the technical scheme of the high-frequency prepreg is as follows:
a high-frequency prepreg comprises a resin matrix, wherein glass fiber cloth is compounded or not compounded in the resin matrix, and coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel are uniformly filled in the resin matrix;
the coupling agent modified internal hydrophobic aerogel is spherical silicon dioxide aerogel, the internal hydrophobic modification is performed, and the surface coupling agent modification is performed;
the mass percentage sum of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is 100%, the resin matrix accounts for 75-98.9%, the coupling agent modified internal hydrophobic aerogel accounts for 0.1-10%, the coupling agent modified chopped fibers account for 1-15%, and the preferable proportion is 85-98.9%, the coupling agent modified internal hydrophobic aerogel accounts for 0.5-5%, and the coupling agent modified chopped fibers account for 1-15%.
According to the invention, the coupling agent is used for modifying the internal hydrophobic aerogel, so that damage to the internal pore structure of the aerogel caused by the permeation of a water solvent can be avoided in the manufacturing process of a prepreg or a copper-clad plate, the low dielectric and low dielectric loss characteristics of the silicon dioxide aerogel can be exerted, and the coupling agent is used for modifying the surface of the internal hydrophobic aerogel, so that the bonding strength of low dielectric resins such as inorganic silicon dioxide aerogel and PTFE resin is improved.
The silicon dioxide aerogel with the spherical structure has the characteristics of good fluidity and isotropy, a filling structure which is relatively uniform and good in isotropy is conveniently constructed, and the consistency of dielectric properties is improved while the dielectric constant and the dielectric loss of a prepreg are reduced.
The diameter of the coupling agent modified internal hydrophobic aerogel is 0.1-20 mu m. The spherical aerogel with a single diameter is used, the larger the diameter is, the lower the cost is, the larger the pores among the fillers are, the nonuniform micro-morphology is realized, and the filling uniformity under the high aerogel volume filling proportion can be effectively improved by compounding aerogel microspheres with different particle sizes.
When the coupling agent modified internal hydrophobic aerogel consists of two aerogels with different average diameters, the diameters are r from large to small1、r2，r2＝(0.4～0.5)r1，r1Diameter aerogel, r2The filling mass ratio of the diameter aerogel is 1: 0.06-0.08; or when the coupling agent modified internal hydrophobic aerogel consists of three aerogels with different average diameters, the diameters are r from large to small1、r2、r3，r2＝(0.4～0.5)r1，r3＝(0.2～0.3)r1，r1Diameter aerogel, r2Diameter aerogel, r3The filling mass ratio of the diameter aerogel is 1: 0.06-0.08: 0.02-0.03. By adopting the filling mode, a more compact, uniform and isotropic filling structure can be obtained by using lower cost, so that the improvement effect on the dielectric layer of the copper-clad plate is further improved.
The technical scheme of the high-frequency copper-clad plate is as follows:
a high-frequency copper-clad plate comprises a metal foil and a dielectric layer compounded with the metal foil, wherein the dielectric layer comprises a resin matrix, glass fiber cloth is compounded or not compounded in the resin matrix, and coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel are uniformly filled in the resin matrix;
the coupling agent modified internal hydrophobic aerogel is spherical silicon dioxide aerogel, the internal hydrophobic modification is performed, and the surface coupling agent modification is performed;
the sum of the mass percentages of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is 100%, the resin matrix accounts for 75-98.9%, the coupling agent modified internal hydrophobic aerogel accounts for 0.1-10%, and the coupling agent modified chopped fibers account for 1-15%.
The high-frequency copper-clad plate has the same structural characteristics of the dielectric layer as the high-frequency prepreg, has lower dielectric constant and dielectric loss, and basically keeps or improves the mechanical property.
The optimization mode of modifying the internal hydrophobic aerogel by the coupling agent is the same as the technical scheme of the prepreg, and the description is omitted here.
The technical scheme of the preparation method of the high-frequency copper-clad plate is as follows:
a preparation method of a high-frequency copper-clad plate comprises the following steps:
1) uniformly mixing the resin glue solution, the dispersing agent and the defoaming agent to obtain a mixed glue solution; the solvent used for mixing the glue solution is water;
2) dispersing the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel into the mixed glue solution, adding a thickening agent, and uniformly mixing to obtain a gum dipping solution;
3) dipping the glass fiber cloth in a dipping solution for one time or a plurality of times, drying, and roasting to prepare a prepreg; or coating the metal foil with the dipping solution for one or more times, drying, baking to obtain the glued metal foil, and laminating the glued metal foil with another metal foil or the glued metal foil.
By adopting the preparation method of the invention and adopting the coupling agent to modify the internal hydrophobic aerogel for filling, the internal and surface characteristics of the aerogel can be improved, the damage to the aerogel structure caused by the wetting of the solvent to the inside of the aerogel is avoided, and the preparation method is favorable for improving the interface bonding performance of the aerogel and the resin matrix.
The coupling agent used for modifying the surface of the aerogel can be a hydrophilic silane coupling agent, a hydrophobic silane coupling agent or a coupling agent system compounded by the hydrophilic silane coupling agent and the hydrophobic silane coupling agent, and is selected mainly based on the adhesion improvement effect of the aerogel on different resins. For example, a hydrophobic silane coupling agent such as Z-6032 silane coupling agent available from Dow Corning (U.S.) may be selected, and the like, is preferable for the PTFE resin.
The hydrophilic coupling agent and the hydrophobic coupling agent can be any commercially available conventional coupling agent. The hydrophilic coupling agent comprises gamma-glycidyl ether oxypropyltrimethoxysilane, water-soluble modified fluorosilicone and the like; examples of the hydrophobic coupling agent include phenyltrimethyoxysilane, cationic styrylamino, tridecafluorooctyltriethoxysilane and the like.
In step 1), the resin solution may be an emulsion or suspension of a thermoplastic resin, such as Polytetrafluoroethylene (PTFE) emulsion, perfluoroethylene propylene copolymer (FEP) resin emulsion, copolymer of perfluoropropyl perfluorovinyl ether and Polytetrafluoroethylene (PFA) emulsion or a mixture of multiple resin emulsions, preferably FEP/PTFE resin mixture, wherein the FEP resin component is preferably 30 wt% of the solid content of the FEP/PTFE resin mixture.
The dispersant is used for reducing the surface energy of the spherical aerogel powder and the chopped fiber powder and simultaneously improving the wettability and the dispersion effect of the spherical aerogel powder and the chopped fiber powder in a solvent, and is preferably a dispersant with a dispersing function and a wetting function, the conventionally used hydrophilic dispersant is fatty acid, polyethylene, derivatives of polyamide polycondensate or polyethylene oxide and other materials, the hydrophilic dispersant is used in an aqueous dispersion system, and the dosage of the dispersant is generally 0.1-10 wt% of the total mass of the dispersion system.
The defoaming agent is used for reducing bubbles generated in the dispersing process of the coupling agent and the dispersing agent, preferably, in the step 3), the defoaming agent is a defoaming agent of mineral oil, alcohol, fatty acid ester, amide, phosphate, organosilicon, polyether modified polysiloxane and other materials, and the dosage of the defoaming agent is generally 0.1-1 wt% of the weight of the solvent.
In the step 2), the thickener is used for improving the viscosity of the system, so that the system is kept in a uniform and stable suspension state or an emulsion state, the layering speed of aerogel and chopped fiber powder in the mixed resin solution is reduced, and the stability of the dispersion liquid is improved, wherein the common thickener is a polyacrylic acid thickener, and the addition amount of the polyacrylic acid thickener is 0.2-2 wt% of the solid content of the resin glue. After the thickener is added, the mixture is stirred and dispersed for a certain time to be fully mixed. Generally speaking, the mixture is stirred at a speed of 500 to 2000r/min for 10 to 60 min.
The mesh number of the chopped fibers used by the coupling agent modified chopped fibers is 100 meshes or more, and the diameter of the chopped fibers is 1-10 mu m. The chopped fiber is one or two of glass fiber and quartz fiber. The glass fiber is preferably E-glass fiber, NE-glass fiber, T-glass fiber, L-glass fiber, S-glass fiber and other glass fiber materials with low dielectric constant and dielectric loss.
The bulk density of the coupling agent modified internal hydrophobic aerogel is 0.18-0.23 g/cm3The sphericity is 50-100%.
In the step 3), the glass fiber cloth can be subjected to one or more dipping and drying procedures to obtain a prepreg meeting the design requirements. Each dipping time is generally 2-15 min, during drying, air drying can be carried out for 30-60 min at room temperature (25 ℃), then drying is carried out for 30-120 min at 100-150 ℃, after the final dipping and drying, the prepreg product meeting the design requirements can be prepared by roasting for 2-30 min at 260-330 ℃ (the dipping amount is controlled to be 20-70 wt%, and the dipping amount refers to the mass fraction of dipping components on the glass fiber cloth in the prepreg). And then, pressing the prepared prepregs and the metal foils together on a copper-clad plate hot press according to the thickness requirement of the dielectric layer to prepare the copper-clad plate. The pressing condition varies according to the resin used, for example, polytetrafluoroethylene resin, the pressure is generally 6-10 MPa, the temperature is 360-400 ℃, and the time is 2-5 h.
Aiming at the situation of preparing the gummed metal foil, the gumming solution can be coated on the metal foil, and then the metal foil prepared by drying and roasting can be coated and dried for one time or multiple times, so that the coating thickness is improved; for example, the mixture can be dried at 100-150 ℃ for 30-120 min and then roasted at 260-330 ℃ for 2-30 min. And then the coated metal foil is laminated with another metal foil or coated metal foil to prepare the copper-clad plate without the glass fiber cloth.
According to the preparation method of the copper-clad plate, the spherical aerogel powder is added into the resin glue solution, so that the aerogel is uniformly dispersed in the resin glue solution, and meanwhile, the dispersion uniformity and consistency in the prepreg or the dielectric layer are further improved by utilizing the high-fluidity characteristic of the spherical aerogel during pressing, so that the overall dielectric property and consistency of the material are improved, and the product can meet the high-frequency and high-speed application requirements of the existing and future copper-clad plates.
The thickness of the prepreg and the thickness of the glue coating can be determined according to the application requirement of the copper-clad plate. Generally, the thickness of the prepreg is 10 to 250 μm. The coating thickness of the coated metal foil is 25-1000 mu m.
The dielectric layer of the copper-clad plate prepared by the method has the thickness of 25-3000 mu m, the dielectric constant of 1.2-3.0 (10GHz, SPDR) and the dielectric loss of 0.0002-0.020 (10GHz, SPDR).
Drawings
FIG. 1 is a schematic diagram of a copper-clad plate manufactured by the method of embodiment 1 of the invention;
reference numbers in fig. 1: 1-coupling agent modified internal hydrophobic aerogel, 2-upper copper foil, 3-resin matrix, 4-glass fiber cloth, 5-coupling agent modified chopped fiber powder and 6-lower copper foil;
FIG. 2 is a schematic diagram of a copper-clad plate manufactured by the method of embodiment 4 of the invention;
reference numbers in fig. 2: 1-modifying internal hydrophobic aerogel by using a coupling agent, 2-coating copper foil, 3-resin matrix, 5-modifying chopped fiber powder by using the coupling agent, and 6-coating copper foil;
FIG. 3 is a photograph of different aerogels after dispersion is completed and then left to stand for 5 min;
fig. 4 is a photograph of different aerogels after standing for 1h after dispersion is completed.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
Internal hydrophobically modified silica aerogel reference Henan university of Industrial university SiO2The preparation of aerogel microspheres and the study on the properties thereof were carried out by the methods described in the above. The method comprises the steps of firstly carrying out hydrophobic modification on the interior of the spherical silica aerogel by using Trimethylchlorosilane (TMCS), and then carrying out hydrophilic modification on the surface of the spherical silica aerogel by using a 3-aminopropyltrihydroxysilane (KH-553) hydrophilic modifier, wherein a hydrophobic modifier Z-6032 of Dow Corning is used for carrying out surface modification on the spherical silica aerogel in the following examples.
First, an embodiment mode of firstly preparing a prepreg and then preparing a copper-clad plate is adopted
1) Raw material preparation
Hydrophobic coupling agent (such as Z-6032 silane coupling agent provided by Dow Corning (USA)) is used for modifying internal hydrophobic spherical silicon dioxide aerogel powder (the bulk density is 0.18-0.23 g/cm3The sphericity is 50-100%; with average particle diameters of 10 μm, 5 μm and 2 μm, respectively) and a chopped quartz fiber powder (e.g. a powder of quartz fiber provided by a new material from hong Kong Wawa, SiO)2Purity of 99.95%, 500 mesh, fiber diameter of 1-10 μm).
The method for carrying out surface modification by adopting Z-6032 comprises the following steps: mixing 30 parts of Z-6032, 10 parts of glacial acetic acid and 60 parts of water, stirring at normal temperature for 4 hours at the stirring speed of 500-1500 r/min, diluting the concentration of Z-6032 from 30 wt% to 0.3-1 wt% by using water to obtain a treatment solution, adding the spherical silica aerogel with hydrophobic interior into the treatment solution, stirring at high speed of 2000-5000 r/min for more than 2 hours, filtering, air-drying for 30-60 minutes, and finally drying at 100-150 ℃ for 1-3 hours to obtain the inner hydrophobic aerogel with the surface modified by the coupling agent, namely the coupling agent modified inner hydrophobic aerogel.
The method of surface modification of the chopped fiber powder is the same as that of the spherical silica aerogel.
Aqueous emulsions of PTFE resins (60 wt% solids, 15 to 30 mPas viscosity) and aqueous emulsions of FEP resins (50 wt% solids, 15 to 30 mPas viscosity) were obtained from DuPont, USA.
RTF copper foil, 35 μm thick, supplied by suzhou fuda metal.
NE-fiberglass cloth, available from jeidaho.
BYK-163 dispersant, supplied Bick, Germany.
HY-1040A defoaming agent and Beijing Maill chemical supply.
HY-302 thickener provided by Beijing Maier chemical industry.
2) And preparing mixed resin glue solution A.
Selecting PTFE aqueous emulsion and FEP aqueous emulsion to mix, firstly batching according to the proportion of 30 wt% of FEP in the mixed solid content, then adding the two aqueous emulsions into a high-speed dispersion machine together to uniformly disperse under the conditions of the rotating speed of 200-2000 r/min and the time of 30-120 min, and then standing for 5-20 min to obtain mixed resin glue solution A (the viscosity is 10-60 mPa & s at the temperature of 20 ℃, and the solid content is 50-60 wt%).
3) And adding a dispersing agent (such as alkyl polyoxyethylene ether or fatty acid, and the like, the addition amount of which is 0.1-10 wt% of the total weight of the dispersing system) and a defoaming agent (such as mineral oil, modified ether, and the like, and the addition amount of which is 0.1-1 wt% of the weight of the solvent) into the mixed resin glue solution A, and uniformly mixing in a mechanical stirring manner (the rotating speed is 1000-2000 r/min, and the time is 10-60 min) to obtain a mixed glue solution B.
4) And adding the coupling agent modified internal hydrophobic aerogel into the mixed glue solution B (gradually adding the coupling agent modified internal hydrophobic aerogel into the mixed glue solution B from small diameter to large diameter during dispersion), and uniformly dispersing the coupling agent modified internal hydrophobic aerogel into the mixed glue solution B (adding the coupling agent modified internal hydrophobic aerogel into the mixed glue solution B while stirring at the rotating speed of 1000-8000 r/min for 30-120 h) to obtain a mixed glue solution C.
5) And adding the coupling agent modified short-cut quartz fiber powder into the mixed glue solution C, and uniformly dispersing (in a stirring and adding mode, the rotating speed is 1000-2000 r/min, and the time is 30-120 min) to obtain a mixed glue solution D.
6) And adding a certain amount of thickening agent into the mixed glue solution D, and uniformly dispersing (the rotating speed is 500-2000 r/min, and the time is 10-60 min) to obtain a mixed glue solution E.
7) The preparation method comprises the steps of firstly dipping the electronic glass fiber cloth (the selected glass fiber cloth is subjected to pretreatment procedures such as dewaxing, impurity removal, surface modification and drying) for one or more times to obtain a mixed glue solution E, drying (the dipping condition is that the dipping time is 2-15 min, the drying method is that the mixed glue solution E is air-dried at room temperature (25 ℃) for 30-60 min, then the drying time is 30-120 min at the temperature of 100-150 ℃), and roasting at the temperature of 260-330 ℃ for 2-30 min to obtain a prepreg product after the final dipping and drying (the dipping amount is controlled to be 20-70 wt%). And pressing the prepared prepregs and the metal foils on a copper-clad plate hot press according to the thickness requirement of the medium layer to prepare the copper-clad plate (the pressing parameter of the polytetrafluoroethylene resin is pressure intensity of 6-10 MPa, the high temperature section is 360-400 ℃, and the time is 2-5 hours).
The typical structure of the copper-clad plate manufactured by the embodiment is shown in fig. 1, and comprises an upper copper foil 2, a lower copper foil 6 and a dielectric layer compounded between the upper copper foil and the lower copper foil (a prepreg is a material of the copper-clad plate dielectric layer in a semi-cured state before lamination), wherein the dielectric layer comprises a resin matrix 3, a glass fiber cloth 4, a coupling agent modified internal hydrophobic aerogel 1 and a coupling agent modified chopped fiber powder 5 which are uniformly filled in the resin matrix 3.
Second, adopt the way of rubberizing copper foil to prepare the implementation way of the copper-clad plate
Steps 1) to 6) are the same as described in the first section above.
Step 7): and (2) coating the metal foil for one or more times, drying the mixed resin glue solution E (namely, coating and drying are carried out for one or more times in a circulating manner, coating operation with controllable film thickness is carried out on a coating machine, the total coating thickness is 25-1000 mu m), and roasting to prepare the glued metal foil (common drying procedure: drying at 100-150 ℃ for 30-120 min; common roasting procedure: roasting at 260-330 ℃ for 2-30 min), thereby preparing the glued metal foil. Matching the glued metal foil with another metal foil (or glued metal foil), and then pressing the metal foil on a copper-clad plate hot press to prepare the copper-clad plate without glass fiber cloth.
The typical structure of the copper-clad plate manufactured by the embodiment is shown in fig. 2, and comprises an upper copper foil 2, a lower copper foil 6 and a dielectric layer compounded between the upper copper foil and the lower copper foil (a prepreg is a material of the copper-clad plate dielectric layer in a semi-cured state before lamination), wherein the dielectric layer comprises a resin matrix 3, a coupling agent modified internal hydrophobic aerogel 1 and coupling agent modified chopped fiber powder 5 which are uniformly filled in the resin matrix 3.
Third, the specific embodiment of the preparation method of the high-frequency copper-clad plate of the invention
Examples 1 to 3
Referring to the first preparation method of the high-frequency copper-clad plate in embodiments 1 to 3, except for the components listed in table 1 below, the gum dipping amount of the prepreg is controlled to be 50 wt%, and the other materials and process components are the same, so that the copper-clad plate with the dielectric layer thickness of 1.5mm is finally prepared. Wherein BYK-163 is used as the dispersant, and the addition amount is 2 percent of the total mass of the dispersion system; 1040A was used as an antifoaming agent, and the amount added was 0.5% by weight of the solvent. HY-302 is selected as thickener, and the addition amount is 1% of the solid content of the resin glue solution.
TABLE 1 compositional information for examples 1-3 and comparative examples 1-2
Examples 4 to 6
In examples 4 to 6, referring to the second embodiment of the preparation method of the high-frequency copper-clad plate, the copper-clad plate with the dielectric layer thickness of 0.6mm is finally prepared, except the components listed in the following table 2, the other substances and process components are the same. The use conditions of the dispersant, the defoamer and the thickener were the same as those in examples 1 to 3.
TABLE 2 compositional information for examples 4-6
Fourth, the specific embodiment of the high-frequency copper-clad plate of the invention
Example 7
The high-frequency copper-clad plate of embodiment 7 is prepared by the preparation method of the high-frequency copper-clad plate of embodiment 1, and comprises a copper foil and a dielectric layer compounded with the copper foil, wherein the dielectric layer comprises a resin matrix, glass fiber cloth is compounded in the resin matrix, and coupling agent modified chopped fiber powder and coupling agent modified internal hydrophobic aerogel are uniformly filled in the resin matrix.
The resin matrix is composed of 30 wt% of FEP resin and 70 wt% of PTFE resin. The chopped fiber powder type is chopped quartz fiber powder.
The sum of the mass percentages of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is 100%, the resin matrix accounts for 94%, the coupling agent modified internal hydrophobic aerogel accounts for 1%, and the coupling agent modified chopped fiber powder accounts for 5%.
Example 8
The high-frequency copper-clad plate of embodiment 8 is prepared by the preparation method of the high-frequency copper-clad plate of embodiment 4, and is composed of a copper foil and a dielectric layer compounded with the copper foil, wherein the dielectric layer includes a resin matrix, glass fiber cloth is not compounded in the resin matrix, and the resin matrix is uniformly filled with coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel.
The resin matrix is composed of 30 wt% of FEP resin and 70 wt% of PTFE resin. The chopped fiber powder type is chopped quartz fiber powder.
The sum of the mass percentages of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is 100%, the resin matrix accounts for 94%, the coupling agent modified internal hydrophobic aerogel accounts for 1%, and the coupling agent modified chopped fiber powder accounts for 5%.
Fifth, the concrete examples of the prepreg of the present invention
With reference to examples 1 to 3 above, prepreg products were obtained in step 8). The prepreg may be regarded as a precursor of the dielectric layer, and the composition thereof may be regarded as the same as that of the dielectric layer, and may be determined accordingly according to the above embodiments, and will not be described in detail herein.
Sixth, Experimental example
Experimental example 1
This experimental example verifies different silica aerogel's dispersion effect.
The photo of fig. 3 is a photograph of different aerogels after dispersion is completed and then standing for 5min, and the photos are sequentially from left to right: (a) the spherical silicon dioxide aerogel is subjected to internal hydrophobic modification and surface modification, and is dispersed in water; (b) the spherical silicon dioxide aerogel is not subjected to internal hydrophobic modification and surface modification and is dispersed in water; (c) the spherical silicon dioxide aerogel has the dispersion effect in water containing a dispersant and a defoaming agent through internal hydrophobic modification and no surface modification; (d) the aerogel of example 1, dispersion effect in water containing dispersant and defoamer.
FIG. 4 shows the photographs after 1h of standing after the dispersion of the different aerogels was completed. Wherein (a) to (d) correspond to fig. 3.
From sample b in FIG. 3, it can be seen that the aerogel which has not been subjected to internal hydrophobic modification is contacted with an aqueous solventThe silica sol is immediately changed into the silica sol, and the effect of the silica sol after standing in comparison with that in figure 4 is found that the silica sol is obviously settled in a water solvent, which is compared with the density of the aerogel (the bulk density of the aerogel is 0.18-0.23 g/cm)3) The density far lower than that of water is contradictory, which indicates that the internal porous structure of the aerogel is destroyed by the water solvent, and the aerogel without special modification treatment inside cannot be directly dispersed in the solvent.
From the comparison of the samples No. a in fig. 3 and 4, it was found that the internal hydrophobic spherical silica aerogel, which has not been surface-modified, is not destroyed by the water solvent, but is difficult to be directly dispersed in water.
As can be seen from the samples c in fig. 3 and 4, the spherical silica aerogel is subjected to internal hydrophobic modification and no surface modification, and can be well dispersed under the action of the dispersing agent and the defoaming agent.
As can be seen from the samples No. d in fig. 3 and 4, the internal hydrophobically modified spherical silica aerogel product can be stably and uniformly dispersed by the method of example.
In consideration of the bondability of the spherical silica aerogel with a low dielectric resin such as a PTFE resin, the sample d has the best application effect.
Experimental example 2
In the experimental example, the prepreg or the copper-clad plate of the example and the comparative example were subjected to performance tests, and the results are shown in tables 3 and 4 below.
TABLE 3 Performance test results of examples 1 to 3 and comparative examples 1 to 2
TABLE 4 Performance test results of examples 4-6 and comparative example 3
(in tables 3 and 4: 1) "none" means no data reference. 2) Dielectric constant and dielectric loss: tested according to the IPC-TM-6502.5.5.5 method. 3) Water absorption: the test was carried out according to the IPC-TM-650-2.6.2.1 method. 4) Bending strength: according to the test of the IPC-TM-6502.4.4 method, when the bending strength of the copper clad laminate dielectric layer at room temperature is tested, the copper foil on the surface of the copper clad laminate needs to be completely etched by an etching system before the test, and the copper foil is dried to constant weight at 125 ℃. 5) "longitudinal" refers to the direction of the machine direction of impregnation and coating, i.e. parallel to the long sides of the web (fiberglass cloth or copper foil), and "transverse" refers to the direction perpendicular to the longitudinal direction. 6) In the test conditions, "D" indicates soaking in distilled water, after which the first data indicates time and the second data indicates temperature. )
The test results show that the addition of the spherical silica aerogel can effectively reduce the dielectric constant and dielectric loss of the prepreg and the copper-clad plate, meanwhile, the addition of the chopped fiber powder maintains the mechanical property of the copper-clad plate, and in addition, the aerogel is far less than the density of the resin (the bulk density of the aerogel is 0.18-0.23 g/cm3, and the density of the PTFE resin is about 2.2g/cm 3)3The density of the chopped quartz fiber powder is about 2.65g/cm3) Therefore, although the mass fraction of the added aerogel is small (1-2%), the volume fraction of the aerogel is large (the volume fraction of the aerogel is nearly 50-70%), and the impregnation amount of the prepreg can be remarkably reduced by filling the aerogel.
Comparing example 1 and example 2 (or example 4 and example 5), it can be seen that by compounding aerogel microspheres with different particle sizes, the dielectric constant and the dielectric loss can be reduced, and the mechanical properties can be improved, further illustrating that by compounding aerogel microspheres with different particle sizes, the filling uniformity of the aerogel under a high volume ratio can be effectively improved.
In addition, as can be seen from examples 4 to 6 in table 4, the dielectric layer is not compounded with the glass fiber cloth, and after the spherical silica aerogel is filled in a proportion of 1 to 2%, the copper clad laminate has lower dielectric constant and dielectric loss, but the mechanical property is remarkably reduced because no glass fiber cloth is compounded, and the dielectric constant of the copper clad laminate is improved because the conventional amorphous fused silica (the dielectric constant is about 3.8 and the dielectric loss is about 0.0025) and the E-glass fiber powder (the dielectric constant is about 6.13 and the dielectric loss is about 0.0038) are added in the comparative example 3.
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Claims (10)
1. The high-frequency prepreg is characterized by comprising a resin matrix, wherein glass fiber cloth is compounded or not compounded in the resin matrix, and coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel are uniformly filled in the resin matrix;
the coupling agent modified internal hydrophobic aerogel is spherical silicon dioxide aerogel, the internal hydrophobic modification is performed, and the surface coupling agent modification is performed;
the sum of the mass percentages of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is 100%, the resin matrix accounts for 75-98.9%, the coupling agent modified internal hydrophobic aerogel accounts for 0.1-10%, and the coupling agent modified chopped fibers account for 1-15%.
2. The high-frequency prepreg according to claim 1, wherein the coupling agent-modified internal hydrophobic aerogel has a diameter of 0.1 to 20 μm and consists of one or more aerogels having an average diameter.
3. The high-frequency prepreg according to claim 2, wherein when the coupling agent-modified internal hydrophobic aerogel consists of two aerogels having different average diameters, the diameters are r from large to small1、r2，r2＝(0.4～0.5)r1，r1Diameter aerogel, r2The filling mass ratio of the diameter aerogel is 1: 0.06-0.08; or when the coupling agent modified internal hydrophobic aerogel consists of three aerogels with different average diameters, the diameters are r from large to small1、r2、r3，r2＝(0.4～0.5)r1，r3＝(0.2～0.3)r1，r1Diameter aerogel, r2Diameter aerogel, r3The filling mass ratio of the diameter aerogel is 1: 0.06-0.08: 0.02-0.03.
4. The high-frequency copper-clad plate is characterized by consisting of a metal foil and a dielectric layer compounded with the metal foil, wherein the dielectric layer comprises a resin matrix, glass fiber cloth is compounded or not compounded in the resin matrix, and coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel are uniformly filled in the resin matrix;
the coupling agent modified internal hydrophobic aerogel is spherical silicon dioxide aerogel, the internal hydrophobic modification is performed, and the surface coupling agent modification is performed;
the sum of the mass percentages of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is 100%, the resin matrix accounts for 75-98.9%, the coupling agent modified internal hydrophobic aerogel accounts for 0.1-10%, and the coupling agent modified chopped fibers account for 1-15%.
5. The high-frequency copper-clad plate according to claim 4, wherein the diameter of the coupling agent modified internal hydrophobic aerogel is 0.1-20 μm, and the coupling agent modified internal hydrophobic aerogel consists of one or more aerogels with average diameters.
6. The high-frequency copper-clad plate according to claim 5, wherein when the coupling agent modified internal hydrophobic aerogel consists of two aerogels with different average diameters, the diameters are r from large to small1、r2，r2＝(0.4～0.5)r1，r1Diameter aerogel, r2The filling mass ratio of the diameter aerogel is 1: 0.06-0.08; or when the coupling agent modified internal hydrophobic aerogel consists of three aerogels with different average diameters, the diameters are r from large to small1、r2、r3，r2＝(0.4～0.5)r1，r3＝(0.2～0.3)r1，r1Diameter aerogel, r2Diameter aerogel, r3The filling mass ratio of the diameter aerogel is 1: 0.06-0.08: 0.02-0.03.
7. The preparation method of the high-frequency copper-clad plate according to claim 4, which is characterized by comprising the following steps:
1) uniformly mixing the resin glue solution, a dispersing agent and a defoaming agent to obtain a mixed glue solution; the solvent used for mixing the glue solution is water;
2) dispersing the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel into the mixed glue solution, adding a thickening agent, and uniformly mixing to obtain a gum dipping solution;
3) dipping the glass fiber cloth in a dipping solution for one time or a plurality of times, drying, and roasting to prepare a prepreg; or coating the metal foil with the dipping solution for one or more times, drying, roasting to prepare the glued metal foil, and laminating the glued metal foil and another metal foil or the glued metal foil.
8. The preparation method of the high-frequency copper-clad plate according to claim 7, wherein in the step 2), the mesh number of the chopped fibers used by the coupling agent modified chopped fibers is 100 meshes or more, and the diameter is 1-10 μm.
9. The method for preparing the high-frequency copper-clad plate according to claim 8, wherein the chopped fibers are one or two of glass fibers and quartz fibers.
10. The preparation method of the high-frequency copper-clad plate according to any one of claims 7 to 9, wherein the bulk density of the coupling agent modified internal hydrophobic aerogel is 0.18 to 0.23g/cm3The sphericity is 50-100%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116583005A (en) * | 2023-07-11 | 2023-08-11 | 荣耀终端有限公司 | Copper-clad plate, flexible circuit board and electronic equipment |
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| CN114437479B (en) | 2024-01-12 |
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