CN114437479B - High-frequency prepreg, high-frequency copper-clad plate and preparation method of high-frequency prepreg and high-frequency copper-clad plate - Google Patents
High-frequency prepreg, high-frequency copper-clad plate and preparation method of high-frequency prepreg and high-frequency copper-clad plate Download PDFInfo
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- CN114437479B CN114437479B CN202011192044.0A CN202011192044A CN114437479B CN 114437479 B CN114437479 B CN 114437479B CN 202011192044 A CN202011192044 A CN 202011192044A CN 114437479 B CN114437479 B CN 114437479B
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- internal hydrophobic
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- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000004964 aerogel Substances 0.000 claims abstract description 119
- 239000007822 coupling agent Substances 0.000 claims abstract description 93
- 229920005989 resin Polymers 0.000 claims abstract description 82
- 239000011347 resin Substances 0.000 claims abstract description 82
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 68
- 239000000835 fiber Substances 0.000 claims abstract description 49
- 239000011159 matrix material Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003365 glass fiber Substances 0.000 claims abstract description 33
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 29
- 239000004744 fabric Substances 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 18
- 239000003292 glue Substances 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000011888 foil Substances 0.000 claims description 28
- 238000007598 dipping method Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
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- 239000007788 liquid Substances 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims 2
- 238000010168 coupling process Methods 0.000 claims 2
- 238000005859 coupling reaction Methods 0.000 claims 2
- 239000000843 powder Substances 0.000 description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 239000011889 copper foil Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 230000004048 modification Effects 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
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- 239000000839 emulsion Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 239000013530 defoamer Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- -1 Polytetrafluoroethylene Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
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- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
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- 238000009736 wetting Methods 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- 238000004891 communication Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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 is calculated as 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%. In the invention, the spherical silica aerogel has the characteristics of good fluidity and isotropy, so that a more 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 a 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 a circuit. The copper-clad plate is a plate-like material which is mainly prepared by dipping electronic glass fiber cloth or other reinforcing materials with resin, coating copper foil on one side or both sides, and hot-pressing.
With the development of microwave technology, various communication electronic devices are beginning to develop toward high frequency, and high-speed transmission and processing of large-capacity information with low loss in a high frequency band are required. In general, the characteristic impedance is inversely proportional to the dielectric constant, and for a high-power high-load high-frequency substrate, the smaller the dielectric constant, the better; on the other hand, the smaller the dielectric loss, the less the loss representing signal transmission, so the better the transmission quality can be provided by the material with smaller dielectric loss.
High-frequency high-speed copper-clad plates and printed circuit boards have become the mainstream of the current 5G and future 6G ages, and SiO is adopted 2 The production of copper-clad plates and printed wiring boards using particles as fillers has been studied by many enterprises or scientific institutions. Due to conventional SiO 2 The dielectric constant and dielectric loss of the particles are high, and SiO is used for 2 The copper-clad plate with the particles as the filling material cannot meet the requirements of the present and future high-frequency high-speed copper-clad plates.
The Chinese 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 using the copolymer, wherein the prepreg comprises the following raw material components in percentage by weight: 15 to 47 percent of tetrafluoroethylene-vinyl alcohol copolymer, 15 to 47 percent of epoxy resin, 25 to 33 percent of propylene glycol monomethyl ether, 0 to 25 percent of silica aerogel and 0 to 0.05 percent of imidazole accelerator.
The Chinese patent application with publication number of CN103030927A discloses a preparation method of a dielectric substrate and a metamaterial, which mainly uses silicon dioxide aerogel powder and a thermosetting resin system to prepare the substrate with low dielectric constant and low dielectric loss.
Silica aerogel has characteristics of low dielectric constant (1.2 to 3.0 (10 ghz, spdr)) and low dielectric loss (0.002 to 0.020 (10 ghz, spdr)), which is why silica aerogel can adjust dielectric constant, but there are the following problems in that silica aerogel is directly used as a filler:
1) The nano-pore structure of the silica aerogel is extremely easy to be damaged by infiltration of solvents (particularly 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) Uniform filling of irregularly shaped aerogels is difficult to achieve.
4) The aerogel has extremely low density and is easy to delaminate in the dispersing process.
Disclosure of Invention
The invention aims to provide a high-frequency prepreg which can realize the effective filling and uniform filling of silica 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 object 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 silica aerogel is not easy to disperse uniformly.
In order to achieve the above purpose, the technical scheme of the high-frequency prepreg of the invention 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 silica aerogel, the internal hydrophobic aerogel is modified, and the surface coupling agent is modified;
the mass percent of the sum of the resin matrix, the coupling agent modified chopped fiber and the coupling agent modified internal hydrophobic aerogel is calculated as 100 percent, the resin matrix accounts for 75 to 98.9 percent, the coupling agent modified internal hydrophobic aerogel accounts for 0.1 to 10 percent, the coupling agent modified chopped fiber accounts for 1 to 15 percent, more preferably the ratio of the resin matrix accounts for 85 to 98.9 percent, the coupling agent modified internal hydrophobic aerogel accounts for 0.5 to 5 percent, and the coupling agent modified chopped fiber accounts for 1 to 15 percent.
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 infiltration of a water solvent in the manufacturing process of a prepreg or a copper-clad plate can be avoided, the characteristics of low dielectric property and low dielectric loss of the silica aerogel are brought into play, and the coupling agent is used for modifying the surface of the internal hydrophobic aerogel so as to improve the bonding strength of inorganic silica aerogel, PTFE resin and other low dielectric resins.
The silica aerogel with the spherical structure has the characteristics of good fluidity and isotropy, is convenient to construct a more uniform filling structure with good isotropy, and improves the consistency of dielectric properties while reducing the dielectric constant and dielectric loss of the prepreg.
The diameter of the coupling agent modified internal hydrophobic aerogel is 0.1-20 mu m. The spherical aerogel with single diameter is used, the larger the diameter is, the lower the cost is, the larger the pores among fillers are, the micro morphology is uneven, and the filling uniformity under the condition of high aerogel volume filling proportion can be effectively improved by compounding aerogel microspheres with different particle diameters.
When the coupling agent modified internal hydrophobic aerogel is composed of two aerogels with different average diameters, the diameters are respectively r from large to small 1 、r 2 ，r 2 ＝(0.4～0.5)r 1 ，r 1 Diameter aerogel, r 2 Diameter air coagulationThe filling mass ratio of the glue is 1:0.06-0.08; or when the coupling agent modified internal hydrophobic aerogel is composed of three aerogels with different average diameters, the diameters are respectively r from large to small 1 、r 2 、r 3 ，r 2 ＝(0.4～0.5)r 1 ，r 3 ＝(0.2～0.3)r 1 ，r 1 Diameter aerogel, r 2 Diameter aerogel, r 3 The filling mass ratio of the diameter aerogel is 1:0.06-0.08:0.02-0.03. By adopting the filling mode, a tighter, uniform and isotropic filling structure can be obtained by using smaller cost, so that the improvement effect on the copper-clad plate dielectric layer is further improved.
The technical scheme of the high-frequency copper-clad plate is as follows:
the high-frequency copper-clad plate consists 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 the resin matrix is uniformly filled with coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel;
the coupling agent modified internal hydrophobic aerogel is spherical silica aerogel, the internal hydrophobic aerogel is modified, and the surface coupling agent is modified;
the mass percent of the sum of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is calculated as 100 percent, the resin matrix accounts for 75 to 98.9 percent, the coupling agent modified internal hydrophobic aerogel accounts for 0.1 to 10 percent, and the coupling agent modified chopped fibers account for 1 to 15 percent.
The high-frequency copper-clad plate has the structural characteristics of the dielectric layer which are the same as those of the high-frequency prepreg, has lower dielectric constant and dielectric loss, and basically maintains or improves the mechanical properties.
The optimization mode of the coupling agent modified internal hydrophobic aerogel is the same as the technical scheme of the prepreg, and is not described herein.
The technical scheme of the preparation method of the high-frequency copper-clad plate is as follows:
the preparation method of the 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 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, and then adding the thickening agent for uniform mixing to obtain a glue dipping solution;
3) Dipping the glass fiber cloth into the dipping liquid for one or more times, drying, and roasting to prepare a prepreg; or coating the glue dipping liquid on the metal foil for one or more times, drying, roasting to prepare the glue-coated metal foil, and pressing the glue-coated metal foil with another metal foil or the glue-coated metal foil.
According to the preparation method, the coupling agent is used for modifying the internal hydrophobic aerogel to fill, so that the internal and surface characteristics of the aerogel can be improved, the damage to the aerogel structure caused by wetting of the solvent to the inside of the aerogel can be avoided, and the preparation method is beneficial to improving the interface bonding performance of the aerogel and a resin matrix.
The coupling agent used for the surface modification 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 mainly selected based on the adhesive force improving effect of the aerogel on different resins. As the PTFE resin, for example, a hydrophobic silane coupling agent such as Z-6032 silane coupling agent provided by Dow Corning (U.S.) may be selected.
The hydrophilic coupling agent and the hydrophobic coupling agent can be commercially available conventional ones. The hydrophilic coupling agent is gamma-glycidol ether oxygen propyl trimethoxy silane, water-soluble modified fluorosilicone and the like; examples of the hydrophobic coupling agent include phenyltrimethyloxysilane, cationic styrylamino and tridecafluorooctyltriethoxysilane.
In the step 1), the resin glue may be a conventional prepreg, and is typically an emulsion or suspension of a thermoplastic resin, such as Polytetrafluoroethylene (PTFE) emulsion, perfluoroethylene propylene copolymer (FEP) resin emulsion, perfluoropropyl perfluorovinyl ether-polytetrafluoroethylene copolymer (PFA) emulsion, or a mixture of multiple resin emulsions, preferably a FEP/PTFE resin mixture, wherein the FEP resin component accounts for preferably 30wt% of the FEP/PTFE resin mixture in terms of solid content.
The purpose of the use of the dispersing agent is to reduce the surface energy of the spherical aerogel powder and the chopped fiber powder, and simultaneously improve the wettability and the dispersing effect in the solvent, preferably the dispersing agent with the dispersing function and the wetting function, and the conventionally used hydrophilic dispersing agent is materials such as fatty acid, polyethylene, polyamide polycondensate derivatives or polyethylene oxide, and the like, and the use amount of the hydrophilic dispersing agent in the aqueous phase dispersing system is generally 0.1-10wt% of the total mass of the dispersing system.
The purpose of using the defoamer is to reduce bubbles generated in the dispersing process of the coupling agent and the dispersing agent, preferably, in the step 3), the type of the defoamer conventionally used is mineral oil type, alcohol type, fatty acid and fatty acid ester type, amide type, phosphate type, organosilicon type, polyether modified polysiloxane type and other materials, and the use amount of the defoamer is generally 0.1-1 wt% of the weight of the solvent.
In the step 2), the purpose of the thickener is to increase 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 slowed down, the stability of the dispersion is improved, and the common thickener is polyacrylic thickener, and the addition amount of the thickener is 0.2-2 wt% of the solid content of the resin glue solution. After the thickener is added, the mixture is stirred and dispersed for a certain period of time to be fully and uniformly mixed. Generally, the stirring is carried out at a speed of 500 to 2000r/min for 10 to 60 min.
The mesh number of the chopped fibers used for modifying the chopped fibers by the coupling agent is 100 meshes or more, and the diameter 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 constants and dielectric losses.
The bulk density of the coupling agent modified internal hydrophobic aerogel is 0.18-0.23 g/cm 3 The sphericity is 50-100%.
In the step 3), the glass fiber cloth can be subjected to one or more dipping and drying processes to obtain the prepreg meeting the design requirements. The dipping time is generally 2-15 min each time, when drying, the prepreg can be firstly air-dried for 30-60 min at room temperature (25 ℃), then dried for 30-120 min at 100-150 ℃, after the final dipping and drying are finished, the prepreg product meeting the design requirement 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 glass fiber cloth in the prepreg). And then, pressing the prepared amount of prepregs and the metal foil together on a copper-clad plate hot press according to the thickness requirement of the dielectric layer to prepare the copper-clad plate. The laminating conditions are different depending on the resin used, and polytetrafluoroethylene resin is taken as an example, the pressure is generally 6-10 MPa, the temperature is 360-400 ℃, and the time is 2-5 h.
For the situation of preparing the rubberized metal foil, the dipping solution can be coated on the metal foil, and then the metal foil prepared by drying and roasting can be coated and dried once or a plurality of times, so that the coating thickness is increased; if it is possible to dry at 100-150 deg.C for 30-120 min, then bake at 260-330 deg.C for 2-30 min. And then pressing the glue-coated metal foil with another metal foil or glue-coated metal foil to prepare the copper-clad plate without 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, when the spherical aerogel is pressed, the high-fluidity characteristic of the spherical aerogel is utilized, so that the dispersion uniformity and consistency in a prepreg or a dielectric layer are further improved, the overall dielectric property and consistency of the material are improved, and the product can be matched with the high-frequency and high-speed application requirements of the copper-clad plate in the present and future.
The thickness of the prepreg and the glue coating thickness can be determined according to the application requirements of the copper-clad plate. In general, the prepreg has a thickness of 10 to 250. Mu.m. The coating thickness of the rubberized 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 (10 GHz and SPDR) and the dielectric loss of 0.0002-0.020 (10 GHz and SPDR).
Drawings
Fig. 1 is a schematic diagram of a copper-clad plate manufactured by the method of embodiment 1 of the present invention;
reference numerals 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 present invention;
reference numerals in fig. 2: 1-a coupling agent modified internal hydrophobic aerogel, 2-an upper copper foil, 3-a resin matrix, 5-a coupling agent modified chopped fiber powder and 6-a lower copper foil;
FIG. 3 is a photograph of a 5 minute stand after completion of dispersion of various aerogels;
FIG. 4 is a photograph of the different aerogels after they have been dispersed and allowed to stand for 1 hour.
Detailed Description
Embodiments of the present invention will be further described with reference to the accompanying drawings.
Internal hydrophobically modified silica aerogel reference university of Henan Industrial university, siO 2 Preparation of aerogel microspheres and preparation thereof by the method described in research on properties thereof. The hydrophobic modifier Z-6032 of the dacorning is used for modifying the surface of the spherical silica aerogel in the following examples.
1. Adopts the implementation mode of firstly preparing prepreg and then preparing copper-clad plate
1) Raw material preparation
The hydrophobic coupling agent (such as Z-6032 silane coupling agent provided by Dow Corning (USA)) is used for preparing the internal hydrophobically modified spherical silica aerogel powder (bulk density 0.18-0.23 g/cm 3 The sphericity is 50-100%; average particle diameters of 10 μm, 5 μm and 2 μm, respectively) and chopped quartz fiber powder (e.g., quartz fiber powder provided by new material of Lian Yungang Wo Hua, siO) 2 Purity 99.95%,500 mesh, fiber diameter 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 for 4 hours at normal temperature, wherein the stirring speed is 500-1500 r/min, diluting the concentration of Z-6032 from 30wt% to 0.3-1 wt% by using water to obtain a treatment liquid, adding the spherical silica aerogel with internal hydrophobicity into the treatment liquid, stirring for more than 2 hours at a high speed of 2000-5000 r/min, filtering, air-drying for 30-60 minutes, and finally drying for 1-3 hours at 100-150 ℃ to obtain the internal hydrophobic aerogel with the surface modified by the coupling agent, namely the coupling agent modified internal hydrophobic aerogel.
The surface modification method of the chopped fiber powder is the same as that of the spherical silica aerogel.
Aqueous emulsions of PTFE resins (solid content 60wt%, viscosity 15-30 mPas) and aqueous emulsions of FEP resins (solid content 50wt%, viscosity 15-30 mPas) are both available from DuPont, U.S.A.
RTF copper foil, 35 μm thick, available from Futian metal, suzhou.
NE-glass cloth, provided by Nitroong, japan.
BYK-163 dispersant, available from Pick, germany.
HY-1040A defoamer, provided by Beijing Michael chemical industry.
HY-302 thickener, available from Beijing Michael chemical industry.
2) And preparing a mixed resin glue solution A.
Mixing PTFE aqueous emulsion and FEP aqueous emulsion, firstly mixing according to the proportion of FEP accounting for 30wt% in the mixed solid content, then adding the two aqueous emulsions into a high-speed dispersing machine together, uniformly dispersing under the condition of 200-2000 r/min and 30-120 min, and then standing for 5-20 min to obtain mixed resin glue solution A (the viscosity is 10-60 mPa.s and the solid content is 50-60 wt% at 20 ℃).
3) Dispersing agent (such as alkyl polyoxyethylene ether or fatty acid, etc. with the addition amount of 0.1-10wt% of the total weight of the dispersion system) and defoaming agent (such as mineral oil and modified ether, etc. with the addition amount of 0.1-1wt% of the solvent) are added into the mixed resin glue solution A, and the mixture is uniformly mixed by a mechanical stirring mode (the rotating speed is 1000-2000 r/min, and the time is 10-60 min), so as to obtain mixed glue solution B.
4) Adding the coupling agent modified internal hydrophobic aerogel into the mixed glue solution B (gradually adding according to the order of small diameter to large diameter during dispersion), and uniformly dispersing (adding while stirring, and rotating at 1000-8000 r/min for 30-120 h) to obtain the mixed glue solution C.
5) Adding the coupling agent modified chopped quartz fiber powder into the mixed glue solution C, and uniformly dispersing (adopting a mode of adding while stirring, the rotating speed is 1000-2000 r/min, and the time is 30-120 min) to obtain the mixed glue solution D.
6) And adding a certain amount of thickener 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 the mixed glue solution E.
7) The electronic glass fiber cloth (the selected glass fiber cloth is subjected to pretreatment procedures such as dewaxing, impurity removal, surface modification, drying and the like) is firstly subjected to one or more times of dipping and mixing glue solution E and is dried (dipping conditions are dipping time of 2-15 min, the drying method is that the electronic glass fiber cloth is firstly air-dried for 30-60 min at room temperature (25 ℃), then the electronic glass fiber cloth is dried for 30-120 min at 100-150 ℃), and finally the electronic glass fiber cloth is subjected to dipping and drying (the dipping amount is controlled to be 20-70 wt%) and is baked for 2-30 min at 260-330 ℃ to prepare the prepreg product. And pressing the prepared amount of prepregs and metal foils on a copper-clad plate hot press according to the thickness requirement of the dielectric layer to prepare the copper-clad plate (the pressing parameters of polytetrafluoroethylene resin are 6-10 MPa, the high temperature range is 360-400 ℃ and the time is 2-5 h).
The typical structure of the copper-clad plate manufactured by the embodiment is shown in fig. 1, and the copper-clad plate 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, glass fiber cloth 4, coupling agent modified internal hydrophobic aerogel 1 and coupling agent modified chopped fiber powder 5 which are uniformly filled in the resin matrix 3.
2. Implementation mode for preparing copper-clad plate by adopting glue-coated copper foil mode
Steps 1) to 6) are the same as described in the first section above.
Step 7): coating the metal foil one or more times and drying the mixed resin glue solution E (namely, coating and drying are carried out one or more times, coating operation with controllable film thickness is carried out on a coating machine, the total coating thickness is 25-1000 mu m), and baking to obtain the rubberized metal foil (common drying procedure: drying at 100-150 ℃ for 30-120 min and common baking procedure: baking at 260-330 ℃ for 2-30 min). And (3) matching the glue-coated metal foil with another metal foil (or glue-coated metal foil), and pressing 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 the copper-clad plate 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 (the 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.
3. Specific example of the preparation method of the high-frequency copper-clad plate of the invention
Examples 1 to 3
According to the preparation method of the high-frequency copper-clad plate of the embodiment 1-3, referring to the first embodiment of the preparation method of the high-frequency copper-clad plate, except for the components listed in the following table 1, the gum dipping amount of the prepreg is controlled to be 50wt%, the other substances and the process components are the same, and finally the copper-clad plate with the medium layer thickness of 1.5mm is prepared. Wherein BYK-163 is used as a dispersing agent, and the adding amount is 2% of the total mass of the dispersing system; the defoamer was 1040A added in an amount of 0.5% by weight of the solvent. The thickening agent is HY-302, and the addition amount is 1% of the solid content of the resin glue solution.
TABLE 1 component information for examples 1-3 and comparative examples 1-2
Examples 4 to 6
Examples 4 to 6 referring to the second embodiment of the method for producing a high-frequency copper-clad plate above, except for the components listed in table 2 below, the other materials and process components were the same, and finally copper-clad plates each having a dielectric layer thickness of 0.6mm were produced. Among them, the dispersant, defoamer and thickener were used in the same manner as in examples 1 to 3.
TABLE 2 information on the Components of examples 4 to 6
4. Specific example of the high-frequency copper-clad plate of the invention
Example 7
The high-frequency copper-clad plate of the embodiment 7 is prepared by the high-frequency copper-clad plate preparation method of the embodiment 1 and consists of 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 the resin matrix is uniformly filled with coupling agent modified chopped fiber powder and coupling agent modified internal hydrophobic aerogel.
The resin matrix consisted of 30wt% FEP resin and 70wt% PTFE resin. The type of chopped fiber powder is chopped quartz fiber powder.
The mass percent of the sum of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is calculated as 100 percent, the resin matrix accounts for 94 percent, the coupling agent modified internal hydrophobic aerogel accounts for 1 percent, and the coupling agent modified chopped fiber powder accounts for 5 percent.
Example 8
The high-frequency copper-clad plate of the embodiment 8 is prepared by the high-frequency copper-clad plate preparation method of the embodiment 4 and consists of a copper foil and a dielectric layer compounded with the copper foil, wherein the dielectric layer comprises 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 consisted of 30wt% FEP resin and 70wt% PTFE resin. The type of chopped fiber powder is chopped quartz fiber powder.
The mass percent of the sum of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is calculated as 100 percent, the resin matrix accounts for 94 percent, the coupling agent modified internal hydrophobic aerogel accounts for 1 percent, and the coupling agent modified chopped fiber powder accounts for 5 percent.
5. Specific examples of prepregs of the invention
Referring to examples 1 to 3 above, a prepreg product is obtained in step 8). The prepreg may be regarded as a precursor of the dielectric layer, and its composition may be regarded as the same as that of the dielectric layer, and may be determined accordingly according to the above embodiments, which will not be described in detail herein.
6. Experimental example
Experimental example 1
The experimental example verifies the dispersion effect of different silica aerogels.
In fig. 3, photographs of the different aerogels are taken after 5min of standing after dispersing, and the photographs are shown in the following order from left to right: (a) The spherical silica aerogel is subjected to internal hydrophobic modification and is dispersed in water without surface modification; (b) The spherical silica aerogel is dispersed in water without internal hydrophobic modification and surface modification; (c) The spherical silica aerogel has the dispersion effect in water containing a dispersing agent and a defoaming agent after internal hydrophobic modification and without surface modification; (d) The dispersion effect of the aerogel of example 1 in water containing dispersant and defoamer.
FIG. 4 shows a photograph after 1h of standing after completion of the dispersion of the different aerogels. Wherein (a) - (d) correspond to fig. 3.
As can be seen from sample No. b in FIG. 3, the aerogel which has not been subjected to internal hydrophobic modification becomes silica sol immediately after contacting with an aqueous solvent, and it is found that the silica sol undergoes significant sedimentation in the aqueous solvent in comparison with the effect after standing in FIG. 4, which is equivalent to the density of the aerogel itself (bulk density of the aerogel is 0.18 to 0.23g/cm 3 ) The density of the aerogel is far lower than that of water, which is contradictory, so that the internal porous structure of the aerogel is damaged by the water solvent, and the aerogel which is not subjected to special modification treatment cannot be directly dispersed in the solvent.
From the comparison of the samples a in fig. 3 and 4, it was found that the internal hydrophobic spherical silica aerogel having not undergone surface modification was not destroyed by the aqueous solvent, but was difficult to disperse directly in water.
As can be seen from sample c in fig. 3 and 4, the spherical silica aerogel is internally hydrophobically modified, and is not surface modified, and can be well dispersed under the action of a dispersing agent and a defoaming agent.
As can be seen from the d sample in fig. 3 and 4, the internal hydrophobically modified spherical silica aerogel product can be stably and uniformly dispersed by the method of the example.
The sample d has the best application effect in view of the combination of spherical silica aerogel and low dielectric property resin such as PTFE resin.
Experimental example 2
This experimental example performance tests were performed on prepregs or copper clad laminates of examples and comparative examples, and the results are shown in tables 3 and 4 below.
TABLE 3 results of Performance test of examples 1-3 and comparative examples 1-2
Table 4 results of performance tests of examples 4 to 6 and comparative example 3
(1: in tables 3 and 4), "none" means that there is no data reference. 2) Dielectric constant and dielectric loss: tested according to IPC-TM-650 2.5.5.5 method. 3) Water absorption rate: tested according to the IPC-TM-650-2.6.2.1 method. 4) Flexural strength: when the IPC-TM-650 2.4.4 method is used for testing the bending strength of a copper-clad plate dielectric layer at room temperature, the copper foil on the surface of the copper-clad plate needs to be completely etched by an etching system before testing, and is dried to constant weight at 125 ℃. 5) "machine direction" refers to the direction of the machine direction of dipping and coating, i.e., the direction parallel to the long side of the web (fiberglass cloth or copper foil), and "transverse direction" refers to the direction perpendicular to the machine direction. 6) In the test conditions, "D" represents immersion in distilled water, after which the first data represents time and the second data represents temperature. )
From the above test results, it is possible toThe addition of the spherical silica aerogel can effectively reduce the dielectric constant and dielectric loss of the prepreg and the copper-clad plate, and meanwhile, the addition of the chopped fiber powder maintains the mechanical property of the copper-clad plate, and in addition, the density of the aerogel is far smaller than that of the resin (the stacking density of the aerogel is 0.18-0.23 g/cm < 3 >, and the density of PTFE resin is about 2.2 g/cm) 3 The density of the chopped quartz fiber powder is about 2.65g/cm 3 ) Thus, although the mass fraction of the added aerogel is relatively small (1-2%), the volume ratio of the aerogel is very large (the volume ratio of the aerogel is approximately 50-70%), and the filling of the aerogel can remarkably reduce the gum dipping amount of the prepreg.
As can be seen from comparative examples 1 and 2 (or examples 4 and 5), the composition of aerogel microspheres with different particle sizes can reduce dielectric constant and dielectric loss, and improve mechanical properties, and further illustrates that the composition of aerogel microspheres with different particle sizes can effectively improve filling uniformity under high volume ratio of aerogel.
In addition, as can be seen from examples 4 to 6 in table 4, the dielectric layer is not compounded with glass fiber cloth, and the copper-clad plate has lower dielectric constant and dielectric loss after being filled with spherical silica aerogel in a proportion of 1 to 2%, but the mechanical properties are remarkably reduced due to the absence of compounding of glass fiber cloth, and the dielectric constant of the copper-clad plate is improved due to the addition of conventional amorphous fused silica (dielectric constant about 3.8, dielectric loss about 0.0025) and E-glass fiber powder (dielectric constant about 6.13, dielectric loss about 0.0038) in comparative example 3.
Finally, it should be emphasized that the foregoing description is merely illustrative of the preferred embodiments of the invention, and that various changes and modifications can be made by those skilled in the art without departing from the spirit and principles of the invention, and any such modifications, equivalents, improvements, etc. are intended to be included within the scope of the invention.
Claims (6)
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 the resin matrix is uniformly filled with coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel;
the coupling agent modified internal hydrophobic aerogel is spherical silica aerogel, the internal hydrophobic aerogel is modified, and the surface coupling agent is modified;
the mass percent of the sum of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is calculated as 100 percent, the resin matrix accounts for 75 to 98.9 percent, the coupling agent modified internal hydrophobic aerogel accounts for 0.1 to 10 percent, and the coupling agent modified chopped fibers account for 1 to 15 percent;
the diameter of the coupling agent modified internal hydrophobic aerogel is 0.1-20 mu m, the coupling agent modified internal hydrophobic aerogel consists of two or three aerogels with average diameters, and when the coupling agent modified internal hydrophobic aerogel consists of two aerogels with different average diameters, the diameters are respectively r from large to small 1 、r 2 ，r 2 ＝(0 .4～0 .5)r 1 ，r 1 Diameter aerogel, r 2 The filling mass ratio of the diameter aerogel is 1:0.06-0.08; or when the coupling agent modified internal hydrophobic aerogel is composed of three aerogels with different average diameters, the diameters are respectively r from large to small 1 、r 2 、r 3 ，r 2 ＝(0 .4～0 .5)r 1 ，r 3 ＝(0 .2～0 .3)r 1 ，r 1 Diameter aerogel, r 2 Diameter aerogel, r 3 The filling mass ratio of the diameter aerogel is 1:0.06-0.08:0.02-0.03.
2. The high-frequency copper-clad plate is characterized by comprising 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 the resin matrix is uniformly filled with coupling agent modified chopped fibers and coupling agent modified internal hydrophobic aerogel;
the coupling agent modified internal hydrophobic aerogel is spherical silica aerogel, the internal hydrophobic aerogel is modified, and the surface coupling agent is modified;
the mass percent of the sum of the resin matrix, the coupling agent modified chopped fibers and the coupling agent modified internal hydrophobic aerogel is calculated as 100 percent, the resin matrix accounts for 75 to 98.9 percent, the coupling agent modified internal hydrophobic aerogel accounts for 0.1 to 10 percent, and the coupling agent modified chopped fibers account for 1 to 15 percent;
the diameter of the coupling agent modified internal hydrophobic aerogel is 0.1-20 mu m, the coupling agent modified internal hydrophobic aerogel consists of two or three aerogels with average diameters, and when the coupling agent modified internal hydrophobic aerogel consists of two aerogels with different average diameters, the diameters are respectively r from large to small 1 、r 2 ，r 2 ＝(0 .4～0 .5)r 1 ，r 1 Diameter aerogel, r 2 The filling mass ratio of the diameter aerogel is 1:0.06-0.08; or when the coupling agent modified internal hydrophobic aerogel is composed of three aerogels with different average diameters, the diameters are respectively r from large to small 1 、r 2 、r 3 ，r 2 ＝(0 .4～0 .5)r 1 ，r 3 ＝(0 .2～0 .3)r 1 ，r 1 Diameter aerogel, r 2 Diameter aerogel, r 3 The filling mass ratio of the diameter aerogel is 1:0.06-0.08:0.02-0.03.
3. The method for manufacturing a high-frequency copper-clad plate according to claim 2, comprising the steps of:
1) Uniformly mixing the resin glue solution, the dispersing agent and the defoaming agent to obtain 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, and then adding the thickening agent for uniform mixing to obtain a glue dipping solution;
3) Dipping the glass fiber cloth into the dipping liquid for one or more times, drying, and roasting to prepare a prepreg; or coating the glue dipping liquid on the metal foil for one or more times, drying, roasting to prepare the glue-coated metal foil, and pressing the glue-coated metal foil with another metal foil or the glue-coated metal foil.
4. The method of producing a high-frequency copper-clad plate according to claim 3, wherein in the step 2), the number of the chopped fibers used for the coupling agent-modified chopped fibers is 100 mesh or more, and the diameter is 1 to 10. Mu.m.
5. The method for producing a high-frequency copper-clad plate according to claim 4, wherein the chopped fiber is one or both of glass fiber and quartz fiber.
6. The method for producing a high-frequency copper-clad plate according to any one of claims 3 to 5, wherein the bulk density of the coupling agent-modified internal hydrophobic aerogel is 0.18 to 0.23g/cm 3 The sphericity is 50-100%.
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