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WO2022120921A1 - 一种含氟树脂组合物及包含其的树脂胶液、含氟介质片、层压板、覆铜板和印刷电路板 - Google Patents

一种含氟树脂组合物及包含其的树脂胶液、含氟介质片、层压板、覆铜板和印刷电路板 Download PDF

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Publication number
WO2022120921A1
WO2022120921A1 PCT/CN2020/137249 CN2020137249W WO2022120921A1 WO 2022120921 A1 WO2022120921 A1 WO 2022120921A1 CN 2020137249 W CN2020137249 W CN 2020137249W WO 2022120921 A1 WO2022120921 A1 WO 2022120921A1
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WO
WIPO (PCT)
Prior art keywords
fluorine
coupling agent
inorganic filler
resin composition
silane coupling
Prior art date
Application number
PCT/CN2020/137249
Other languages
English (en)
French (fr)
Inventor
柴颂刚
刘潜发
郝良鹏
梁伟
Original Assignee
广东生益科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US17/766,440 priority Critical patent/US11945924B2/en
Priority to KR1020237006692A priority patent/KR20230044270A/ko
Publication of WO2022120921A1 publication Critical patent/WO2022120921A1/zh

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    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • the present invention relates to the technical field of communication materials, in particular to a fluorine-containing resin composition and a resin glue containing the same, a fluorine-containing medium sheet, a laminate, a copper clad laminate and a printed circuit board.
  • CCL is widely used in mobile phones, computers, vending machines, communication base stations, satellites, wearable devices, unmanned vehicles, drones and intelligent robots. It is one of the key basic materials in the electronic communication and information industry. Fluorine-containing resins represented by polytetrafluoroethylene (PTFE) have many excellent properties such as low dielectric constant, low dielectric loss, high thermal stability and chemical stability unmatched by other polymer resins. CCL base material. Since the invention of PTFE-based CCL in the 1950s, researchers have gradually improved its manufacturing process through continuous optimization of formulations and parameters.
  • PTFE polytetrafluoroethylene
  • the polymer chain of fluorine-containing resin is very flexible, and it is often necessary to introduce reinforcing materials such as glass fiber cloth to improve the mechanical strength of the fluorine-containing resin-based copper clad laminate.
  • the dielectric constant of fluorine-containing resin itself is very low (Dk ⁇ 2.2), and the dielectric constant of glass fiber is generally only about 6.5.
  • a large amount of other inorganic fillers are added in the fluororesin matrix, which makes it extremely difficult to produce low dielectric constant fluororesin-based copper clad laminates.
  • people have also started to develop fluorine-containing resin-based copper clad laminates without glass fiber reinforcement.
  • CN104175686A discloses a preparation method of a PTFE composite medium substrate.
  • a dispersion liquid is prepared by mixing a fluororesin emulsion, an inorganic filler and a thickener, and then the dispersion liquid is coated on a releasable substrate and baked, and then the The resin layer is separated from the base material, and then the composite dielectric substrate is prepared by cutting, laminating and sintering processes.
  • US4335180A discloses a microwave circuit board and a method for manufacturing a microwave circuit board.
  • Microfibers, inorganic fillers and flocculants are successively mixed into a PTFE emulsion, followed by filtering-drying to obtain a fluorine-containing resin mixture, which is pressed into a plate, and then mixed with The copper foils are stacked together and then pressed together to obtain a fluorine-containing resin-based copper clad laminate without glass fiber cloth reinforcement.
  • the problem in the aforementioned patent application is that the interaction force between the unmodified inorganic filler and the fluororesin matrix is very poor, especially when the addition amount of the inorganic filler is required to be large, the inorganic filler is in the matrix
  • the dispersibility in the body is extremely poor, the non-uniformity of the dielectric properties of the sheet is extremely serious, and the mechanical properties are difficult to meet the actual use requirements.
  • One of the objectives of the present invention is to provide a fluorine-containing resin composition, in which even if the inorganic filler is not modified or added in a large amount, it can ensure that the sheet prepared from the fluorine-containing resin composition has excellent properties dielectric properties and withstand voltage properties.
  • the present invention provides a fluorine-containing resin composition
  • the fluorine-containing resin composition includes the following components: 30wt%-70wt% of fluorine-containing polymer, 30wt%-70wt% of inorganic filler; the inorganic filler includes the following particle size distribution : D10 is more than 1.5 ⁇ m, D50 is 10-15 ⁇ m.
  • inorganic fillers with specific particle size distribution are added to the fluoropolymer resin system, and even if the inorganic filler is added in a large amount (30wt%-70wt%), it can ensure that the sheet prepared from the fluoropolymer composition has excellent
  • the dielectric properties and withstand voltage properties of the copper clad laminate can meet the performance requirements of high-frequency and high-speed communication fields such as functional diversification and complexity of copper clad laminate materials, high-density circuit layout, and multi-layering.
  • the fluororesin composition includes the following components: 30wt%-70wt% of fluoropolymer, such as 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, 42wt%, 44wt%, 46wt%, 48wt% , 50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt%, 64wt%, 66wt%, 68wt%, etc., inorganic fillers 30wt%-70wt%, such as 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, 42wt%, 44wt%, 46wt%, 48wt%, 50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt%, 64wt%, 66wt%, 68wt%, etc.;
  • the inorganic filler includes the following particle size distribution: D10 is greater than 1.5 ⁇ m, such as 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m, 2 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, etc., D50 is 10 -15 ⁇ m, eg 11.2 ⁇ m, 11.4 ⁇ m, 11.6 ⁇ m, 11.8 ⁇ m, 12 ⁇ m, 12.2 ⁇ m, 12.4 ⁇ m, 12.6 ⁇ m, 12.8 ⁇ m, 13 ⁇ m, 13.2 ⁇ m, 13.4 ⁇ m, 13.6 ⁇ m, 13.8 ⁇ m, 14 ⁇ m, 14.2 ⁇ m, 14.4 ⁇ m, 14.6 ⁇ m, 14.8 ⁇ m, etc.
  • the specific particle size distribution of the present invention is selected based on the fluoropolymer matrix. If D10 is less than 1.5 ⁇ m, the interface between the inorganic filler and the fluoropolymer is too much, resulting in poor dielectric loss; if D50 is less than 10 ⁇ m, the inorganic filler and There are many fluoropolymer interfaces, which leads to poor dielectric loss; if D50 is greater than 15 ⁇ m, inorganic fillers are easy to bridge in the fluoropolymer to form pathways, resulting in poor withstand voltage performance.
  • the inorganic filler further includes the following particle size distribution: D90 is less than 30 ⁇ m, such as 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, etc., D100 is less than 50 ⁇ m, such as 22 ⁇ m, 24 ⁇ m, 26 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 34 ⁇ m, 36 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 44 ⁇ m, 46 ⁇ m, 48 ⁇ m, etc.
  • D90 is less than 30 ⁇ m, such as 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25
  • the specific D90 and D100 values are continued to be preferred.
  • the dielectric properties and resistance of the sheet prepared from the fluororesin composition can be further improved. voltage performance. If D90 is greater than 30 ⁇ m, it will lead to poor voltage withstand performance. If D100 is greater than 50 ⁇ m, large particles will be exposed on the surface of the fluoropolymer, which will reduce the withstand voltage performance of the sheet and the bonding strength between the copper foil and the fluoropolymer.
  • the specific surface area of the inorganic filler is ⁇ 3.0m 2 /g, such as 1.1m 2 /g, 1.2m 2 /g, 1.3m 2 /g, 1.4m 2 /g, 1.5m 2 /g, 1.6m 2 /g, 1.7m 2 /g, 1.8m 2 /g, 1.9m 2 /g, 2m 2 /g, 2.1m 2 /g, 2.2m 2 /g, 2.3m 2 /g, 2.4m 2 /g , 2.5m 2 /g, 2.6m 2 /g, 2.7m 2 /g, 2.8m 2 /g, 2.9m 2 / g, etc., preferably ⁇ 2.0m 2 /g.
  • the specific surface area of the inorganic filler is less than or equal to 3.0 m 2 / g , so as to further improve the dielectric properties and withstand voltage performance of the sheet. The problem of too many interfaces between them leads to a decrease in dielectric properties and withstand voltage properties.
  • the inorganic filler is a spherical inorganic filler.
  • spherical fillers are further preferred. Compared with fillers of other shapes, the spherical fillers have less interface and less stress between the fluoropolymer and the fluoropolymer, so that the dielectric properties and withstand voltage properties can be further improved.
  • the inorganic fillers include SiO 2 , Al 2 O 3 , TiO 2 , BaTiO 3 , SrTiO 3 , AlN, BN, Si 3 N 4 , SiC, CaTiO 3 , ZnTiO 3 , BaSnO 3 , hollow glass beads, Any one of chopped glass fiber powder or chopped quartz fiber powder or a combination of at least two.
  • the inorganic filler includes an inorganic filler treated with a silane coupling agent.
  • the silane coupling agent includes a combination of a polar coupling agent and a non-polar coupling agent.
  • the combination of amphoteric silane coupling agent is preferably used to modify the filler, which can further improve the dielectric properties and withstand voltage performance. Compatibility will deteriorate, resulting in deterioration of dielectric properties and withstand voltage performance. Only non-polar silane coupling agent is used for modification, inorganic fillers are not easy to infiltrate in the emulsion, and voids are easily generated in the product, resulting in poor withstand voltage.
  • the mass ratio of the polar coupling agent to the non-polar coupling agent is 1:5-1:1, such as 1:4, 1:3, 1:2, and the like.
  • the polar and non-polar coupling agents are compounded according to the above specific ratio to modify the inorganic filler, so that the dielectric properties and withstand voltage properties of the sheet can be further improved.
  • the non-polar coupling agent includes a fluorine-containing silane coupling agent, preferably a perfluorosilane coupling agent.
  • the polar coupling agent includes any one of amino silane coupling agent, epoxy silane coupling agent, borate coupling agent, zirconate coupling agent or phosphate coupling agent or a combination of at least two.
  • the silane coupling agent includes a combination of a fluorine-containing silane coupling agent and an epoxy silane coupling agent.
  • the amount of the silane coupling agent in the inorganic filler treated with the silane coupling agent accounts for 0.05wt%-5wt% of the inorganic filler, such as 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 4.8wt%, etc.
  • the magnetic substance content of the inorganic filler is less than 50 ppm.
  • the fluoropolymer includes polytetrafluoroethylene, polyperfluoroethylene propylene, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, Ethylene-chlorotrifluoroethylene copolymer and its derivatives or polyvinylidene fluoride and its derivatives any one or a combination of at least two, preferably polytetrafluoroethylene and tetrafluoroethylene-perfluoroalkoxy vinyl A combination of ether copolymers.
  • the fluororesin composition further includes a surfactant, preferably a nonionic surfactant.
  • the added amount of the surfactant is 1wt%-10wt%, such as 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% and the like.
  • the second object of the present invention is to provide a resin glue solution, the resin glue solution includes the fluorine-containing resin composition described in the first object and a solvent.
  • the solvent in the present invention is not particularly limited, and the solvent can be introduced after the components of the fluororesin composition are mixed, or the solvent can be introduced through the resin raw material, for example, the fluoropolymer emulsion is directly mixed with other components to form the resin glue.
  • the third object of the present invention is to provide a fluorine-containing dielectric sheet containing the fluorine-containing resin composition described in one of the objects.
  • the fluorine-containing dielectric sheet does not contain continuous reinforcing material.
  • the preparation method of the fluorine-containing dielectric sheet includes: scraping the resin glue described in the second objective on a clean high temperature resistant film to form a film, and drying, sintering and peeling off to prepare the fluorine-containing dielectric sheet.
  • the drying temperature is 100-260°C, such as 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, and the like.
  • the drying time is 10min-2h, such as 20min, 40min, 1h, 1h20min, 1h40min and the like.
  • the sintering temperature is 200-400°C, such as 220°C, 240°C, 260°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, and the like.
  • the sintering time is 2-12h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h and the like.
  • the sintering is carried out in an inert gas atmosphere.
  • the inert gas includes nitrogen and/or argon.
  • the high temperature resistant film includes a polyimide (PI) film.
  • PI polyimide
  • the fourth object of the present invention is to provide a laminate comprising at least one fluorine-containing medium sheet according to the third object.
  • the preparation method of the laminate is a laminate made by bonding one or more fluorine-containing medium sheets of the third purpose through a lamination process.
  • the temperature of the lamination is 200-400°C, such as 220°C, 240°C, 260°C, 280°C, 300°C, 320°C, 340°C, 360°C, 380°C, and the like.
  • the pressure of the lamination is 70-250kg/cm 2 , such as 80kg/cm 2 , 100kg/cm 2 , 120kg/cm 2 , 140kg/cm 2 , 160kg/cm 2 , 180kg/cm 2 , 200kg/ cm 2 , 220kg/cm 2 , 240kg/cm 2 , etc.
  • the lamination time is 2-12h, such as 3h, 4h, 6h, 7h, 8h, 9h, 10h, 11h, 12h and the like.
  • the thickness of the laminate is 0.01-10 mm, such as 0.1 mm, 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm and the like.
  • the fifth object of the present invention is to provide a copper clad laminate, the copper clad laminate containing at least one fluorine-containing dielectric sheet as described in the third object and a metal foil covering one or both sides of the laminated fluorine-containing dielectric sheet .
  • the metal foil is copper foil, nickel foil, aluminum foil, SUS foil, or the like.
  • the sixth object of the present invention is to provide a printed circuit board, which includes the laminate described in the fourth object or the copper clad laminate described in the fifth object.
  • the printed circuit board is a high frequency printed circuit board.
  • "high frequency” is defined as a frequency of 1 GHz or more.
  • the present invention has the following beneficial effects:
  • inorganic fillers with specific particle size distribution are added to the fluoropolymer resin system, and even if the amount of inorganic fillers added is relatively large, it can ensure that the sheet prepared from the fluoropolymer composition has excellent dielectric properties and withstand voltage. Therefore, it can meet various performance requirements such as the functional diversification and complexity of CCL materials in the field of high-frequency and high-speed communication, high-density circuit layout, and multi-layering.
  • the Dk (10GHz) of the copper clad laminate provided by the present invention is below 3.15, the Df (10GHz) is below 0.0010, and the breakdown voltage is above 50kV.
  • This embodiment provides a fluorine-containing resin composition, comprising the following components: PTFE resin (247.5 g), inorganic filler A (300 g), and thickener (4 g).
  • the preparation method of above-mentioned fluorine-containing resin composition is as follows: get 450g PTFE resin emulsion (particle size 0.25 ⁇ m, resin content 55wt%, Japan Daikin company produces, trade mark: D210C), add 300g inorganic filler A and 4g thickener (poly Oxyethylene distyrenated phenyl ether, Kao Co., Ltd., trade name EMULGEN A-60), was stirred and mixed for 2 h to obtain a fluororesin composition resin glue.
  • This embodiment also provides a copper clad laminate, and the preparation method is as follows:
  • the above resin glue solution was coated on the surface of the PI film with a coating machine, and a resin layer with a thickness of 129 ⁇ m was applied to obtain a glue-coated PI film.
  • a resin layer with a thickness of 129 ⁇ m was applied to obtain a glue-coated PI film.
  • the peeling was performed to obtain a resin layer with a uniform thickness and good appearance.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler B.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with an inorganic filler A whose surface is modified with a silane coupling agent, wherein the silane coupling agent is a polar coupling agent with a mass ratio of 1:3 (full Combination of fluorosilane, Shandong Silicon, F823) and non-polar coupling agent (silane coupling agent with epoxy group, Shin-Etsu Chemical, product name KBM403), the amount of silane coupling agent is 0.5 of the mass of inorganic filler A %.
  • the silane coupling agent is a polar coupling agent with a mass ratio of 1:3 (full Combination of fluorosilane, Shandong Silicon, F823) and non-polar coupling agent (silane coupling agent with epoxy group, Shin-Etsu Chemical, product name KBM403)
  • the amount of silane coupling agent is 0.5 of the mass of inorganic filler A %.
  • silane coupling agent is only a non-polar coupling agent (perfluorosilane, Shandong Silicon, F823), and the amount is 0.5% of the mass of the inorganic filler A.
  • silane coupling agent is only a polar coupling agent (silane coupling agent with epoxy group, Shin-Etsu Chemical, product name KBM403), and the dosage is 0.5% of the mass of inorganic filler A.
  • Example 3 The only difference from Example 3 is that the mass ratios of the polar coupling agent and the non-polar coupling agent are 1:1 (Example 6), 1:2 (Example 7), 1:4 (Example 7), respectively.
  • Example 8 1, 1:5 (Example 9).
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler C.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler I.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler J.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler K.
  • This embodiment provides a fluorine-containing resin composition, comprising the following components: PTFE resin (300 g), and inorganic filler A (696 g).
  • the above-mentioned fluorine-containing resin composition is the same as the preparation method of Example 1, and the difference is only to take 545g of PTFE resin emulsion.
  • This embodiment also provides a copper clad laminate, and the preparation method is the same as that of Embodiment 1.
  • This example provides a fluorine-containing resin composition, which differs from Example 1 only in that the fluorine-containing resin composition further contains tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (448.5 g).
  • the preparation method of above-mentioned fluorine-containing resin composition is the same as that of Example 1, and the difference is only that it also includes: get 200g of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (purchased from Sichuan Chenguang, and the trade mark is PFA-E50, The solid content is 50%) and 634g of PTFE resin emulsion (particle size 0.25 ⁇ m, resin content 55wt%, produced by Japan Daikin Company, brand: D210C).
  • This embodiment also provides a copper clad laminate, and the preparation method is the same as that of Embodiment 1.
  • Example 15 The only difference from Example 15 is that the inorganic filler A is replaced with the same quality of the inorganic filler L.
  • Example 15 The only difference from Example 15 is that the inorganic filler A is replaced with the same quality of the inorganic filler M.
  • Example 15 The only difference from Example 15 is that the inorganic filler A is replaced with the same quality of the inorganic filler N.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler D.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler E.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler F.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler G.
  • Example 1 The only difference from Example 1 is that the inorganic filler A is replaced with the same quality of the inorganic filler H.
  • Dk and Df test use SPDR (splite post dielectric resonator) method to test, the test condition is A state and the frequency is 10GHz.
  • Magnetic substance test After 300 g of inorganic filler was dispersed in water, adsorbed in a beaker with a 4000 Gauss magnet, and weighed the adsorbed substance.
  • Example 1 Dk(10GHz) Df(10GHz) Breakdown Voltage (KV)
  • Example 2 3.02 0.0008 56
  • Example 3 3.01 0.0006 60
  • Example 4 2.99 0.0006 55
  • Example 5 2.98 0.0009 50
  • Example 6 2.97 0.0008 60
  • Example 7 2.97 0.0007 65
  • Example 8 2.98 0.0006 60
  • Example 9 2.99 0.0007 60
  • Example 10 3.01 0.0008 52
  • Example 11 2.99 0.0009 52
  • Example 12 2.99 0.0010 51
  • Example 13 2.95 0.0010 50
  • Example 14 3.15 0.0010 50
  • Example 15 2.85 0.0007 50
  • Example 16 2.75 0.0007 55
  • Example 17 2.80 0.0008 56
  • Example 18 2.78 0.0009 56
  • Comparative Example 1 3.20 0.0015 35
  • Comparative Example 2 3.23 0.0013 25
  • Comparative Example 3 2.99 0.0009 45
  • Comparative Example 4 2.96 0.0011 40
  • Comparative Example 5 2.98 0.0013 30
  • the fluorine-containing resin composition provided by the present invention can ensure that the prepared sheet has excellent dielectric properties and withstand voltage properties even if the inorganic filler is not modified or the addition amount is large, and can further meet the requirements of high frequency.
  • the functional diversification and complexity of CCL materials, high-density circuit layout, and multi-layer performance requirements are possible.
  • Example 12 By comparing Examples 1, 11 and 12, it can be seen that when the D90 of the inorganic filler is less than 30 ⁇ m and the D100 is less than 50 ⁇ m (Example 1), the dielectric properties and withstand voltage properties of the copper clad laminate can be further improved. D90 is greater than 30 ⁇ m (Example 11) or D100 is greater than 50 ⁇ m (Example 12), both of which will lead to poor dielectric properties and withstand voltage properties.
  • Example 1 By comparing Example 1 and Example 13, it can be seen that in the fluoropolymer system, the spherical inorganic filler (Example 1) is more conducive to improving the dielectric properties and resistance of copper clad laminates than other shapes (Example 13). voltage performance.
  • the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented.
  • Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

一种含氟树脂组合物及包含其的树脂胶液、含氟介质片、层压板、覆铜板和印刷电路板，所述含氟树脂组合物包括如下组分：含氟聚合物30wt％-70wt％，无机填料30wt％-70wt％；所述无机填料包括如下粒径分布：D10为大于1.5μm，D50为10-15μm。通过选用特定粒径分布的无机填料，即使无机填料添加量较大，也能够保证含氟树脂组合物制备得到的板材具有优异的介电性能和耐电压性能。

Description

一种含氟树脂组合物及包含其的树脂胶液、含氟介质片、层压板、覆铜板和印刷电路板 技术领域
本发明涉及通信材料技术领域，尤其涉及一种含氟树脂组合物及包含其的树脂胶液、含氟介质片、层压板、覆铜板和印刷电路板。
背景技术
覆铜板广泛应用在手机、电脑、自动售货机、通信基站、卫星以及可穿戴设备、无人驾驶汽车、无人机和智能机器人等领域,是电子通讯和信息行业的关键基础材料之一。以聚四氟乙烯(PTFE)为代表的含氟树脂拥有其他聚合物树脂无法比拟的低介电常数、低介电损耗、高热稳定性和化学稳定性等多种优异性能，是一种理想的覆铜板基体材料。自上世纪50年代PTFE基覆铜板发明以来，研究人员经过配方和参数的不断优化，逐步完善其制造工艺。含氟树脂的高分子链柔性大，常需要引入玻纤布等增强材料以提高含氟树脂基覆铜板的机械强度。此外，含氟树脂本身的介电常数很低(Dk≤2.2)，而玻纤的介电常数一般也仅在6.5左右，在基板的制造过程中，大量玻纤布的使用又限制了向含氟树脂基体内添加大量其他的无机填料，这造成了低介电常数的含氟树脂基覆铜板的生产极为困难。当然，人们也曾着手研发过无玻纤增强的含氟树脂基覆铜板。
CN104175686A公开了一种PTFE复合介质基板的制备方法，将氟树脂乳液、无机填料和增稠剂混合后制得分散液，然后将分散液涂覆在可离型的基材上烘烤，后将树脂层与基材分离，再经裁剪、叠合和烧结等工艺制备复合介质基板。US4335180A公开了一种微波电路板和微波电路板的制造方法，向PTFE乳液中 先后混入微纤维、无机填料和絮凝剂，后经过滤-干燥等步骤得到含氟树脂混合物，压制成板后，与铜箔叠合在一起再压合得到无玻纤布增强的含氟树脂基覆铜板。然而，前述专利申请中存在的问题是：未经修饰的无机填料与含氟树脂基体之间的相互作用力是很差的，尤其是当无机填料的添加量要求很大时，无机填料在基体内的分散性极差、板材介电性能的不均匀性极为严重，机械性能也难以满足实际使用需求。
因此，本领域亟待解决未修饰的无机填料与PTFE树脂基体相互作用力差的问题，以及PTFE树脂体系大量添加无机填料造成的电性能下降、耐电压性能下降的问题。
发明内容
本发明的目的之一在于提供一种含氟树脂组合物，所述含氟树脂组合物中无机填料即使未经修饰或者添加量较大，也能够保证含氟树脂组合物制备得到的板材具有优异的介电性能和耐电压性能。
为达此目的，本发明采用以下技术方案：
本发明提供一种含氟树脂组合物，所述含氟树脂组合物包括如下组分：含氟聚合物30wt％-70wt％，无机填料30wt％-70wt％；所述无机填料包括如下粒径分布：D10为大于1.5μm，D50为10-15μm。
本发明在含氟聚合物树脂体系中，添加具有特定粒径分布的无机填料，即使无机填料添加量较大(30wt％-70wt％)，也能够保证含氟树脂组合物制备得到的板材具有优异的介电性能和耐电压性能，进而能够满足高频、高速通信领域对覆铜板材料的功能多元化和复杂化、线路布置高密度化、多层化等各项性能要求。
所述含氟树脂组合物包括如下组分：含氟聚合物30wt％-70wt％，例如32 wt％、34wt％、36wt％、38wt％、40wt％、42wt％、44wt％、46wt％、48wt％、50wt％、52wt％、54wt％、56wt％、58wt％、60wt％、62wt％、64wt％、66wt％、68wt％等，无机填料30wt％-70wt％，例如32wt％、34wt％、36wt％、38wt％、40wt％、42wt％、44wt％、46wt％、48wt％、50wt％、52wt％、54wt％、56wt％、58wt％、60wt％、62wt％、64wt％、66wt％、68wt％等；
所述无机填料包括如下粒径分布：D10为大于1.5μm，例如1.6μm、1.7μm、1.8μm、1.9μm、2μm、2.1μm、2.2μm、2.3μm、2.4μm、2.5μm等，D50为10-15μm，例如11.2μm、11.4μm、11.6μm、11.8μm、12μm、12.2μm、12.4μm、12.6μm、12.8μm、13μm、13.2μm、13.4μm、13.6μm、13.8μm、14μm、14.2μm、14.4μm、14.6μm、14.8μm等。
本发明的特定粒径分布是基于含氟聚合物基体进行的选择，若D10小于1.5μm，无机填料与含氟聚合物界面过多，导致介电损耗变差；若D50小于10μm，无机填料与含氟聚合物界面多，导致介电损耗变差；若D50大于15μm，无机填料在含氟聚合物中容易架桥，形成通路，导致耐电压性能变差。
优选地，所述无机填料还包括如下粒径分布：D90小于30μm，例如15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm等，D100小于50μm，例如22μm、24μm、26μm、28μm、30μm、32μm、34μm、36μm、38μm、40μm、42μm、44μm、46μm、48μm等。
在本发明的优选技术方案中，在特定D10和D50的基础上，继续优选特定的D90和D100数值，在上述范围内，能够进一步提高含氟树脂组合物制备得到的板材的介电性能和耐电压性能。D90大于30μm，会导致耐电压性能变差，D100大于50μm，会导致大颗粒在氟聚合物表面裸露，降低板材的耐电压性能 和降低铜箔与氟聚合物的粘结强度。
优选地，所述无机填料的比表面积≤3.0m 2/g，例如1.1m 2/g、1.2m 2/g、1.3m 2/g、1.4m 2/g、1.5m 2/g、1.6m 2/g、1.7m 2/g、1.8m 2/g、1.9m 2/g、2m 2/g、2.1m 2/g、2.2m 2/g、2.3m 2/g、2.4m 2/g、2.5m 2/g、2.6m 2/g、2.7m 2/g、2.8m 2/g、2.9m 2/g等，优选≤2.0m 2/g。
本发明进一步优选无机填料的比表面积≤3.0m 2/g，从而进一步提高板材的介电性能和耐电压性能，若比表面积高于3.0m 2/g，容易出现无机填料和含氟聚合物之间界面过多的问题，从而导致介电性能和耐电压性能降低。
优选地，所述无机填料为球形无机填料。
本发明进一步优选球形填料，相较于其他形状的填料，球形填料与含氟聚合物之间界面少，应力小，从而能够更进一步提高介电性能和耐电压性能。
优选地，所述无机填料包括SiO 2、Al 2O 3、TiO 2、BaTiO 3、SrTiO 3、AlN、BN、Si 3N 4、SiC、CaTiO 3、ZnTiO 3、BaSnO 3、空心玻璃微珠、短切玻璃纤维粉或短切石英纤维粉中的任意一种或至少两种组合。
优选地，所述无机填料包括经硅烷偶联剂处理的无机填料。
优选地，所述硅烷偶联剂包括极性偶联剂和非极性偶联剂的组合。
本发明优选采用两性硅烷偶联剂组合对填料进行改性，能够进一步提高介电性能和耐电压性能，若仅使用极性硅烷偶联剂改性，加工过程中无机填料与含氟聚合物的相容性会变差，从而导致介电性能和耐电压性能恶化，仅使用非极性硅烷偶联剂改性，无机填料在乳液中不易浸润，产品的中易产生空洞，耐压变差。
优选地，所述极性偶联剂和非极性偶联剂的质量比为1:5-1:1，例如1:4、1:3、1:2等。
本发明更进一步优选极性和非极性偶联剂按照上述特定比例复合对无机填料进行改性，从而可以更进一步提高板材的介电性能和耐电压性能。
优选地，所述非极性偶联剂包括含氟硅烷偶联剂，优选全氟硅烷偶联剂。
优选地，所述极性偶联剂包括胺基硅烷偶联剂、环氧基硅烷偶联剂、硼酸酯偶联剂、锆酸酯偶联剂或磷酸酯偶联剂中的任意一种或至少两种组合。
优选地，所述硅烷偶联剂包括含氟硅烷偶联剂和环氧基硅烷偶联剂的组合。
优选地，所述经过硅烷偶联剂处理的无机填料中硅烷偶联剂的用量占所述无机填料的0.05wt％-5wt％，例如0.1wt％、0.5wt％、1wt％、1.5wt％、2wt％、2.5wt％、3wt％、3.5wt％、4wt％、4.5wt％、4.8wt％等。
优选地，所述无机填料的磁性物质含量小于50ppm。
优选地，所述含氟聚合物包括聚四氟乙烯、聚全氟乙丙烯、四氟乙烯-全氟烷氧基乙烯基醚共聚物、乙烯-四氟乙烯共聚物、聚三氟氯乙烯、乙烯-三氟氯乙烯共聚物及其衍生物或聚偏二氟乙烯及其衍生物中的任意一种或至少两种组合，优选聚四氟乙烯和四氟乙烯-全氟烷氧基乙烯基醚共聚物的组合。
优选地，所述含氟树脂组合物中还包括表面活性剂，优选非离子表面活性剂。
优选地，所述表面活性剂的添加量为1wt％-10wt％，例如2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％等。
本发明的目的之二在于提供一种树脂胶液，所述树脂胶液包括目的之一所述的含氟树脂组合物和溶剂。
作为本发明中的溶剂，没有特别的限定，可以在含氟树脂组合物各组分混合之后引入溶剂，也可以通过树脂原料引入溶剂，例如直接采用含氟聚合物乳液与其他组分混合，形成所述树脂胶液。
本发明的目的之三在于提供一种含氟介质片，所述含氟介质片中含有目的之一所述的含氟树脂组合物。
优选地，所述含氟介质片中不含有连续增强材料。
优选地，所述含氟介质片的制备方法包括：将目的之二所述的树脂胶液于干净的耐高温膜上刮涂成膜，经烘干、烧结、剥离制备得到含氟介质片。
优选地，所述烘干的温度为100-260℃，例如120℃、140℃、160℃、180℃、200℃、220℃、240℃、250℃等。
优选地，所述烘干的时间为10min-2h，例如20min、40min、1h、1h20min、1h40min等。
优选地，所述烧结的温度为200-400℃，例如220℃、240℃、260℃、280℃、300℃、320℃、340℃、360℃、380℃等。
优选地，所述烧结的时间为2-12h，例如3h、4h、5h、6h、7h、8h、9h、10h、11h等。
优选地，所述烧结在惰性气体气氛中进行。
优选地，所述惰性气体包括氮气和/或氩气。
优选地，所述耐高温膜包括聚酰亚胺(PI)薄膜。
本发明的目的之四在于提供一种层压板，所述层压板包括至少一张目的之三所述的含氟介质片。
优选地，所述层压板的制备方法为经过层压工艺，使一片或两片以上的目的之三所述的含氟介质片粘合在一起而制成的层压板。
优选地，所述层压的温度为200-400℃，例如220℃、240℃、260℃、280℃、300℃、320℃、340℃、360℃、380℃等。
优选地，所述层压的压力为70-250kg/cm 2，例如80kg/cm 2、100kg/cm 2、 120kg/cm 2、140kg/cm 2、160kg/cm 2、180kg/cm 2、200kg/cm 2、220kg/cm 2、240kg/cm 2等。
优选地，所述层压的时间为2-12h，例如3h、4h、6h、7h、8h、9h、10h、11h、12h等。
优选地，所述层压板的厚度为0.01-10mm，例如0.1mm、0.5mm、1mm、2mm、3mm、4mm、5mm、6mm、7mm、8mm、9mm等。
本发明的目的之五在于提供一种覆铜板，所述覆铜板含有至少一张目的之三所述的含氟介质片以及覆于叠合后的含氟介质片一侧或两侧的金属箔。
优选地，所述金属箔为铜箔、镍箔、铝箔或SUS箔等。
本发明的目的之六在于提供一种印刷电路板，所述印刷电路板包括目的之四所述的层压板或目的之五所述的覆铜板。
优选地，所述印刷电路板为高频印刷电路板。本发明中，“高频”定义为频率在1GHz以上。
相对于现有技术，本发明具有以下有益效果：
本发明在含氟聚合物树脂体系中，添加具有特定粒径分布的无机填料，即使无机填料添加量较大，也能够保证含氟树脂组合物制备得到的板材具有优异的介电性能和耐电压性能，进而能够满足高频、高速通信领域对覆铜板材料的功能多元化和复杂化、线路布置高密度化、多层化等各项性能要求。
本发明提供的覆铜板的Dk(10GHz)在3.15以下，Df(10GHz)在0.0010以下，击穿电压在50kV以上。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
以下实施例和对比例中所使用的无机填料的具体粒径分布情况详见表1。
表1
Figure PCTCN2020137249-appb-000001
实施例1
本实施例提供一种含氟树脂组合物，包含如下组分：PTFE树脂(247.5g)，无机填料A(300g)，增稠剂(4g)。
上述含氟树脂组合物的制备方法如下：取450g PTFE树脂乳液(粒径0.25μm，树脂含量55wt％，日本大金公司生产，牌号：D210C)，添加300g无机填 料A和4g增稠剂(聚氧乙烯基联苯乙烯化苯基醚，花王株式会社，牌号EMULGEN A-60)，进行搅拌混合2h，得到含氟树脂组合物树脂胶液。
本实施例还提供一种覆铜板，制备方法如下：
将上述树脂胶液用涂覆机涂覆在PI膜表面上，涂覆厚度为129μm的树脂层，得到涂胶的PI膜。将涂胶的PI膜置于100℃的真空烘箱中，烘烤1h，去除分水，在260℃下烘烤1h去除助剂，在350℃下烘烤10min，冷却后将树脂层与PI膜进行剥离，得到厚度均一表观良好的树脂层。为制得0.127mm厚的板材，将2张129μm厚的PTFE树脂层进行叠合，尺寸大小为250×250mm，在叠合好的树脂层的上下两面覆盖1OZ厚的铜箔进行层压，施加压力约400PSI，最高温度和保留时间为380℃/60min，即得到PTFE覆铜板。
实施例2
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料B。
实施例3
与实施例1的区别仅在于，将无机填料A替换为使用硅烷偶联剂进行表面改性的无机填料A，其中，硅烷偶联剂为质量比为1:3的极性偶联剂(全氟硅烷，山东硅科，F823)和非极性偶联剂(带环氧基的硅烷偶联剂，信越化学，产品名KBM403)的组合，硅烷偶联剂的用量为无机填料A质量的0.5％。
实施例4
与实施例3的区别仅在于，硅烷偶联剂仅为非极性偶联剂(全氟硅烷，山东硅科，F823)，用量为无机填料A质量的0.5％。
实施例5
与实施例3的区别仅在于，硅烷偶联剂仅为极性偶联剂(带环氧基的硅烷偶联剂，信越化学，产品名KBM403)，用量为无机填料A质量的0.5％。
实施例6-9
与实施例3的区别分别仅在于，极性偶联剂和非极性偶联剂的质量比分别为1:1(实施例6)、1:2(实施例7)、1:4(实施例8)、1:5(实施例9)。
实施例10
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料C。
实施例11
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料I。
实施例12
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料J。
实施例13
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料K。
实施例14
本实施例提供一种含氟树脂组合物，包含如下组分：PTFE树脂(300g)，无机填料A(696g)。
上述含氟树脂组合物与实施例1的制备方法相同，区别仅在于取545g PTFE树脂乳液。
本实施例还提供一种覆铜板，制备方法与实施例1相同。
实施例15
本实施例提供一种含氟树脂组合物，与实施例1的区别仅在于，含氟树脂组合物中还含有四氟乙烯-全氟烷氧基乙烯基醚共聚物(448.5g)。
上述含氟树脂组合物的制备方法与实施例1相同，区别仅在于还包括：取200g四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(购于四川晨光，牌号为PFA-E50，固含量为50％)与634g PTFE树脂乳液(粒径0.25μm，树脂含量 55wt％，日本大金公司生产，牌号：D210C)混合。
本实施例还提供一种覆铜板，制备方法与实施例1相同。
实施例16
与实施例15的区别仅在于，将无机填料A替换为等质量的无机填料L。
实施例17
与实施例15的区别仅在于，将无机填料A替换为等质量的无机填料M。
实施例18
与实施例15的区别仅在于，将无机填料A替换为等质量的无机填料N。
对比例1
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料D。
对比例2
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料E。
对比例3
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料F。
对比例4
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料G。
对比例5
与实施例1的区别仅在于，将无机填料A替换为等质量的无机填料H。
性能测试
针对上述指标、实施例和对比例制备得到的覆铜板进行如下性能测试：
(1)Dk和Df测试：采用SPDR(splite post dielectric resonator)法进行测试，测试条件为A态，频率为10GHz。
(2)击穿电压测试：IPC-TM-650 2.5.6方法。
(3)粒径测试：采用马尔文2000激光粒度分析仪测试。
(4)比表面积测试：采用美国麦克型号GEMINI VII2390(A)测试。
(5)磁性物质测试：300g无机填料在水中分散后，用4000高斯磁铁在烧杯中吸附，称量吸附物质的重量。
上述测试结果如表2所示。
表2
  Dk(10GHz) Df(10GHz) 击穿电压(KV)
实施例1 2.97 0.0009 55
实施例2 3.02 0.0008 56
实施例3 3.01 0.0006 60
实施例4 2.99 0.0006 55
实施例5 2.98 0.0009 50
实施例6 2.97 0.0008 60
实施例7 2.97 0.0007 65
实施例8 2.98 0.0006 60
实施例9 2.99 0.0007 60
实施例10 3.01 0.0008 52
实施例11 2.99 0.0009 52
实施例12 2.99 0.0010 51
实施例13 2.95 0.0010 50
实施例14 3.15 0.0010 50
实施例15 2.85 0.0007 50
实施例16 2.75 0.0007 55
实施例17 2.80 0.0008 56
实施例18 2.78 0.0009 56
对比例1 3.20 0.0015 35
对比例2 3.23 0.0013 25
对比例3 2.99 0.0009 45
对比例4 2.96 0.0011 40
对比例5 2.98 0.0013 30
由表2可知，本发明提供的含氟树脂组合物，即使无机填料未经修饰或者添加量较大，也能够保证制备得到的板材具有优异的介电性能和耐电压性能，进而能够满足高频、高速通信领域对覆铜板材料的功能多元化和复杂化、线路布置高密度化、多层化等各项性能要求。
其中，对比例1采用的无机填料由于粒径较小，尤其是小颗粒偏多，覆铜板中无机材料与PTFE树脂的界面大，从而介电损耗大。对比例2中，由于无机填料粒径较大，造成板材的击穿电压性能恶化。且对比例1和2中填料磁性物质含量较高，也会造成介电损耗大。另外，对比例3的无机填料仅D10不在本发明的范围之内，对比例4-5的无机填料仅D50不在本发明的范围之内，其得到的覆铜板介电性能和耐电压性能均不及实施例，由此证明，本发明通过对于特定粒径分布的选择，有效提高了覆铜板的介电性能和耐电压性能。
通过对比实施例3-5可知，选用极性偶联剂和非极性偶联剂共同对无机填料进行改性(实施例3)，相较于单一类型的偶联剂改性(实施例4和5)，能够进一步提高覆铜板的介电性能和耐电压性能。
通过对比实施例1、11和12可知，当无机填料的D90小于30μm、D100小于50μm时(实施例1)，能够进一步提高覆铜板的介电性能和耐电压性能。D90大于30μm(实施例11)或者D100大于50μm(实施例12)，均会导致介电性能和耐电压性能变差。
通过对比实施例1和实施例13可知，在含氟聚合物体系中，球形无机填料(实施例1)相较于其他形状(实施例13)，更有利于提高覆铜板的介电性能和耐电压性能。
本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种含氟树脂组合物，其特征在于，所述含氟树脂组合物包括如下组分：含氟聚合物30wt％-70wt％，无机填料30wt％-70wt％；
    所述无机填料包括如下粒径分布：D10为大于1.5μm，D50为10-15μm。
  2. 根据权利要求1所述的含氟树脂组合物，其特征在于，所述无机填料还包括如下粒径分布：D90小于30μm，D100小于50μm；
    优选地，所述无机填料的比表面积≤3.0m 2/g，优选≤2.0m 2/g；
    优选地，所述无机填料为球形无机填料；
    优选地，所述无机填料包括SiO 2、Al 2O 3、TiO 2、BaTiO 3、SrTiO 3、AlN、BN、Si 3N 4、SiC、CaTiO 3、ZnTiO 3、BaSnO 3、空心玻璃微珠、短切玻璃纤维粉或短切石英纤维粉中的任意一种或至少两种组合。
  3. 根据权利要求1或2所述的含氟树脂组合物，其特征在于，所述无机填料包括经硅烷偶联剂处理的无机填料；
    优选地，所述硅烷偶联剂包括极性偶联剂和非极性偶联剂的组合；
    优选地，所述极性偶联剂和非极性偶联剂的质量比为1:5-1:1；
    优选地，所述非极性偶联剂包括含氟硅烷偶联；
    优选地，所述极性偶联剂包括胺基硅烷偶联剂、环氧基硅烷偶联剂、硼酸酯偶联剂、锆酸酯偶联剂或磷酸酯偶联剂中的任意一种或至少两种组合；
    优选地，所述硅烷偶联剂包括含氟硅烷偶联剂和环氧基硅烷偶联剂的组合；
    优选地，所述经过硅烷偶联剂处理的无机填料中硅烷偶联剂的用量占所述无机填料的0.05wt％-5wt％；
    优选地，所述无机填料的磁性物质含量小于50ppm。
  4. 根据权利要求1-3中任一项所述的含氟树脂组合物，其特征在于，所述含氟聚合物包括聚四氟乙烯、聚全氟乙丙烯、四氟乙烯-全氟烷氧基乙烯基醚共 聚物、乙烯-四氟乙烯共聚物、聚三氟氯乙烯、乙烯-三氟氯乙烯共聚物及其衍生物或聚偏二氟乙烯及其衍生物中的任意一种或至少两种组合，优选聚四氟乙烯和四氟乙烯-全氟烷氧基乙烯基醚共聚物的组合。
  5. 根据权利要求1-4中任一项所述的含氟树脂组合物，其特征在于，所述含氟树脂组合物中还包括表面活性剂，优选非离子表面活性剂；
    优选地，所述表面活性剂的添加量为1wt％-10wt％。
  6. 一种树脂胶液，其特征在于，所述树脂胶液包括权利要求1-5中任一项所述的含氟树脂组合物和溶剂。
  7. 一种含氟介质片，其特征在于，所述含氟介质片中含有权利要求1-5中任一项所述的含氟树脂组合物。
  8. 一种层压板，其特征在于，所述层压板包括至少一张权利要求7所述的含氟介质片。
  9. 一种覆铜板，其特征在于，所述覆铜板含有至少一张权利要求7所述的含氟介质片以及覆于叠合后的含氟介质片一侧或两侧的金属箔。
  10. 一种印刷电路板，其特征在于，所述印刷电路板包括权利要求8所述的层压板或权利要求9所述的覆铜板。
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