A fluorine-containing resin-based resin composition and use thereof

Abstract

This invention provides a fluoropolymer-based resin composition and its applications, more specifically relating to a fluoropolymer-based resin composition, a resin film, a metal-coated foil, and a printed circuit board. The fluoropolymer-based resin composition comprises the following components in parts by weight: 30-60 parts of fluoropolymer, 31-67 parts of chemically produced spherical silica with an average particle size ≥4 μm, and 3-9 parts of quartz short fibers with an average diameter ≥4 μm; the chemically produced spherical silica is obtained by organosilicon hydrolysis followed by calcination at a temperature above 800°C; the quartz short fibers have an aspect ratio ≥5:1 and a length ≤100 μm. This invention, through the design of the specific composition of the fluoropolymer-based resin composition, has prepared a high-performance fluoropolymer-based resin composition, ultimately resulting in a PTFE metal-coated foil with a dielectric loss of less than 0.05% and a controllable dimensional expansion / contraction value within 1000 ppm, without supporting material.

Description

Technical Field

[0001] This invention belongs to the technical field of copper clad laminate materials, specifically relating to a fluorinated resin-based resin composition and its application, and more specifically to a fluorinated resin-based resin composition, resin film, metal-clad laminate, and printed circuit board. Background Technology

[0002] In recent years, with the continuous development of 5G communication technology, satellite communication, radar systems, automotive collision avoidance systems, electronic navigation, and advanced integrated circuit technology, electronic products are constantly evolving towards higher frequency and higher speed signal transmission. The increasing demands for high frequency and high speed on circuit boards have led end-users to require copper-clad laminates (CCLs) with dielectric loss below 0.05% in 224GHz applications. On the other hand, advancements in chip mounting technology have resulted in an increasing number of pins and mounting density for components. Simultaneously, printed circuit board (PCB) products are trending towards lighter, thinner, shorter, and smaller designs, with increasingly smaller absolute deviations and higher precision requirements. This necessitates that CCLs exhibit minimal and controllable dimensional expansion and contraction (i.e., dimensional stability).

[0003] Unsupported PTFE copper-clad laminates are mainly prepared by laminating copper foil onto the surface of a PTFE film. The PTFE film is mainly produced by blow molding, extrusion, cutting, or casting. During production, the PTFE film will generate internal stress due to the stress. During the PCB manufacturing process, after etching to remove copper or after heat treatment, some of the internal stress is released, causing PTFE to shrink. Because unsupported PTFE copper-clad laminates do not have internal support such as fiberglass cloth, this dimensional shrinkage will be more obvious and seriously affect the processing accuracy.

[0004] To address the dimensional shrinkage issue of PTFE copper-clad laminates (CCLs), researchers have implemented physical or chemical modifications to the PTFE layer. CN114369239A discloses a low-thermal-expansion fluorinated resin-based high-frequency CCL, which involves adding a linear polyaromatic amide with a benzo[4] four-membered ring structure to a fluorinated resin dielectric sheet. The linear polyaromatic amide undergoes high-temperature baking under a protective atmosphere, causing it to react in situ to form a dibenzo[8] eight-membered ring structure with thermal shrinkage and expansion characteristics. Simultaneously, a cross-linked network is formed within the fluorinated resin matrix, reducing the thermal expansion coefficient of the high-frequency CCL and improving its dimensional stability. However, this approach suffers from high preparation costs for the linear polyaromatic amide with the benzo[4] four-membered ring structure, making the raw materials difficult to obtain. Furthermore, ensuring the linear polyaromatic amide fully reacts significantly prolongs the lamination time for CCL preparation, increasing the difficulty of CCL fabrication, reducing production efficiency, and hindering industrial applications. CN115503316A discloses a flexible copper-clad laminate, which is formed by laminating a first copper foil, a dielectric material, and a second copper foil. The dielectric material includes a first adhesive layer, a first core layer, and an optional second adhesive layer. The thickness of the first core layer is 25-500 μm, and it is composed of a fluorinated resin modified with inorganic fillers. The thicknesses of the first and second adhesive layers are 5-35 μm, respectively, and they are mainly composed of fluorinated molten resin. Although this flexible copper-clad laminate has good peel strength and low water absorption, its coefficient of thermal expansion is still high, and it has obvious dimensional expansion and contraction problems, resulting in insufficient dimensional stability and difficulty in meeting the performance requirements of copper-clad laminates under high-precision and high-density processing.

[0005] Therefore, developing copper-clad laminates with excellent dielectric loss performance and good dimensional stability to meet the requirements of high-density and high-precision PCB processing in 224GHz applications for substrate loss and dimensional expansion and contraction performance is an urgent problem to be solved in this field. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a fluoropolymer-based resin composition and its applications, more specifically relating to a fluoropolymer-based resin composition, a resin film, a metal-coated foil, and a printed circuit board. The present invention designs the specific composition of the fluoropolymer-based resin composition, further utilizes the synergistic effect of chemically synthesized silica and short quartz fibers, and controls the amounts of both within a specific range to prepare a high-performance fluoropolymer-based resin composition. Ultimately, it yields a metal-coated foil without support material, with a dielectric loss of less than 0.05% and a controllable absolute value of dimensional expansion and contraction within 1000ppm.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a fluoropolymer-based resin composition, the fluoropolymer-based resin composition comprising the following components in parts by weight:

[0009] 30-60 parts of fluorinated resin;

[0010] 31-67 parts of chemically produced spherical silica with an average particle size ≥4μm;

[0011] 3-9 parts of short quartz fibers with an average diameter ≥4μm;

[0012] The chemically produced spherical silicon is obtained by organosilicon hydrolysis followed by calcination at a temperature above 800°C.

[0013] The quartz short fibers have an aspect ratio ≥ 5:1 and a length ≤ 100 μm.

[0014] This invention designs the specific composition of a fluorinated resin-based resin composition, further utilizes the synergistic effect of chemically synthesized silica and quartz short fibers, and controls the amount of both within a specific range to prepare a high-performance fluorinated resin-based resin composition. Ultimately, it prepares a metal-clad foil plate without support material with a dielectric loss of less than 0.05% and a controllable absolute value of dimensional expansion and contraction within 1000ppm.

[0015] In this invention, if the average particle size of chemically produced spherical silicon is less than 4 μm or the average particle size of quartz short fibers is less than 4 μm, when chemically produced spherical silicon is used in combination with quartz short fibers, the interface between fluorinated resin and inorganic fillers (including chemically produced spherical silicon, quartz short fibers and optional other inorganic fillers) increases, resulting in a PTFE-coated metal foil loss of more than 0.05%.

[0016] When the amount of quartz short fiber is less than 3 parts, the synergistic effect of quartz short fiber and chemically produced spherical silica in improving dimensional expansion and contraction performance is not good. When the amount of quartz short fiber is more than 9 parts, the loss of the metal-coated foil deteriorates, with a loss of more than 0.05%. When the amount of chemically produced spherical silica is less than 31 parts, the synergistic effect of chemically produced spherical silica and quartz short fiber in improving dimensional expansion and contraction is not good. When the amount of chemically produced spherical silica is more than 67 parts, the filler in the resin composition is too high, which will lead to defects such as voids.

[0017] Chemically synthesized spherical silicon (spherical silica) by hydrolysis of organosilicon contains a large number of polar groups such as hydroxyl groups on its surface, which leads to high loss. After calcination at a high temperature above 800°C, the hydroxyl groups on its surface can be removed. PTFE-coated metal foil made from chemically synthesized spherical silicon obtained by hydrolysis of organosilicon and calcination at a temperature above 800°C has better loss performance.

[0018] When the aspect ratio of quartz short fibers is less than 5:1, the synergistic effect of chemically produced spherical silicon and quartz short fibers in improving dimensional expansion and contraction is not good; when the length of quartz short fibers exceeds 100μm, quartz short fibers are prone to re-agglomeration in the resin composition, entangled and aggregated together, resulting in agglomeration defects on the surface of the produced resin film, and the effect of improving dimensional stability deteriorates.

[0019] It should be noted that in this invention, the fluorinated resin can be mixed with other components (chemically produced silica, short quartz fibers, optional other inorganic fillers, optional thickeners, etc.) in the form of a fluorinated resin emulsion to prepare a fluorinated resin-based resin composition. This invention does not have any restrictions on the solid content of the fluorinated resin emulsion, and exemplary contents include, but are not limited to, 30%, 40%, 50%, or 60%.

[0020] It should also be noted that when fluorinated resin is mixed with other components in the form of fluorinated resin emulsion, the weight parts of fluorinated resin in the fluorinated resin-based resin composition refer to the weight parts of the fluorinated resin itself, not the weight parts of the fluorinated resin emulsion. In other words, the weight parts of the solvent in the emulsion are not included.

[0021] In this invention, the weight parts of the fluorinated resin in the fluorinated resin-based resin composition can be 30 parts, 33 parts, 36 parts, 39 parts, 42 parts, 45 parts, 48 ​​parts, 51 parts, 54 parts, 57 parts, or 60 parts, etc.

[0022] The weight percentage of chemically produced silica in the fluorinated resin-based resin composition can be 31, 34, 37, 40, 42, 45, 48, 52, 55, 57, 60, 63, 66, or 67 parts, etc.

[0023] The weight percentage of quartz short fibers in the fluorinated resin-based resin composition can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, or 9 parts, etc.

[0024] The average particle size of chemically produced spherical silicon can be 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 11μm or 12μm, etc.

[0025] The chemically produced spherical silicon is obtained by hydrolysis of organosilicon and calcination at a temperature above 800°C (e.g., 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C, 900°C, 910°C, 920°C, 930°C, 940°C, 950°C, 960°C, 980°C, 1000°C, or 1050°C).

[0026] The average diameter of quartz short fibers can be 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 11μm or 12μm, etc., and the aspect ratio can be 5:1, 5.5:1, 6.5:1, 8:1, 11:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 or 50:1, etc., and the length can be 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm or 100μm, etc.

[0027] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0028] As a preferred embodiment of the present invention, the specific surface area of ​​the chemically produced spherical silicon is ≤1m². 2 / g (for example, it could be 0.1m) 2 / g, 0.2m 2 / g, 0.3m 2 / g, 0.4m 2 / g, 0.5m 2 / g, 0.6m 2 / g, 0.7m 2 / g, 0.8m 2 / g, 0.9m 2 / g or 1m 2 / g, etc.), with a purity ≥99% (e.g., it can be 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or 99.99%, etc.).

[0029] When the specific surface area of ​​chemically produced spherical silicon is greater than 1m² 2 When the value is / g, it will lead to an increase in filler interface defects in the metal-coated foil substrate and a worsening of metal-coated foil loss.

[0030] Preferably, the chemically synthesized silicon spheres include unmodified chemically synthesized silicon spheres and / or modified chemically synthesized silicon spheres, and more preferably modified chemically synthesized silicon spheres.

[0031] Preferably, the modifier A used to prepare the modified chemically synthesized spherical silicon is selected from any one or a combination of at least two of fluorinated silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, or alkyl silane coupling agents.

[0032] In this invention, there are no special restrictions on the specific selection of fluorinated silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, and alkyl silane coupling agents. The above-mentioned silane coupling agents commonly used in the art are all applicable, and the same applies below.

[0033] Preferably, in the modified chemically produced spherical silicon, based on the mass percentage of the chemically produced spherical silicon being 100%, the mass percentage of the modifier A is 0.01-1%, for example, it can be 0.01%, 0.05%, 0.1%, 0.01%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1.0%.

[0034] It should be noted that there are no special restrictions on the source of the modified chemically produced spherical silicon in this invention; it can be a commercially available product or a self-made product. If it is a self-made product, there are no special restrictions on the preparation method of the modified chemically produced spherical silicon in this invention; commonly used methods for modifying chemically produced spherical silicon in this field are applicable, including but not limited to:

[0035] The dry modification process for chemically produced spherical silicon involves the following steps:

[0036] Modifier A and ethanol are mixed at a mass ratio of 1:2 to form a solution. The chemically synthesized silica spheres are placed in a high-speed mixer and stirred and heated at 7-15 Hz (e.g., 7 Hz, 8 Hz, 9 Hz, 10 Hz, 11 Hz, 12 Hz, 13 Hz, 14 Hz, or 15 Hz, etc.). The temperature is raised to 60-80℃ (e.g., 60℃, 62℃, 64℃, 66℃, 68℃, 70℃, 72℃, 74℃, 76℃, 78℃, or 80℃, etc.). The above mixture is sprayed into the atomizer and mixed at high speed for 8-15 minutes (e.g., 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, or 15 minutes) at 20-30 Hz (e.g., 20 Hz, 21 Hz, 22 Hz, 23 Hz, 24 Hz, 25 Hz, 26 Hz, 27 Hz, 28 Hz, 29 Hz, or 30 Hz, etc.) to obtain the modified chemically produced spherical silicon.

[0037] As a preferred embodiment of the present invention, the purity of the quartz short fiber is ≥99.9% (e.g., it can be 99.9%, 99.91%, 99.92%, 99.93%, 99.94%, 99.95%, 99.96%, 99.97%, 99.98%, or 99.99%), and the mass percentage content of the magnetic material is ≤10ppm (e.g., it can be 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, or 10ppm).

[0038] When the purity of quartz short fibers is less than 99.9% or the content of magnetic materials exceeds 10ppm, the loss performance of copper-clad laminates will deteriorate.

[0039] Preferably, the average diameter of the quartz short fiber is 4-9 μm, for example, it can be 4 μm, 5 μm, 6 μm, 7 μm, 8 μm or 9 μm.

[0040] When the diameter of the quartz short fiber is 4-9μm, the copper clad laminate exhibits the best overall performance in terms of dielectric loss and dimensional expansion / contraction. When the diameter of the short fiber exceeds 9μm, the improvement effect on dimensional expansion / contraction performance deteriorates.

[0041] Preferably, the quartz short fibers include unmodified quartz short fibers and / or modified quartz short fibers, and more preferably modified quartz short fibers.

[0042] Preferably, the modifier B used to prepare the modified quartz short fiber is selected from any one or a combination of at least two of fluorinated silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, or alkyl silane coupling agents.

[0043] Preferably, in the modified quartz short fiber, based on the mass percentage of the quartz short fiber being 100%, the mass percentage of the modifier B is 0.01-1%, for example, it can be 0.01%, 0.05%, 0.1%, 0.01%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1.0%.

[0044] It should be noted that there are no special restrictions on the source of the modified quartz short fibers in this invention; they can be commercially available products or self-made products. If the products are self-made, there are no special restrictions in the art regarding the preparation method of the modified quartz short fibers; commonly used methods for modifying quartz short fibers in the art are applicable, and exemplary modification methods include, but are not limited to:

[0045] Quartz wool and / or quartz fiber filaments, water, modifier B, and zirconium beads are added to a ball mill, ball-milled, and dried to obtain modified quartz short fibers.

[0046] As a preferred embodiment of the present invention, the fluorinated resin includes any one or a combination of at least two of the following: polytetrafluoroethylene resin, polytetrafluoroethylene-fluoropropyl perfluorovinyl ether copolymer, perfluoroethylene propylene, polytetrafluoroethylene-perfluoroalkoxy perfluorovinyl ether copolymer, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, or ethylene-chlorotrifluoroethylene copolymer.

[0047] Preferably, the fluorinated resin includes polytetrafluoroethylene resin.

[0048] The length and diameter of the quartz short fibers were determined using electron microscopy; the particle size of the inorganic fillers (chemically produced spherical silica, other inorganic fillers, etc.) was determined using a Malvern 3000 laser particle size analyzer; the specific surface area of ​​the chemically produced spherical silica was determined using a gas adsorption method (BET method) specific surface area analyzer; the purity of the chemically produced spherical silica and quartz short fibers was determined using inductively coupled plasma optical emission spectrometry (ICP). By measuring the unique spectral lines and intensities of each element and comparing them with standard solutions, the types and contents of elements contained in the sample were determined; the magnetic material content of the quartz short fibers was determined by dispersing 300g of quartz short fibers in 1.5L of pure water, stirring at a low speed of 300-600 rpm, and then immersing a sleeved magnetic rod with a magnetic strength ≥8000 Gauss in the dispersion for 1 hour. The magnetic material on the sleeve of the magnetic rod was then rinsed into a weighing bottle, dried at 105℃, and the magnetic material content was weighed; the viscosity of the adhesive solution was determined using a Brookfield rotational viscometer.

[0049] As a preferred embodiment of the present invention, the fluorinated resin-based resin composition further includes 3-10 parts by weight of other inorganic fillers, such as 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight.

[0050] Preferably, the other inorganic fillers include unmodified other inorganic fillers and / or modified other inorganic fillers, and more preferably modified other inorganic fillers.

[0051] Preferably, the other inorganic fillers include any one or a combination of at least two of the following: titanium dioxide, barium titanate, strontium titanate, aluminum oxide, boron nitride, silicon nitride, hollow quartz microspheres, hollow glass microspheres, or hollow silicon dioxide.

[0052] Preferably, the modifier C used to prepare the modified inorganic filler is selected from any one or a combination of at least two of fluorinated silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, or alkyl silane coupling agents.

[0053] Preferably, in the modified inorganic filler, based on the mass percentage of the inorganic filler being 100%, the mass percentage of the modifier C is 0.01-1%, for example, it can be 0.01%, 0.05%, 0.1%, 0.01%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1.0%.

[0054] It should be noted that there are no special restrictions on the source of the modified inorganic filler in this invention; it can be a commercially available product or a self-made product. If it is a self-made product, there are no special restrictions in the art on the preparation method of the modified inorganic filler; commonly used methods for modifying inorganic fillers in the art are applicable, including but not limited to:

[0055] The dry modification process for inorganic fillers includes the following steps:

[0056] Modifier C and ethanol are mixed at a mass ratio of 1:2 to form a solution. The inorganic filler is placed in a high-speed mixer and stirred and heated at 7-15 Hz (e.g., 7 Hz, 8 Hz, 9 Hz, 10 Hz, 11 Hz, 12 Hz, 13 Hz, 14 Hz, or 15 Hz, etc.). The temperature is raised to 60-80℃ (e.g., 60℃, 62℃, 64℃, 66℃, 68℃, 70℃, 72℃, 74℃, 76℃, 78℃, or 80℃, etc.). The above mixture is injected using a syringe and mixed at high speed for 8-15 minutes (e.g., 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, or 15 minutes) at 20-30 Hz (e.g., 20 Hz, 21 Hz, 22 Hz, 23 Hz, 24 Hz, 25 Hz, 26 Hz, 27 Hz, 28 Hz, 29 Hz, or 30 Hz) to obtain the modified inorganic filler.

[0057] As a preferred embodiment of the present invention, based on 100 parts by weight of the total solids of fluorinated resin, chemically produced spherical silica, quartz short fibers and other inorganic fillers, the fluorinated resin comprises 30-60 parts, the chemically produced spherical silica with an average particle size ≥4μm comprises 31-67 parts, the quartz short fibers with an average diameter ≥4μm comprises 3-9 parts, and optionally other inorganic fillers comprises 3-10 parts by weight.

[0058] As a preferred embodiment of the present invention, the fluorinated resin-based resin composition further includes a thickener.

[0059] Thickener is used to adjust the viscosity of the adhesive to 250-300 mPa·s. The amount of thickener is not specifically limited, but can be 1-5 parts by weight, such as 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or 5 parts by weight.

[0060] Preferably, the thickener is selected from any one or a combination of at least two of polyoxyethylene distyrene phenyl ether, sodium dodecylbenzene sulfonate, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, or polydimethylsilane.

[0061] In this invention, there are no special limitations on the preparation method of the fluorinated resin-based resin composition; commonly used preparation methods in the art are applicable, including but not limited to:

[0062] The fluorinated resin, chemically produced silica gel, other inorganic fillers, and quartz short fibers in the fluorinated resin-based resin composition are mixed and stirred evenly. Then, a thickener is added while stirring until the viscosity is 250-300 mPa·s. The mixture is stirred and stirred evenly to obtain the fluorinated resin-based resin composition.

[0063] In a second aspect, the present invention provides a resin film comprising the fluorinated resin-based resin composition as described in the first aspect.

[0064] In this invention, there are no special limitations on the preparation method of the resin film; commonly used preparation methods in the art are applicable, such as blow molding, extrusion, cutting, and casting. For example, exemplary preparation methods include, but are not limited to:

[0065] After coating the fluoropolymer-based resin composition onto the substrate surface, it is placed in a vacuum oven at 100°C to dry and remove moisture. Then, it is baked at 250-270°C (e.g., 250°C, 252°C, 254°C, 256°C, 258°C, 260°C, 262°C, 264°C, 266°C, 268°C, or 270°C, etc.) for 0.5-2 hours (e.g., 0.5 hours, 1 hour, 1.5 hours, or 2 hours, etc.) to remove the additives (thickeners). After baking at 340-360℃ (e.g., 340℃, 342℃, 344℃, 346℃, 348℃, 350℃, 352℃, 354℃, 356℃, 358℃ or 360℃, etc.) for 7-15 minutes (e.g., 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes, etc.), the substrate is cooled and peeled off to obtain a resin film.

[0066] Preferably, the substrate comprises a PI film (polyimide film).

[0067] In this invention, there are no special limitations on the thickness of the resin film, which can be designed according to actual needs. Exemplary examples include, but are not limited to, 25-127μm, such as 25μm, 30μm, 40μm, 50μm, 55μm, 60μm, 65μm, 70μm, 75μm, 80μm, 85μm, 90μm, 95μm, 100μm, 110μm, 120μm or 127μm, etc.

[0068] Thirdly, the present invention provides a metal-clad foil plate, the metal-clad foil plate comprising at least one resin film as described in the second aspect and metal foils covering both sides of the laminated resin film.

[0069] In this invention, there are no special limitations on the preparation method of the metal-clad laminate; commonly used preparation methods in the art are applicable, including but not limited to:

[0070] The metal foil, at least one resin film, and another metal foil are stacked and then laminated to obtain the metal foil-coated plate.

[0071] Fourthly, the present invention provides a printed circuit board comprising at least one of a resin film as described in the second aspect or a metal-clad foil as described in the third aspect.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] (1) This invention designs the specific composition of the fluorinated resin-based resin composition, and further utilizes the synergistic effect of chemically produced spherical silica with an average particle size ≥4μm and quartz short fibers with an average diameter ≥4μm, an aspect ratio ≥5:1, and a length ≤100μm, and controls the amount of both within a specific range to prepare a high-performance fluorinated resin-based resin composition. Finally, a PTFE-coated metal foil plate with unsupported material is prepared, which has a dielectric loss of less than 0.05% and a controllable absolute value of dimensional expansion and contraction within 1000ppm.

[0074] (2) The present invention further designs the specific composition of the fluorinated resin-based resin composition, and further achieves an average particle size ≥4μm and a specific surface area ≤1m². 2 The synergistic effect of chemically produced spherical silicon and short quartz fibers with an average diameter ≥4μm, purity ≥99.9%, and magnetic material content ≤10ppm further improves the comprehensive performance of the fluorinated resin-based resin composition. Finally, a PTFE-coated metal foil board with unsupported material and controllable dielectric loss of less than 0.05% and dimensional expansion and contraction absolute value within 1000ppm was prepared. Detailed Implementation

[0075] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0076] The sources of some components in the examples and comparative examples are shown in Table 1 below:

[0077] Table 1

[0078]

[0079]

[0080] The modified chemically synthesized spherical silicon / modified titanium dioxide particles of different sizes in Table 1 were prepared using the following methods:

[0081] A mixture of tridecafluorooctyltrimethoxysilane (YJ-H03 from Shandong Yuanjin New Materials Co., Ltd.) and ethanol was prepared at a mass ratio of 1:2. Chemically produced spherical silica or titanium dioxide of the corresponding particle size was placed in a high-speed mixer and stirred and heated at 10 Hz. When the temperature reached 80 ℃, the mixture was sprayed into the mixture using an atomizer and mixed at high speed at 25 Hz for 10 min to obtain modified chemically produced spherical silica (denoted as modified chemically produced spherical silica) or modified titanium dioxide (denoted as modified titanium dioxide) of the corresponding particle size. The mass ratio of tridecafluorooctyltrimethoxysilane (YJ-H03 from Shandong Yuanjin New Materials Co., Ltd.) to chemically produced spherical silica (or titanium dioxide) was 0.8:100.

[0082] The preparation methods of quartz short fibers in Table 1 are as follows: Quartz fibers to be ground are prepared using the following methods to obtain quartz short fibers of the corresponding lengths shown in Table 1:

[0083] Quartz fiber filaments to be ground, water, and zirconium beads are added to a ball mill in a ratio of 1:2:5, ball milled, and dried to obtain quartz short fibers of the appropriate size.

[0084] The modified quartz short fibers in Table 1 are prepared by the following methods to obtain the modified quartz short fibers of the corresponding lengths in Table 1.

[0085] The fiber to be ground, water, and zirconium beads are added to a ball mill in a ratio of 1:2:5. Based on the 100% mass percentage of the added fiber, 0.2% of tridecafluorooctyltrimethoxysilane (YJ-H03 from Shandong Yuanjin New Materials Co., Ltd.) modifier is added to the ball mill. After ball milling and drying, modified quartz short fibers of the corresponding size are obtained.

[0086] Examples 1-10, Comparative Examples 1-15

[0087] Examples 1-10 and Comparative Examples 1-15 each provide a fluorinated resin-based resin composition. The specific composition of the fluorinated resin-based resin composition is shown in Tables 2-4 below. The amounts of each component in Tables 2-4 are all by weight. The weight parts of the fluorinated resin refer to the weight parts of the resin itself excluding the solvent.

[0088] The preparation method of the fluorinated resin-based resin composition is as follows:

[0089] Mix all components except the thickener, add the thickener while stirring to adjust the viscosity to 270 mPa·s, and mix at high speed for 2 hours to obtain a fluorinated resin-based resin composition.

[0090] Resin films were prepared using the fluorinated resin-based resin compositions provided in the examples and comparative examples, respectively. The specific preparation methods are as follows:

[0091] A fluorinated resin-based resin composition was coated onto one side surface of a PI film using a coating machine to obtain a resin layer with a coating thickness of 80 μm, thus obtaining a coated PI film. The coated PI film was placed in a vacuum oven at 100°C and baked for 1 hour to remove moisture. It was then baked at 260°C for 1 hour to remove the thickener and at 350°C for 10 minutes. After cooling, the resin layer was peeled off from the PI film to obtain a resin film with uniform thickness.

[0092] The resin film prepared using the fluorinated resin-based resin composition provided in the above examples and comparative examples is further used to prepare a metal-clad laminate (PTFE copper-clad laminate), and the preparation method is as follows:

[0093] Two 80μm thick resin films are stacked together, with a size of 250×380mm. A 1oz thick copper foil (purchased from Changchun Copper Foil Group) is then placed on both sides of the stacked resin layer for lamination. A pressure of 400PSI is applied, and the maximum temperature and holding time are 380℃ / 60min, thus obtaining a metal-coated foil board.

[0094] The dielectric constant (Dk), dielectric loss (Df), dimensional expansion and contraction, voids, and dispersion of the fluorinated resin-based resin compositions provided in the above embodiments and comparative examples and the PTFE copper-clad laminates prepared therefrom were evaluated. The specific evaluation methods are as follows:

[0095] Dielectric constant (Dk) and dielectric loss (Df): Tested using a vector network analyzer according to the IEC-61189-2-721-2015 (SPDR) method at a test frequency of 10 GHz;

[0096] Dimensional expansion and contraction: Tested using IPC-TM-650 2.2.4 method;

[0097] Dispersibility: When preparing the resin film, observe the appearance of the adhesive coating on the PI film. If there are no obvious particles or scratches on the surface, it indicates good dispersion. If there are particles or scratches on the surface, it indicates poor dispersion and agglomeration.

[0098] Substrate void test: The PTFE copper clad laminate sample is made into a slice, and the cross-section of the slice is observed with an electron microscope to see if there are void defects.

[0099] The performance test results are shown in Tables 2-4 below:

[0100] Table 2

[0101]

[0102]

[0103] Table 3

[0104]

[0105]

[0106] Table 4

[0107]

[0108]

[0109] As can be seen from the above, this invention, through the design of the specific composition of the fluoropolymer-based resin composition, and further through the synergistic effect of chemically produced spherical silica with an average particle size ≥4μm and short quartz fibers with an average diameter ≥4μm, an aspect ratio ≥5:1, and a length ≤100μm, and by controlling the amount of both within a specific range, prepared a fluoropolymer-based resin composition with excellent performance and good dispersibility. Ultimately, it produced a PTFE-coated metal foil with a dielectric loss of less than 0.05% and a controllable absolute value of dimensional expansion and contraction within 1000ppm, and a dielectric loss (Df) of (0.32-0.50)×10⁻¹⁰. -3 It has no holes or defects.

[0110] As can be seen from Examples 4 and 11, the present invention further reduces the dielectric loss of the fluorinated resin-based resin composition and improves the overall performance of the fluorinated resin-based resin composition by using modified chemically synthesized spherical silicon and modified quartz short fibers.

[0111] As can be seen from Example 4 and Comparative Examples 3-5 and 9-12, the present invention further designs the specific composition of the fluorinated resin-based resin composition, and further achieves an average particle size ≥4μm and a specific surface area ≤1m². 2 The synergistic effect of chemically produced spherical silicon and short quartz fibers with an average diameter ≥4μm, purity ≥99.9%, and magnetic material content ≤10ppm further improves the comprehensive performance of the fluorinated resin-based resin composition. Finally, a PTFE-coated metal foil board with unsupported material and controllable dielectric loss of less than 0.05% and dimensional expansion and contraction absolute value within 1000ppm was prepared.

[0112] As can be seen from Examples 1, 2, 4 and Comparative Examples 1-2 and 7-8, the present invention prepares a high-performance fluorinated resin-based resin composition by controlling the amount of chemically synthesized silica and quartz short fibers within a specific range, and finally prepares a high-performance PTFE-coated metal foil.

[0113] As can be seen from Example 4 and Comparative Examples 13-15, the present invention prepares a high-performance fluorinated resin-based resin composition through the synergistic effect of chemically synthesized silica and quartz short fibers, and then prepares a PTFE-coated metal foil plate with low dielectric loss and small absolute value of dimensional expansion and contraction without support.

[0114] In summary, this invention, through the design of the specific composition of the fluoropolymer-based resin composition, prepared a fluoropolymer-based resin composition with excellent performance and good dispersibility. Ultimately, it yielded a PTFE-coated metal foil board with a dielectric loss of less than 0.05% and a controllable absolute value of dimensional expansion and contraction within 1000ppm, without any supporting material.

[0115] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A fluorinated resin-based resin composition, characterized in that, The fluoropolymer-based resin composition comprises the following components in parts by weight: 30-60 parts of fluorinated resin; 31-67 parts of chemically produced spherical silica with an average particle size ≥4μm; 3-9 parts of short quartz fibers with an average diameter ≥4μm; The chemically produced spherical silicon is obtained by organosilicon hydrolysis followed by calcination at a temperature above 800°C. The quartz short fibers have an aspect ratio ≥ 5:1 and a length ≤ 100 μm.

2. The fluorinated resin-based resin composition according to claim 1, characterized in that, The specific surface area of ​​the chemically produced spherical silicon is ≤1m². 2 / g, purity ≥99%; Preferably, the chemically synthesized silicon spheres include unmodified chemically synthesized silicon spheres and / or modified chemically synthesized silicon spheres, and more preferably modified chemically synthesized silicon spheres; Preferably, the modifier for the modified chemically synthesized silica is selected from any one or a combination of at least two of fluorinated silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, or alkyl silane coupling agents.

3. The fluorinated resin-based resin composition according to claim 1 or 2, characterized in that, The quartz short fibers have a purity of ≥99.9% and a magnetic material content of ≤10ppm by mass. Preferably, the average diameter of the quartz short fibers is 4-9 μm; Preferably, the quartz short fiber includes unmodified quartz short fiber and / or modified quartz short fiber, and more preferably modified quartz short fiber; Preferably, the modifier for the modified quartz short fiber is selected from any one or a combination of at least two of fluorinated silane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents, or alkyl silane coupling agents.

4. The fluorinated resin-based resin composition according to any one of claims 1-3, characterized in that, The fluorinated resin includes any one or a combination of at least two of the following: polytetrafluoroethylene resin, polytetrafluoroethylene-fluoropropyl perfluorovinyl ether copolymer, perfluoroethylene propylene, polytetrafluoroethylene-perfluoroalkoxy perfluorovinyl ether copolymer, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, or ethylene-chlorotrifluoroethylene copolymer. Preferably, the fluorinated resin includes polytetrafluoroethylene resin.

5. The fluorinated resin-based resin composition according to any one of claims 1-4, characterized in that, The fluorinated resin-based resin composition also includes 3-10 parts by weight of other inorganic fillers.

6. The fluorinated resin-based resin composition according to claim 5, characterized in that, The other inorganic fillers include unmodified other inorganic fillers and / or modified other inorganic fillers, more preferably modified other inorganic fillers; Preferably, the other inorganic fillers include any one or a combination of at least two of the following: titanium dioxide, barium titanate, strontium titanate, aluminum oxide, boron nitride, silicon nitride, hollow quartz microspheres, hollow glass microspheres, or hollow silicon dioxide.

7. The fluorinated resin-based resin composition according to any one of claims 1-6, characterized in that, The fluoropolymer-based resin composition also includes a thickener; Preferably, the thickener is selected from any one or a combination of at least two of polyoxyethylene distyrene phenyl ether, sodium dodecylbenzene sulfonate, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, or polydimethylsilane.

8. A resin film, characterized in that, The resin film comprises the fluorinated resin-based resin composition as described in any one of claims 1-7.

9. A metal-clad foil plate, characterized in that, The metal-clad foil plate includes at least one resin film as described in claim 7 and metal foils covering both sides of the laminated resin film.

10. A printed circuit board, characterized in that, The printed circuit board includes at least one of the resin film as described in claim 8 or the metal foil as described in claim 9.

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