A fluorine-containing resin-based resin composition and its application

Abstract

The present invention provides a fluorine-containing resin-based resin composition and its application. The fluorine-containing resin-based resin composition comprises a combination of a fluorine-containing resin and an inorganic filler; the mass of the fluorine-containing resin is 25-50 parts based on the total mass of the fluorine-containing resin and the inorganic filler as 100 parts; the inorganic filler comprises titanium dioxide; the average particle size of the titanium dioxide is 1-6 μm, and the maximum particle size is less than 10 μm. The fluorine-containing resin-based resin composition and the fluorine-containing resin-based dielectric sheet and metal foil-clad plate containing the same have excellent dielectric and insulating properties, a low dielectric loss factor, and high resistivity. Moreover, the fluorine-containing resin-based resin composition has good dispersibility of the components and uniformity of the glue, excellent coating properties, controllable product thickness, and good performance consistency, fully meeting the various requirements for copper-clad plate materials in the field of high-frequency and high-speed communications.

Description

Technical Field

[0001] The invention belongs to the technical field of copper clad laminates, and particularly relates to a fluorine-containing resin-based resin composition and application thereof. Background Art

[0002] In recent years, with the continuous development of 5G communication technology, satellite communications, radar systems, automotive anti-collision systems, electronic navigation, and advanced integrated circuit technology, electronic products have continued to move towards higher-frequency and higher-speed signal transmission. In the field of high-frequency copper-clad laminates, fluororesins, represented by polytetrafluoroethylene (PTFE), offer a variety of excellent properties unmatched by other polymers, including low dielectric constant, low dielectric loss, high thermal stability, and chemical stability, making them an ideal copper-clad laminate substrate material.

[0003] Since the discovery of PTFE-based copper-clad laminates, researchers have continuously optimized their formulations and parameters, gradually refining their performance and manufacturing processes. Simultaneously, with the advancement of electronic technology and the expansion of its application areas, higher performance requirements have been placed on copper-clad laminates. For example, applications such as communication antennas, power amplifiers, and radar require high-frequency copper-clad laminates with high dielectric constants and low losses. Currently, the industry primarily uses the addition of large amounts of inorganic functional ceramic fillers such as titanium dioxide and strontium titanate to increase the dielectric constant of PTFE copper-clad laminates.

[0004] CN109155163A discloses a dielectric substrate comprising unsintered polytetrafluoroethylene and a high-dielectric-constant filler; the high-dielectric-constant filler has a dielectric constant of ≥35 and is selected from a combination of one or more of titanium dioxide, calcium titanate, strontium titanate, and barium titanate. The dielectric substrate has a dielectric constant of 11.5 or greater at a frequency of 10 GHz. However, the addition of high-dielectric-constant inorganic fillers also increases the dielectric loss of the copper-clad laminate and affects its insulation properties.

[0005] CN112477359A discloses a process for preparing a high-sizing polytetrafluoroethylene glass fiber copper-clad laminate, comprising the following steps: uniformly mixing a polytetrafluoroethylene emulsion, an inorganic filler, a thickener, and a defoamer to prepare a polytetrafluoroethylene dispersion; impregnating glass fiber cloth with the polytetrafluoroethylene dispersion and baking and drying the resulting polytetrafluoroethylene glass fiber impregnated sheet; laminating the impregnated sheets, and then covering both sides with copper foil to produce a copper-clad laminate; wherein the inorganic filler comprises one or a combination of silicon dioxide, titanium dioxide, aluminum oxide, perovskite, and magnesium oxide. The copper-clad laminate obtained by this method has a dielectric constant adjustable between 2.55 and 3.55, but has high dielectric loss and insufficient insulation properties such as electrical strength.

[0006] CN108656683A discloses a fluororesin-based copper-clad laminate with a high dielectric constant and a preparation method thereof. The preparation method comprises: first preparing a dispersion containing an inorganic filler having a solid content of 10-80 wt / v%, then adding a coupling agent and a portion of a fluoropolymer to the dispersion for modification, then adding a fluororesin emulsion, mixing uniformly, forming a film, drying, and sintering to obtain a fluororesin-based dielectric sheet; and then laminating the dielectric sheet with the film, copper foil, and the like to obtain a copper-clad laminate. The inorganic filler is a high-dielectric-constant ceramic filler such as AlN, BN, aluminum oxide, titanium dioxide, silicon nitride, SiC, or titanate, and the filler accounts for 50-85 wt% of the fluororesin-based dielectric sheet. The resulting fluororesin-based dielectric sheet has uniform dielectric properties and a high dielectric constant. However, the dielectric ceramic filler has slightly poor insulation properties, and its large addition to the copper-clad laminate can lead to a decrease in insulation properties such as the substrate resistivity and electrical strength.

[0007] Therefore, developing a copper clad laminate with excellent dielectric and insulating properties is an urgent problem to be solved in this field. Summary of the Invention

[0008] In response to the shortcomings of the existing technology, the purpose of the present invention is to provide a fluorine-containing resin-based resin composition and its application. By introducing titanium dioxide of a specific particle size, the fluorine-containing resin-based resin composition and the fluorine-containing resin-based dielectric sheet and metal foil-clad plate containing the same have excellent dielectric and insulating properties, controllable dielectric constant, low dielectric loss, and high volume resistivity, thereby meeting the various performance requirements of copper-clad plate materials in the high-frequency communication field.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a fluorine-containing resin-based resin composition, comprising a fluorine-containing resin and an inorganic filler; based on 100 parts by total weight of the fluorine-containing resin and the inorganic filler, the weight of the fluorine-containing resin is 25-50 parts.

[0011] The inorganic filler includes titanium dioxide; the average particle size of the titanium dioxide is 1-6 μm, and the maximum particle size is less than 10 μm.

[0012] In the fluorine-containing resin-based resin composition provided by the present invention, a fluorine-containing resin is compounded with titanium dioxide of a specific particle size, so that the fluorine-containing resin-based resin composition and the fluorine-containing resin-based dielectric sheet and metal foil-clad plate containing the same have excellent dielectric and insulating properties, a dielectric constant of 6.0-15 at 10 GHz, a dielectric loss factor of less than 0.002, and a high volume resistivity. In addition, the glue liquid has good uniformity during the production process, the thickness is easy to control, and the product performance is consistent, fully meeting various requirements for copper-clad plate materials in the field of high-frequency and high-speed communications.

[0013] In the fluorine-containing resin-based resin composition, based on the total mass of the fluorine-containing resin and the inorganic filler as 100 parts, the mass of the fluorine-containing resin is 25-50 parts, for example, it can be 26 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts or 48 parts, as well as specific point values between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0014] The average particle size of titanium dioxide (D 50 ) is 1-6μm, for example, it can be 1.2μm, 1.5μm, 1.8μm, 2μm, 2.2μm, 2.5μm, 2.8μm, 3μm, 3.2μm, 3.5μm, 3.8μm, 4μm, 4.2μm, 4.5μm, 4.8μm, 5μm, 5.2μm, 5.5μm or 5.8μm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the said range; titanium dioxide in the above particle size range can impart excellent dielectric properties to the fluorine-containing resin-based resin composition, the fluorine-containing resin-based dielectric sheet and the metal-clad foil plate, significantly improves the insulation performance, is easy to disperse, has good uniformity of the glue, and the thickness of the prepared fluorine-containing resin-based dielectric sheet and the metal-clad foil plate is controllable, and the processability and consistency of product performance are well guaranteed. If the average particle size of titanium dioxide is too low, the filler will be difficult to disperse in the fluororesin system and agglomeration will be obvious, thereby reducing the insulation of the substrate; if the particle size of titanium dioxide is larger than the above range, the insulation of the fluororesin-based resin composition, the fluororesin-based dielectric sheet and the plate will be poor, and the resistivity of the metal foil-clad plate will be low.

[0015] The maximum particle size of titanium dioxide (D 100 )<10μm, for example, it can be 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm, 5.5μm, 6μm, 6.5μm, 7μm, 7.5μm, 8μm, 8.5μm, 9μm or 9.5μm, etc.

[0016] In the present invention, the particle size data of titanium dioxide (D 50 、D 100 ) was obtained by Malvern 3000 laser particle size analyzer.

[0017] In the present invention, the total mass of the fluorine-containing resin and the inorganic filler, the mass of the fluorine-containing resin, etc. are all calculated based on their solid content (active ingredients), excluding the solvent, dispersant, diluent, etc. in the system.

[0018] In the present invention, the titanium dioxide can be purchased from the market or prepared in-house, by processing large-particle titanium dioxide through ball milling / sand milling to obtain titanium dioxide with a specific particle size.

[0019] Preferably, the electrical conductivity of the titanium dioxide is ≤20 μs / cm, for example, it can be 3 μs / cm, 5 μs / cm, 7 μs / cm, 9 μs / cm, 10 μs / cm, 11 μs / cm, 13 μs / cm, 15 μs / cm, 17 μs / cm or 19 μs / cm.

[0020] For example, the conductivity of the titanium dioxide is obtained by adding 10 g of titanium dioxide powder to be tested into 100 mL of ultrapure water, stirring the mixture thoroughly, allowing the mixture to stand, and then testing the conductivity of the supernatant using a conductivity tester.

[0021] Preferably, the dielectric constant of the titanium dioxide is greater than 80, for example, it may be 82, 84, 86, 88, 90, 92, 94, 96 or 98.

[0022] In the present invention, the dielectric constant of the titanium dioxide is prepared by a powder tableting method, and is tested by a TE01δ mode resonant cavity method at a test frequency greater than 3 GHz.

[0023] Preferably, the titanium dioxide comprises rutile titanium dioxide.

[0024] Preferably, the titanium dioxide is spherical titanium dioxide and / or angular titanium dioxide, and angular titanium dioxide is more preferably.

[0025] As a preferred technical solution of the present invention, the titanium dioxide is angular titanium dioxide, which helps the fluorine-containing resin-based resin composition, the fluorine-containing resin-based dielectric sheet and the metal foil-clad plate to obtain better insulation performance.

[0026] Preferably, based on 100 parts by total mass of the fluorine-containing resin and the inorganic filler, the mass of the titanium dioxide is 10-70 parts, for example, it can be 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts or 65 parts, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0027] Preferably, the titanium dioxide comprises surface-treated titanium dioxide.

[0028] Preferably, the surface treatment agent includes any one of a silane coupling agent, a borate coupling agent, a titanate coupling agent, a zirconate coupling agent or a phosphate coupling agent, or a combination of at least two thereof, and a silane coupling agent is more preferred.

[0029] Preferably, the silane coupling agent includes any one of a fluorine-containing silane coupling agent, an epoxy silane coupling agent or a vinyl silane coupling agent, or a combination of at least two thereof.

[0030] Preferably, based on the mass of the titanium dioxide to be treated as 100%, the mass of the surface treatment agent is 0.01-1.0%, for example, it can be 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0031] As a preferred technical solution of the present invention, the titanium dioxide is surface-treated to improve the interface between the filler and the fluororesin in the fluororesin-based resin composition matrix, reduce defects within the matrix, and improve insulation properties. The mass of the surface treatment agent is 0.01-1.0%, based on 100% mass of the titanium dioxide to be treated, achieving good surface treatment and modification effects. If the amount of surface treatment agent used is too low, the modification effect is not significant, and the filler-resin interface problem is not effectively solved. If the amount of surface treatment agent used is too high, the modification cost increases.

[0032] Preferably, the fluorine-containing resin includes any one or a combination of at least two of polytetrafluoroethylene, tetrafluoroethylene-fluoropropyl perfluorovinyl ether copolymer, polyperfluoroethylene propylene, tetrafluoroethylene-perfluoroalkoxy perfluorovinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polytrifluorochloroethylene, ethylene-trifluorochloroethylene copolymer or polyvinylidene fluoride, and polytetrafluoroethylene is more preferred.

[0033] Preferably, the inorganic filler further includes any one or a combination of at least two of non-hollow silica, barium titanate, strontium titanate, chopped glass fiber, alumina, boron nitride, silicon nitride, hollow glass microspheres or hollow silica, and non-hollow silica is more preferred.

[0034] Preferably, based on 100 parts by mass of the inorganic filler, the mass of the titanium dioxide is 60-100 parts, for example, it can be 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 95 parts, as well as specific point values between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range; that is, the inorganic filler can be entirely titanium dioxide, or it can be a combination of titanium dioxide and other inorganic fillers.

[0035] Preferably, the inorganic filler is a surface-treated inorganic filler.

[0036] Preferably, the surface treatment agent includes any one of a silane coupling agent, a borate coupling agent, a titanate coupling agent, a zirconate coupling agent or a phosphate coupling agent, or a combination of at least two thereof, and a silane coupling agent is more preferred.

[0037] Preferably, the silane coupling agent includes any one of a fluorine-containing silane coupling agent, an epoxy silane coupling agent or a vinyl silane coupling agent, or a combination of at least two thereof.

[0038] Preferably, based on the mass of the inorganic filler to be treated as 100%, the mass of the surface treatment agent is 0.01-1.0%, for example, it can be 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0039] As a preferred technical solution of the present invention, the inorganic filler is surface treated to improve the interface between the inorganic filler and the fluorine-containing resin in the matrix of the fluorine-containing resin-based resin composition, reduce defects inside the matrix, and improve insulation.

[0040] Exemplarily, the surface treatment method of the inorganic filler includes a dry method, a wet method, a gas phase method, a processing method and other surface modification methods.

[0041] Preferably, the surface treatment method of the inorganic filler includes dry modification, comprising the following steps: mixing the surface treatment reagent with a solvent to obtain a mixed liquid; stirring and heating the inorganic filler to be treated in a mixer, spraying the mixed liquid into the mixer when the temperature reaches 70-90°C, and mixing it with the inorganic filler at high speed for 5-20 minutes to obtain the surface-treated inorganic filler.

[0042] Preferably, the solvent includes an alcohol solvent, more preferably ethanol.

[0043] Preferably, the inorganic filler comprises titanium dioxide and optionally other inorganic fillers.

[0044] Preferably, the fluorine-containing resin-based resin composition further comprises a thickener.

[0045] Preferably, the thickener comprises any one of polyoxyethylene distyrenated phenyl ether, dodecylbenzene sulfonate, nonylphenol polyoxyethylene ether, dodecyl sulfate or polydimethylsilane, or a combination of at least two thereof.

[0046] Illustratively, the fluorine-containing resin-based resin composition is prepared by the following method, which includes: mixing a fluorine-containing resin and an inorganic filler and then dispersing them uniformly to obtain the fluorine-containing resin-based resin composition.

[0047] Preferably, the fluorine-containing resin is mixed with the inorganic filler in the form of an emulsion.

[0048] Preferably, the solid content of the emulsion (i.e., the mass percentage of the fluorine-containing resin) is 50-70%, for example, it can be 51%, 53%, 55%, 57%, 59%, 60%, 61%, 63%, 65%, 67% or 69%, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.

[0049] During the preparation process, a thickener, dispersant, or solvent may be added to the fluororesin-based resin composition. The amount of addition is determined by those skilled in the art based on experience and process requirements to achieve an appropriate viscosity for facilitating impregnation, coating, and application of the fluororesin-based resin composition. During subsequent drying and sintering steps, additives such as thickeners and dispersants may partially or completely evaporate.

[0050] In a second aspect, the present invention provides a fluorine-containing resin-based dielectric sheet, wherein the material of the fluorine-containing resin-based dielectric sheet includes the fluorine-containing resin-based resin composition as described in the first aspect.

[0051] Preferably, the fluorine-containing resin-based dielectric sheet is prepared by coating the fluorine-containing resin-based resin composition on a substrate and then drying and / or sintering.

[0052] Preferably, the drying temperature is 100-260°C, for example, 110°C, 130°C, 150°C, 170°C, 190°C, 200°C, 210°C, 230°C or 250°C.

[0053] Preferably, the drying time is 10-120 min, for example, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min or 110 min.

[0054] Preferably, the sintering temperature is 200-400°C, for example, it can be 210°C, 230°C, 250°C, 270°C, 290°C, 300°C, 310°C, 330°C, 350°C, 370°C or 390°C.

[0055] Preferably, the sintering time is 0.1-12 h, for example, it can be 0.2 h, 0.25 h, 0.5 h, 0.75 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or 11 h.

[0056] Preferably, the substrate comprises a release material.

[0057] Preferably, the substrate comprises a polyimide (PI) film.

[0058] In a third aspect, the present invention provides a prepreg comprising a reinforcing material and the fluorine-containing resin-based resin composition according to the first aspect attached to the reinforcing material.

[0059] Preferably, the fluorine-containing resin-based resin composition is attached to the reinforcing material by impregnation, drying and / or sintering.

[0060] Preferably, the reinforcing material includes any one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers, or a combination of at least two thereof; illustratively including but not limited to: any one of quartz cloth, quartz glass blended cloth, glass fiber cloth, glass fiber paper, non-woven fabric, aramid cloth, or aramid paper, or a combination of at least two thereof.

[0061] In a fourth aspect, the present invention provides a metal foil-clad plate comprising a metal foil and at least one of the fluorine-containing resin-based dielectric sheet according to the second aspect or the prepreg according to the third aspect.

[0062] Preferably, the metal foil is copper foil, and the metal foil-clad plate is a copper-clad plate.

[0063] Illustratively, the metal foil clad plate is prepared by the following method, which includes: stacking a metal foil and at least one of a fluorine-containing resin-based dielectric sheet or a prepreg in sequence and then laminating them to obtain the metal foil clad plate.

[0064] Preferably, the lamination temperature is 200-400°C, for example, 210°C, 230°C, 250°C, 270°C, 290°C, 300°C, 310°C, 330°C, 350°C, 370°C or 390°C.

[0065] Preferably, the lamination pressure is 300-500 PSI, for example, 310 PSI, 330 PSI, 350 PSI, 370 PSI, 390 PSI, 400 PSI, 410 PSI, 430 PSI, 450 PSI, 470 PSI or 490 PSI.

[0066] Preferably, the lamination time is 0.5-12 h, for example, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or 11 h, etc.

[0067] In a fifth aspect, the present invention provides a printed circuit board, comprising at least one of the fluorine-containing resin-based dielectric sheet as described in the second aspect, the prepreg as described in the third aspect, or the metal-clad foil board as described in the fourth aspect.

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] (1) In the fluorine-containing resin-based resin composition provided by the present invention, a fluorine-containing resin is compounded with a specific titanium dioxide, so that the fluorine-containing resin-based resin composition and the fluorine-containing resin-based dielectric sheet and metal foil-clad plate containing the same have excellent dielectric properties and insulation properties, a dielectric constant of 6.0-15 at 10 GHz, a dielectric loss factor of less than 0.002, a high resistivity, and a volume resistivity of 5.29×10 5 -8.25×10 7 mΩ·cm, fully meeting the various requirements of high-frequency and high-speed communication fields for copper clad laminate materials.

[0070] (2) The fluorine-containing resin-based resin composition has good dispersibility, and there is no sedimentation, agglomeration and other defects during the production process. The uniformity of the adhesive is good, the coating property is excellent, the product thickness is easy to control, and the performance consistency of the fluorine-containing resin-based dielectric sheet and the metal foil-clad plate is good, which can significantly improve the production efficiency and product yield. DETAILED DESCRIPTION

[0071] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0072] The materials involved in the following examples and comparative examples of the present invention are as follows:

[0073] (1) Fluorine-containing resin

[0074] Polytetrafluoroethylene (PTFE) resin emulsion, SFN-3SH, solid content 60%, Chenguang;

[0075] Polytetrafluoroethylene (PTFE) resin emulsion, Teflon DISP 30, solid content 60%, DuPont.

[0076] (2) Titanium dioxide

[0077] 2.1. The raw materials of titanium dioxide are as follows:

[0078] STO-500D, angular titanium dioxide, Shandong National Ceramics, D 50 6.5-7.5μm, D 100 30μm;

[0079] STO-25, spherical titanium dioxide, Shandong National Ceramics, D 50 25-30μm, D 100 60-70μm;

[0080] T-RS-3-XF, angular titanium dioxide, Longao Electronics, D 50 25-30μm, D 100 60-70μm;

[0081] TR-28, spherical titanium dioxide, Huntsman, D 50 0.2μm, D 100 <10μm;

[0082] 2.2 Preparation of titanium dioxide

[0083] Use ball milling / sand milling to obtain D 50 1-6μm, D 100 Target titanium dioxide samples with a diameter less than 10 μm can be surface treated by adding a surface treatment agent during the crushing process to obtain surface treated titanium dioxide. The specific preparation method is as follows:

[0084] T-RS-3-XF angular titanium dioxide, water, surface treatment reagents, and zirconium beads were added to a ball mill and milled for 1 h and 3 h, respectively. The powder was filtered using a 10 μm filter (to remove large particles, so that the maximum particle size of the obtained titanium dioxide powder is D 100 <10μm), D 50 6μm and 3μm, D 100 <10μm titanium dioxide slurry, after drying the slurry, the surface treated D 50 6μm and 3μm, D 100 Titanium dioxide powder <10μm.

[0085] Using the above D 50 3μm, D 100 Titanium dioxide slurry with a particle size of less than 10 μm was added to a sand mill and sanded for 30 min and 1 h, respectively, to obtain D 50 1μm and 0.4μm, D 100 <10μm titanium dioxide slurry, after drying the slurry, the surface treated D 50 1μm and 0.4μm, D 100 Titanium dioxide powder <10μm.

[0086] In a specific embodiment, the inorganic filler may be surface treated by a dry modification process, and the specific method is as follows:

[0087] A certain amount of surface treatment reagent was weighed and mixed with ethanol in a ratio of 1:2 to prepare a mixed solution; the inorganic filler to be treated was added to a high-speed mixer, stirred and heated at 10 Hz, and when the temperature reached 80° C., the mixed solution was sprayed into the high-speed mixer using a syringe and mixed with the inorganic filler at a high speed of 25 Hz for 10 minutes to obtain a surface-treated inorganic filler.

[0088] The aforementioned reagent for surface treatment is a silane coupling agent, including:

[0089] F823, perfluorosilane coupling agent, Shandong Sike;

[0090] KBM-403, epoxy silane coupling agent, Shin-Etsu Chemical;

[0091] KBM-1003, vinyl silane coupling agent, Shin-Etsu Chemical.

[0092] (3) Thickener

[0093] Polyoxyethylene distyrenated phenyl ether, EMULGEN A-60, Kao Corporation.

[0094] (4) Other inorganic fillers

[0095] Spherical silica, DQ1028L, D 50 3μm, D 100 10μm, Jiangsu Lianrui.

[0096] Example 1

[0097] This embodiment provides a fluorine-containing resin-based resin composition, which comprises the following components in parts by mass: 83.4 parts of PTFE resin emulsion SFN-3SH (solid content 60%, fluorine-containing resin mass 50 parts), 50 parts of surface-treated titanium dioxide; wherein the titanium dioxide D 50 3μm, D 100 <10μm, the surface treatment agent is epoxy silane coupling agent KBM-403, the amount used is 0.5% of the mass of titanium dioxide.

[0098] This embodiment also provides a fluorine-containing resin-based dielectric sheet and a copper-clad laminate comprising the aforementioned fluorine-containing resin-based resin composition. The specific preparation method is as follows:

[0099] (1) According to the aforementioned formula, PTFE resin emulsion and surface-treated titanium dioxide were stirred and mixed for 2 hours, 0.3 parts of thickener were added and stirred for 2 hours to obtain a glue solution; the glue solution was coated on the surface of the PI film by a coating machine to coat a resin layer with a thickness of 80 μm to obtain a glue-coated PI film; the glue-coated PI film was placed in a vacuum oven at 100°C and baked for 1 hour to remove water, baked at 260°C for 1 hour to remove the additive, and baked at 350°C for 10 minutes. After cooling, the resin layer and the PI film were peeled off to obtain a fluorine-containing resin-based dielectric sheet with uniform thickness and good appearance;

[0100] (2) To obtain a 0.127 mm thick plate, two 80 μm thick fluorine-containing resin-based dielectric sheets were stacked to a size of 250 mm × 380 mm. 1 OZ thick copper foil was covered on both the upper and lower surfaces of the stacked fluorine-containing resin-based dielectric sheets for lamination. A pressure of approximately 400 PSI was applied, and the maximum temperature and retention time were 380° C. / 60 min to obtain the copper-clad laminate.

[0101] Example 2

[0102] This embodiment provides a fluorine-containing resin-based resin composition, which comprises the following components in parts by mass: 61 parts of PTFE resin emulsion SFN-3SH (solid content 60%, fluorine-containing resin mass 36.6 parts), 40 parts of surface-treated titanium dioxide, and 23.4 parts of surface-treated spherical silicon dioxide DQ1028L; wherein the titanium dioxide D 50 6μm, D 100 <10μm, the surface treatment reagents of titanium dioxide and silicon dioxide are both perfluorosilane coupling agent F823, and the dosage is 0.01% of the filler mass.

[0103] This embodiment also provides a fluorine-containing resin-based dielectric sheet and a copper-clad laminate comprising the aforementioned fluorine-containing resin-based resin composition. The specific preparation method is as follows:

[0104] (1) According to the aforementioned formula, PTFE resin emulsion SFN-3SH, surface-treated titanium dioxide, and surface-treated spherical silicon dioxide were stirred and mixed for 2 hours, 0.3 parts of a thickener was added and stirred for 2 hours to obtain a glue solution; the glue solution was coated on the surface of a PI film by a coating machine to coat a resin layer with a thickness of 80 μm to obtain a glue-coated PI film; the glue-coated PI film was placed in a vacuum oven at 100° C. and baked for 1 hour to remove water, baked at 260° C. for 1 hour to remove the additive, and baked at 350° C. for 10 minutes. After cooling, the resin layer and the PI film were peeled off to obtain a fluorine-containing resin-based dielectric sheet with uniform thickness and good appearance;

[0105] (2) To obtain a 0.127 mm thick plate, two 80 μm thick fluorine-containing resin-based dielectric sheets were stacked to a size of 250 mm × 380 mm. 1 OZ thick copper foil was covered on both the upper and lower surfaces of the stacked fluorine-containing resin-based dielectric sheets for lamination. A pressure of approximately 400 PSI was applied, and the maximum temperature and retention time were 380° C. / 60 min to obtain the copper-clad laminate.

[0106] Example 3

[0107] This embodiment provides a fluorine-containing resin-based resin composition, a fluorine-containing resin-based dielectric sheet and a copper-clad laminate containing the same. The only difference between this embodiment and embodiment 2 is that the titanium dioxide D 50 1μm, D 100 <10μm, the surface treatment reagents of titanium dioxide and silicon dioxide are both vinyl coupling agent KBM-1003, and the amount used is 1.0% of the filler mass; other materials, amounts and preparation methods are the same as those in Example 2.

[0108] Example 4

[0109] This embodiment provides a fluorine-containing resin-based resin composition, which comprises the following components in parts by mass: 50 parts of PTFE resin emulsion SFN-3SH (solid content 60%, fluorine-containing resin mass 30 parts), 62.5 parts of surface-treated titanium dioxide, and 7.5 parts of surface-treated spherical silicon dioxide DQ1028L; wherein the titanium dioxide D 50 6μm, D 100 <10μm, the surface treatment reagents of titanium dioxide and silicon dioxide are both perfluorosilane coupling agent F823, and the dosage is 0.3% of the filler mass.

[0110] This embodiment also provides a fluorine-containing resin-based dielectric sheet and a copper-clad laminate comprising the aforementioned fluorine-containing resin-based resin composition, and the preparation method is the same as that of Example 2.

[0111] Example 5

[0112] This embodiment provides a fluorine-containing resin-based resin composition, which comprises the following components in parts by mass: 41.67 parts of PTFE resin emulsion Teflon DISP 30 (solid content 60%, fluorine-containing resin mass 25 parts), 63 parts of surface-treated titanium dioxide, and 12 parts of surface-treated spherical silicon dioxide DQ1028L; wherein, the titanium dioxide D 50 6μm, D 100 <10μm, the surface treatment reagents of titanium dioxide and silicon dioxide are both perfluorosilane coupling agent F823, and the dosage is 0.3% of the filler mass.

[0113] This embodiment also provides a fluorine-containing resin-based dielectric sheet and a copper-clad laminate comprising the aforementioned fluorine-containing resin-based resin composition, and the preparation method is the same as that of Example 2.

[0114] Example 6

[0115] This embodiment provides a fluorine-containing resin-based resin composition, a fluorine-containing resin-based dielectric sheet and a copper-clad laminate containing the same. The only difference between this embodiment and Example 2 is that the titanium dioxide and silicon dioxide used are not surface-modified; other materials, amounts and preparation methods are the same as those in Example 2.

[0116] Comparative Example 1

[0117] This comparative example provides a fluorine-containing resin-based resin composition, a fluorine-containing resin-based dielectric sheet and a copper-clad laminate containing the same. The difference between the comparative example and the embodiment 1 is that the titanium dioxide used is TR-28 and its D 50 0.2μm, D 100 <10μm; other materials, amounts and preparation methods are the same as those in Example 1.

[0118] Comparative Example 2

[0119] This comparative example provides a fluorine-containing resin-based resin composition, a fluorine-containing resin-based dielectric sheet and a copper-clad laminate containing the same. The difference between the comparative example and the embodiment 2 is that the titanium dioxide D 50 0.4μm, D 100 <10μm; other materials, amounts and preparation methods are the same as those in Example 2.

[0120] Comparative Example 3

[0121] This comparative example provides a fluorine-containing resin-based resin composition, a fluorine-containing resin-based dielectric sheet and a copper-clad laminate containing the same. The difference between this comparative example and Example 4 is that the titanium dioxide used is T-RS-3-XF, and its D 50 The other materials, amounts and preparation methods are the same as those in Example 4.

[0122] Comparative Example 4

[0123] This comparative example provides a fluorine-containing resin-based resin composition, a fluorine-containing resin-based dielectric sheet and a copper-clad laminate containing the same. The difference between this comparative example and Example 4 is that the titanium dioxide used is STO-25, and its D 50 The other materials, amounts and preparation methods are the same as those in Example 4.

[0124] Comparative Example 5

[0125] This comparative example provides a fluorine-containing resin-based resin composition, a fluorine-containing resin-based dielectric sheet and a copper-clad laminate containing the same. The difference between this comparative example and Example 5 is that the titanium dioxide used is STO-500D. 50 6.5-7.5μm, D 100 The other materials, amounts and preparation methods are the same as those in Example 5.

[0126] The copper clad laminates provided in Examples 1-6 and Comparative Examples 1-5 were subjected to performance tests, and the specific methods are as follows:

[0127] (1) Dielectric constant Dk and dielectric loss factor Df: Tested using a vector network analyzer according to the IEC-61189-2-721-2015 (SPDR) method at a test frequency of 10 GHz;

[0128] (2) Volume resistivity: Tested using a high resistance meter according to IPC-TM-650-2.5.17.1A method;

[0129] (3) Dispersibility: Observe the surface of the glue solution coated on the PI film. If there are no obvious particles or scratches on the surface, it means that the dispersion is good. If there are particles or scratches on the surface, it means that the dispersion is poor.

[0130] The test results are shown in Table 1:

[0131] Table 1

[0132]

[0133] As can be seen from Table 1, Examples 1-5 use D 50 In 1-6 μm, D 100 After the surface-treated titanium dioxide with a thickness of less than 10 μm is mixed with PTFE resin to prepare a copper-clad laminate, the dielectric constant at 10 GHz is 6.0-15, the dielectric loss factor is 0.0010-0.0017, and the volume resistivity reaches 5.29×10 5 -8.25×10 7 mΩ·cm, its dielectric loss and volume resistivity are significantly better than those of copper clad plates made of nano-sized titanium dioxide (Comparative Examples 1-2) or large-particle titanium dioxide (Comparative Examples 3-5). As can be seen from Comparative Examples 3-4, the insulation of angular silicon dioxide is better than that of spherical titanium dioxide. Comparative Examples 1-2 use titanium dioxide with an average particle size of less than 1 μm, which is poorly dispersed in the PTFE resin emulsion, and the filler specific surface area increases sharply, the interface between the filler and the PTFE resin increases, and the interface defects increase, causing the insulation of the plate to decrease and the dielectric loss of the plate to increase. Comparative Examples 3-5 use an average particle size of >6 μm, D 100 Titanium dioxide with a thickness of >10μm has poor insulation properties.

[0134] The applicant declares that the present invention uses the above-described embodiments to illustrate the fluorine-containing resin-based resin composition and its applications. However, the present invention is not limited to the above-described embodiments, which does not necessarily mean that the present invention must rely on the above-described embodiments in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for various raw materials in the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A fluorine-containing resin-based resin composition, characterized in that The fluorine-containing resin-based resin composition comprises a fluorine-containing resin and an inorganic filler; based on 100 parts by weight of the total weight of the fluorine-containing resin and the inorganic filler, the weight of the fluorine-containing resin is 30-50 parts; The inorganic filler includes titanium dioxide; the D 50 1-6μm, D 100 <10μm; The titanium dioxide is angular titanium dioxide; Based on 100 parts by mass of the inorganic filler, the mass of the titanium dioxide is 60-100 parts by mass.

2. The fluorine-containing resin-based resin composition according to claim 1, characterized in that The electrical conductivity of the titanium dioxide is ≤20 μs / cm.

3. The fluorine-containing resin-based resin composition according to claim 1, characterized in that The dielectric constant of the titanium dioxide is greater than 80.

4. The fluorine-containing resin-based resin composition according to claim 1, characterized in that The titanium dioxide includes rutile titanium dioxide.

5. The fluorine-containing resin-based resin composition according to claim 1, characterized in that Based on 100 parts by weight of the total weight of the fluorine-containing resin and the inorganic filler, the weight of the titanium dioxide is 10-70 parts by weight.

6. The fluorine-containing resin-based resin composition according to claim 1, characterized in that The titanium dioxide includes surface-treated titanium dioxide.

7. The fluorine-containing resin-based resin composition according to claim 6, characterized in that The surface treatment agent includes any one of a silane coupling agent, a borate coupling agent, a titanate coupling agent, a zirconate coupling agent or a phosphate coupling agent, or a combination of at least two thereof.

8. The fluorine-containing resin-based resin composition according to claim 7, characterized in that The surface treatment agent is a silane coupling agent.

9. The fluorine-containing resin-based resin composition according to claim 7, characterized in that The silane coupling agent includes any one of a fluorine-containing silane coupling agent, an epoxy silane coupling agent or a vinyl silane coupling agent, or a combination of at least two thereof.

10. The fluorine-containing resin-based resin composition according to claim 6, characterized in that Based on the mass of the titanium dioxide to be treated being 100%, the mass of the surface treatment agent is 0.01-1.0%.

11. The fluorine-containing resin-based resin composition according to claim 1, characterized in that The fluorine-containing resin includes any one of polytetrafluoroethylene, tetrafluoroethylene-fluoropropyl perfluorovinyl ether copolymer, polyperfluoroethylene-propylene copolymer, tetrafluoroethylene-perfluoroalkoxy perfluorovinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer or polyvinylidene fluoride, or a combination of at least two thereof.

12. The fluorine-containing resin-based resin composition according to claim 11, characterized in that The fluorine-containing resin is polytetrafluoroethylene.

13. The fluorine-containing resin-based resin composition according to claim 1, characterized in that The inorganic filler further includes any one or a combination of at least two of non-hollow silica, barium titanate, strontium titanate, chopped glass fiber, alumina, boron nitride, silicon nitride, hollow glass microspheres or hollow silica.

14. The fluorine-containing resin-based resin composition according to claim 13, characterized in that The inorganic filler is non-hollow silica.

15. The fluorine-containing resin-based resin composition according to claim 1, characterized in that The fluorine-containing resin-based resin composition further includes a thickener; The thickener includes any one of polyoxyethylene distyrenated phenyl ether, dodecylbenzene sulfonate, nonylphenol polyoxyethylene ether, dodecyl sulfate or polydimethylsilane, or a combination of at least two thereof.

16. A fluorine-containing resin-based dielectric sheet, characterized in that: The material of the fluorine-containing resin-based dielectric sheet comprises the fluorine-containing resin-based resin composition according to any one of claims 1 to 15.

17. The fluorine-containing resin-based dielectric sheet according to claim 16, characterized in that: The fluorine-containing resin-based dielectric sheet is prepared by coating the fluorine-containing resin-based resin composition on a substrate and then drying and / or sintering the coating.

18. A prepreg, characterized in that The prepreg comprises a reinforcing material and the fluorine-containing resin-based resin composition according to any one of claims 1 to 15 attached to the reinforcing material.

19. The prepreg according to claim 18, characterized in that The fluorine-containing resin-based resin composition is attached to the reinforcing material by impregnation, drying and / or sintering.

20. A metal foil-clad plate, characterized in that: The metal foil-clad plate includes a metal foil and at least one of the fluorine-containing resin-based dielectric sheet according to claim 16 or 17 or the prepreg according to claim 18 or 19.

21. A printed circuit board, characterized in that: The printed circuit board comprises at least one of the fluorine-containing resin-based dielectric sheet according to claim 16 or 17, the prepreg according to claim 18 or 19, or the metal-clad foil board according to claim 20.

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