KR-102964819-B1 - Fluorine-containing resin composition and resin adhesive containing the same, fluorine-containing dielectric sheet, laminate, copper clad laminate and printed circuit board

Abstract

A fluorine-containing resin composition and a resin adhesive containing the same, a fluorine-containing dielectric sheet, a laminate, a copper clad laminate, and a printed circuit board are provided. The fluorine-containing resin composition comprises 30 wt%-70 wt% of a fluorine-containing polymer and 30 wt%-70 wt% of an inorganic filler as compositional components; the inorganic filler has a D10 greater than 1.5 μm and a D50 of 10-15 μm. By selecting an inorganic filler having a specific particle size distribution, it is possible to ensure that a plate obtained by manufacturing with the fluorine-containing resin composition has excellent dielectric performance and dielectric strength even when the amount of inorganic filler added is large.

Inventors

• 차이, 송강
• 류, 치옌파
• 하오, 리양펑
• 리양, 웨이

Assignees

• 셍기 테크놀로지 코. 엘티디.

Dates

Publication Date

20260513

Application Date

20201217

Priority Date

20201209

Claims (10)

1. In a fluorine-containing resin composition, The above fluorine-containing resin composition comprises 30 wt%-70 wt% of a fluorine-containing polymer and 30 wt%-70 wt% of an inorganic filler as compositional components; The above-mentioned inorganic filler comprises a particle size distribution in which D10 is greater than 1.5 μm and D50 is 10-15 μm; The above-mentioned inorganic filler also includes a particle size distribution in which D90 is smaller than 30 μm and D100 is smaller than 50 μm; The specific surface area of the above-mentioned inorganic filler is ≤2.0 m² /g; The above-mentioned weapon filler is a spherical weapon filler; The above-mentioned inorganic filler is a fluorine -containing resin composition comprising any one or a combination of at least two of SiO2 , Al2O3 , TiO2 , AlN, BN , Si3N4 , SiC, BaSnO3 , hollow glass microbeads, cut glass fiber powder, or cut quartz fiber powder.
2. In Article 1, The above-mentioned inorganic filler comprises an inorganic filler treated with a silane coupling agent; The above silane coupling agent comprises a combination of a polar coupling agent and a non-polar coupling agent; The mass ratio of the polar coupling agent and the non-polar coupling agent is 1:5-1:1; The above-mentioned nonpolar coupling agent includes a fluorine-containing silane coupling agent; The above polar coupling agent comprises any one or a combination of at least two of an amine-based silane coupling agent, an epoxy-based silane coupling agent, a boric acid ester coupling agent, a zirconate coupling agent, or a phosphate coupling agent; The amount of silane coupling agent used in the inorganic filler treated with the above silane coupling agent accounts for 0.05 wt% to 5 wt% of the above inorganic filler; A fluorine-containing resin composition comprising a magnetic material content of the above-mentioned inorganic filler that is less than 50 ppm.
3. In Article 1, The above fluorine-containing polymer is a fluorine-containing resin composition comprising any one or at least two combinations of polytetrafluoroethylene, polyperfluoroethylene-propylene, tetrafluoroethylene-perfluoroalkoxyvinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polytrifluorochloroethylene, ethylene-trifluorochloroethylene copolymer and derivatives, or polyvinylidene difluoride and derivatives.
4. In Article 1, The above fluorine-containing resin composition further comprises a surfactant, and The above surfactant includes a nonionic surfactant; A fluorine-containing resin composition characterized by the amount of the above surfactant added being 1 wt% to 10 wt%.
5. A resin adhesive liquid comprising a fluorine-containing resin composition and a solvent according to claim 1.
6. A fluorine-containing dielectric sheet containing a fluorine-containing resin composition according to claim 1.
7. A laminate comprising at least one fluorine-containing dielectric sheet according to claim 6.
8. A copper clad laminate comprising at least one fluorine-containing dielectric sheet according to claim 6 and a metal foil coated on one or both sides of the fluorine-containing dielectric sheet after lamination.
9. A printed circuit board comprising a laminate according to claim 7 or a copper clad laminate according to claim 8.
10. delete

Description

Fluorine-containing resin composition and resin adhesive containing the same, fluorine-containing dielectric sheet, laminate, copper clad laminate and printed circuit board The present invention relates to the field of communication materials technology, and in particular to a fluorine-containing resin composition and a resin adhesive containing the same, a fluorine-containing dielectric sheet, a laminate, a copper clad laminate, and a printed circuit board. Copper clad laminates are widely used in fields such as mobile phones, computers, vending machines, telecommunication base stations, satellites, wearable devices, autonomous vehicles, drones, and intelligent robots, and are one of the core basic materials of the electronics, telecommunications, and information industries. Fluorine-containing resins, represented by polytetrafluoroethylene (PTFE), possess superior performance characteristics—such as low dielectric constant, low dielectric loss, high thermal stability, and chemical stability—unlike other polymer resins, making them ideal matrix materials for copper clad laminates. Since the invention of PTFE-based copper clad laminates in the 1950s, researchers have gradually improved manufacturing processes through continuous optimization of constituent components and parameters. Because the polymer chains of fluorine-containing resins are highly flexible, reinforcing materials such as glass fibers are often introduced to enhance the mechanical strength of fluorine-containing resin-based copper clad laminates. In addition, the dielectric constant of the fluorine-containing resin itself is very low (Dk≤2.2), and the dielectric constant of glass fiber is generally only about 6.5. Furthermore, the use of a large amount of glass fiber in the substrate manufacturing process also limits the addition of large amounts of other inorganic fillers to the fluorine-containing resin matrix, which has made it extremely difficult to produce low-dielectric fluorine-containing resin-based copper clad laminates. Of course, research on glass fiber-reinforced fluorine-containing resin-based copper clad laminates has also taken place. CN104175686A discloses a method for manufacturing a PTFE composite organic substrate, wherein a dispersion is prepared by mixing a fluoropolymer emulsion, an inorganic filler, and a thickener, the dispersion is coated onto a release-capable substrate and baked, the resin layer and the substrate are separated, and a composite dielectric substrate is manufactured through processes such as cutting, overlapping, and sintering. US4335180A discloses a microwave circuit board and a method for manufacturing a microwave circuit board, wherein a fluorine-containing resin mixture is obtained by sequentially mixing microfibers, an inorganic filler, and a coagulant into a PTFE emulsion, followed by steps such as filtration and drying, and is manufactured into a plate by pressing, and then overlapped with a copper foil and pressed again to obtain a glass-free fiber-reinforced fluorine-containing resin-based copper clad laminate. However, the problem with the aforementioned patent application is that the interaction between the unmodified inorganic filler and the fluorine-containing resin matrix is very poor; in particular, when the amount of inorganic filler added is large, the dispersibility of the inorganic filler within the matrix is very poor, the non-uniformity of the plate dielectric performance is very severe, and the mechanical performance is difficult to meet actual usage requirements. Therefore, this field must address the problem of reduced interaction force between unmodified inorganic fillers and the PTFE resin matrix, as well as the problem of degraded electrical performance and reduced dielectric strength resulting from the addition of large amounts of inorganic fillers to the PTFE resin system. The first objective of the present invention is to provide a fluorine-containing resin composition, and even if the inorganic filler in the fluorine-containing resin composition is not modified or the amount added is large, it is possible to ensure that a plate obtained by manufacturing the fluorine-containing resin composition has excellent dielectric performance and dielectric strength performance. To achieve the said objective, the present invention adopts the following technical solution. The present invention provides a fluorine-containing resin composition, wherein the fluorine-containing resin composition comprises 30 wt%-70 wt% of a fluorine-containing polymer and 30 wt%-70 wt% of an inorganic filler as compositional components; and the inorganic filler comprises a particle size distribution in which D10 is greater than 1.5 μm and D50 is 10-15 μm. The present invention ensures that a plate obtained by manufacturing a fluorine-containing resin composition possesses excellent dielectric performance and dielectric strength even when the amount of inorganic filler added is high (30 wt%-70 wt%) by add