Fluorine-Containing Resin Composition, and Resin Vanish, Fluorine-Containing Dielectric Sheet, Laminate, Copper Clad Laminate and Printed Circuit Board Containing the Same

Abstract

The present invention relates to a fluorine-containing resin composition, and a resin vanish, a fluorine-containing dielectric sheet, a laminate, a copper clad laminate and a printed circuit board containing the same. The fluorine-containing resin composition comprises 30 wt. %-70 wt. % of a fluorine-containing polymer, 30 wt. %-70 wt. % of an inorganic filler which includes the following particle size distribution: D10 is greater than 1.5 μm; and D50 is 10-15 μm. In the present invention, the selection of an inorganic filler with a specific particle size distribution can ensure that the boards prepared by the fluorine-containing resin composition have excellent dielectric properties and voltage resistance performance, even if the inorganic filler is added in a large amount.

Claims

1. A fluorine-containing resin composition, comprising 30 wt. %-70 wt. % of a fluorine-containing polymer, and 30 wt. %-70 wt. % of an inorganic filler, wherein the inorganic filler includes the following particle size distribution: D10 is greater than 1.5 μm; and D50 is 10-15 μm.

2. The fluorine-containing resin composition claimed in claim 1, wherein the inorganic filler further includes the following particle size distribution: D90 is less than 30 μm; and D100 is less than 50 μm.

3. The fluorine-containing resin composition claimed in claim 1 wherein the inorganic filler comprises an inorganic filler treated with a silane coupling agent.

4. The fluorine-containing resin composition claimed in claim 1, wherein the fluorine-containing polymer is any one selected from the group consisting of polytetrafluoroethylene, polyperfluoroethylene propylene, tetrafluoro-ethylene-perfluoroalkoxy vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer and derivatives thereof, polyvinylidene fluoride and derivatives thereof, and a combination of at least two selected therefrom.

5. The fluorine-containing resin composition claimed in claim 1, wherein the fluorine-containing resin composition further comprises a surfactant the surfactant is added in an amount of 1 wt. %-10 wt. %.

6. (canceled)

7. A fluorine-containing dielectric sheet comprising the fluorine-containing resin composition claimed in claim 1.

8. (canceled)

9. A copper clad laminate comprising at least one fluorine-containing dielectric sheet claimed in claim 7 and metal foil(s) covered on one or both sides of the laminated fluorine-containing dielectric sheet.

10. A printed circuit board comprising the copper clad laminate claimed in claim 9.

11. The fluorine-containing resin composition claimed in claim 1, wherein the inorganic filler has a specific surface area less than or equal to 3.0 m.sup.2/g.

12. The fluorine-containing resin composition claimed in claim 1, wherein the inorganic filler is a spherical inorganic filler.

13. The fluorine-containing resin composition claimed in claim 1, wherein the inorganic filler comprises any one of SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, BaTiO.sub.3, SrTiO.sub.3, AlN, BN, Si.sub.3N.sub.4, SiC, CaTiO.sub.3, ZnTiO.sub.3, BaSnO.sub.3, hollow glass beads, chopped glass fiber powder, chopped quartz fiber powder, and a combination of at least two selected therefrom.

14. The fluorine-containing resin composition claimed in claim 3, wherein the silane coupling agent comprises a combination of a polar coupling agent and a non-polar coupling agent.

15. The fluorine-containing resin composition claimed in claim 14, wherein the polar coupling agent and the non-polar coupling agent has a mass ratio of 1:5-1:1.

16. The fluorine-containing resin composition claimed in claim 14, wherein the non-polar coupling agent comprises a fluorine-containing silane coupling agent.

17. The fluorine-containing resin composition claimed in claim 14, wherein the polar coupling agent comprises any one selected from the group consisting of an amino silane coupling agent, an epoxy silane coupling agent, a borate coupling agent, a zirconate coupling agent, a phosphate coupling agent, and a combination of at least two selected therefrom.

18. The fluorine-containing resin composition claimed in claim 14, wherein the silane coupling agent comprises a combination of a fluorine-containing silane coupling agent and an epoxy silane coupling agent.

19. The fluorine-containing resin composition claimed in claim 3, wherein the amount of the silane coupling agent in the inorganic filler treated with a silane coupling agent accounts for 0.05 wt. % to 5 wt. % of the inorganic filler.

20. The fluorine-containing resin composition claimed in claim 1, wherein the magnetic substance content of the inorganic filler is less than 50 ppm.

21. The fluorine-containing resin composition claimed in claim 1, wherein the fluorine-containing polymer is any one selected from the group consisting of polytetrafluoroethylene, polyperfluoroethylene propylene, tetrafluoro-ethylene-perfluoroalkoxy vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer and derivatives thereof, polyvinylidene fluoride and derivatives thereof, and a combination of at least two selected therefrom.

22. The fluorine-containing resin composition claimed in claim 1, wherein the fluorine-containing resin composition further comprises a surfactant; the surfactant is added in an amount of 1 wt. %-10 wt. %.

Description

EXAMPLE 1

[0059] This example provides a fluorine-containing resin composition comprising the following components: a PTFE resin (247.5 g), an inorganic filler A (300 g), and a thickener (4 g).

[0060] The method for the preparation of the above-mentioned fluorine-containing resin composition comprised taking 450 g of a PTFE resin emulsion (with a particle size of 0.25 μm, a resin content of 55 wt. %, produced by Japan Daikin Industries, brand name: D210C), adding 300 g of an inorganic filler A and 4 g of a thickener (Polyoxyethylene distyrenated phenyl ether, Kao Co., Ltd., brand name: EMULGEN A-60), stirring and mixing for 2 h to obtain a resin vanish of the fluorine-containing resin composition.

[0061] This example also provides a copper clad laminate, and the preparation method is as follows.

[0062] The above resin vanish was coated on a surface of a PI film with a coater, and a resin layer with a thickness of 129 μm was coated to obtain a glued PI film. The glued PI film was placed in a vacuum oven at 100° C., baked for 1 h to remove water, baked at 260° C. for 1 h to remove additives, and baked at 350° C. for 10 min. After cooling, the resin layer was peeled off from the PI film to obtain a resin layer with uniform thickness and good appearance. In order to produce a board having a thickness of 0.127 mm, two PTFE resin layers having a thickness of 129 μm were laminated with a size of 250×250 mm. The top and bottom of the laminated resin layers were covered with a copper foil having a thickness of 1 OZ for lamination. The pressure was about 400 PSI, and the maximum temperature and retention time were 380° C./60 min, to obtain a PTFE copper clad laminate.

EXAMPLE 2

[0063] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler B of equal mass.

EXAMPLE 3

[0064] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler A which was surface-modified with a silane coupling agent, wherein the silane coupling agent was a combination of a polar coupling agent (Perfluorosilane, Sico Performance Material (Shandong) Co., Ltd., F823) and a non-polar coupling agent (a silane coupling agent with epoxy groups, Shin-Etsu Chemical, product name KBM403) with a mass ratio of 1:3; and the amount of the silane coupling agent was 0.5% of the mass of the inorganic filler A.

EXAMPLE 4

[0065] The only difference from Example 3 is that the silane coupling agent was a non-polar coupling agent (Perfluorosilane, Sico Performance Material (Shandong) Co., Ltd., F823) with an amount of 0.5% of the mass of the inorganic filler A.

EXAMPLE 5

[0066] The only difference from Example 3 is that the silane coupling agent was a polar coupling agent (a silane coupling agent with epoxy groups, Shin-Etsu Chemical, product name KBM403) with an amount of 0.5% of the mass of the inorganic filler A.

EXAMPLE 6-9

[0067] The only difference from Example 3 is that the mass ratios of the polar coupling agent to the non-polar coupling agent were 1:1 (Example 6), 1:2 (Example 7), 1:4 (Example 8) and 1:5 (Example 9).

EXAMPLE 10

[0068] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler C of equal mass.

EXAMPLE 11

[0069] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler 1 of equal mass.

EXAMPLE 12

[0070] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler J of equal mass.

EXAMPLE 13

[0071] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler K of equal mass.

EXAMPLE 14

[0072] This example provides a fluorine-containing resin composition comprising the following components: a PTFE resin (300 g) and an inorganic filler A (696 g).

[0073] The preparation method of the above fluorine-containing resin composition was the same as that of Example 1, except that 545 g of a PTFE resin emulsion was taken.

[0074] This example also provides a copper clad laminate, and the preparation method was the same as that of Example 1.

EXAMPLE 15

[0075] This example provides a fluorine-containing resin composition, which is different from Example 1 only in that the fluorine-containing resin composition further contained a tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (448.5 g).

[0076] The preparation method of the above-mentioned fluorine-containing resin composition was the same as that of Example 1, except that it further included taking 200 g of the tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (purchased from Sichuan Chenguang, brand name: PFA-E50, having a solid content of 50%) to mix with 634 g of a PTFE resin emulsion (with a particle size of 0.25 μm, a resin content of 55 wt. %, produced by Japan Daikin Industries, brand name: D210C).

[0077] This example also provides a copper clad laminate, and the preparation method was the same as that in Example 1.

EXAMPLE 16

[0078] The only difference from Example 15 is that the inorganic filler A was replaced with an inorganic filler L of equal mass.

EXAMPLE 17

[0079] The only difference from Example 15 is that the inorganic filler A was replaced with an inorganic filler M of equal mass.

EXAMPLE 18

[0080] The only difference from Example 15 is that the inorganic filler A was replaced with an inorganic filler N of equal mass.

COMPARATIVE EXAMPLE 1

[0081] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler D of equal mass.

COMPARATIVE EXAMPLE 2

[0082] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler E of equal mass.

COMPARATIVE EXAMPLE 3

[0083] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler F of equal mass.

COMPARATIVE EXAMPLE 4

[0084] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler G of equal mass.

COMPARATIVE EXAMPLE 5

[0085] The only difference from Example 1 is that the inorganic filler A was replaced with an inorganic filler H of equal mass.

Performance Tests

[0086] For the above indicators, the copper clad laminates prepared in the examples and comparative examples were subjected to the following performance tests.

[0087] (1) Dk and Df test: tested by the SPDR (splite post dielectric resonator) method with a test condition of A state and a frequency of 10 GHz.

[0088] (2) Breakdown voltage test: IPC-TM-650 2.5.6 method.

[0089] (3) Particle size test: tested with Malvern 2000 laser particle size analyzer.

[0090] (4) Specific surface area test: tested with American Micromeritics model GEMINI VII2390(A) analyzer.

[0091] (5) Magnetic substance test: dispersing 300 g of an inorganic filler in water, adsorbing in a beaker with a 4000 Gauss magnet, weighing the adsorbed substance.

[0092] The results of the above tests are shown in Table 2.

TABLE-US-00002 TABLE 2 Breakdown Dk (10 GHz) Df (10 GHz) voltage (KV) Example 1 2.97 0.0009 55 Example 2 3.02 0.0008 56 Example 3 3.01 0.0006 60 Example 4 2.99 0.0006 55 Example 5 2.98 0.0009 50 Example 6 2.97 0.0008 60 Example 7 2.97 0.0007 65 Example 8 2.98 0.0006 60 Example 9 2.99 0.0007 60 Example 10 3.01 0.0008 52 Example 11 2.99 0.0009 52 Example 12 2.99 0.0010 51 Example 13 2.95 0.0010 50 Example 14 3.15 0.0010 50 Example 15 2.85 0.0007 50 Example 16 2.75 0.0007 55 Example 17 2.80 0.0008 56 Example 18 2.78 0.0009 56 Comp. Exmp. 1 3.20 0.0015 35 Comp. Exmp. 2 3.23 0.0013 25 Comp. Exmp. 3 2.99 0.0009 45 Comp. Exmp. 4 2.96 0.0011 40 Comp. Exmp. 5 2.98 0.0013 30

[0093] It can be seen from Table 2 that the fluorine-containing resin composition provided by the present invention, even if the inorganic filler is unmodified or added in a large amount, can ensure that the prepared board has excellent dielectric properties and voltage resistance performance, so as to meet various performance requirements in the high-frequency and high-speed communication fields, such as diversified and complicated functions of copper clad laminate materials, the high-density and multi-layer wiring layout, etc.

[0094] Since the inorganic filler used in Comparative Example 1 has a small particle size, especially a large number of small particles, the interface between the inorganic material and the PTFE resin in the copper clad laminate is large, resulting in a great dielectric loss. In Comparative Example 2, the breakdown voltage performance of the board deteriorates due to the large particle size of the inorganic filler. In addition, the relatively high content of magnetic substance existing in fillers in Comparative Examples 1 and 2 will also cause large dielectric loss.

[0095] In addition, only D10 of the inorganic filler in Comparative Example 3 is not within the scope of the present invention, and only D50 of the inorganic fillers in Comparative Examples 4-5 is not within the scope of the present invention. The resulting copper clad laminates are inferior in dielectric properties and voltage resistance performance as compared with those in the examples. It thus proves that the present invention effectively improves the dielectric properties and voltage resistance performance of the copper clad laminate by selecting a specific particle size distribution.

[0096] By comparing Examples 3-5, it can be seen that using a combination of a polar coupling agent and a non-polar coupling agent to modify an inorganic filler (Example 3) can further improve the dielectric properties and voltage resistance performance of the copper clad laminate, as compared with the modification processed by a single type of coupling agent (Examples 4 and 5).

[0097] By comparing Examples 1, 11 and 12, it can be seen that when the D90 of the inorganic filler is less than 30 μm, and the D100 is less than 50 μm (Example 1), the dielectric properties and voltage resistance performance of the copper clad laminate can be further improved. If D90 is greater than 30 μm (Example 11), or D100 is greater than 50 μm (Example 12), it will result in poor dielectric properties and voltage resistance performance.

[0098] By comparing Example 1 and Example 13, it can be seen that in the fluorine-containing polymer system, the spherical inorganic filler (Example 1) is more conducive to improving the dielectric properties and voltage resistance performance of copper clad laminates than other shapes (Example 13).

[0099] The present invention illustrates the detailed methods of the present invention with the above-mentioned examples. However, the present invention is not limited to the above-mentioned detailed methods, which means that the present invention does not have to rely on the above-mentioned detailed methods to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, selection of specific methods and etc. all fall within the scope of protection and disclosure of the present invention.