CN114516993A - PTFE (polytetrafluoroethylene) -hollow glass microsphere composite material as well as preparation method and application thereof - Google Patents
PTFE (polytetrafluoroethylene) -hollow glass microsphere composite material as well as preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 150
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 26
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 26
- -1 polytetrafluoroethylene Polymers 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 42
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- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
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- 239000000919 ceramic Substances 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a PTFE-hollow glass microsphere composite material and a preparation method and application thereof. The preparation method of the PTFE-hollow glass microsphere composite material comprises the following steps: (1) mixing PTFE particles and hollow glass microspheres according to a certain mass ratio to obtain a dry mixture; (2) adding a lubricant into the dry mixture obtained in the step (1), and stirring to uniformly mix the mixture to obtain a wet mixture; (3) and (3) pressing the wet mixed material prepared in the step (2) into sheets to obtain the PTFE-hollow glass microsphere composite material. The PTFE-hollow glass microsphere composite material prepared by the invention has the advantages of uniform performance, low dielectric constant and low dielectric loss, and is suitable for preparing printed circuit boards in the 5G field.
Description
Technical Field
The invention relates to the technical field of printed circuit boards, in particular to a PTFE-hollow glass microsphere composite material and a preparation method and application thereof.
Background
The 5G communication technology breaks through the limitation of the prior art in many fields by virtue of the characteristics of high-speed mass data transmission, low delay and the like exceeding 4G, and shows huge revolutionary application prospects, such as the interconnection of everything, the analysis and transmission of automatic driving real-time road condition video information, unmanned aerial vehicle control and data transmission, military radar and the like. This technology has become an advanced technology system in competition among countries in the world and will create immeasurable enormous value, but it places extremely demanding performance requirements on existing hardware facilities. Because the 5G communication adopts a high-frequency communication mode, signal transmission is fast and delay is low at high frequency, but the defects are that signal loss is serious and signal transmission distance is short, and the research and development of a novel low-dielectric-loss printed circuit board becomes an irreparable key technology on the way of popularizing 5G.
Polytetrafluoroethylene (PTFE) is the first choice for a 5G low dielectric loss material because of its excellent dielectric loss resistance due to its special molecular structure. Since PTFE has a large thermal expansion coefficient (109X 10)-6K-1) And the size stability is poor, so that the PTFE is filled with ceramic powder such as titanium dioxide, aluminum oxide, silicon nitride, silicon dioxide and the like so as to reduce the overlarge thermal expansion coefficient of the PTFE, and the dielectric constant of the PTFE copper-clad plate is regulated and controlled according to the application requirement. However, the PTFE composite material prepared by filling PTFE with ceramic powder in the prior art often has the problems of poor homogeneity, high dielectric constant, high dielectric loss and the like, and cannot meet the requirements of 5G low dielectric loss materials. Therefore, it is necessary to develop a PTFE composite material having a low dielectric constant and a low dielectric loss.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims at providing a PTFE-hollow glass microsphere composite material and a preparation method and application thereof.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a PTFE-hollow glass microsphere composite material. The preparation method comprises the following steps:
(1) mixing PTFE particles and hollow glass microspheres according to a certain mass ratio to obtain a dry mixture;
(2) adding a lubricant into the dry mixture obtained in the step (1), and stirring to uniformly mix the mixture to obtain a wet mixture;
(3) and (3) pressing the wet mixed material prepared in the step (2) into sheets to obtain the PTFE-hollow glass microsphere composite material.
According to the preparation method, preferably, the content (mass percentage) of the hollow glass microspheres in the dry mixture is 0.1-20%. More preferably, the content (mass percentage) of the hollow glass microspheres in the dry mixture is 1-15%.
According to the preparation method, preferably, the particle size of the hollow glass microsphere is 8-25 μm, and the shell thickness of the hollow glass microsphere is 1-5 μm. More preferably, the particle size of the hollow glass microsphere is 10-20 μm. Most preferably, the hollow glass microspheres have a particle size of 15 μm.
According to the preparation method, the particle size of the PTFE particles is preferably 80-140 nm.
According to the above production method, preferably, in the step (3), the wet kneaded material is heated at 30 ℃ to (t-10) ° c for 5 to 60 minutes before the wet kneaded material is subjected to rolling treatment, t representing the boiling point of the lubricant. The heat treatment may be carried out in an oven.
According to the preparation method, the thickness of the PTFE-hollow glass microsphere composite material is preferably 10-1000 μm.
According to the preparation method, the dosage of the lubricant is preferably 5-35% of the total mass of the dry mixture.
According to the above production method, preferably, the lubricant is a lubricating oil, naphtha or ethanol. More preferably, the lubricating oil is Isopar G.
According to the preparation method, preferably, the wet mixture is pressed into a sheet shape in the step (3) by adopting a rolling treatment method, and the pressure of the rolling treatment is 5-30 MPa.
The invention provides a PTFE-hollow glass microsphere composite product, which is prepared by the preparation method of the first aspect.
In a third aspect, the invention provides a use of the PTFE-hollow glass microsphere composite product of the second aspect. The PTFE-hollow glass microsphere composite material product can be used for preparing copper clad plates or circuit boards; more preferably, the circuit board is a printed circuit board.
The fourth aspect of the invention provides a preparation method of a copper-clad plate. The preparation method comprises the following specific steps: stretching the PTFE-hollow glass microsphere composite material product of the second aspect at 100-300 ℃; and coating adhesive glue on the upper surface and the lower surface of the stretched PTFE-hollow glass microsphere composite material product, then respectively coating copper foils on the upper surface and the lower surface, and then carrying out thickness adjustment and hot pressing treatment to obtain the copper-clad plate.
According to the above production method, the stretching ratio of the stretching treatment is preferably 110% to 200%.
According to the above production method, preferably, the stretching treatment is transverse uniaxial stretching or longitudinal uniaxial stretching or transverse and longitudinal biaxial stretching. More preferably, the stretching ratio of the transverse uniaxial stretching is 110% to 200%; the stretching ratio of the longitudinal unidirectional stretching is 110-200%; when the fiber is stretched in both the transverse direction and the longitudinal direction, the stretching ratio of the transverse stretching is 110 to 200 percent, and the stretching ratio of the longitudinal stretching is 110 to 200 percent.
According to the preparation method, the pressure applied in the vacuum hot pressing process is preferably 100t to 1000 t.
According to the above preparation method, preferably, the adhesive glue is an epoxy resin.
According to the above preparation method, preferably, the thickness of the copper foil is 5 to 20 μm.
The fifth aspect of the invention provides a copper-clad plate. The copper-clad plate is prepared by the method for preparing the copper-clad plate in the fourth aspect.
According to the copper-clad plate, preferably, the thickness of the copper foil is 5-20 μm.
The sixth aspect of the invention provides an application of the copper-clad plate of the fifth aspect in a circuit board. The copper-clad plate can be used as a substrate material of a circuit board to prepare the circuit board. Preferably, the circuit board is a printed circuit board.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) according to the invention, PTFE particles and hollow glass microspheres are used as raw materials to prepare the PTFE-hollow glass microsphere composite material, the hollow glass microspheres in the prepared PTFE-hollow glass microsphere composite material are uniformly dispersed, and the spherical shape of the composite material is well maintained; moreover, the copper-clad plate prepared from the PTFE-hollow glass microsphere composite material has the dielectric constant of 1.66, the dielectric loss of only 0.00062 and the dielectric constant and the dielectric loss which are obviously lower than those of the existing commercial products. Therefore, the PTFE-hollow glass microsphere composite material prepared by the invention has the advantages of uniform performance, low dielectric constant and low dielectric loss, and is suitable for preparing printed circuit boards in the field of 5G.
(2) When the PTFE-hollow glass microsphere composite material is prepared, the mass percentage of the hollow glass microspheres in the dry mixture is controlled within the range of 0.1-20%, because when the content of the hollow glass microspheres in the dry mixture is lower than 0.1%, the dielectric constant is not obviously reduced due to too low content of the hollow glass microspheres, and the dielectric constant of the prepared PTFE-hollow glass microsphere composite material is higher; when the mass percentage content of the hollow glass microspheres in the dry mixture is controlled within the range of 0.1-20%, the prepared PTFE-hollow glass microsphere composite material has uniform texture and good dielectric property; when the content of the hollow glass microspheres exceeds 20%, the PTFE-hollow glass microsphere composite material prepared by the method is low in density, low in strength and poor in mechanical property due to excessive filling of the hollow glass microspheres, so that the PTFE-hollow glass microsphere composite material cannot be processed into a film and cannot be used for preparing a copper-clad plate.
(3) The wet mixed material is heated at 30-10 ℃ before being pressed, so that the lubricant can be promoted to be fully contacted with the PTFE particles and the hollow glass microspheres by heating, the lubricant can be uniformly covered on the surfaces of the PTFE particles and the hollow glass microspheres to play a role in protecting the PTFE particles and the hollow glass microspheres, and the built-in defects caused by scratching of the PTFE particles and the hollow glass microspheres by processing equipment in the pressing process can be effectively prevented.
(4) According to the invention, the hollow glass microspheres with the particle size of 8-25 microns and the shell thickness of 1-5 microns are selected as the filler to prepare the PTFE-hollow glass microsphere composite material, the hollow glass microspheres with the particle size can be uniformly dispersed in a PTFE matrix, the prepared PTFE-hollow glass microsphere composite material has good uniformity and high strength, and the copper-clad plate prepared from the PTFE-hollow glass microsphere composite material has low dielectric constant and low dielectric loss.
(5) When the copper-clad plate is prepared, the PTFE-hollow glass microsphere composite material product is respectively stretched transversely and longitudinally at the temperature of 100-300 ℃, and the stretching temperature is controlled at 100-300 ℃, so that the motion capability of a molecular chain is improved, the material is easier to stretch, and the molecular chain is prevented from being broken in the stretching process; and the stretching treatment can form micropore gaps in the PTFE-hollow glass microsphere composite material, and the existence of the micropore gaps can further reduce the dielectric constant and the thermal expansion coefficient of the composite material.
Drawings
FIG. 1 is a MicroCT representation of a PTFE-hollow glass microsphere composite material prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Study experiment on the amount of hollow glass microspheres
In order to study the influence of the amount of the hollow glass microspheres on the performance of the prepared PTFE-hollow glass microsphere composite material, the inventors conducted the following experiments, and the details of examples 1 to 8 and examples 1 to 8 are as follows.
Example 1:
a preparation method of a PTFE-hollow glass microsphere composite material comprises the following steps:
(1) mixing PTFE particles and hollow glass microspheres according to a certain mass ratio to obtain a dry mixture, wherein the mass percentage content of the hollow glass microspheres in the dry mixture is 0.1%, the granularity of the PTFE particles is 80-140nm, the particle size of the hollow glass microspheres is 15 microns, and the shell thickness of the hollow glass microspheres is 3 microns;
(2) adding a lubricant into the dry mixture obtained in the step (1), wherein the using amount of the lubricant is 20% of the total mass of the dry mixture, and stirring to uniformly mix to obtain a wet mixed material, wherein the lubricant is Isopar G;
(3) baking the wet mixed material prepared in the step (2) at 60 ℃ for 30min, putting the baked wet mixed material into a blank making machine, applying 1MPa pressure to form the wet mixed material into a blank with certain mechanical strength, putting the blank into a piston type extruder to extrude (the extrusion pressure is 20MPa), and obtaining a rectangular plate; and then, carrying out rolling treatment on the rectangular plate (the pressure is 25MPa) to prepare the PTFE-hollow glass microsphere composite material with the thickness of 60 microns, thus obtaining the PTFE-hollow glass microsphere composite material product.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment.
The preparation method of the copper-clad plate comprises the following steps: respectively carrying out transverse stretching and longitudinal stretching on the PTFE-hollow glass microsphere composite material product at the temperature of 200 ℃, wherein the stretching ratio of the transverse stretching is 150%, and the stretching ratio of the longitudinal stretching is 150%; coating epoxy resin (the thickness of the epoxy resin is 5 mu m) on the upper surface and the lower surface of the stretched PTFE-hollow glass microsphere composite material product, then respectively covering copper foils (the thickness of the copper foils is 18 mu m) on the upper surface and the lower surface of the PTFE-hollow glass microsphere composite material product coated with the epoxy resin, and carrying out thickness adjustment and vacuum hot-pressing treatment at 200 ℃ for 2h to completely cure the adhesive, thus obtaining the copper-clad plate.
Example 2:
the content of example 2 is substantially the same as that of example 1, except that: in the step (1), the mass percentage of the hollow glass microspheres in the dry mixture is 1%.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 3:
the content of example 3 is substantially the same as that of example 1, except that: in the step (1), the hollow glass microspheres in the dry mixture account for 5% by mass.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 4:
the content of example 4 is substantially the same as that of example 1, except that: the mass percentage of the hollow glass microspheres in the dry mixture in the step (1) is 10%.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 5:
the content of example 5 is substantially the same as that of example 1, except that: the mass percentage of the hollow glass microspheres in the dry mixture in the step (1) is 15%.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 6:
the contents of example 6 are substantially the same as those of example 1, except that: the mass percentage content of the hollow glass microspheres in the dry mixture in the step (1) is 20%.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 7:
example 7 is substantially the same as example 1 except that: the mass percentage of the hollow glass microspheres in the dry mixture in the step (1) is 25%.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 8:
the contents of example 8 are substantially the same as those of example 1, except that: the mass percentage of the hollow glass microspheres in the dry mixture in the step (1) is 30%.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
The copper-clad plate is prepared from the PTFE-hollow glass microsphere composite material prepared by the embodiment. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
The performance of the PTFE-hollow glass microsphere composite and the copper-clad plate prepared in the above examples 1 to 8 was tested, and the test results are shown in table 1.
TABLE 1 influence of hollow glass microsphere content on PTFE-hollow glass microsphere composite and copper-clad plate performance
As can be seen from table 1, when the content of the hollow glass microspheres in the dry mixture is in the range of 0.1% to 20%, the density and the breaking strength of the PTFE-hollow glass microsphere composite are gradually reduced with the increase of the content of the hollow glass microspheres; when the content of the hollow glass microspheres exceeds 20%, the prepared PTFE-hollow glass microsphere composite material has low strength and poor mechanical property, is very easy to break after being rolled, and cannot be used for preparing a copper-clad plate.
With the increase of the content of the hollow glass microspheres, the dielectric constant of the copper-clad plate tends to decrease first and then increase, the dielectric loss of the copper-clad plate gradually increases, and when the content of the hollow glass microspheres is within the range of 0.1-20%, the dielectric constant and the dielectric loss of the prepared copper-clad plate are both low, and the dielectric property is good; when the content of the hollow glass microspheres is 5%, the prepared PTFE-hollow glass microsphere composite material has high mechanical strength, the dielectric constant of the prepared copper-clad plate reaches the lowest value (1.80), and the dielectric loss is only 0.00079 when the dielectric loss is low.
The PTFE-hollow glass microsphere composite material prepared in the embodiment 3 is characterized by using MicroCT, and a MicroCT characterization result chart is shown in FIG. 1. As can be seen from FIG. 1, the hollow glass microspheres are uniformly dispersed in the PTFE substrate without agglomeration, and the PTFE-hollow glass microsphere composite material has uniform texture and good uniformity; moreover, the spherical profile of the hollow glass microspheres remained good, and the glass microspheres did not break.
Therefore, by integrating the performance of the PTFE-hollow glass microsphere composite material and the performance of the prepared copper-clad plate, the content of the hollow glass microspheres is preferably 0.1-20%; more preferably 1% to 15%, most preferably 5%.
(II) particle size discussion experiment of hollow glass microspheres:
in order to investigate the influence of the particle size of the hollow glass microspheres on the properties of the prepared PTFE-hollow glass microsphere composite, the inventors conducted the following experiments, and the details of examples 9 to 13 and examples 9 to 13 are as follows.
Example 9:
example 9 is substantially the same as example 1 except that: in the step (1), the dry mixture contains 5% by mass of hollow glass microspheres, the particle size of the hollow glass microspheres is 8 μm, and the shell thickness of the hollow glass microspheres is 3 μm.
Example 10:
the contents of example 10 are substantially the same as those of example 1, except that: in the step (1), the dry mixture contains 5% by mass of hollow glass microspheres, the particle size of the hollow glass microspheres is 10 μm, and the shell thickness of the hollow glass microspheres is 3 μm.
Example 11:
example 11 is substantially the same as example 1 except that: in the step (1), the dry mixture contains 5% by mass of hollow glass microspheres, the particle size of the hollow glass microspheres is 20 μm, and the shell thickness of the hollow glass microspheres is 3 μm.
Example 12:
the contents of example 12 are substantially the same as those of example 1, except that: in the step (1), the dry mixture contains 5% by mass of hollow glass microspheres, the particle size of the hollow glass microspheres is 25 μm, and the shell thickness of the hollow glass microspheres is 3 μm.
Example 13:
the contents of example 13 are substantially the same as those of example 1, except that: in the step (1), the dry mixture contains 5% by mass of hollow glass microspheres, the particle size of the hollow glass microspheres is 30 μm, and the shell thickness of the hollow glass microspheres is 3 μm.
The performance of the PTFE-hollow glass microsphere composite and the copper-clad plate prepared in the above examples 9 to 13 were tested, and the test results are shown in table 2.
TABLE 2 influence of particle size of hollow glass microsphere on the performance of PTFE-hollow glass microsphere composite material and copper-clad plate
As shown in Table 2, as the particle size of the hollow glass microsphere increases, the volume of the inner cavity of the hollow glass microsphere increases gradually, which results in a decrease in the dielectric constant of the composite material. However, the mechanical property of the PTFE-hollow glass microsphere composite material is reduced due to the excessively large particle size, and the PTFE-hollow glass microsphere composite material is easy to crack in the rolling process, so that the performance of the PTFE-hollow glass microsphere composite material is affected. Therefore, the particle size of the hollow glass microspheres is preferably 8-25 μm by combining the performance of the PTFE-hollow glass microsphere composite material and the performance of the prepared copper-clad plate; more preferably 10-20 μm.
(III) discussion experiment of stretching treatment in copper-clad plate preparation process
In order to research the influence of the stretching treatment in the preparation process of the copper-clad plate on the performance of the prepared copper-clad plate, the inventor carries out the following experiments, and the specific contents of the examples 14 to 16 are as follows.
Example 14:
a preparation method of a copper-clad plate comprises the following specific operations: transversely and unidirectionally stretching the PTFE-hollow glass microsphere composite material product prepared in example 3 at 200 ℃, wherein the stretching ratio of transverse unidirectional stretching is 150%; coating epoxy resin (the thickness of the epoxy resin is 5 micrometers) on the upper surface and the lower surface of the stretched PTFE-hollow glass microsphere composite product, then respectively covering copper foils (the thickness of the copper foils is 18 micrometers) on the upper surface and the lower surface of the PTFE-hollow glass microsphere composite product coated with the epoxy resin, and carrying out thickness adjustment and vacuum hot-pressing treatment at 200 ℃ for 2 hours to completely cure the adhesive, thus obtaining the copper-clad plate.
Example 15:
example 15 is the same as example 14 except that: the PTFE-hollow glass microsphere composite product prepared in example 3 was longitudinally uniaxially stretched at 200 ℃ at a stretch ratio of 150%.
Example 16:
a preparation method of a copper-clad plate comprises the following specific operations: epoxy resin (the thickness of the epoxy resin is 5 μm) is coated on the upper surface and the lower surface of the PTFE-hollow glass microsphere composite material product prepared in the embodiment 3, then copper foils (the thickness of the copper foils is 18 μm) are respectively coated on the upper surface and the lower surface of the PTFE-hollow glass microsphere composite material product coated with the epoxy resin, and the copper clad laminate is obtained by adjusting the thickness and carrying out vacuum hot pressing treatment at 200 ℃ for 2h to completely cure the adhesive.
The copper-clad plates prepared in the above examples 14 to 16 were subjected to performance testing, and the test results are shown in table 3.
TABLE 3 influence of stretching treatment on the copper clad laminate Properties
As can be seen from table 3, the dielectric constant of the copper-clad plate prepared by stretching treatment is significantly higher than that of the copper-clad plate prepared without stretching treatment, because the stretching treatment can form a micropore gap inside the PTFE-hollow glass microsphere composite material, and the existence of the micropore gap can further reduce the dielectric constant of the composite material; compared with unidirectional stretching, the copper-clad plate prepared by transverse and longitudinal bidirectional stretching treatment has lower dielectric constant because the bidirectional stretching can form more micropore gaps in the composite material, thereby improving the porosity of the composite film and reducing the dielectric constant of the composite film.
(IV) research experiment of transverse stretching ratio and longitudinal stretching ratio in copper-clad plate preparation process
In order to research the influence of the transverse stretching ratio and the longitudinal stretching ratio on the performance of the prepared copper-clad plate in the preparation process of the copper-clad plate, the inventor carries out the following experiments and specific contents of examples 17 to 21 are as follows.
Example 17:
a preparation method of a copper-clad plate comprises the following specific operations: respectively stretching the PTFE-hollow glass microsphere composite material product prepared in the example 3 in the transverse direction and the longitudinal direction at the temperature of 200 ℃, wherein the stretching ratio of the transverse stretching is 110 percent, and the stretching ratio of the longitudinal stretching is 110 percent; coating epoxy resin (the thickness of the epoxy resin is 5 mu m) on the upper surface and the lower surface of the stretched PTFE-hollow glass microsphere composite material product, then respectively covering copper foils (the thickness of the copper foils is 18 mu m) on the upper surface and the lower surface of the PTFE-hollow glass microsphere composite material product coated with the epoxy resin, and carrying out thickness adjustment and vacuum hot-pressing treatment at 200 ℃ for 2h to completely cure the adhesive, thus obtaining the copper-clad plate.
Example 18:
example 18 is the same as example 17 except that: the stretching ratio in the transverse direction was 170%, and the stretching ratio in the longitudinal direction was 170%.
Example 19:
example 19 is the same as example 17 except that: the draw ratio in the transverse direction was 200%, and the draw ratio in the longitudinal direction was 200%.
Example 20:
example 20 is the same as example 17 except that: the stretching ratio in the transverse direction was 220%, and the stretching ratio in the longitudinal direction was 220%.
Example 21:
example 21 is the same as example 17 except that: the stretching ratio in the transverse direction was 250% and the stretching ratio in the longitudinal direction was 250%.
The copper-clad plates prepared in the above examples 17 to 21 were subjected to performance testing, and the test results are shown in table 4.
TABLE 4 influence of transverse and longitudinal stretching ratio on the copper clad laminate performance
It can be seen from table 4 that the dielectric properties of the final copper-clad plate can be improved by proper stretching because the increase of the porosity is helpful to reduce the dielectric constant and the dielectric loss of the material, but when the stretching ratio is greater than 200%, the dielectric properties are reduced because the overstretching can destroy the original pore structure to cause the collapse of the pore wall and the closure of the pores. Therefore, the stretching ratio in the transverse and longitudinal directions in the present invention is preferably 200%.
And (V) comparing the performance of the copper-clad plate prepared by the invention with that of the existing commercial copper-clad plate:
taking the copper-clad plate prepared in the embodiment 19 of the invention as an example, the performance of the copper-clad plate is compared with the copper-clad plate produced by Rogers and Takangli, and the comparison result is shown in Table 5.
TABLE 5 comparison of the Performance of the copper clad laminate prepared in accordance with the present invention with that of the existing commercial copper clad laminate
As can be seen from Table 5, the dielectric constant and dielectric loss of the copper clad laminate prepared by the invention are significantly lower than those of the existing commercial products. Compared with the existing commercial products, the copper-clad plate prepared by the invention has obvious advantages in dielectric property.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the PTFE-hollow glass microsphere composite material is characterized by comprising the following steps:
(1) mixing PTFE particles and hollow glass microspheres according to a certain mass ratio to obtain a dry mixture;
(2) adding a lubricant into the dry mixture obtained in the step (1), and stirring to uniformly mix the mixture to obtain a wet mixture;
(3) and (3) pressing the wet mixed material prepared in the step (2) into sheets to obtain the PTFE-hollow glass microsphere composite material.
2. The method according to claim 1, wherein the hollow glass microspheres are contained in the dry mixture in an amount of 0.1% to 20%.
3. The preparation method according to claim 2, wherein the particle size of the hollow glass microspheres is 8 to 25 μm, and the shell thickness of the hollow glass microspheres is 1 to 5 μm.
4. The preparation method according to claim 2, wherein in the step (3), the wet mixture is heated at 30 ℃ to (t-10) ° c for 5 to 60 minutes before being subjected to the compression treatment, t representing the boiling point of the lubricant; the thickness of the PTFE-hollow glass microsphere composite material is 10-1000 μm.
5. A PTFE-hollow glass microsphere composite product prepared by the preparation method of any one of claims 1 to 4.
6. The PTFE-hollow glass microsphere composite product of claim 5, which is applied to copper clad laminate or circuit board.
7. A preparation method of a copper-clad plate is characterized by comprising the following steps: stretching the PTFE-hollow glass microsphere composite product of claim 5 at 100 ℃ to 300 ℃; and coating adhesive glue on the upper surface and the lower surface of the stretched PTFE-hollow glass microsphere composite material product, then respectively coating copper foils on the upper surface and the lower surface, and then carrying out thickness adjustment and hot pressing treatment to obtain the copper-clad plate.
8. The method according to claim 7, wherein the stretching ratio of the stretching treatment is 110% to 200%; the stretching treatment is transverse unidirectional stretching or longitudinal unidirectional stretching or transverse and longitudinal bidirectional stretching.
9. A copper-clad plate product prepared by the preparation method of claim 7 or 8.
10. The use of the copper clad laminate product of claim 9 in circuit boards.
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| EP0304699A2 (en) * | 1987-08-28 | 1989-03-01 | Junkosha Co. Ltd. | Composite material of low dielectric constant and method of producing it |
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| EP0304699A2 (en) * | 1987-08-28 | 1989-03-01 | Junkosha Co. Ltd. | Composite material of low dielectric constant and method of producing it |
| JP2002305373A (en) * | 2001-04-09 | 2002-10-18 | Sumitomo Electric Fine Polymer Inc | High-frequency circuit board or antenna substrate, and manufacturing method thereof |
| JP2007027396A (en) * | 2005-07-15 | 2007-02-01 | Japan Gore Tex Inc | Circuit board and its production method |
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