CN114516993B - PTFE-hollow glass microsphere composite material and preparation method and application thereof - Google Patents
PTFE-hollow glass microsphere composite material and preparation method and application thereof Download PDFInfo
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- CN114516993B CN114516993B CN202011311278.2A CN202011311278A CN114516993B CN 114516993 B CN114516993 B CN 114516993B CN 202011311278 A CN202011311278 A CN 202011311278A CN 114516993 B CN114516993 B CN 114516993B
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- 239000011521 glass Substances 0.000 title claims abstract description 148
- 239000004005 microsphere Substances 0.000 title claims abstract description 148
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract 2
- 238000011282 treatment Methods 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000011889 copper foil Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 5
- 230000002457 bidirectional effect Effects 0.000 claims description 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical group CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000003490 calendering Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 description 13
- 229920000647 polyepoxide Polymers 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004891 communication Methods 0.000 description 4
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- 239000011148 porous material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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 mixed material; (2) Adding a lubricant into the dry blend in the step (1), and stirring to uniformly mix to obtain a wet blend; (3) And (3) pressing the wet mixed material prepared in the step (2) into a sheet shape to obtain the PTFE-hollow glass microsphere composite material. The PTFE-hollow glass microsphere composite material prepared by the invention has 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 limitations of the prior art in a plurality of fields by virtue of the characteristics of high-speed mass data transmission, low delay and the like of the 5G communication technology exceeding 4G, and shows great revolutionary application prospects, such as everything interconnection, automatic driving real-time road condition video information analysis and transmission, unmanned plane control and data transmission, military radar and the like. This technology has become a high point of technology for world-wide world competition and will create immeasurable great value, but it places extremely demanding performance demands on existing hardware facilities. Because the 5G communication adopts a high-frequency communication mode, the signal transmission is fast and the delay is low under the high frequency, but the defects are serious signal loss and short signal transmission distance, and the research and development of a novel low dielectric loss printed circuit board has become an indistinct key technology on the way of popularizing 5G.
Poly (tetra)Vinyl fluoride (PTFE) is the first choice for 5G low dielectric loss materials because of its excellent dielectric loss resistance due to its particular molecular structure. Since PTFE itself has a large thermal expansion coefficient (109X 10 -6 K -1 ) And the dimensional stability is poor, so that ceramic powder such as titanium dioxide, aluminum oxide, silicon nitride and silicon dioxide is often adopted to fill PTFE so as to reduce the overlarge thermal expansion coefficient of PTFE, and the dielectric constant of the PTFE copper-clad plate is regulated and controlled according to application requirements. However, the PTFE composite material prepared by filling PTFE with ceramic powder in the prior art has the problems of poor uniformity, high dielectric constant, high dielectric loss and the like, and cannot meet the requirement of a 5G low dielectric loss material. Therefore, there is a need to develop a PTFE composite material with low dielectric constant and low dielectric loss.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention aims at a PTFE-hollow glass microsphere composite material and a preparation method and application thereof.
In order to achieve the aim 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 mixed material;
(2) Adding a lubricant into the dry blend in the step (1), and stirring to uniformly mix to obtain a wet blend;
(3) And (3) pressing the wet mixed material prepared in the step (2) into a sheet shape to obtain the PTFE-hollow glass microsphere composite material.
According to the preparation method, preferably, the content (mass percent) of the hollow glass microspheres in the dry blend is 0.1-20%. More preferably, the content (mass percent content) of the hollow glass microspheres in the dry blend is 1-15%.
According to the above-mentioned production method, it is preferable that the hollow glass microspheres have a particle diameter of 8 to 25 μm and a shell thickness of 1 to 5 μm. More preferably, the hollow glass microspheres have a particle size of 10 to 20 μm. Most preferably, the hollow glass microspheres have a particle size of 15 μm.
According to the above-described production method, the particle size of the PTFE particles is preferably 80 to 140nm.
According to the above preparation method, preferably, in the step (3), before the wet mixed material is subjected to the rolling treatment, the wet mixed material is heated at 30 ℃ to (t-10) ℃ for 5 to 60 minutes, wherein t represents the boiling point of the lubricant. The heat treatment may be carried out in a toaster.
According to the above-described production method, preferably, the thickness of the PTFE-hollow glass microsphere composite is 10 μm to 1000. Mu.m.
According to the preparation method, preferably, the using amount of the lubricant is 5-35% of the total mass of the dry blend.
According to the above preparation method, preferably, the lubricant is lubricating oil, naphtha or ethanol. More preferably, the lubricating oil is Isopar G.
According to the above preparation method, preferably, in the step (3), the wet mixed material is pressed into a sheet shape by a rolling treatment method, and the rolling treatment pressure is 5 to 30MPa.
In a second aspect, the invention provides a PTFE-hollow glass microsphere composite product prepared by the method of the first aspect.
In a third aspect the invention provides the use of a PTFE-hollow glass microsphere composite product according to the second aspect above. 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 in 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 covering copper foil on the upper surface and the lower surface, and performing thickness adjustment and hot pressing treatment to obtain the copper-clad plate.
According to the above-mentioned production method, preferably, the stretching ratio of the stretching treatment is 110% to 200%.
According to the above-described production method, preferably, the stretching treatment is transverse unidirectional stretching or longitudinal unidirectional stretching or transverse and longitudinal bidirectional stretching. More preferably, the stretching ratio of the transverse unidirectional stretching is 110% -200%; the stretching ratio of the longitudinal unidirectional stretching is 110% -200%; when stretching in both the transverse and longitudinal directions, the stretching ratio of the transverse stretching is 110-200%, and the stretching ratio of the longitudinal stretching is 110-200%.
According to the above preparation method, preferably, the pressure applied in the vacuum autoclave process is 100 t-1000 t.
According to the above preparation method, preferably, the adhesive is an epoxy resin.
According to the above-mentioned production method, preferably, the copper foil has a thickness of 5 to 20 μm.
The fifth aspect of the invention provides a copper-clad plate. The copper-clad plate is prepared by adopting the preparation method of 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 in the 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 positive beneficial effects that:
(1) The PTFE particles and the hollow glass microspheres are used as raw materials to prepare the PTFE-hollow glass microsphere composite material, the hollow glass microspheres of the prepared PTFE-hollow glass microsphere composite material are uniformly dispersed, and the spherical shape of the PTFE-hollow glass microsphere composite material is kept good; moreover, the dielectric constant of the copper-clad plate prepared from the PTFE-hollow glass microsphere composite material can reach 1.66, the dielectric loss is only 0.00062, and the dielectric constant and the dielectric loss are obviously lower than those of the existing commercial products. Therefore, the PTFE-hollow glass microsphere composite material prepared by the invention has uniform performance, low dielectric constant and low dielectric loss, and is suitable for preparing printed circuit boards in the 5G field.
(2) When the PTFE-hollow glass microsphere composite material is prepared, the mass percent of the hollow glass microspheres in the dry blend is controlled within the range of 0.1-20%, because when the content of the hollow glass microspheres in the dry blend is lower than 0.1%, the dielectric constant of the prepared PTFE-hollow glass microsphere composite material is not obviously reduced due to the excessively low content of the hollow glass microspheres; when the mass percentage of the hollow glass microspheres in the dry blend 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 prepared PTFE-hollow glass microsphere composite material is low in density, strength and mechanical property due to the fact that the hollow glass microspheres are excessively filled, so that the PTFE-hollow glass microsphere composite material cannot be processed into a film and cannot be used for preparing copper-clad plates.
(3) According to the invention, before the wet mixed material is subjected to compression treatment, the wet mixed material is subjected to heating treatment at 30-t-10 ℃, and the heating can promote the lubricant to be fully contacted with the PTFE particles and the hollow glass microspheres, so that the lubricant can be uniformly covered on the surfaces of the PTFE particles and the hollow glass microspheres, the effect of protecting the PTFE particles and the hollow glass microspheres is achieved, and the defect that the PTFE particles and the hollow glass microspheres are scratched by processing equipment in the compression process can be effectively prevented, and the built-in defects are caused.
(4) According to the invention, the hollow glass microspheres with the particle size of 8-25 mu m and the shell thickness of 1-5 mu m 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 transversely and longitudinally stretched at the temperature of 100-300 ℃, the stretching temperature is controlled at 100-300 ℃, the molecular chain movement capability is improved, the material is easier to stretch, and meanwhile, the breakage of the molecular chain in the stretching process is prevented; 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 graph of the MicroCT characterization of the 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 by way of the following specific examples, which are not intended to limit the scope of the present invention.
Hollow glass microsphere dosage discussion experiment
In order to investigate the effect of the amount of hollow glass microspheres on the performance of the prepared PTFE-hollow glass microsphere composite, the inventors conducted the following experiments, and the details of examples 1 to 8, were as follows.
Example 1:
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 mixed material, wherein the mass percentage of the hollow glass microspheres in the dry mixed material is 0.1%, the particle size of the PTFE particles is 80-140nm, the particle size of the hollow glass microspheres is 15 mu m, and the shell thickness of the hollow glass microspheres is 3 mu m;
(2) Adding a lubricant into the dry blend in the step (1), wherein the dosage of the lubricant is 20% of the total mass of the dry blend, and stirring to uniformly mix the dry blend to obtain a wet blend, and 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 a blank with certain mechanical strength, and putting the blank into a piston type extruder for extrusion (the extrusion pressure is 20 MPa) to obtain a rectangular plate; then the rectangular plate is subjected to calendaring treatment (the pressure is 25 MPa) to prepare the PTFE-hollow glass microsphere composite material with the thickness of 60 mu m, and the PTFE-hollow glass microsphere composite material product is obtained.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate.
The preparation method of the copper-clad plate comprises the following steps: respectively transversely and longitudinally stretching the PTFE-hollow glass microsphere composite material product at 200 ℃, wherein the stretching ratio of the transverse stretching is 150%, and the stretching ratio of the longitudinal stretching is 150%; and 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 coating copper foil (the thickness of the copper foil 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 vacuum hot pressing treatment at 200 ℃ for 2 hours through thickness adjustment to completely solidify the adhesive glue, thus obtaining the copper-clad plate.
Example 2:
the content of example 2 is substantially the same as that of example 1, except that: the mass percentage of the hollow glass microspheres in the dry blend in the step (1) is 1%.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. 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: the mass percentage of the hollow glass microspheres in the dry blend in the step (1) is 5%.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. 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 blend in the step (1) is 10%.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. 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 blend in the step (1) is 15%.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 6:
the content of example 6 is substantially the same as that of example 1, except that: the mass percentage of the hollow glass microspheres in the dry blend in the step (1) is 20%.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 7:
the content of example 7 is substantially the same as that of example 1, except that: the mass percentage of the hollow glass microspheres in the dry blend in the step (1) is 25%.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
Example 8:
the content of example 8 is substantially the same as that of example 1, except that: the mass percentage of the hollow glass microspheres in the dry blend in the step (1) is 30%.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. The preparation method of the copper-clad plate is the same as that of the embodiment 1.
The PTFE-hollow glass microsphere composite material prepared in the embodiment is used for preparing a copper-clad plate. 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 material and the copper-clad plate prepared in examples 1 to 8 were measured, and the measurement 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 hollow glass microsphere content in the dry blend is in the range of 0.1% -20%, the density and breaking strength of the PTFE-hollow glass microsphere composite material gradually decrease as the hollow glass microsphere content increases; 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 extremely easy to crack after being rolled, and cannot be used for preparing copper-clad plates.
With the increase of the content of the hollow glass microspheres, the dielectric constant of the copper-clad plate has the tendency of decreasing firstly and then increasing, the dielectric loss of the copper-clad plate gradually increases, and when the content of the hollow glass microspheres is in the range of 0.1-20%, the dielectric constant and the dielectric loss of the prepared copper-clad plate are lower, and the dielectric property is good; when the content of the hollow glass microspheres is 5%, the mechanical strength of the prepared PTFE-hollow glass microsphere composite material is higher, the dielectric constant of the prepared copper-clad plate reaches the lowest (1.80), and the dielectric loss is lower and only 0.00079.
The PTFE-hollow glass microsphere composite material prepared in example 3 above was characterized by MicroCT, and the result of MicroCT characterization is shown in fig. 1. As can be seen from FIG. 1, the hollow glass microspheres are uniformly dispersed in the PTFE base material, no agglomeration is seen, 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, the content of the hollow glass microspheres is preferably 0.1-20% by combining the performance of the PTFE-hollow glass microsphere composite material and the performance of the prepared copper-clad plate; more preferably 1% -15%, most preferably 5%.
(II) hollow glass microsphere particle size discussion experiment:
in order to investigate the influence of the particle size of the hollow glass microspheres on the performance of the prepared PTFE-hollow glass microsphere composite, the inventors conducted the following experiments, and the details of examples 9 to 13, were as follows.
Example 9:
the content of example 9 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 blend is 5%, the particle size of the hollow glass microspheres is 8 mu m, and the shell thickness of the hollow glass microspheres is 3 mu m.
Example 10:
the content of example 10 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 blend is 5%, the particle size of the hollow glass microspheres is 10 mu m, and the shell thickness of the hollow glass microspheres is 3 mu m.
Example 11:
the content of example 11 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 blend is 5%, the particle size of the hollow glass microspheres is 20 mu m, and the shell thickness of the hollow glass microspheres is 3 mu m.
Example 12:
the content of example 12 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 blend is 5%, the particle size of the hollow glass microspheres is 25 mu m, and the shell thickness of the hollow glass microspheres is 3 mu m.
Example 13:
the content of example 13 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 blend is 5%, the particle size of the hollow glass microspheres is 30 mu m, and the shell thickness of the hollow glass microspheres is 3 mu m.
The performance of the PTFE-hollow glass microsphere composite material and the copper-clad plate prepared in examples 9 to 13 were measured, and the measurement results are shown in Table 2.
TABLE 2 influence of particle size of hollow glass microspheres on PTFE-hollow glass microsphere composite and copper-clad plate properties
As can be seen from table 2, as the particle size of the hollow glass microspheres increases, the volume of the hollow glass microsphere internal cavity gradually increases, 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 calendaring process, so that the performance of the PTFE-hollow glass microsphere composite material is affected. Therefore, the particle size of the hollow glass microsphere is preferably 8-25 mu m 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. Mu.m.
Discussion experiment of stretching treatment in preparation process of copper-clad plate
To investigate the influence of the stretching treatment on the performance of the prepared copper clad laminate during the preparation of the copper clad laminate, the inventors conducted the following experiments, and the concrete contents of examples 14 to 16 were as follows.
Example 14:
the preparation method of the copper-clad plate comprises the following specific operations: the PTFE-hollow glass microsphere composite material product prepared in the example 3 is subjected to transverse unidirectional stretching at 200 ℃, and the stretching ratio of the transverse unidirectional stretching is 150%; and 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 coating copper foil (the thickness of the copper foil 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 vacuum hot pressing treatment at 200 ℃ for 2 hours through thickness adjustment to completely solidify the adhesive glue, thus obtaining the copper-clad plate.
Example 15:
the content of example 15 is the same as that of example 14, except that: the PTFE-hollow glass microsphere composite product prepared in example 3 was subjected to longitudinal unidirectional stretching at 200℃at a stretching ratio of 150%.
Example 16:
the preparation method of the copper-clad plate comprises the following specific operations: epoxy resin (the thickness of the epoxy resin is 5 mu m) is coated on the upper surface and the lower surface of the PTFE-hollow glass microsphere composite material product prepared in the embodiment 3, copper foil (the thickness of the copper foil is 18 mu m) is 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 plate is obtained after thickness adjustment and vacuum hot pressing treatment at 200 ℃ for 2 hours, so that the adhesive is completely cured.
The performance of the copper clad laminates prepared in examples 14 to 16 was measured, and the measurement results are shown in table 3.
TABLE 3 influence of stretching treatments on copper-clad plate properties
As shown in table 3, the dielectric constant of the copper-clad plate prepared by the stretching treatment is obviously higher than that of the copper-clad plate prepared without the stretching treatment, because the stretching treatment can form micropore gaps inside the PTFE-hollow glass microsphere composite material, and the existence of the micropore gaps can further reduce the dielectric constant of the composite material; compared with unidirectional stretching, the dielectric constant of the copper-clad plate prepared by the transverse and longitudinal bidirectional stretching treatment is lower, because the bidirectional stretching can form more micropore gaps in the composite material, the porosity of the composite film can be improved, and the dielectric constant of the composite film can be reduced.
(IV) discussion experiment of transverse stretching ratio and longitudinal stretching ratio in preparation process of copper-clad plate
In order to study 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 inventors conducted the following experiments, and the specific contents of examples 17 to 21 are as follows.
Example 17:
the preparation method of the copper-clad plate comprises the following specific operations: the PTFE-hollow glass microsphere composite material product prepared in example 3 is respectively subjected to transverse stretching and longitudinal stretching at 200 ℃, wherein the stretching ratio of the transverse stretching is 110%, and the stretching ratio of the longitudinal stretching is 110%; and 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 coating copper foil (the thickness of the copper foil 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 vacuum hot pressing treatment at 200 ℃ for 2 hours through thickness adjustment to completely solidify the adhesive glue, thus obtaining the copper-clad plate.
Example 18:
the content of example 18 is the same as that of example 17, except that: the draw ratio of the transverse direction draw was 170%, and the draw ratio of the longitudinal direction draw was 170%.
Example 19:
example 19 is identical to example 17 except that: the draw ratio of the transverse direction draw was 200%, and the draw ratio of the longitudinal direction draw was 200%.
Example 20:
the content of example 20 is the same as that of example 17, except that: the draw ratio of the transverse direction draw was 220%, and the draw ratio of the longitudinal direction draw was 220%.
Example 21:
the content of example 21 is the same as that of example 17, except that: the draw ratio of the transverse direction draw was 250% and the draw ratio of the longitudinal direction draw was 250%.
The performance of the copper clad laminates prepared in examples 17 to 21 was measured, and the measurement results are shown in table 4.
TABLE 4 influence of transverse and longitudinal draw ratio on copper-clad plate Performance
As can be seen from table 4, proper stretching will improve the dielectric properties of the final copper-clad plate, because the increase of porosity helps to reduce the dielectric constant and dielectric loss of the material, but when the stretching ratio is greater than 200%, the dielectric properties are reduced, because excessive stretching will destroy the original pore structure, resulting in collapse of the pore walls and closure of the pores. Therefore, the stretching ratio of the transverse and longitudinal biaxial stretching in the present invention is preferably 200%.
And (V) comparing the performance of the copper-clad plate prepared by the method with that of the traditional 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 that of a copper-clad plate produced by Rojies company, takara, and the comparison result is shown in Table 5.
TABLE 5 comparison of the Performance of the copper-clad laminate prepared by the present invention and 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 present invention were significantly lower than those of the existing commercial products. Compared with the existing commercial products, the copper-clad plate prepared by the method has obvious advantages in dielectric property.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (4)
1. The preparation method of the copper-clad plate is characterized by comprising the following steps: stretching the PTFE-hollow glass microsphere composite material product at 100-300 ℃; coating adhesive glue on the upper surface and the lower surface of the stretched PTFE-hollow glass microsphere composite material product, then respectively covering copper foil on the upper surface and the lower surface, and performing thickness adjustment and hot pressing treatment to obtain a copper-clad plate;
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 mixed material, wherein the content of the hollow glass microspheres in the dry mixed material is 5%, the particle size of the hollow glass microspheres is 15 mu m, and the shell thickness of the hollow glass microspheres is 3 mu m;
(2) Adding a lubricant into the dry blend in the step (1), and stirring to uniformly mix to obtain a wet blend, wherein the lubricant is Isopar G;
(3) And (3) baking the wet mixed material prepared in the step (2) at 60 ℃ for 30min, and then pressing the wet mixed material into a sheet shape by adopting a calendaring treatment method to obtain the PTFE-hollow glass microsphere composite material, wherein the thickness of the PTFE-hollow glass microsphere composite material is 10-1000 mu m.
2. The method according to claim 1, 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.
3. A copper-clad laminate product produced by the production method of claim 1 or 2.
4. The use of the copper-clad laminate product of claim 3 in a circuit board.
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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 |
| CN104558689A (en) * | 2014-12-26 | 2015-04-29 | 广东生益科技股份有限公司 | Filler composition and application thereof |
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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 |
| CN104558689A (en) * | 2014-12-26 | 2015-04-29 | 广东生益科技股份有限公司 | Filler composition and application thereof |
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