CN116330765A - High-frequency flexible copper-clad plate material with multilayer structure and preparation method thereof - Google Patents

High-frequency flexible copper-clad plate material with multilayer structure and preparation method thereof Download PDF

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CN116330765A
CN116330765A CN202310294187.XA CN202310294187A CN116330765A CN 116330765 A CN116330765 A CN 116330765A CN 202310294187 A CN202310294187 A CN 202310294187A CN 116330765 A CN116330765 A CN 116330765A
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fluororesin
filling powder
clad plate
plate material
copper
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张启龙
程建林
夏昭岳
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B32B38/1858—Handling of layers or the laminate using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A30/00—Adapting or protecting infrastructure or their operation

Abstract

The invention relates to the field of material science and engineering, and aims to provide a high-frequency flexible copper-clad plate material with a multilayer structure and a preparation method thereof. The copper-clad plate material has a laminated structure which is sequentially overlapped, and comprises: two copper foil layers positioned on the outermost surface, a filling powder/fluororesin paint layer positioned in the center, and two liquid crystal polymer film layers positioned between the copper foil layers and the filling powder/fluororesin paint layer; the filling powder/fluororesin varnish layer is formed by taking glass fiber cloth as a substrate and attaching a mixture of nitride filling powder and fluororesin to the surface of the glass fiber cloth through dipping, sintering and vacuum hot pressing treatment. The product of the invention has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high thermal decomposition temperature, high dimensional stability and the like; the formed heat conduction path meets the application scene of high frequency and high speed; can keep the same performance index as other similar materials in water absorption, thermal decomposition temperature, dimensional stability and the like.

Description

High-frequency flexible copper-clad plate material with multilayer structure and preparation method thereof
Technical Field
The invention relates to a high-frequency flexible copper-clad plate material and a preparation method thereof, belonging to the fields of material science and engineering.
Background
The flexible printed circuit board (Flexible Printing Circuit, FPC) is made of flexible insulating materials, has the characteristics of high integration density, light weight, flexibility and the like, and provides more design space and potential for the product in the aspects of modeling and reliability. The development of the flexible substrate accords with the development trend of miniaturization and light weight of electronic products in the current society, and has wide application prospect in consumer electronics such as smart phones, tablet computers, wearable equipment and other communication fields. In the production of FPCs, flexible Copper Clad Laminate (FCCL) is an important base material. The flexible copper-clad plate comprises an insulating resin film with flexibility and a copper foil attached to the insulating resin film. In general, a flexible copper clad laminate is formed by laminating copper foil on both sides of an insulating resin and applying pressure, and Polyimide (PI) or Polyester (PET) is mainly used as an insulating resin film. But PI or PET can only be used in the MHz band; if the frequency of use of the signal increases, reaching GHz, the dielectric loss increases significantly and the signal-to-noise ratio of the transmitted signal may decrease significantly. The reduction of dielectric loss of the material under high-frequency and high-speed working conditions is one of effective methods for solving the problems. Meanwhile, in recent years, due to miniaturization and integration of electronic devices, realization of high heat dissipation of electronic devices has become an important point of attention. Therefore, the flexible copper-clad plate with low dielectric loss and high heat conductivity has great application prospect.
The Liquid Crystal Polymer (LCP) has high strength, high modulus, high heat resistance, low dielectric property, excellent bending resistance, chemical corrosion resistance, aging resistance, high radiation resistance and molding processability, and meanwhile, the linear thermal expansion coefficient is close to that of copper, so that the material requirement of 5G communication products can be met. The injection molding grade LCP resin can be used for PCB main boards, SMT connectors and the like, and the film grade LCP resin can be used for high-frequency signal transmission carriers such as mobile phone antennas. However, LCP also has problems such as low bending resistance and high price.
At present, fluororesins have also received a great deal of attention for their excellent dielectric properties. Compared with other polymer materials, the fluororesin is excellent in heat resistance, drug resistance, weather resistance, electrical characteristics and the like, and has specific properties such as non-tackiness, self-lubricity and the like. A typical fluororesin applied to the field of high-frequency copper-clad plates is Polytetrafluoroethylene (PTFE), which has low dielectric constant and dielectric loss, but poor processability and film forming capability limit its application in the field of flexible substrates. Soluble Polytetrafluoroethylene (PFA) is a copolymer of a small amount of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene. Melt adhesion is enhanced and melt viscosity is reduced without change in performance compared to polytetrafluoroethylene. At 10GHz, the dielectric constant of PFA is 2.1, the dielectric loss is 0.0003, and compared with PTFE, the dielectric constant is equivalent, and the dielectric loss is slightly higher. But the processability, especially the film-forming properties, are greatly improved.
The incorporation of inorganic fillers into polymeric substrates for compounding is a common method of improving the overall properties of the material. At present, the common method is to directly compound the filler and the polymer by hot melt blending and other modes to obtain blended granules, and then prepare the obtained granules into a composite substrate by vacuum hot pressing. Although the direct blending approach is simpler to operate, there are also disadvantages. Firstly, the filler tends to be uniformly distributed in the matrix, so that the performance of the filler is improved poorly in certain aspects, and a larger filler content is often required to achieve the required performance; in addition, part of the filler is exposed on the surface of the composite substrate, so that the surface flatness of the material can be affected, and on the other hand, although certain high-performance fillers have better dielectric properties, the exposure of the fillers to the outside has a great influence on the final service performance of the substrate due to acid, alkali and water mist in the environment.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-frequency flexible copper-clad plate material with a multilayer structure and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following solutions:
the high-frequency flexible copper-clad plate material with the multilayer structure is provided, and has a laminated structure which is sequentially overlapped, and comprises the following components: two copper foil layers positioned on the outermost surface, a filling powder/fluororesin paint layer positioned in the center, and two liquid crystal polymer film layers positioned between the copper foil layers and the filling powder/fluororesin paint layer;
the filling powder/fluororesin varnish layer is formed by taking glass fiber cloth as a substrate, and attaching a mixture of nitride filling powder and fluororesin to the surface of the glass fiber cloth through dipping, sintering and vacuum hot pressing treatment; the nitride filling powder is one or two of aluminum nitride and boron nitride.
As a preferable scheme of the invention, in the filling powder/fluororesin varnish layer, the mass ratio of the nitride filling powder to the fluororesin is 1.5-2.3:1.
As a preferred embodiment of the present invention, the fluororesin is polytetrafluoroethylene perfluoroalkyl vinyl ether (PFA).
As a preferable scheme of the invention, the nitride filling powder is boron nitride and aluminum nitride, and the mass ratio of the boron nitride to the aluminum nitride is 0.3-1.6:1.
As a preferable mode of the present invention, the thickness of the copper foil layer is 12 μm; alternatively, the thickness of the filler powder/fluororesin varnish layer is 150 μm; alternatively, the thickness of the liquid crystal polymer film layer is 25 μm.
As a preferable scheme of the invention, the thickness of each copper foil layer is the same; alternatively, the thickness of each liquid crystal polymer film layer is the same.
As a preferred embodiment of the present invention, the sum of the thicknesses of the two liquid crystal polymer layers and the filler powder/fluororesin varnish layer is 200. Mu.m.
The invention further provides a preparation method of the high-frequency flexible copper-clad plate material with the multilayer structure, which comprises the following steps:
(1) Adding the nitride filling powder into the fluororesin emulsion, and obtaining uniformly dispersed mixed slurry after ultrasonic stirring and vacuum defoaming;
(2) Dipping the glass fiber cloth into the mixed slurry, and drying, sintering and carrying out vacuum hot pressing treatment to obtain filling powder/fluororesin varnished cloth;
(3) Sequentially stacking all layers of materials according to the sequence of the copper foil, the liquid crystal polymer film, the filling powder/fluororesin varnished cloth, the liquid crystal polymer film and the copper foil; and then placing the material in a vacuum hot press for hot pressing to obtain the high-frequency flexible copper-clad plate material with the multilayer structure.
In the step (2), the temperature is controlled to be 90 ℃ and the time is 10min during drying; the sintering temperature is 320 ℃ and the sintering time is 10min; the pressure is controlled to be 10MPa, the temperature is 320 ℃, the time is 20min, and the vacuum degree is-0.085 MPa during hot pressing.
As a preferable mode of the present invention, in the step (3), parameters of the hot pressing process are set as follows: the pressure is 5MPa, the temperature is 315 ℃, the time is 5min, and the vacuum degree is-0.085 MPa.
Description of the inventive principles:
the invention prepares the high-frequency flexible copper-clad plate by adopting the liquid crystal polymer resin film to sandwich the filling powder/fluororesin composite film based on the characteristics of excellent high-frequency dielectric property, low water absorption, excellent corrosion resistance, heat resistance, flexibility, dimensional stability and the like of the liquid crystal polymer. The high-performance glass fiber cloth is adopted as the reinforcing phase, so that the structural strength of the copper-clad plate is ensured, the dimensional stability of the material is improved, and the PFA resin is adopted as the intermediate layer, so that the flexibility and the good dielectric property of the copper-clad plate are both considered. The addition of the filler can greatly improve the heat conduction performance of the material and further improve the dimensional stability of the material while not damaging the flexibility of the material. The liquid crystal polymer has the characteristics of low dielectric constant, low dielectric loss and low water absorption, and the structural design of layered inclusion can prevent the middle filling powder/fluororesin lacquer layer from directly contacting with the external environment, so that the overall water absorption is effectively reduced. The liquid crystal polymer film also has excellent flexibility and good dimensional stability, and the introduction of the liquid crystal polymer layer does not have negative influence on the flexibility and the dimensional stability of the whole copper-clad plate.
Compared with the prior art, the invention has the beneficial effects that:
1. the copper-clad plate prepared by the invention is prepared by vacuum hot pressing of liquid crystal polymer, fluororesin matched filling powder and glass fiber cloth copper-clad foil, and has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high thermal decomposition temperature, high dimensional stability and the like.
2. Compared with the MPI and LCP copper-clad plate with more applications at present, the flexible copper-clad plate material prepared by the invention has a multi-layer structure, is beneficial to forming a heat conduction path by packaging the heat conduction filler in the core layer, has great advantages in heat conduction performance, has excellent dielectric performance, and well meets the current application scene under high frequency and high speed.
3. The flexible copper-clad plate material prepared by the invention has a multilayer structure, and the surface of the flexible copper-clad plate material is covered with the liquid crystal polymer layer with high dimensional stability and extremely low water absorption, so that the flexible copper-clad plate material can keep the same performance indexes as other similar materials in terms of water absorption, thermal decomposition temperature, dimensional stability and the like.
4. The invention adopts the fluororesin and the liquid crystal polymer as the matrix, improves the comprehensive performance of the material by using the layered composite structural design, and has wide application prospect in the field of high-frequency flexible copper-clad plates.
Detailed Description
The present invention will be further described in detail with reference to the following examples, which are not intended to limit the scope of the invention.
The fluororesin used in each example was polytetrafluoroethylene perfluoroalkyl vinyl ether (PFA) emulsion, which was obtained from a commercial product (3M 6900 GZ) and contained 50% (m/m) of PFA.
Example 1:
step (1): taking a certain amount of PFA emulsion, adding boron nitride powder, ultrasonically stirring for 30min, and removing bubbles in vacuum to obtain uniformly dispersed mixed slurry, wherein the mass ratio of the boron nitride powder to the emulsion is 0.77:1 (the mass ratio of the converted nitride filling powder to the pure PFA is 1.5:1);
step (2): using 1080 glass fiber cloth, dipping the glass fiber cloth into the mixed slurry of the filling powder and the PFA obtained in the step (1), drying for 10min at 90 ℃, drying the solvent, sintering for 10min at 320 ℃, and performing vacuum hot pressing for 20min at 320 ℃ under 10MPa to form the filling powder/the PFA paint cloth with the thickness of 150 mu m; the vacuum degree during vacuum hot pressing is-0.085 MPa.
Step (3): covering the upper and lower surfaces of the filling powder/PFA varnished cloth obtained in the step (2) with liquid crystal polymer films, then placing the filling powder/PFA varnished cloth between double-sided copper-clad foils, and then transferring the filling powder/PFA varnished cloth into a vacuum hot press for hot pressing to obtain the high-frequency flexible copper-clad plate material, wherein the thickness of the copper foil is 12 micrometers, the thickness of the liquid crystal polymer film is 25 micrometers, the hot pressing temperature is 315 ℃, the hot pressing pressure is 5MPa, the hot pressing time is 5min, and the vacuum degree during vacuum hot pressing is-0.085 MPa.
The flexible high-frequency copper-clad plate material prepared according to the formula and the process formula prepared by the process steps comprises the following performance indexes: dielectric constant 3.4 (10 Ghz), dielectric loss 1.7X10 -3 (10 Ghz), the thermal conductivity is 4.3W/(mK), the water absorption is 0.04%, the dimensional stability is 0.014%, the thermal decomposition temperature is 447.0 ℃, the final thickness of the flexible high-frequency copper-clad plate material is 224 microns, and the sum of the thicknesses of the two liquid crystal polymer layers and the filling powder/fluororesin paint layer is 200 microns.
Example 2:
step (1): adding a certain amount of PFA emulsion into aluminum nitride powder, ultrasonically stirring for 30min, and removing bubbles in vacuum to obtain uniformly dispersed mixed slurry, wherein the mass ratio of aluminum nitride particles to the emulsion is 1.14:1 (the mass ratio of converted nitride filling powder to pure PFA is 2.3:1);
step (2): using 1080 glass fiber cloth, dipping the glass fiber cloth into the mixed slurry of the filling powder and the PFA obtained in the step (1), drying for 10min at 90 ℃, drying the solvent, sintering for 10min at 320 ℃, and performing vacuum hot pressing for 20min at 320 ℃ under 10MPa to form the filling powder/the PFA paint cloth with the thickness of 150 mu m; the vacuum degree during vacuum hot pressing is-0.085 MPa.
Step (3): covering the upper and lower surfaces of the filling powder/PFA varnished cloth obtained in the step (2) with liquid crystal polymer films, then placing the filling powder/PFA varnished cloth between double-sided copper-clad foils, and then transferring the filling powder/PFA varnished cloth into a vacuum hot press for hot pressing to obtain the high-frequency flexible copper-clad plate material, wherein the thickness of the copper foil is 12 micrometers, the thickness of the liquid crystal polymer film is 25 micrometers, the hot pressing temperature is 315 ℃, the hot pressing pressure is 5MPa, the hot pressing time is 5min, and the vacuum degree during vacuum hot pressing is-0.085 MPa.
The flexible high-frequency copper-clad plate material prepared according to the formula and the process formula prepared by the process steps comprises the following performance indexes: dielectric constant 3.8 (10 Ghz), dielectric loss 6.7X10 -3 (10 Ghz), the heat conductivity is 1.9W/(mK), the water absorption is 0.1%, the dimensional stability is 0.43%, the thermal decomposition temperature is 453.3 ℃, the final thickness of the flexible high-frequency copper-clad plate material is 224 microns, and the sum of the thicknesses of the two liquid crystal polymer layers and the filling powder/fluororesin paint layer is 200 microns.
Example 3:
step (1): adding a certain amount of PFA emulsion, ultrasonically stirring for 30min, and removing bubbles in vacuum to obtain uniformly dispersed mixed slurry, wherein the mass ratio of the boron nitride to the aluminum nitride to the PFA emulsion is 9.6:5.9:17.2 (the mass ratio of the converted nitride filling powder to the pure PFA is 1.8:1, and the mass ratio of the boron nitride to the aluminum nitride is 1.6:1);
step (2): using 1080 glass fiber cloth, dipping the glass fiber cloth into the mixed slurry of the filling powder and the PFA obtained in the step (1), drying for 10min at 90 ℃, drying the solvent, sintering for 10min at 320 ℃, and performing vacuum hot pressing for 20min at 320 ℃ under 10MPa to form the filling powder/the PFA paint cloth with the thickness of 150 mu m; the vacuum degree during vacuum hot pressing is-0.085 MPa.
Step (3): covering the upper and lower surfaces of the filling powder/PFA varnished cloth obtained in the step (2) with liquid crystal polymer films, then placing the filling powder/PFA varnished cloth between double-sided copper-clad foils, and then transferring the filling powder/PFA varnished cloth into a vacuum hot press for hot pressing to obtain a high-frequency flexible copper-clad plate material, wherein the thickness of the copper foil is 12 micrometers, the thickness of the liquid crystal polymer film is 25 micrometers, the hot pressing temperature is 315 ℃, the hot pressing pressure is 5MPa, the hot pressing time is 5min, and the vacuum degree during vacuum hot pressing is-0.085 MPa
The flexible high-frequency copper-clad plate material prepared according to the formula and the process formula prepared by the process steps comprises the following performance indexes: dielectric constant 3.4 (10 Ghz), dielectric loss 3.0X10 -3 (10 Ghz), thermal conductivity 5.5W/(mK),the water absorption rate is 0.04%, the dimensional stability is 0.022%, the thermal decomposition temperature is 462.7 ℃, the final thickness of the flexible high-frequency copper-clad plate material is 224 microns, and the sum of the thicknesses of the two liquid crystal polymer layers and the filling powder/fluororesin paint layer is 200 microns.
Example 4:
step (1): adding a certain amount of PFA emulsion, ultrasonically stirring for 30min, and removing bubbles in vacuum to obtain uniformly dispersed mixed slurry, wherein the mass ratio of the boron nitride to the aluminum nitride to the PFA emulsion is 4.14:13.7:17.2 (the mass ratio of the converted nitride filling powder to the pure PFA is 2.1:1, and the mass ratio of the boron nitride to the aluminum nitride is 0.3:1);
step (2): using 1080 glass fiber cloth, dipping the glass fiber cloth into the mixed slurry of the filling powder and the PFA obtained in the step (1), drying for 10min at 90 ℃, drying the solvent, sintering for 10min at 320 ℃, and performing vacuum hot pressing for 20min at 320 ℃ under 10MPa to form the filling powder/the PFA paint cloth with the thickness of 150 mu m; the vacuum degree during vacuum hot pressing is-0.085 MPa.
Step (3): covering the upper and lower surfaces of the filling powder/PFA varnished cloth obtained in the step (2) with liquid crystal polymer films, then placing the filling powder/PFA varnished cloth between double-sided copper-clad foils, and then transferring the filling powder/PFA varnished cloth into a vacuum hot press for hot pressing to obtain a high-frequency flexible copper-clad plate material, wherein the thickness of the copper foil is 12 micrometers, the thickness of the liquid crystal polymer film is 25 micrometers, the hot pressing temperature is 315 ℃, the hot pressing pressure is 5MPa, the hot pressing time is 5min, and the vacuum degree during vacuum hot pressing is-0.085 MPa
The flexible high-frequency copper-clad plate material prepared according to the formula and the process formula prepared by the process steps comprises the following performance indexes: dielectric constant 3.8 (10 Ghz), dielectric loss 5.3X10 -3 (10 Ghz), the thermal conductivity is 3.2W/(mK), the water absorption is 0.08%, the dimensional stability is 0.081 ℃, the thermal decomposition temperature is 452.2 ℃, the final thickness of the flexible high-frequency copper-clad plate material is 224 micrometers, and the sum of the thicknesses of the two liquid crystal polymer layers and the filling powder/fluororesin paint layer is 200 micrometers.
Example 5:
step (1): adding a certain amount of PFA emulsion, ultrasonically stirring for 30min, and removing bubbles in vacuum to obtain uniformly dispersed mixed slurry, wherein the mass ratio of the boron nitride to the aluminum nitride to the PFA emulsion is 6.9:9.8:17.2 (the mass ratio of the converted nitride filling powder to the pure PFA is 1.9:1, and the mass ratio of the boron nitride to the aluminum nitride is 0.7:1);
step (2): using 1080 glass fiber cloth, dipping the glass fiber cloth into the mixed slurry of the filling powder and the PFA obtained in the step (1), drying for 10min at 90 ℃, drying the solvent, sintering for 10min at 320 ℃, and performing vacuum hot pressing for 20min at 320 ℃ under 10MPa to form the filling powder/the PFA paint cloth with the thickness of 150 mu m; the vacuum degree during vacuum hot pressing is-0.085 MPa.
Step (3): covering the upper and lower surfaces of the filling powder/PFA varnished cloth obtained in the step (2) with liquid crystal polymer films, then placing the filling powder/PFA varnished cloth between double-sided copper-clad foils, and then transferring the filling powder/PFA varnished cloth into a vacuum hot press for hot pressing to obtain the high-frequency flexible copper-clad plate material, wherein the thickness of the copper foil is 12 micrometers, the thickness of the liquid crystal polymer film is 25 micrometers, the hot pressing temperature is 315 ℃, the hot pressing pressure is 5MPa, the hot pressing time is 5min, and the vacuum degree during vacuum hot pressing is-0.085 MPa.
The flexible high-frequency copper-clad plate material prepared according to the formula and the process formula prepared by the process steps comprises the following performance indexes: dielectric constant 3.7 (10 Ghz), dielectric loss 5.0X10 -3 (10 Ghz), thermal conductivity of 4.2W/(mK), water absorption of 0.08%, dimensional stability of 0.054%, thermal decomposition temperature of 453.9 ℃, final thickness of the flexible high-frequency copper-clad plate material of 224 micrometers, and sum of thicknesses of the two liquid crystal polymer layers and the filling powder/fluororesin paint layer of 200 micrometers.
Comparative example 1:
step (1): adding a certain amount of PFA emulsion, ultrasonically stirring for 30min, and removing bubbles in vacuum to obtain uniformly dispersed mixed slurry, wherein the mass ratio of the boron nitride to the aluminum nitride to the PFA emulsion is 9.6:5.9:17.2 (the mass ratio of the converted nitride filling powder to the pure PFA is 1.8:1, and the mass ratio of the boron nitride to the aluminum nitride is 1.6:1);
step (2): using 1080 glass fiber cloth, dipping the glass fiber cloth into the mixed slurry of the filling powder and the PFA obtained in the step (1), drying for 10min at 90 ℃, drying the solvent, sintering for 10min at 320 ℃, and performing vacuum hot pressing for 20min at 320 ℃ under 10MPa to form the filling powder/the PFA paint cloth with the thickness of 150 mu m; the vacuum degree during vacuum hot pressing is-0.085 MPa.
Step (3): arranging the filling powder/PFA paint obtained in the step (2) between the double-sided copper clad laminate, and then transferring the double-sided copper clad laminate into a vacuum hot press for hot pressing to obtain a high-frequency flexible copper clad laminate material, wherein the thickness of the copper foil is 12 micrometers, the hot pressing temperature is 315 ℃, the hot pressing pressure is 5MPa, the hot pressing time is 5min, and the vacuum degree during vacuum hot pressing is-0.085 MPa
The flexible high-frequency copper-clad plate material prepared according to the formula and the process formula prepared by the process steps comprises the following performance indexes: dielectric constant 3.7 (10 Ghz), dielectric loss 2.8X10 -3 (10 Ghz), the thermal conductivity is 5.7W/(mK), the water absorption is 2.45%, the dimensional stability is 0.006%, the thermal decomposition temperature is 444 ℃, and the final thickness of the flexible high-frequency copper-clad plate material is 175 microns.
Comparative example 2:
step (1): taking a certain amount of pure PFA powder, liquid Crystal Polymer (LCP) powder and boron nitride ceramic particles, and accurately weighing the PFA powder, the LCP powder and the boron nitride ceramic particles so that the mass ratio of the PFA powder to the LCP powder to the boron nitride ceramic particles is 9:4:7;
step (2): premixing the powder weighed in the step (1), putting the premixed powder into a double-screw extruder for hot melt blending, and then extruding and granulating to obtain composite granules, wherein the temperature of a screw is 325 ℃, the rotating speed of the screw is 100r/min, and the blending time is 5 min;
step (3): putting the granules obtained in the step (2) into a vacuum hot press for hot press molding to obtain a composite flexible high-frequency substrate, wherein the hot press temperature is 325 ℃, the hot press pressure is 5MPa, the hot press time is 2min, and the vacuum degree is-0.085 MPa;
step (4): placing the composite flexible high-frequency substrate obtained in the step (3) between the double-sided copper clad laminates, and then transferring the composite flexible high-frequency substrate into a vacuum hot press for hot pressing to obtain a high-frequency flexible copper clad laminate material, wherein the thickness of the copper clad laminate is 12 micrometers, the hot pressing temperature is 325 ℃, the hot pressing pressure is 5MPa, the hot pressing time is 5min, and the vacuum degree is-0.085 MPa.
The flexible high-frequency copper-clad plate material is prepared according to the formula and the process formula obtained by the process stepsThe performance indexes are as follows: dielectric constant 3.7 (10 Ghz), dielectric loss 2.6X10 -3 (10 Ghz), the thermal conductivity is 4.25W/(mK), the water absorption is 0.02%, the dimensional stability is 0.018%, the thermal decomposition temperature is 472 ℃, and the final thickness of the flexible high-frequency copper-clad plate material is 180 microns.
According to the performance test data, the high-frequency flexible copper-clad plates prepared by the special design of the multilayer structure in the embodiments 1 to 5 have excellent dielectric properties, dk at 10GHz is 3.4 to 3.8, df can reach 0.0017 at the lowest, the dimensional stability is good, the water absorption is low and is within +/-0.1 percent, the water absorption is low and is within 0.1 percent, the high-frequency flexible copper-clad plates have high thermal conductivity and can reach 5.5W/(mK) at the highest, the thermal stability is good, and the thermal decomposition temperature is above 400 ℃.
In contrast to the examples of the present invention, the product of comparative example 1 did not use a liquid crystal polymer film layer, and the final product was a three-layer sandwich structure applied by conventional techniques. As can be seen from the product index of comparative example 3 and comparative example 1, the surface of example 3 is coated with the liquid crystal polymer film, which effectively isolates the moisture in the environment. The flexible high-frequency copper-clad plate material prepared in the comparative example 1 has better indexes such as dimensional stability and thermal conductivity, but the excessively high water absorption rate limits the practical application of the product in the high-frequency radio frequency field.
In comparison with the present example, although the liquid crystal polymer and the fluororesin component were also used in this comparative example 2, the fluororesin was not used for preparing the filler powder/fluororesin varnish layer to realize the independent use, and the final product was still a conventional copper-clad plate structure. As can be seen from the product indexes of comparative examples 1 and 2, example 1 achieves higher heat conductivity than the conventional blending process by the layered structural design, and simultaneously shows similar dielectric properties, water absorption and dimensional stability.
In conclusion, the layered structure design has remarkable effect in improving the comprehensive performance of the material.

Claims (10)

1. The high-frequency flexible copper-clad plate material with the multilayer structure is characterized by comprising a laminated structure which is sequentially overlapped, and the high-frequency flexible copper-clad plate material comprises the following components in parts by weight: two copper foil layers positioned on the outermost surface, a filling powder/fluororesin paint layer positioned in the center, and two liquid crystal polymer film layers positioned between the copper foil layers and the filling powder/fluororesin paint layer;
the filling powder/fluororesin varnish layer is formed by taking glass fiber cloth as a substrate, and attaching a mixture of nitride filling powder and fluororesin to the surface of the glass fiber cloth through dipping, sintering and vacuum hot pressing treatment; the nitride filling powder is one or two of aluminum nitride and boron nitride.
2. The high-frequency flexible copper-clad plate material according to claim 1, wherein the mass ratio of the nitride filling powder to the fluororesin in the filling powder/fluororesin varnish layer is 1.5-2.3:1.
3. The high-frequency flexible copper-clad plate material according to claim 1, wherein the fluororesin is polytetrafluoroethylene perfluoroalkyl vinyl ether.
4. The high-frequency flexible copper-clad plate material according to claim 1, wherein the nitride filling powder is boron nitride and aluminum nitride, and the mass ratio of the boron nitride to the aluminum nitride is 0.3-1.6:1.
5. The high-frequency flexible copper-clad plate material according to claim 1, wherein the thickness of the copper foil layer is 12 μm; alternatively, the thickness of the filler powder/fluororesin varnish layer is 150 μm; alternatively, the thickness of the liquid crystal polymer film layer is 25 μm.
6. The high-frequency flexible copper-clad plate material according to claim 1, wherein the thickness of each copper foil layer is the same; alternatively, the thickness of each liquid crystal polymer film layer is the same.
7. The high-frequency flexible copper-clad plate material according to claim 1, wherein the sum of the thicknesses of the two liquid crystal polymer layers and the filler powder/fluororesin varnish layer is 200 μm.
8. The method for preparing the high-frequency flexible copper-clad plate material with the multilayer structure as claimed in claim 1, which is characterized by comprising the following steps:
(1) Adding the nitride filling powder into the fluororesin emulsion, and obtaining uniformly dispersed mixed slurry after ultrasonic stirring and vacuum defoaming;
(2) Dipping the glass fiber cloth into the mixed slurry, and drying, sintering and carrying out vacuum hot pressing treatment to obtain filling powder/fluororesin varnished cloth;
(3) Sequentially stacking all layers of materials according to the sequence of the copper foil, the liquid crystal polymer film, the filling powder/fluororesin varnished cloth, the liquid crystal polymer film and the copper foil; and then placing the material in a vacuum hot press for hot pressing to obtain the high-frequency flexible copper-clad plate material with the multilayer structure.
9. The method according to claim 8, wherein in the step (2), the drying is performed at a controlled temperature of 90 ℃ for 10min; the sintering temperature is 320 ℃ and the sintering time is 10min; the pressure is controlled to be 10MPa, the temperature is 320 ℃, the time is 20min, and the vacuum degree is-0.085 MPa during hot pressing.
10. The method according to claim 8, wherein in the step (3), parameters of the hot pressing process are set as follows: the pressure is 5MPa, the temperature is 315 ℃, the time is 5min, and the vacuum degree is-0.085 MPa.
CN202310294187.XA 2023-03-24 2023-03-24 High-frequency flexible copper-clad plate material with multilayer structure and preparation method thereof Pending CN116330765A (en)

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