WO2012151820A1 - 复合材料、用其制作的高频电路基板及其制作方法 - Google Patents

复合材料、用其制作的高频电路基板及其制作方法 Download PDF

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Publication number
WO2012151820A1
WO2012151820A1 PCT/CN2011/079650 CN2011079650W WO2012151820A1 WO 2012151820 A1 WO2012151820 A1 WO 2012151820A1 CN 2011079650 W CN2011079650 W CN 2011079650W WO 2012151820 A1 WO2012151820 A1 WO 2012151820A1
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Prior art keywords
composite material
frequency circuit
dielectric loss
film
powder
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PCT/CN2011/079650
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English (en)
French (fr)
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苏民社
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广东生益科技股份有限公司
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Priority to EP20110865413 priority Critical patent/EP2706088A4/en
Priority to US14/115,748 priority patent/US10194528B2/en
Priority to KR1020137029305A priority patent/KR101575944B1/ko
Publication of WO2012151820A1 publication Critical patent/WO2012151820A1/zh

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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
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/038—Use of an inorganic compound to impregnate, bind or coat a foam, e.g. waterglass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/024—Dielectric details, e.g. changing the dielectric material around a transmission line
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0116—Porous, e.g. foam
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0323—Carbon
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249958—Void-containing component is synthetic resin or natural rubbers
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

  • the present invention relates to the field of composite materials, and in particular to a composite material, a high-frequency circuit substrate produced therefrom, and a method of fabricating the same. Background technique
  • high-frequency circuit substrates use low dielectric constant resins to obtain good high-frequency properties.
  • These low-k dielectric resins include polyphenylene ether, cyanate esters, and carbon-carbon-free double bonds.
  • CCL is generally made of fiberglass cloth as a reinforcing material.
  • the glass fiber cloth has a dielectric constant of at least 3.7 (Q glass). Due to the large dielectric constant of the glass fiber cloth, the dielectric constant of the copper-clad board made of other resins is hard to be reduced except for PTFE.
  • the dielectric constant in the circuit board is made by using a woven material as a reinforcing material (such as a glass fiber cloth), a woven fiber cloth due to weaving, and a node at the intersection of the woven fibers. It is not isotropic in the X and Y directions of the plane, and there is a difference in dielectric constant in the X and Y directions.
  • a high-frequency signal is transmitted in a high-frequency circuit substrate, signal attenuation occurs due to a difference in dielectric constants in the X and Y directions, which affects signal transmission stability.
  • U.S. Patent No. 6,218,815 uses two kinds of polytetrafluoroethylene resins and a mixture of fillers to cast a film to form a circuit board.
  • the circuit material produced by this method is made of a thermoplastic polytetrafluoroethylene resin, and has excellent dielectric properties, and there is no difference in dielectric constant between the X and Y directions.
  • this casting method is prone to cracks when a thick film is formed.
  • the yield is not high; especially when it is necessary to make a circuit board with a large thickness, a plurality of layers of thin films are required to be stacked together, and the production efficiency is not high.
  • U.S. Patent No. 4,772,509 uses a porous expanded polytetrafluoroethylene film to impregnate polyimide to form a prepreg, and then fabricates the circuit substrate.
  • U.S. Patent No. 5,652,055 uses a porous expanded polytetrafluoroethylene film to impregnate a thermosetting resin to form a circuit substrate.
  • these two patents are made of thermosetting resins with a large dielectric loss tangent (dielectric loss tangent greater than 0.01).
  • the fabrication of the circuit board has a dielectric property that is inferior to that of the circuit board made of polytetrafluoroethylene resin in the patent US6218015. Summary of the invention
  • the object of the present invention is to provide a composite material, which adopts a porous ePTFE film as a carrier material, and provides a dielectric constant of a prepreg and a high-frequency circuit substrate in the X and Y directions, thereby reducing the dielectric of the high-frequency circuit substrate. Constant and dielectric loss tangent.
  • Another object of the present invention is to provide a high-frequency circuit substrate fabricated using the above composite material, which has a dielectric constant in the X and Y directions, and a high-frequency dielectric property, which is better in signal transmission of a high-frequency circuit. .
  • Still another object of the present invention is to provide a method for producing a high-frequency circuit substrate produced by using the above composite material, which comprises a porous ePTFE film as a carrier material, has good formability, does not cause cracks, and operates a cylinder.
  • the present invention provides a composite material, the composition of which comprises:
  • ePTFE film a porous expanded polytetrafluoroethylene film
  • the fluoropolymer having low dielectric loss is in polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), and perfluoroethylene propylene copolymer (FEP).
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer
  • FEP perfluoroethylene propylene copolymer
  • the porous expanded polytetrafluoroethylene film is made of a polytetrafluoroethylene resin to which no ceramic filler is added or added.
  • the porous expanded polytetrafluoroethylene film is produced by an expansion stretching method, and has a pore diameter of 1 to 100 ⁇ m, a porosity of 30 to 98%, and a thickness of 0.5 to 300 ⁇ m.
  • the content of the powder filler accounts for 0 to 70% by volume of the total amount of the fluoropolymer dispersion emulsion and the powder filler having a low dielectric loss; the particle size of the powder filler is 0.01-15 ⁇ m, and the maximum particle diameter does not exceed 100. ⁇ m.
  • the powder filler is selected from the group consisting of crystalline silica, molten silica, spherical silica, alumina, barium titanate, barium titanate, barium titanate, boron nitride, aluminum nitride, carbonization.
  • crystalline silica molten silica, spherical silica, alumina, barium titanate, barium titanate, barium titanate, boron nitride, aluminum nitride, carbonization.
  • an adjuvant comprising an emulsifier and a dispersing agent.
  • the present invention also provides a high-frequency circuit substrate comprising: a plurality of prepregs superposed on each other and metal foils respectively pressed on both sides thereof, the plurality of prepregs being made of the composite material.
  • the gold It is a foil, which is copper, brass, aluminum, nickel, or an alloy or composite metal foil of these metals.
  • the present invention provides a method of fabricating the above high frequency circuit substrate, comprising the steps of:
  • Step 1 Weigh the composition of the composite material: (1) a fluoropolymer dispersion emulsion having a low dielectric loss; (2) a porous expanded polytetrafluoroethylene film; (3) a powder filler;
  • Step 2 dispersing the fluoropolymer dispersion emulsion with low dielectric loss, diluting with water to a suitable viscosity, and then adjusting the pH to 8-12 with ammonia water, mixing the powder filler and the auxiliary agent, and adding to the above-mentioned adjusted dispersion emulsion Medium, stirring and mixing, uniformly dispersing the powder filler therein to obtain a glue;
  • Step 3 impregnating the porous expanded polytetrafluoroethylene film with the above glue, and controlling to a suitable thickness, and then baking at 80 to 300 ° C to remove moisture and additives to form a prepreg;
  • Step 4 stacking the plurality of prepregs as described above, pressing each of the metal foils up and down, placing them in a press for hot pressing to obtain the high-frequency circuit substrate, and having a hot pressing temperature of 350 to 400 ° C.
  • the pressure is 25 ⁇ 100 Kg/cm 2 .
  • the glue has a solid content of 30 to 80%; the glue forms a fluoropolymer resin layer on the surface of the porous expanded polytetrafluoroethylene film, and the thickness thereof is controlled to be less than 20 ⁇ m.
  • a porous ePTFE film having excellent dielectric properties as a carrier material can reduce the dielectric constant and dielectric loss tangent of the composite material and the high-frequency circuit substrate;
  • the porous ePTFE film has good flatness and uniformity, and the high-frequency circuit substrate and prepreg which are prepared as the carrier material have dielectric constants in the X and Y directions; again, prepreg
  • the thickness can be adjusted according to the thickness of the porous ePTFE film of different thicknesses, avoiding the problem of cracking caused by the use of casting in the prior art (e.g., US Pat. No. 6,218,015). detailed description
  • the present invention provides a composite material comprising: (1) a fluoropolymer dispersed emulsion having a low dielectric loss; (2) a porous expanded polytetrafluoroethylene film (ePTFE film); (3) a powder filler.
  • a fluoropolymer dispersed emulsion having a low dielectric loss comprising: (1) a fluoropolymer dispersed emulsion having a low dielectric loss; (2) a porous expanded polytetrafluoroethylene film (ePTFE film); (3) a powder filler.
  • ePTFE film porous expanded polytetrafluoroethylene film
  • fluoropolymer dispersion emulsion having a low dielectric loss of the present invention examples include polytetrafluoroethylene, a fluorine-containing copolymer, and the like, and examples thereof include a polytetrafluoroethylene (PTFE) dispersion emulsion and a tetrafluoroethylene group.
  • PTFE polytetrafluoroethylene
  • a perfluoroalkoxy vinyl ether copolymer (PFA) dispersion emulsion, a perfluoroethylene propylene copolymer (FEP) dispersion emulsion, and the above dispersion emulsion may be used in combination of one or more.
  • the dispersion emulsion of the present invention disperses 25% to 60% of fluoropolymer particles in water as a medium. In water, it is in a stable dispersion state by a nonionic surfactant to form an emulsion.
  • the particle size of the fluoropolymer particles in the dispersion emulsion is in the range of 0.02 to 0.5 ⁇ m to facilitate subsequent impregnation.
  • the porous ePTFE film of the present invention may be formed by an expansion stretching method in which a large number of open pores are formed, and the pores are preferably sized to facilitate entry of the resin and the filler.
  • the porous ePTFE film is selected from the group consisting of an ePTFE film having a pore diameter of 1 to 100 ⁇ m, a porosity of 30 to 98%, and a thickness of 0.5 to 300 ⁇ m, preferably having a pore diameter of 3 to 50 ⁇ m, and a porosity. It is an ePTFE film of 50 to 98% and a thickness of 30 to 300 ⁇ m.
  • the ePTFE film has a large amount of pores inside, and can easily disperse the entry of materials such as emulsions and powder fillers during immersion.
  • the porous ePTFE film of the present invention may be made of a pure PTFE resin (polytetrafluoroethylene resin) or a PTFE resin to which a ceramic filler is added.
  • the surface of the porous ePTFE film is preferably subjected to a certain treatment, preferably a plasma treatment.
  • the composite material of the present invention can also be added to a powder filler, and the powder filler serves the purpose of improving dimensional stability and lowering CTE.
  • the content of the powder filler accounts for 0 to 70 Vol% (volume percent), preferably 30 to 55 Vol%, of the total amount of the fluoropolymer and the powder filler having a low dielectric loss.
  • the powder filler includes crystalline silica, molten silica, spherical silica, barium titanate, barium titanate, barium titanate, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, Titanium dioxide, glass powder, glass chopped fiber, talc powder, mica powder, carbon black, carbon nanotubes, metal powder, polyphenylene sulfide, etc., the above fillers may be used alone or in combination, wherein the optimum filler is a molten type Silica or titanium dioxide.
  • the median diameter of the filler is 0.01 ⁇ 15 ⁇ ⁇ , and the maximum particle size is not more than ⁇ ⁇ ⁇ , and the median diameter of the filler is preferably 0.5 ⁇ 10 ⁇ ⁇ .
  • the surface of the powder filler can be treated, such as with a coupling agent. Also included are auxiliaries, including emulsifiers and dispersants.
  • the method for manufacturing a high-frequency circuit substrate using the above composite material comprises the following steps: Step 1. Weigh the composition of the composite material: (1) a fluoropolymer dispersion emulsion having a low dielectric loss; (2) a porous expansion a polytetrafluoroethylene film; (3) a powder filler.
  • Step 2 dispersing the fluoropolymer dispersion emulsion with low dielectric loss, diluting to a suitable viscosity with water, and then adjusting the enthalpy value to 8-12 with ammonia water, mixing the powder filler and the auxiliary agent, and adding to the above-mentioned adjusted dispersion emulsion Medium, stirring and mixing, uniformly dispersing the powder filler therein to obtain a glue;
  • Step 3 Impregnate the porous ePTFE film with the above glue, and control to a suitable thickness, and then bake at 80 to 300 ° C to remove moisture, additives and the like to form a prepreg.
  • the glue forms a fluoropolymer resin layer on the surface of the porous expanded polytetrafluoroethylene film, and the thickness of the prepreg passes The thickness of the porous ePTFE film and the fluoropolymer resin layer on the porous ePTFE film are determined together.
  • a porous ePTFE film of different thickness may be used.
  • the ePTFE film is controlled after the glue is filled with the pores of the ePTFE film.
  • the thickness of the resin layer above 20 microns, preferably below 10 microns, ensures that a thicker (greater than 250 microns) prepreg is made to avoid cracking of the fluoropolymer resin layer impregnated on the porous ePTFE film.
  • the thickness of the fluoropolymer resin layer on the porous ePTFE film is controlled by the solid content of the resin and filler of the fluoropolymer dispersion emulsion.
  • the solid content of the resin mixture i.e., the glue
  • the solid content of the resin mixture can be adjusted between 30 and 80%, preferably between 35 and 50%.
  • the immersion operation can be carried out by a general-purpose dip-coating machine made of a copper-clad board.
  • the temperature of the sizing machine oven can be set in stages. The oven is used at a temperature range of 80-300 ° C to remove moisture and emulsifiers and dispersants.
  • Step 4 stacking the plurality of prepregs as described above, pressing each of the metal foils up and down, placing them in a press for hot pressing to obtain the high-frequency circuit substrate, and having a hot pressing temperature of 350 to 400 ° C.
  • the pressure is 25 ⁇ 100 Kg/cm 2 .
  • the metal foil is copper, brass, aluminum, nickel, or an alloy of these metals or a composite metal foil.
  • the produced high-frequency circuit substrate comprises: a plurality of prepregs superposed on each other and metal foils respectively pressed on both sides thereof, the plurality of prepregs being made of the composite material.
  • dielectric properties of the above-described high-frequency circuit substrate that is, dielectric constant and dielectric loss tangent, high-frequency performance, and heat resistance are further described and described in the following embodiments.
  • the polytetrafluoroethylene dispersion emulsion having a solid content of 60% was adjusted to a viscosity of 20 mPa-s (20 ° C) with deionized water, and then the enthalpy was adjusted to 11 with ammonia water, and the mixture was uniformly stirred.
  • An ePTFE film having a thickness of 40 ⁇ m and a porosity of 92% was impregnated with the above-mentioned adjusted polytetrafluoroethylene dispersion emulsion, and then sent to an oven for baking at 280 ° C to remove moisture and auxiliary agents (emulsifiers, dispersants).
  • auxiliary agents emulsifiers, dispersants
  • the obtained high-frequency circuit substrate was tested to have a dielectric constant of 2.08 (10 GHz) and a dielectric loss tangent of 0.0002 (10 GHz).
  • the polytetrafluoroethylene dispersion emulsion with a solid content of 60% was adjusted to a viscosity of 15 mPa.s (20 ° C) with deionized water, and then the enthalpy value was adjusted to about 11 with ammonia water, and the mixture was stirred and mixed uniformly.
  • Will The molten silica powder (weight ratio of silicon powder to PTFE is 1:1) is added to the above emulsion, and the silica is uniformly dispersed in the emulsion by stirring to obtain an impregnable gum.
  • the ePTFE film having a thickness of 300 ⁇ m and a porosity of 95% was impregnated with the above-mentioned adjusted glue, and then sent to an oven for baking at 280 ° C to remove moisture and additives (emulsifiers, dispersants) to prepare a prepreg.
  • the resulting prepreg had a thickness of 308 microns and was free of cracks.
  • One sheet of the above prepreg was taken, one piece of copper foil was pressed up and down, and placed in a press for hot pressing to obtain the high-frequency circuit substrate, the temperature was 380 ° C, and the pressure was 70 kg/cm 2 .
  • the obtained high-frequency circuit substrate was tested to have a dielectric constant of 2.53 (10 GHz) and a dielectric loss tangent of 0.0003 (10 GHz).
  • the polytetrafluoroethylene dispersion emulsion with a solid content of 60% was adjusted to a viscosity of 15 mPa.s (20 ° C) with deionized water, and then the enthalpy value was adjusted to about 11 with ammonia water, and the mixture was stirred and mixed uniformly.
  • the molten silica powder (weight ratio of silicon powder to PTFE was 1:1) was added to the above emulsion, and the silica was uniformly dispersed in the emulsion by stirring to obtain an impregnable gum.
  • An ePTFE film filled with a fused silica filler having a thickness of 120 ⁇ m and a porosity of 95% (the content of the fused silica filler in the film was 50%) was impregnated with the above-mentioned adjusted glue, and then sent to an oven at 280. Baking, removal of moisture and auxiliaries (emulsifiers, dispersants), and preparation of prepregs, the resulting prepreg had a thickness of 128 microns and was free of cracks.
  • One sheet of the above prepreg was taken, and one piece of copper foil was pressed up and down, and placed in a press to be hot pressed to obtain the high-frequency circuit substrate at a temperature of 380 ° C and a pressure of 100 kg/cm 2 .
  • the obtained high-frequency circuit substrate was tested to have a dielectric constant of 2.65 (10 GHz) and a dielectric loss tangent of 0.0003 (10 GHz).
  • An ePTFE film having a thickness of 40 ⁇ m and a porosity of 92% was impregnated with the above glue, and then baked in an oven at 155 ° C to remove the solvent dimethylformamide to prepare a prepreg having a thickness of 54 ⁇ m.
  • a polyimide resin synthesized from a dianhydride and a diamine was dissolved in dimethylformamide, and an appropriate amount of triphenylphosphine was added as a curing accelerator to prepare a gum solution.
  • An ePTFE film having a thickness of 40 ⁇ m and a porosity of 92% was impregnated with the above glue, and then baked in an oven at 155 ° C to remove the solvent dimethylformamide to prepare a prepreg having a thickness of 50 ⁇ m.
  • the obtained high-frequency circuit substrate was tested to have a dielectric constant of 3.32 (10 GHz) and a dielectric loss tangent of 0.006 (10 GHz).
  • the above examples and comparative examples refer to the IPC4101 standard for the detection of copper clad laminates.
  • the dielectric properties are tested by the SPDR (splite post dielectric resonator) method.
  • the test conditions are A state, 10 GHz.
  • the thickness of the prepared prepreg can be adjusted without cracks, and the obtained high-frequency circuit substrate material has a low dielectric constant and dielectric loss angle, and high frequency performance is good.
  • the woven fiber is not used as the reinforcing material, the uniformity inside the substrate is good, and there is no difference in the dielectric constant in the X/Y direction.
  • the dielectric loss tangent ratio of the resulting circuit substrate is made of a thermoplastic fluoropolymer resin and a porous ePTFE.
  • the circuit board used in conjunction with the film has a much larger dielectric constant. Therefore, the circuit board used in combination with the thermoplastic fluoropolymer resin and the porous gap ePTFE film has more excellent high-frequency performance and is more effective in signal transmission of high-frequency circuits.
  • the circuit board of the present invention has more excellent dielectric properties than a general copper foil substrate, i.e., has a low dielectric constant and dielectric loss tangent, and has high frequency performance.

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Description

复合材料、 用其制作的高频电路基板及其制作方法 技术领域
本发明涉及复合材料技术领域， 尤其涉及一种复合材料、 用其制作的 高频电路基板及其制作方法。 背景技术
近年来， 随着信息通讯设备高性能化、 高功能化以及网络化的发展， 为了高速传输及处理大容量信息， 操作信号趋向于高频化， 电子产品的使 用频率持续走高， 要求基板材料的介电常数越来越低， 介电损耗越来越 小， 而且要求基板介电常数的均匀性要好。
目前高频电路基板使用低介电常数的树脂来获得良好的高频性能， 这 些低介电常数的树脂包括有由聚苯醚、 氰酸酯、 含有碳 -碳不饱和双键的只 由碳氢元素构成的热固性树脂、 PTFE 等几种树脂。 覆铜板一般使用玻璃 纤维布作为增强材料。 但是玻璃纤维布的介电常数最低只可以做到 3.7(Q 玻璃)， 受玻璃纤维布介电常数大的影响， 除 PTFE外， 其它树脂制作的覆 铜板的介电常数很难降低。
另一方面， 在目前高频电路基板中， 因使用编织材料做增强材料（如 玻璃纤维布） ， 编织纤维布因编织的原因以及编织纤维交叉部分的节点存 在， 使得电路板中的介电常数在平面的 X、 Y方向的不是各向同性， 存在 X、 Y 方向的介电常数差异。 这样高频信号在高频电路基板中传输时， 因 在 X、 Y 方向的介电常数的不同产生信号的衰减， 影响信号传输的稳定 性。
美国专利 US6218015采用两种聚四氟乙烯树脂配合并混合填料浇铸成 薄膜后进行电路基板的制作。 这种方法制作的电路材料因整板采用热塑性 聚四氟乙烯树脂， 介电性能优异， X、 Y 方向的介电常数也不存在差异， 但这种浇注方法制作较厚的薄膜时容易产生裂纹， 成品率不高； 特别是在 需要制作厚度较大的电路板时， 需要许多层薄膜叠加在一起制成， 生产效 率不高。
美国专利 US4772509采用多孔隙的膨胀聚四氟乙烯薄膜浸渍聚酰亚胺 制作成半固化片， 然后进行电路基板的制作。 美国专利 US5652055采用多 孔隙的膨胀聚四氟乙烯薄膜浸渍热固性树脂制作电路基板。 但是这两个专 利因采用介质损耗角正切大（介质损耗角正切大于 0.01 ) 的热固性树脂进 行电路基板的制作， 其介电性能要比专利 US6218015采用聚四氟乙烯树脂 制作的电路基板介电性能差。 发明内容
本发明的目的在于提供一种复合材料， 采用多孔隙的 ePTFE薄膜为载 体材料， 提供预浸料及高频电路基板介电常数在 X、 Y方向各向同性， 能 够降低高频电路基板的介电常数和介质损耗角正切。
本发明的另一目的在于提供使用上述复合材料制作的高频电路基板， 具有介电常数在 X、 Y方向各向同性， 及高频介电性能， 在高频电路的信 号传输中效果更好。
本发明的再一目的在于提供使用上述复合材料制作的高频电路基板的 制作方法， 采用多孔隙的 ePTFE薄膜为载体材料， 具有良好的成型性， 不 产生裂纹， 工艺操作筒便。
为实现上述目的， 本发明提供一种复合材料， 其组成物包括：
( 1 )具有低介电损耗的氟聚合物分散乳液；
( 2 ) 多孔隙的膨胀聚四氟乙烯薄膜（ePTFE薄膜） ； 及
( 3 )粉末填料。
所述具有低介电损耗的氟聚合物为聚四氟乙烯（PTFE ) 、 四氟乙烯- 全氟烷氧基乙烯基醚共聚物 （PFA ) 、 及全氟乙烯丙烯共聚物 （FEP ) 中 的一种或多种。
所述多孔隙的膨胀聚四氟乙烯薄膜由聚四氟乙烯树脂制成， 该聚四氟 乙烯树脂不添加或添加有陶瓷填料。
所述多孔隙的膨胀聚四氟乙烯薄膜是通过膨胀拉伸方法制作而成， 其 孔径为 1~100 μ ιη, 孔隙率为 30~98% , 厚度为 0.5~300 μ m。
所述粉末填料含量占具有低介电损耗的氟聚合物分散乳液和粉末填料 总量的 0~70体积％; 粉末填料的粒径中度值为 0.01-15 μ ιη, 最大粒径不 超过 100 μ m。
所述粉末填料选自结晶型二氧化硅、 熔融型的二氧化硅、 球型二氧化 硅、 氧化铝、 钛酸锶、 钛酸钡、 钛酸锶钡、 氮化硼、 氮化铝、 碳化硅、 二 氧化钛、 玻璃粉、 玻璃短切纤维、 滑石粉、 云母粉、 碳黑、 碳纳米管、 金 属粉、 及聚^ £醚中的一种或多种。
还包括（4 )助剂， 该助剂包括有乳化剂及分散剂。
本发明还提供一种高频电路基板， 包括： 数张相互叠合的预浸料及分 别压覆于其两侧的金属箔， 该数张预浸料均由所述复合材料制作。 所述金 属箔， 为铜、 黄铜、 铝、 镍、 或这些金属的合金或复合金属箔。
同时， 本发明提供一种上述高频电路基板的制作方法， 包括下述步 骤：
步骤 1、 称取复合材料的组成物： （1 )具有低介电损耗的氟聚合物分 散乳液； （ 2 ) 多孔隙的膨胀聚四氟乙烯薄膜； （ 3 )粉末填料；
步骤 2、 将具有低介电损耗的氟聚合物分散乳液， 用水稀释至适当的 粘度， 然后用氨水调节 PH值至 8-12, 将粉末填料和助剂混合， 加入到上 述调节好的分散乳液中， 搅拌混合， 使粉末填料均一的分散在其中， 制得 胶液；
步骤 3、 用上述胶液浸渍多孔隙的膨胀聚四氟乙烯薄膜， 并控制到合 适的厚度， 然后于 80~300°C烘烤去除水分及助剂， 形成预浸料；
步骤 4、 将上述的预浸料数张相叠合， 上下各压覆一张金属箔， 放进 压机进行热压制得所述高频电路基板， 热压温度为 350~400°C , 热压压力 为 25~100 Kg/cm2。
所述胶液的固体含量为 30~80%； 所述胶液在多孔隙的膨胀聚四氟乙 烯薄膜表面上形成氟聚合物树脂层， 其厚度控制在 20微米以下。
本发明的有益效果： 首先， 采用介电性能优异的多孔隙的 ePTFE薄膜 作为载体材料， 能够降低复合材料及高频电路基板的介电常数和介质损耗 角正切；
其次， 多孔隙的 ePTFE薄膜平整度、 均匀性好， 用其作为载体材料， 制作成的高频电路基板及预浸料具有介电常数在 X、 Y方向各向同性； 再次， 预浸料的厚度可以根据采用不同厚度的多孔隙的 ePTFE薄膜的 厚度调节， 避免了现有技术（如 US6218015专利） 中使用浇注法生产厚膜 产生的裂纹问题。 具体实施方式
本发明提供一种复合材料， 包括： （1 ) 具有低介电损耗的氟聚合物 分散乳液； （ 2 ) 多孔隙的膨胀聚四氟乙烯薄膜（ ePTFE 薄膜） ； （ 3 )粉 末填料。
作为本发明的具有低介电损耗的氟聚合物分散乳液的实例， 包括聚四 氟乙烯， 和含氟的共聚物等， 可以列举的有聚四氟乙烯 （PTFE ) 分散乳 液、 四氟乙烯一全氟烷氧基乙烯基醚共聚物 （PFA ) 分散乳液、 全氟乙烯 丙烯共聚物 （FEP ) 分散乳液， 上述分散乳液可一种或多种混合使用。 本 发明所述的分散乳液是以水为介质， 将 25%~60%的氟聚合物微粒分散在 水里， 通过非离子表面活性剂使之处于稳定分散状态， 形成一种乳液。 分 散乳液中氟聚合物微粒粒径在 0.02~0.5微米范围内， 以方便后面的浸渍。
本发明所述的多孔隙的 ePTFE薄膜， 这种薄膜可以是通过膨胀拉伸方 法制作而成， 在其中有大量的开口的孔隙， 孔隙的大小以可方便树脂和填 料进入为好。 根据本发明， 所述的多孔隙的 ePTFE薄膜选用孔径为 1~100 μ ιη、 孔隙率为 30~98%、 厚度 0.5~300 μ m 的 ePTFE薄膜， 优选孔径为 3~50 μ ιη、 孔隙率为 50~98%、 厚度 30~300 μ m的 ePTFE薄膜。 该 ePTFE 薄膜因内部有大量孔隙存在， 在浸渍时， 可以方便分散乳液、 粉末填料等 材料的进入。
本发明所述的多孔隙的 ePTFE薄膜， 可以是纯 PTFE树脂 （聚四氟乙 烯树脂）制成的， 也可以是添加了陶瓷填料的 PTFE树脂制成。 根据本发 明， 所述的多孔隙的 ePTFE薄膜表面以经过一定的处理为好， 优选等离子 体处理。
本发明的复合材料还可加入粉末填料， 粉末填料起着改善尺寸稳定 性、 降低 CTE等目的。 所述粉末填料的含量占具有低介电损耗的氟聚合物 和粉末填料总量的 0~70 Vol % (体积百分比） ， 优选 30~55Vol%。 粉末填 料包括有结晶型二氧化硅、 熔融型的二氧化硅、 球型二氧化硅、 钛酸锶、 钛酸钡、 钛酸锶钡、 氮化硼、 氮化铝、 碳化硅、 氧化铝、 二氧化钛、 玻璃 粉、 玻璃短切纤维、 滑石粉、 云母粉、 碳黑、 碳纳米管、 金属粉、 聚苯硫 醚等， 以上填料可以单独使用或混合使用， 其中， 最佳填料是熔融型的二 氧化硅或二氧化钛。 为方便填料可以进入到 ePTFE薄膜的孔隙中， 填料的 粒径中度值为 0.01~15 μ ιη, 最大粒径不超过 ΙΟΟ μ ιη, 优选填料的粒径中 度值为 0.5~10 μ ιη。 为达到更好的性能， 粉末填料的表面可以经过处理， 如使用偶联剂进行处理等。 还包括助剂， 助剂包括有乳化剂及分散剂等。
使用上述复合材料制作高频电路基板的方法， 包括下述步骤： 步骤 1、 称取复合材料的组成物： （1 )具有低介电损耗的氟聚合物分 散乳液； （ 2 ) 多孔隙的膨胀聚四氟乙烯薄膜； （ 3 )粉末填料。
步骤 2、 将具有低介电损耗的氟聚合物分散乳液， 用水稀释至适当的 粘度， 然后用氨水调节 ΡΗ值至 8-12, 将粉末填料和助剂混合， 加入到上 述调节好的分散乳液中， 搅拌混合， 使粉末填料均一的分散在其中， 制得 胶液；
步骤 3、 用上述胶液浸渍多孔隙的 ePTFE 薄膜， 并控制到合适的厚 度， 然后在 80~300°C烘烤除去水分、 助剂等形成预浸料。 所述胶液在多孔 隙的膨胀聚四氟乙烯薄膜表面上形成氟聚合物树脂层， 预浸料的厚度通过 多孔隙的 ePTFE薄膜， 以及多孔隙的 ePTFE薄膜上的氟聚合物树脂层的 厚度共同决定。 为了获取不同厚度的预浸料， 可以采用不同厚度的多孔隙 的 ePTFE薄膜， 在浸渍由所述氟聚合物分散乳液等形成的胶液后， 在胶液 填充满 ePTFE薄膜孔隙后， 控制 ePTFE薄膜上的树脂层厚度在 20微米以 下， 优选控制在 10微米以下， 这样可以保证制作更厚（大于 250微米） 的预浸料而避免多孔隙的 ePTFE薄膜上浸渍的氟聚合物树脂层产生裂纹。
所述多孔隙的 ePTFE薄膜上的氟聚合物树脂层厚度通过氟聚合物分散 乳液的树脂及填料的固体含量来控制。 树脂混合物 （即胶液） 的固体含量 可调节在 30~80%之间， 优选 35~50%。
浸渍操作可以采用覆铜板制作的通用浸渍上胶机进行， 上胶机烘箱的 温度可以分段设定， 烘箱采用的温度范围为 80~300°C , 以去除水分以及乳 化剂、 分散剂等。
步骤 4、 将上述的预浸料数张相叠合， 上下各压覆一张金属箔， 放进 压机进行热压制得所述高频电路基板， 热压温度为 350~400°C , 热压压力 为 25~100 Kg/cm2。 所述金属箔， 为铜、 黄铜、 铝、 镍、 或这些金属的合 金或复合金属箔。
所制作的高频电路基板， 包括： 数张相互叠合的预浸料及分别压覆于 其两侧的金属箔， 该数张预浸料均由所述复合材料制作。
针对上述制成的高频电路基板的介电性能， 即介电常数和介质损耗角 正切、 高频性能及耐热性能， 如下述实施例进一步给予详加说明与描述。
实施例 1
将固含量为 60 %的聚四氟乙烯分散乳液用去离子水调节粘度为 20mPa-s ( 20°C ) , 然后用氨水调节 ΡΗ值至 11 , 搅拌混合均匀。
用上述调节好的聚四氟乙烯分散乳液浸渍厚度为 40微米、 孔隙率为 92%的 ePTFE薄膜， 然后送入烘箱于 280°C烘烤， 除去水分和助剂 （乳化 剂、 分散剂） ， 制作成预浸料， 预浸料厚度为 51 微米， 该制成的预浸料 没有裂紋。
取 5 张上述的预浸料相叠合， 上下各压覆一张铜箔， 放进压机进行热 压制得所述高频电路基板， 热压温度为 350 °C ~400 °C , 热压压力为 70Kg/cm2。 测试该制得的高频电路基板， 介电常数为 2.08 ( 10GHZ ) , 介 质损耗角正切为 0.0002 ( 10GHZ ) 。
实施例 2
将固含量为 60 %的聚四氟乙烯分散乳液用去离子水调节粘度为 15mPa.s ( 20°C ) , 然后用氨水调节 ΡΗ值至 11 左右， 搅拌混合均匀。 将 熔融型的二氧化硅粉末（硅 粉和 PTFE的重量比为 1: 1 ) 加入以上乳液 中， 搅拌使二氧化硅均一的分散在乳液中， 制得可浸渍的胶液。
用上述调节好的胶液浸渍厚度为 300微米、 孔隙率为 95%的 ePTFE薄 膜， 然后送入烘箱于 280°C烘烤， 除去水分和助剂 （乳化剂、 分散剂） ， 制作成预浸料， 该制成的预浸料厚度为 308微米， 没有裂纹。
取上述的预浸料 1 张， 上下各压覆一张铜箔， 放进压机进行热压制得 所述高频电路基板， 温度为 380°C , 压力为 70Kg/cm2。 测试该制得的高频 电路基板， 介电常数为 2.53 ( 10GHZ ) , 介质损耗角正切为 0.0003 ( 10GHZ ) 。
实施例 3
将固含量为 60 %的聚四氟乙烯分散乳液用去离子水调节粘度为 15mPa.s ( 20°C ) , 然后用氨水调节 ΡΗ值至 11 左右， 搅拌混合均匀。 将 熔融型的二氧化硅粉末（硅 粉和 PTFE的重量比为 1: 1 ) 加入以上乳液 中， 搅拌使二氧化硅均一的分散在乳液中， 制得可浸渍的胶液。
用上述调节好的胶液浸渍厚度为 120微米、 孔隙率为 95%的填充有熔 融二氧化硅填料的 ePTFE 薄膜 （薄膜中熔融二氧化硅填料的含量为 50% ) , 然后送入烘箱于 280°C烘烤， 除去水分和助剂 （乳化剂、 分散 剂） ， 制作成预浸料， 该制成的预浸料厚度为 128微米， 没有裂纹。
取上述的预浸料 1 张， 上下各压覆一张铜箔， 放进压机进行热压制得 所述高频电路基板， 温度为 380°C , 压力为 100Kg/cm2。 测试该制得的高 频电路基板， 介电常数为 2.65 ( 10GHZ ) , 介质损耗角正切为 0.0003 ( 10GHZ ) 。
比较例 1
将双酚 A环氧树脂 （环氧树脂 A ) 、 溴化环氧树脂 （环氧树脂 B )溶 解在二甲基甲酰胺中， 并添加相对于环氧树脂 0.7摩尔比胺当量的双氰胺 作固化剂和适量 2-MI ( 2-甲基咪唑）做促进剂， 然后在室温下混合得到胶 液。
用以上胶液浸渍厚度为 40微米、 孔隙率为 92%的 ePTFE薄膜， 然后 送入烘箱于 155°C烘烤， 除去溶剂二甲基甲酰胺， 制作成厚度为 54微米的 预浸料。
取 5 张上述的预浸料相叠合， 上下各压覆一张铜箔， 放进压机进行热 压制得所述高频电路基板， 固化温度为 177°C , 固化压力为 50Kg/cm2, 固 化时间为 90 分钟。 测试该制得的高频电路基板， 介电常数为 3.54 ( 10GHZ ) , 介质损耗角正切为 0.008 ( 10GHZ ) 。 比较例 2
将用二酐和二胺合成的聚酰亚胺树脂溶解在二甲基甲酰胺中， 并加入 适量的三苯基膦作为固化促进剂， 制作成胶液。
用以上胶液浸渍厚度为 40微米、 孔隙率为 92%的 ePTFE薄膜， 然后 送入烘箱于 155°C烘烤， 除去溶剂二甲基甲酰胺， 制作成厚度为 50微米的 预浸料。
取 5 张上述的预浸料相叠合， 上下各压覆一张铜箔， 放进压机进行热 压制得所述高频电路基板， 固化温度为 260°C , 固化压力为 50Kg/cm2, 固 化时间为 120 分钟。 测试该制得的高频电路基板， 介电常数为 3.32 ( 10GHZ ) , 介质损耗角正切为 0.006 ( 10GHZ ) 。
以上实施例和比较例皆参照 IPC4101 标准对覆铜板进行检测， 介电性 能的检测方法采用 SPDR ( splite post dielectric resonator ) 法进行测试， 测 试条件为 A态， 10GHz。
从以上实施例 1、 2、 3 可以看出， 所制作的预浸料厚度可以调节， 且 没有裂纹， 制得的高频电路基板材料介电常数和介质损耗角低， 高频性能 好。 另外， 因没有采用编织纤维做增强材料， 基板内部的均匀性很好， 在 X/Y 方向介电常数不存在差异。 从比较例可以看出， 因为使用了介质损耗 角正切大的热固性树脂和多孔隙的 ePTFE薄膜配合使用， 制成的电路基板 的介质损耗角正切比采用热塑性的氟聚合物树脂和多孔隙的 ePTFE薄膜配 合使用的电路基板的介电常数大很多。 因此热塑性的氟聚合物树脂和多孔 隙的 ePTFE薄膜配合使用的电路基板具有更加优异的高频性能， 在高频电 路的信号传输中效果更好。
如上所述， 与一般的铜箔基板相比， 本发明的电路基板拥有更加优异 的介电性能， 即具有较低的介电常数和介质损耗角正切， 高频性能很好。
以上实施例， 并非对本发明的组合物的含量作任何限制， 凡是依据本 发明的技术实质或组合物成重量份或含量对以上实施例所作的任何细微修 改、 等同变化与修饰， 均仍属于本发明技术方案的范围内。

Claims

权 利 要 求
1、 一种复合材料， 其组成物包括：
( 1 )具有低介电损耗的氟聚合物分散乳液；
( 2 ) 多孔隙的膨胀聚四氟乙烯薄膜； 及
( 3 )粉末填料。
2、 如权利要求 1 所述的复合材料， 其中， 所述具有低介电损耗的氟 聚合物为聚四氟乙烯、 四氟乙烯-全氟烷氧基乙婦基醚共聚物、 及全氟乙烯 丙烯共聚物中的一种或多种。
3、 如权利要求 1 所述的复合材料， 其中， 所述多孔隙的膨胀聚四氟 乙烯薄膜由聚四氟乙烯树脂制成， 该聚四氟乙烯树脂不添加或添加有陶瓷 填料。
4、 如权利要求 1 所述的复合材料， 其中， 所述多孔隙的膨胀聚四氟 乙烯薄膜是通过膨胀拉伸方法制作而成， 其孔径为 1~100 μ ιη, 孔隙率为 30~98%, 厚度为 0.5~300 μ ιη。
5、 如权利要求 1 所述的复合材料， 其中， 所述粉末填料含量占具有 低介电损耗的氟聚合物分散乳液和粉末填料总量的 0~70体积％; 粉末填料 的粒径中度值为 0.01-15 μ ιη, 最大粒径不超过 100 μ m。
6、 如权利要求 1 或 5 所述的复合材料， 其中， 所述粉末填料选自结 晶型二氧化硅、 熔融型的二氧化硅、 球型二氧化硅、 氧化铝、 钛酸锶、 钛 酸钡、 钛酸锶钡、 氮化硼、 氮化铝、 碳化硅、 二氧化钛、 玻璃粉、 玻璃短 切纤维、 滑石粉、 云母粉、 碳黑、 碳纳米管、 金属粉、 及聚苯硫醚中的一 种或多种。
7、 如权利要求 1 所述的复合材料， 其中， 还包括（4 )助剂， 该助剂 包括有乳化剂及分散剂。
8、 一种使用如权利要求 1 所述的复合材料制作的高频电路基板， 包 括： 数张相互叠合的预浸料及分别压覆于其两侧的金属箔， 其中， 该数张 预浸料均由所述复合材料制作。
9、 一种制作如权利要求 8 所述的高频电路基板的方法， 包括下述步 骤：
步骤 1、 称取复合材料的组成物： （1 )具有低介电损耗的氟聚合物分 散乳液； （ 2 ) 多孔隙的膨胀聚四氟乙烯薄膜； （ 3 )粉末填料；
步骤 2、 将具有低介电损耗的氟聚合物分散乳液， 用水稀释至适当的 粘度， 然后用氨水调节 PH值至 8-12, 将粉末填料和助剂混合， 加入到上 述调节好的分散乳液中， 搅拌混合， 使粉末填料均一的分散在其中， 制得 胶液；
步骤 3、 用上述胶液浸渍多孔隙的膨胀聚四氟乙烯薄膜， 并控制到合 适的厚度， 然后于 80~300°C烘烤去除水分及助剂， 形成预浸料；
步骤 4、 将上述的预浸料数张相叠合， 上下各压覆一张金属箔， 放进 压机进行热压制得所述高频电路基板， 热压温度为 350~400°C , 热压压力 为 25~100 Kg/cm2。
10、 如权利要求 9所述的高频电路基板的制作方法， 其中， 所述胶液 的固体含量为 30~80%； 所述胶液在多孔隙的膨胀聚四氟乙烯薄膜表面上 形成氟聚合物树脂层， 其厚度控制在 20微米以下。
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