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CN118325261A - Composite material - Google Patents

Composite material Download PDF

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Publication number
CN118325261A
CN118325261A CN202410569864.9A CN202410569864A CN118325261A CN 118325261 A CN118325261 A CN 118325261A CN 202410569864 A CN202410569864 A CN 202410569864A CN 118325261 A CN118325261 A CN 118325261A
Authority
CN
China
Prior art keywords
powder
filler
ptfe
composite material
microns
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202410569864.9A
Other languages
Chinese (zh)
Inventor
苏民社
蔡旺
付艺伟
焦志慧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Linzhou Zhiyuan Electronic Technology Co ltd
Original Assignee
Linzhou Zhiyuan Electronic Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Linzhou Zhiyuan Electronic Technology Co ltd filed Critical Linzhou Zhiyuan Electronic Technology Co ltd
Priority to CN202410569864.9A priority Critical patent/CN118325261A/en
Publication of CN118325261A publication Critical patent/CN118325261A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • B32B15/08—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 of synthetic resin
    • B32B15/085—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 of synthetic resin comprising polyolefins
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a 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
    • 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
    • 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
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • B32B5/024—Woven fabric
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B32B5/262—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a woven fabric layer
    • B32B5/263—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a woven fabric layer next to one or more woven fabric layers
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin 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
    • B32B2457/00—Electrical equipment
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a composite material, which relates to the technical field of composite materials, and comprises fluorine-containing polymer dispersed emulsion, PTFE woven cloth, powder filler and an auxiliary agent, wherein the fluorine-containing polymer comprises one or more of polytetrafluoroethylene emulsion, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer and perfluoroethylene propylene copolymer, the PTFE woven cloth is prepared from PTFE resin, the PTFE resin is added with the filler, and the auxiliary agent comprises an emulsifying agent, a dispersing agent and a rheological auxiliary agent.

Description

Composite material
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite material.
Background
In recent years, with the development of high performance, high functionality, and networking of information communication apparatuses, in order to transmit and process large-capacity information at high speed, operation signals tend to be high-frequency, the frequency of use of electronic products continues to be high, dielectric constants of substrate materials are required to be lower and lower, dielectric losses are required to be smaller, and uniformity of dielectric constants of substrates is required to be good.
At present, high-frequency circuit substrates use resins with low dielectric constants to obtain good high-frequency performance, wherein the resins with low dielectric constants comprise polyphenyl ether, cyanate ester, hydrocarbon resin, PTFE and the like, glass fibers are generally used as reinforcing materials for the circuit substrates, but the dielectric constants of glass fiber cloth are relatively large (the dielectric constant of E-glass is 6.6 and the dielectric constant of Q glass is 3.8), and the dielectric constants of the circuit substrates made of other resins except PTFE are hardly reduced due to the large influence of the dielectric constants of the glass fiber cloth.
In addition, although a Q glass cloth having a low dielectric loss tangent is used for a circuit board to obtain a low dielectric loss, the Q glass cloth is brittle in glass component and is easily broken, and a defect is easily generated in a composite material or a circuit board to be manufactured.
Disclosure of Invention
The present invention has an object to provide a composite material which uses a PTFE woven fabric added with a filler as a carrier material, provides a prepreg and a high-frequency circuit board manufactured therefrom, and can reduce the dielectric constant and dielectric loss tangent of the high-frequency circuit board, thereby solving the problem that the dielectric constant and dielectric loss tangent of the circuit board manufactured from the conventional materials proposed in the prior art are hardly reduced.
Another object of the present invention is to provide a high-frequency circuit board made of the above composite material and a method for manufacturing the same, wherein the PTFE woven fabric added with the filler is used as a carrier material, which has good formability, good strength, and is not easy to break, and the process is easy to operate, so as to solve the problem that the circuit board made of the above-mentioned background art is easy to have defects inside.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A composite material comprises a fluoropolymer dispersion emulsion, PTFE woven cloth and powder filler, wherein the fluoropolymer comprises one or more of polytetrafluoroethylene emulsion, tetrafluoroethylene-perfluoro alkoxy vinyl ether copolymer and perfluoro ethylene propylene copolymer, the fluoropolymer dispersion emulsion takes water as a medium, 25% -60% of fluoropolymer particles are dispersed in the water, the fluoropolymer particles are in a stable dispersion state through nonionic surfactant to form an emulsion, the particle size of the fluoropolymer particles in the dispersion emulsion is in the range of 0.02-0.5 microns so as to facilitate subsequent impregnation, the PTFE woven cloth is made of PTFE resin, and the PTFE resin is added with the filler, the filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder, and the powder filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder.
As a further scheme of the invention: the monofilament diameter of the PTFE knitted cloth is from 1 micron to 9 microns, alternatively 1 micron, 3 microns, 5 microns, 7 microns and 9 microns, and the thickness of the knitted PTFE knitted cloth is from 0.03 mm to 0.2 mm, alternatively 0.03 mm, 0.05 mm, 0.06 mm, 0.1 mm and 0.2 mm.
As still further aspects of the invention: the PTFE woven cloth is formed by cutting a PTFE sintered film (manufactured by extrusion, rolling and expansion stretching) added with a filler into filaments, and then weaving the cut filaments by adopting a plain weaving method.
As still further aspects of the invention: the content of the powder filler is 0-70% of the total amount of the fluorine-containing polymer and the powder filler, the particle size median value of the powder filler is 0-15 microns, and the maximum particle size is not more than 100 microns.
As still further aspects of the invention: the composite material further includes an adjuvant comprising an emulsifier, a dispersant, and a rheology aid.
A circuit substrate made of composite material comprises a plurality of prepregs which are mutually overlapped and metal foils respectively pressed on two sides of the prepregs, wherein the prepregs are made of composite material, and the metal foils are copper, brass, aluminum, nickel or alloys of the metals or composite metal foils.
As still further aspects of the invention: the manufacturing method of the circuit substrate made of the composite material comprises the following steps,
S1, weighing a composition of the composite material;
S2, diluting the fluorine-containing polymer dispersion liquid with water to a proper viscosity, then regulating the pH value to 8-12 with ammonia water, mixing the powder filler and the auxiliary agent, adding the mixture into the regulated dispersion emulsion, stirring and mixing to uniformly disperse the powder filler therein, and preparing a glue solution, wherein the solid content of the glue solution is 30-80%; the glue solution forms a resin layer on the surface of the PTFE woven cloth added with the filler, and the thickness of the resin layer is controlled below 100 micrometers;
s3, impregnating the PTFE woven cloth added with the filler by using the glue solution, controlling the thickness to be proper, and then baking at 80-300 ℃ to remove moisture and auxiliary agents to form prepreg;
And S4, laminating a plurality of prepregs, respectively pressing one metal foil up and down, and putting the prepregs into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 350-400 ℃, and the hot pressing pressure is 25-130 Kg/cm 2.
Compared with the prior art, the invention has the beneficial effects that:
1. The composite material or the circuit board prepared by adopting the PTFE woven cloth added with the filler and having excellent dielectric property as the carrier material has good dielectric constant and low dielectric loss tangent.
2. The invention adopts PTFE woven cloth added with filler to prepare prepreg, and the prepared composite material or circuit substrate has lower thermal expansion coefficient and dielectric property stability.
3. The invention adopts PTFE woven cloth added with filler to prepare the prepreg, the process operability is good, and the thickness flatness of the prepared prepreg is good.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a composite material, which comprises fluoropolymer dispersion emulsion, PTFE woven cloth added with filler, powder filler and auxiliary agent.
Examples of the fluoropolymer dispersion emulsion of the present invention include polytetrafluoroethylene and fluorine-containing copolymers, and there may be mentioned polytetrafluoroethylene dispersion emulsion, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer dispersion emulsion and perfluoroethylene propylene copolymer dispersion emulsion, the above dispersion emulsions may be used in combination of one or more, and the dispersion emulsion of the present invention is obtained by dispersing 25 to 60% of fluoropolymer particles in water with a medium of water, and bringing the fluoropolymer particles into a stable dispersion state with a nonionic surfactant to form an emulsion, and the fluoropolymer particles in the dispersion emulsion have a particle diameter in the range of 0.02 to 0.5 μm to facilitate subsequent impregnation.
The PTFE woven cloth with the filler is prepared by cutting a PTFE sintered film (prepared by extrusion, rolling and expansion stretching) with the filler into filaments, weaving the filaments into PTFE fiber cloth with the filler by adopting a plain weaving method, wherein the monofilament diameter of the woven fiber cloth is from 1 micron to 9 microns, and the thickness of the woven PTFE woven cloth with the filler is from 0.03 millimeter to 0.2 millimeter, and the thickness of the woven PTFE woven cloth with the filler is from 0.03 millimeter to 0.05 millimeter, 0.06 millimeter, 0.1 millimeter and 0.2 millimeter, and the powder filler is one or more selected from crystalline silica, fused silica, spherical silica, alumina, titanium dioxide, strontium titanate, barium titanate, strontium barium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fibers, glass powder, talcum powder, mica powder, carbon black, carbon nano tubes, metal powder, magnetic powder and polyphenylene sulfide powder.
The PTFE woven cloth added with the filler is prepared by an extrusion, rolling and expansion stretching method, the content of the powder filler accounts for 0-70 percent, preferably 5-30 percent, and less than 5 percent of the total amount of the fluorine-containing polymer and the powder filler, and the aim of improving the dimensional stability is not achieved, the strength of the prepared fiber is not high, the formability is poor, the particle size of the powder filler is 0-15 microns, the maximum particle size is not more than 100 microns.
The composite material also comprises powder filler, wherein the powder filler is selected from one or more of crystalline silicon dioxide, fused silicon dioxide, spherical silicon dioxide, aluminum oxide, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder, and the content of the powder filler accounts for 0-70 percent, preferably 30-50 percent of the total content of the fluorine-containing polymer and the powder filler. The powder filler has a median particle size of 0-15 microns and a maximum particle size of not more than 100 microns, and the above fillers may be used alone or in combination, and the surface of the powder filler may be treated, for example with a coupling agent, to achieve better properties.
According to the invention, auxiliaries are also included, which include emulsifiers, dispersants and rheology auxiliaries.
The method for manufacturing the circuit substrate by using the composite material comprises the following steps,
S1, weighing a composition of the composite material;
S2, diluting the fluorine-containing polymer dispersion liquid with water to a proper viscosity, then regulating the pH value to 8-12 with ammonia water, mixing the powder filler and the auxiliary agent, adding the mixture into the regulated dispersion emulsion, stirring and mixing the mixture to uniformly disperse the powder filler therein, thereby preparing a glue solution, wherein the solid content of the glue solution is 30-80%, preferably 40-60%, more preferably 45-50%;
s3, impregnating the PTFE woven cloth added with the filler by using the glue solution, controlling the thickness to be proper, and then baking at 80-300 ℃ to remove moisture and auxiliary agents to form prepreg;
In order to obtain prepregs with different thicknesses, PTFE woven fabrics with different thicknesses and added with fillers can be adopted, the PTFE woven fabrics with the fillers are prepared by cutting PTFE sintered films with the fillers (prepared by extrusion, rolling and expansion stretching methods) into filaments, then weaving the filaments into PTFE fiber fabrics with the fillers by adopting a plain weaving method, wherein the monofilament diameters of the fiber fabrics are from 1 micron to 9 microns, 1 micron, 3 microns, 5 microns, 7 microns and 9 microns, and the thickness of the PTFE woven fabrics with the fillers is from 0.03 millimeter to 0.2 millimeter, 0.05 millimeter, 0.06 millimeter, 0.1 millimeter and 0.2 millimeter. The glue solution forms a resin layer on the surface of the PTFE woven cloth added with the filler, and the thickness of the resin layer is controlled below 100 microns, preferably below 50 microns, more preferably below 20 microns;
the dipping operation can be carried out by adopting a general gluing machine for manufacturing the copper-clad plate, the temperature of a baking oven of the gluing machine can be set in a sectional manner, and the temperature range adopted by the baking oven is 80-300 ℃ so as to remove water, emulsifying agent and dispersing agent.
S4, laminating a plurality of prepregs, respectively pressing one metal foil up and down, putting the prepregs into a press for hot pressing to obtain a circuit substrate, wherein the hot pressing temperature is 350-400 ℃, the hot pressing pressure is 25-130 Kg/cm 2, and the metal foil is copper, brass, aluminum, nickel or alloy or composite metal foil of the metals.
The manufactured circuit substrate comprises: a plurality of prepregs which are mutually overlapped and metal foils respectively pressed on two sides of the prepregs, wherein the prepregs are made of composite materials.
The dielectric properties, namely, the dielectric constant and the loss tangent of value and the heat resistance of the circuit substrate manufactured as described above are further illustrated and described in the following examples.
Example 1
The viscosity of the polytetrafluoroethylene dispersion emulsion with the solid content of 60% is regulated to 22mPas (20 ℃) by deionized water, then the PH value is regulated to 11 by ammonia water, and the mixture is stirred and mixed uniformly.
And (3) impregnating PTFE woven cloth with the filler and 100 micrometers in thickness with the regulated polytetrafluoroethylene dispersion emulsion, and then sending the PTFE woven cloth into an oven to bake at 290 ℃ to remove water and auxiliary agents, so as to prepare the prepreg, wherein the thickness of the prepreg is 150 micrometers.
And (3) superposing 5 pieces of the prepared prepreg, respectively covering one piece of copper foil on each of the upper and lower parts, putting the prepreg into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 350-400 ℃, the hot pressing pressure is 76Kg/cm 2, and testing the prepared circuit substrate, wherein the dielectric constant is 3.0 (10 GHz), and the dielectric loss tangent is 0.0002 (10 GHz).
Example 2
The viscosity of the polytetrafluoroethylene dispersion emulsion with the solid content of 60% is regulated to be 14mPas (20 ℃) by deionized water, then the PH value is regulated to be about 11 by ammonia water, the mixture is stirred and mixed uniformly, and fused silica powder (the weight ratio of the powder to PTFE is 1.5:1) is added into the emulsion to prepare the glue solution which can be used for dipping.
And (3) impregnating the PTFE woven cloth added with the filler and with the regulated polytetrafluoroethylene dispersion emulsion, which is 50 micrometers thick, and then sending the PTFE woven cloth into an oven to bake at 290 ℃ to remove water and auxiliary agents, so as to prepare the prepreg, wherein the thickness of the prepreg is 70 micrometers.
And (3) laminating 5 pieces of the prepared prepreg, respectively coating one piece of copper foil on the upper and lower parts of the prepreg, and putting the prepreg into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 350-400 ℃, and the hot pressing pressure is 76Kg/cm 2. The resulting circuit board was tested to have a dielectric constant of 3.2 (10 GHz) and a dielectric loss tangent of 0.0003 (10 GHz).
Example 3
The viscosity of the polytetrafluoroethylene dispersion emulsion with the solid content of 60% is regulated to be 14mPas (20 ℃) by deionized water, then the PH value is regulated to be about 11 by ammonia water, the mixture is stirred and mixed uniformly, and the mixed powder of fused silica micropowder and fused aluminum trioxide (the weight ratio of the powder to PTFE is 1:1) is added into the emulsion to prepare the glue solution which can be used for dipping.
And (3) impregnating the PTFE woven cloth filled with the fused silica filler with the regulated polytetrafluoroethylene dispersion emulsion, which is 30 micrometers thick, and then sending the PTFE woven cloth into an oven to bake at 290 ℃ to remove water and auxiliary agents, so as to prepare the prepreg, wherein the thickness of the prepreg is 45 micrometers.
And (3) superposing 5 pieces of the prepared prepreg, respectively covering one piece of copper foil on each of the upper and lower parts, putting the prepreg into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 350-400 ℃, the hot pressing pressure is 76Kg/cm 2, and testing the prepared circuit substrate, wherein the dielectric constant is 3.5 (10 GHz), and the dielectric loss tangent is 0.0003 (10 GHz).
Comparative example 1
Bisphenol A epoxy resin and brominated epoxy resin are dissolved in dimethylformamide, dicyandiamide with the amine equivalent weight of 0.7 mol ratio relative to the epoxy resin is added as a curing agent and a proper amount of 2-MI (2-methylimidazole) is taken as an accelerator, and then the mixture is mixed at room temperature to obtain a glue solution.
The PTFE woven cloth added with the filler and having the thickness of 50 micrometers is immersed in the above glue solution, and then is sent to an oven for baking at 155 ℃ to remove solvent dimethylformamide, so as to prepare the prepreg having the thickness of 67 micrometers.
And 5 pieces of the prepared prepreg are overlapped, one piece of copper foil is respectively covered on the upper part and the lower part, the circuit substrate is prepared by placing the circuit substrate in a press for hot pressing, the curing temperature is 177 ℃, the curing pressure is 45Kg/cm 2, the curing time is 90 minutes, and the prepared circuit substrate is tested to have a dielectric constant of 3.62 (10 GHz) and a dielectric loss tangent of 0.007 (10 GHz).
Comparative example 2
The viscosity of the polytetrafluoroethylene dispersion emulsion with the solid content of 60% is regulated to be 14mPas (20 ℃) by deionized water, then the PH value is regulated to be about 11 by ammonia water, the mixture is stirred and mixed uniformly, and fused silica powder (the weight ratio of the powder to PTFE is 1.5:1) is added into the emulsion to prepare the glue solution which can be used for dipping.
And (3) dipping 1080 type E-glass cloth by using the regulated polytetrafluoroethylene dispersion emulsion, then sending the E-glass cloth into an oven to bake at 290 ℃ to remove water and auxiliary agents, and preparing the prepreg with the thickness of 70 microns.
And (3) superposing 5 pieces of the prepared prepreg, respectively covering one piece of copper foil on each of the upper and lower parts, putting the prepreg into a press for hot pressing to obtain the circuit substrate, wherein the hot pressing temperature is 350-400 ℃, the hot pressing pressure is 76Kg/cm 2, and testing the prepared circuit substrate, wherein the dielectric constant is 3.78 (10 GHz), and the dielectric loss tangent is 0.003 (10 GHz).
The above examples and comparative examples all refer to IPC4101 standard for testing circuit substrates, and the dielectric properties were tested by SPDR (splite post dielectric resonator) method under the conditions of a-state, 10GHz.
As can be seen from examples 1,2 and 3, the thickness of the prepreg produced can be adjusted, the dielectric constant and dielectric loss tangent of the circuit board produced are low, and the high frequency performance is good, as can be seen from comparative example 1, since the thermosetting resin having a large dielectric loss tangent is used in combination with the PTFE woven cloth, the dielectric constant and dielectric loss tangent of the circuit board produced are much larger, and as can be seen from comparative example 2, since the glass cloth having a large dielectric constant is used in combination with the PTFE resin, the dielectric constant of the circuit board produced is much larger, and therefore, the PTFE woven cloth having excellent dielectric performance and the fluororesin polymer are used in combination, and the composite material and the circuit board having excellent dielectric performance can be obtained, and the effect of signal transmission in the high frequency circuit can be better.
Although the present invention has been described with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements and changes may be made without departing from the spirit and principles of the present invention.

Claims (9)

1. A composite material comprising a fluoropolymer dispersion emulsion, a PTFE braid and a powder filler, characterized in that: the fluorine-containing polymer comprises one or more of polytetrafluoroethylene emulsion, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer and perfluoroethylene propylene copolymer, the PTFE woven cloth is made of PTFE resin, the PTFE resin is added with filler, the filler is selected from one or more of crystalline silica, fused silica, spherical silica, alumina, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, aluminum nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder, and the powder filler is selected from one or more of crystalline silica, fused silica, spherical silica, aluminum oxide, titanium dioxide, strontium titanate, barium strontium titanate, boron nitride, silicon carbide, glass chopped fiber, glass powder, talcum powder, mica powder, carbon black, carbon nano tube, metal powder, magnetic powder and polyphenylene sulfide powder.
2. A composite material according to claim 1, wherein: the monofilament diameter of the PTFE knitted cloth is from 1 micron to 9 microns, alternatively 1 micron, 3 microns, 5 microns, 7 microns and 9 microns, and the thickness of the knitted PTFE knitted cloth is from 0.03 mm to 0.2 mm, alternatively 0.03 mm, 0.05 mm, 0.06 mm, 0.1 mm and 0.2 mm.
3. A composite material according to claim 1, wherein: the PTFE woven cloth is formed by cutting a PTFE sintered film (manufactured by extrusion, rolling and expansion stretching) added with a filler into filaments, and then weaving the cut filaments by adopting a plain weaving method.
4. A composite material according to claim 1, wherein: the content of the powder filler is 0-70% of the total amount of the fluorine-containing polymer and the powder filler, the particle size median value of the powder filler is 0-15 microns, and the maximum particle size is not more than 100 microns.
5. A composite material according to claim 1, wherein: the composite material further includes an adjuvant comprising an emulsifier, a dispersant, and a rheology aid.
6. A circuit substrate made of a composite material, comprising a plurality of prepregs laminated with each other and metal foils respectively laminated on both sides thereof, each of the prepregs being made of the composite material according to any one of claims 1 to 5, characterized in that: the metal foil is copper, brass, aluminum, nickel or alloy or composite metal foil of the metals.
7. The circuit board of claim 6, wherein the method comprises the steps of,
S1, weighing a composition of the composite material;
S2, diluting the fluorine-containing polymer dispersion liquid with water to a proper viscosity, then regulating the pH value to 8-12 with ammonia water, mixing the powder filler and the auxiliary agent, adding the powder filler and the auxiliary agent into the regulated dispersion emulsion, and stirring and mixing to uniformly disperse the powder filler in the dispersion emulsion to obtain a glue solution;
s3, impregnating the PTFE woven cloth added with the filler by using the glue solution, controlling the thickness to be proper, and then baking at 80-300 ℃ to remove moisture and auxiliary agents to form prepreg;
And S4, laminating a plurality of prepregs, respectively pressing one metal foil up and down, and putting the prepregs into a press for hot pressing to obtain the circuit substrate.
8. A circuit substrate made of composite material according to claim 7, wherein: the hot pressing temperature in the S4 is 350-400 ℃, and the hot pressing pressure is 25-130 Kg/cm 2.
9. A circuit substrate made of composite material according to claim 7, wherein: the solid content of the glue solution in the step S2 is 30-80%; the glue solution forms a resin layer on the surface of the PTFE woven cloth added with the filler, and the thickness of the resin layer is controlled below 100 micrometers.
CN202410569864.9A 2024-05-09 2024-05-09 Composite material Pending CN118325261A (en)

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