CN114771050A - High-frequency copper-clad plate and preparation method thereof - Google Patents

High-frequency copper-clad plate and preparation method thereof Download PDF

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Publication number
CN114771050A
CN114771050A CN202210378334.7A CN202210378334A CN114771050A CN 114771050 A CN114771050 A CN 114771050A CN 202210378334 A CN202210378334 A CN 202210378334A CN 114771050 A CN114771050 A CN 114771050A
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copper
para
aramid
clad plate
temperature
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CN114771050B (en
Inventor
李双昌
庄锐
张云奎
高晓佳
田伟
周鹏飞
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Chambroad Chemical Industry Research Institute Co Ltd
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Chambroad Chemical Industry Research Institute Co Ltd
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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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or 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
    • B32B15/20—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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B5/08—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 the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2262/0261—Polyamide fibres

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a preparation method of a high-frequency copper-clad plate, which comprises the following steps: A) after the para-aramid raw paper subjected to high-temperature treatment passes through a gluing system, a prepreg is obtained; the para-aramid fiber felt is prepared by wet-process papermaking of para-aramid chopped fibers and para-aramid nanofibers; B) assembling the prepreg according to the structure of copper foil-bonding sheet-prepreg-bonding sheet-copper foil, and then curing and molding to obtain a copper-clad plate blank; C) and carrying out post-treatment on the copper-clad plate blank to obtain a finished product copper-clad plate product. The invention makes full use of the advantage of low dielectric constant of the para-aramid and the polytetrafluoroethylene resin, and makes the para-aramid paper into the substrate with low dielectric constant by curing the polytetrafluoroethylene resin under the conditions of high temperature and high pressure. The middle substrate and the two sides of the electrolytic copper foil are welded together through the fusion of the FEP film, the defect of poor bonding performance of polytetrafluoroethylene resin is overcome, and the peeling strength of the copper-clad plate is improved.

Description

High-frequency copper-clad plate and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a high-frequency copper-clad plate and a preparation method thereof.
Background
As the human society enters the information age, modern information technologies such as computers, networks, mobile communication, etc. are full of people's lives. Printed Circuit Boards (PCBs) that are substrates of electronic information products are used in electronic products more and more widely, and are used as a mother Board of electronic products, in which the PCB serves as a channel for connecting various electronic components, serves as a skeleton for supporting components, and a bridge for transmitting electrical signals, and provides mechanical assembly support and electrical connection for the various electronic components thereon, so that the components are designed in advance to form a Printed Circuit, and almost all electronic products use the PCBs. The copper-clad plate as the PCB substrate accounts for 40% of the production cost of the PCB, has the functions of conductivity, insulation and support 3 in the PCB, and determines the performance, quality and reliability of the PCB in the processing process to a great extent.
The copper-clad plate is a plate-shaped material prepared by impregnating a reinforcing material with resin, coating copper foil on one surface or two surfaces of the reinforcing material and performing hot pressing. The copper clad laminate can be manufactured into a Printed Circuit Board (PCB) commonly used in the electronic industry after being subjected to a series of supply and demand such as exposure, etching, drilling, green oil coating and the like. With the rapid development of the electronic information industry, PCBs used as substrates of electronic information products face many new challenges, and under the trend of 5G communication technology development, signals are required to have faster propagation speed and better propagation quality. Generally, the transmission rate of signals is inversely proportional to the square root of the dielectric constant of a material, a high dielectric constant easily causes signal transmission delay, the smaller the dielectric constant of the copper-clad plate is, the more stable the transmission is, the loss in the signal propagation process is mainly influenced by the dielectric loss of the material, the smaller the dielectric loss is, the smaller the loss in the signal transmission is, and the better the quality of signal transmission is.
The general operating frequency is more than 5GHz, the copper-clad plate is suitable for the ultrahigh frequency field, has ultralow loss characteristic (ultralow signal transmission loss), can be applied to the microwave/millimeter wave field and is called as a high-frequency copper-clad plate, the low loss factor of the high-frequency copper-clad plate is expressed by Dk (dielectric constant) and Df (dielectric loss <0.005), and the lower the index is, the better the performance is. Therefore, how to reduce the dielectric constant and low dielectric loss of the copper-clad plate for the communication field to enable the signal propagation to obtain a faster propagation speed and a more stable propagation quality is a problem to be solved at present.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a high-frequency copper-clad plate and a preparation method thereof, wherein the high-frequency copper-clad plate provided by the present invention has the characteristics of low dielectric constant and low dielectric loss.
The invention provides a preparation method of a high-frequency copper-clad plate, which comprises the following steps:
A) after the para-aramid raw paper subjected to high-temperature treatment passes through a gluing system, a prepreg is obtained;
the para-aramid raw paper is prepared by wet-process papermaking of para-aramid chopped fibers and para-aramid nano fibers;
B) assembling the prepreg according to the structure of copper foil-bonding sheet-prepreg-bonding sheet-copper foil, and then curing and molding to obtain a copper-clad plate blank;
C) and carrying out post-treatment on the copper-clad plate blank to obtain a finished product copper-clad plate product.
Preferably, the proportion of the short cut fibers to the nano fibers in the para-aramid raw paper is 60: 40-75: 25;
the para-aramid fiber raw paper is raw paper which is not subjected to high-temperature calendering after wet papermaking.
Preferably, in the step A), the high-temperature treatment is carried out at 350-400 ℃ for 50-60 min, and nitrogen protection is required in the treatment process.
Preferably, the method for processing the para-aramid raw paper by the sizing system comprises the following steps:
and (3) soaking the para-aramid fiber raw paper in glue solution, taking out, and sequentially drying, baking and sintering to obtain a prepreg.
Preferably, the glue solution is polytetrafluoroethylene resin, and the solid content of the polytetrafluoroethylene resin is 30-45%;
the dipping times are 3-5 times;
the drying temperature is 80-90 ℃, and the drying time is 6-8 min;
the baking temperature is 130-150 ℃, and the baking time is 3-5 min;
the sintering temperature is 380-400 ℃, and the sintering time is 15-30 min;
the glue application amount of the prepreg is 50-60%.
Preferably, the bonding sheet is selected from FEP bonding sheets.
Preferably, the copper foil is selected from electrolytic copper foil, and the thickness of the copper foil is 20-50 μm.
Preferably, the curing and molding process comprises the following steps: the hot pressing temperature is 370-380 ℃, the hot pressing pressure is 3-5 MPa, the hot pressing time is 15-30 min, and the vacuum degree is-0.1 MPa.
Preferably, the post-treatment method comprises the following steps:
the temperature is reduced in the process of keeping the pressure of the copper-clad plate at 3-5 MPa, the temperature reduction rate is 3-5 ℃ per minute, and the mold is opened to take the plate when the temperature is reduced to below 50 ℃.
The invention also provides a high-frequency copper clad laminate prepared by the preparation method, wherein the thickness of the high-frequency copper clad laminate is 0.5-2.0 mm, and the density is 1.3-1.5 g/cm3。
Compared with the prior art, the invention provides a preparation method of a high-frequency copper-clad plate, which comprises the following steps: A) after the para-aramid raw paper subjected to high-temperature treatment passes through a gluing system, a prepreg is obtained; the para-aramid raw paper is prepared by wet-process papermaking of para-aramid chopped fibers and para-aramid nano fibers; B) assembling the prepreg according to the structure of copper foil-bonding sheet-prepreg-bonding sheet-copper foil, and then curing and molding to obtain a copper-clad plate blank; C) and carrying out post-treatment on the copper-clad plate blank to obtain a finished product copper-clad plate product. The invention makes full use of the advantage of low dielectric constant of the para-aramid and the polytetrafluoroethylene resin, and makes the para-aramid paper into the substrate with low dielectric constant by curing the polytetrafluoroethylene resin under the conditions of high temperature and high pressure. The middle substrate and the two sides of the electrolytic copper foil are welded together through the fusion of the FEP film, the defect of poor bonding performance of polytetrafluoroethylene resin is overcome, and the peeling strength of the copper-clad plate is improved. The invention produces the copper-clad plate with low dielectric constant, and can enable electric signals to have higher transmission speed in a printed circuit board processed by the copper-clad plate.
Detailed Description
The invention provides a preparation method of a high-frequency copper-clad plate, which comprises the following steps:
A) after the para-aramid raw paper subjected to high-temperature treatment passes through a gluing system, a prepreg is obtained;
the para-aramid raw paper is prepared by wet-process papermaking of para-aramid chopped fibers and para-aramid nano fibers;
B) assembling the prepreg according to the structure of copper foil-bonding sheet-prepreg-bonding sheet-copper foil, and then curing and molding to obtain a copper-clad plate blank;
C) and carrying out post-treatment on the copper-clad plate blank to obtain a finished product copper-clad plate product.
The preparation method adopts para-aramid fiber paper as a preparation raw material, wherein the para-aramid fiber paper is prepared from para-aramid chopped fibers and para-aramid nano fibers through wet papermaking; the proportion of short cut fibers and nano fibers in the para-aramid wool paper is 60: 40-75: 25, preferably 60:40, 65:35, 70:30, 75:25, or 60: 40-75: any value between 25;
the para-aramid fiber raw paper is raw paper which is not subjected to high-temperature calendering after wet papermaking.
The method comprises the following steps of firstly carrying out high-temperature treatment on the para-aramid fiber raw paper to remove easily decomposed impurities in the paper. The high-temperature treatment is carried out at 350-400 ℃, preferably at 350, 360, 370, 380, 390, 400 or at any value between 350-400 ℃, for 50-60 min, preferably at any value between 50, 52, 54, 56, 58, 60 or at any value between 50-60 min, and nitrogen protection is required in the treatment process.
And then, passing the para-aramid raw paper subjected to high-temperature treatment through a gluing system to obtain a prepreg.
The method for the para-aramid raw paper to pass through the gluing system comprises the following steps:
and (3) soaking the para-aramid fiber raw paper in glue solution, taking out, and sequentially drying, baking and sintering to obtain a prepreg.
Specifically, the para-aramid fiber raw paper subjected to high-temperature treatment is impregnated with polytetrafluoroethylene resin with the solid content of 30% -45% in a sizing system, dried for 6-8 min at the temperature of 80-90 ℃ through a three-stage oven, baked for 3-5 min at the temperature of 130-150 ℃, sintered for 15-30 min at the temperature of 380-400 ℃, and subjected to gum dipping-drying processes for 3-5 times to obtain a para-aramid fiber paper/polytetrafluoroethylene prepreg with the glue application amount of 50% -60%.
Wherein the glue solution is polytetrafluoroethylene resin, and the solid content of the polytetrafluoroethylene resin is 30-45%, preferably 30%, 35%, 40%, 45%, or any value between 30-45%;
the dipping times are 3-5 times, preferably 3, 4, 5 or any value between 3-5 times;
the drying temperature is 80-90 ℃, preferably any value between 80, 82, 84, 86, 88 and 90 or between 80-90 ℃, and the drying time is 6-8 min, preferably any value between 6, 7, 8 or between 6-8 min;
the baking temperature is 130-150 ℃, preferably any value between 130, 135, 140, 145, 150 or 130-150 ℃, and the baking time is 3-5 min, preferably any value between 3, 4, 5 or 3-5 min;
the sintering temperature is 380-400 ℃, preferably any value between 380, 385, 390, 395 and 400, or 380-400 ℃, and the sintering time is 15-30 min, preferably any value between 15, 20, 25 and 30, or 15-30 min;
the sizing amount of the prepreg is 50% to 60%, preferably 50%, 55%, 60%, or any value between 50% to 60%.
And (3) assembling the prepreg according to the structure of copper foil-bonding sheet-prepreg-bonding sheet-copper foil, and then curing and molding to obtain the copper-clad plate blank.
Wherein the copper foil is selected from electrolytic copper foil, and the thickness of the copper foil is 20-50 μm. The surface of the copper foil, which is in contact with the prepreg, is subjected to electroplating treatment, so that the surface area is increased, and the composite strength of the copper foil and the substrate is improved.
The bonding sheet is selected from an FEP bonding sheet.
The curing and molding process comprises the following steps: the hot pressing temperature is 370-380 ℃, preferably 370, 375, 380 or any value between 370-380 ℃, the hot pressing pressure is 3-5 MPa, preferably any value between 3, 3.5, 4, 4.5, 5 or 3-5 MPa, the hot pressing time is 15-30 min, preferably any value between 15, 20, 25, 30 or 15-30 min, and the vacuum degree is-0.1 MPa.
The method comprises the following specific steps:
the first step is as follows: assembling the copper foil, the bonding sheet, the prepreg, the bonding sheet and the copper foil according to the structure, and putting the assembly into a vacuum hot press;
the second step: starting a vacuum pump, and pumping the air pressure in the hot pressing cabin to-0.1 MPa;
the third step: and closing the hot press by pressurizing, pressurizing to 3-5 MPa, heating to 370-380 ℃, and maintaining the pressure for 15-30 min.
And finally, carrying out post-treatment on the copper-clad plate blank to obtain a finished product copper-clad plate product.
The post-treatment method comprises the following steps:
cooling in the process of maintaining pressure of the copper-clad plate at the cooling rate of 3-5 ℃ per minute, and opening the mold to take out the plate when the temperature is reduced to below 50 ℃.
The invention is formed by high-heat-pressing under vacuum condition according to the structural assembly of electrolytic copper foil, FEP bonding sheet, para-aramid paper/polytetrafluoroethylene prepreg, FEP bonding sheet and electrolytic copper foil, wherein the electrolytic copper foil plays a role of electric conduction in the structure, the FEP film plays a role of bonding the copper foil and an aramid/polytetrafluoroethylene substrate together, and the aramid/polytetrafluoroethylene composite substrate plays a role of supporting and insulating.
According to the invention, the p-aramid fiber raw paper is impregnated with polytetrafluoroethylene resin and cured into the substrate, and the substrate is bonded with the electrolytic copper foil through the FEP film, so that the copper-clad plate with low dielectric constant and low dielectric loss is obtained.
The invention provides a preparation method of a copper-clad plate which is characterized by low dielectric constant, low dielectric loss, light weight and easy processing. The method uses para-aramid raw paper, polytetrafluoroethylene resin, an FEP bonding sheet and electrolytic copper foil as raw materials, makes full use of the low dielectric properties of the para-aramid paper and the polytetrafluoroethylene resin, and the high bonding strength of the FEP bonding sheet, and can better and tightly combine aramid paper and copper foil in the forming process to obtain the copper-clad plate with high peel strength and low dielectric properties. The copper-clad plate prepared by the invention is prepared from para-aramid paper, polytetrafluoroethylene resin, FEP bonding sheets and electrolytic copper foil, the thickness of the copper-clad plate is 0.5-2.0 mm, and the density of the copper-clad plate is 1.3-1.5 g/cm3The method is suitable for the fields of communication, high-end servers, military and the like.
In order to further understand the invention, the high-frequency copper-clad plate and the preparation method thereof provided by the invention are described below with reference to the following embodiments, and the protection scope of the invention is not limited by the following embodiments.
Example 1
Putting para-aramid paper into a muffle furnace, introducing nitrogen, carrying out heat treatment for 50min at 350 ℃, impregnating polytetrafluoroethylene resin with 30% of solid content in a horizontal gluing machine, drying for 6min at 80 ℃ through a three-stage drying oven, baking for 3min at 130 ℃, sintering for 1min at 380 ℃, carrying out impregnation-drying for 3 times to obtain aramid paper/polytetrafluoroethylene prepreg, assembling a copper foil-adhesive sheet-prepreg-adhesive sheet-copper foil structure, starting a vacuum pump, pumping the pressure in a hot press cabin to-0.1 MPa, pressurizing and closing a hot press, pressurizing to 3MPa, increasing the temperature to 370 ℃, maintaining the pressure for 15min, opening a cooling device to start cooling, reducing the cooling rate to 3-5 ℃ per minute, reducing the temperature to 50 ℃, opening the mold, taking out copper clad laminate products, and obtaining test results shown in table 1.
Example 2
Putting para-aramid paper into a muffle furnace, introducing nitrogen, carrying out heat treatment at 380 ℃ for 50min, dipping polytetrafluoroethylene resin with 35% of solid content in a horizontal gluing machine, drying for 6min at 80 ℃ through a three-stage oven, baking for 3min at 150 ℃, sintering for 1min at 400 ℃, carrying out 3 times of dipping and drying to obtain aramid paper/polytetrafluoroethylene prepreg, assembling a copper foil-adhesive sheet-prepreg-adhesive sheet-copper foil structural blank, starting a vacuum pump, pumping the pressure in a hot press cabin to-0.1 MPa, pressurizing and closing a hot press to 5MPa, heating to 370 ℃, maintaining the pressure for 20min, opening a cooling device to start cooling, reducing the cooling rate to 3-5 ℃ per minute, reducing the temperature to 50 ℃, opening the die and taking out a copper-clad plate product, wherein the test result is shown in table 1.
Example 3
Putting para-aramid paper into a muffle furnace, introducing nitrogen, carrying out heat treatment for 60min at 400 ℃, impregnating polytetrafluoroethylene resin with 45% of solid content in a horizontal gluing machine, drying for 8min at 90 ℃ through a three-stage drying oven, baking for 5min at 150 ℃, sintering for 15min at 380 ℃, carrying out 4 times of impregnation and drying to obtain aramid paper/polytetrafluoroethylene prepreg, assembling a copper foil-adhesive sheet-prepreg-adhesive sheet-copper foil structure, starting a vacuum pump, pumping the pressure in a hot press cabin to-0.1 MPa, pressurizing and closing a hot press, pressurizing to 3MPa, increasing the temperature to 380 ℃, maintaining the pressure for 15min, opening a cooling device to start cooling, reducing the cooling rate to 3-5 ℃ per minute, reducing the temperature to 50 ℃, opening the mold, and taking out a copper-clad plate product, wherein the test result is shown in table 1.
Example 4
Putting para-aramid paper into a muffle furnace, introducing nitrogen, carrying out heat treatment at 380 ℃ for 50min, dipping polytetrafluoroethylene resin with 40% of solid content in a horizontal gluing machine, drying for 8min at 80 ℃ through a three-stage oven, baking for 5min at 130 ℃, sintering for 15min at 380 ℃, carrying out 5-time dipping and drying to obtain aramid paper/polytetrafluoroethylene prepreg, assembling a copper foil-adhesive sheet-prepreg-adhesive sheet-copper foil structure blank, starting a vacuum pump, pumping the pressure in a hot press cabin to-0.1 MPa, pressurizing and closing a hot press to 5MPa, heating to 370 ℃, maintaining the pressure for 15min, opening a cooling device to start cooling, reducing the cooling rate to 3-5 ℃ per minute, reducing the temperature to 50 ℃, opening the die and taking out a copper-clad plate product, wherein the test result is shown in table 1.
Example 5
Putting para-aramid paper into a muffle furnace, introducing nitrogen, carrying out heat treatment for 60min at the temperature of 380 ℃, impregnating polytetrafluoroethylene resin with the solid content of 45% in a horizontal gluing machine, drying for 6min at the temperature of 100 ℃ through a three-stage drying oven, baking for 3min at the temperature of 150 ℃, sintering for 15min at the temperature of 400 ℃, carrying out 5 times of impregnation and drying to obtain aramid paper/polytetrafluoroethylene prepreg, assembling a copper foil-adhesive sheet-prepreg-adhesive sheet-copper foil structure, starting a vacuum pump, pumping the pressure in a hot press cabin to-0.1 MPa, pressurizing and closing a hot press, pressurizing to 5MPa, increasing the temperature to 370 ℃, maintaining the pressure for 15min, opening a cooling device to start cooling, reducing the cooling rate to 3-5 ℃ per minute, reducing the temperature to 50 ℃, opening the mold, taking out copper-clad laminate products, and testing results are shown in table 1.
Comparative example 1
The meta-aramid paper is put into a muffle furnace, nitrogen is introduced, heat treatment is carried out for 60min at the temperature of 300 ℃, polytetrafluoroethylene resin with the solid content of 45% is soaked in a horizontal gluing machine, the meta-aramid paper passes through a three-stage oven, drying is carried out for 6min at the temperature of 100 ℃, baking is carried out for 3min at the temperature of 150 ℃, sintering is carried out for 15min at the temperature of 400 ℃, and the meta-aramid paper is seriously decomposed at the temperature of 400 ℃, so that aramid paper/polytetrafluoroethylene prepreg cannot be prepared.
Comparative example 2
Putting glass fiber cloth into a muffle furnace, introducing nitrogen, carrying out heat treatment for 50min at the temperature of 450 ℃, dipping polytetrafluoroethylene resin with the solid content of 40% in a horizontal gluing machine, drying for 8min at the temperature of 80 ℃ through a three-stage oven, baking for 5min at the temperature of 130 ℃, sintering for 15min at the temperature of 380 ℃, carrying out 5 times of dipping and drying to obtain glass fiber cloth/polytetrafluoroethylene prepreg, assembling a copper foil-bonding sheet-prepreg-bonding sheet-copper foil structure, starting a vacuum pump, pumping the pressure in a hot press cabin to-0.1 MPa, pressurizing and closing a hot press to 5MPa, heating to 370 ℃, maintaining the pressure for 15min, opening a cooling device to start cooling, reducing the cooling rate to 3-5 ℃ per minute, lowering the temperature to 50 ℃, opening the die and taking out a copper clad laminate product, wherein the test result is shown in Table 2.
Comparative example 3
Putting para-position glass fiber cloth into a muffle furnace, introducing nitrogen, carrying out heat treatment for 60min at the temperature of 450 ℃, impregnating polytetrafluoroethylene resin with the solid content of 45% in a horizontal gluing machine, drying for 6min at the temperature of 100 ℃ through a three-stage drying oven, baking for 3min at the temperature of 150 ℃, sintering for 15min at the temperature of 400 ℃, carrying out 5 times of impregnation and drying to obtain glass fiber cloth/polytetrafluoroethylene prepreg, assembling a copper foil-bonding sheet-prepreg-bonding sheet-copper foil structure, starting a vacuum pump, pumping the pressure in a hot press cabin to-0.1 MPa, pressurizing and closing a hot press, pressurizing to 5MPa, raising the temperature to 370 ℃, maintaining the pressure for 15min, opening a cooling device to start cooling, reducing the cooling rate to 3-5 ℃ per minute, reducing the temperature to 50 ℃, opening the mold, and taking out a copper-clad laminate product, wherein the test result is shown in table 2.
The invention carries out performance index detection on the low dielectric constant copper-clad plate, and the detection items and the method are as follows:
dielectric properties: refer to GB/T4722-2017 rigid copper clad laminate test method for printed circuit board
TABLE 1 test results of the examples
Figure BDA0003591736140000081
Table 2 comparative example test results
Figure BDA0003591736140000082
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the high-frequency copper-clad plate is characterized by comprising the following steps:
A) after the para-aramid raw paper subjected to high-temperature treatment passes through a gluing system, a prepreg is obtained;
the para-aramid raw paper is prepared by wet-process papermaking of para-aramid chopped fibers and para-aramid nano fibers;
B) assembling the prepreg according to the structure of copper foil-bonding sheet-prepreg-bonding sheet-copper foil, and then curing and molding to obtain a copper-clad plate blank;
C) and carrying out post-treatment on the copper-clad plate blank to obtain a finished product copper-clad plate product.
2. The preparation method of claim 1, wherein the ratio of chopped fibers to nano fibers in the para-aramid raw paper is 60: 40-75: 25;
the para-aramid fiber raw paper is raw paper which is not subjected to high-temperature calendering after wet papermaking.
3. The preparation method of claim 1, wherein in the step A), the high-temperature treatment is performed at 350-400 ℃ for 50-60 min, and nitrogen protection is required in the treatment process.
4. The preparation method of claim 1, wherein the method for the para-aramid raw paper to pass through a sizing system comprises the following steps:
and (3) soaking the para-aramid fiber raw paper in glue solution, taking out, and sequentially drying, baking and sintering to obtain a prepreg.
5. The preparation method according to claim 4, wherein the glue solution is polytetrafluoroethylene resin, and the solid content of the polytetrafluoroethylene resin is 30-45%;
the dipping times are 3-5 times;
the drying temperature is 80-90 ℃, and the drying time is 6-8 min;
the baking temperature is 130-150 ℃, and the baking time is 3-5 min;
the sintering temperature is 380-400 ℃, and the sintering time is 15-30 min;
the glue application amount of the prepreg is 50-60%.
6. The method of claim 1, wherein the bonding sheet is selected from FEP bonding sheets.
7. The method of claim 1, wherein the copper foil is selected from electrolytic copper foils and has a thickness of 20 to 50 μm.
8. The preparation method according to claim 1, wherein the curing and molding process is as follows: the hot pressing temperature is 370-380 ℃, the hot pressing pressure is 3-5 MPa, the hot pressing time is 15-30 min, and the vacuum degree is-0.1 MPa.
9. The method of claim 1, wherein the post-treatment comprises:
the temperature is reduced in the process of keeping the pressure of the copper-clad plate at 3-5 MPa, the temperature reduction rate is 3-5 ℃ per minute, and the mold is opened to reduce the temperature to below 50 ℃ to take out the plate.
10. The high-frequency copper-clad plate prepared by the preparation method according to any one of claims 1 to 9, wherein the high-frequency copper-clad plate has a thickness of 0.5 to 2.0mm and a density of 1.3 to 1.5g/cm3。
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