CN110228239B - Low-dielectric poly (perfluoroethylene propylene) copper-clad plate and preparation method thereof - Google Patents

Low-dielectric poly (perfluoroethylene propylene) copper-clad plate and preparation method thereof Download PDF

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CN110228239B
CN110228239B CN201910430029.6A CN201910430029A CN110228239B CN 110228239 B CN110228239 B CN 110228239B CN 201910430029 A CN201910430029 A CN 201910430029A CN 110228239 B CN110228239 B CN 110228239B
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copper
glass fiber
clad plate
propylene
dielectric
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CN110228239A (en
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刘德桃
李映辉
徐科
林美燕
欧阳豪
苏灵峰
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South China University of Technology SCUT
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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
    • B32B15/04—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
    • B32B15/20—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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • 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
    • H05K1/0366—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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric

Abstract

The invention discloses a preparation method of a low-dielectric poly (perfluoroethylene propylene) copper-clad plate. The preparation method comprises the steps of pretreating chopped glass fibers, modifying the chopped glass fibers by using a silane coupling agent, adding a dispersing agent, and defibering the chopped glass fibers by using a defibering machine to uniformly disperse the glass fibers; drying the dispersed glass fiber to remove moisture, then adding the fluorinated ethylene-propylene emulsion, uniformly mixing the fluorinated ethylene-propylene emulsion and the glass fiber, and dehydrating and concentrating; uniformly coating the concentrated solution on a high-temperature resistant film by using an automatic coating machine; vacuum drying, cooling and taking out to prepare a polyperfluorinated ethylene propylene prepreg; and (3) adhering copper foil on the prepreg, and pressing the prepreg into the copper-clad plate by using a hot press. The copper-clad plate is prepared from the fluorinated ethylene propylene resin, the dielectric constant value of the copper-clad plate is 2-2.5, the dielectric loss value is 0.0008-0.0015, and the water absorption rate is 0.02-0.05%. The copper-clad plate disclosed by the invention is good in dielectric property, low in water absorption, good in cohesiveness and strong in processability.

Description

Low-dielectric poly (perfluoroethylene propylene) copper-clad plate and preparation method thereof
Technical Field
The invention relates to a manufacturing method of a copper-clad plate, in particular to a low-dielectric poly (perfluoroethylene propylene) copper-clad plate for high frequency and high speed and a manufacturing method thereof.
Background
With the development of modern communication technology, computer, network and satellite communication have been deeply carried out in every corner of people's life. With the development of information communication technologies of mobile phones and satellite communication technologies to multiple channels, high performance and multiple functions, the frequency of wireless networks, satellite communication and radar is continuously increased. Because the traditional printed circuit board such as phenolic aldehyde/paper base, epoxy resin/glass fiber and the like has poor dielectric property, large thermal expansion and poor humidity resistance, the traditional printed circuit board is not suitable for the modern requirement on high-frequency performance.
Although the polytetrafluoroethylene resin has a low dielectric constant and low dielectric loss, the application of the polytetrafluoroethylene resin is limited due to poor processability and weak bonding ability with glass fibers and electrolytic copper foil. The polyfluorinated ethylene propylene is a copolymer of tetrafluoroethylene and hexafluoroethylene, has slightly lower molecular weight than that of the polytetrafluoroethylene, and has the mechanical property, chemical stability, water absorption property and electrical property equivalent to those of the polytetrafluoroethylene. The polyfluorinated ethylene propylene has low melting temperature, much lower viscosity than polytetrafluoroethylene in a molten state, good flow property, strong fiber penetrating capability, strong bonding force with copper foil and strong processability. The copper-clad plate prepared by the method has high resin content, and the dielectric property of the resin is far stronger than that of the glass fiber, so that the method has low dielectric loss and low dielectric constant, and compared with the method for impregnating the glass fiber paper, the method saves the process of repeated impregnation, and the gel content is far greater than that of the impregnation method. The copper-clad plate prepared by the method has the advantages of good cohesiveness, uniform glue solution distribution, consistent thickness, relatively flat copper-clad plate, good dielectric property, low water absorption and the like.
Chinese patent application 201810760578 and 5 disclose a preparation method of a high-frequency polytetrafluoroethylene copper-clad plate. Firstly, slowly adding 60-250 parts by weight of electronic grade titanium dioxide powder, dispersing for one minute at a high speed to obtain titanium dioxide slurry, then adding 100-400 parts by weight of polytetrafluoroethylene emulsion, stirring at a low speed, and placing a glue solution in an environment at 25 ℃ for 24-48 hours to obtain titanium dioxide/polytetrafluoroethylene glue solution; and (3) soaking the glass fiber in titanium dioxide/polytetrafluoroethylene glue solution, putting the titanium dioxide/polytetrafluoroethylene glue solution into an oven, sintering and cooling to obtain a primary soaking film, and repeating the soaking process to obtain a plurality of times of soaking films so as to ensure that the copper-clad plate has sufficient glue content. The copper-clad plate prepared by the method has the dielectric loss of 0.002-0.003 and the dielectric constant of 3.5-10. The high-frequency copper-clad plate prepared by the method has low dielectric loss ratio, but has high dielectric constant, complex operation, long gum dipping process time and difficult dispersion of titanium dioxide.
The time required for dipping the film for one time is 20min, and the time required for dipping the film for multiple times is 60 min-120 min, and the method needs to press a plurality of films to prepare the prepreg with a certain glue content. The method takes longer time for gum dipping and has a complicated gum dipping process.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a low-dielectric poly (perfluoroethylene propylene) copper-clad plate and a preparation method thereof.
According to the preparation method, the chopped glass fiber and the polyfluorinated ethylene propylene resin are mixed, coated on the polytetrafluoroethylene film and dried to obtain the prepreg, the prepreg meeting the requirements can be prepared without multiple gum dipping and multiple layers of films, and the preparation method is short in required time, simple to operate and excellent in dielectric property. The high-frequency copper-clad plate is prepared by adopting the fluorinated ethylene propylene resin reinforced glass fiber paper, the dielectric constant of the copper-clad plate under 10GHz is 2-2.5, the dielectric loss value is 0.0008-0.0015, and the water absorption rate is 0.02-0.05%. Completely meets the requirement of high frequency of signal transmission.
The method for preparing the low-dielectric copper-clad plate mainly adopts polytetrafluoroethylene resin which has excellent dielectric property and chemical property, but has larger thermal expansion coefficient, difficult molding and low thermal conductivity, and can easily cause thermal fatigue and thermal deformation. The method comprises the steps of selecting electronic grade chopped glass fibers with good insulating property, fluorinated ethylene propylene resin with low dielectric constant and a silane coupling agent as raw materials, adding the modified chopped glass fibers into fluorinated ethylene propylene emulsion, uniformly mixing the chopped glass fibers by using a homogenizing dispersion machine, concentrating the mixture by using a rotary evaporation instrument, coating a concentrated solution on a polytetrafluoroethylene high-temperature-resistant film, drying the mixture to form a prepreg, and attaching copper foils to two sides of the prepreg to press the prepreg into the copper-clad plate. The copper-clad plate prepared by the method has good dielectric property, simple operation and strong processability.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a low-dielectric poly (perfluoroethylene propylene) copper-clad plate is characterized by comprising the following steps and process conditions:
(1) pretreatment of glass fibers: putting 1-5 parts of chopped glass fibers in 5-10 parts of deionized water by weight, adjusting the pH value of the glass fiber suspension by using a dilute acid, and controlling the pH value to be 2.5-3.5;
(2) modification of glass fiber: putting 1-5 parts of silane coupling agent into 5-10 parts of deionized water, heating to fully hydrolyze the silane coupling agent, and putting the hydrolyzed coupling agent into a glass fiber suspension;
(3) dispersion of glass fibers: adding a dispersing agent into the glass fiber suspension, and defibering the chopped glass fibers by using a defibering machine;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and drying;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene emulsion and the chopped glass fiber;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber to obtain a concentrated solution;
(7) preparing a prepreg: pouring the concentrated solution on a high-temperature resistant membrane, and uniformly coating the concentrated solution on the high-temperature resistant membrane by using an automatic coating machine;
(8) and (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution, cooling and taking out to obtain a low dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (3) placing an electrolytic copper foil with the same size on the upper surface and the lower surface of the prepreg obtained in the step (8), heating to 200-350 ℃, keeping the temperature, slowly cooling to the normal temperature, gradually increasing the pressure to 4-8 MPa, and keeping the pressure for more than 12 hours.
To further achieve the object of the present invention, preferably, the glass fiber is one or more of electronic grade glass fiber of type 106, 1080, 2116 or 76; the dilute acid is dilute hydrochloric acid or dilute sulfuric acid, and the volume concentration is 0.5-5%.
Preferably, the silane coupling agent is one or more of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (KH602), thiopropyltrimethoxysilane (KH590) and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-N-octylsilane (F8261); the heating temperature in the step (2) is 20-100 ℃, and the heating time is 1-60 min.
Preferably, the dispersant is polyethylene oxide, and the drying in the step (4) is drying in a vacuum oven; and (4) drying at the temperature of 50-150 ℃ for 1-60 min.
Preferably, the mass concentration of the concentrate is 40-80%, and the resin content is 60-90%.
Preferably, the vacuum drying temperature is 50-100 ℃, and the vacuum drying time is 1-60 min; the high-temperature resistant film is a polytetrafluoroethylene high-temperature resistant film.
Preferably, the step of uniformly mixing the fluorinated ethylene propylene resin and the chopped glass fibers is to mix the fluorinated ethylene propylene resin and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 1-60 min.
Preferably, the dehydration concentration is carried out by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa.
A low dielectric poly perfluoroethylene propylene copper-clad plate is prepared by the preparation method.
The low dielectric poly perfluoro ethylene propylene copper clad laminate has a dielectric constant value of 2-2.5, a dielectric loss value of 0.0008-0.0015 and a water absorption rate of 0.02-0.05%.
The invention adopts electronic grade chopped glass fiber with excellent dielectric property, fluorinated ethylene propylene resin with low dielectric constant and silane coupling agent as raw materials, adds the modified chopped glass fiber into fluorinated ethylene propylene emulsion, uniformly mixes the raw materials by a homogenizing dispersion machine, then concentrates the mixture by a rotary evaporation instrument, then coats the concentrated solution on a polytetrafluoroethylene high-temperature resistant film and dries the mixture into a prepreg, laminates a plurality of prepregs, attaches copper foils on two sides of the prepregs and presses the prepregs into the copper-clad plate.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the copper-clad plate is prepared by blending the chopped glass fiber and the fluorinated ethylene propylene emulsion, the resin content is high, and the dielectric property is good.
(2) Compared with the method for preparing the prepreg by the dipping method, the method for preparing the prepreg by the coating method has the advantages of simple operation, short time and strong processability.
(3) The copper-clad plate prepared by the invention has low water absorption rate, so that the dielectric performance of the copper-clad plate is relatively stable in the using process.
Detailed Description
In order to further understand the present invention, the following examples are further provided to illustrate the present invention, and it should be noted that the scope of the present invention is not limited to the examples.
In the following examples, the peel strength test was performed using the GB/T2791-1995 national Standard test; the dielectric constant and the dielectric loss factor are tested by GB/T1693-2007 standard; the water absorption test adopts GB1034-70 standard test.
Example 1
A method for manufacturing a low-dielectric poly (perfluoroethylene propylene) copper-clad plate comprises the following steps and process conditions:
(1) pretreatment of glass fibers: 1 part of 1080 type chopped glass fiber is placed in 5 parts of deionized water, and the pH value of the glass fiber suspension is adjusted by using dilute hydrochloric acid, wherein the pH value is controlled to be 2.5;
(2) modification of glass fiber: 1 part of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (KH602) coupling agent is put into 5 parts of deionized water, heated at 50 ℃ for 20min to fully hydrolyze the silane coupling agent, and the hydrolyzed coupling agent is put into the glass fiber suspension;
(3) dispersion of glass fibers: adding polyoxyethylene into the glass fiber suspension, and defibering the short glass fibers by 1000r by using a defibering machine;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and then putting the glass fiber suspension into a vacuum oven to be dried for 20min at 60 ℃ to remove water;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene resin and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 10 min;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa;
(7) preparing a prepreg: and pouring the concentrated solution onto a polytetrafluoroethylene high-temperature-resistant membrane, and uniformly coating the concentrated solution onto the polytetrafluoroethylene high-temperature-resistant membrane by using an automatic coating machine, wherein the mass concentration of the concentrated solution is 60%.
(8) And (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution at the temperature of 60 ℃ for 8min, and taking out after cooling to obtain a low-dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (4) placing an electrolytic copper foil with the same size on the upper surface and the lower surface of the prepreg obtained in the step (8), heating to 200 ℃, keeping the temperature for 50min, and slowly cooling to the normal temperature. The pressure was gradually increased to 4MPa and kept at this stage.
Through tests, the low dielectric poly (perfluoroethylene propylene) copper-clad plate prepared by the embodiment has the dielectric constant value of 2.5, the dielectric loss value of 0.0012, the water absorption rate of 0.04 percent, and the time for preparing the prepreg is 18 min.
According to the preparation method, the chopped glass fiber and the polyfluorinated ethylene propylene resin are mixed, coated on a polytetrafluoroethylene high-temperature-resistant film and dried to obtain the prepreg, and the prepreg meeting the requirements can be prepared without multiple gum dipping and multiple layers of films; the copper-clad plate with excellent dielectric property can be prepared by respectively placing an electrolytic copper foil with the same size on two sides of the prepreg, the operation is simple, the preparation time is short, the processability is strong, the processing efficiency is high, and the processing advantages are outstanding.
Example 2
A method for manufacturing a low-dielectric poly (perfluoroethylene propylene) copper-clad plate comprises the following steps and process conditions:
(1) pretreatment of glass fibers: 2 parts of 1080 type chopped glass fibers are placed in 5 parts of deionized water, and the pH value of the glass fiber suspension is adjusted by using dilute hydrochloric acid, and the pH value is controlled to be 3;
(2) modification of glass fiber: 2 parts of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (KH602) coupling agent is put into 6 parts of deionized water, heated at 60 ℃ for 30min to fully hydrolyze the silane coupling agent, and the hydrolyzed coupling agent is put into the glass fiber suspension;
(3) dispersion of glass fibers: adding polyoxyethylene into the glass fiber suspension, and defibering the chopped glass fibers by a defibering machine for 1500 r;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and then putting the glass fiber suspension into a vacuum oven to be dried for 30min at 60 ℃ to remove water;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene resin and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 20 min;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa;
(7) preparing a prepreg: and pouring the concentrated solution onto a polytetrafluoroethylene high-temperature-resistant membrane, and uniformly coating the concentrated solution onto the polytetrafluoroethylene high-temperature-resistant membrane by using an automatic coating machine, wherein the mass concentration of the concentrated solution is 65%.
(8) And (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution at the temperature of 65 ℃ for 12min, and taking out after cooling to obtain a low-dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (4) placing an electrolytic copper foil with the same size on the upper surface and the lower surface of the prepreg obtained in the step (8), heating to 220 ℃, keeping the temperature for 60min, and slowly cooling to the normal temperature. The pressure was gradually increased to 5MPa and kept at this stage.
Through tests, the low dielectric poly (perfluoroethylene propylene) copper-clad plate prepared by the embodiment has the dielectric constant value of 2.4, the dielectric loss value of 0.001, the water absorption rate of 0.04 percent and the time for preparing the prepreg of 22 min.
Example 3
A method for manufacturing a low-dielectric poly (perfluoroethylene propylene) copper-clad plate comprises the following steps and process conditions:
(1) pretreatment of glass fibers: placing 2 parts of 106 type chopped glass fibers in 6 parts of deionized water, adjusting the pH value of the glass fiber suspension by using dilute hydrochloric acid, and controlling the pH value to be 3;
(2) modification of glass fiber: 2 parts of thiopropyltrimethoxysilane (KH590) coupling agent is put into 6 parts of deionized water, the mixture is heated for 15min at 65 ℃ to fully hydrolyze the silane coupling agent, and the hydrolyzed coupling agent is put into the glass fiber suspension;
(3) dispersion of glass fibers: adding polyoxyethylene into the glass fiber suspension, and defibering the chopped glass fibers by 2000r by using a defibering machine;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and then putting the glass fiber suspension into a vacuum oven to be dried for 15min at 70 ℃ to remove water;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene resin and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 15 min;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa;
(7) preparing a prepreg: and pouring the concentrated solution onto a polytetrafluoroethylene high-temperature-resistant membrane, and uniformly coating the concentrated solution onto the polytetrafluoroethylene high-temperature-resistant membrane by using an automatic coating machine, wherein the mass concentration of the concentrated solution is 75%.
(8) And (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution at the temperature of 60 ℃ for 15min, and taking out after cooling to obtain a low-dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (4) placing an electrolytic copper foil with the same size on the upper surface and the lower surface of the prepreg obtained in the step (8), heating to 250 ℃, keeping the temperature for 60min, and slowly cooling to the normal temperature. The pressure was gradually increased to 6MPa and kept at this stage all the time.
Through tests, the low dielectric poly (perfluoroethylene propylene) copper-clad plate prepared by the embodiment has the dielectric constant value of 2.3, the dielectric loss value of 0.001, the water absorption rate of 0.03 percent and the time for preparing the prepreg of 25 min.
Example 4
A method for manufacturing a low-dielectric poly (perfluoroethylene propylene) copper-clad plate comprises the following steps and process conditions:
(1) pretreatment of glass fibers: 3 parts of 1080 type chopped glass fibers are placed in 8 parts of deionized water, and the pH value of the glass fiber suspension is adjusted by using dilute sulfuric acid, wherein the pH value is controlled to be 3.5;
(2) modification of glass fiber: 1 part of thiopropyl trimethoxy silane (KH590) coupling agent is put into 5 parts of deionized water, heated at 70 ℃ for 30min to fully hydrolyze the silane coupling agent, and the hydrolyzed coupling agent is put into glass fiber suspension;
(3) dispersion of glass fibers: adding polyoxyethylene into the glass fiber suspension, and defibering the chopped glass fibers by a defibering machine for 2500 r;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and then drying in a vacuum oven at 80 ℃ for 10min to remove water;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene resin and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 30 min;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa;
(7) preparing a prepreg: and pouring the concentrated solution onto a polytetrafluoroethylene high-temperature-resistant membrane, and uniformly coating the concentrated solution onto the polytetrafluoroethylene high-temperature-resistant membrane by using an automatic coating machine, wherein the mass concentration of the concentrated solution is 75%.
(8) And (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution at the temperature of 80 ℃ for 18min, and taking out after cooling to obtain a low dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (4) placing an electrolytic copper foil with the same size on the upper surface and the lower surface of the prepreg stack obtained in the step (8), heating to 270 ℃, keeping the temperature for 70min, and slowly cooling to the normal temperature. The pressure was gradually increased to 6MPa and kept at this stage all the time.
Through tests, the low dielectric poly (perfluoroethylene propylene) copper-clad plate prepared by the embodiment has the dielectric constant value of 2, the dielectric loss value of 0.0008, the water absorption rate of 0.03 percent, and the time for preparing the prepreg is 28 min.
Example 5
A method for manufacturing a low-dielectric poly (perfluoroethylene propylene) copper-clad plate comprises the following steps and process conditions:
(1) pretreatment of glass fibers: 2 parts of 2116 type chopped glass fibers are placed in 8 parts of deionized water, and the pH value of the glass fiber suspension is adjusted by using dilute sulfuric acid, wherein the pH value is controlled to be 3;
(2) modification of glass fiber: 2 parts of triethoxy-1H, 1H, 2H, 2H-tridecafluoro-N-octylsilane (F8261) coupling agent are put into 8 parts of deionized water, heated for 20min at 100 ℃ to fully hydrolyze the silane coupling agent, and the hydrolyzed coupling agent is put into the glass fiber suspension;
(3) dispersion of glass fibers: adding polyoxyethylene into the glass fiber suspension, and defibering the chopped glass fibers by 2000r by using a defibering machine;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and then putting the glass fiber suspension into a vacuum oven to be dried for 20min at 120 ℃ to remove water;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene resin and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 40 min;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa;
(7) preparing a prepreg: and pouring the concentrated solution onto a polytetrafluoroethylene high-temperature-resistant membrane, and uniformly coating the concentrated solution onto the polytetrafluoroethylene high-temperature-resistant membrane by using an automatic coating machine, wherein the mass concentration of the concentrated solution is 70%.
(8) And (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution at the temperature of 100 ℃ for 20min, and taking out after cooling to obtain a low-dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (4) placing an electrolytic copper foil with the same size on the upper surface and the lower surface of the prepreg obtained in the step (8), heating to 300 ℃, keeping the temperature for 30min, and slowly cooling to the normal temperature. The pressure was gradually increased to 6MPa and kept at this stage all the time.
Through tests, the low dielectric poly (perfluoroethylene propylene) copper-clad plate prepared by the embodiment has the dielectric constant value of 2.1, the dielectric loss value of 0.001, the water absorption rate of 0.04 percent and the time for preparing the prepreg of 30 min.
Example 6
A method for manufacturing a low-dielectric poly (perfluoroethylene propylene) copper-clad plate comprises the following steps and process conditions:
(1) pretreatment of glass fibers: 2 parts of 2116 type chopped glass fibers are placed in 6 parts of deionized water, and the pH value of the glass fiber suspension is adjusted by using dilute hydrochloric acid, wherein the pH value is controlled to be 2.5;
(2) modification of glass fiber: 1 part of triethoxy-1H, 1H, 2H, 2H-tridecafluoro-N-octyl silane (F8261) coupling agent is put into 5 parts of deionized water, heated for 40min at 60 ℃ to lead the silane coupling agent to be fully hydrolyzed, and the hydrolyzed coupling agent is put into glass fiber suspension;
(3) dispersion of glass fibers: adding polyoxyethylene into the glass fiber suspension, and defibering the chopped glass fibers by a defibering machine for 3000 r;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and then putting the glass fiber suspension into a vacuum oven to be dried for 20min at 120 ℃ to remove water;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene resin and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 25 min;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa;
(7) preparing a prepreg: and pouring the concentrated solution onto a polytetrafluoroethylene high-temperature-resistant membrane, and uniformly coating the concentrated solution onto the polytetrafluoroethylene high-temperature-resistant membrane by using an automatic coating machine, wherein the mass concentration of the concentrated solution is 70%.
(8) And (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution at the temperature of 80 ℃ for 15min, and taking out after cooling to obtain a low dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (4) placing an electrolytic copper foil with the same size on the upper surface and the lower surface of the prepreg obtained in the step (8), heating to 270 ℃, keeping the temperature for 60min, and slowly cooling to the normal temperature. The pressure was gradually increased to 6MPa and kept at this stage all the time.
Through tests, the low dielectric poly (perfluoroethylene propylene) copper-clad plate prepared by the embodiment has the dielectric constant value of 2.2, the dielectric loss value of 0.001, the water absorption rate of 0.05 percent and the time for preparing the prepreg of 25 min.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.

Claims (7)

1. A preparation method of a low-dielectric poly (perfluoroethylene propylene) copper-clad plate is characterized by comprising the following steps and process conditions:
(1) pretreatment of glass fibers: putting 1-5 parts of chopped glass fibers in 5-10 parts of deionized water by weight, adjusting the p H value of the glass fiber suspension by using a dilute acid, and controlling p H = 2.5-3.5; the glass fiber is one or more of 106, 1080, 2116 or 76 type electronic grade glass fibers; the dilute acid is dilute hydrochloric acid or dilute sulfuric acid, and the volume concentration is 0.5-5%;
(2) modification of glass fiber: putting 1-5 parts of silane coupling agent into 5-10 parts of deionized water, heating to fully hydrolyze the silane coupling agent, and putting the hydrolyzed coupling agent into a glass fiber suspension; the silane coupling agent is one or more of N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, thiopropyltrimethoxysilane and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-N-octylsilane; the heating temperature in the step (2) is 20-100 ℃, and the heating time is 1-60 min;
(3) dispersion of glass fibers: adding a dispersing agent into the glass fiber suspension, and defibering the chopped glass fibers by using a defibering machine;
(4) drying the glass fiber: filtering water in the glass fiber suspension, and drying;
(5) preparation of a mixture of fluorinated ethylene propylene emulsion and glass fiber: uniformly mixing the fluorinated ethylene propylene emulsion and the chopped glass fiber;
(6) concentration of the perfluoroethylene-propylene emulsion and glass fiber mixture: dehydrating and concentrating the mixture of the fluorinated ethylene propylene emulsion and the glass fiber to obtain a concentrated solution;
(7) preparing a prepreg: uniformly coating the concentrated solution on a high-temperature resistant film by using an automatic coating machine;
(8) and (3) drying the prepreg: vacuum drying the coated polyperfluorinated ethylene propylene concentrated solution, cooling and taking out to obtain a low dielectric polyperfluorinated ethylene propylene prepreg;
(9) preparing a copper-clad plate: and (3) placing an electrolytic copper foil with the same size on each of the upper surface and the lower surface of the prepreg obtained in the step (8), heating to 200-350 ℃, keeping the temperature, slowly cooling to normal temperature, gradually increasing the pressure to 4-8 MPa, and keeping the pressure for more than 12 hours.
2. The preparation method of the low dielectric polyperfluoroethylene propylene copper-clad plate according to claim 1, wherein the dispersing agent is polyethylene oxide, the drying of the glass fiber in the step (4) is drying in a vacuum oven at a temperature of 50-150 ℃ for 1-60 min.
3. The method for preparing the low-dielectric poly (perfluoroethylene propylene) copper-clad plate according to claim 1, wherein the mass concentration of the concentrated solution is 40-80%, and the resin content is 60-90%.
4. The preparation method of the low-dielectric polyperfluoroethylene propylene copper-clad plate according to claim 1, wherein the vacuum drying temperature is 50-100 ℃, and the vacuum drying time is 1-60 min; the high-temperature resistant film is a polytetrafluoroethylene high-temperature resistant film.
5. The preparation method of the low-dielectric polyperfluoroethylene-propylene copper-clad plate according to claim 1, wherein the step of uniformly mixing the polyperfluoroethylene-propylene emulsion and the chopped glass fibers is to mix the polyperfluoroethylene-propylene emulsion and the chopped glass fibers by using a homogenizing and dispersing machine, wherein the rotating speed of the homogenizing and dispersing machine is 1500r/min, and the dispersing time is 1-60 min.
6. The method for preparing the low dielectric polyperfluoroethylene propylene copper-clad plate according to claim 1, wherein the dehydration concentration is performed by a rotary evaporator under the conditions of 90 ℃ and vacuum degree of-0.1 MPa.
7. A low dielectric poly perfluoroethylene propylene copper-clad plate, which is characterized in that it is prepared by the preparation method of any one of claims 1 to 6; the low-dielectric poly-perfluoroethylene-propylene copper-clad plate has a dielectric constant value of 2-2.5, a dielectric loss value of 0.0008-0.0015 and a water absorption rate of 0.02-0.05%.
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