CN114369239A - Non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and preparation method thereof - Google Patents

Non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and preparation method thereof Download PDF

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CN114369239A
CN114369239A CN202111303865.1A CN202111303865A CN114369239A CN 114369239 A CN114369239 A CN 114369239A CN 202111303865 A CN202111303865 A CN 202111303865A CN 114369239 A CN114369239 A CN 114369239A
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fluorine
containing resin
clad plate
preparation
coupling agent
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俞卫忠
俞丞
顾书春
冯凯
赵琳
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Changzhou Zhongying Science&technology Co ltd
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Changzhou Zhongying Science&technology Co ltd
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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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    • B32—LAYERED PRODUCTS
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
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    • B32B2307/00—Properties of the layers or laminate
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    • 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
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    • 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
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Abstract

The invention belongs to the technical field of communication materials, and particularly relates to a fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and a preparation method thereof. The low-thermal-expansion type high-frequency copper-clad plate is effectively prepared by adding the linear polyaramide with the benzo quaternary ring structure into the fluorine-containing resin medium sheet. The invention has the following advantages: the linear polyaramid with a benzo quaternary ring structure is introduced into a fluorine-containing resin mixture, and the fluorine-containing resin is subjected to high-temperature baking/sintering/mould pressing/calendering/injection molding and other molding processes under the protection of atmosphere, so that the fluorine-containing resin reacts in situ to form a dibenzo eight-membered ring structure with heat shrinkage and cold expansion characteristics, and a cross-linked network structure is synchronously formed in the fluorine-containing resin matrix, thereby synergistically reducing the thermal expansion coefficient of the high-frequency copper-clad plate, and remarkably improving the bending strength, mechanical rigidity and dimensional stability of the plate.

Description

Non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and preparation method thereof
Technical Field
The invention belongs to the technical field of communication materials, and particularly relates to a fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and a preparation method thereof.
Background
At present, the electronic communication and information industry is rapidly developing and becoming one of the mainstay industries of all countries in the world. Copper-clad plates, which are one of key materials in the electronic communication and information industries, are widely used in the fields of mobile phones, computers, vending machines, communication base stations, satellites, gradually-emerging wearable devices, unmanned vehicles, unmanned aerial vehicles, intelligent robots and the like, and thus are receiving wide attention from the industry and academia.
Fluorine-containing resins represented by Polytetrafluoroethylene (PTFE) have various excellent properties such as low dielectric constant, low dielectric loss, high thermal stability, and chemical stability, which are incomparable with other polymer resins, due to their specific chemical structures. U.S. Pat. No. 4,510,194 discloses a copper-clad plate using PTFE as a substrate resin and a method for manufacturing the same, and since then, people continuously optimize the formula, the manufacturing process and the parameters so as to obtain a fluorine-containing resin-based copper-clad plate with higher comprehensive performance.
In general, the fluorine-containing resin has a very flexible polymer chain, and it is often necessary to introduce a reinforcing material such as glass cloth to improve the mechanical strength of the fluorine-containing resin substrate. However, the use of a reinforcing material such as a glass cloth inevitably increases the dielectric constant of the fluorine-containing resin substrate, thereby decreasing the adjustability of the dielectric properties of the fluorine-containing resin substrate.
At present, electronic products are rapidly developing towards the direction of miniaturization, light weight, thinning and multi-functionalization, and copper-clad plates serving as main carriers of electronic components have higher and higher integration level and more obvious multi-layer trend, so that the copper-clad plates are required to have extremely low thermal expansion coefficients.
The traditional idea of reducing the thermal expansion coefficient is to introduce a large amount of inorganic filler into the plate matrix to inhibit the thermal expansion process of the polymer matrix, however, the reduction effect of the thermal expansion coefficient of the copper-clad plate brought by the scheme has a remarkable limit value. In addition, the introduction of excessive inorganic filler can cause problems such as poor dispersibility of materials in the plate matrix, increased defects in the plate matrix, and poor uniformity and reliability of plate properties.
In 2013, the Jennifer Lu subject group of the university of California and the Wang Changchun subject group of the university of Redand jointly discover that the polymer containing the dibenzo eight-membered ring structural unit has unique reversible thermal shrinkage and cold expansion characteristics, and the coefficient of thermal expansion of the polymer can be more than 1200ppm/K (nat. chem., 2013, 5, 1035; Chinese patent application 201710360230.2; Chinese patent application 201910474075.6), and the characteristic is derived from reversible conformation change of the dibenzo eight-membered ring structural unit from a twist ship type to a chair type.
Disclosure of Invention
The invention provides a fiber-reinforced low-thermal expansion type fluorine-containing resin-based high-frequency copper-clad plate and a preparation method thereof, and the low-thermal expansion type high-frequency copper-clad plate can be effectively prepared by adding linear polyaramide with a benzo quaternary ring structure into a fluorine-containing resin medium sheet.
The technical scheme adopted by the invention for solving the problems is as follows: the non-fiber reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate comprises a fluorine-containing resin medium sheet, wherein the raw material of the fluorine-containing resin medium sheet comprises linear polyaramide with a benzo quaternary ring structure, and the chemical structure of the linear polyaramide with the benzo quaternary ring structure is
Figure RE-RE-RE-DEST_PATH_IMAGE002
Wherein R is
Figure RE-RE-RE-DEST_PATH_IMAGE004
Or is or
Figure RE-RE-RE-DEST_PATH_IMAGE006
Or is or
Figure RE-RE-RE-DEST_PATH_IMAGE008
Or is or
Figure RE-RE-RE-DEST_PATH_IMAGE010
Or is or
Figure RE-RE-RE-DEST_PATH_IMAGE012
Or is or
Figure RE-RE-RE-DEST_PATH_IMAGE014
Or is or
Figure RE-RE-RE-DEST_PATH_IMAGE016
Or is or
Figure RE-RE-RE-DEST_PATH_IMAGE018
Any one or a mixture of several of them.
The further preferred technical scheme is as follows: the raw material of the fluorine-containing resin medium sheet also comprises fluorine-containing resin and a modified filler, wherein the modified filler is an inorganic filler jointly modified by a coupling agent and a part of fluorine-containing polymer.
The further preferred technical scheme is as follows: the fluorine-containing resin is any one or a mixture of polytetrafluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene and ethylene-chlorotrifluoroethylene copolymer;
the inorganic filler is SiO2、AlN、Al(OH)3、Mg2TiO4、BaSnO3、ZnZrO3Any one or a mixture of a plurality of lead magnesium niobate, graphite and bentonite;
the coupling agent is any one or a mixture of more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a borate coupling agent, a zirconate coupling agent, a rare earth coupling agent, a phosphate coupling agent and a sulfonyl azide coupling agent;
the part of the fluorine-containing polymer is any one or a mixture of several of ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer and polyvinylidene fluoride.
A preparation method of a non-fiber reinforced low-thermal expansion type fluorine-containing resin-based high-frequency copper-clad plate comprises the following steps in sequence:
a1, preparing a uniform dispersion of the inorganic filler,
2, adding the coupling agent into the uniform dispersion liquid, stirring for reaction, adding the partial emulsion of the fluorine-containing polymer, continuing stirring for reaction, filtering to remove the solvent, and drying to obtain the modified filler;
or is
b1, adding the coupling agent into the inorganic filler, and carrying out a first stirring reaction,
b2, adding the part of the fluorine-containing polymer, and carrying out a second stirring reaction to obtain the modified filler.
In the invention, the content of the inorganic filler in a1 is 1-80wt/v%, the time of the two stirring reactions in a2 is 0.5-72h, and the temperature is 20-100 ℃.
In the invention, the time of the first stirring reaction in b1 is 0.5-72h, the temperature is 20-150 ℃, the time of the second stirring reaction is 0.5-72h, and the temperature is 230-330 ℃.
In the present invention, the partial fluoropolymer emulsion has a solid content of 10 to 70% by weight/v and a viscosity of 7 to 45 mPa.s (25 ℃), and is used in an amount of 1 to 100% by weight based on the inorganic filler.
The further preferred technical scheme is as follows: the fluorine-containing resin medium sheet is prepared by molding, rolling or injection molding of a fluorine-containing resin mixture or casting of a fluorine-containing resin mixed dispersion.
In the invention, the molding temperature in the molding method is 340-380 ℃, and the molding pressure is 45-145kg/cm2The mould pressing time is 30min-24h, and the atmosphere is inert gas atmosphere; the temperature of a roller in the calendering method is 320-390 ℃, the calendering speed is 2-80m/min, and the atmosphere is inert gas atmosphere; the temperature of a charging barrel in the injection molding method is 340-380 ℃, the temperature of a mold is 60-150 ℃, the injection molding pressure is 90-140MPa, and the atmosphere is inert gas atmosphere.
In the invention, the drying temperature in the casting method is 20-150 ℃, the drying time is 0.5-72h, the sintering temperature is 340-380 ℃, the sintering time is 5min-72h, and the atmosphere is inert gas atmosphere.
In the invention, the thickness of the fluorine-containing resin medium sheet is 0.1-10 mm.
The further preferable technical scheme is that the preparation method of the fluorine-containing resin mixture sequentially comprises the following steps:
c1, adding the linear polyaramid with the benzoquaternary ring structure and the modified filler into the fluorine-containing resin,
c2, and stirring and mixing the whole system at high temperature to obtain the fluorine-containing resin mixture.
In the present invention, the linear polyaramid having a benzoquaternaryring structure is used in an amount of 5 to 50wt% based on the fluorine-containing resin mixture, and the stirring time in c2 is 0.5 to 72 hours.
In the present invention, the inorganic filler accounts for 1 to 50wt% of the fluorine-containing resin mixture, and the coupling agent is used in an amount of 0.1 to 3.0wt% of the inorganic filler.
The further preferable technical scheme is that the preparation method of the fluorine-containing resin mixed dispersion liquid sequentially comprises the following steps:
d1, adding the linear polyaramid with the benzoquaternary ring structure and the modified filler into the fluorine-containing resin emulsion,
d2, and stirring and dispersing the whole system to obtain the fluorine-containing resin mixed dispersion liquid.
In the present invention, the fluorine-containing resin mixed dispersion has a solid content of 20 to 60wt/v%, the fluorine-containing resin emulsion has a solid content of 20 to 80wt/v%, and a viscosity of 9 to 50 mPa.s (25 ℃).
A further preferred embodiment is a method for converting the fluorine-containing resin mixed dispersion to the fluorine-containing resin mixture, comprising the following steps in this order:
e1, adding a flocculating settling agent into the fluorine-containing resin mixed dispersion liquid, stirring for reaction,
e2, and then filtering and drying the whole system to obtain the fluorine-containing resin mixture.
In the present invention, the fluororesin mixed dispersion liquid obtained by the steps a1, a2, d1 and d2 in this order, or the fluororesin mixture obtained by the steps a1, a2, d1, d2, e1 and e2 in this order, are referred to as wet process.
The dry method is also referred to as a dry method, in which the fluororesin mixture is obtained in the order of steps b1, b2, c1 and c2, or the fluororesin mixed dispersion is obtained in the order of steps b1, b2, d1 and d 2.
In the invention, the addition concentration of the e1 flocculating settling agent is 0.1-20wt/v%, the stirring time is 0.5-12h, and the flocculating settling agent is any one or a mixture of more of ketone, alcohol, ether, ester, furan, N-dimethylformamide and dimethyl sulfoxide.
In the invention, the drying operation temperature of e2 is 50-150 ℃, the atmosphere is inert gas atmosphere, and the drying time is 0.5-72 h.
The further preferred technical scheme is as follows: and overlapping the fluorine-containing resin dielectric sheet and the copper foil coated on the surface together, and laminating to obtain the non-fiber reinforced low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate.
In the invention, the laminating temperature is 340-380 ℃, and the laminating pressure is 30-150kg/cm2The laminating time is 30min-48h, and the atmosphere is inert gas atmosphere.
The further preferred technical scheme is as follows: and a film is arranged between the fluorine-containing resin medium sheet and the copper foil.
The present invention has the following advantages.
Firstly, the linear polyaramid with a benzo quaternary ring structure is introduced into a fluorine-containing resin mixture, and the fluorine-containing resin is subjected to high-temperature baking/sintering/mould pressing/calendering/injection molding and other molding processes under the protection of atmosphere, so that the linear polyaramid reacts in situ to form a dibenzo eight-membered ring which is a structure with thermal shrinkage and cold expansion characteristics, and a cross-linked network structure is synchronously formed in a fluorine-containing resin matrix, thereby synergistically reducing the thermal expansion coefficient of the high-frequency copper-clad plate and remarkably improving the bending strength, the mechanical rigidity and the dimensional stability of the plate.
Secondly, the inorganic filler is modified by the coupling agent and part of the fluorine-containing polymer, so that the interaction force between the inorganic filler and the fluorine-containing resin matrix can be obviously improved, the dispersibility of the inorganic filler in the fluorine-containing resin is improved, and the stability of the comprehensive performance of the high-frequency copper-clad plate is improved.
Drawings
FIG. 1 shows the main performance test results of the fiber-reinforced fluorine-containing resin substrate for the high-frequency copper-clad plate in each embodiment and comparative example of the invention.
Detailed Description
The following description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention.
Example 1
To a mixed solvent composed of 80 parts of water and 20 parts of ethanol, 120 parts of silica was added(Xinyi Hongrun), 30 parts of alumina (Zibo Hengbang) and 10 parts of titanium dioxide (Tianjin Zhongzheng Huamei science and technology), and stirring uniformly at room temperature; adding 1.8 parts of coupling agent perfluorodecyl trimethoxy silane, heating the system to 60 ℃, and continuing stirring for 12 hours; then, adding 3 parts of ETFE emulsion (DuPont Teflon 532 + 6210), stirring at room temperature for 6h, filtering to remove the solvent, and drying the solid at 110 ℃ for 12h to obtain the inorganic filler with the surface modified by the perfluorodecyl trimethoxy silane and the ETFE together; weighing 125 parts of polytetrafluoroethylene emulsion (DuPont Teflon PTFE DISP30 with solid content of 60%) and 140 parts of polyfluorinated ethylene propylene emulsion (DuPont Teflon ®®FEPD121, solid content 54%), 70 parts of linear polyaramide with a benzo-four-ring structure (R is a diphenyl ether structure) and the inorganic filler modified by the perfluorodecyl trimethoxy silane and the ETFE together, stirring for 12 hours at room temperature, dropwise adding ethyl acetate until no white viscous precipitate appears, pouring out the solvent, and drying the solid for 12 hours at 120 ℃ to obtain a fluorine-containing resin mixture; the molding temperature is set to 380 ℃ and the molding pressure is set to 120-130 kg/cm2The mould pressing time is 6 hours, and the fluorine-containing resin medium sheet with the thickness of 0.260mm is prepared under the argon atmosphere; taking 3 sheets of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and subjecting the obtained mixture to pressure of 50-90kg/cm2And laminating for 6 hours under the condition of an argon atmosphere and at the temperature of 380 ℃ to prepare the non-fiber reinforced low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate.
Example 2
Adding 200 parts of silicon oxide (Xinyi macrorun) to a mixed solvent composed of 75 parts of water and 25 parts of ethanol, and uniformly stirring at room temperature; adding 2 parts of coupling agent perfluorodecyl trimethoxy silane, heating the system to 60 ℃, and continuously stirring for 12 hours; then, 6.3 parts of ETFE emulsion (DuPont Teflon 532 + 6210) is added, the mixture is stirred for 6 hours at room temperature, then the solvent is removed by filtration, and the solid is dried for 12 hours at 110 ℃, so as to obtain the inorganic filler jointly modified by perfluorodecyl trimethoxy silane and ETFE; weighing 50 parts of polytetrafluoroethylene emulsion (DuPont Teflon PTFE DISP30 with solid content of 60%), 210 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon PFAD 335D with solid content of 60%), 40 parts of benzene-quaternary ring structure linear PTFE structureStirring polyaryl amide (R is a diphenyl ether structure) and the inorganic filler jointly modified by the perfluorodecyl trimethoxy silane and the ETFE for 12 hours at room temperature, dropwise adding ethyl acetate until no white viscous precipitate appears, pouring out the solvent, and drying the solid for 12 hours at 120 ℃ to obtain a fluorine-containing resin mixture; setting the temperature of a charging barrel of an injection molding machine to be 360 ℃, the temperature of a mold to be 120 ℃, the injection molding pressure to be 140MPa, and carrying out injection molding under argon atmosphere to obtain a fluorine-containing resin medium sheet with the thickness of 0.260 mm; taking 3 sheets of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and subjecting the obtained mixture to pressure of 50-90kg/cm2And laminating for 6 hours under the condition of an argon atmosphere and at the temperature of 380 ℃ to prepare the non-fiber reinforced low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate.
Example 3
Adding 150 parts of silicon oxide (Xinyi macrorun) and 10 parts of aluminum oxide (ZiboHengbang) into a mixed solvent consisting of 80 parts of water and 20 parts of ethanol, and uniformly stirring at room temperature; adding 2 parts of silane coupling agent KH570, heating the system to 55 ℃, and continuously stirring for 12 hours; subsequently, 4.5 parts of ETFE emulsion (DuPont Teflon 532-; weighing 125 parts of polytetrafluoroethylene emulsion (DuPont Teflon PTFE DISP30 with solid content of 60%), 80 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon PFAD 335D with solid content of 60%), 50 parts of polyfluorinated ethylene propylene (DuPont Teflon FEPD121 with solid content of 54%), 60 parts of linear polyaramide with a benzo-quaternary ring structure (R is a diphenyl sulfone structure) and the inorganic filler jointly modified by KH570 and ETFE, and stirring at room temperature for 12 hours to obtain uniform dispersion liquid; uniformly casting the dispersion on a flat and clean glass plate, drying at 90 ℃ for 2h, heating to 375 ℃, and sintering in an argon atmosphere for 15min to prepare a fluorine-containing resin medium sheet with the thickness of 0.105 mm; taking 5 sheets of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and applying pressure of 50-90kg/cm2And laminating for 6 hours under the condition of argon atmosphere and temperature of 375 ℃ to obtain the low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate without fiber reinforcement.
Example 4
Adding 120 parts of silicon oxide (New Yiyun Hongrun) and 30 parts of titanium dioxide (Tianjin Zhenghuamei science and technology) into a mixed solvent consisting of 70 parts of water and 30 parts of ethanol, and uniformly stirring at room temperature; adding 2 parts of coupling agent perfluorodecyl triethoxysilane, heating the system to 55 ℃, and continuing stirring for 12 hours; subsequently, 4 parts of ETFE emulsion (DuPont Teflon 532 + 6210) are added, the mixture is stirred for 6 hours at room temperature, then the solvent is removed by filtration, and the solid is dried for 12 hours at 120 ℃, so that the inorganic filler jointly modified by the perfluorodecyl triethoxysilane and the ETFE is obtained; weighing 55 parts of polytetrafluoroethylene emulsion (DuPont Teflon PTFE DISP30 with solid content of 60%), 195 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon PFAD 335D with solid content of 60%), 20 parts of linear polyaramide with a benzene-quaternary ring structure (R is a diphenylmethane structure) and the inorganic filler modified by the perfluorodecyl triethoxysilane and ETFE together, stirring for 12 hours at room temperature, adding acetone dropwise until no white sticky precipitate appears, pouring off the solvent, and drying the solid for 12 hours at 120 ℃ to obtain a fluorine-containing resin mixture; setting the temperature of a roller at 370 ℃, the rolling speed at 4m/min and the atmosphere at argon atmosphere, and rolling to obtain a fluorine-containing resin medium sheet with the thickness of 0.259 mm; taking 1 sheet of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and subjecting the sheet and the copper foil to pressure of 50-90kg/cm2And laminating for 6 hours under the condition of an argon atmosphere and at the temperature of 380 ℃ to prepare the non-fiber reinforced low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate.
Example 5
Weighing 40 parts of silicon oxide (Xinyi macrorun), 10 parts of aluminum oxide (ZiboHengbang), 100 parts of titanium dioxide (Tianjin Zhenghuamei technology) and 1.5 parts of coupling agent perfluorodecyl trimethoxy silane, and stirring at 80 ℃ for 24 hours; adding 7 parts of ETFE (DuPont Tefzel ETFE 200), heating the system to 310 ℃, and continuously stirring for 12 hours to obtain the inorganic filler jointly modified by the perfluorodecyl trimethoxy silane and the ETFE; 100 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (DuPont PFA 350), 50 parts of polyfluoroethylene propylene (DuPont FEP 6100), 60 parts of linear polyaramide (R is diphenyl ether structure) having a benzoquaterpary ring structure, and the copolymer modified by perfluorodecyltrimethoxysilane and ETFEStirring the decorated inorganic filler at a high speed for 6 hours to obtain a fluorine-containing resin mixture; at a temperature of 360 ℃ and a pressure of 130 to 140kg/cm2Molding for 6 hours under argon atmosphere to prepare a fluorine-containing resin medium sheet with the thickness of 0.263 mm; taking 1 sheet of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and applying pressure of 135-145 kg/cm2And laminating for 6 hours under the condition of argon atmosphere and the temperature of 370 ℃ to prepare the low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate without fiber reinforcement.
Example 6
Weighing 180 parts of silicon oxide (Xinyi macrorun), 5 parts of aluminum oxide (ZiboHengbang), 5 parts of titanium dioxide (Tianjin Zhenghuamei science and technology) and 1.5 parts of coupling agent perfluorodecyl triethoxysilane, and stirring at 80 ℃ for 24 hours; adding 6.5 parts of ETFE (DuPont Tefzel ETFE 280), heating the system to 310 ℃, and continuously stirring for 12 hours to obtain the inorganic filler jointly modified by the perfluorodecyl triethoxysilane and the ETFE; weighing 20 parts of polytetrafluoroethylene (DuPont PTFE 6C), 30 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (DuPont PFA 350), 100 parts of polyfluoroethylene propylene (DuPont FEP 6100), 10 parts of linear polyaramide (R is diphenyl ether structure) with a benzo quaternary ring structure and the inorganic filler jointly modified by the perfluorodecyl triethoxysilane and ETFE, and stirring at high speed for 6h to obtain a fluorine-containing resin mixture; setting the charging barrel temperature of an injection molding machine to 365 ℃, the mold temperature to 100 ℃ and the injection molding pressure to 140MPa, and preparing a fluorine-containing resin medium sheet with the thickness of 0.262mm by injection molding; taking 1 sheet of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and subjecting the sheet and the copper foil to pressure of 50-90kg/cm2And laminating for 6 hours under the condition of an argon atmosphere and at the temperature of 380 ℃ to prepare the non-fiber reinforced low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate.
Example 7
Weighing 150 parts of silicon oxide (Xinyi macrorun), 40 parts of aluminum oxide (Zibo Hengbang) and 1.5 parts of coupling agent KH570, stirring at 80 ℃ for 24 hours, adding 6.5 parts of ETFE (DuPont Tefzel ETFE 280), heating the system to 310 ℃, and continuously stirring for 12 hours to obtain inorganic filler jointly modified by KH570 and ETFE; weighing 10 parts of polytetrafluoroethylene (DuPont PTFE 6C), 80 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (DuPont PFA 350) and 70 parts of polyPerfluoroethylene propylene (DuPont FEP 6100), 70 parts of linear polyaramide with a benzo-quaternary ring structure (R is a diphenyl sulfone structure) and the inorganic filler modified by KH570 and ETFE, and stirring at high speed for 6h to obtain a fluorine-containing resin mixture; at a temperature of 360 ℃ and a pressure of 130 to 140kg/cm2Molding for 6 hours under argon atmosphere to prepare a fluorine-containing resin medium sheet with the thickness of 0.260 mm; taking 2 sheets of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and applying pressure of 50-905 kg/cm2And laminating for 6 hours under the condition of argon atmosphere and the temperature of 370 ℃ to prepare the low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate without fiber reinforcement.
Example 8
Weighing 100 parts of silicon oxide (Xinyi macrorun), 30 parts of aluminum oxide (Zibo Hengbang), 20 parts of titanium dioxide (Tianjin Zhenghuamei technology) and 1.5 parts of coupling agent perfluorodecyl triethoxysilane, stirring at 80 ℃ for 24 hours, adding 7 parts of ETFE (DuPont Tefzel ETFE 200), heating the system to 310 ℃, and continuously stirring for 12 hours to obtain the inorganic filler jointly modified by the perfluorodecyl triethoxysilane and the ETFE; weighing 30 parts of polytetrafluoroethylene (DuPont PTFE 6C), 90 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (DuPont PFA 350), 40 parts of polyfluoroethylpropylene (DuPont FEP 6100), 60 parts of linear polyaramide (R is a diphenylmethane structure) with a benzo quaternary ring structure and the inorganic filler jointly modified by the perfluorodecyl triethoxysilane and the ETFE, and stirring at high speed for 6 hours to obtain a fluorine-containing resin mixture; setting the temperature of a roller at 360 ℃, the rolling speed at 4.5m/min and the atmosphere at argon atmosphere, and rolling to prepare a fluorine-containing resin medium sheet with the thickness of 0.105 mm; taking 5 sheets of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and applying pressure of 60-100 kg/cm2And laminating for 6 hours under the condition of argon atmosphere and temperature of 375 ℃ to obtain the low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate without fiber reinforcement.
Comparative example 1
Adding 120 parts of silicon oxide (Xinyi macrorun), 30 parts of aluminum oxide (Zibo Hengbang) and 10 parts of titanium dioxide (Tianjin Zhongzheng Huamei science and technology) into a mixed solvent consisting of 80 parts of water and 20 parts of ethanol, and uniformly stirring at room temperature; adding 1.8 parts of coupling agent perfluorodecyl trimethoxy silaneThen, heating the system to 60 ℃, and continuing stirring for 12 hours; then, adding 3 parts of ETFE emulsion (DuPont Teflon 532 + 6210), stirring at room temperature for 6h, filtering to remove the solvent, and drying the solid at 110 ℃ for 12h to obtain the inorganic filler with the surface modified by the perfluorodecyl trimethoxy silane and the ETFE together; weighing 125 parts of polytetrafluoroethylene emulsion (DuPont Teflon PTFE DISP30 with solid content of 60%), 140 parts of polyfluorinated ethylene propylene emulsion (DuPont Teflon FEPD121 with solid content of 54%) and the inorganic filler jointly modified by the perfluorodecyl trimethoxy silane and the ETFE, stirring for 12 hours at room temperature, dropwise adding ethyl acetate until no white viscous precipitate appears, pouring off the solvent, and drying the solid for 12 hours at 120 ℃ to obtain a fluorine-containing resin mixture; the molding temperature is set to 380 ℃ and the molding pressure is set to 120-130 kg/cm2The mould pressing time is 6h, and a fluorine-containing resin medium sheet with the thickness of 0.259mm is prepared under the argon atmosphere; taking 1 sheet of the fluorine-containing resin medium sheet and 2 sheets of copper foil, and subjecting the sheet and the copper foil to pressure of 50-90kg/cm2And laminating for 6 hours at the temperature of 380 ℃ in the argon atmosphere to obtain the fluorine-containing resin-based high-frequency copper-clad plate without fiber reinforcement.
Comparative example 2
Weighing 40 parts of silicon oxide (Xinyi macrorun), 10 parts of aluminum oxide (ZiboHengbang), 100 parts of titanium dioxide (Tianjin Zhenghuamei technology) and 1.5 parts of coupling agent perfluorodecyl trimethoxy silane, and stirring at 80 ℃ for 24 hours; adding 7 parts of ETFE (DuPont Tefzel ETFE 200), heating the system to 310 ℃, and continuously stirring for 12 hours to obtain the inorganic filler jointly modified by the perfluorodecyl trimethoxy silane and the ETFE; weighing 100 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (DuPont PFA 350), 50 parts of fluorinated ethylene propylene (DuPont FEP 6100) and the inorganic filler modified by the perfluorodecyl trimethoxy silane and the ETFE together, and stirring at high speed for 6 hours to obtain a fluorine-containing resin mixture; at a temperature of 370 ℃ and a pressure of 130 to 140kg/cm2Molding for 6 hours under argon atmosphere to prepare a fluorine-containing resin medium sheet with the thickness of 0.517 mm; taking 1 sheet of the above fluororesin medium sheet and 2 sheets of copper foil, and subjecting to pressure of 50-90kg/cm2And laminating for 6 hours at the temperature of 380 ℃ in the argon atmosphere to obtain the fluorine-containing resin-based high-frequency copper-clad plate without fiber reinforcement.
Finally, 8 examples, as well as comparative examples 1 and 2, were tested, and the properties are shown in FIG. 1.
As shown in comparative examples 1 and 2, no matter the wet method or the dry method is adopted, under the condition that the linear polyaramide with a benzo quaternary ring structure is not added, the coefficient of thermal expansion CTE of the fiber-free reinforced fluorine-containing resin substrate for the high-frequency copper-clad plate in the Z-axis direction is up to 160 ppm/K; when a small amount of the linear polyaramid with a benzo-quaternary ring structure is introduced, for example, in example 6, the coefficient of thermal expansion CTE of the fiber-free reinforced fluorine-containing resin substrate for the high-frequency copper-clad plate in the Z-axis direction can be remarkably reduced to 80 ppm/K; when the content of the linear polyaramid with the benzoquaternary ring structure is further increased, the coefficient of thermal expansion CTE of the fiber-free reinforced fluorine-containing resin substrate for the high-frequency copper-clad plate in the Z-axis direction can be reduced to be extremely low, namely 25ppm/K as in example 1.
The linear polyaramid with a benzo-quaternary ring structure is introduced, and can react in situ to form a structure with thermal shrinkage and cold expansion characteristics, namely a dibenzo-eight-membered ring, in the high-temperature forming process under the atmosphere protection, and a cross-linked network structure is synchronously formed in the fluorine-containing resin matrix, so that the thermal expansion coefficient of the fluorine-containing resin substrate is synergistically reduced, and the bending strength, the mechanical rigidity and the dimensional stability of the plate are remarkably improved. The prepared substrate for the high-frequency copper-clad plate has good thermal-mechanical property, high stability and low hygroscopicity, and can meet various comprehensive performance requirements of different communication fields on the copper-clad plate. In conclusion, the method has the advantages of simple operation process, mild preparation conditions, low production cost, easiness for batch and large-scale production, good industrial production basis and wide application prospect.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various modifications can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. These are non-inventive modifications, which are intended to be protected by patent laws within the scope of the claims appended hereto.

Claims (10)

1. The low-thermal expansion type fluorine-containing resin based high-frequency copper-clad plate without fiber reinforcement is characterized in that: the fluorine-containing resin dielectric sheet comprises a fluorine-containing resin dielectric sheet, wherein the raw material of the fluorine-containing resin dielectric sheet comprises linear polyaramide with a benzoquaternary ring structure, and the chemical structure of the linear polyaramide with the benzoquaternary ring structure is
Figure RE-RE-DEST_PATH_IMAGE002
Wherein R is
Figure RE-RE-DEST_PATH_IMAGE004
Or is or
Figure RE-RE-DEST_PATH_IMAGE006
Or is or
Figure RE-RE-DEST_PATH_IMAGE008
Or is or
Figure RE-RE-DEST_PATH_IMAGE010
Or is or
Figure RE-RE-DEST_PATH_IMAGE012
Or is or
Figure RE-RE-DEST_PATH_IMAGE014
Or is or
Figure RE-RE-DEST_PATH_IMAGE016
Or is or
Figure RE-RE-DEST_PATH_IMAGE018
Any one or a mixture of several of them.
2. The non-fiber reinforced low-thermal-expansion type fluorine-containing resin-based high-frequency copper-clad plate according to claim 1, characterized in that: the raw material of the fluorine-containing resin medium sheet also comprises fluorine-containing resin and a modified filler, wherein the modified filler is an inorganic filler jointly modified by a coupling agent and a part of fluorine-containing polymer.
3. The non-fiber reinforced low-thermal-expansion type fluorine-containing resin-based high-frequency copper-clad plate according to claim 2, wherein: the fluorine-containing resin is any one or a mixture of polytetrafluoroethylene, fluorinated ethylene propylene, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene and ethylene-chlorotrifluoroethylene copolymer;
the inorganic filler is SiO2、AlN、Al(OH)3、Mg2TiO4、BaSnO3、ZnZrO3Any one or a mixture of a plurality of lead magnesium niobate, graphite and bentonite;
the coupling agent is any one or a mixture of more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a borate coupling agent, a zirconate coupling agent, a rare earth coupling agent, a phosphate coupling agent and a sulfonyl azide coupling agent;
the part of the fluorine-containing polymer is any one or a mixture of several of ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer and polyvinylidene fluoride.
4. The preparation method of the non-fiber reinforced low-thermal expansion type fluorine-containing resin based high-frequency copper-clad plate according to claim 3, characterized in that the preparation method of the modified filler sequentially comprises the following steps:
a1, preparing a uniform dispersion of the inorganic filler,
2, adding the coupling agent into the uniform dispersion liquid, stirring for reaction, adding the partial emulsion of the fluorine-containing polymer, continuing stirring for reaction, filtering to remove the solvent, and drying to obtain the modified filler;
or is
b1, adding the coupling agent into the inorganic filler, and carrying out a first stirring reaction,
b2, adding the part of the fluorine-containing polymer, and carrying out a second stirring reaction to obtain the modified filler.
5. The preparation method of the non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate according to claim 4, wherein the preparation method comprises the following steps: the fluorine-containing resin medium sheet is prepared by molding, rolling or injection molding of a fluorine-containing resin mixture or casting of a fluorine-containing resin mixed dispersion.
6. The preparation method of the non-fiber reinforced low-thermal expansion type fluorine-containing resin based high-frequency copper-clad plate according to claim 5, wherein the preparation method of the fluorine-containing resin mixture comprises the following steps in sequence:
c1, adding the linear polyaramid with the benzoquaternary ring structure and the modified filler into the fluorine-containing resin,
c2, and stirring and mixing the whole system at high temperature to obtain the fluorine-containing resin mixture.
7. The preparation method of the non-fiber-reinforced low-thermal-expansion type fluorine-containing resin-based high-frequency copper-clad plate according to claim 5, wherein the preparation method of the fluorine-containing resin mixed dispersion liquid sequentially comprises the following steps:
d1, adding the linear polyaramid with the benzoquaternary ring structure and the modified filler into the fluorine-containing resin emulsion,
d2, and stirring and dispersing the whole system to obtain the fluorine-containing resin mixed dispersion liquid.
8. The preparation method of the non-fiber reinforced low-thermal expansion type fluorine-containing resin based high-frequency copper-clad plate according to claim 5, wherein the conversion method from the fluorine-containing resin mixed dispersion liquid to the fluorine-containing resin mixture comprises the following steps in sequence:
e1, adding a flocculating settling agent into the fluorine-containing resin mixed dispersion liquid, stirring for reaction,
e2, and then filtering and drying the whole system to obtain the fluorine-containing resin mixture.
9. The preparation method of the non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate according to claim 4, wherein the preparation method comprises the following steps: and overlapping the fluorine-containing resin dielectric sheet and the copper foil coated on the surface together, and laminating to obtain the non-fiber reinforced low-thermal expansion type fluorine-containing resin base high-frequency copper-clad plate.
10. The preparation method of the non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate according to claim 9, wherein the preparation method comprises the following steps: and a film is arranged between the fluorine-containing resin medium sheet and the copper foil.
CN202111303865.1A 2021-11-05 2021-11-05 Non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and preparation method thereof Pending CN114369239A (en)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JPH11112117A (en) * 1997-10-03 1999-04-23 Nippon Aramido Kk Substrate material for printed wiring, substrate and manufacture thereof
CN106590452A (en) * 2016-11-25 2017-04-26 常州中英科技股份有限公司 Adhesive sheet for copper-clad laminate
CN106854330A (en) * 2016-11-25 2017-06-16 常州中英科技股份有限公司 A kind of fluorine resin mixture and its prepreg and the copper-clad plate of preparation
CN108656683A (en) * 2018-04-16 2018-10-16 常州中英科技股份有限公司 A kind of fluorine resin base copper-clad plate of high-k and preparation method thereof
CN110194836A (en) * 2019-06-02 2019-09-03 复旦大学 Crosslinking Nomex and its preparation method and application with near-zero thermal expansion coefficient
CN111574818A (en) * 2020-05-25 2020-08-25 常州中英科技股份有限公司 Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and carbon-hydrogen copper-clad plate prepared from polyarylether base composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11112117A (en) * 1997-10-03 1999-04-23 Nippon Aramido Kk Substrate material for printed wiring, substrate and manufacture thereof
CN106590452A (en) * 2016-11-25 2017-04-26 常州中英科技股份有限公司 Adhesive sheet for copper-clad laminate
CN106854330A (en) * 2016-11-25 2017-06-16 常州中英科技股份有限公司 A kind of fluorine resin mixture and its prepreg and the copper-clad plate of preparation
CN108656683A (en) * 2018-04-16 2018-10-16 常州中英科技股份有限公司 A kind of fluorine resin base copper-clad plate of high-k and preparation method thereof
CN110194836A (en) * 2019-06-02 2019-09-03 复旦大学 Crosslinking Nomex and its preparation method and application with near-zero thermal expansion coefficient
CN111574818A (en) * 2020-05-25 2020-08-25 常州中英科技股份有限公司 Polyarylether base composition containing reversible thermal shrinkage and cold expansion structural unit and prepreg and carbon-hydrogen copper-clad plate prepared from polyarylether base composition

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