CN115075057B - Low dielectric loss non-woven fabric and preparation method and application thereof - Google Patents

Low dielectric loss non-woven fabric and preparation method and application thereof Download PDF

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Publication number
CN115075057B
CN115075057B CN202210790750.8A CN202210790750A CN115075057B CN 115075057 B CN115075057 B CN 115075057B CN 202210790750 A CN202210790750 A CN 202210790750A CN 115075057 B CN115075057 B CN 115075057B
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dielectric loss
low dielectric
nonwoven fabric
emulsion
fibers
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CN115075057A (en
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柴颂刚
刘潜发
梁伟
郝良鹏
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Abstract

The invention provides a low dielectric loss non-woven fabric, a preparation method and application thereof. The non-woven fabric disclosed by the invention has good dielectric property and obvious reinforcing effect, and can meet various performance requirements of the copper-clad plate material in the field of high-frequency communication.

Description

Low dielectric loss non-woven fabric and preparation method and application thereof
Technical Field
The invention belongs to the technical field of laminated boards, and relates to a low dielectric loss non-woven fabric, and a preparation method and application thereof.
Background
The copper-clad plate is widely applied to the fields of mobile phones, computers, automatic vending machines, communication base stations, satellites, wearable equipment, unmanned vehicles, unmanned aerial vehicles, intelligent robots and the like, and is one of key basic materials in electronic communication and information industries. The fluorine-containing resin represented by Polytetrafluoroethylene (PTFE) has various excellent performances such as low dielectric constant, low dielectric loss, high thermal stability and chemical stability which are incomparable with other polymer resins, and is an ideal copper-clad plate matrix material.
Along with the stronger and stronger isotropy requirement of the high-frequency copper-clad plate base material, an isotropy reinforcing material needs to be developed, so that the PTFE composite material has excellent Dk consistency and extremely low dielectric loss, and simultaneously has better mechanical strength compared with a PTFE film without the reinforcing material. Currently, there are no isotropic reinforcing materials with very low dielectric losses.
The traditional non-woven fabrics have the characteristics of reinforcement and isotropy, but epoxy adhesives, acrylic adhesives, melamine adhesives or polyvinyl alcohol adhesives are generally adopted, and the dielectric loss of the adhesives is large. The polytetrafluoroethylene has low dielectric loss, but the melting point is as high as 325-340 ℃, the sintering temperature requirement is high, and the energy consumption is high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low dielectric loss non-woven fabric and a preparation method and application thereof. The non-woven fabric disclosed by the invention has the advantages of good dielectric property, obvious enhancement effect, low sintering temperature requirement and low energy consumption, and can meet various performance requirements of copper-clad plate materials in the field of high-frequency communication.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a low dielectric loss non-woven fabric, which consists of inorganic fibers and a binder, wherein the binder is fluorine-containing resin emulsion, and the melting point of the fluorine-containing resin emulsion is 200-300 ℃.
In the invention, the adhesive is used to ensure that the non-woven fabric has low dielectric loss, good uniformity, consistent thickness, consistent fiber directional distribution and high tensile strength, and the low dielectric loss high-frequency copper-clad laminate is prepared.
In the present invention, the low dielectric loss nonwoven fabric means that the dielectric loss of the nonwoven fabric is less than 0.0015 (10 GHz).
In the present invention, the permittivity and dielectric loss were measured by SPDR (split post dielectric resonator) method, and the frequency was 10GHz.
In the present invention, the binder is a fluorine-containing resin emulsion and has a melting point of 200 to 300 ℃, for example 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃, 270 ℃, 290 ℃, or 300 ℃. The melting point is higher than 300 ℃, the sintering temperature of the non-woven fabric is higher than 300 ℃, the energy consumption is high, and the temperature of a most non-woven fabric production line baking oven can not be reached at present; the melting point is lower than 200 ℃, such as PVDF resin, the dielectric constant is too high (Dk is 7), the loss is too large (Df is 0.1), and the non-woven fabric pressed circuit board prepared by using the PVDF resin as a binder has too large dielectric loss and low peel strength.
Preferably, the fluorine-containing resin emulsion is selected from any one or a combination of at least two of a perfluoroethylene propylene emulsion, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, an ethylene-tetrafluoroethylene copolymer emulsion, a polytrifluoroethylene emulsion or an ethylene-chlorotrifluoroethylene copolymer emulsion.
Preferably, the fluorine-containing resin emulsion has a solids content of 30-70%, for example 30%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65% or 70%.
Preferably, the weight percentage of inorganic fibers in the low dielectric loss nonwoven is 60-95% (e.g., 60%, 62%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 88%, 90%, 93%, or 95%), and the weight percentage of binder is 5% -40% (e.g., 5%, 8%, 10%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38%, or 40%). In the invention, if the weight percentage of the binder is too low, the binder cannot continuously form a film, resulting in low strength of the non-woven fabric, and if the weight percentage of the binder is too high, more voids and defects are generated in the non-woven fabric, resulting in low strength of the non-woven fabric, thereby affecting dielectric loss and adhesiveness.
The binder can be added with a solvent according to the requirement to be dissolved and diluted to a proper viscosity, so that the fibers and the binder in the prepared non-woven fabric are uniformly dispersed, and the solvent comprises deionized water and the like. The solvent volatilizes along with the drying and sintering of the non-woven fabric in the preparation process.
Preferably, the inorganic fiber is selected from any one or a combination of at least two of E glass fiber, NE glass fiber, L glass fiber, quartz fiber, alumina fiber, boron nitride fiber, silicon carbide fiber, zinc oxide fiber, magnesium oxide fiber, silicon nitride fiber, boron carbide fiber, aluminum nitride fiber, aluminum oxide whisker, boron nitride whisker, silicon carbide whisker, zinc oxide whisker, magnesium oxide whisker, silicon nitride whisker, boron carbide whisker or aluminum nitride whisker.
Preferably, the inorganic fibers have an average diameter of less than 10 microns, such as 9 microns, 8 microns, 7 microns, 6 microns, 5 microns, 4 microns, 3 microns, 2 microns, 1 micron, or 0.5 microns, etc., preferably 0.5-5 microns. Inorganic fiber diameter refers to the diameter of the filaments of the inorganic fiber, typically the length of the filaments is greater than the diameter of the filaments, preferably the aspect ratio of the filaments is greater than 10, or greater than 50, or greater than 100. The average diameter and the average length of the inorganic fibers are obtained by adopting a scanning electron microscope observation test.
Preferably, the binder further comprises an antifoaming agent selected from any one or a combination of at least two of mineral oil antifoaming agents, silicone oil antifoaming agents, or acrylic acid ester antifoaming agents.
Preferably, the weight percentage of defoamer in the binder is 0.01-1%, e.g. 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8% or 1%.
Preferably, the binder may further include a dispersant, a thickener, a filler, and the like.
The dispersing agent is selected from any one or a combination of at least two of amine surfactants, amide cationic surfactants and nonionic surfactants.
The thickener is selected from any one or a combination of at least two of cellulose thickeners, polyacrylate type, polyurethane associated type macromolecule thickeners and derivative thickeners thereof.
The filler is selected from any one or a combination of at least two of titanium dioxide, barium titanate, strontium titanate, aluminum oxide, boron nitride, silicon nitride, hollow glass beads or hollow silicon dioxide.
Preferably, the low dielectric loss nonwoven fabric is a surface-treated low dielectric loss nonwoven fabric.
Preferably, the surface-treated treating agent is selected from one or a mixture of at least two of fluorine-containing silane coupling agent, amino silane coupling agent, epoxy silane coupling agent, vinyl silane coupling agent, alkyl silane coupling agent, borate coupling agent, zirconate coupling agent, or phosphate coupling agent.
Preferably, the low dielectric loss nonwoven fabric has a single weight (also known as mass per unit area) of 20 to 200 grams per square meter, for example 20 grams per square meter, 25 grams per square meter, 30 grams per square meter, 35 grams per square meter, 40 grams per square meter, 50 grams per square meter, 60 grams per square meter, 80 grams per square meter, 100 grams per square meter, 120 grams per square meter, 150 grams per square meter, 180 grams per square meter or 200 grams per square meter, preferably 20 to 100 grams per square meter.
In the present invention, the laboratory prepares different single weight nonwoven fabrics by adjusting the weight of the inorganic fibers and the adhesive. The industrial production is to prepare different single-weight non-woven fabrics by adjusting the solubility of inorganic fibers and adhesives and the solvent and the speed of the vehicle.
On the other hand, the invention provides a preparation method of the low dielectric loss non-woven fabric, which comprises the steps of mixing and impregnating inorganic fibers with a binder, forming by papermaking, drying and sintering to obtain the low dielectric loss non-woven fabric.
Preferably, the time of the impregnation is 40 to 50min, for example 40min, 43min, 45min, 48min or 50min.
Preferably, the temperature of the drying is 120-150 ℃, such as 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, for a period of time of 1-30 min, such as 1min, 3min, 5min, 8min, 10min, 13min, 15min, 18min, 20min, 25min, 28min or 30min.
Preferably, the sintering temperature is 200 ℃ to 300 ℃, such as 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃, 270 ℃, 290 ℃, or 300 ℃, and the sintering time is 1 to 20min, such as 1min, 3min, 5min, 8min, 10min, 13min, 15min, 18min or 20min.
In another aspect, the present invention provides a prepreg comprising the low dielectric loss nonwoven fabric as described above and a resin composition attached thereto by impregnation.
Preferably, the resin composition includes one or a combination of at least two of a fluorine-containing resin emulsion, a polyphenylene ether resin, a polybutadiene resin, a butadiene-styrene copolymer, a styrene-butadiene-styrene triblock copolymer, a polyfunctional vinyl aromatic copolymer, a silicone resin, a cyanate ester resin, or a maleimide compound.
Since the fluorine-containing resin has excellent dielectric properties, and the compatibility of the fluorine-containing resin with the fluorine-containing resin nonwoven fabric is better. Therefore, the resin composition of the present invention is preferably a fluorine-containing resin emulsion.
Preferably, the fluorine-containing resin emulsion is selected from any one or a combination of at least two of polytetrafluoroethylene emulsion, perfluoroethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polytrifluoroethylene emulsion or ethylene-trifluorochloroethylene copolymer emulsion.
In another aspect, the invention provides a copper-clad laminate comprising a copper foil and a prepreg as described above.
In another aspect, the present invention provides a printed circuit board comprising a copper foil, and a prepreg as described above.
Compared with the prior art, the invention has the following beneficial effects:
the non-woven fabric disclosed by the invention has the advantages of low dielectric loss, good uniformity, uniform thickness, uniform fiber directional distribution and high tensile strength, and can be used for preparing a high-frequency copper-clad plate with low dielectric loss and high peel strength by adding more dielectric filler when impregnating low dielectric loss resin.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw materials used in the following examples and comparative examples are as follows:
PTFE resin emulsion with a melting point of 327 ℃ and a solid content of 55wt%, manufactured by Japanese big gold company, brand: D210C.
PFA resin emulsion with a melting point of 300 ℃ and a solid content of 55wt%, manufactured by Japanese big gold company, brand: AD-2CR.
ETFE resin emulsion, melting point 270 ℃, solid content 50wt%, and mountain east Yue sample.
FEP resin emulsion, melting point 250 ℃, solid content 50wt%, produced by Japanese big gold company, brand: ND-110.
PVDF resin emulsion, melting point 170 ℃, solid content 50wt%, nishan Dongyue sample.
Low coefficient of thermal expansion resin a: 450g of the PTFE resin emulsion was stirred and mixed at a high speed for 2 hours to obtain a uniform resin composition.
Thermosetting resin a: 30 parts by weight of ethylene propylene rubber (number average molecular weight 80000g/mol, american lion chemical Co., ltd.), 40 parts by weight of polybutadiene (molecular weight 3200g/mol, japanese Cato Co., ltd.), 2 parts by weight of benzoyl peroxide (Shanghai Kanglang Biotechnology Co., ltd.) were dissolved in 50 parts by weight of xylene, and uniformly mixed to obtain a uniform resin composition.
E glass fiber with average diameter of 5 μm, china boulder Co Ltd
NE glass fiber having an average diameter of 5 μm, china boulder Co., ltd
Quartz fibers having average diameters of 0.5 μm and 5 μm, chinese rose
E glass fiber with average diameter of 8 μm, china boulder Co Ltd
Nonwoven fabric prepared from epoxy binder and E glass fiber with average diameter of 13 μm, shanxi Huate.
Nonwoven fabric prepared from acrylate binder and E glass fiber with average diameter of 13 μm, shanxi Huate.
Nonwoven fabric prepared from melamine binder and E glass fibers with average diameter of 13 μm, shanxi Huate.
In this embodiment, a low dielectric loss nonwoven fabric composed of inorganic fibers and a binder is provided. Inorganic fibers, a binder and a solvent are mixed and impregnated, and the mixture is placed in a round standard sheet machine (Kumagaya Riki Kogyo Co., ltd), fully stirred and filtered, and formed by papermaking, dried and sintered to obtain a round non-woven fabric with the diameter of 80 mm. The weight of the inorganic fiber and the adhesive is adjusted to prepare the non-woven fabrics with different single weights.
The preparation method comprises the following steps:
example 1
95 parts by weight of E glass fiber (with the average diameter of 5 micrometers), 5 parts by weight of FEP binder and a proper amount of deionized water are immersed for 45min, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 15min in a high-temperature baking oven at 270 ℃, taken out and cooled to obtain the non-woven fabric A with the single weight of 20 g/square meter.
Example 2
85 parts by weight of NE glass fiber (average diameter of 5 microns), 15 parts by weight of FEP binder and a proper amount of deionized water are immersed for 45min, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 15min in a high-temperature baking oven at 270 ℃, and taken out and cooled to obtain the non-woven fabric B with the single weight of 75 g/square meter.
Example 3
70 parts by weight of quartz fiber (average diameter of 0.5 μm and 5 μm, weight ratio of 1:4) is soaked with 30 parts by weight of ETFE binder and proper amount of deionized water for 45min, formed by papermaking, dried by using a 140 ℃ oven, sintered for 25min in a high-temperature oven at 280 ℃, taken out and cooled to prepare the non-woven fabric C with the single weight of 75 g/square meter.
Example 4
60 parts by weight of E glass fiber (average diameter of 8 micrometers), 40 parts by weight of PFA binder and a proper amount of deionized water are immersed for 45min, formed by papermaking, dried by a 140 ℃ oven, sintered for 15min in a high-temperature oven at 300 ℃, taken out and cooled to obtain the non-woven fabric D with the single weight of 75 g/square meter.
Example 5
85 parts by weight of E glass fiber (with the average diameter of 8 micrometers), 15 parts by weight of FEP binder, 0.01 part by weight of organic silicone oil defoamer (BYK-044) and a proper amount of deionized water are soaked for 45 minutes, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 5 minutes at 270 ℃ of a high-temperature baking oven, taken out and cooled, and then the non-woven fabric E with the single weight of 75 g/square meter is prepared.
Comparative example 1
85 parts by weight of E glass fiber (with the average diameter of 8 micrometers), 15 parts by weight of PVDF binder and a proper amount of deionized water are immersed for 45 minutes, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 5 minutes in a high-temperature baking oven at 170 ℃, taken out and cooled, and then the non-woven fabric F with the single weight of 75 g/square meter is prepared.
Comparative example 2
85 parts by weight of E glass fiber (with the average diameter of 8 micrometers), 15 parts by weight of PTFE binder and a proper amount of deionized water are immersed for 45 minutes, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 5 minutes in a high-temperature baking oven at 300 ℃, taken out and cooled, and then the non-woven fabric G with the single weight of 75G/square meter is prepared.
The main materials and parameters of the nonwoven fabrics of the above examples and comparative examples are summarized in the following table 1:
TABLE 1
Example 6
In this embodiment, a PTFE copper-clad plate is provided, and the preparation method specifically includes the following steps:
step (1): the low thermal expansion coefficient resin A glue solution was applied to the nonwoven fabric A of example 1 by a sizing machine to obtain a prepreg having a sizing resin content of 90%.
Step (2): and (3) placing the prepreg obtained in the step (1) in a vacuum oven at 100 ℃ for 1h, baking to remove water, baking at 260 ℃ for 1h to remove auxiliary agent, and baking at 350 ℃ for 10min to obtain the bonding sheet with the thickness of 0.25 mm.
Step (3): and (3) laminating copper foils with thickness of 1OZ on the upper and lower surfaces of the single bonding sheet, applying pressure of 400PSI, and obtaining the PTFE copper-clad plate with the highest temperature and the retention time of 380 ℃/60 min.
Example 7
The only difference from example 6 is that the nonwoven fabric a in step (1) was changed to the nonwoven fabric B to obtain a prepreg.
Example 8
The only difference from example 6 is that the nonwoven fabric a in step (1) was changed to nonwoven fabric C to obtain a prepreg.
Example 9
The only difference from example 6 is that the nonwoven fabric a in step (1) was changed to nonwoven fabric D to obtain a prepreg.
Example 10
In this embodiment, a high-frequency circuit substrate is provided, and the preparation method specifically includes the following steps:
step (1): the thermosetting resin A was applied to the nonwoven fabric E of example 5 by dipping with a sizing machine to obtain a prepreg having a sizing resin content of 90%.
Step (2): and (3) placing the prepreg in the step (1) in an oven at 100 ℃, baking for 1h, and removing the solvent to obtain the bonding sheet.
Step (3): covering 1OZ thick copper foil on the upper and lower surfaces of the resin layer of a single bonding sheet for lamination, and placing into a press for curing to obtain a high-frequency circuit substrate, wherein the curing temperature is 200 ℃, the curing time is 90min, and the curing pressure is 50kg/cm 2 。
Comparative example 3
The only difference from example 6 is that the nonwoven fabric A in step (1) was changed to a nonwoven fabric of an epoxy binder, and the rest was the same.
Comparative example 4
The only difference from example 6 is that the nonwoven fabric A in step (1) was changed to the nonwoven fabric F in comparative example 1, and the rest was identical.
Comparative example 5
The only difference from example 6 is that the nonwoven fabric A in step (1) was changed to the nonwoven fabric G in comparative example 2, and the rest was identical.
Comparative example 6
The only difference from example 6 is that the nonwoven fabric A in step (1) was changed to the acrylate binder nonwoven fabric, and the rest was the same.
Comparative example 7
The only difference from example 6 is that the nonwoven fabric A of step (1) was changed to a melamine-bonded nonwoven fabric, and the rest was identical.
Comparative example 8
The only difference from example 10 is that the nonwoven fabric E in step (1) was changed to a nonwoven fabric of an epoxy binder, and the rest was the same.
Comparative example 9
The difference from example 6 is only that the binder in the nonwoven A of step (1) is in excess, the proportion is 50%, the remainder being exactly the same.
The specific preparation method of the excessive binder non-woven fabric in the comparative example comprises the following steps:
50 parts by weight of E glass fiber (average diameter of 5 micrometers) and 50 parts by weight of FEP emulsion are immersed for 45min, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 10min in a high-temperature baking oven at 280 ℃, taken out and cooled, and then the non-woven fabric with the single weight of 20 g/square meter is prepared.
The performance of the copper-clad laminates or the high-frequency circuit boards of examples 6 to 10 and comparative examples 3 to 9 was evaluated as follows:
1. dk and Df: the test was carried out by SPDR (split post dielectric resonator) method under the conditions of A-state and frequency of 10GHz.
2. Peel strength: GB/T4722-2017.2 method.
The test results are shown in tables 2 and 3.
TABLE 2
TABLE 3 Table 3
As can be seen from tables 2 and 3:
examples 6-9 show that after the non-woven fabrics prepared by the low-loss adhesive are mixed with PTFE to prepare the copper-clad plate, the dielectric loss (Dk (10 GHz) is lower than 2.68 and even lower than 2.25, df (10 GHz) is lower than 0.0034 and even lower than 0.0013) and the peel strength (more than 0.8N/mm) of the copper-clad plate prepared by the common non-woven fabrics adopted in comparative examples 3 and 6-8 are obviously better than those of the copper-clad plate prepared by the common non-woven fabrics.
Comparative example 4 after a copper-clad plate was prepared from a non-woven fabric prepared by using a PVDF binder having a melting point of 170 c and a PTFE resin, the dielectric constant, dielectric loss and peel strength were significantly inferior to those of the copper-clad plate prepared in the examples.
The adhesive used in comparative example 5 had too high a melting point, and could not be melted when baked at 300 c, resulting in low strength of nonwoven fabric, and could not produce a copper-clad laminate.
Comparison of comparative examples 3, 6-7 and example 6 shows that the use of the common nonwoven fabric results in an increase in dielectric loss and a decrease in peel strength of the prepared copper-clad laminate, and comparison of comparative example 8 and example 10 shows that the use of the common nonwoven fabric results in an increase in dielectric loss and a decrease in peel strength of the prepared copper-clad laminate.
In comparative example 9, it was found that too high a proportion of the binder was used, and voids were large in the nonwoven fabric, and the voids were likely to absorb water, resulting in a slight decrease in Dk, an increase in Df, and a decrease in peel strength.
The applicant states that the present invention is described by way of the above examples as a low dielectric loss nonwoven fabric of the present invention and its preparation and use, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (16)

1. The low dielectric loss non-woven fabric is characterized by comprising inorganic fibers and a binder, wherein the binder is fluorine-containing resin emulsion, and the melting point of the fluorine-containing resin emulsion is 200-300 ℃;
the weight percentage of the inorganic fiber in the low dielectric loss non-woven fabric is 70-95%, and the weight percentage of the binder is 5-30%;
the fluorine-containing resin emulsion is selected from any one or a combination of at least two of a perfluoroethylene propylene emulsion, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, an ethylene-tetrafluoroethylene copolymer emulsion, a polytrifluoroethylene emulsion or an ethylene-trifluorochloroethylene copolymer emulsion.
2. The low dielectric loss nonwoven fabric according to claim 1, wherein the fluorine-containing resin emulsion has a solid content of 30 to 70%.
3. The low dielectric loss nonwoven fabric according to claim 1, wherein the inorganic fibers are selected from any one or a combination of at least two of E glass fibers, NE glass fibers, L glass fibers, quartz fibers, alumina fibers, boron nitride fibers, silicon carbide fibers, zinc oxide fibers, magnesium oxide fibers, silicon nitride fibers, boron carbide fibers, aluminum nitride fibers, aluminum oxide whiskers, boron nitride whiskers, silicon carbide whiskers, zinc oxide whiskers, magnesium oxide whiskers, silicon nitride whiskers, boron carbide whiskers, or aluminum nitride whiskers.
4. The low dielectric loss nonwoven fabric according to claim 1, wherein said inorganic fibers have an average diameter of less than 10 microns.
5. The low dielectric loss nonwoven fabric according to claim 1, wherein the inorganic fibers have an average diameter of 0.5 to 5 μm.
6. The low dielectric loss nonwoven fabric according to claim 1, wherein the low dielectric loss nonwoven fabric is a surface-treated low dielectric loss nonwoven fabric.
7. The low dielectric loss nonwoven fabric according to claim 6, wherein the surface-treated treating agent is selected from one or a mixture of at least two of a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, an alkylsilane coupling agent, a borate coupling agent, a zirconate coupling agent, or a phosphate coupling agent.
8. The low dielectric loss nonwoven fabric according to claim 1, wherein the low dielectric loss nonwoven fabric has a single weight of 20-200 grams per square meter.
9. The low dielectric loss nonwoven fabric according to claim 8, wherein the low dielectric loss nonwoven fabric has a single weight of 20 to 100 grams per square meter.
10. The method for producing a low dielectric loss nonwoven fabric according to any one of claims 1 to 9, characterized in that the method for producing comprises the steps of:
and mixing and impregnating inorganic fibers with a binder, forming by papermaking, and drying and sintering to obtain the low dielectric loss non-woven fabric.
11. A prepreg comprising the low dielectric loss nonwoven fabric according to any one of claims 1 to 9 and a resin composition attached thereto by impregnation.
12. The prepreg of claim 11, wherein the resin composition comprises one or a combination of at least two of a fluorine-containing resin emulsion, a polyphenylene ether resin, a polybutadiene resin, a butadiene-styrene copolymer, a styrene-butadiene-styrene triblock copolymer, a multifunctional vinyl aromatic copolymer, a silicone resin, a cyanate ester resin, or a maleimide compound.
13. The prepreg of claim 12 wherein the resin composition is a fluorine-containing resin emulsion.
14. The prepreg according to claim 13, wherein the fluorine-containing resin emulsion is selected from any one or a combination of at least two of polytetrafluoroethylene emulsion, perfluoroethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polytrifluoroethylene emulsion or ethylene-chlorotrifluoroethylene copolymer emulsion.
15. A copper-clad plate comprising a copper foil and the prepreg according to any one of claims 11 to 14.
16. A printed circuit board comprising copper foil and the prepreg according to any one of claims 11-14.
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