CN115198564B - 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
CN115198564B
CN115198564B CN202210790692.9A CN202210790692A CN115198564B CN 115198564 B CN115198564 B CN 115198564B CN 202210790692 A CN202210790692 A CN 202210790692A CN 115198564 B CN115198564 B CN 115198564B
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dielectric loss
low dielectric
nonwoven fabric
emulsion
fibers
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CN115198564A (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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using 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
    • 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
    • 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
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0386—Paper sheets
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • 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

Abstract

The invention provides a low dielectric loss non-woven fabric, and preparation 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.
Accordingly, it is desirable in the art to be able to develop a reinforcing material that is isotropic and that is able to have very low dielectric losses.
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 provided by the invention has isotropy, good dielectric property and obvious reinforcing effect, 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 present invention provides a low dielectric loss nonwoven fabric composed of inorganic fibers and a binder, the binder comprising a fluorine-containing resin emulsion and a defoaming agent.
According to the invention, the binder is used, so that the non-woven fabric has low dielectric loss, good uniformity, uniform thickness, uniform fiber distribution and high tensile strength, and more dielectric filler can be added when the low dielectric loss resin is impregnated to prepare the low dielectric loss high-frequency copper-clad laminate. Wherein the fluorine-containing resin emulsion has low dielectric loss due to low dielectric loss, and the prepared non-woven fabric has low dielectric loss; the fluorine-containing resin emulsion has good heat resistance, and the prepared non-woven fabric can be used for a long time at high temperature, such as 260 ℃. However, the fluorochemical emulsions all contain a proportion (e.g., 1-10%) of surfactant for emulsion stability. The inorganic fiber can generate a large amount of bubbles in the process of impregnating the fluorine-containing emulsion, so that the proportion of the adhesive is reduced, the tensile strength of the prepared non-woven fabric is reduced, the foam generation can be inhibited by adding the defoaming agent into the adhesive, the tensile strength of the non-woven fabric is ensured, and the dielectric property of the plate prepared from the non-woven fabric is further influenced. From the viewpoint of low dielectric properties and tensile strength, the binder comprises a fluorine-containing resin emulsion and a defoaming agent.
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).
The dielectric constant and dielectric loss of the invention are tested by adopting a SPDR (split post dielectric resonator) method, and the frequency is 10GHz.
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 dissolved and diluted to a proper viscosity by adding a solvent according to the requirement, so that the fibers and the binder 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 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.
Preferably, the fluorine-containing resin emulsion has a solids content of 30 to 70%, for example 30%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65% or 70%.
Preferably, the weight percentage of the antifoaming agent in the binder is 0.01-1%, for example 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8% or 1%, and the content of the antifoaming agent is too low in the present invention to achieve the purpose of defoaming, while if the content of the antifoaming agent is too high, the dielectric loss properties of the nonwoven fabric are affected.
Preferably, the defoaming agent is selected from any one or a combination of at least two of mineral oil type defoaming agents, silicone oil type defoaming agents or acrylic ester type defoaming agents, and further preferably silicone oil type defoaming agents.
Preferably, the defoamer further comprises hydrophobic particles. The hydrophobic particles are typically inorganic particles, such as surface-modified white carbon black and the like.
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 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 thickeners, polyurethane associated type macromolecule thickeners and derivatives thereof.
The filler in the binder 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.
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.
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.
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 ℃, e.g. 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, for a period of time of 1-30 min, e.g. 1min, 3min, 5min, 8min, 10min, 13min, 15min, 18min or 20min.
Preferably, the sintering temperature is 250 ℃ to 350 ℃, such as 250 ℃, 270 ℃, 290 ℃, 300 ℃, 320 ℃, 340 ℃ or 350 ℃, 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, and 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, high tensile strength, capability of adding more dielectric fillers when being impregnated with low dielectric loss resin, low dielectric constant and dielectric loss, high peel strength and obvious reinforcing effect, and can meet various performance requirements of the copper-clad plate material in the field of high-frequency communication.
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:
FEP resin emulsion, solid content 50wt%, produced by Japanese Dajin Co., ltd., brand: ND-110.
PFA resin emulsion, 55wt% solids, manufactured by Japanese big gold company, brand: AD-2CR.
PTFE resin emulsion, with a solid content of 55wt%, manufactured by Japanese big gold company, brand: D210C.
Mineral oil defoamer, BYK-033, BYK, germany.
Silicone oil defoamer (containing hydrophobic particle white carbon black), BYK-044, BYK company, germany.
Acrylate defoamer, BYK-0359, BYK company, germany.
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 (average diameter of 5 micrometers), 5 parts by weight of FEP emulsion, 0.05 part by weight of BYK-033 defoamer and a proper amount of deionized water are immersed for 45 minutes, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 10 minutes in a high-temperature baking oven at 280 ℃, taken out and cooled, and then the non-woven fabric A with the single weight of 20 g/square meter is prepared.
Example 2
85 parts by weight of NE glass fiber (average diameter of 5 micrometers), 15 parts by weight of PFA emulsion, 0.015 part by weight of BYK-044 defoamer and a proper amount of deionized water are immersed for 45min, formed by papermaking, dried by a baking oven at 150 ℃, sintered for 10min in a high-temperature baking oven at 300 ℃, and taken out for cooling 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) and 30 parts by weight of PTFE emulsion, 0.3 part by weight of BYK-0359 defoamer and proper amount of deionized water are immersed for 45min, formed by papermaking, dried by a 140 ℃ oven, sintered for 20min at 320 ℃ by a high temperature oven, taken out and cooled to obtain the non-woven fabric C with single weight of 75 g/square meter.
Example 4
61 parts by weight of E glass fiber (average diameter of 8 micrometers) and 39 parts by weight of FEP emulsion, 0.4 part by weight of BYK-033 defoamer and a proper amount of deionized water are immersed for 45min, formed by papermaking, dried by a 140 ℃ oven, sintered for 8min 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.
Comparative example 1
61 parts by weight of E glass fiber (average diameter of 8 micrometers) and 39 parts by weight of FEP emulsion and a proper amount of deionized water are soaked for 45 minutes, paper making and molding are carried out, then the mixture is dried by using a 140 ℃ oven, and then sintered for 8 minutes in a high-temperature oven at 300 ℃, and finally the mixture is taken out and cooled to obtain the non-woven fabric E with the single weight of 75 g/square meter.
Comparative example 2
The difference from example 2 was that no antifoaming agent was added and the rest was exactly the same, to prepare nonwoven fabric F.
Comparative example 3
The difference from example 3 was that no antifoaming agent was added and the rest was exactly the same, to prepare nonwoven fabric G.
Comparative example 4
The difference from example 1 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 preparation method comprises the following steps:
50 parts by weight of E glass fiber (average diameter of 5 micrometers), 50 parts by weight of FEP emulsion and 0.5 part by weight of BYK-033 defoamer 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 ℃, and taken out and cooled to prepare the non-woven fabric H with the single weight of 20 g/square meter.
The main materials and parameters of the nonwoven fabrics of the above examples and comparative examples are summarized in the following table 1, and the nonwoven fabric strength test method is as follows:
tensile strength: in the GB/T24218 method, a nonwoven fabric sample was stretched to break at a speed of 100mm/min and the maximum stretching force was recorded.
TABLE 1
As can be seen from table 1:
comparative examples 1-3 the E glass fiber produced a large amount of air bubbles when immersed in the FEP emulsion, resulting in lower nonwoven fabric strength, since no defoamer was added.
Comparative example 4 the nonwoven fabric strength was low due to the excessive amount of defoamer.
Example 5
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 6
The only difference from example 5 is that the nonwoven fabric a in step (1) is changed to a nonwoven fabric B;
example 7
The only difference from example 5 is that the nonwoven fabric a in step (1) is changed to nonwoven fabric C.
Example 8
The only difference from example 5 is that the nonwoven fabric A in step (1) is changed to nonwoven fabric D.
Example 9
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 glue solution was applied to the nonwoven fabric a of example 5 by 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 5
The only difference from example 9 is that the nonwoven fabric A in step (1) was changed to nonwoven fabric E, and the rest was the same.
Comparative example 6
The only difference from example 5 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 7
The only difference from example 5 is that the nonwoven fabric A of step (1) was changed to a nonwoven fabric of acrylate binder, and the rest was the same.
Comparative example 8
The only difference from example 5 is that the nonwoven fabric A of step (1) was changed to a melamine-bonded nonwoven fabric, and the rest was identical.
Comparative example 9
The only difference from example 9 is that the nonwoven fabric A in step (1) was changed to nonwoven fabric G, and the rest was the same.
Comparative example 10
The only difference from example 5 is that the nonwoven fabric A in step (1) is changed to a nonwoven fabric H, and the rest is the same.
Comparative example 11
The only difference from example 5 is that the nonwoven fabric A in step (1) is changed to nonwoven fabric F, and the rest is the same.
The performance of the copper clad laminate or the high frequency circuit board of examples 5 to 9 and comparative examples 5 to 11 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 5-8 can 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 2.69 and even lower than 2.24, df (10 GHz) is lower than 0.0025 and even lower than 0.0013) and the peel strength (more than 1.0N/mm) of the copper-clad plate prepared by the common non-woven fabrics adopted in comparative examples 6-9 are obviously better than those of the copper-clad plate prepared by the common non-woven fabrics.
Comparing example 5 with comparative examples 6-9, it can be seen that the dielectric loss and peel strength of the copper-clad laminate prepared from the non-woven fabric prepared by the low-loss adhesive and the PTFE system are significantly better than those of the copper-clad laminate prepared from the common non-woven fabric used in comparative examples 6-9.
As can be seen from the comparison of example 9 with comparative example 5 and example 5 with comparative example 11, the dielectric loss and peel strength of the nonwoven fabric prepared by using the low-loss adhesive with the defoamer are significantly better than those of the nonwoven fabric without the defoamer.
As can be seen from comparative example 10, the non-woven fabric had a large number of voids due to the excessively high proportion of the binder. The void sites readily absorb water, resulting in a decrease in Dk, but 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 well as methods of making and using the same, but the present invention is not limited to, i.e., does not mean 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 (19)

1. The low dielectric loss non-woven fabric is characterized by comprising inorganic fibers and a binder, wherein the binder comprises fluorine-containing resin emulsion and a defoaming agent;
the weight percentage of the inorganic fibers in the low dielectric loss non-woven fabric is 60-95%, and the weight percentage of the binder is 5-40%;
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;
the weight percentage of the defoaming agent in the adhesive is 0.1-1%.
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 antifoaming agent is 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.
4. The low dielectric loss nonwoven fabric according to claim 1, wherein said antifoaming agent is selected from silicone oil-based antifoaming agents.
5. The low dielectric loss nonwoven fabric according to claim 1, wherein said antifoaming agent further comprises hydrophobic particles.
6. 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.
7. The low dielectric loss nonwoven fabric according to claim 1, wherein said inorganic fibers have an average diameter of less than 10 microns.
8. The low dielectric loss nonwoven fabric according to claim 1, wherein the inorganic fibers have an average diameter of 0.5 to 5 μm.
9. 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.
10. The low dielectric loss nonwoven fabric according to claim 9, wherein 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.
11. 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.
12. The low dielectric loss nonwoven fabric according to claim 11, wherein the low dielectric loss nonwoven fabric has a single weight of 20-100 grams per square meter.
13. The method for producing a low dielectric loss nonwoven fabric according to any one of claims 1 to 12, 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.
14. A prepreg comprising the low dielectric loss nonwoven fabric according to any one of claims 1 to 12 and a resin composition attached thereto by impregnation.
15. The prepreg of claim 14, 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, a maleimide compound.
16. The prepreg of claim 14 wherein the resin composition is a fluorine-containing resin emulsion.
17. The prepreg according to claim 16, 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.
18. A copper-clad plate comprising a copper foil and the prepreg according to any one of claims 14 to 17.
19. A printed circuit board comprising copper foil and the prepreg according to any one of claims 14-17.
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Publication number Priority date Publication date Assignee Title
JP2002076545A (en) * 2000-08-28 2002-03-15 Nippon Pillar Packing Co Ltd Fluororesin printed board and its manufacturing method
JP2005307371A (en) * 2004-04-19 2005-11-04 Oji Paper Co Ltd Wet method nonwoven fabric, prepreg and composite material
WO2018117636A1 (en) * 2016-12-23 2018-06-28 주식회사 두산 Metal laminate and method for manufacturing same
CN113597121A (en) * 2021-07-29 2021-11-02 江西倍韬新材料科技有限公司 Manufacturing method of glass fiber cloth reinforced copper-clad plate
CN113652042A (en) * 2021-08-12 2021-11-16 广东生益科技股份有限公司 Fluorine-containing resin-based resin composition and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002076545A (en) * 2000-08-28 2002-03-15 Nippon Pillar Packing Co Ltd Fluororesin printed board and its manufacturing method
JP2005307371A (en) * 2004-04-19 2005-11-04 Oji Paper Co Ltd Wet method nonwoven fabric, prepreg and composite material
WO2018117636A1 (en) * 2016-12-23 2018-06-28 주식회사 두산 Metal laminate and method for manufacturing same
CN113597121A (en) * 2021-07-29 2021-11-02 江西倍韬新材料科技有限公司 Manufacturing method of glass fiber cloth reinforced copper-clad plate
CN113652042A (en) * 2021-08-12 2021-11-16 广东生益科技股份有限公司 Fluorine-containing resin-based resin composition and application thereof

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