CN115198564A - 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
CN115198564A
CN115198564A CN202210790692.9A CN202210790692A CN115198564A CN 115198564 A CN115198564 A CN 115198564A CN 202210790692 A CN202210790692 A CN 202210790692A CN 115198564 A CN115198564 A CN 115198564A
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emulsion
dielectric loss
low dielectric
nonwoven fabric
fibers
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CN202210790692.9A
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CN115198564B (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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

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

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, 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, chemical stability and the like which are incomparable with other polymer resins, and is an ideal copper-clad plate base material.
With the increasing requirement of isotropy of the high-frequency copper-clad plate base material, an isotropic reinforcing material needs to be developed, so that the PTFE composite material has excellent Dk consistency and extremely low dielectric loss, and has better mechanical strength compared with a PTFE film without the reinforcing material. Currently, there are no isotropic reinforcements with very low dielectric loss.
The traditional non-woven fabric has the characteristics of reinforcement and isotropy, but generally adopts epoxy adhesives, acrylate adhesives, melamine adhesives or polyvinyl alcohol adhesives, and the dielectric loss of the adhesives is large.
Therefore, it is desirable in the art to be able to develop a reinforcing material that is isotropic and that is capable of having extremely low dielectric loss.
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 has isotropy, good dielectric property and obvious reinforcing effect, and can meet various performance requirements of the high-frequency communication field on copper clad plate materials.
In order 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 is composed of inorganic fibers and a binder, wherein the binder comprises a fluorine-containing resin emulsion and an antifoaming agent.
According to the invention, by using the adhesive, the non-woven fabric has low dielectric loss, good uniformity, consistent thickness, consistent fiber isotropic distribution and high tensile strength, and more dielectric fillers can be added during the impregnation of low dielectric loss resin to prepare the low dielectric loss high-frequency copper-clad laminate. The fluorine-containing resin emulsion has low dielectric loss, so that the prepared non-woven fabric has low dielectric loss; the fluorine-containing resin emulsion has good heat resistance, so that the prepared non-woven fabric can be used at high temperature, such as 260 ℃ for a long time. However, the fluorochemical emulsions contain a proportion (e.g., 1-10%) of surfactant for emulsion stability. Inorganic fiber can produce a large amount of bubbles in the process of dipping fluorine-containing emulsion, so that the proportion of the adhesive is reduced, the tensile strength of the prepared non-woven fabric is reduced, and the defoaming agent is added into the adhesive to inhibit the generation of bubbles, so that the tensile strength of the non-woven fabric is ensured, and the dielectric property of the plate prepared from the non-woven fabric is influenced. The binder comprises fluorine-containing resin emulsion and defoaming agent from the aspects of low dielectric property and tensile strength.
In the present invention, the low dielectric loss nonwoven fabric means a nonwoven fabric having a dielectric loss of less than 0.0015 (10 GHz).
The dielectric constant and dielectric loss in the present invention were measured by the SPDR (split post dielectric resonator) method, and the frequency was 10GHz.
Preferably, the low dielectric loss nonwoven fabric has a weight percentage of inorganic fibers of 60% to 95% (e.g., 60%, 62%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 88%, 90%, 93%, or 95%) and a weight percentage of binder of 5% to 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, so that the strength of the non-woven fabric is low, and if the weight percentage of the binder is too high, the non-woven fabric has many internal cavities and many defects, so that the strength of the non-woven fabric is low, and further the dielectric loss and the cohesiveness are influenced.
The binder may be dissolved and diluted to a suitable viscosity by adding a solvent as needed to uniformly disperse the fibers and the binder, wherein the solvent exemplarily includes deionized water and the like. The solvent can volatilize along with the drying and sintering of the non-woven fabric preparation process.
Preferably, the fluorine-containing resin emulsion is selected from any one of or a combination of at least two of polytetrafluoroethylene emulsion, fluorinated ethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polychlorotrifluoroethylene emulsion, or ethylene-chlorotrifluoroethylene copolymer emulsion.
Preferably, the fluorine-containing resin emulsion has a solids content of 30 to 70%, such as 30%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.
Preferably, the weight percentage of the defoamer 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%, in the present invention too low a defoamer content does not serve the purpose of defoaming, while if too high a defoamer content affects the dielectric loss performance of the nonwoven.
Preferably, the defoaming agent is selected from any one or a combination of at least two of mineral oil defoaming agents, silicone oil defoaming agents or acrylate defoaming agents, and further preferably silicone oil defoaming agents.
Preferably, the defoamer also contains hydrophobic particles. The hydrophobic particles are generally inorganic particles, such as surface-modified white carbon black and the like.
Preferably, the inorganic fiber is selected from any one 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, alumina whisker, boron nitride whisker, silicon carbide whisker, zinc oxide whisker, magnesium oxide whisker, silicon nitride whisker, boron carbide whisker or aluminum nitride whisker or a combination of at least two thereof.
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, and the like, preferably 0.5 to 5 microns. Inorganic fiber diameter refers to the filament diameter of the inorganic fiber, typically the filament length is greater than the filament diameter, preferably the filament length to diameter ratio is greater than 10, alternatively greater than 50, alternatively 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 of amine surfactants, amide cationic surfactants and nonionic surfactants or the combination of at least two of the amine surfactants, the amide cationic surfactants and the nonionic surfactants.
The thickening agent is selected from any one or the combination of at least two of cellulose thickening agent, polyacrylate thickening agent, polyurethane associated polymer thickening agent and derivatives thereof.
The filler in the binder is selected from any one or combination of at least two of titanium dioxide, barium titanate, strontium titanate, alumina, boron nitride, silicon nitride, hollow glass beads or hollow silicon dioxide.
Preferably, the low dielectric loss non-woven fabric is a surface-treated low dielectric loss non-woven fabric.
Preferably, the surface-treated treating agent is one or a mixture of at least two selected from a fluorine-containing silane coupling agent, an amino silane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, an alkyl silane coupling agent, a borate coupling agent, a zirconate coupling agent and a phosphate coupling agent.
Preferably, the low dielectric loss nonwoven has a basis weight (also referred to as mass per unit area) of 20 to 200g/m, for example 20 g/m, 25 g/m, 30 g/m, 35 g/m, 40 g/m, 50 g/m, 60 g/m, 80 g/m, 100 g/m, 120 g/m, 150 g/m, 180 g/m or 200g/m, preferably 20 to 100 g/m.
In another aspect, the present invention provides a method for preparing the low dielectric loss non-woven fabric, wherein the low dielectric loss non-woven fabric is obtained by mixing inorganic fibers with a binder, impregnating, papermaking, forming, drying and sintering.
In the present invention, the laboratory prepared nonwoven fabrics of different basis weights by adjusting the weight of the inorganic fiber and the adhesive. The industrial production can prepare the non-woven fabrics with different single weights by adjusting the solubility of inorganic fibers, adhesives and solvents and the vehicle speed.
Preferably, the time of the impregnation is 40 to 50min, such as 40min, 43min, 45min, 48min or 50min.
Preferably, the drying temperature is 120-150 deg.C, such as 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C, 145 deg.C or 150 deg.C, for 1-30 min, such as 1min, 3min, 5min, 8min, 10min, 13min, 15min, 18min or 20min.
Preferably, the sintering temperature is 250-350 ℃, such as 250 ℃, 270 ℃, 290 ℃, 300 ℃, 320 ℃, 340 ℃ or 350 ℃, and the sintering time is 1-20 min, 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 comprises one or a combination of at least two of fluorine-containing resin emulsion, polyphenylene ether resin, polybutadiene resin, butadiene-styrene copolymer, styrene-butadiene-styrene triblock copolymer, polyfunctional vinyl aromatic copolymer, silicone resin, cyanate ester resin and maleimide compound.
The fluorine-containing resin has excellent dielectric properties, and the fluorine-containing resin has better compatibility with the fluorine-containing resin non-woven fabric. 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 of or a combination of at least two of a polytetrafluoroethylene emulsion, a polyperfluoroethylpropylene emulsion, a polyvinylidene fluoride emulsion, a tetrafluoroethylene-perfluoroalkylvinylether copolymer emulsion, an ethylene-tetrafluoroethylene copolymer emulsion, a polychlorotrifluoroethylene emulsion, or an ethylene-chlorotrifluoroethylene copolymer emulsion.
On the other hand, the invention provides a copper-clad plate which comprises a copper foil and the prepreg.
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 has low dielectric loss, good uniformity, consistent thickness, consistent fiber distribution in all directions and high tensile strength, and more dielectric fillers can be added when the non-woven fabric is impregnated with low-dielectric-loss resin.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw materials used in the following examples and comparative examples were as follows:
FEP resin emulsion, solid content 50wt%, manufactured by Japan Dajin corporation, trade mark: and ND-110.
PFA resin emulsion, solid content 55wt%, manufactured by Japan Dajin corporation, trade mark: AD-2CR.
PTFE resin emulsion, solid content 55wt%, manufactured by Japan Dajin corporation, trade mark: and D210C.
Mineral oil antifoam, BYK-033, BYK, germany.
Organic silicone oil defoamer (containing hydrophobic particulate white carbon black), BYK-044, germany, inc.
Acrylate defoamer, BYK-0359, BYK, germany.
Low thermal expansion coefficient 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, lion chemical Co., U.S.A.), 40 parts by weight of polybutadiene (molecular weight 3200g/mol, nippon Kazakh Co., ltd.), and 2 parts by weight of benzoyl peroxide (Shanghai Kanglang Biotech Co., ltd.) were dissolved in 50 parts by weight of xylene and mixed uniformly to obtain a uniform resin composition.
E glass fibers having an average diameter of 5 μm, megaku Ltd, china
NE glass fibers having an average diameter of 5 μm, china megalithic corporation
Quartz fiber with average diameter of 0.5 μm and 5 μm, chinese Rose
E glass fibers having an average diameter of 8 μm, megaku Ltd, china
Non-woven fabric, made of epoxy binder and E glass fibers with an average diameter of 13 μm, shaanxi walt.
The non-woven fabric is prepared from acrylate adhesive and E glass fiber with the average diameter of 13 mu m, and is Shaanxi Huate.
Non-woven fabric, made of melamine binder and E glass fibers with an average diameter of 13 μm, shaanxi walter.
In this embodiment, a low dielectric loss nonwoven fabric is provided, which is composed of inorganic fibers and a binder. Mixing and soaking inorganic fibers, a binder and a solvent, placing the mixture into a round standard sheet machine (Kumagaya Riki Kogyo Co., ltd.), fully stirring and filtering, and obtaining the round non-woven fabric with the diameter of 80mm through paper making molding, drying and sintering. The non-woven fabrics with different single weights are prepared by adjusting the weights of the inorganic fibers and the adhesive. The preparation method comprises the following steps:
example 1
Soaking 95 parts by weight of E glass fiber (with the average diameter of 5 microns), 5 parts by weight of FEP emulsion, 0.05 part by weight of BYK-033 defoaming agent and a proper amount of deionized water for 45min, forming by papermaking, drying by using a 150 ℃ oven, sintering for 10min at the temperature of 280 ℃ in a high-temperature oven, taking out and cooling to obtain the non-woven fabric A with the single weight of 20 g/square meter.
Example 2
Soaking 85 parts by weight of NE glass fiber (with the average diameter of 5 micrometers), 15 parts by weight of PFA emulsion, 0.015 part by weight of BYK-044 defoaming agent and a proper amount of deionized water for 45min, papermaking and forming, drying by using a 150 ℃ oven, sintering for 10min in a high-temperature oven at 300 ℃, taking out and cooling to obtain the non-woven fabric B with the unit weight of 75 g/square meter.
Example 3
Soaking 70 parts by weight of quartz fiber (average diameter of 0.5 mu m and 5 mu m, weight ratio of 1.
Example 4
Dipping 61 parts by weight of E glass fiber (with the average diameter of 8 microns) with 39 parts by weight of FEP emulsion, 0.4 part by weight of BYK-033 defoamer and a proper amount of deionized water for 45min, papermaking and forming, drying by using a 140 ℃ oven, sintering for 8min in a high-temperature oven at 300 ℃, taking out and cooling to obtain the non-woven fabric D with the unit weight of 75 g/square meter.
Comparative example 1
And (3) soaking 61 parts by weight of E glass fiber (with the average diameter of 8 microns) with 39 parts by weight of FEP emulsion and a proper amount of deionized water for 45min, papermaking and forming, drying by using a 140 ℃ oven, sintering for 8min in a high-temperature oven at 300 ℃, taking out and cooling to obtain the non-woven fabric E with the single weight of 75 g/square meter.
Comparative example 2
Except for the difference from example 2, the nonwoven fabric F was produced in the same manner as in example 2 except that no defoaming agent was added.
Comparative example 3
Except for the difference from example 3, the nonwoven fabric G was produced in the same manner as in example 3 except that no defoaming agent was added.
Comparative example 4
The only difference from example 1 is that the binder in the nonwoven fabric A in step (1) was in excess, the proportion was 50%, and the rest was the same.
The preparation method comprises the following steps:
soaking 50 parts by weight of E glass fiber (with the average diameter of 5 microns), 50 parts by weight of FEP emulsion and 0.5 part by weight of BYK-033 defoaming agent for 45min, papermaking and forming, drying by using a 150 ℃ oven, sintering for 10min at the temperature of 280 ℃ in a high-temperature oven, taking out and cooling to obtain 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: GB/T24218 method, the nonwoven fabric sample width of 50mm, in 100mm/min speed stretching to fracture, record the maximum stretching force.
TABLE 1
Figure BDA0003730085390000091
Figure BDA0003730085390000101
As can be seen from table 1:
comparative examples 1 to 3 had low strength of the nonwoven fabric due to the fact that the E glass fiber produced a large amount of bubbles when impregnated with the FEP emulsion without adding an antifoaming agent.
Comparative example 4 had a lower strength of the nonwoven fabric due to an excess of the defoaming agent.
Example 5
The embodiment provides a PTFE copper-clad plate, and the preparation method specifically comprises the following steps:
step (1): the low coefficient of thermal expansion resin a glue solution was dipped on the nonwoven fabric a of example 1 with a glue applicator to obtain a prepreg with 90% of the sizing resin content.
Step (2): and (2) placing the prepreg obtained in the step (1) in a vacuum oven at 100 ℃, baking for 1h, removing water, baking for 1h at 260 ℃ to remove the auxiliary agent, and baking for 10min at 350 ℃ to obtain a bonding sheet with the thickness of 0.25 mm.
And (3): and covering copper foils with the thickness of 1OZ on the upper surface and the lower surface of the single bonding sheet for lamination, applying pressure of 400PSI, and keeping the highest temperature and the retention time at 380 ℃/60min to obtain the PTFE copper-clad plate.
Example 6
The only difference from example 5 is that in step (1), nonwoven fabric A was changed to nonwoven fabric B;
example 7
The only difference from example 5 is that the nonwoven fabric A in step (1) was changed to nonwoven fabric C.
Example 8
The only difference from example 5 is that nonwoven fabric A in step (1) was changed to nonwoven fabric D.
Example 9
In this embodiment, a method for manufacturing a high-frequency circuit substrate includes the following steps:
step (1): the thermosetting resin a glue solution was dipped on the nonwoven fabric a in example 5 with a glue applicator to obtain a prepreg having a content of the sizing resin of 90%.
Step (2): and (3) placing the prepreg obtained in the step (1) in an oven at 100 ℃, baking for 1h, and removing the solvent to obtain the bonding sheet.
And (3): covering copper foils with the thickness of 1OZ on the upper surface and the lower surface of a resin layer of a single bonding sheet for overlapping, putting the resin layer into a press for curing to obtain the 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 difference from example 5 is only that the nonwoven fabric A in step (1) is changed to a nonwoven fabric with an epoxy adhesive, and the rest is the same.
Comparative example 7
The difference from example 5 is only that the nonwoven fabric A in step (1) was changed to a nonwoven fabric with an acrylate binder, and the rest was the same.
Comparative example 8
The only difference from example 5 is that the nonwoven fabric A in step (1) was changed to a melamine-bonded nonwoven fabric, and the rest was the same.
Comparative example 9
The difference from example 9 is only that nonwoven fabric A in step (1) was changed to nonwoven fabric G, and the rest was the same.
Comparative example 10
The difference from example 5 is only 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) was changed to a nonwoven fabric F, and the rest was the same.
The copper-clad plates or high-frequency circuit substrates of examples 5 to 9 and comparative examples 5 to 11 were subjected to performance evaluation by the following method:
1. dk and Df: the test was carried out by the SPDR (split post dielectric resonator) method under the test conditions of the A state and the frequency of 10GHz.
2. Peeling strength: GB/T4722-2017.2 method.
The test results are shown in tables 2 and 3.
TABLE 2
Figure BDA0003730085390000121
TABLE 3
Figure BDA0003730085390000122
Figure BDA0003730085390000131
As can be seen from tables 2 and 3:
examples 5-8 show that the dielectric loss (Dk (10 GHz)) and the Df (10 GHz) are lower than 2.69 and even lower than 2.24, and 0.0025 and even lower than 0.0013, respectively, and the peel strength (more than 1.0N/mm) of the copper clad laminate prepared by mixing the non-woven fabric prepared by the low-loss binder and the PTFE are obviously superior to the performance of the copper clad laminate prepared by the common non-woven fabric adopted in comparative examples 6-9.
The comparison between the embodiment 5 and the comparative examples 6 to 9 shows that the dielectric loss and the peel strength of the copper-clad plate prepared from the non-woven fabric prepared from the low-loss binder and the PTFE system are obviously superior to those of the copper-clad plate prepared from the common non-woven fabric in the comparative examples 6 to 9.
The comparison between the embodiment 9 and the comparative example 5 and between the embodiment 5 and the comparative example 11 shows that after the copper-clad plate is prepared by the non-woven fabric prepared by the low-loss binder added with the defoaming agent, the dielectric loss and the peel strength of the copper-clad plate are obviously superior to those of the copper-clad plate prepared by the non-woven fabric without the defoaming agent.
It can be seen from comparative example 10 that the nonwoven fabric had many voids therein due to the excessively high proportion of the binder used. The void site tends to absorb water, resulting in a decrease in Dk, but Df increases, and the peel strength decreases.
The applicant states that the invention is illustrated by the above examples of the low dielectric loss nonwoven fabric of the invention and the preparation method and application thereof, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The low dielectric loss non-woven fabric is characterized by consisting of inorganic fibers and a binder, wherein the binder comprises fluorine-containing resin emulsion and a defoaming agent.
2. The low dielectric loss nonwoven fabric of claim 1, wherein the low dielectric loss nonwoven fabric comprises 60-95 wt% of inorganic fibers and 5-40 wt% of binder.
3. The low dielectric loss nonwoven fabric of claim 1 or 2, wherein the fluorine-containing resin emulsion is selected from any one of or a combination of at least two of a polytetrafluoroethylene emulsion, a fluorinated ethylene propylene emulsion, a polyvinylidene fluoride emulsion, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, an ethylene-tetrafluoroethylene copolymer emulsion, a polychlorotrifluoroethylene emulsion, or an ethylene-chlorotrifluoroethylene copolymer emulsion;
preferably, the fluorine-containing resin emulsion has a solid content of 30 to 70%.
4. The low dielectric loss nonwoven fabric of any of claims 1-3, wherein the weight percentage of the defoaming agent in the binder is 0.01-1%;
preferably, the defoaming agent is selected from any one or a combination of at least two of mineral oil defoaming agents, silicone oil defoaming agents or acrylate defoaming agents, and further preferably silicone oil defoaming agents;
preferably, the defoaming agent also contains hydrophobic particles.
5. The low dielectric loss nonwoven fabric of any of claims 1-4, wherein the inorganic fibers are selected from any one of 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, alumina whiskers, boron nitride whiskers, silicon carbide whiskers, zinc oxide whiskers, magnesium oxide whiskers, silicon nitride whiskers, boron carbide whiskers, or aluminum nitride whiskers;
preferably, the inorganic fibers have an average diameter of less than 10 microns, preferably 0.5 to 5 microns.
6. The low dielectric loss nonwoven fabric according to any one of claims 1 to 5, wherein 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 a fluorine-containing silane coupling agent, an amino silane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, an alkyl silane coupling agent, a borate coupling agent, a zirconate coupling agent or a phosphate coupling agent;
preferably, the low dielectric loss nonwoven fabric has a basis weight of 20 to 200g/m, preferably 20 to 100 g/m.
7. The method for preparing the low dielectric loss nonwoven fabric according to any one of claims 1 to 6, wherein the method comprises the steps of:
and mixing inorganic fibers with a binder, soaking, papermaking forming, drying and sintering to obtain the low dielectric loss non-woven fabric.
8. A prepreg comprising the low dielectric loss nonwoven fabric according to any one of claims 1 to 7 and a resin composition attached thereto by impregnation;
preferably, the resin composition comprises one or a combination of at least two of fluorine-containing resin emulsion, polyphenylene ether resin, polybutadiene resin, butadiene-styrene copolymer, styrene-butadiene-styrene triblock copolymer, multifunctional vinyl aromatic copolymer, silicone resin, cyanate ester resin and maleimide compound;
preferably, the resin composition is a fluorine-containing resin emulsion;
preferably, the fluorine-containing resin emulsion is selected from any one of or a combination of at least two of polytetrafluoroethylene emulsion, fluorinated ethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polychlorotrifluoroethylene emulsion, or ethylene-chlorotrifluoroethylene copolymer emulsion.
9. A copper-clad plate, characterized in that it comprises a copper foil and the prepreg of claim 8.
10. A printed circuit board comprising copper foil and the prepreg of claim 8.
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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

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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