CN111303788A - High-frequency composite material and preparation method thereof - Google Patents
High-frequency composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of electronic materials, and discloses a high-frequency composite material and a preparation method thereof, wherein the high-frequency composite material comprises at least two layers of low-k polymer porous membranes and an impregnating adhesive layer which are arranged in a laminated manner, and the impregnating adhesive layer is formed inside and outside each layer of low-k polymer porous membrane in a penetrating manner; the impregnating adhesive layer comprises the following components in parts by mass: 100 parts of epoxy resin, 5-130 parts of curing agent, 0.5-25 parts of foaming agent, 1-15 parts of heat conducting agent, 5-20 parts of flame retardant and 0.5-5 parts of coupling agent. According to the invention, the low-k polymer porous membrane and the impregnated adhesive layer can reduce the dielectric constant and dielectric loss of the high-frequency composite material, and can improve the mechanical strength, compressive strength, tensile strength, heat resistance, corrosion resistance, heat conductivity and flame retardance of the high-frequency composite material.
Description
Technical Field
The invention relates to the field of electronic materials, in particular to a high-frequency composite material and a preparation method thereof.
Background
The high-frequency base material is a basic material for the development of the high-frequency communication industry, and in the 5G era, the traditional base material causes the phenomenon of 'distortion' caused by larger transmission loss of signals. In high frequency systems, signal loss is mainly due to the loss of the filler medium and the copper shell, where the medium plays a decisive role. The dielectric constant is relatively high, the tangent loss angle is large, and the stability at high frequency is poor, so that there is a large loss at the time of transmitting a high frequency signal, and therefore, improvement of dielectric properties of a substrate becomes important and urgent.
The epoxy resin matrix is an important base material for preparing high-frequency mobile phone materials, and has the main technical characteristics and application: the electric insulation performance is stable, the flatness is good, the surface is smooth, no pit is formed, the thickness tolerance is standard, and the electric insulation material is suitable for products with high-performance electronic insulation requirements. The improvement of the dielectric property of the epoxy resin matrix is the key for obtaining high-performance high-frequency mobile phone materials.
The main means for improving the dielectric properties of epoxy resin matrix at present include (1) using styrene-maleic anhydride copolymer as curing agent for epoxy resin, for example, disclosed in patent application No. CN201310753184, wherein styrene structure has excellent dielectric properties, and low dielectric constant and dielectric loss factor can be achieved by introducing into the cured cross-linked structure. (2) The use of glycidyl ether containing low-polarity styrene structure, for example, patent application No. CN200910189730, discloses that glycidyl ether containing low-polarity styrene structure has better thermal stability and humidity resistance, and the prepared prepreg has the characteristics of low dielectric constant, low dielectric dissipation factor, and the like. (3) Active ester is used as a curing agent, the active ester is a compound obtained after carboxylic acid groups are blocked by alcohol, and the cured product has low polarity and good dielectric property. For example, patent application No. CN201310247061 discloses an active ester containing a dicyclopentadiene structure, wherein dicyclopentadiene has an alicyclic structure, and the dielectric loss can be further reduced. For example, patent application No. CN201410232763 discloses a phosphorus-containing active ester curing agent, which can maintain the composition to have a low moisture absorption rate, a good moist heat resistance and an excellent dielectric property on the premise of improving the flame retardancy of the resin composition. (4) The epoxy resin substrate for copper clad laminate with excellent dielectric property can be obtained by modifying with polyphenylene ether resin, for example, in patent application with application number of CN 201010581146.
However, the above improvement effect is not good, the obtained high-frequency composite material has high dielectric constant and dielectric loss, and can only meet the requirements of medium-low end products, and the requirements of high-end products in the 5G era on ultra-low dielectric constant and ultra-low dielectric loss are greatly different.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-frequency composite material with low dielectric constant, low dielectric loss, high mechanical strength, high flame retardance and high thermal conductivity and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a high-frequency composite material comprises at least two layers of low-k polymer porous membranes which are arranged in a laminated mode and an impregnation glue layer which permeates into the low-k polymer porous membranes in an impregnation mode and is attached to the outer sides of the low-k polymer porous membranes;
the impregnating glue layer comprises the following components in parts by mass: 100 parts of epoxy resin, 5-130 parts of curing agent, 0.5-25 parts of foaming agent, 1-15 parts of heat conducting agent, 5-20 parts of flame retardant and 0.5-5 parts of coupling agent.
In one embodiment, the material of the low-k polymer porous membrane includes at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEKEKK, PEEKK, PI, and MPI.
In one embodiment, the epoxy resin has an epoxy equivalent of 0.15 to 0.50.
In one embodiment, the curing agent is a high temperature curing agent having a curing temperature greater than 100 ℃.
In one embodiment, the blowing agent comprises at least one of azodicarbonamide, azobisisobutyronitrile, N '-dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide, and p-toluenesulfonylhydrazide.
In one embodiment, the thermal conductive agent comprises a nano boron nitride dispersion liquid that is highly dissociatively dispersed in a liquid component.
In one embodiment, the flame retardant comprises dimethyl methylphosphonate; or the coupling agent comprises a silane coupling agent.
A preparation method of a high-frequency composite material comprises the following steps:
mixing epoxy resin, a curing agent, a foaming agent, a flame retardant, a coupling agent and a heat conducting agent, and uniformly stirring to obtain a premix; carrying out heat treatment on the premix to obtain an epoxy resin adhesive; wherein the mass ratio of the epoxy resin, the curing agent, the foaming agent, the heat conducting agent, the flame retardant and the coupling agent is 100: (5-130): (0.5-25): (1-15): (5-20): (0.5 to 5);
dipping at least two layers of laminated low-k polymer porous membranes into the epoxy resin adhesive for lamination so as to form dipping glue layers inside and outside each layer of the low-k polymer porous membranes to obtain a prepared composite membrane; and curing the prepared composite film to obtain the high-frequency composite material.
In one embodiment, the temperature of the heat treatment is 100-150 ℃, and the time of the heat treatment is 2.0-6.0 h; or the temperature of the curing treatment is 200-250 ℃, and the time of the curing treatment is 1-24 h.
In one embodiment, before the operation of mixing the epoxy resin, the curing agent, the foaming agent, the flame retardant, the coupling agent and the heat conducting agent, nano boron nitride powder is further added into a liquid component to obtain a boron nitride mixed liquid; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain the heat-conducting agent.
Compared with the prior art, the invention has at least the following advantages:
the invention takes the low-k polymer porous membrane as the reinforcing material to improve the mechanical strength, the compressive strength and the tensile strength of the high-frequency composite material and reduce the dielectric constant and the dielectric loss of the high-frequency composite material; the dipping glue layer is used as an adhesive to increase the bonding force between two adjacent layers of low-k polymer porous membranes, and the adopted dipping glue layer takes epoxy resin with low dielectric constant as a main raw material and is added with a curing agent, a foaming agent, a heat-conducting agent, a flame retardant and a coupling agent in proper proportion to improve the heat resistance, the corrosion resistance, the heat-conducting property and the flame retardant property of the dipping glue layer; and then the porous structure of the low-k polymer porous membrane further reduces the dielectric constant and dielectric loss of the porous membrane and increases the adhesive force between the porous membrane and the impregnated glue layer. Therefore, the low-k polymer porous membrane and the impregnating adhesive layer can reduce the dielectric constant and dielectric loss of the high-frequency composite material, and can improve the mechanical strength, compressive strength, tensile strength, heat resistance, corrosion resistance, heat conductivity and flame retardance of the high-frequency composite material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flowchart illustrating steps of a method for manufacturing a high-frequency composite material according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a high-frequency composite material according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, referring to fig. 2, a high frequency composite material 10 includes at least two layers of low-k polymer porous films 110 stacked one on another and an impregnation adhesive layer 120 penetrating into the low-k polymer porous films 110 by impregnation and attached to the outer sides of the low-k polymer porous films 110; the impregnation glue layer 120 comprises the following components in parts by mass: 100 parts of epoxy resin, 5-130 parts of curing agent, 0.5-25 parts of foaming agent, 1-15 parts of heat conducting agent, 5-20 parts of flame retardant and 0.5-5 parts of coupling agent.
The low-k porous polymer film 110 is a porous polymer film with a low dielectric constant and a low dielectric loss, and the invention uses the low-k porous polymer film 110 as a reinforcing material to improve the mechanical strength, the compressive strength and the tensile strength of the high-frequency composite material 10 and reduce the dielectric constant and the dielectric loss of the high-frequency composite material 10; the dipping glue layer 120 is used as an adhesive to increase the bonding force between two adjacent layers of the low-k polymer porous membrane 110, and the adopted dipping glue layer 120 takes epoxy resin with low dielectric constant as a main raw material and is added with a curing agent, a foaming agent, a heat-conducting agent, a flame retardant and a coupling agent in proper proportion to improve the heat resistance, the corrosion resistance, the heat-conducting property and the flame retardant property of the dipping glue layer 120; and then the low-k polymer porous membrane 110 has a porous structure to further reduce its dielectric constant and dielectric loss, and increase its adhesion with the prepreg layer 120. Thus, the low-k polymer porous membrane 110 and the impregnation adhesive layer 120 can reduce the dielectric constant and the dielectric loss of the high-frequency composite material 10, and can improve the mechanical strength, the compressive strength, the tensile strength, the heat resistance, the corrosion resistance, the heat conductivity and the flame retardant property of the high-frequency composite material 10.
In order to further reduce the dielectric constant and dielectric loss of the high frequency composite material 10 and improve the mechanical strength, compressive strength, tensile strength, electrical insulation property, chemical resistance, heat resistance and service temperature range of the high frequency composite film 10, in one embodiment, the low k polymer porous film 110 is a fiber woven film or a hollow fiber film. This can further reduce the dielectric constant and dielectric loss of the high-frequency composite material 10. In order to further reduce the dielectric constant and the dielectric loss of the high-frequency composite material 10 and improve the mechanical strength, the compressive strength and the tensile strength of the high-frequency composite material 10, in one embodiment, the material of the low-k polymer porous membrane 110 includes at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEEKK, PI and MPI. For example, the material of the low-k polymer porous membrane 110 includes PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEEKK, PI, or MPI. Thus, polymer insulating film materials such as PTFE (polytetrafluoroethylene), PSF (polysulfone), PPO (poly-2, 6-dimethyl-1, 4-phenylene oxide), PPS (polyphenylene sulfide), PEEK (polyether ether ketone), PEK (polyether ketone), PEKK (polyether ketone), PEEKK (polyether ether ketone), PI (polyimide), MPI (polyimide resin) and the like are selected, and the polymer insulating film materials contain low dielectric groups such as aromatic polymer, fluorine-containing groups, silicon-containing groups and the like, so that the polymer insulating film materials have low dielectric constant and low dielectric loss, and also have excellent mechanical strength, compressive strength, tensile strength, electrical insulating property, chemical corrosion resistance and heat resistance, wide use temperature range, low water absorption, small dielectric property change in high frequency range, and the dielectric constant and the dielectric loss of the high-frequency composite film 10 can be further reduced, the mechanical strength, the compressive strength, the tensile strength, the electrical insulation performance, the chemical resistance, the heat resistance and the service temperature range of the high-frequency composite film 10 are improved.
In order to further improve the mechanical strength, compressive strength, tensile strength, heat resistance, corrosion resistance, thermal conductivity, and heat dissipation performance of the impregnation adhesive layer 120, in one embodiment, the thermal conductive agent includes a nano boron nitride dispersion liquid with high dissociation dispersion in a liquid component. For example, the nano boron nitride dispersion preferably contains nano boron nitride at a concentration of 1mg/mL to 100 mg/mL. For example, the nano boron nitride dispersion contains nano boron nitride at a concentration of 1mg/mL, 5mg/mL, 10mg/mL, 15mg/mL, 20mg/mL, 25mg/mL, 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL, 50mg/mL, 55mg/mL, 60mg/mL, 65mg/mL, 70mg/mL, 75mg/mL, 80mg/mL, 85mg/mL, 90mg/mL, 95mg/mL, or 100 mg/mL. For example, the nano boron nitride dispersion liquid contains nano boron nitride at a concentration of more preferably 5mg/mL to 20 mg/mL. For example, the nano boron nitride dispersion liquid contains a liquid component of an aqueous sodium chloride solution having a concentration of 0.1 wt% to 5.0 wt%. For example, the concentration of the aqueous sodium chloride solution is 0.1 wt%, 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, or 5.0 wt%. For example, the concentration of the aqueous sodium chloride solution is preferably 0.5 wt% to 2.5 wt%. Boron nitride itself has excellent properties such as mechanical strength, electrical insulation, thermal conductivity, chemical resistance, high temperature resistance, radiation resistance, and oxidation resistance. The problem that the nanoscale boron nitride is difficult to uniformly mix in the epoxy resin with high viscosity is solved by selecting the nanoscale boron nitride, wherein the smaller the particle is, the better the reinforcing effect on the epoxy resin is, dispersing the nanoscale boron nitride in the liquid component through high dissociation, and then mixing the nanoscale boron nitride with the epoxy resin, so that the nanoscale boron nitride can be well uniformly dispersed in an epoxy resin system, and the mechanical strength, the compression strength, the tensile strength, the electrical insulation property, the heat resistance, the corrosion resistance, the oxidation resistance, the heat conductivity and the heat dissipation performance of the impregnating adhesive layer 120 can be further improved.
In order to obtain a more suitable viscosity for the impregnation glue layer 120, in one embodiment, the epoxy equivalent of the epoxy resin is preferably 0.15 to 0.50. For example, the epoxy resin has an epoxy equivalent of 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, or 0.50. This allows the size layer 120 to achieve a more suitable viscosity. For example, the epoxy equivalent of the epoxy resin is more preferably 0.20 to 0.30. This allows the size layer 120 to achieve a more suitable viscosity.
In order to further improve the mechanical strength, heat resistance and wear resistance of the impregnation glue layer 120, in one embodiment, the curing agent is preferably a high-temperature curing agent with a curing temperature greater than 100 ℃. For example, the curing agent includes at least one of metaphenylene diamine, dicyandiamide, sebacic dihydrazide, maleic anhydride, phthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, "70" anhydride, nadic anhydride, polyazelaic anhydride, and 3,3',4,4' -benzophenonetetracarboxylic dianhydride. For example, the curing agent includes m-phenylenediamine and sebacic dihydrazide. For example, the curing agent is preferably a high-temperature curing agent having a curing temperature of 150 to 250 ℃. For example, the curing agent includes at least one of sebacic dihydrazide, maleic anhydride, phthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, "70" anhydride, nadic anhydride, polyazelaic anhydride, and 3,3',4,4' -benzophenonetetracarboxylic dianhydride. For example, the curing agent includes sebacic dihydrazide, maleic anhydride, phthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, "70" anhydride, nadic anhydride, polyazelaic anhydride, or 3,3',4,4' -benzophenonetetracarboxylic dianhydride. For example, the curing agents include maleic anhydride and phthalic anhydride. This can further improve the mechanical strength, heat resistance, and wear resistance of the impregnation adhesive layer 120.
In order to further improve the compressive strength and tensile strength of the impregnation rubber layer 120, in one embodiment, the foaming agent includes at least one of azodicarbonamide, azodiisobutyronitrile, N '-dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide and p-toluenesulfonylhydrazide. For example, the blowing agent includes azodicarbonamide, azobisisobutyronitrile, N '-dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide or p-toluenesulfonylhydrazide. For example, the blowing agent includes azodicarbonamide and azobisisobutyronitrile. This can further improve the compressive strength and tensile strength of the size layer 120.
To further improve the flame retardant performance of the size coat 120, in one embodiment, the flame retardant comprises dimethyl methylphosphonate. This can further improve the flame retardant properties of the size layer 120.
In order to further improve the mechanical strength, electrical properties, and weather resistance of the size coat 120, the coupling agent includes a silane coupling agent according to an embodiment. For example, the coupling agent comprises at least one of a KH550 coupling agent, a KH560 coupling agent, a KH570 coupling agent, a KH792 coupling agent, and a DL602 coupling agent. For example, the coupling agent includes a KH550 coupling agent, a KH560 coupling agent, a KH570 coupling agent, a KH792 coupling agent, or a DL602 coupling agent. For example, the coupling agent includes a KH550 coupling agent and a KH560 coupling agent. Thus, by erecting a 'molecular bridge' between the interfaces of the epoxy resin and the inorganic materials such as the heat-conducting agent and the like through the silane coupling agent, the dispersibility and the adhesive force of the inorganic materials such as the heat-conducting agent and the like in the epoxy resin can be improved, and the compatibility between the inorganic materials and the epoxy resin can be improved, so that the mechanical strength, the electrical property and the weather resistance of the impregnating adhesive layer 120 are further improved.
In another embodiment, the size layer 120 comprises the following components by mass: 100 parts of epoxy resin, 30-80 parts of curing agent, 5-20 parts of foaming agent, 3-13 parts of heat conducting agent, 8-16 parts of flame retardant and 2-4 parts of coupling agent. Thus, the heat resistance, corrosion resistance, heat conductivity and flame retardancy of the impregnation adhesive layer 120 can be further improved.
Referring to fig. 1 and 2, a method for preparing a high frequency composite material 10 includes the following steps:
s110, adding the nano boron nitride powder into the liquid component to obtain a boron nitride mixed solution; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain the heat-conducting agent.
Thus, the nano-boron nitride is selected, the smaller the particles are, the better the reinforcing effect on the epoxy resin is, and then is dispersed in the liquid component through high dissociation and then is mixed with the epoxy resin, so that the problem that the nano-boron nitride is difficult to be uniformly mixed in the epoxy resin with higher viscosity is solved, the nano-boron nitride can be well and uniformly dispersed in an epoxy resin system, and the mechanical strength, the compression strength, the tensile strength, the electric insulation property, the heat resistance, the corrosion resistance, the oxidation resistance, the heat conduction performance and the heat dissipation performance of the impregnating adhesive layer 120 can be further improved.
In order to further improve the mechanical strength, compressive strength, tensile strength, electrical insulation, heat resistance, corrosion resistance, oxidation resistance, thermal conductivity, and heat dissipation of the impregnation rubber layer 120, for example, the nano boron nitride dispersion preferably contains nano boron nitride at a concentration of 1mg/mL to 100 mg/mL. For example, the nano boron nitride dispersion liquid contains nano boron nitride at a concentration of more preferably 5mg/mL to 20 mg/mL. For example, the nano boron nitride dispersion liquid contains a liquid component of an aqueous sodium chloride solution having a concentration of 0.1 wt% to 5.0 wt%. For example, the concentration of the aqueous sodium chloride solution is preferably 0.5 wt% to 2.5 wt%. Therefore, the mechanical strength, the compressive strength, the tensile strength, the electrical insulation property, the heat resistance, the corrosion resistance, the oxidation resistance, the heat conductivity and the heat dissipation performance of the impregnation adhesive layer 120 can be further improved.
In order to further improve the dispersing effect of the ultrasonic dispersing operation, for example, the ultrasonic dispersing operation is specifically carried out for 1.0h to 3.0h in a water bath under a closed condition. For example, the ultrasonic dispersion operation is specifically to perform the ultrasonic dispersion operation in a water bath for 1.0h, 1.5h, 2.0h, 2.5h or 3.0h under a closed condition. Thus, the dispersion effect of the ultrasonic dispersion operation can be further improved, and the nano boron nitride dispersion liquid with high dissociation and uniform dispersion can be obtained.
S120, mixing the epoxy resin, the curing agent, the foaming agent, the flame retardant, the coupling agent and the heat conducting agent, and uniformly stirring to obtain a premix; carrying out heat treatment on the premix to obtain an epoxy resin adhesive; wherein the mass ratio of the epoxy resin, the curing agent, the foaming agent, the heat conducting agent, the flame retardant and the coupling agent is 100: (5-130): (0.5-25): (1-15): (5-20): (0.5-5).
Thus, the epoxy resin adhesive takes the epoxy resin with low dielectric constant as a main raw material, and is added with a curing agent, a foaming agent, a heat-conducting agent, a flame retardant and a coupling agent in a proper proportion to improve the heat resistance, the corrosion resistance, the heat-conducting property and the flame retardant property of the epoxy resin adhesive; and then the stress of the epoxy resin adhesive is eliminated by heat treatment, and the performance of the epoxy resin adhesive is improved.
In one embodiment, the epoxy equivalent of the epoxy resin is preferably 0.15 to 0.50. For example, the epoxy equivalent of the epoxy resin is more preferably 0.20 to 0.30. This enables the epoxy adhesive to obtain a more suitable viscosity. In one embodiment, the curing agent is preferably a high temperature curing agent with a curing temperature greater than 100 ℃. For example, the curing agent is preferably a high-temperature curing agent having a curing temperature of 150 to 250 ℃. For example, the curing agent includes at least one of sebacic dihydrazide, maleic anhydride, phthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, "70" anhydride, nadic anhydride, polyazelaic anhydride, and 3,3',4,4' -benzophenonetetracarboxylic dianhydride. Therefore, the mechanical strength, the heat resistance and the wear resistance of the epoxy resin adhesive can be further improved. In one embodiment, the blowing agent comprises at least one of azodicarbonamide, azobisisobutyronitrile, N '-dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide, and p-toluenesulfonylhydrazide. Thus, the compression strength and tensile strength of the epoxy resin adhesive can be further improved. In one embodiment, the flame retardant comprises dimethyl methylphosphonate. Thus, the flame retardant property of the epoxy resin adhesive can be further improved. In one embodiment, the coupling agent comprises a silane coupling agent. For example, the coupling agent comprises at least one of a KH550 coupling agent, a KH560 coupling agent, a KH570 coupling agent, a KH792 coupling agent, and a DL602 coupling agent. Thus, the mechanical strength, the electrical property and the weather resistance of the epoxy resin adhesive can be further improved.
In order to further improve the treatment effect of the heat treatment, eliminate the stress of the epoxy adhesive, and improve the performance of the epoxy adhesive, in one embodiment, the temperature of the heat treatment is 100 ℃ to 150 ℃, for example, the temperature of the heat treatment is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃. For example, the time of the heat treatment is 2.0h to 6.0 h; for example, the heat treatment time is 2.0h, 2.5h, 3.0h, 3.50h, 4.0h, 4.5h, 5.0h, 5.5h, or 6.0 h. Therefore, the treatment effect of heat treatment can be further improved, the stress of the epoxy resin adhesive is eliminated, and the performance of the epoxy resin adhesive is improved.
S130, dipping at least two layers of the low-k polymer porous membrane 110 stacked in layers in the epoxy resin adhesive for lamination to form a dipping glue layer 120 inside and outside each layer of the low-k polymer porous membrane 110, so as to obtain a prepared composite membrane; and curing the prepared composite film to obtain the high-frequency composite material 10.
Thus, the present invention uses the low-k polymer porous membrane 110 as a reinforcing material to improve the mechanical strength, compressive strength and tensile strength of the high-frequency composite material 10 and reduce the dielectric constant and dielectric loss of the high-frequency composite material 10, and uses the impregnated glue layer 120 as an adhesive to increase the adhesive force between two adjacent layers of low-k polymer porous membranes 110 so as to firmly adhere the hierarchical structure, thereby obtaining the high-frequency composite material 10 with low dielectric constant, low dielectric loss, high mechanical strength, high compressive strength and high tensile strength. And then the cross-linking effect of the impregnation adhesive layer 120 is improved by curing treatment, and the mechanical strength, heat resistance and wear resistance of the impregnation adhesive layer 120 are improved.
In one embodiment, the low-k polymer porous membrane 110 is a fiber woven membrane or a hollow fiber membrane. This can further reduce the dielectric constant and dielectric loss of the high-frequency composite material 10. In order to further reduce the dielectric constant and the dielectric loss of the high-frequency composite material 10 and improve the mechanical strength, the compressive strength and the tensile strength of the high-frequency composite material 10, in one embodiment, the material of the low-k polymer porous membrane 110 includes at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEEKK, PI and MPI. Thus, the dielectric constant and the dielectric loss of the high-frequency composite material 10 can be further reduced, and the mechanical strength, the compressive strength, and the tensile strength of the high-frequency composite material 10 can be improved.
In order to further improve the treatment effect of the curing treatment, improve the crosslinking effect of the impregnation rubber layer 120, and improve the mechanical strength, heat resistance, and wear resistance of the impregnation rubber layer 120, in one embodiment, the temperature of the curing treatment is 200 ℃ to 250 ℃, for example, the temperature of the curing treatment is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, or 250 ℃. For example, the curing treatment time is 1 to 24 hours. For example, the curing treatment time is 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, or 24 h. For example, the time for the curing treatment is preferably 2 to 6 hours. Thus, the treatment effect of the curing treatment can be further improved, the crosslinking effect of the impregnation adhesive layer 120 can be improved, and the mechanical strength, heat resistance and wear resistance of the impregnation adhesive layer 120 can be improved.
In order to further improve the adhesion property of the surface of the low-k polymer porous membrane 110 and further improve the adhesion property of the high-frequency composite material 10 and the conductive metal material, in an embodiment, after the operation of obtaining the high-frequency composite material 10, the high-frequency composite material 10 is further subjected to plasma treatment, and new hydrophilic hydroxyl groups are introduced to the surface of the low-k polymer porous membrane 110 through the plasma treatment, so as to improve the wettability and the hydrophilicity of the surface of the low-k polymer porous membrane 110; and some tiny macroscopic invisible nano-scale grooves and protruding nano-scale short and fine stripes are formed on the low-k polymer porous membrane 110 to improve the roughness of the surface of the low-k polymer porous membrane 110, so that the bonding performance of the surface of the low-k polymer porous membrane 110 can be further improved, and the bonding performance of the high-frequency composite material 10 and the conductive metal material can be further improved.
In order to further improve the processing effect of the plasma processing, in one embodiment, the operation of performing the plasma processing on the low-k polymer porous membrane 110 specifically includes: sequentially performing ultrasonic cleaning operation and drying operation on the low-k polymer porous membrane 110; arranging a conductive active mesh enclosure in a container, putting the low-k polymer porous membrane 110 into the conductive active mesh enclosure, and then sealing the container; vacuumizing the container, and introducing a treatment gas into the container; the container is provided with a conductive container wall, and plasma equipment transmits electricity to the conductive container wall and the conductive active mesh enclosure, so that the conductive container wall is an anode, the conductive active mesh enclosure is a cathode, the processing gas is ionized to generate plasma, and the low-k polymer porous membrane 110 is subjected to plasma processing.
In order to further improve the processing effect of the plasma processing, in one embodiment, the plasma device is a dc plasma device or an ac plasma device, for example, the rf output by the dc plasma device is 100MHz to 100GHz, for example, the rf output by the dc plasma device is 50GHz, for example, the microwave output by the ac plasma device is 1GHz or more. For example, the AC plasma device outputs microwaves of 1GHz, 5GHz, 10GHz, 50GHz or 100 GHz. For example, the distance between the low dielectric constant base film and the conductive active mesh is 5mm to 100 mm. For example, the distance between the low dielectric constant base film and the conductive active mesh is 50 mm. For example, the processing pressure of the plasma processing is 10 to 500 Pa. For example, the processing pressure of the plasma treatment is 2500 Pa. For example, the treatment temperature of the plasma treatment is 50 ℃ to 250 ℃. For example, the processing temperature of the plasma treatment is 150 ℃. For example, the plasma treatment time is 5min to 5 hours. For example, the processing time of the plasma treatment is 2.5 h. For example, the process gas includes at least one of argon, nitrogen, hydrogen, methane, and oxygen. For example, the material of the conductive container wall comprises at least one of stainless steel, copper, silver, nickel and aluminum. For example, the material of the conductive active mesh enclosure includes at least one of stainless steel, copper, silver, nickel and aluminum. This can further improve the processing effect of the plasma processing.
Compared with the prior art, the invention has at least the following advantages:
the invention takes the low-k polymer porous membrane 110 as a reinforcing material to improve the mechanical strength, the compressive strength and the tensile strength of the high-frequency composite material 10 and reduce the dielectric constant and the dielectric loss of the high-frequency composite material 10; the dipping glue layer 120 is used as an adhesive to increase the bonding force between two adjacent layers of the low-k polymer porous membrane 110, and the adopted dipping glue layer 120 takes epoxy resin with low dielectric constant as a main raw material and is added with a curing agent, a foaming agent, a heat-conducting agent, a flame retardant and a coupling agent in proper proportion to improve the heat resistance, the corrosion resistance, the heat-conducting property and the flame retardant property of the dipping glue layer 120; and then the low-k polymer porous membrane 110 has a porous structure to further reduce its dielectric constant and dielectric loss, and increase its adhesion with the prepreg layer 120. Thus, the low-k polymer porous membrane 110 and the impregnation adhesive layer 120 can reduce the dielectric constant and the dielectric loss of the high-frequency composite material 10, and can improve the mechanical strength, the compressive strength, the tensile strength, the heat resistance, the corrosion resistance, the heat conductivity and the flame retardant property of the high-frequency composite material 10.
The following are detailed description of the embodiments
Example 1
S111, adding the nano boron nitride powder into a 0.5 wt% sodium chloride aqueous solution to prepare a 5mg/mL boron nitride mixed solution; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution in a water bath under a closed condition so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain a nano boron nitride dispersion solution.
S121, mixing 100g of epoxy resin with the epoxy equivalent of 0.20, 30g of phthalic anhydride, 5g N, N' -dinitrosopentamethylenetetramine, 8g of dimethyl methylphosphonate, 2g of KH570 coupling agent and 3g of nano boron nitride dispersion liquid, and uniformly stirring to obtain a premix; and carrying out heat treatment on the premix at the temperature of 120 ℃ for 4.0h to obtain the epoxy resin adhesive.
S131, dipping two layers of laminated PPO fiber woven membranes into the epoxy resin adhesive for lamination operation to form dipping glue layers inside and outside each layer of PPO fiber woven membrane to obtain a prepared composite membrane; the preliminary composite film was subjected to curing treatment at a temperature of 220 ℃ for 6 hours to obtain a high-frequency composite material of example 1.
A laminate was prepared using the high-frequency composite material of example 1, and a copper foil was laminated on one side of the laminate to obtain a high-frequency circuit board.
Example 2
S112, adding the nano boron nitride powder into a 2.5 wt% sodium chloride aqueous solution to prepare a boron nitride mixed solution with the concentration of 20 mg/mL; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution in a water bath under a closed condition so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain a nano boron nitride dispersion solution.
S122, mixing 100g of epoxy resin with the epoxy equivalent of 0.30, 80g of maleic anhydride, 20g of azobisisobutyronitrile, 16g of dimethyl methylphosphonate, 4g of KH560 coupling agent and 13g of nano boron nitride dispersion, and uniformly stirring to obtain a premix; and carrying out heat treatment on the premix at the temperature of 140 ℃ for 3.0h to obtain the epoxy resin adhesive.
S132, dipping two layers of laminated PSF fiber woven membranes into the epoxy resin adhesive for lamination so as to form dipping glue layers inside and outside each layer of PSF fiber woven membrane and obtain a prepared composite membrane; and curing the prepared composite film at the temperature of 240 ℃ for 2h to obtain the high-frequency composite material.
A laminate was prepared by using the high-frequency composite material of example 2, and a copper foil was laminated on one side of the laminate to obtain a high-frequency circuit board.
Example 3
S113, adding the nanometer boron nitride powder into a 1.5 wt% sodium chloride aqueous solution to prepare a 12mg/mL boron nitride mixed solution; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution in a water bath under a closed condition so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain a nano boron nitride dispersion solution.
S123, mixing 100g of epoxy resin with the epoxy equivalent of 0.25, 60g of sebacic dihydrazide, 13g of azodicarbonamide, 12g of dimethyl methylphosphonate, 3g of KH550 coupling agent and 6g of nano boron nitride dispersion liquid, and uniformly stirring to obtain a premix; and carrying out heat treatment on the premix at the temperature of 130 ℃ for 4.0h to obtain the epoxy resin adhesive.
S133, dipping two layers of laminated PTFE fiber woven membranes in the epoxy resin adhesive for lamination so as to form dipping glue layers inside and outside each layer of the PTFE fiber woven membrane and obtain a prepared composite membrane; and curing the prepared composite film for 4 hours at the temperature of 230 ℃ to obtain the high-frequency composite material.
A laminate was prepared by using the high-frequency composite material of example 3, and a copper foil was laminated on one side of the laminate to obtain a high-frequency circuit board.
Example 4
S114, adding the nano boron nitride powder into a 0.1 wt% sodium chloride aqueous solution to prepare a 1mg/mL boron nitride mixed solution; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution in a water bath under a closed condition so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain a nano boron nitride dispersion solution.
S124, mixing 100g of epoxy resin with the epoxy equivalent of 0.15, 5g of 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 0.5g of p-toluenesulfonyl hydrazide, 5g of dimethyl methyl phosphate, 0.5g of DL602 coupling agent and 1g of nano boron nitride dispersion liquid, and uniformly stirring to obtain a premix; and carrying out heat treatment on the premix at the temperature of 100 ℃ for 6.0h to obtain the epoxy resin adhesive.
S134, dipping the three layers of laminated PEEK hollow fiber membranes in the epoxy resin adhesive for lamination operation so as to form dipping glue layers in the interior and the outer side of each layer of PEEK hollow fiber membrane and obtain a prepared composite membrane; and curing the prepared composite film at the temperature of 200 ℃ for 24 hours to obtain the high-frequency composite material.
A laminate was prepared using the high-frequency composite material of example 4, and a copper foil was laminated on one side of the laminate to obtain a high-frequency circuit substrate.
Example 5
S115, adding the nano boron nitride powder into a 5.0 wt% sodium chloride aqueous solution to prepare a 100mg/mL boron nitride mixed solution; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution in a water bath under a closed condition so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain a nano boron nitride dispersion solution.
S125, mixing 100g of epoxy resin with the epoxy equivalent of 0.50, 130g of polyazelaic anhydride, 25g of 4,4' -oxybis-benzenesulfonylhydrazide, 20g of methyl dimethyl phosphate, 5g of KH792 coupling agent and 15g of nano boron nitride dispersion liquid, and uniformly stirring to obtain a premix; and carrying out heat treatment on the premix at the temperature of 150 ℃ for 2.0h to obtain the epoxy resin adhesive.
S135, dipping the three layers of the PPS hollow fiber membranes which are arranged in a stacked mode into the epoxy resin adhesive for lamination operation, so that dipping glue layers are formed inside and outside each layer of PPS hollow fiber membranes, and a prepared composite membrane is obtained; and curing the prepared composite film at the temperature of 250 ℃ for 1h to obtain the high-frequency composite material.
A laminate was prepared using the high-frequency composite material of example 5, and a copper foil was laminated on one side of the laminate to obtain a high-frequency circuit substrate.
Comparative example 1
Dipping two layers of PTFE films which are arranged in a stacked mode in a common epoxy resin adhesive for lamination operation, so that dipping glue layers are formed inside and outside each layer of PTFE film, and a prepared composite film is obtained; and curing the prepared composite film for 4 hours at the temperature of 230 ℃ to obtain the high-frequency composite material.
A laminate was prepared using the high-frequency composite material of comparative example 1, and a copper foil was laminated on one side of the laminate to obtain a high-frequency circuit substrate.
The high-frequency circuit substrates prepared from the high-frequency composite materials of examples 1 to 5 and comparative example 1 were subjected to performance tests, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, compared with the high-frequency circuit substrate prepared from the high-frequency composite material of comparative example 1, the high-frequency circuit substrate prepared from the high-frequency composite materials of examples 1 to 5 has more excellent dielectric property, heat resistance, heat conductivity and flame retardancy, and the dielectric constant of the high-frequency circuit substrate is within a range of 2.8 to 3.2 (28 GHz); the dielectric loss is less than 0.001(28GHz), and the dielectric loss is applied to high-frequency electronic materials, so that the integration level of devices can be improved, the delay time is reduced, the crosstalk and the energy consumption are reduced, and the dielectric loss has a very high application prospect in the aspect of high-frequency electronic materials above 28 GHz.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The high-frequency composite material is characterized by comprising at least two layers of laminated low-k polymer porous membranes and an impregnation glue layer which permeates into the low-k polymer porous membranes in an impregnation mode and is attached to the outer sides of the low-k polymer porous membranes;
the impregnating glue layer comprises the following components in parts by mass: 100 parts of epoxy resin, 5-130 parts of curing agent, 0.5-25 parts of foaming agent, 1-15 parts of heat conducting agent, 5-20 parts of flame retardant and 0.5-5 parts of coupling agent.
2. The high-frequency composite material according to claim 1, wherein the material of the low-k polymer porous membrane includes at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEEKK, PI, and MPI.
3. The high-frequency composite material according to claim 1, wherein the epoxy resin has an epoxy equivalent of 0.15 to 0.50.
4. The high frequency composite according to claim 1, wherein the curing agent is a high temperature curing agent having a curing temperature of more than 100 ℃.
5. The high frequency composite according to claim 1, wherein the blowing agent comprises at least one of azodicarbonamide, azobisisobutyronitrile, N '-dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide and p-toluenesulfonylhydrazide.
6. The high-frequency composite material according to claim 1, wherein the heat conductive agent comprises a nano boron nitride dispersion liquid highly dispersed by dissociation in a liquid component.
7. The high-frequency composite material according to claim 1, wherein the flame retardant comprises dimethyl methylphosphonate; or the coupling agent comprises a silane coupling agent.
8. The preparation method of the high-frequency composite material is characterized by comprising the following steps of:
mixing epoxy resin, a curing agent, a foaming agent, a flame retardant, a coupling agent and a heat conducting agent, and uniformly stirring to obtain a premix; carrying out heat treatment on the premix to obtain an epoxy resin adhesive; wherein the mass ratio of the epoxy resin, the curing agent, the foaming agent, the heat conducting agent, the flame retardant and the coupling agent is 100: (5-130): (0.5-25): (1-15): (5-20): (0.5 to 5);
dipping at least two layers of laminated low-k polymer porous membranes into the epoxy resin adhesive for lamination so as to form dipping glue layers inside and outside each layer of the low-k polymer porous membranes to obtain a prepared composite membrane; and curing the prepared composite film to obtain the high-frequency composite material.
9. The method for preparing a high-frequency composite material according to claim 8, wherein the temperature of the heat treatment is 100 ℃ to 150 ℃, and the time of the heat treatment is 2.0h to 6.0 h; or the temperature of the curing treatment is 200-250 ℃, and the time of the curing treatment is 1-24 h.
10. The method for preparing a high-frequency composite material according to claim 8, wherein before the operation of mixing the epoxy resin, the curing agent, the foaming agent, the flame retardant, the coupling agent and the heat conducting agent, nano boron nitride powder is further added to a liquid component to obtain a boron nitride mixed solution; and then carrying out ultrasonic dispersion operation on the boron nitride mixed solution so as to uniformly disperse the nano boron nitride powder in the liquid component to obtain the heat-conducting agent.
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