CN109796706B - Polydopamine modified fluorine-containing resin mixture and prepreg and copper-clad plate prepared from same - Google Patents
Polydopamine modified fluorine-containing resin mixture and prepreg and copper-clad plate prepared from same Download PDFInfo
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Abstract
The invention relates to a Polydopamine (PDA) modified fluorine-containing resin mixture and a prepreg and a copper-clad plate prepared from the same. The surface of the inorganic filler is modified with amino, and then the PDA is chemically bonded to the surface of the inorganic filler through the reaction of the amino and dopamine; the invention decorates PDA to the glass fiber cloth; therefore, on one hand, the compatibility between the inorganic filler and the fluorine-containing resin is improved, the dispersibility of the inorganic filler in the fluorine-containing resin matrix is promoted, and on the other hand, the interaction force among the inorganic filler, the fluorine-containing resin, the glass fiber cloth and the copper foil is enhanced. Furthermore, the high-frequency copper clad laminate manufactured by the prepreg, the film and the copper foil has good thermal-mechanical property, excellent dielectric property, good comprehensive property stability and good uniformity, particularly the copper foil has high peel strength, and can meet various comprehensive property requirements of the high-frequency communication field on substrate materials.
Description
Technical Field
The invention belongs to the field of communication materials, and particularly relates to a polydopamine modified fluorine-containing resin mixture, and a prepreg and a copper-clad plate prepared from the same.
Background
At present, the information electronics industry is in a high-speed development stage, and is gradually becoming one of the post industries of various countries. Copper-clad plates are one of key materials in the information electronics industry, and have been widely applied to communication base stations, satellites, vending machines, computers, mobile phones and even a plurality of fields such as wearable equipment, unmanned vehicles, unmanned aerial vehicles and intelligent robots which are gradually emerging.
Heretofore, various processes for producing fluorine-containing resin-based copper-clad plates have been developed, such as U.S. Pat. nos. US3136680, US4335180, US4849284, US5024871, US5922453, US2539329, US4623505, US4647508, US4886699, and chinese patents CN2014103766915, CN201010180034, etc. The fluorine-containing resin has extremely low dielectric constant and dielectric loss, high thermal stability and chemical stability due to the specific chemical structure of the fluorine-containing resin, and is an ideal material for manufacturing the high-frequency copper-clad plate. However, the extremely great chemical inertness of the copper clad laminate causes that the interaction force between the fluorine-containing resin and the inorganic filler, the glass fiber cloth and the copper foil is not high, the temperature required by the lamination process of the fluorine-containing resin-based copper clad laminate is high, the time is long, and the energy consumption of the production process is huge. Particularly, when the fluorine-containing resin-based copper-clad plate with high dielectric constant and/or high thermal conductivity is prepared, the high-filled inorganic filler can further reduce the compatibility and the dispersibility among materials in the copper-clad plate matrix, so that the dielectric property, the thermal-mechanical property, the thermal expansion coefficient and the like of the copper-clad plate are obviously non-uniform.
The coupling agent is used for surface modification of inorganic filler, glass fiber cloth or copper foil, and is a common method for enhancing the interaction force of the inorganic filler, the glass fiber cloth or the copper foil and the fluorine-containing resin matrix. However, since the fluororesin generally does not chemically react with the coupling agent, it is difficult to form a chemical bond between the fluororesin substrate and the inorganic filler, the glass cloth, or the copper foil. In addition, common alkane chains at one end of the common coupling agent and the fluorine-containing polymerThe interaction of the chains is also weak. Journal of scienceScience2007, 318, 426.) reports that Polydopamine (PDA), a substance that can be rapidly and tightly adsorbed on the surface of almost all materials by self-polymerization, is not exceptional on the surface of fluorine-containing resin, i.e., stronger interaction between PDA and fluorine-containing resin can be formed. Therefore, PDA is a substance which is potentially effective in improving the interaction force and the bonding force among materials in the fluorine-containing resin-based copper-clad plate substrate.
Disclosure of Invention
The invention aims to provide a fluorine-containing resin-based prepreg which has good compatibility among inorganic filler, glass fiber cloth and fluorine-containing resin.
The invention also aims to provide a high-frequency copper-clad plate which is prepared from the prepreg and has excellent thermo-mechanical property, good dielectric property and high copper foil peeling strength.
The technical scheme adopted by the invention for solving the problems is that the prepreg prepared from the polydopamine modified fluorine-containing resin mixture is prepared by the following preparation steps in sequence:
s1, preparing 0.1-45 wt/v% of uniform dispersion liquid of inorganic filler, then adding a coupling agent with terminal amino groups, stirring and reacting for 0.5-48 h at 50-130 ℃, filtering, washing and drying to obtain the product inorganic filler modified by the coupling agent with terminal amino groups, and marking as inorganic filler-NH2；
S2, preparing 0.1-100 mg/mL dopamine Tris (hydroxymethyl) aminomethane-hydrochloric acid (Tris-HCl) buffer solution, and then adding 0.1-25 wt/v% of the inorganic filler-NH2Uniformly stirring and dispersing the mixture in a non-inert atmosphere, soaking the mixture for 5 to 1440min, filtering the mixture to obtain a product, soaking the product in an organic solvent for 5 to 180min to remove polydopamine with weak adhesion, soaking the product in water to remove the organic solvent, and finally filtering, washing and drying the product to obtain the product, namely the inorganic filler with the surface chemically bonded with the polydopamine, which is marked as polydopamine @ inorganic filler;
s3, soaking glass fiber cloth in 0.1-100 mg/mL dopamine-trihydroxymethyl aminomethane-hydrochloric acid buffer solution, airing in a non-inert atmosphere for 5-1440 min, soaking the glass fiber cloth in an organic solvent for 5-180 min to remove polydopamine with weak adhesion, then soaking in water to remove the organic solvent, and finally drying to obtain a product, namely the polydopamine-modified glass fiber cloth, which is marked as polydopamine-glass fiber cloth;
s4, preparing a uniform dispersion liquid of a fluorine-containing resin mixture with a solid content of 20-75 wt/v%, wherein the fluorine-containing resin mixture comprises three components, namely fluorine-containing resin emulsion, polydopamine @ inorganic filler and auxiliary materials;
and S5, impregnating polydopamine-glass fiber cloth with the uniform dispersion liquid of the fluorine-containing resin mixture, and baking and drying to obtain a prepreg.
The further preferred technical scheme is as follows: in step S1, the inorganic filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、BN、SiC、Si3N4、Al(OH)3、Mg(OH)2、SrTiO3、BaTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass microspheres, hollow glass microspheres, glass fibers, basalt fibers and carbon fibers;
the particle size of the inorganic filler is less than or equal to 100um, and the usage amount of the inorganic filler accounts for 1-65 wt% of the fluorine-containing resin mixture;
the coupling agent with the terminal amino is a mixture of one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, a bimetallic coupling agent and a rare earth coupling agent, wherein the terminal group of the silane coupling agent is amino;
the mass ratio of the coupling agent with the terminal amino groups to the inorganic filler is 1: 1000-100: 1000;
the solvent of the uniform dispersion liquid of the inorganic filler is one or a mixture of a plurality of organic solvents which can dissolve the coupling agent with the terminal amino and can uniformly disperse the inorganic filler;
the water content of the homogeneous dispersion of the inorganic filler is more than 0.1 wt%.
The further preferred technical scheme is as follows: in steps S2 and S3, the tris-hcl buffer solution is an alkaline aqueous solution having a pH > 7;
the organic solvent is one or a mixture of more of solvents capable of dissolving polydopamine;
the non-inert atmosphere is an atmosphere containing oxygen, wherein the content of the oxygen in the non-inert gas is more than or equal to 3 v/v%;
the polydopamine in the polydopamine @ inorganic filler accounts for 0.05-2.5 wt% of the mass of the inorganic filler;
the polydopamine in the polydopamine-glass fiber cloth accounts for 0.03-2 wt% of the glass fiber cloth.
The further preferred technical scheme is as follows: in step S3, the glass fiber cloth is one of 106, 1080, 2116 and 7628 electronic grade alkali-free glass fiber cloth.
The further preferred technical scheme is as follows: in step S4, the fluorine-containing resin emulsion is an emulsion of one or a mixture of several of polytetrafluoroethylene, polyperfluoroethylpropylene, tetrafluoroethylene-perfluoroalkylvinylether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer and derivatives thereof;
the fluorine-containing resin emulsion has a solid content of 20-70 wt/v% and a viscosity of 9-45 mPa & s at 25 ℃;
the auxiliary material is one or a mixture of more of ultra-high molecular weight polyethylene fiber, Kevlar fiber, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetherketone, polyphenylene sulfide and derivatives thereof;
the amount of the auxiliary material accounts for 0-20 wt% of the fluorine-containing resin mixture;
the solvent of the uniform dispersion liquid of the fluorine-containing resin mixture is one or a mixture of water and organic solvent which can uniformly disperse the fluorine-containing resin mixture.
The further preferred technical scheme is as follows: in the step S5, the baking and drying are divided into two stages, wherein the baking and drying temperature of the first stage is 50-120 ℃, the baking and drying time is 3-10 min, and the baking and drying temperature of the second stage is 150-370 ℃, and the baking and drying time is 5-40 min.
A copper-clad plate manufactured by a prepreg prepared by a polydopamine modified fluorine-containing resin mixture is manufactured by the following manufacturing steps in sequence: laminating the prepreg, the film and the copper foil coated on the surface layer together to obtain the copper-clad plate, wherein the number of the prepreg is more than or equal to 1, the number of the film is more than or equal to 1, the number of the copper foil is 1 or 2, the laminating temperature is 200-370 ℃, and the laminating pressure is 50-130 kg/cm2The laminating time is 30 min-24 h.
The further preferred technical scheme is as follows: the film is polyolefin, polyamide, polyimide, polyetherketone, polyetheretherketone, polycarbonate, polyphenylene sulfide, polyarylethersulfone, polyarylsulfone, polyaryletherketone, polyarylsulfone, polyethersulfoneketone, polyarylethersulfonenitrile, polyarylethersulfonesulfonenitrile, polyphenylquinoxaline, phenolic resin, epoxy resin, cyanate ester resin, polyurethane, polyoxymethylene, polycarbonate, acrylonitrile-styrene-acrylate copolymer, acrylonitrile-styrene copolymer, methacrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, SEBS, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-polyolefin-styrene copolymer, ethylene-tetrafluoroethylene copolymer, styrene-butadiene rubber, styrene-co-olefin copolymer, styrene-co-polymer, styrene-co-tetrafluoroethylene copolymer, styrene-butadiene rubber, styrene-co-ethylene-styrene copolymer, styrene-co-ethylene-butadiene rubber, styrene-co-ethylene-, A film of nitrile rubber and one or more mixtures of cellulose and its derivatives.
The surface of the inorganic filler is modified with amino, and then the PDA is chemically bonded to the surface of the inorganic filler through the reaction of the amino and dopamine; the invention utilizes the characteristic that PDA can strongly adsorb on the surfaces of almost all substances, and the PDA is modified on the glass fiber cloth, even on the surfaces of substances with extremely high chemical inertness, such as fluorine-containing resin, the PDA can also have good adhesive force. Therefore, the invention greatly improves the compatibility between the inorganic filler and the fluorine-containing resin, promotes the dispersibility of the inorganic filler in the fluorine-containing resin matrix, and obviously enhances the interaction force among the inorganic filler, the fluorine-containing resin, the glass fiber cloth and the copper foil. Especially, when preparing prepregs and copper-clad plates with high dielectric constant and/or high thermal conductivity, i.e. the addition amount of the inorganic filler in the fluororesin-containing matrix is high, the improvement of the performance becomes more necessary. Therefore, in the invention, the dispersion liquid of the fluorine-containing resin mixture is soaked in the PDA-fiberglass cloth, and the prepreg prepared by baking and drying has the advantages of uniform gel content, good gum dipping quality, strong resin adhesive force, smooth surface and proper toughness and viscosity. Furthermore, the high-frequency copper clad laminate manufactured by the prepreg, the film and the copper foil has good thermal-mechanical property, excellent dielectric property, good comprehensive property stability and good uniformity, particularly the copper foil has high peel strength, and can meet various comprehensive property requirements of the high-frequency communication field on substrate materials.
The applicant finds that the modification amount of the PDA on the inorganic filler and the glass fiber cloth cannot be too small, otherwise the interaction force among the inorganic filler, the glass fiber cloth, the fluorine-containing resin and the copper foil is not obviously improved; but the modification amount of the PDA is not too much, otherwise, the dielectric loss of the copper-clad plate is increased.
The method has the advantages of mild preparation conditions, low production cost, easiness in batch and large-scale production, strong universality, good industrial production basis and wide application prospect.
Detailed Description
The invention provides a prepreg made of Polydopamine (PDA) modified fluorine-containing resin mixture and a high-frequency copper-clad plate prepared from the prepreg through further detail description by embodiments. However, this example is provided only as an illustration, and does not limit the present invention.
Example 1
60 parts of silicon oxide (Xinyi macrorun) and 20 parts of aluminum oxide (Ziboheng) are uniformly dispersed in 500 parts of ethanol, slowlySlowly dropwise adding 6 parts of 3-Aminopropyltriethoxysilane (APS) at 60oAnd C, stirring and reacting for 6 hours, and then filtering, washing with ethanol, drying and the like to obtain a product: APS modified SiO2/Al2O3Composite inorganic fillers, noted as "SiO2/Al2O3-NH2". Under the air atmosphere, the' SiO2/Al2O3-NH2"stirring and soaking in 600 parts of Tris-HCl (pH = 8.6) buffer solution containing 1.0wt% of dopamine for 30min, taking out, stirring and soaking in isopropanol for 20min to remove PDA with weak adhesion, and finally soaking in water to remove isopropanol to prepare SiO with surface chemically bonded with PDA2/Al2O3Composite inorganic Filler noted "PDA @ SiO2/Al2O3". The 1080 fiberglass cloth is soaked in 0.8wt% of dopamine in Tris-HCl (pH = 8.6) buffer solution for 30min and then taken out, then soaked in isopropanol for 10min to remove PDA with weak adhesion, and finally soaked in water to remove isopropanol, so that the 1080 fiberglass cloth with the PDA modified on the surface is prepared and is marked as 'PDA-1080 fiberglass cloth'. Taking 50 parts of polytetrafluoroethylene emulsion (DuPont Teflon)®PTFE DISP30, solid content 60%), 120 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon)®PFAD 335D, 60% solids content), 40 parts of "PDA @ SiO @ SiO @2/Al2O3"and 10 parts of polysulfone powder (BASF Ultrason S2010), and mixing them with stirring to obtain a uniform dispersion, and adding a diluent water so that the solid content of the dispersion is controlled to about 50 wt/v%. General' PDA&1080 glass fiber cloth is dipped in the uniform dispersion liquid of the fluororesin-containing mixture and then baked to obtain a prepreg. Wherein the first stage baking temperature is 100 deg.CoC, the time is 4min, the baking temperature in the second stage is 320 ℃, and the time is 20 min; taking 8 prepregs and 4 DuPon Kapton®XP film and 3 DuPont Kapton® 6051 laminating, attaching loz copper foils on both sides, and vacuum-pressing at 75-85 kg/cm2And laminating for 10 hours at the temperature of 360 ℃ to obtain the copper-clad plate.
Example 2
70 parts of silicon oxide (Xinyi macrorun) and 30 parts of aluminum oxide (Ziboheng) are uniformly dispersed in 700 parts of ethanol, 7.5 parts of 3-Aminopropyltriethoxysilane (APS) are slowly added dropwise at 60%oAnd C, stirring and reacting for 6 hours, and then filtering, washing with ethanol, drying and the like to obtain a product: APS modified SiO2/Al2O3Composite inorganic fillers, noted as "SiO2/Al2O3-NH2". Under the air atmosphere, the' SiO2/Al2O3-NH2"stirring in 750 parts of 2.0wt% dopamine in Tris-HCl (pH = 8.6) buffer solution, soaking for 45min, taking out, stirring in isopropanol, soaking for 25min to remove weakly adhered PDA, and finally soaking in water to remove isopropanol to prepare SiO with surface chemically bonded with PDA2/Al2O3Composite inorganic Filler noted "PDA @ SiO2/Al2O3". Soaking 1080 fiberglass cloth in 0.8wt% dopamine Tris-HCl (pH = 8.6) buffer solution for 30min, taking out, soaking in isopropanol for 10min to remove PDA with weak adhesion, and soaking in water to remove isopropanol to obtain 1080 fiberglass cloth with PDA modified surface, which is marked as PDA&1080 fiberglass cloth ". 60 parts of polytetrafluoroethylene emulsion (DuPont Teflon)®PTFE DISP30, 60% solids content), 110 parts of polyfluorinated ethylene propylene emulsion (DuPont Teflon)®FEPD121, solids content 54%), 50 parts of "PDA @ SiO2/Al2O3"and 5 parts of polyethersulfone powder (BASF Ultrason E2010), stirring and mixing to obtain a uniform dispersion, and adding diluent water to control the solid content of the dispersion to be about 60 wt/v%. General' PDA&1080 glass fiber cloth is dipped in the uniform dispersion liquid of the fluororesin-containing mixture and then baked to obtain a prepreg. Wherein the first stage baking temperature is 100 deg.C and time is 5min, and the second stage baking temperature is 290 deg.C and time is 30 min; taking 8 prepregs and 7 DuPon Kapton®Laminating the F films together, respectively attaching loz copper foils on two sides, and applying pressure of 55-70 kg/cm2And laminating for 16 hours at the temperature of 340 ℃ to obtain the copper-clad plate.
Example 3
Uniformly dispersing 70 parts of titanium oxide (Zhengqianmei science and technology in Tianjin) and 20 parts of aluminum oxide (Zibohenbang) in 650 parts of ethanol, slowly dropwise adding 6.7 parts of 3-aminopropyl triethoxysilane (APS) to the mixture at 60 parts of ethanoloAnd C, stirring and reacting for 6 hours, and then filtering, washing with ethanol, drying and the like to obtain a product: APS modified TiO2/Al2O3Composite inorganic filler, noted as "TiO2/Al2O3-NH2". Under air atmosphere, adding "TiO2/Al2O3-NH2"stirring and soaking in 500 parts of Tris-HCl (pH = 8.6) buffer solution containing 1.5wt% of dopamine for 35min, taking out, stirring and soaking in isopropanol for 20min to remove PDA with weak adhesion, and finally soaking in water to remove isopropanol to prepare TiO with PDA chemically bonded on surface2/Al2O3Composite inorganic Filler noted "PDA @ TiO2/Al2O3". Soaking 1080 fiberglass cloth in 0.8wt% dopamine Tris-HCl (pH = 8.6) buffer solution for 30min, taking out, soaking in isopropanol for 10min to remove PDA with weak adhesion, and soaking in water to remove isopropanol to obtain 1080 fiberglass cloth with PDA modified surface, which is marked as PDA&1080 fiberglass cloth ". Taking 50 parts of polytetrafluoroethylene emulsion (DuPont Teflon)®PTFE DISP30, solid content 60%), 60 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon)®PFAD 335D, 60% solids content), 50 parts of polyperfluoroethylpropylene (dupont Teflon @)®FEPD121, solid content 54%), 45 parts of "PDA-TiO2/Al2O3"and 5 parts of polyethersulfone powder (BASF Ultrason E2010), stirring and mixing to obtain a uniform dispersion, and adding diluent water to control the solid content of the dispersion to be about 45 wt/v%. General' PDA&1080 glass fiber cloth is dipped in the uniform dispersion liquid of the fluororesin-containing mixture and then baked to obtain a prepreg. Wherein the first stage baking temperature is 100 deg.C for 4min, and the second stage baking temperature is 300 deg.C for 25 min; taking 8 prepregs and 4 DuPon Kapton®XP film and 3 DuPont Kapton® Laminating 100HN films, respectively attaching loz copper foils on two sides, and applying a pressure of 60-70 kg/cm2And laminating for 10 hours at the temperature of 350 ℃ to obtain the copper-clad plate.
Example 4
Uniformly dispersing 40 parts of silicon oxide (Xinyi macrorun) and 40 parts of aluminum oxide (Ziboheng) in 500 parts of ethanol, slowly dropwise adding 6 parts of 3-Aminopropyltriethoxysilane (APS) at 60 parts of ethanoloAnd C, stirring and reacting for 6 hours, and then filtering, washing with ethanol, drying and the like to obtain a product: APS modified SiO2/Al2O3Composite inorganic fillers, noted as "SiO2/Al2O3-NH2". Under the air atmosphere, the' SiO2/Al2O3-NH2"stirring and soaking in 500 parts of Tris-HCl (pH = 8.6) buffer solution containing 1.5wt% of dopamine for 30min, taking out, stirring and soaking in isopropanol for 20min to remove PDA with weak adhesion, and finally soaking in water to remove isopropanol to prepare SiO with surface chemically bonded with PDA2/Al2O3Composite inorganic fillers, noted "PDA-SiO2/Al2O3". Soaking 1080 fiberglass cloth in 0.8wt% dopamine Tris-HCl (pH = 8.6) buffer solution for 30min, taking out, soaking in isopropanol for 10min to remove PDA with weak adhesion, and soaking in water to remove isopropanol to obtain 1080 fiberglass cloth with PDA modified surface, which is marked as PDA&1080 fiberglass cloth ". 100 parts of polytetrafluoroethylene emulsion (DuPont Teflon)®PTFE DISP30, solid content 70%), 70 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon)®PFAD 335D, 60% solids content), 40 parts of "PDA @ SiO @ SiO @2/Al2O3"and 10 parts of polysulfone powder (BASF Ultrason S2010) were mixed with stirring to obtain a uniform dispersion, and the solid content of the dispersion was controlled to be about 55 wt/v%. General' PDA&1080 glass fiber cloth is dipped in the uniform dispersion liquid of the fluororesin-containing mixture and then baked to obtain a prepreg. Wherein the first stage baking temperature is 120 deg.CoC, the time is 5min, and the second stage baking temperature is 300At 30 min; taking 8 prepregs and 4 DuPon Kapton®XP film and 3 DuPont Kapton® 6051 laminating, attaching loz copper foils on two sides respectively, and pressing under 80-110 kg/cm2And laminating for 10 hours at the temperature of 360 ℃ to obtain the copper-clad plate.
Example 5
Uniformly dispersing 40 parts of titanium oxide (Zhengqianmei science and technology in Tianjin) and 40 parts of aluminum oxide (Zibohenbang) in 500 parts of ethanol, slowly dropwise adding 6 parts of 3-aminopropyl triethoxysilane (APS) at 60 parts of ethanoloAnd C, stirring and reacting for 6 hours, and then filtering, washing with ethanol, drying and the like to obtain a product: APS modified TiO2/Al2O3Composite inorganic filler, noted as "TiO2/Al2O3-NH2". Under air atmosphere, adding "TiO2/Al2O3-NH2"stirring and soaking in 600 parts of 2.0wt% dopamine in Tris-HCl (pH = 8.6) buffer solution for 40min, taking out, stirring and soaking in isopropanol for 20min to remove PDA with weak adhesion, and finally soaking in water to remove isopropanol to prepare TiO with PDA chemically bonded on surface2/Al2O3Composite inorganic Filler noted "PDA @ TiO2/Al2O3". Soaking 1080 fiberglass cloth in 0.8wt% dopamine Tris-HCl (pH = 8.6) buffer solution for 30min, taking out, soaking in isopropanol for 10min to remove PDA with weak adhesion, and soaking in water to remove isopropanol to obtain 1080 fiberglass cloth with PDA modified surface, which is marked as PDA&1080 fiberglass cloth ". 80 parts of polytetrafluoroethylene emulsion (DuPont Teflon)®PTFE DISP30, solid content 60%), 40 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon)®PFAD 335D, 60% solids content), 40 parts of polyfluorinated ethylene propylene (dupont Teflon @)®FEPD121, solids content 54%) and 40 parts of "PDA @ TiO2/Al2O3", a uniform dispersion was obtained by stirring and mixing, and a diluent water was added so that the solid content of the dispersion was controlled to be about 55 wt/v%. General' PDA&1080 glass fiber cloth "made of the above-mentioned fluororesin-containing mixtureAnd dipping the uniform dispersion liquid, and baking to obtain the prepreg. Wherein the first stage baking temperature is 100 deg.CoC, the time is 10min, and the second stage baking temperature is 290oC, the time is 30 min; taking 8 prepregs and 3 DuPon Kapton®XP film and 4 DuPont Kapton® Laminating 100HN films, respectively attaching loz copper foils on two sides, and applying a pressure of 75-95 kg/cm2At a temperature of 330oAnd C, laminating for 8 hours to obtain the copper-clad plate.
Comparative example 1
50 parts of polytetrafluoroethylene emulsion (DuPont Teflon) are weighed®PTFE DISP30, solid content 60%), 120 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon)®PFAD 335D, solid content 60%), 30 parts of silica (new Yiyi moistening) and 10 parts of alumina (zibo Hengbang), and stirring and mixing to obtain a uniform dispersion; the diluent water was added so that the solid content of the dispersion was controlled to be around 50 wt/v%. Dipping glue in the uniform dispersion liquid of the fluororesin-containing mixture by adopting 1080 glass fiber cloth, and baking to obtain a prepreg. Wherein the first stage baking temperature is 100 deg.CoC, the time is 5min, and the second stage baking temperature is 320oC, the time is 25 min; taking 8 prepregs and 4 DuPon Kapton®XP film and 3 DuPont Kapton® 6051 laminating the films together, attaching loz copper foils on two sides respectively, and pressing at 95-115 kg/cm2And laminating for 12 hours at the temperature of 380 ℃ to obtain the copper-clad plate.
Comparative example 2
50 parts of polytetrafluoroethylene emulsion (DuPont Teflon) are weighed®PTFE DISP30, solid content 60%), 120 parts of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer emulsion (DuPont Teflon)®PFAD 335D, solid content 60%), 30 parts of silica (new-yi macrorun), 10 parts of alumina (zibo henbang) and 3 parts of coupling agent KH550 (Nanjing eosin chemical industry Co., Ltd.), and stirring and mixing to obtain a uniform dispersion liquid; the diluent water was added so that the solid content of the dispersion was controlled to be around 50 wt/v%. Dipping 1080 glass fiber cloth in the homogeneous dispersion of the mixture containing fluororesin, and stovingAnd baking to obtain the prepreg. Wherein the first stage baking temperature is 100 deg.CoC, the time is 4min, and the second stage baking temperature is 320oC, the time is 25 min; taking 8 prepregs and 4 DuPon Kapton®XP film and 3 DuPont Kapton® 6051 laminating the films together, attaching loz copper foils on two sides respectively, and pressing under 90-110 kg/cm2And laminating for 12 hours under the condition that the temperature is 370 @toobtain the copper-clad plate.
As shown in comparative example 1, under the condition of not adding a coupling agent, the interaction force between the fluorine-containing resin and the inorganic filler is weak, which is not beneficial to the dispersibility of the inorganic filler in the fluorine-containing resin matrix, so that the dielectric loss of the copper-clad plate is increased; at the moment, the bonding force between the fluorine-containing resin and the glass fiber cloth is also weaker, the gluing amount is obviously reduced, the flatness and uniformity of the prepreg are reduced, and the breakdown voltage of the prepared copper-clad plate and the peeling strength of the copper foil are reduced. The result of the comparative example 2 shows that the silane coupling agent modified on the surface of the inorganic filler can actually enhance the interaction force between the inorganic filler and the fluorine-containing resin, so that the comprehensive performance of the prepreg and the copper-clad plate is obviously improved. However, it is apparent from the results of examples 1 to 5 that if PDA is modified on both the inorganic filler and the surface of the glass cloth, the interaction force between the fluorine-containing resin, the inorganic filler, the glass cloth and the copper foil can be further enhanced, and the peel strength of the copper foil can be further improved.
The preparation method has the advantages of mild preparation conditions, low production cost, easiness in batch and large-scale production, good industrial production basis and wide application prospect.
The above examples are not intended to limit the amount of the composition of the present invention. Any minor modifications, equivalent changes and modifications to the above embodiments in accordance with the technical spirit or composition ingredients or contents of the present invention are within the scope of the technical solution of the present invention.
Claims (7)
1. The prepreg prepared from the polydopamine modified fluorine-containing resin mixture is characterized by being prepared through the following preparation steps in sequence:
s1, preparing 0.1-45 wt/v% of uniform dispersion liquid of inorganic filler, then adding a coupling agent with terminal amino groups, stirring and reacting for 0.5-48 h at 50-130 ℃, filtering, washing and drying to obtain the product inorganic filler modified by the coupling agent with terminal amino groups, and marking as inorganic filler-NH2；
S2, preparing 0.1-100 mg/mL dopamine trihydroxymethyl aminomethane-hydrochloric acid buffer solution, and then adding 0.1-25 wt/v% of the inorganic filler-NH2Uniformly stirring and dispersing the mixture in a non-inert atmosphere, soaking the mixture for 5 to 1440min, filtering the mixture to obtain a product, soaking the product in an organic solvent for 5 to 180min to remove polydopamine with weak adhesion, soaking the product in water to remove the organic solvent, and finally filtering, washing and drying the product to obtain the product, namely the inorganic filler with the surface chemically bonded with the polydopamine, which is marked as polydopamine @ inorganic filler;
s3, soaking glass fiber cloth in 0.1-100 mg/mL dopamine-trihydroxymethyl aminomethane-hydrochloric acid buffer solution, airing in a non-inert atmosphere for 5-1440 min, soaking the glass fiber cloth in an organic solvent for 5-180 min to remove polydopamine with weak adhesion, then soaking in water to remove the organic solvent, and finally drying to obtain a product, namely the polydopamine-modified glass fiber cloth, which is marked as polydopamine-glass fiber cloth;
s4, preparing a uniform dispersion liquid of a fluorine-containing resin mixture with a solid content of 20-75 wt/v%, wherein the fluorine-containing resin mixture comprises three components, namely fluorine-containing resin emulsion, polydopamine @ inorganic filler and auxiliary materials;
s5, dipping the polydopamine-glass fiber cloth in the uniform dispersion liquid of the fluorine-containing resin mixture, baking and drying to obtain a prepreg,
in steps S2 and S3, the tris-hcl buffer solution is an alkaline aqueous solution having a pH > 7;
the organic solvent is one or a mixture of more of solvents capable of dissolving polydopamine;
the non-inert atmosphere is an atmosphere containing oxygen, wherein the content of the oxygen in the non-inert gas is more than or equal to 3 v/v%;
the polydopamine in the polydopamine @ inorganic filler accounts for 0.05-2.5 wt% of the mass of the inorganic filler;
the polydopamine in the polydopamine-glass fiber cloth accounts for 0.03-2 wt% of the glass fiber cloth.
2. The prepreg prepared from the polydopamine-modified fluorine-containing resin mixture according to claim 1, characterized in that: in step S1, the inorganic filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、BN、SiC、Si3N4、Al(OH)3、Mg(OH)2、SrTiO3、BaTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3One or a mixture of more of graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, clay, solid glass microspheres, hollow glass microspheres, glass fibers, basalt fibers and carbon fibers;
the particle size of the inorganic filler is less than or equal to 100um, and the usage amount of the inorganic filler accounts for 1-65 wt% of the fluorine-containing resin mixture;
the coupling agent with the terminal amino is a mixture of one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, a bimetallic coupling agent and a rare earth coupling agent, wherein the terminal group of the silane coupling agent is amino;
the mass ratio of the coupling agent with the terminal amino groups to the inorganic filler is 1: 1000-100: 1000;
the solvent of the uniform dispersion liquid of the inorganic filler is one or a mixture of a plurality of organic solvents which can dissolve the coupling agent with the terminal amino and can uniformly disperse the inorganic filler;
the water content of the homogeneous dispersion of the inorganic filler is more than 0.1 wt%.
3. The prepreg prepared from the polydopamine-modified fluorine-containing resin mixture according to claim 1, characterized in that: in step S3, the glass fiber cloth is one of 106, 1080, 2116 and 7628 electronic grade alkali-free glass fiber cloth.
4. The prepreg prepared from the polydopamine-modified fluorine-containing resin mixture according to claim 1, characterized in that: in step S4, the fluorine-containing resin emulsion is an emulsion of one or a mixture of several of polytetrafluoroethylene, polyperfluoroethylpropylene, tetrafluoroethylene-perfluoroalkylvinylether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer and derivatives thereof;
the fluorine-containing resin emulsion has a solid content of 20-70 wt/v% and a viscosity of 9-45 mPa & s at 25 ℃;
the auxiliary material is one or a mixture of more of ultra-high molecular weight polyethylene fiber, Kevlar fiber, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetherketone, polyphenylene sulfide and derivatives thereof;
the amount of the auxiliary material accounts for 0-20 wt% of the fluorine-containing resin mixture;
the solvent of the uniform dispersion liquid of the fluorine-containing resin mixture is one or a mixture of water and organic solvent which can uniformly disperse the fluorine-containing resin mixture.
5. The prepreg prepared from the polydopamine-modified fluorine-containing resin mixture according to claim 1, characterized in that: in the step S5, the baking and drying are divided into two stages, wherein the baking and drying temperature of the first stage is 50-120 ℃, the baking and drying time is 3-10 min, and the baking and drying temperature of the second stage is 150-370 ℃, and the baking and drying time is 5-40 min.
6. The copper-clad plate manufactured by the prepreg prepared by the polydopamine modified fluorine-containing resin mixture according to claim 1 is characterized by being manufactured by the following manufacturing steps in sequence: laminating the prepreg, the film and the copper foil coated on the surface layer together to obtain the copper-clad plate, wherein the number of the prepreg is more than or equal to 1, the number of the film is more than or equal to 1, the number of the copper foil is 1 or 2, the laminating temperature is 200-370 ℃, and the laminating pressure is 50-130 kg/cm2The laminating time is 30 min-24 h.
7. The copper-clad plate prepared from the prepreg and prepared from the polydopamine-modified fluorine-containing resin mixture according to claim 6, wherein the copper-clad plate is characterized in that: the film is polyolefin, polyamide, polyimide, polyetherketone, polyetheretherketone, polycarbonate, polyphenylene sulfide, polyarylethersulfone, polyarylsulfone, polyaryletherketone, polyarylsulfone, polyethersulfoneketone, polyarylethersulfonenitrile, polyarylethersulfonesulfonenitrile, polyphenylquinoxaline, phenolic resin, epoxy resin, cyanate ester resin, polyurethane, polyoxymethylene, polycarbonate, acrylonitrile-styrene-acrylate copolymer, acrylonitrile-styrene copolymer, methacrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, SEBS, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-polyolefin-styrene copolymer, ethylene-tetrafluoroethylene copolymer, styrene-butadiene rubber, styrene-co-olefin copolymer, styrene-co-polymer, styrene-co-tetrafluoroethylene copolymer, styrene-butadiene rubber, styrene-co-ethylene-styrene copolymer, styrene-co-ethylene-butadiene rubber, styrene-co-ethylene-, A film of nitrile rubber and one or more mixtures of cellulose and its derivatives.
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| CN112726206A (en) * | 2020-12-28 | 2021-04-30 | 安徽省临泉县万隆塑料包装有限公司 | Ultraviolet-resistant polyethylene non-woven fabric and preparation method thereof |
| CN113801432B (en) * | 2021-09-18 | 2022-11-04 | 中国科学院金属研究所 | Fatigue wear resistant composite material and preparation method and application thereof |
| CN113698901B (en) * | 2021-10-11 | 2023-04-11 | 桐城市火炬手建材有限公司 | Bi-component epoxy ceramic tile crack beautifying agent and preparation method thereof |
| CN114044991A (en) * | 2021-11-29 | 2022-02-15 | 杨春生 | Flame-retardant PVC material and preparation method thereof |
| CN115449185B (en) * | 2022-09-21 | 2023-05-23 | 华南理工大学 | Glass fiber reinforced epoxy resin composite material and preparation method and application thereof |
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