CN109796706A - A kind of fluorine resin mixture of poly-dopamine modified lithium and its prepreg and the copper-clad plate of preparation - Google Patents
A kind of fluorine resin mixture of poly-dopamine modified lithium and its prepreg and the copper-clad plate of preparation Download PDFInfo
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Abstract
The present invention relates to a kind of poly-dopamine (PDA) modified fluorine resin mixture and its prepreg and the copper-clad plates of preparation.The present invention modifies upper amino in inorganic filler surface, and PDA chemical bond is connected to inorganic filler surface with reacting for dopamine by amino afterwards；The present invention modifies PDA onto glass-fiber-fabric；The compatibility between inorganic filler and fluorine resin is on the one hand improved as a result, is promoted inorganic filler in the intracorporal dispersibility of fluorine resin base, is on the other hand enhanced the interaction force between inorganic filler, fluorine resin, glass-fiber-fabric and copper foil.Further, the high-frequency copper-clad plate made of the prepreg, film and copper foil, its heat-mechanical performance is good, dielectric properties are excellent, comprehensive performance stability is good, uniformity is good, and the peel strength of especially copper foil is very high, is able to satisfy every comprehensive performance requirement of the high-frequency communication field to baseplate material.
Description
Technical field
The invention belongs to communicate Material Field, and in particular to a kind of the fluorine resin mixture and its system of poly-dopamine modified lithium
Standby prepreg and copper-clad plate.
Background technique
Instantly, information electronic industries are in the high speed development stage, just gradually become one of the pillar industry of various countries.Copper-clad plate
It is one of the critical material of information electronic industries, has been widely used and be in communication base station, satellite, automatic vending machine, computer, mobile phone
To multiple fields such as wearable device, pilotless automobile, unmanned plane and the intelligent robots gradually risen.
So far, such as United States Patent (USP) US3136680, US4335180, US4849284, US5024871,
US5922453, US2539329, US4623505, US4647508, US4886699 and Chinese patent CN2014103766915,
CN201010180034 etc. is developed the preparation method of a variety of fluorine resin base copper-clad plates.Fluorine resin is peculiar because of its own
Chemical structure and possess extremely low dielectric constant and dielectric loss, high thermal stability and chemical stability, be that a kind of production is high
The ideal material of frequency copper-clad plate.However, exactly its great chemical inertness causes fluorine resin and inorganic filler, glass-fiber-fabric and copper
Interaction force between foil is not high, and temperature needed for fluorine resin base copper-clad plate lamination process is high, the time is long, production process energy
It consumes huge.Especially when preparing high dielectric constant and/or high thermal conductivity type fluorine resin base copper-clad plate, highly filled inorganic filler
The compatibility and dispersibility in copper-clad plate matrix between each material will be further decreased, dielectric properties, the heat-of copper-clad plate are caused
Apparent inhomogeneities is presented in mechanical performance and thermal expansion coefficient etc..
Modify upper coupling agent in inorganic filler, glass-fiber-fabric or copper foil surface, be it is a kind of commonly enhance they with it is fluorine-containing
The method of resin matrix interaction force.However, fluorine resin cannot generally be chemically reacted with coupling agent, therefore, it is difficult to
Chemical bond is generated between fluorine resin matrix and inorganic filler, glass-fiber-fabric or copper foil.In addition, the common alkane of common coupling agent one end
The interaction force of hydrocarbon chain and fluoro containing polymers chain is also very weak." science " magazine (Science2007,318,426.) report
A kind of substance --- poly-dopamine (PDA) that can be adsorbed rapidly and tightly by autohemagglutination on the surface of nearly all material,
Fluorine resin surface is no exception, i.e. stronger interaction can be equally formed between PDA and fluorine resin.Therefore, PDA is one
Kind is potentially effectively improved the substance of interaction force and cohesive force between each material in fluorine resin base copper-clad plate matrix.
Summary of the invention
Contain the purpose of the present invention is to provide the compatibility between a kind of inorganic filler, glass-fiber-fabric and fluorine resin is good
Fluororesin base prepreg.
That it is another object of the present invention to provide a kind of heat-mechanical performances being prepared by the prepreg is excellent,
Dielectric properties are good, the very high high-frequency copper-clad plate of peel strength of copper foil.
The present invention solve the above problems the technical solution adopted is that a kind of poly-dopamine modified lithium fluorine resin mixture system
Standby prepreg passes sequentially through following preparation step and is made:
S1, the uniform dispersion for preparing 0.1 ~ 45wt/v% inorganic filler, subsequent coupling agent of the addition with Amino End Group, 50 ~ 130
It after being stirred to react 0.5 ~ 48h at DEG C, is filtered, washed, dries inorganic filling out for the coupling agent modification for obtaining product band Amino End Group
Material, is denoted as inorganic filler-NH2；
S2, trishydroxymethylaminomethane-hydrochloric acid (Tris-HCl) buffer solution for preparing 0.1 ~ 100mg/mL dopamine then add
Enter the inorganic filler-NH of 0.1 ~ 25wt/v%2, and be dispersed with stirring uniformly under non-inert atmosphere, after impregnating 5 ~ 1440min
Through product is obtained by filtration, impregnates 5 ~ 180min in organic solvent and adhere to weaker poly-dopamine to remove, after be soaked in again
To remove the organic solvent in water, finally it is filtered, washed, dries and obtain product, i.e., surface chemistry key has connected poly- DOPA
The inorganic filler of amine is denoted as poly-dopamine@inorganic filler；
S3, glass-fiber-fabric is impregnated with trishydroxymethylaminomethane-hydrochloric acid buffer solution of 0.1 ~ 100mg/mL dopamine, in non-inert
After hanging 5 ~ 1440min in atmosphere, the glass is distributed in and impregnates 5 ~ 180min in organic solvent to remove and adhere to weaker gather
Dopamine, after be soaked in again to remove the organic solvent in water, be most dried to obtain product afterwards, i.e. the glass of poly-dopamine modification
Fine cloth is denoted as poly-dopamine-glass-fiber-fabric；
S4, the uniform dispersion that configuration solid content is 20 ~ 75wt/v% fluorine resin mixture, the fluorine resin mixture packet
Include fluorine-containing resin emulsion, poly-dopamine@inorganic filler and auxiliary material three classes component；
S5, the uniform dispersion of the fluorine resin mixture is impregnated to poly-dopamine-glass-fiber-fabric, it is toasted to be dried to obtain half admittedly
Change piece.
Further preferred technical solution is: 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、ZnZrO3, graphite oxide, fluorographite, talcum powder, mica
One of powder, kaolin, clay, solid glass micro-bead, hollow glass micropearl, glass fibre, basalt fibre and carbon fiber
Or several mixture；
Partial size≤100um of the inorganic filler, dosage account for 1 ~ 65wt% of the fluorine resin mixture；
The coupling agent with Amino End Group is silane coupling agent, titanate coupling agent, aluminate coupling agent, the zirconium that end group is amino
The mixture of one or more of acid esters coupling agent, bimetallic coupling agent and rare-earth coupling agent；
The coupling agent with Amino End Group and the mass ratio of the inorganic filler are 1:1000 ~ 100:1000；
The solvent of the uniform dispersion of the inorganic filler be can dissolving band Amino End Group coupling agent can be uniformly dispersed again it is inorganic
The mixture of one or more of the organic solvent of filler；
The moisture content > 0.1wt% of the uniform dispersion of the inorganic filler.
Further preferred technical solution is: in step S2 and S3, the trishydroxymethylaminomethane-hydrochloride buffer
Solution is the alkaline aqueous solution of pH > 7；
The organic solvent is the mixture that can dissolve one or more of solvent of poly-dopamine；
The non-inert atmosphere is the atmosphere containing oxygen, and wherein oxygen accounts for content >=3v/v% of non-inert gas；
Poly-dopamine in the poly-dopamine@inorganic filler accounts for 0.05 ~ 2.5wt% of inorganic filler quality；
Poly-dopamine in the poly-dopamine-glass-fiber-fabric accounts for 0.03 ~ 2wt% of glass-fiber-fabric quality.
Further preferred technical solution is: in step S3, the glass-fiber-fabric is 106,1080,2116 and 7628 electronics
One of grade alkali-free glass fiber cloth.
Further preferred technical solution is: in step S4, the fluorine-containing resin emulsion is polytetrafluoroethylene (PTFE), poly- perfluor
Second propylene, tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer, ethylene-tetrafluoroethylene copolymer, polytrifluorochloroethylene and second
Alkene-one or more of chlorotrifluoroethylene and its derivative mixture lotion；
The solid content of the fluorine-containing resin emulsion is 20 ~ 70wt/v%, and viscosity is 9 ~ 45mPas at 25 DEG C；
The auxiliary material is ultra high molecular weight polyethylene fiber, Kafra fiber, polyimides, polyetherimide, polysulfones, polyethers
Sulfone, polyether-ketone and one of polyphenylene sulfide and its derivative or several mixtures；
The dosage of the auxiliary material accounts for 0 ~ 20wt% of the fluorine resin mixture；
The solvent of the uniform dispersion of the fluorine resin mixture be the water that may make that the fluorine resin mixture is evenly dispersed,
The mixture of one or more of organic solvent.
Further preferred technical solution is: in step S5, the baking is dry to be divided into two stages, and the first stage dries
Roasting drying temperature is 50 ~ 120 DEG C, and the time is 3 ~ 10min, and it is 150 ~ 370 DEG C that second stage, which toasts drying temperature, the time is 5 ~
40min。
A kind of copper-clad plate of prepreg production prepared by the fluorine resin mixture using poly-dopamine modified lithium, successively leads to
It crosses following making step to be made: by the prepreg, film and being overlying on the copper foil on surface layer and be superimposed together, it is laminated to obtain covering copper
Plate, wherein number >=1 of the prepreg, number >=1 of film, the number of copper foil are 1 or 2, laminating temperature is 200 ~ 370
DEG C, lamination pressure is 50 ~ 130kg/cm2, lamination times are 30min ~ for 24 hours.
Further preferred technical solution is: the film is polyolefin, polyamide, polyimides, polyether-ketone, polyethers ether
Ketone, polycarbonate, polyphenylene sulfide, polyether sulphone, polyaryl thioether sulfone, poly(aryl ether ketone), polyarylene sulfide ketone, polyethersulfone ketone, polyarylether
Sulfone nitrile, polyphenylene quinoxaline, phenolic resin, epoxy resin, cyanate ester resin, polyurethane, polyformaldehyde, gathers polyaryl thioether sulfone nitrile
Carbonic ester, acrylonitrile-styrene-acrylic ester copolymer, acrylonitritrile-styrene resin, methacrylate-styrene are total
Polymers, acrylonitrile-butadiene-styrene copolymer, SEBS, styrene-butadiene-styrene, styrene-isoamyl two
Alkene-styrol copolymer, styrene-polyolefin-styrol copolymer, ethylene-tetrafluoroethylene copolymer, butadiene-styrene rubber, butyronitrile
The film of one of rubber and cellulose and its derivates or a variety of mixtures.
The present invention first modifies upper amino in inorganic filler surface, rear reacting PDA chemical bond by amino and dopamine
It is connected to inorganic filler surface；The present invention recycles PDA can be in the characteristic of the strong absorption in the surface of nearly all substance, by PDA
It modifies on glass-fiber-fabric, even the material surface high in fluorine resin this kind chemical inertness, PDA can equally possess good
Good cohesive force.Therefore, the compatibility between inorganic filler and fluorine resin greatly improved in one aspect of the present invention, promotes nothing
On the other hand machine filler significantly enhances inorganic filler, fluorine resin, glass-fiber-fabric and copper in the intracorporal dispersibility of fluorine resin base
Interaction force between foil.Especially when preparing prepreg and the copper-clad plate of high dielectric constant and/or high thermal conductivity,
That is the very high situation of additive amount of the inorganic filler in fluorine resin matrix, the promotion of above-mentioned performance will become more added with must
It wants.Therefore, in the present invention, with the dispersion liquid of PDA- glass-fiber-fabric dipping fluorine resin mixture, again made from toasted drying
Prepreg gel content is uniformly, impregnation quality is good, resin adhesive force is strong, surfacing, toughness and viscosity are suitable for.Further,
The high-frequency copper-clad plate made of the prepreg, film and copper foil, heat-mechanical performance is good, dielectric properties are excellent, comprehensive performance is steady
It is qualitative it is good, uniformity is good, the peel strength of especially copper foil is very high, be able to satisfy high-frequency communication field to baseplate material items it is comprehensive
Close performance requirement.
It is found by the applicant that modification amount of the PDA in inorganic filler and glass-fiber-fabric can not be very few, otherwise inorganic filler, glass
Interaction force between cloth, fluorine resin and copper foil is promoted unobvious；But the modification amount of PDA also can not be excessive, otherwise covers copper
The dielectric loss of plate will increase.
Preparation condition of the present invention is mild, production cost is low, be easy to mass and large-scale production, universality are strong, has good
Good industrialized production basis and wide application prospect.
Specific embodiment
The a kind of of offer that present invention be described in more detail by the following examples contains using poly-dopamine (PDA) is modified
The prepreg of fluoro-resin mixture production and the high-frequency copper-clad plate being prepared with the prepreg.However, the embodiment
It is merely possible to provide explanation, rather than limits the present invention.
Embodiment 1
60 parts of silica (Xinyi Hong Run) and 20 parts of aluminium oxide (Zibo perseverance nation) are evenly dispersed in 500 parts of ethyl alcohol, slowly
6 parts of 3-aminopropyltriethoxysilane (APS) are added dropwise, 60oAfter being stirred to react 6h under C, through filtering-ethanol washing-drying
And etc. product is prepared: the SiO that APS has been modified2/Al2O3Compound inorganic stuffing is denoted as " SiO2/Al2O3-NH2".In sky
Under gas atmosphere, by " SiO2/Al2O3-NH2" in Tris-HCl(pH=8.6 of 600 parts of 1.0wt% dopamines) stir in buffer solution
Mix, impregnate 30min after take out, stirred in isopropanol, impregnate 20min and adhere to weaker PDA to remove, be finally soaked in again
To remove isopropanol in water, the SiO that surface chemistry key has connected PDA has been prepared2/Al2O3Compound inorganic stuffing is denoted as " PDA@
SiO2/Al2O3".1080 glasses are distributed in Tris-HCl(pH=8.6 of 0.8wt% dopamine) impregnate 30min in buffer solution after
It takes out, impregnates 10min in isopropanol to remove and adhere to weaker PDA, be finally soaked in again to remove isopropanol in water, system
It is standby to have obtained 1080 glass-fiber-fabrics of surface modification PDA, it is denoted as " PDA-1080 glass-fiber-fabric ".Take 50 parts of ptfe emulsions
(Du Pont Teflon®PTFE DISP30, solid content 60%), 120 parts of tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymers creams
Liquid (Du Pont Teflon®PFAD 335D, solid content 60%), 40 parts of " PDA@SiO2/Al2O3" and 10 parts of polysulfones powder (BASF
Ultrason S2010), it is agitated to be mixed to get uniform dispersion, diluent water is added so that the dispersion liquid solid content control
System is in 50wt/v% or so.By " PDA&1080 glass-fiber-fabric " in the uniform dispersion of above-mentioned fluorine resin mixture impregnation, then pass through
Baking obtains prepreg.Wherein first stage baking temperature is 100oC, time 4min, second stage baking temperature are 320
DEG C, time 20min；Take 8 prepregs, 4 Du Pont Kapton®XP film and 3 Du Pont Kapton® 6051 folded films close
Together, loz copper foil is enclosed on two sides respectively, is 75 ~ 85kg/cm in vacuum, pressure2, temperature be 360 DEG C of situation laminated 10h, system
Obtain copper-clad plate.
Embodiment 2
70 parts of silica (Xinyi Hong Run) and 30 parts of aluminium oxide (Zibo perseverance nation) are evenly dispersed in 700 parts of ethyl alcohol, slowly
7.5 parts of 3-aminopropyltriethoxysilane (APS) are added dropwise, 60oIt is dry through filtering-ethanol washing-after being stirred to react 6h under C
It is dry and etc. that product is prepared: the SiO that APS has been modified2/Al2O3Compound inorganic stuffing is denoted as " SiO2/Al2O3-NH2".?
Under air atmosphere, by " SiO2/Al2O3-NH2" in Tris-HCl(pH=8.6 of 750 parts of 2.0wt% dopamines) stir in buffer solution
Mix, impregnate 45min after take out, stirred in isopropanol, impregnate 25min and adhere to weaker PDA to remove, be finally soaked in again
To remove isopropanol in water, the SiO that surface chemistry key has connected PDA has been prepared2/Al2O3Compound inorganic stuffing is denoted as " PDA@
SiO2/Al2O3".1080 glasses are distributed in Tris-HCl(pH=8.6 of 0.8wt% dopamine) impregnate 30min in buffer solution after
It takes out, impregnates 10min in isopropanol to remove and adhere to weaker PDA, be finally soaked in again to remove isopropanol in water, system
It is standby to have obtained 1080 glass-fiber-fabrics of surface modification PDA, it is denoted as " PDA&1080 glass-fiber-fabric ".Take 60 parts of ptfe emulsions
(Du Pont Teflon®PTFE DISP30, solid content 60%), 110 parts of perfluoroethylene-propylene emulsion (Du Pont Teflon®
FEPD121, solid content 54%), 50 parts of " PDA@SiO2/Al2O3" and 5 parts of polyether sulfone powder (BASF Ultrason E2010), warp
It is stirred to obtain uniform dispersion, diluent water is added so that the solid content of the dispersion liquid is controlled in 60wt/v% or so.It will
" PDA&1080 glass-fiber-fabric " carries out impregnation in the uniform dispersion of above-mentioned fluorine resin mixture, then toasted obtains semi-solid preparation
Piece.Wherein first stage baking temperature is 100 DEG C, time 5min, and second stage baking temperature is 290 DEG C, and the time is
30min；Take 8 prepregs, 7 Du Pont Kapton®F film is superimposed together, and loz copper foil is enclosed on two sides respectively, in pressure 55
~70kg/cm2, temperature be 340 DEG C of situation laminated 16h, be made copper-clad plate.
Embodiment 3
70 parts of titanium oxide (just magnificent science and technology in Tianjin) and 20 parts of aluminium oxide (Zibo perseverance nation) are dispersed in 650 parts of ethyl alcohol
In, 6.7 parts of 3-aminopropyltriethoxysilane (APS) are slowly added dropwise, 60oAfter being stirred to react 6h under C, through filtering-ethyl alcohol
Product is prepared in washing-drying and other steps: the TiO that APS has been modified2/Al2O3Compound inorganic stuffing is denoted as " TiO2/Al2O3-
NH2".In air atmosphere, by " TiO2/Al2O3-NH2" in Tris-HCl(pH=8.6 of 500 parts of 1.5wt% dopamines) and buffering it is molten
It stirs in liquid, taken out after immersion 35min, stirred in isopropanol, impregnate 20min to remove the weaker PDA of adherency, finally again
It is soaked in water and the TiO that surface chemistry key has connected PDA has been prepared to remove isopropanol2/Al2O3Compound inorganic stuffing, note
For " PDA@TiO2/Al2O3".1080 glasses are distributed in Tris-HCl(pH=8.6 of 0.8wt% dopamine) it impregnates in buffer solution
It is taken out after 30min, impregnates 10min in isopropanol to remove and adhere to weaker PDA, be finally soaked in again different to remove in water
1080 glass-fiber-fabrics of surface modification PDA have been prepared in propyl alcohol, are denoted as " PDA&1080 glass-fiber-fabric ".Take 50 parts of polytetrafluoroethyl-nes
Alkene lotion (Du Pont Teflon®PTFE DISP30, solid content 60%), the copolymerization of 60 parts of tetrafluoroethylene-perfluoro alkoxy vinyl ethers
Object lotion (Du Pont Teflon®PFAD 335D, solid content 60%), 50 parts of perfluoroethylene-propylene (Du Pont Teflon®FEPD121,
Solid content 54%), 45 parts of " PDA-TiO2/Al2O3" and 5 parts of polyether sulfone powder (BASF Ultrason E2010), agitated mixing
Uniform dispersion is obtained, diluent water is added so that the solid content of the dispersion liquid is controlled in 45wt/v% or so.By " PDA&
1080 glass-fiber-fabrics " carry out impregnation in the uniform dispersion of above-mentioned fluorine resin mixture, then toasted obtain prepreg.Its
Middle first stage baking temperature is 100 DEG C, time 4min, and second stage baking temperature is 300 DEG C, time 25min；Take 8
Open prepreg, 4 Du Pont Kapton®XP film and 3 Du Pont Kapton® 100HN film is superimposed together, and two sides is enclosed respectively
Loz copper foil is 60 ~ 70kg/cm in pressure2, temperature be 350 DEG C of situation laminated 10h, be made copper-clad plate.
Embodiment 4
40 parts of silica (Xinyi Hong Run) and 40 parts of aluminium oxide (Zibo perseverance nation) are dispersed in 500 parts of ethyl alcohol, are slowly dripped
Add 6 parts of 3-aminopropyltriethoxysilane (APS), 60oAfter being stirred to react 6h under C, through filtering-ethanol washing-drying etc.
Product is prepared in step: the SiO that APS has been modified2/Al2O3Compound inorganic stuffing is denoted as " SiO2/Al2O3-NH2".In air
Under atmosphere, by " SiO2/Al2O3-NH2" in Tris-HCl(pH=8.6 of 500 parts of 1.5wt% dopamines) stirring in buffer solution,
It is taken out after impregnating 30min, is stirred in isopropanol, impregnates 20min to remove the weaker PDA of adherency, be finally soaked in water again
In to remove isopropanol, the SiO that surface chemistry key has connected PDA has been prepared2/Al2O3Compound inorganic stuffing is denoted as " PDA-
SiO2/Al2O3".1080 glasses are distributed in Tris-HCl(pH=8.6 of 0.8wt% dopamine) impregnate 30min in buffer solution after
It takes out, impregnates 10min in isopropanol to remove and adhere to weaker PDA, be finally soaked in again to remove isopropanol in water, system
It is standby to have obtained 1080 glass-fiber-fabrics of surface modification PDA, it is denoted as " PDA&1080 glass-fiber-fabric ".Take 100 parts of ptfe emulsions
(Du Pont Teflon®PTFE DISP30, solid content 70%), 70 parts of tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer emulsions
(Du Pont Teflon®PFAD 335D, solid content 60%), 40 parts of " PDA@SiO2/Al2O3" and 10 parts of polysulfones powder (BASF
Ultrason S2010), it is agitated to be obtained by mixing uniform dispersion, by the solid content control of the dispersion liquid on the left side 55wt/v%
It is right." PDA&1080 glass-fiber-fabric " is subjected to impregnation in the uniform dispersion of above-mentioned fluorine resin mixture, then toasted is obtained
Prepreg.Wherein first stage baking temperature is 120oC, time 5min, second stage baking temperature are 300 DEG C, the time
For 30min；Take 8 prepregs, 4 Du Pont Kapton®XP film and 3 Du Pont Kapton® 6051 folded films are combined, and two
Loz copper foil is enclosed in face respectively, is 80 ~ 110kg/cm in pressure2, temperature be 360 DEG C of situation laminated 10h, be made copper-clad plate.
Embodiment 5
40 parts of titanium oxide (just magnificent science and technology in Tianjin) and 40 parts of aluminium oxide (Zibo perseverance nation) are dispersed in 500 parts of ethyl alcohol
In, 6 parts of 3-aminopropyltriethoxysilane (APS) are slowly added dropwise, 60oAfter being stirred to react 6h under C, washed through filtering-ethyl alcohol
Wash-product is prepared in drying and other steps: the TiO that APS has been modified2/Al2O3Compound inorganic stuffing is denoted as " TiO2/Al2O3-
NH2".In air atmosphere, by " TiO2/Al2O3-NH2" in Tris-HCl(pH=8.6 of 600 parts of 2.0wt% dopamines) and buffering it is molten
It stirs in liquid, taken out after immersion 40min, stirred in isopropanol, impregnate 20min to remove the weaker PDA of adherency, finally again
It is soaked in water and the TiO that surface chemistry key has connected PDA has been prepared to remove isopropanol2/Al2O3Compound inorganic stuffing, note
For " PDA@TiO2/Al2O3".1080 glasses are distributed in Tris-HCl(pH=8.6 of 0.8wt% dopamine) it impregnates in buffer solution
It is taken out after 30min, impregnates 10min in isopropanol to remove and adhere to weaker PDA, be finally soaked in again different to remove in water
1080 glass-fiber-fabrics of surface modification PDA have been prepared in propyl alcohol, are denoted as " PDA&1080 glass-fiber-fabric ".Take 80 parts of polytetrafluoroethyl-nes
Alkene lotion (Du Pont Teflon®PTFE DISP30, solid content 60%), the copolymerization of 40 parts of tetrafluoroethylene-perfluoro alkoxy vinyl ethers
Object lotion (Du Pont Teflon®PFAD 335D, solid content 60%), 40 parts of perfluoroethylene-propylene (Du Pont Teflon®FEPD121,
Solid content 54%) and 40 parts of " PDA@TiO2/Al2O3", it is agitated to be mixed to get uniform dispersion, diluent water is added so that should
The solid content of dispersion liquid is controlled in 55wt/v% or so.By " PDA&1080 glass-fiber-fabric " in the uniform of above-mentioned fluorine resin mixture
Impregnation is carried out in dispersion liquid, then toasted obtains prepreg.Wherein first stage baking temperature is 100oC, time is
10min, second stage baking temperature are 290oC, time 30min；Take 8 prepregs, 3 Du Pont Kapton®XP film and
4 Du Pont Kapton® 100HN film is superimposed together, and loz copper foil is enclosed on two sides respectively, is 75 ~ 95kg/cm in pressure2, temperature
It is 330oCopper-clad plate is made in C situation laminated 8h.
Comparative example 1
Weigh 50 parts of ptfe emulsion (Du Pont Teflon®PTFE DISP30, solid content 60%), 120 parts of tetrafluoroethene-
Perfluorinated alkoxy vinyl ether copolymer lotion (Du Pont Teflon®PFAD 335D, solid content 60%), 30 parts of silica (Xinyis
It is agitated to be obtained by mixing uniform dispersion Hong Run) with 10 parts of aluminium oxide (Zibo perseverance nation)；Diluent water is added so that this point
The solid content of dispersion liquid is controlled in 50wt/v% or so.Using 1080 glass-fiber-fabrics, in the uniform dispersion of above-mentioned fluorine resin mixture
Middle carry out impregnation, then toasted obtain prepreg.Wherein first stage baking temperature is 100oC, time 5min, second-order
Section baking temperature is 320oC, time 25min；Take 8 prepregs, 4 Du Pont Kapton®XP film and 3 Du Ponts
Kapton® 6051 folded films are combined, and loz copper foil is enclosed on two sides respectively, are 95 ~ 115kg/cm in pressure2, temperature be 380 DEG C
Copper-clad plate is made in situation laminated 12h.
Comparative example 2
Weigh 50 parts of ptfe emulsion (Du Pont Teflon®PTFE DISP30, solid content 60%), 120 parts of tetrafluoroethene-
Perfluorinated alkoxy vinyl ether copolymer lotion (Du Pont Teflon®PFAD 335D, solid content 60%), 30 parts of silica (Xinyis
Hong Run), 10 parts of aluminium oxide (Zibo perseverance nation) and 3 parts of coupling agent KH550(Nanjing Shuguang Chemical General Plant), it is agitated to be obtained by mixing
Uniform dispersion；Diluent water is added so that the solid content of the dispersion liquid is controlled in 50wt/v% or so.Using 1080 glasses
Cloth carries out impregnation in the uniform dispersion of above-mentioned fluorine resin mixture, then toasted obtains prepreg.Wherein the first rank
Section baking temperature is 100oC, time 4min, second stage baking temperature are 320oC, time 25min；Take 8 semi-solid preparations
Piece, 4 Du Pont Kapton®XP film and 3 Du Pont Kapton® 6051 folded films are combined, and loz copper foil is enclosed on two sides respectively,
It is 90 ~ 110kg/cm in pressure2, temperature be 370 situation laminated 12h, be made copper-clad plate.
Interaction force as shown in comparative example 1, in the case where coupling agent is not added, between fluorine resin and inorganic filler
It is weak, it is unfavorable for inorganic filler in the intracorporal dispersibility of fluorine resin base, the dielectric loss of copper-clad plate is caused to rise；Fluorine-containing tree at this time
The cohesive force of rouge and glass-fiber-fabric is also weaker, and spread is decreased obviously, and the flatness of prepreg and uniformity is caused to reduce, made
The standby obtained breakdown voltage of copper-clad plate, the peel strength of copper foil is declined.Comparative example 2 the results show that inorganic
Filler surface modifies upper silane coupling agent, can actually enhance its interaction force between fluorine resin, so that semi-solid preparation
Piece and the resultant performance enhancements of copper-clad plate are obvious.But from the result of embodiment 1 ~ 5, if in inorganic filler and glass-fiber-fabric table
PDA is modified in face, and the interaction force between fluorine resin, inorganic filler, glass-fiber-fabric and copper foil can further enhance, copper foil
Peel strength further increase.
Preparation condition of the present invention is mild, and production cost is low, is easy to mass, large-scale production, has good industrialization
Production basis and wide application prospect.
Above embodiments not impose any restrictions the content of composition in the present invention.All technologies according to the present invention are real
Matter or composition composition or content any subtle modifications, equivalent variations and modifications to the above embodiments still fall within this
In the range of inventive technique scheme.
Claims (8)
1. prepreg prepared by a kind of fluorine resin mixture of poly-dopamine modified lithium, it is characterised in that pass sequentially through following system
Standby step is made:
S1, the uniform dispersion for preparing 0.1 ~ 45wt/v% inorganic filler, subsequent coupling agent of the addition with Amino End Group, 50 ~ 130
It after being stirred to react 0.5 ~ 48h at DEG C, is filtered, washed, dries inorganic filling out for the coupling agent modification for obtaining product band Amino End Group
Material, is denoted as inorganic filler-NH2；
S2, prepare 0.1 ~ 100mg/mL dopamine trishydroxymethylaminomethane-hydrochloric acid buffer solution, then be added 0.1 ~
Inorganic filler-the NH of 25wt/v%2, and be dispersed with stirring uniformly under non-inert atmosphere, through filtering after 5 ~ 1440min of immersion
Obtain product, impregnate 5 ~ 180min in organic solvent to remove and adhere to weaker poly-dopamine, after be soaked in water again with
The organic solvent is removed, is finally filtered, washed, dried and obtain product, is i.e. the surface chemistry key nothing that has connected poly-dopamine
Machine filler is denoted as poly-dopamine@inorganic filler；
S3, glass-fiber-fabric is impregnated with trishydroxymethylaminomethane-hydrochloric acid buffer solution of 0.1 ~ 100mg/mL dopamine, in non-inert
After hanging 5 ~ 1440min in atmosphere, the glass is distributed in and impregnates 5 ~ 180min in organic solvent to remove and adhere to weaker gather
Dopamine, after be soaked in again to remove the organic solvent in water, be most dried to obtain product afterwards, i.e. the glass of poly-dopamine modification
Fine cloth is denoted as poly-dopamine-glass-fiber-fabric；
S4, the uniform dispersion that configuration solid content is 20 ~ 75wt/v% fluorine resin mixture, the fluorine resin mixture packet
Include fluorine-containing resin emulsion, poly-dopamine@inorganic filler and auxiliary material three classes component；
S5, the uniform dispersion of the fluorine resin mixture is impregnated to poly-dopamine-glass-fiber-fabric, it is toasted to be dried to obtain half admittedly
Change piece.
2. prepreg prepared by a kind of fluorine resin mixture of poly-dopamine modified lithium according to claim 1, special
Sign is: 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、ZnZrO3, graphite oxide, fluorographite, talcum powder, mica powder, kaolin, clay, solid glass micro-bead,
One of hollow glass micropearl, glass fibre, basalt fibre and carbon fiber or several mixtures；
Partial size≤100um of the inorganic filler, dosage account for 1 ~ 65wt% of the fluorine resin mixture；
The coupling agent with Amino End Group is silane coupling agent, titanate coupling agent, aluminate coupling agent, the zirconium that end group is amino
The mixture of one or more of acid esters coupling agent, bimetallic coupling agent and rare-earth coupling agent；
The coupling agent with Amino End Group and the mass ratio of the inorganic filler are 1:1000 ~ 100:1000；
The solvent of the uniform dispersion of the inorganic filler be can dissolving band Amino End Group coupling agent can be uniformly dispersed again it is inorganic
The mixture of one or more of the organic solvent of filler；
The moisture content > 0.1wt% of the uniform dispersion of the inorganic filler.
3. prepreg prepared by a kind of fluorine resin mixture of poly-dopamine modified lithium according to claim 1, special
Sign is: in step S2 and S3, the trishydroxymethylaminomethane-hydrochloric acid buffer solution is the alkaline aqueous solution of pH > 7；
The organic solvent is the mixture that can dissolve one or more of solvent of poly-dopamine；
The non-inert atmosphere is the atmosphere containing oxygen, and wherein oxygen accounts for content >=3v/v% of non-inert gas；
Poly-dopamine in the poly-dopamine@inorganic filler accounts for 0.05 ~ 2.5wt% of inorganic filler quality；
Poly-dopamine in the poly-dopamine-glass-fiber-fabric accounts for 0.03 ~ 2wt% of glass-fiber-fabric quality.
4. prepreg prepared by a kind of fluorine resin mixture of poly-dopamine modified lithium according to claim 1, special
Sign is: in step S3, the glass-fiber-fabric is one of 106,1080,2116 and 7628 electron level alkali-free glass fiber cloth.
5. prepreg prepared by a kind of fluorine resin mixture of poly-dopamine modified lithium according to claim 1, special
Sign is: in step S4, the fluorine-containing resin emulsion is polytetrafluoroethylene (PTFE), perfluoroethylene-propylene, tetrafluoroethylene-perfluoro alkoxy
Vinyl ether co-polymer, ethylene-tetrafluoroethylene copolymer, polytrifluorochloroethylene and ethylene-chlorotrifluoro-ethylene copolymer and its spread out
The lotion of one or more of biology mixture；
The solid content of the fluorine-containing resin emulsion is 20 ~ 70wt/v%, and viscosity is 9 ~ 45mPas at 25 DEG C；
The auxiliary material is ultra high molecular weight polyethylene fiber, Kafra fiber, polyimides, polyetherimide, polysulfones, polyethers
Sulfone, polyether-ketone and one of polyphenylene sulfide and its derivative or several mixtures；
The dosage of the auxiliary material accounts for 0 ~ 20wt% of the fluorine resin mixture；
The solvent of the uniform dispersion of the fluorine resin mixture be the water that may make that the fluorine resin mixture is evenly dispersed,
The mixture of one or more of organic solvent.
6. prepreg prepared by a kind of fluorine resin mixture of poly-dopamine modified lithium according to claim 1, special
Sign is: in step S5, the baking is dry to be divided into two stages, and it is 50 ~ 120 DEG C that the first stage, which toasts drying temperature, the time
For 3 ~ 10min, it is 150 ~ 370 DEG C that second stage, which toasts drying temperature, and the time is 5 ~ 40min.
7. a kind of prepreg prepared by the fluorine resin mixture using poly-dopamine modified lithium as described in claim 1 makes
Copper-clad plate, it is characterised in that pass sequentially through following making step be made: by the prepreg, film and the copper foil for being overlying on surface layer
It is superimposed together, it is laminated to obtain copper-clad plate, wherein number >=1 of the prepreg, number >=1 of film, the number of copper foil
It is 1 or 2, laminating temperature is 200 ~ 370 DEG C, and lamination pressure is 50 ~ 130kg/cm2, lamination times are 30min ~ for 24 hours.
8. prepreg production prepared by a kind of fluorine resin mixture of poly-dopamine modified lithium according to claim 7
Copper-clad plate, it is characterised in that: the film is polyolefin, polyamide, polyimides, polyether-ketone, polyether-ether-ketone, polycarbonate, gathers
Diphenyl sulfide, polyether sulphone, polyaryl thioether sulfone, poly(aryl ether ketone), polyarylene sulfide ketone, polyethersulfone ketone, polyether sulphone nitrile, polyaryl thioether sulfone
Nitrile, polyphenylene quinoxaline, phenolic resin, epoxy resin, cyanate ester resin, polyurethane, polyformaldehyde, polycarbonate, acrylonitrile-benzene
Vinyl-acrylate copolymer, acrylonitritrile-styrene resin, methacrylate-styrol copolymer, acrylic nitrile-butadiene two
Alkene-styrol copolymer, SEBS, styrene-butadiene-styrene, styrene-isoprene-styrene copolymer,
Styrene-polyolefin-styrol copolymer, ethylene-tetrafluoroethylene copolymer, butadiene-styrene rubber, nitrile rubber and cellulose and its
The film of one of derivative or a variety of mixtures.
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