CN106928650A - A kind of PAEK composite containing filler, sheet material and the circuit substrate containing it - Google Patents

A kind of PAEK composite containing filler, sheet material and the circuit substrate containing it Download PDF

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Publication number
CN106928650A
CN106928650A CN201511028636.8A CN201511028636A CN106928650A CN 106928650 A CN106928650 A CN 106928650A CN 201511028636 A CN201511028636 A CN 201511028636A CN 106928650 A CN106928650 A CN 106928650A
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CN
China
Prior art keywords
filler
fiber
paek
fibre
space network
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Granted
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CN201511028636.8A
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Chinese (zh)
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CN106928650B (en
Inventor
孟运东
杨中强
张艳华
方克洪
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • H—ELECTRICITY
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  • Chemical & Material Sciences (AREA)
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Abstract

The invention belongs to copper-clad plate technical field, it is related to a kind of PAEK composite containing filler, sheet material and circuit substrate.The composite containing filler includes space network material and the filler being dispersed in space network material hole, wherein, the space network material is mainly mutually overlapped or bonded and formed by PAEK fiber；The PAEK fiber it is main by selected from backbone structure containing ketonic bond and ehter bond as repeat unit Linear aromatic macromolecular compound, such as polyether-ether-ketone, polyether-ketone and polyetherketoneetherketoneketone etc., and its in modifier any one or at least two combination be obtained.The composite containing filler assigns the sheet material that obtains using it and circuit substrate has dielectric constant in X, Y-direction isotropism and low dielectric constant and dielectric loss and excellent mechanical property, proof voltage energy and processing characteristics.

Description

A kind of PAEK composite containing filler, sheet material and the circuit substrate containing it
Technical field
The invention belongs to copper-clad plate technical field, it is related to a kind of PAEK composite, piece containing filler Material and the circuit substrate containing it.
Background technology
In recent years, with the development of information communication device high performance, multifunction and networking, in order to High-speed transfer and treatment Large Copacity information, operation signal are intended to higher frequency, the frequency of use of electronic product Continued, it is desirable to which the dielectric constant of baseplate material is more and more lower, dielectric loss requirement is less and less, and It is required that the uniformity of substrate dielectric constant will get well.
At present, high-frequency high-speed circuit substrate obtains good high frequency performance using the resin of low-k, The resin of these low-ks mainly have polyphenylene oxide, cyanate, containing unsaturated double-bond only by hydrocarbon unit Thermosetting resin, polytetrafluoroethylene (PTFE) and polyimide resin that element is constituted etc..And typically use glass fibre Cloth is used as reinforcing material.But, the dielectric constant of glass fabric is minimum can only to accomplish 3.7, therefore, it is subject to The influence bigger than normal of glass fabric dielectric constant, the dielectric of the circuit substrate that resin/glass fiber cloth system makes Constant is difficult to reduce.
On the other hand, in current high-frequency circuit board, because reinforcing material is braided material so that electricity There is anisotropy in the XY directions of plane in base board, i.e., in braided material node, and braided material Dielectric properties through broadwise are different.Therefore, when high-frequency signal is transmitted on high-frequency circuit board, can be because each To dielectric properties it is different and cause that the weak degree of the signal on each circuit is different, signal transmission delay degree is not Together, stable signal transmission is ultimately resulted in go wrong.
PAEK can in atmosphere in 260 DEG C or so continuous firings, and highest can be in 310 DEG C of short time works Make, and the dielectric properties relatively stablized kept below 260 DEG C, and with rigidity and hardness be high, high temperature resistant, Outstanding chemical resistance and resistant to hydrolysis ability, at the same have high creep strength, fabulous dimensional stability, Outstanding anti-ultraviolet property, outstanding resistant to high energy radiation performance, and with low combustible, cigarette is produced in burning Few the advantages of.From performance indications, PAEK is the fabulous material of circuit substrate application aspect, but It is that PAEK is difficult to be used as epoxy resin.
The circuit substrate as reinforcing material, polyether-ether-ketone using organic fiber cloth are mentioned in CN104582254 It is applied in circuit substrate as organic fiber cloth material.Polyether-ether-ketone is in the prior art only as a kind of Dystectic material, does not embody its application advantage completely, and the circuit substrate can not solve to weave material Expect anisotropic problem.
Short glass fiber or aramid staple fiber are mixed into thermosetting tree as filler in CN102573276 In fat glue, circuit substrate making is subsequently used for, to increase the intensity of thin plate.Mentioned in the prior art by Polyether-ether-ketone does not refer to its concrete application mode and spy as a kind of possible component in thermosetting resin Point.
Also it is applied to polyether-ether-ketone as a kind of thermoplastic in template casting in CN1254512, but it is right Do not referred to directly in the method that polyether-ether-ketone is used for thin circuit substrate, and the method for being cast into thin plate Yield rate general on the implementation is very low, and the intensity of its thin plate is also bad.
The content of the invention
Based on the problem in prior art, an object of the present invention is to provide a kind of poly- aryl containing filler Ether ketone composite, the composite includes space network material and is dispersed in space network Filler in material hole.
In the present invention, the space network material is mainly mutually overlapped or glued by PAEK fiber Knot is formed；
In the present invention, the main various combination by ether and ketone group of the polyaryl ether ketone fiber is used as repetition In the Linear aromatic macromolecular compound and its modified product of unit any one or at least two group Close and be obtained.The PAEK fiber is by any one in polyether-ether-ketone, polyether-ketone and polyetherketoneetherketoneketone Plant or at least two combination is obtained, and/or by polyether-ether-ketone modifier, polyether-ketone modifier and polyether-ketone In in ether ketone ketone modifier any one or at least two combination be obtained.
In the present invention, those skilled in the art fiber-forming process can obtain according to disclosed in prior art PAEK fiber of the present invention.Exemplary fiber-forming process such as, dry spinning, wet spinning, Melt process and method of electrostatic spinning etc..
In the present invention, the modified polyetheretherketonefiber can be using the modified side of polyether-ether-ketone disclosed in prior art Method is obtained, and its main modified method has particles filled polyether-ether-ketone, polyether-ether-ketone surface modified and polymer Blending and modifying polyether-ether-ketone.The particles filled polyether-ether-ketone for example can be by adding inorganic filler, metal Powder and nano-particle are modified to it.The polyether-ether-ketone surface it is modified can by plasma method or Laser modified method is realized.Further, it is also possible to pass through to add PEI, PTFE, PES and LCP to polyethers ether Ketone carries out blending and modifying.
Additionally, polyether-ketone and polyetherketoneetherketoneketone can equally use modified similar with above-mentioned polyether-ether-ketone As method, it is only necessary to above-mentioned polyether-ether-ketone is replaced with into polyether-ketone or polyetherketoneetherketoneketone.
In the present invention, the space network material refers to that PAEK fiber mutually overlaps or bond shape Into non-woven fabrics (non-weaving cloth), can be sheet or bulk material.
PAEK fiber is mutually overlapped or bonded and forms space network material by the present invention first, and By dispersed filler in its hole.In the present invention, the composite except space network material and Outside filler, can also include other components, but its do not contain other except PAEK fibers form other The material of any existence of PAEK in addition, such as polyaryl ether ketone resin, powder, die casting Film, dispersion liquid and organic fiber cloth etc., and other kinds of resin organic fiber cloth.
The present invention uses the non-woven fabrics (non-weaving cloth) for mutually being overlapped by PAEK fiber or being bonded, Without using braided material (woven cloths), PAEK (such as organic fiber cloth or the pressure of other existences Casting film) make the PAEK composite imparting containing filler using its sheet material for obtaining there is dielectric constant to exist X, Y-direction isotropism, low dielectric constant and dielectric loss and excellent proof voltage energy and processability.
In addition, the PAEK composite containing filler also assigns sheet material following performance：
(1) assign the space network material excellent mechanical property because fiber-wall-element model is crystallized, make piece The intensity of material is higher relative to the film in prior art or die casting film strength and toughness, is not susceptible to crackle Etc. defect；
(2) because space network material has flourishing pore structure, functional filler can be uniform Respectively in hole, being uniformly distributed for filler is realized, impart sheet material specific function；
(3) because uniform filling is dispersed in hole, therefore, sheet material will not produce space, it is to avoid directly There is space and increase hygroscopic shortcoming in the sheet material obtained using PAEK fiber hot pressing；
(4) because the space network material has flourishing pore structure, more fillers can be introduced In space network material, the content of filler is remarkably improved.
In the present invention, it is preferred to, have in space network material, between PAEK fiber straight Footpath be about 0.1-60 μm (such as 5 μm, 10 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 50 μm or 60 μm) hole.Pore size in space network is impossible whole phase With, the pore diameter of the space network material refers to maximum 20 examined under a microscope The average value of pore diameter.Hole in space network is irregular shape, and the pore diameter is The diameter of the maximum spherical that be may pass through in finger-hole gap.
In the present invention, the interfibrous hole of PAEK is the open pores with extraneous intercommunication, hole Diameter has highly important influence to the processing of composite and quality.Pore diameter is bigger, and filler is easy to Into hole, be conducive to processing, but filler is excessive in hole, then can cause filling out in composite after hot pressing Material is excessively concentrated.Ratio between pore size and fibre diameter is particularly significant, preferably PAEK fiber Between pore diameter size be 0.1~30 times of PAEK fibre diameter, such as 0.2 times, 0.8 times, 3 times, 6 times, 12 times, 15 times, 19 times, 22 times, 26 times, 28 times etc..In order to be applied to conventional at present filling out Material and fiber, and processing is taken into account, a diameter of 0.1~50 μm of further preferred interfiber pore.
The diameter of PAEK fiber and the porosity of space network determine the average of interfiber pore Size.I.e. under the conditions of identical porosity, the diameter of fiber is bigger, then interfibrous pore diameter is bigger. In the present invention, the size of porosity determines the number of the filler that space network material can be accommodated. The porosity of space network material is bigger, then the filer content of composite is general higher, but porosity It is excessive, then filler distribution can be made uneven, and filler is easy to fall off in composite, reduces composite Intensity.The porosity of raw material, the space network material is selected to be preferably 40%-90% for convenience, Further preferred porosity is 50% to 85%.
In the present invention, the thickness of the space network material is bigger, and filler is well into solid netted The difficulty of structural material is bigger, and thickness is smaller, then space network material is got over to the limitation capability of filler It is weak.PAEK fibre diameter, porosity and application field are larger to the thickness effect of material, specifically Thickness requirements be determined on a case-by-case basis.It is preferred that the thickness of space network material is 10 μm -500 μm.
Preferably, a diameter of 0.01-100 μm of the PAEK fiber, such as 0.1 μm, 0.5 μm, 1μm、2μm、2.5μm、3μm、5μm、7μm、9μm、10μm、13μm、20μm、30μm、40μm、 50 μm, 60 μm, 70 μm, 80 μm or 100 μm.For the ease of the uniformity of sheet material after processing and hot pressing, It is preferred that 0.1-50 μm, the space network material that the fiber in the diameter range is made is more easy to meet above-mentioned fibre Pore diameter requirement between dimension.
Can also contain in order to reduce difficulty of processing, in the PAEK fiber compatible with PAEK Property good other polymers, it is including polystyrene, polyarylate, PEI, polyether sulfone, polysulfones, poly- Any one in alkene, polyester, makrolon, polyamidoimide, polyamide and polytetrafluoroethylene (PTFE) etc. Or at least two combination.
In the present invention, it is preferred to, additive can also be contained in the PAEK fiber, the addition The agent auxiliary agent such as including functional nano-particle and superfine fibre.
In the present invention, the space network material is mainly mutually overlapped or glued by PAEK fiber Knot is formed, it is intended that, the space network material only can mutually be overlapped or glued by PAEK fiber Knot is formed, it is also possible to contain other fibers.For example, liquid can also be contained in the space network material Brilliant polyester fiber, polyester fiber, polycarbonate, polyethylene fibre, polypropylene fibre, polyamide are fine Dimension, polyacrylonitrile fibre, polyimide fiber, polyphenylether fibre, polyphenylene sulfide fibre, polytetrafluoroethylene (PTFE) In fiber, styroflex, glass fibre, basalt fibre or carbon fiber etc. any one or at least Two kinds of combination, its shared mass ratio in space network material is less than 50%.
Preferably, in the present invention, the particle diameter of filler is less than the interfibrous pore diameter of PAEK.It is excellent Selection of land, the particle diameter D90 of filler is less than 30 μm, such as 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 7 μm, 11 μm, 15 μm, 18 μm, 21 μm, 24 μm or 27 μm, further preferred filler D50 be 0.1-5 μm, such as 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 2.5 μm, 3 μm, 4 μm or 5 μm.
Preferably, described filler is inorganic filler and/or organic filler.
Preferably, the inorganic filler is selected from carbon black, silicon powder, alundum (Al2O3), titanate, metatitanic acid Salt, titanium dioxide, draw ratio less than 20 staple glass fibre, draw ratio less than 20 quartzy chopped fiber or In metal dust etc. any one or at least two combination.
Preferably, the organic filler is selected from polyphenylene ether powder, pps powder, polyflon In powder, polyimide resin powder end or rubber particle etc. any one or at least two combination.
Preferably, described filler type be functional filler, preferably dielectric ceramics filler, heat-resistant filler, Fire-retardant filler, heat filling, conductive filler, fluorescer, UV absorbents, magnetic fillers or reactive filler In any one or at least two combination.
Preferably, the conductive filler be metal powder, draw ratio less than 20 carbon fiber it is short fibre in one kind or At least two combination.
The second object of the present invention is to provide a kind of sheet material, and the sheet material is by containing filler as described above The resin film that PAEK composite hot pressing is obtained.
By the PAEK composite hot pressing containing filler as described above, in hot pressing, particle diameter is small In pore diameter filler during sheet material is formed, can be melted or the PAEK of adhesion is fine Dimension is firmly blocked or sticked in hole, and PAEK fiber forms resin film in hot pressing, enters And obtain sheet material.
The third object of the present invention is to provide a kind of preparation method of sheet material, be the described method comprises the following steps：
(1) incorporate fillers into and constitute solid netted is mainly mutually overlapped or bonded by PAEK fiber In the hole of structural material, the PAEK composite containing filler is formed；
(2) side that the lamination formed by least one PAEK composite containing filler is passed through into hot pressing Formula obtains sheet material.
In the present invention, the space network material is mainly mutually overlapped or glued by PAEK fiber Knot is formed；
In the present invention, the main various combination by ether and ketone group of the polyaryl ether ketone fiber is used as repetition In the Linear aromatic macromolecular compound and its modified product of unit any one or at least two group Close and be obtained.Such as polyether-ether-ketone, polyether-ketone and polyetherketoneetherketoneketone etc., and its any one in modifier Or at least two combination is obtained.
In the present invention, those skilled in the art fiber-forming process can obtain according to disclosed in prior art PAEK fiber of the present invention.Exemplary fiber-forming process such as, dry spinning, wet spinning, Melt process and method of electrostatic spinning etc..
In the present invention, the modified polyetheretherketonefiber can be using the modified side of polyether-ether-ketone disclosed in prior art Method is obtained, and its main modified method has particles filled polyether-ether-ketone, polyether-ether-ketone surface modified and polymer Blending and modifying polyether-ether-ketone.The particles filled polyether-ether-ketone for example can be by adding inorganic filler, metal Powder and nano-particle are modified to it.The polyether-ether-ketone surface it is modified can by plasma method or Laser modified method is realized.Further, it is also possible to pass through to add PEI, PTFE, PES and LCP to polyethers ether Ketone carries out blending and modifying.
Additionally, polyether-ketone and polyetherketoneetherketoneketone can equally use modified similar with above-mentioned polyether-ether-ketone As method, it is only necessary to above-mentioned polyether-ether-ketone is replaced with into polyether-ketone or polyetherketoneetherketoneketone.
In the present invention, the space network material refers to that PAEK fiber mutually overlaps or bond shape Into non-woven fabrics (non-weaving cloth), can be sheet or bulk material.
PAEK fiber is mutually overlapped or bonded and forms space network material by the present invention first, and By dispersed filler in its hole.In the present invention, the composite except space network material and Outside filler, can also include other components, but its do not contain other except PAEK fibers form other The material of any existence of PAEK in addition, such as polyaryl ether ketone resin, powder, die casting Film, dispersion liquid and organic fiber cloth etc., and other kinds of resin organic fiber cloth.
The present invention uses the non-woven fabrics (non-weaving cloth) for mutually being overlapped by PAEK fiber or being bonded, Without using braided material (woven cloths), PAEK (such as organic fiber cloth or the pressure of other existences Casting film) make the PAEK composite imparting containing filler using its sheet material for obtaining there is dielectric constant to exist X, Y-direction isotropism, low dielectric constant and dielectric loss and excellent proof voltage energy and processability.
In addition, the PAEK composite containing filler also assigns sheet material following performance：
(1) assign the space network material excellent mechanical property because fiber-wall-element model is crystallized, make piece The intensity of material is higher relative to the film in prior art or die casting film strength and toughness, is not susceptible to crackle Etc. defect；
(2) because space network material has flourishing pore structure, functional filler can be uniform Respectively in hole, being uniformly distributed for filler is realized, impart sheet material specific function；
(3) because uniform filling is dispersed in hole, therefore, sheet material will not produce space, it is to avoid directly There is space and increase hygroscopic shortcoming in the sheet material obtained using PAEK fiber hot pressing；
(4) because the space network material has flourishing pore structure, more fillers can be introduced In space network material, the content of filler is remarkably improved.
In the present invention, it is preferred to, have in space network material, between PAEK fiber straight Footpath be about 0.1-60 μm (such as 5 μm, 10 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 50 μm or 60 μm) hole.Pore size in space network is impossible whole phase With, the pore diameter of the space network material refers to maximum 20 examined under a microscope The average value of pore diameter.Hole in space network is irregular shape, and the pore diameter is The diameter of the maximum spherical that be may pass through in finger-hole gap.
In the present invention, the interfibrous hole of PAEK is the open pores with extraneous intercommunication, hole Diameter has highly important influence to the processing of composite and quality.Pore diameter is bigger, and filler is easy to Into hole, be conducive to processing, but filler is excessive in hole, then can cause filling out in composite after hot pressing Material is excessively concentrated.Ratio between pore size and fibre diameter is particularly significant, preferably PAEK fiber Between pore diameter size be 0.1~30 times of PAEK fibre diameter, such as 0.2 times, 0.8 times, 3 times, 6 times, 12 times, 15 times, 19 times, 22 times, 26 times, 28 times etc..In order to be applied to conventional at present filling out Material and fiber, and processing is taken into account, a diameter of 0.1~50 μm of further preferred interfiber pore.
The diameter of PAEK fiber and the porosity of space network determine the average of interfiber pore Size.I.e. under the conditions of identical porosity, the diameter of fiber is bigger, then interfibrous pore diameter is bigger. In the present invention, the size of porosity determines the number of the filler that space network material can be accommodated. The porosity of space network material is bigger, then the filer content of composite is general higher, but porosity It is excessive, then filler distribution can be made uneven, and filler is easy to fall off in composite, reduces composite Intensity.The porosity of raw material, the space network material is selected to be preferably 40%-90% for convenience, Further preferred porosity is 50% to 85%.
In the present invention, the thickness of the space network material is bigger, and filler is well into solid netted The difficulty of structural material is bigger, and thickness is smaller, then space network material is got over to the limitation capability of filler It is weak.PAEK fibre diameter, porosity and application field are larger to the thickness effect of material, specifically Thickness requirements be determined on a case-by-case basis.It is preferred that the thickness of space network material is 10 μm -500 μm.
Preferably, a diameter of 0.01-100 μm of the PAEK fiber, such as 0.1 μm, 0.5 μm, 1μm、2μm、2.5μm、3μm、5μm、7μm、9μm、10μm、13μm、20μm、30μm、40μm、 50 μm, 60 μm, 70 μm, 80 μm or 100 μm.For the ease of the uniformity of sheet material after processing and hot pressing, It is preferred that 0.1-50 μm, the space network material that the fiber in the diameter range is made is more easy to meet above-mentioned fibre Pore diameter requirement between dimension.
Can also contain in order to reduce difficulty of processing, in the PAEK fiber compatible with PAEK Property good other polymers, it is including polystyrene, polyarylate, PEI, polyether sulfone, polysulfones, poly- In alkene, polyester, makrolon, polyamidoimide, polyamide and polytetrafluoroethylene (PTFE) any one or The combination of person at least two.
In the present invention, it is preferred to, additive can also be contained in the PAEK fiber, the addition The agent auxiliary agent such as including functional nano-particle and superfine fibre.
In the present invention, the space network material is mainly mutually overlapped or glued by PAEK fiber Knot is formed, it is intended that, the space network material only can mutually be overlapped or glued by PAEK fiber Knot is formed, it is also possible to contain other fibers.For example, liquid can also be contained in the space network material Brilliant polyester fiber, polyester fiber, polycarbonate, polyethylene fibre, polypropylene fibre, polyamide are fine Dimension, polyacrylonitrile fibre, polyimide fiber, polyphenylether fibre, polyphenylene sulfide fibre, polytetrafluoroethylene (PTFE) Any one in fiber, styroflex, glass fibre, basalt fibre or carbon fiber or at least two The combination planted, its shared mass ratio in space network material is less than 50%.
Preferably, in the present invention, the particle diameter of filler is less than the interfibrous pore diameter of PAEK.It is excellent Selection of land, the particle diameter D90 of filler is less than 30 μm, such as 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 7 μm, 11 μm, 15 μm, 18 μm, 21 μm, 24 μm or 27 μm, further preferred filler D50 be 0.1-5 μm, such as 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 2.5 μm, 3 μm, 4 μm or 5 μm.
Preferably, described filler is inorganic filler and/or organic filler.
Preferably, the inorganic filler is selected from carbon black, silicon powder, alundum (Al2O3), titanate, metatitanic acid Salt, titanium dioxide, draw ratio less than 20 staple glass fibre, draw ratio less than 20 quartzy chopped fiber or In metal dust any one or at least two combination.
Preferably, the organic filler is selected from polyphenylene ether powder, pps powder, polyflon In powder, polyimide resin powder end or rubber particle etc. any one or at least two combination.
Preferably, described filler type be functional filler, preferably dielectric ceramics filler, heat-resistant filler, Fire-retardant filler, heat filling, conductive filler, fluorescer, UV absorbents, magnetic fillers or reactive filler In any one or at least two combination.
Preferably, the conductive filler be metal powder, draw ratio less than 20 carbon fiber it is short fibre in one kind or At least two combination.
Preferably, filler is pre-dispersed in mounting medium, then is introduced into space network material Hole in.
Preferably, the mounting medium is liquid flux and optionally auxiliary agent.
Preferably, the liquid flux be water, halogenated hydrocarbon solvent, halogenated phenols solvent, ether solvents, ketone solvent, Ester solvent, carbonate solvent, amine solvent, nitrogenous heterocyclic aromatic compounds solvent, nitrile solvent, acid amides are molten Appointing in agent, carbamide compound solvent, nitro compound solvent, sulphur compound solvent or phosphorus compound solvent etc. Meaning it is a kind of or at least two combinations.
Preferably, the auxiliary agent is used to disperse and stablize filler, and auxiliary agent includes coupling agent, dispersant or surface In tension force inorganic agent etc. any one or at least two combination.
Preferably, the mounting medium can also be gas.
Preferably, the gas is including air, nitrogen, carbon dioxide or inert gas etc..
Preferably, the solid netted knot for mainly mutually being overlapped by PAEK fiber and being constituted is incorporated fillers into Method in the hole of structure material includes：Extrusion, infusion process, ultrasonic method, vacuum decompression method, gunite Or in dynamic negative-pressure method etc. any one or at least two combination.Various action intensities are so that stereoscopic graticule Shape structural material is broken or damaged for the upper limit.
In the present invention, various incorporating fillers into mainly mutually is overlapped constitute vertical by PAEK fiber The action intensity in method in the hole of body mesh material is so that space network Materials Fracture or broken It is the upper limit to damage.
Preferably, the extrusion refers to space network material under some tension effect with roll shaft or Other objects contact, or space network material the mutual extruding of two or more quantity object it Between, cause space network material to be squeezed power, its mesopore is produced with the external world in extrusion process Pressure differential, pressure differential promotes the filler near space network material to enter in hole.
In the present invention, the infusion process, refers to be pre-dispersed in filler to form filler point in mounting medium Dispersion liquid, the mounting medium is liquid flux and optionally auxiliary agent, then soaks space network material In stain filler dispersion liquid, so that filler is introduced into hole in the diffusion process of mounting medium.
In the present invention, the ultrasonic method, refer to by space network material impregnate filler dispersion liquid in, And it is aided with ultrasound, further promote filler to be introduced into hole in the diffusion process of mounting medium.
In the present invention, the vacuum decompression method, refers to place filler or to fill out in the side of stereo net material The dispersion liquid of material, opposite side applying vacuum decompression, make material both sides produce pressure differential, promote filler or Filler dispersion liquid moves to opposite side by side, so that filler enters in hole.
In the present invention, the gunite, the one or both sides injection for being directed to space network material is filled out Material or filler dispersion liquid, make filler enter in material hole.
In the present invention, the dynamic negative-pressure method, refers to apply one in the one or both sides of stereo net material Determine the hydraulic pressure or air pressure change of frequency change, so that dynamic pressure differential is produced with extraneous in material hole, Filler or filler dispersion liquid is promoted to enter in hole.
Preferably, when mounting medium is liquid flux and optional auxiliary agent, methods described is additionally included in heat Before pressure the step of removal liquid flux.
By the way of the removal liquid flux is typically using being heat-treated, it is molten that the temperature of heat treatment is preferably greater than liquid The boiling point of agent；When heat treatment temperature is less than 220 DEG C, convection oven or heat radiation baking oven can be used, work as heat When treatment temperature is more than 220 DEG C, vacuum drying oven need to be used, or in the inert gas environments such as nitrogen at heating Reason.Heat treatment time need to meet following condition：Material after heat treatment more than 20 DEG C of liquid adjuvants boiling point with On temperature drying 1h, its weightlessness be less than 3%.In order to further avoid for fugitive constituent introducing sheet material or circuit It is preferably weightless to be less than 1% in substrate.
Preferably, methods described is additionally included in before hot pressing the step of the filler for removing space network material surface Suddenly.
The treatment for removing surface filler of the present invention can be before or after liquid flux be removed.Removing liquid Before body solvent, the filler dispersion liquid of space network material surface can be scraped off using scraper or folder axle.Removing After removing liquid flux, the filler on surface can be removed using beating or by the way of striking off.Removing the filler on surface is In order that the fiber of space network material is exposed come, to ensure to have preferably between lamination during hot pressing Bonding force.
In the present invention, the purpose of hot pressing is to make PAEK fibers melt or semi-molten, so that poly- aryl Ether ketone fibers melt is sticked together.In hot pressing, the filler in hole is forming the process of sheet material In, can be melted or adhesion PAEK fiber cladding, block or stick to resin.
The mode of hot pressing of the present invention, refers to the lamination by individual or multiple composites for containing filler Hot pressing obtains sheet material in being placed on hot press.Hot pressing temperature be 250 DEG C~450 DEG C, such as 270 DEG C, 290 DEG C, 310 DEG C, 330 DEG C, 350 DEG C, 370 DEG C, 390 DEG C, 410 DEG C or 430 DEG C, preferably 300 DEG C~380 DEG C.Heat Pressure pressure be 2MPa~20MPa, such as 3MPa, 5MPa, 7MPa, 9MPa, 11MPa, 13MPa, 15MPa, 17MPa or 19MPa, preferably 6MPa~11MPa.
Hot pressing of the present invention, it is also possible to refer to the PAEK composite wood that individual or multiple are contained into filler What material was formed is stacked on carries out hot-pressing processing on high temperature roll squeezer, obtain sheet material.
Hot pressing temperature be 250 DEG C~450 DEG C, such as 270 DEG C, 290 DEG C, 310 DEG C, 330 DEG C, 350 DEG C, 370 DEG C, 390 DEG C, 410 DEG C or 430 DEG C, preferably 300 DEG C~380 DEG C, hot pressing pressure is generally 8-18kN, preferably 10-15kN.Can be to lamination embryo material preheating before high temperature roll squeezer hot-pressing processing, 160 DEG C of preheating temperature is extremely 280 DEG C, can be further heat-treated after hot-pressing processing, 160 DEG C to 340 DEG C of heat treatment temperature.
Can be used PI films or nitrogen to be protected in hot pressing and front and rear processing procedure, prevent Copper Foil from aoxidizing.
Mould release membrance need to be used in hot pressing, the temperature in use of the mould release membrance should be greater than actual hot pressing temperature, with Prevent from being bonded between the space network material containing filler, polluted product.Mould release membrance can use glass fibre The enhanced tenon sheet of cloth or surface scribble metal foil or plate of the high temperature mould release such as silicone grease etc..
The fourth object of the present invention is to provide a kind of circuit substrate, i.e., at least one poly- aryl containing filler Conductive film is covered in the one or both sides of the lamination of ether ketone composite or sheet material composition, and then hot pressing is obtained together.
In the hot pressing of circuit substrate of the present invention, according to actual needs, can be inserted among lamination Enhancement layer and/or tack coat.
The enhancement layer is including inorfil cloth, inorganic fibre paper, by inorfil cloth impregnating resin composition The prepreg of preparation, the prepreg, ceramic wafer, the gold that are prepared by inorganic fibre paper impregnating resin composition Belong to the combination of one or more in film or thin plate of plate etc..
The tack coat includes that the thermosetting resin film not being fully cured, melt temperature are less than the heat of hot pressing temperature Plastic resin film or toner etc..
Conductive film of the present invention, including Copper Foil, aluminium foil, silver foil, goldleaf or electrically conductive high score Sub- film etc..
When only simultaneously conductive film is covered in lamination, another side needs to cover mould release membrance.Using for mould release membrance is warm Degree should be greater than actual hot pressing temperature.
Compared with the prior art, the present invention has the advantages that：
The present invention is formed by using to be dispersed in filler mainly mutually to be overlapped or bonded by PAEK fiber Space network material in, without using braided material (woven cloths), other existences poly- aryl Ether ketone (such as die casting film or organic fiber cloth), is assigned the PAEK composite containing filler and is obtained using it To sheet material have dielectric constant in X, Y-direction isotropism, low dielectric constant and dielectric loss and Excellent proof voltage energy and processability.
In addition, the PAEK composite containing filler also assigns sheet material and circuit substrate is as follows Performance：
(1) assign the space network material excellent mechanical property because fiber-wall-element model is crystallized, make piece The intensity of material is higher relative to the film in prior art or die casting film strength and toughness, is not susceptible to crackle Etc. defect；For example the tensile strength of polyether-ether-ketone resin film is 80MPa, and by the polyethers of oriented crystalline The tensile strength of ether ketone fiber is then more than 200MPa.Therefore the tensile strength ratio of PAEK bonded fabric product Film class intensity and toughness are higher；
(2) because space network material has flourishing pore structure, functional filler can be uniform Respectively in hole, being uniformly distributed for filler is realized, impart sheet material specific function；
(3) because uniform filling is dispersed in hole, therefore, sheet material will not produce space, it is to avoid directly There is space and increase hygroscopic shortcoming in the sheet material obtained using PAEK fiber hot pressing；
(4) because the space network material has flourishing pore structure, more fillers can be introduced In space network material, the content of filler is remarkably improved.
(5) compared with the mixture for directly using resin and filler, due to the surface area of PAEK fiber More greatly, the heating surface area therefore in hot pressing is big, easily melting, makes it easier for being bonded with metal foil such as Copper Foil, The adhesion of circuit substrate is improve, peel strength can reach more than 0.6N/mm.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Preparation example
Polyether-ether-ketone non-woven fabrics is prepared using meltblown.Use single axle extruding machine (bore 30mm, L/D=24) Being imported after polyether-ether-ketone resin (Solvay, KetaSpire KT-810) is melted, there is flow to adjust knot The special dies of structure and heating air guiding structure, spinning-nozzle then from mould (has 10 circles Molten resin discharge hole (400 μm of internal diameter) and slit-shaped gas discharge hole (1mm wide), these melt Melt resin discharge hole is formed a line with the effective width of 5cm, and the gas discharge Kong Nengyu orientations are flat Heating air is sprayed capablely, so as to apply tensile stress to molten resin.) middle ejection, stretch and form fiber. And collect on the surface of film-like substrate the fiber, form that width is about 5cm treats dressed nonwoven fabrics.Then This is treated into dressed nonwoven fabrics by between a pair of heating rollers being made up of metallic roll and rubber rollers, so that it is received Turn into the non-woven fabrics of specific thicknesses to hot pressing.
The fineness of fiber is adjusted by the flow for adjusting the heating air in gas discharge hole, is collected by adjusting The translational speed of the film-like substrate of fiber adjusts the substance of non-woven fabrics, by adjusting temperature, pressure during hot pressing Power and two roller gaps adjust the thickness of non-woven fabrics.So as to obtain the non-woven fabrics of following corresponding index.
(avarage fiber diameter is 3 μm to polyether-ether-ketone non-woven fabrics, and substance is 40g/m2, 100 μm of thickness, Porosity is about 70%, and interfiber pore diameter is about 14 μm)
(avarage fiber diameter is 3 μm to polyether-ether-ketone non-woven fabrics, and substance is 40g/m2, 100 μm of thickness, Porosity is about 70%, and interfiber pore diameter is about 14 μm)
(avarage fiber diameter is 7 μm to polyether-ether-ketone non-woven fabrics, and substance is 40g/m2, 100 μm of thickness, Porosity is about 70%, and interfiber pore diameter is about 30 μm)
(avarage fiber diameter is 3 μm to polyether-ether-ketone non-woven fabrics, and substance is 18g/m2, 150 μm of thickness, Porosity is about 92%, and interfiber pore diameter is about 70 μm)
(avarage fiber diameter is 3 μm to polyether-ether-ketone non-woven fabrics, and substance is 40g/m2, 35 μm of thickness, hole Gap rate is about 17%, and interfiber pore diameter is about 0.1 μm)
(avarage fiber diameter is 45 μm to polyether-ether-ketone non-woven fabrics, and substance is 115g/m2, 220 μm of thickness, Porosity is about 60%, and interfiber pore diameter is about 50 μm)；
(avarage fiber diameter is 0.5 μm to polyether-ether-ketone non-woven fabrics, and substance is 16g/m2, 50 μm of thickness, Porosity is about 75%, and interfiber pore diameter is about 8 μm)；
Embodiment 1
By the polyether-ether-ketone non-woven fabrics of sheet, (avarage fiber diameter is 3 μm, and substance is 40g/m2, thickness 100 μm, porosity is about 70%, and interfiber pore diameter is about 14 μm), in ball-shaped silicon micro powder slurry (ball Type silicon powder particle diameter D90 is 3 μm, and D50 is about 1 μm, and slurry is 70% butanone suspension) middle leaching Stain, then by the gap of 0.15mm, scrapes off surface size, dries and removes solvent, then infiltrates again, leads to Cross gap and dry and remove solvent, repeatedly for three times.The non-woven fabrics of slurry will be impregnated with convection oven in 155 DEG C 5min is dried, the non-woven fabrics that will be dried is patted, and removes the filler on surface, obtain the polyether-ether-ketone containing filler and be combined Material.Then by 6 polyether-ether-ketone composite material laminations containing filler, two sides is coated with 35 μ of mould release M Copper Foils (Copper Foil light facing to non-woven fabrics) as mould release membrance, in 360 DEG C, under vacuum environment, in electric heating Hot pressing 1h in press, pressure is 8MPa, obtains the polyether-ether-ketone resin sheet material containing filler.
Comparative example 1
With extruder, by polyether-ether-ketone resin (commercially available) and ball-shaped silicon micro powder, (ball-type silicon powder particle diameter D90 is 3 μm, D50 is about 1 μm, powder) well mixed, about 370 DEG C of processing temperature, mixed proportion is 4:6. Then mixture tiling is put into hot press, surrounding places the thick epoxy resin glass-fiber-plates of 0.4mm to be used to limit Thickness, two sides is coated with 35 μm of Copper Foils (Copper Foil light facing to non-woven fabrics) of mould release as mould release membrance, in 360 DEG C, under vacuum environment, the hot pressing 1h in electric heating press, pressure is 8MPa, obtains the polyethers containing filler Ether ketone sheet material.
Comparative example 2
By 6 polyether-ether-ketone non-woven fabrics of sheet, (avarage fiber diameter is 3 μm, and substance is 40g/m2, it is thick 100 μm of degree, porosity is about 70%, and interfiber pore diameter is about 14 μm) lamination, two sides is coated with 35 μm of Copper Foils (Copper Foil light facing to non-woven fabrics) of mould release as mould release membrance, in 360 DEG C, vacuum ring Under border, the hot pressing 1h in electric heating press, pressure is 8MPa, obtains the polyether-ether-ketone sheet material without filler.
Comparative example 3
A kind of polyether-ether-ketone sheet material containing the short fibre of glass fibre.Preparation method is identical with comparative example 1, but will Ball-shaped silicon micro powder replace with glass fibre it is short it is fine (fibre diameter is 7 μm, and 10) draw ratio is about, resin with The short fine mixed proportion of glass fibre is 10:1.
Embodiment 2
A square box is made, is opened wide above box, a suction pipe, suction pipe connection vacuum are connected in side Pump.By the polyether-ether-ketone non-woven fabrics of sheet, (avarage fiber diameter is 7 μm, and substance is 40g/m2, thickness 100 μm, porosity is about 70%, and interfiber pore diameter is about 30 μm) box top is placed on, and will Non-woven fabrics is fully contacted with the edge of box opening, then by glass fibre it is short it is fine (fibre diameter is 7 μm, The aqueous dispersions that 10) draw ratio is about are drenched on non-woven fabrics, open vavuum pump, and persistently spread glass fibre Short fine dispersion liquid.After spreading 1min, vavuum pump is closed, scrape off the short fibre of nonwoven surface, in 160 DEG C of bakings Dry 30min, then faces up the another of non-woven fabrics, repeats above-mentioned to spread dispersion liquid and drying operation. The non-woven fabrics of drying is patted, the filler on surface is removed, the polyether-ether-ketone composite material containing filler is obtained.So The polyether-ether-ketone composite material lamination containing filler after 6 are processed afterwards, two sides is coated with 35 μ of mould release M Copper Foils (Copper Foil light facing to non-woven fabrics) as mould release membrance, in 360 DEG C, under vacuum environment, in electric heating Hot pressing 1h in press, pressure is 6MPa, is obtained containing the short fine polyether-ether-ketone sheet material of glass fibre.
Embodiment 3
Polyether-ether-ketone circuit substrate containing filler.The preparation method and reality of the polyether-ether-ketone composite material containing filler Apply example 1 identical, then by 6 polyether-ether-ketone composite material laminations, 18 μm of Copper Foils (Copper Foil hair is covered on two sides Facing to composite), in 360 DEG C, under vacuum environment, the hot pressing 1h in electric heating press, pressure is 6MPa, Obtain the polyether-ether-ketone circuit substrate containing filler.
Embodiment 4
Polyether-ether-ketone circuit substrate containing filler, preparation method is same as Example 3, but by embodiment 3 Ball-shaped silicon micro powder slurry replace with dispersion liquid of the barium titanate in EGME (barium titanate D90 be about 3 μm, D50 is about 2 μm, and 80%) solid content is.
Embodiment 5
By the polyether-ether-ketone resin non-woven fabrics of sheet, (avarage fiber diameter is 3 μm, and substance is 40g/m2, it is thick 100 μm of degree, porosity is about 70%, and interfiber pore diameter is about 14 μm) even up, and horizontal positioned. Barium titanate powder (barium titanate D90 is about 3 μm, and D50 is about 2 μm) is uniformly sprinkled upon on non-woven fabrics, And ceaselessly shake non-woven fabrics.Then non-woven fabrics top and bottom are exchanged, and barium titanate powder is uniformly sprinkled with again, and Shake non-woven fabrics.After clapping except surface filler powder, by 3 polyether-ether-ketone composite material laminations containing filler, 18 μm of Copper Foils are covered on two sides, and in 350 DEG C, under vacuum environment, the hot pressing 1h in electric heating press is obtained containing and filled out The polyether-ether-ketone resin circuit substrate of material.
Embodiment 6
Polyether-ether-ketone sheet material containing filler, preparation method is same as Example 1, but by the piece in embodiment 1 Shape polyether-ether-ketone resin non-woven fabrics replaces with porosity non-woven fabrics higher, and (avarage fiber diameter is 3 μm, single Weight is 18g/m2, 150 μm of thickness, porosity is about 92%, and interfiber pore diameter is about 70 μm).
Embodiment 7
Polyether-ether-ketone resin sheet material containing filler, preparation method is same as Example 1, but by embodiment 1 Sheet polyether-ether-ketone resin non-woven fabrics replace with the relatively low non-woven fabrics of porosity (avarage fiber diameter be 3 μ M, substance is 40g/m2, 35 μm of thickness, porosity is about 17%, and interfiber pore diameter is about 0.1 μ m).Non-woven fabrics used is that appropriate hot pressing is obtained in electric heating press by the polyether-ether-ketone non-woven fabrics in embodiment 1. Embodiment 8
Polyether-ether-ketone sheet material containing filler, preparation method is same as Example 1, but by the piece in embodiment 1 Shape polyether-ether-ketone non-woven fabrics replaces with polyether-ether-ketone non-woven fabrics, and (avarage fiber diameter is 45 μm, and substance is 115g/m2, 220 μm of thickness, porosity is about 60%, and interfiber pore diameter is about 50 μm)；By ball Shape silicon powder slurry replace with melting silicon powder slurry (molten silicon grain size of micropowder D90 is about 20 μm, D50 About 5 μm, slurry is 75% butanone suspension)；Lamination during by hot pressing is changed to 2 layers of polyethers containing filler Ether ketone composite.
Embodiment 9
Polyether-ether-ketone sheet material containing filler, preparation method is same as Example 1, but by the piece in embodiment 1 Shape polyether-ether-ketone non-woven fabrics replaces with polyether-ether-ketone non-woven fabrics, and (avarage fiber diameter is 0.8 μm, and substance is 16g/m2, 50 μm of thickness, porosity is about 75%, and interfiber pore diameter is about 8 μm)；By spherical silicon Micro mist slurry replaces with the lower slurry of solid content, and (ball-type silicon powder particle diameter D90 is about 3 μm, and D50 is about It it is 1 μm, slurry is 45% butanone suspension)；Lamination during by hot pressing is changed to 10 layers of polyethers containing filler Ether ketone composite.
The performance of each embodiment and comparative example see the table below shown.
Table 1
Continued 1
In above-described embodiment and comparative example, preferably, filer content is high for the sheet material dielectric properties of the gained of embodiment 1, And be evenly distributed, cross section tight etc., preferably, water absorption rate is very low for tensile strength.Embodiment 3 is and reality The corresponding circuit substrate of example 1 is applied, performance is close with embodiment 1, and its peel strength reaches 0.8N/mm, meets the demand of circuit substrate.
Comparative example 1 is that compressing tablet is obtained resin sheet after mixing resin and filler, and the sheet material time is apparent poor, There is crack defect, tensile strength is very low.Non-woven fabrics hot pressing is obtained resin sheet by comparative example 2 for direct, Its dielectric properties and tensile strength preferably, but due in hot pressing fiber cannot melted completely, cause There is substantial amounts of space inside sheet material, the water absorption rate in test is higher.
Comparative example 3 is using resin sheet, embodiment obtained in compressing tablet after the short fine mixing of resin and glass fibre 2 is that the inventive method is obtained and the component identical sheet material of comparative example 3.Result shows, the secondary table of comparative example 3 Sight is poor, there is the defects such as crackle, and the tensile strength of embodiment 2 is far above comparative example 3.
Dielectric ceramics filler barium titanate is used in embodiment 4 and embodiment 5, properties are preferable, and Sheet material and circuit substrate high-k are assigned, capacitor can be met, the application demands such as capacitive circuit are buried.It is real Apply and used the excessive or too small non-woven fabrics of porosity, the obtained sheet of embodiment 6 respectively in example 6 and embodiment 7 The filer content of material is very high, but lacks the support of resin, and sheet material is frangible, easy dry linting.The hole of embodiment 7 Smaller, so that filler cannot be introduced into inside non-woven fabrics, the filer content of resulting sheet is very low, and almost divides Cloth is in the top layer of non-woven fabrics, skewness, therefore preferable porosity 40% to 90%
Sheet structure prepared by embodiment 8 and embodiment 9 is complete, and defect is less, and dielectric properties and stretching are strong Spend.
The method of testing of above characteristic is as follows：
(1) thickness of dielectric layers：With the thickness of miking insulating barrier (if circuit substrate, by Copper Foil Etch away).
(2) peel strength：With reference to IPC-TM-6502.4.8 measurement of test method, test condition is normality.
(3) dielectric constant of 5GHz, dielectric loss angle tangent：With reference to IPC-TM-6502.5.5.9 experiments Method tests capacity plate antenna method.
(4) section space：Sheet material cross-sectional slices are observed using SEM, is in observation sample It is no to there is space.
(5) dry linting rate：Composite sample that size is 100mm*100mm is taken (without Copper Foil, or by copper After paper tinsel etching), on a piece of smooth A4 paper, it is size that above-mentioned composite sample is cut out The strip of 10mm*100mm, then picks up bar samples, measures drop powder or disintegrating slag on A4 paper Quality and former composite sample mass ratio.
(6) it is secondary apparent：Visually observe apparent after Copper Foil etching.
(7) filer content：By mass change of the space network material before and after filler is added, calculating is filled out Material quality proportion in the composite, as filer content.
(8) tensile strength：Tensile strength test, Sample Width 15mm, folder are carried out using Material Testing Machine Head is apart from 50.8mm, speed of experiment 12.5mm/min.
(9) water absorption rate：The composite sample of 100mm*100mm (without Copper Foil, or Copper Foil is etched 24h in 25 DEG C of water is immersed in afterwards), the water stain of wipe samples surface is then taken out, then determination sample leaching Ratio between the difference and proper mass of the quality before and after bubble.
Applicant states that the present invention illustrates method detailed of the invention, but the present invention by above-described embodiment Above-mentioned method detailed is not limited to, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement. Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, to each original of product of the present invention Addition, selection of concrete mode of the equivalence replacement and auxiliary element of material etc., all fall within protection model of the invention Within the scope of enclosing and disclosing.

Claims (10)

1. a kind of PAEK composite containing filler, the composite includes space network material Expect and be dispersed in the filler in space network material hole, wherein, the space network material Mainly mutually overlapped or bonded by PAEK fiber and formed；The PAEK fiber is main by being selected from In backbone structure containing ketonic bond and ehter bond as repeat unit Linear aromatic macromolecular compound.
2. composite as claimed in claim 1, it is characterised in that the PAEK fiber is by gathering In ether ether ketone, polyether-ketone and polyetherketoneetherketoneketone any one or at least two combination be obtained, and/or By any one in polyether-ether-ketone modifier, polyether-ketone modifier and polyetherketoneetherketoneketone modifier or The combination of person at least two is obtained；
Preferably, in space network material, 0.1-60 μm is about with diameter between PAEK fiber Hole, there is between further preferred fiber a diameter of 0.1-50 μm of hole；
Preferably, in space network material, PAEK interfiber pore diameter is poly- virtue 0.1~30 times of base ether ketone fibre diameter；
Preferably, PAEK fibre diameter is 0.01-100 μm, preferably 0.1-50 μm；
Preferably, the particle diameter of filler is less than the interfibrous pore diameter of PAEK；
Preferably, the particle diameter D90 of filler is less than 30 μm, and the D50 of preferred filler is 0.1~5m；
Preferably, the porosity of the space network material is 40% to 90%, further preferred hole Rate is 50% to 85%.
3. composite as claimed in claim 1 or 2, it is characterised in that the PAEK fiber In also containing polystyrene, polyarylate, PEI, polyether sulfone, polysulfones, polyolefin, polyester, poly- In carbonic ester, polyamidoimide, polyamide and polytetrafluoroethylene (PTFE) any one or at least two group Close；
Preferably, liquid crystalline polyester fiber, polyester fiber, poly- carbon are also contained in the space network material Acid esters fiber, polyethylene fibre, polypropylene fibre, Fypro, polyacrylonitrile fibre, polyimides Fiber, polyphenylether fibre, polyphenylene sulfide fibre, polytetrafluoroethylene fibre, styroflex, glass fibers In dimension, basalt fibre or carbon fiber any one or at least two combination, it is in space network Shared mass ratio is less than 50% in material；
Preferably, described filler is inorganic filler and/or organic filler；
Preferably, the inorganic filler is selected from carbon black, silicon powder, alundum (Al2O3), titanate, metatitanic acid Salt, titanium dioxide, draw ratio less than 20 staple glass fibre, draw ratio less than 20 quartzy chopped fiber, Carbon fiber of the draw ratio less than 20 be short fine or metal dust in any one or at least two combination；
Preferably, the organic filler is selected from polyphenylene ether powder, pps powder, polyflon Powder, polyimide resin powder end or rubber particle in any one or at least two combination；
Preferably, described filler type be functional filler, preferably dielectric ceramics filler, heat-resistant filler, Fire-retardant filler, heat filling, conductive filler, fluorescer, UV absorbents, magnetic fillers or reactive filler In any one or at least two combination；
Preferably, the conductive filler be metal powder, draw ratio less than 20 carbon fiber it is short fibre in one kind or At least two combination.
4. a kind of sheet material, the sheet material be as at least one as described in one of claim 1-3 containing filler The resin film that PAEK composite hot pressing is obtained.
5. a kind of preparation method of sheet material as claimed in claim 4, the described method comprises the following steps：
(1) incorporate fillers into and constitute solid netted is mainly mutually overlapped or bonded by PAEK fiber In the hole of structural material, the PAEK composite containing filler is formed；
(2) side that the lamination formed by least one PAEK composite containing filler is passed through into hot pressing Formula obtains sheet material.
6. method as claimed in claim 5, it is characterised in that in space network material, gathers virtue It is about with diameter between base ether ketone fiber between 0.1-60 μm of hole, further preferred fiber with a diameter of 0.1-50 μm of hole；
Preferably, in space network material, PAEK interfiber pore diameter is poly- virtue 0.1~30 times of base ether ketone fibre diameter；
Preferably, PAEK fibre diameter is 0.01-100 μm, preferably 0.1-50 μm；
Preferably, the particle diameter of filler is less than the interfibrous pore diameter of PAEK；
Preferably, the particle diameter D90 of filler is less than 30 μm, and the D50 of preferred filler is 0.1-5 μm；
Preferably, the porosity of the space network material is 40% to 90%, further preferred hole Rate is 50% to 85%.
7. the method as described in claim 5 or 6, it is characterised in that in the PAEK fiber also Contain polystyrene, polyarylate, PEI, polyether sulfone, polysulfones, polyolefin, polyester, poly- carbonic acid In ester, polyamidoimide, polyamide and polytetrafluoroethylene (PTFE) any one or at least two combination；
Preferably, liquid crystalline polyester fiber, polyester fiber, poly- carbon are also contained in the space network material Acid esters fiber, polyethylene fibre, polypropylene fibre, Fypro, polyacrylonitrile fibre, polyimides Fiber, polyphenylether fibre, polyphenylene sulfide fibre, polytetrafluoroethylene fibre, styroflex, glass fibers In dimension, basalt fibre or carbon fiber any one or at least two combination, it is in space network Shared mass ratio is less than 50% in material；
Preferably, described filler is inorganic filler and/or organic filler；
Preferably, the inorganic filler is selected from carbon black, silicon powder, alundum (Al2O3), titanate, metatitanic acid Salt, titanium dioxide, draw ratio less than 20 staple glass fibre, draw ratio less than 20 quartzy chopped fiber, Carbon fiber of the draw ratio less than 20 be short fine or metal dust in any one or at least two combination；
Preferably, the organic filler is selected from polyphenylene ether powder, pps powder, polyflon Powder, polyimide resin powder end or rubber particle in any one or at least two combination；
Preferably, described filler type be functional filler, preferably dielectric ceramics filler, heat-resistant filler, Fire-retardant filler, heat filling, conductive filler, fluorescer, UV absorbents, magnetic fillers or reactive filler In any one or at least two combination.
8. the method as described in one of claim 5-7, it is characterised in that filler is pre-dispersed in carrier In medium, then it is introduced into the hole of space network material；
Preferably, the mounting medium is liquid flux and optionally auxiliary agent；
Preferably, the liquid flux be water, halogenated hydrocarbon solvent, halogenated phenols solvent, ether solvents, ketone solvent, Ester solvent, carbonate solvent, amine solvent, nitrogenous heterocyclic aromatic compounds solvent, nitrile solvent, acid amides are molten It is any in agent, carbamide compound solvent, nitro compound solvent, sulphur compound solvent or phosphorus compound solvent It is a kind of or at least two combination；
Preferably, combination of the auxiliary agent including any one in coupling agent, dispersant or at least two；
Preferably, the mounting medium is gas；
Preferably, the gas includes air, nitrogen, carbon dioxide or inert gas；
Preferably, the solid netted knot for mainly mutually being overlapped by PAEK fiber and being constituted is incorporated fillers into Method in the hole of structure material includes：Extrusion, infusion process, ultrasonic method, vacuum decompression method, gunite Or in dynamic negative-pressure method any one or at least two combination；
Preferably, when mounting medium is liquid flux and optional auxiliary agent, methods described is additionally included in heat Before pressure the step of removal liquid flux；
Preferably, methods described also includes：The filler of space network material surface is removed before hot pressing Step.
9. the method as described in one of claim 5-8, it is characterised in that the mode of the hot pressing, refer to The lamination that the composite for containing filler by least is formed is placed on hot pressing in the hot press for heating up and down；
Preferably, hot pressing temperature is 250 DEG C~450 DEG C, preferably 300 DEG C~380 DEG C；
Preferably, hot pressing pressure is 2MPa~20MPa, preferably 6MPa~11MPa；
Preferably, the mode of the hot pressing, refers to the lamination for forming at least one composite containing filler In carrying out hot-pressing processing on high temperature roll squeezer；
Preferably, hot pressing temperature is 250 DEG C~450 DEG C, preferably 300 DEG C~380 DEG C；
Preferably, hot pressing pressure is 8~18kN, preferably 10~15kN.
10. a kind of circuit substrate, it is mainly contained by by least one by one of claim 1-3 is described The lamination that sheet material described in the PAEK composite of filler or at least one claim 4 is formed Conductive film is covered in one or both sides, and then hot pressing is obtained；
Preferably, there are enhancement layer and/or tack coat in the lamination.
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