CN108752931A - Micro-nano inorganic particle hybrid modified black matt polyimide film and preparation method thereof - Google Patents
Micro-nano inorganic particle hybrid modified black matt polyimide film and preparation method thereof Download PDFInfo
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- CN108752931A CN108752931A CN201810674029.6A CN201810674029A CN108752931A CN 108752931 A CN108752931 A CN 108752931A CN 201810674029 A CN201810674029 A CN 201810674029A CN 108752931 A CN108752931 A CN 108752931A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention discloses a kind of black matt polyimide films that micro-nano inorganic particle hybrid is modified, including polyimide polymer and inorganic filler, wherein polyimide polymer is synthesized by conventional dianhydride monomer and diamine monomer, and inorganic filler includes that the group of following parts by weight is grouped as：1.0 parts of low conductive black, 0.4~2.0 part of flatting silica, 0.1~1.2 part of titanium dioxide, 0.014 ~ 0.8 part of anti-settling agent, the present invention in black polyamic acid resin by adding anti-settling agent, the sinking speed of filler in dispersion liquid is extenuated, further improve the dispersion stabilization of filler dispersion liquid, by filler dispersion liquid and the compound obtained modified polyimide of polyamic acid resin, micro-and nano-particles inhibit the plastic deformation of Kapton, improve the elasticity modulus of film, so that the black matt polyimide film that the micro-nano inorganic particle hybrid prepared is modified has good rigidity, elasticity modulus has reached 4.6GPa.
Description
Technical field
The invention belongs to electric thin insulating materials preparing technical fields, and in particular to a kind of micro-nano inorganic particle hybrid
Modified black matt polyimide film and preparation method thereof.
Background technology
In the past few years, the research of inorganic particle hybrid modification Kapton is a lot of, is concentrated mainly on raising polyimides
Thermal stability, dimensional stability, optical transparence and corona resistance of film etc..And micro-and nano-particles composite hybridization is modified and gathers
The report that imide membrane improves mechanical property is few, and micro-and nano-particles are used in compounding, and can not only improve the dispersion of dispersion liquid
Property and dispersion stabilization, moreover it is possible to further increase the mechanical property of Kapton.
With the fast development and the improvement of people's living standards of photovoltaic in the market, consumer start to pursue appearance and
The consumer electrical products such as mobile phone, the camera of the inside and outside soft delustring cloudy surface of color gloss.This certainly will be to covering as photovoltaic
The glossiness of the black matt polyimide film of epiphragma is put forward higher requirements, that is, requires black thin film glossiness being reduced to
30GU is hereinafter, and can keep the preferable mechanical performance of black thin film.According to domestic black matt polyimide film performance evaluation,
The tensile strength of 12.5 μm of film is below 180MPa, and elasticity modulus is less than 4.0GPa, is less than the performance level of import, in state
The interior market competitiveness is not strong, cannot be satisfied the requirement of domestic large-scale producer.In order to meet market development requirement, domestic matt is improved
The mechanical property of black film will be necessary trend.
Invention content
One kind is provided by containing carbon black, titanium white it is an object of the invention to overcome the deficiencies in the prior art
Anti-settling agent is added in the filler dispersion liquid of powder and silica, the micro particles rate of settling is extenuated, improves the stability of filler, it will be micro-
The micro-nano inorganic particle hybrid modified black matt polyimide film that nano-particle is prepared with polyamic acid resin composite hybridization
And preparation method thereof, the plastic deformation of the presence inhibition polyimides of Ti-O-Ti structures, makes its elasticity modulus rise in system,
Further improve the rigidity of black polyamide thin film.
The object of the present invention is achieved like this：
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, including polyimide polymer and inorganic filling out
Material, which is characterized in that inorganic filler includes that the group of following parts by weight is grouped as：1.0 parts of low conductive black, flatting silica 0.4~
2.0 parts, 0.1~1.2 part of titanium dioxide, 0.014~0.8 part of anti-settling agent.
It calculates in percentage by weight, with polyimide polymer and the total amount of inorganic filler for 100%, inorganic filler accounts for
4.25~25%。
The polyimide polymer is prepared by 150 parts of polyamic acid resins, and polyamic acid resin solid content is
10%~22%.The inorganic filler is added in polyimides in the form of filler dispersion liquid, specifically by 19.514 ~ 58.2
Part inorganic filler dispersion liquid is prepared.
Inorganic filler dispersion liquid is specifically the component by following parts by weight：1.0 parts of low conductive black, flatting silica 0.4~
2.0 parts, 0.1~1.2 part of titanium dioxide, 0.014~0.8 part of anti-settling agent, 18.0~53.2 parts of polar organic solvent.
The low conductive black is sheet resistance >=10 of 10~500nm of ecosystem grain size8The low electrical-conductive nanometer charcoal of nanometer
It is black；The flatting silica is vapor phase method and any one silica that the precipitation method produce, preferably fumed silica, grain size
It is 1~8 μm, is micron silica；The titanium dioxide is any one of rutile-type, Detitanium-ore-type and mixed crystal type,
The rutile type titanium white crystal structure is fine and close, and refractive index is higher, and covering power is stronger, preferably rutile type titanium white, excellent
It is 0.1~3.0 μm to select rutile-type, grain size, is submicron order titanium dioxide.
The anti-settling agent be aerosil, it is contemplated that aerosil particles' interaction and form hydrogen bond,
Anti-settling agent containing hydrogen bond action be more advantageous to it is anti-settling, specifically Cabot Cabots CAB-O- SIL aerosils M-5,
PTG, MS-55, M-7D, WACKER watts grams of aerosils N20, V15, T4, and the gas phase dioxy of other models both at home and abroad
Any one in SiClx.
The polyamic acid resin be by being prepared for aromatic diamine, aromatic dianhydride and polar organic solvent,
Middle aromatic diamine is 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), biphenyl two
Any one in amine or two kinds of mixtures；Aromatic dianhydride is pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracids two
Acid anhydride, any one in 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracid dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides or two kinds
Any of the above than mixture；The polar organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl
The combination of the arbitrary ratio of one or more of sulfoxide, N- methyl pyrrolidones and gamma-butyrolacton.The polyimides
Synthesis is using conventional synthetic methods in industry, using any one in in-situ polymerization, solution polycondensation, random copolymerization and block polymerization,
The aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1, ensure polyamic acid resin according to mass percent
Solid content is 10~22%, and synthesis temperature is controlled at 0~40 DEG C, and the reaction time is 3~10h after aromatic dianhydride adds, and is gathered
Amic acid resin viscosity is with rotational viscometer observing and controlling system in the mpas of 1000mpas ~ 150,000.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes in accordance with the following steps
It is prepared：
Step 1）, temperature be 0~40 DEG C under conditions of, according to conventional polyamide acid synthetic method, aromatic diamine is dissolved
In polar organic solvent, aromatic dianhydride is added, the reaction time between 3~12h, obtains polyamic acid resin, and
Ensure that its solid content is 10~22% according to mass percent, viscosity is controlled in the mpas of 1000mpas ~ 150,000；It is wherein described
Aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1；
Step 2）, take according to parts by weight 19.5~58.2 parts of filler dispersion liquid and above-mentioned steps 1）150 parts of polyamic acids
Resin is mixed obtained black polyamic acid resin and defoams black polyamic acid resin according to conventional biaxial tension method, flows
Prolong film forming, then through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
The filler dispersion liquid is prepared in accordance with the following steps：
Step 2.1）, at 10~40 DEG C, 1.0 parts of low conductive blacks and 9.0 parts of polar organic solvents are mixed according to parts by weight
Close, be transferred in cutter, shear velocity be 500~5000 turns/min under conditions of disperse 1~10h, after be transferred to milling apparatus
In, 0~4h is disperseed under the conditions of grinding rate is 500~5000 turns/min, obtains black dispersion liquid；
Step 2.2）, at 10~40 DEG C, according to parts by weight by 0.4~2.0 part of grain size be 1~8 μm of flatting silica and 0.1~
1.2 parts of grain sizes are that 0.1~3.0 μm of titanium dioxide is mixed with 9.0~44.2 parts of polar organic solvents, are then added 0.014~0.8 part
Anti-settling agent is uniformly mixed, and is transferred to that shearing, ultrasound, emulsification, homogeneous dissipates, magnetic force divides in any one in dispersing apparatus, in rate
To disperse 1~5h under conditions of 500~5000 turns/min, white dispersion liquid is obtained；
Step 2.3）, at 10~40 DEG C, by above-mentioned steps 2.1）Obtained black dispersion liquid and step 2.2）Obtained white
Dispersion liquid mixes, and is transferred in cutter, 0.5~10h of shearing dispersion under conditions of shear velocity is 500~5000 turns/min,
Obtain filler dispersion liquid.
In step 2.1）In milling apparatus be ball mill, sand mill, planetary ball mill or three-roll grinder in appoint
Meaning is a kind of, and wherein ball mill, sand mill, planetary ball mill are zirconium oxide bead, zirconium pearl, ceramic bead, glass equipped with abrasive media
Any one in pearl and stainless shot, the abrasive media particle size are 0.1~5mm.
Above-mentioned steps 2.1）To step 2.3）Involved in cutter equipped with shearing disk material be stainless steel, polytetrafluoro material
The edge of any one of matter, preferably stainless steel shearing disk, the shearing disk is zigzag.
In view of filler grain is assembled in a solvent, cutter that the present invention uses equipped with shearing disk for stainless steel,
The edge of any one of polytetrafluoro material, preferably stainless steel shearing disk, the shearing disk is zigzag.In view of point of filler
Efficiency is dissipated, the unit sizes of the mating shearing disk of the cutter that the present invention uses, reactor and liquid level follow following ratio,
That is reaction kettle diameter：Shear disk diameter：Liquid level is 100:（25~75）:（50~100）.In view of the efficiency of filler dispersion
Than shear rate of the present invention is can with the naked eye observe at the swirl center in shearing container caused by being dispersed with stirring liquid
Subject to shearing disk, specially 500 ~ 5000 turns/min.In view of between filler grain shock and friction can be with depolymerization filler grain
Aggregation, i.e., in system filer content it is relatively low be unfavorable for occur particle between friction and shock and influence dispersion effect, filler
The higher viscosity that can directly influence system of content, the present invention in inorganic filler be in the form of dispersion liquid addition polyimide resin
In.
The present invention has following good effect：
The present invention uses the black matt polyimide film that above-mentioned preparation method obtains, and compared with prior art, the present invention is slow
The sinking speed for having subtracted filler in slurry further improves the dispersion stabilization of filler dispersion liquid, it is suppressed that polyimides is thin
The plastic deformation of film improves thin flexible film modulus so that the micro-nano inorganic particle hybrid containing the dispersion liquid is modified black
Color matt polyimide film has good rigidity.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film：It is by 95.75% polyamides according to weight percent hundred
Imine polymer and 4.25% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
19.514 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：Grain size is the low conductive black 1.0 thousand of 10nm
Gram, using vapor phase method production 3 μm of grain size silica as 0.4 kilogram of flatting silica, the mixed-crystal titanium pigment 0.1 of 0.1 μm of grain size
Kilogram, 0.014 kilogram of anti-settling agent M-5, polar organic solvent be 18.0 kilograms of n,N-Dimethylformamide.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 15.8 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 117 kilograms of n,N-dimethylacetamide, adds 17.2 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
150 kilograms of polyamic acid resins；Its solid content is 22%, viscosity 12000mpas；
Step 2）, take 19.514 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing
Stirring is made black polyamic acid resin and is defoamed black polyamic acid resin, casting film-forming according to conventional biaxial tension method,
Again through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 10 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 500 turns/min under conditions of, shearing dispersion 10h, after be transferred to planetary type ball-milling
It is 5000 turns/min in rotating speed, abrasive media is zirconium oxide bead, and grain size is grinding distribution 0.5h under conditions of 1mm, is obtained in machine
Black dispersion liquid
Step 2.2）, at 10 DEG C, 0.4 kilogram of flatting silica and 0.1 kilogram of titanium dioxide and 9.0 kilograms of polarity is organic molten
Agent mixes, and 0.014 portion of anti-settling agent is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk, 500 turns/
Shearing dispersion 5h, obtains white dispersion liquid under conditions of min；
Step 2.3）, at 10 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：25：50）In,
Shearing dispersion 0.5h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid content under conditions of 3000 turns/min
It is 7.7%.
Embodiment 2
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film：It is by 75% polyamides Asia according to weight percent hundred
Amine polymer and 25% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is 58.2
Kilogram.Inorganic filler dispersion liquid is the component according to following weight grams：Grain size be 10nm 1.0 kilograms of low conductive black, with
Vapor phase method production 3 μm of grain size silica be 2.0 kilograms of flatting silica, 0.1 μm of grain size 1.2 kilograms of mixed-crystal titanium pigment,
0.8 kilogram of anti-settling agent M-5, polar organic solvent are 53.2 kilograms of n,N-Dimethylformamide.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 4.0 kilograms of 4,4- diamino
Diphenyl ether and 2.2 kilograms of p-phenylenediamine are dissolved in 135 kilograms of n,N-dimethylacetamide, add 8.8 kilograms of equal benzene tetramethyls
Acid dianhydride, reaction 5h obtain polyamic acid resin；Its solid content is 10%, viscosity 1000mpas；
Step 2）, take 57.4 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 10 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 500 turns/min under conditions of, shearing dispersion 10h, after be transferred to planetary type ball-milling
It is 5000 turns/min in rotating speed, abrasive media is zirconium oxide bead, and grain size is grinding distribution 0.5h under conditions of 1mm, is obtained in machine
Black dispersion liquid
Step 2.2）, at 10 DEG C, 2.0 kilograms of flatting silica and 1.2 kilograms of titanium dioxide and 44.2 kilograms of polarity is organic
Solvent mixes, and 0.8 portion of anti-settling agent is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk, 500 turns/
Shearing dispersion 5h, obtains white dispersion liquid under conditions of min；
Step 2.3）, at 10 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：70：125）
In, shearing dispersion 0.5h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid contains under conditions of 3000 turns/min
Amount is 7.3%.
Embodiment 3
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 93.46% polyamides according to weight percent hundred
Imine polymer and 6.54% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
21 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：Grain size be 10nm 1.0 kilograms of low conductive black,
Using the silica of 3 μm of the grain size of vapor phase method production as 1.0 kilograms of flatting silica, the mixed-crystal titanium pigment 0.1 thousand of 0.1 μm of grain size
Gram, 0.11 kilogram of anti-settling agent M-5, polar organic solvent be 18.9 kilograms of n,N-Dimethylformamide.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes in accordance with the following steps
It is prepared：
Step 1）, under conditions of temperature is 0 DEG C, according to conventional polyamide acid synthetic method, by 14.4 kilogram 4,4 '-diaminos
Yl diphenyl ether is dissolved in 120 kilograms of n,N-Dimethylformamide, adds 15.6 kilograms of pyromellitic acid anhydride, reaction time
In 3h, polyamic acid resin, solid content 20%, viscosity 1000mpas are obtained；
Step 2）, take 21.0 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 10 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 500 turns/min under conditions of, shearing dispersion 10h, after be transferred to planetary type ball-milling
It is 5000 turns/min in rotating speed, abrasive media is zirconium oxide bead, and grain size is grinding distribution 0.5h under conditions of 1mm, is obtained in machine
Black dispersion liquid
Step 2.2）, at 10 DEG C, 1.0 kilograms of flatting silica and 0.1 kilogram of titanium dioxide and 9.9 kilograms of polarity is organic molten
Agent mixes, and 0.11 portion of anti-settling agent is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk, 500 turns/
Shearing dispersion 5h, obtains white dispersion liquid under conditions of min；
Step 2.3）, at 10 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：110）
In, shearing dispersion 0.5h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid contains under conditions of 3000 turns/min
Amount is 10%.
Embodiment 4
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 91.46% polyamides according to weight percent hundred
Imine polymer and 8.54% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
28 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 50nm, with
The rutile type titanium white for 2.0 μm of .0 kilograms of silica 1, the grain size that 5 μm of the grain size of precipitation method production is used as flatting silica
0.8 kilogram, 0.18 kilogram of M-5 anti-settling agents, 25.2 kilograms of the n,N-dimethylacetamide used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 20 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time exists
5h obtains polyamic acid resin, and ensures that its solid content is 20% according to mass percent, viscosity 1000mpas；
Step 2）, take 28.0 grams of filler dispersion liquid and above-mentioned steps 1）150 kilograms of obtained polyamic acid resins are mixed
Black polyamic acid resin is made to defoam black polyamic acid resin, casting film-forming, then pass through according to conventional biaxial tension method
Biaxial tension, high temperature imidization obtain micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, step 1）, at 20 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of rotating speed is 1200 turns/min, shearing dispersion 6h, after be transferred to row
It is 4000 turns/min in rotating speed, abrasive media is zirconium oxide bead, and grain size is grinding distribution under conditions of 1mm in planetary ball mill
2h obtains black dispersion liquid
Step 2.2）, at 20 DEG C, 1.0 kilograms of flatting silica and 0.8 kilogram of titanium dioxide and 16.2 kilograms of polarity is organic
Solvent mixes, and 0.18 portion of anti-settling agent is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk, 800 turns/
Shearing dispersion 4h, obtains white dispersion liquid under conditions of min；
Step 2.3）, at 20 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：100）
In, shearing dispersion 2h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid content under conditions of 2500 turns/min
It is 10%.
Embodiment 5
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 86.88% polyamides according to weight percent hundred
Imine polymer and 13.12% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
40.3 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 100nm,
The rutile titanium dioxide of 8 μm of .0 kilograms of silica 1s used as flatting silica of grain size, 3.0 μm of grain size for being produced using vapor phase method
1.2 kilograms of powder, 0.33 kilogram of M-5 anti-settling agents, 36.8 kilograms of the dimethyl sulfoxide (DMSO) used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 15 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of dimethyl sulfoxide (DMSO)s, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time in 8h, obtains
Ensure that its solid content is 20% to polyamic acid resin, and according to mass percent, viscosity 9000mpas；
Step 2）, take 40.3 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, step 1）, at 30 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
It is transferred in the cutter equipped with zigzag shearing disk, under conditions of rotating speed is 3000 turns/min, shearing dispersion 4h obtains black
Dispersion liquid；
Step 2.2）, at 30 DEG C, 1.0 kilograms of flatting silica and 1.2 kilograms of titanium dioxide and 27.8 kilograms of polarity is organic
Solvent mixes, and 0.33 kilogram of anti-settling agent is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk, 1200
Turn/min under conditions of shearing dispersion 3h, obtain white dispersion liquid；
Step 2.3）, at 30 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：100）
In, shearing dispersion 4h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid content under conditions of 2000 turns/min
It is 8.0%.
Embodiment 6
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, includes the component of following weight grams：According to
Weight percent hundred is made of 91.46% polyimide polymer and 8.54% inorganic filler, and particularly polyamic acid resin is
150 kilograms, inorganic filler dispersion liquid is 20.8 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：Grain size
The silica 0.4 thousand that 1.0 kilograms of the low conductive black of 300nm, 2 μm of the grain size produced using vapor phase method are used as flatting silica
Gram, 2.0 μm of grain size 0.6 kilogram of rutile type titanium white, the N- 0.8 kilogram of M-5 anti-settling agents, used as polar organic solvent
18.0 kilograms of methyl pyrrolidone.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 40 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of N- methyl pyrrolidones, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time exists
8h obtains polyamic acid resin, and according to mass percent, its solid content is 20%, viscosity 9000mpas；
Step 2）, take 20.8 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 40 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 4000 turns/min under conditions of, shearing dispersion 2h, after be transferred to three-roll grinder
In, grinding distribution 1h under conditions of rotating speed is 2000 turns/min obtains black dispersion liquid；
Step 2.2）, at 40 DEG C, 0.4 kilogram of flatting silica and 0.6 kilogram of titanium dioxide and 9.0 kilograms of polarity is organic molten
Agent mixes, and 0.8 kilogram of M-5 anti-settling agent is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk, 2000
Turn/min under conditions of shearing dispersion 2h, obtain white dispersion liquid；
Step 2.3）, at 40 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 8h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid content under conditions of 1200 turns/min
10%。
Embodiment 7
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 92.59% polyamides according to weight percent hundred
Imine polymer and 7.41% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
24 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 500nm, with
The rutile type titanium white of 1 μm of 0.1 μm of 0.8 kilogram of silica, grain size used as flatting silica of grain size of vapor phase method production
0.6 kilogram, 0.014 kilogram of M-5 anti-settling agents, 21.6 kilograms of the gamma-butyrolacton used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 40 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of gamma-butyrolactons, adds 15.6 kilograms of pyromellitic acid anhydride, the reaction time in 10h, obtains
Ensure that its solid content is 20% to polyamic acid resin, and according to mass percent, viscosity 15000mpas；
Step 2）, take 24.0 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, step 1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of rotating speed is 5000 turns/min, shearing dispersion 1h, after be transferred to row
It is 500 turns/min in rotating speed, abrasive media is zirconium oxide bead, and grain size is grinding distribution under conditions of 1mm in planetary ball mill
4h obtains black dispersion liquid；
Step 2.2）, at 15 DEG C, 0.8 kilogram of flatting silica and 0.6 kilogram of titanium dioxide and 12.6 kilograms of polarity is organic
Solvent mixes, and 0.014 kilogram of anti-settling agent is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk,
Shearing dispersion 1h, obtains white dispersion liquid under conditions of 3000 turns/min；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 10h, obtains a kind of filler dispersion liquid of stabilization, dispersion liquid solid content is under conditions of 500 turns/min
10%。
Embodiment 8
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 90.03% polyamides according to weight percent hundred
Imine polymer and 9.97% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
33 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 25nm, with
The rutile type titanium white for 0.4 μm of .3 kilograms of silica 1, the grain size that 5 μm of the grain size of vapor phase method production is used as flatting silica
1.0 kilograms, 0.05 kilogram of M-5 anti-settling agents, the 14.8 kilograms of DMAC N,N' dimethyl acetamides used as polar organic solvent and
14.9 kilograms of N- crassitude alcohol/ketone mixtures.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 60 kilograms of n,N-dimethylacetamide and 60 kilograms of N- methyl pyrrolidones, adds Pyromellitic Acid
15.6 kilograms of dianhydride, reaction time in 10h, obtain polyamic acid resin, and its solid content is 20% according to mass percent,
Viscosity 18000mpas；
Step 2）, take 33.0 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 15 DEG C, by 1.0 kilograms of low conductive black, 4.5 kilograms of n,N-dimethylacetamide and 4.5 kilograms
N- crassitude alcohol/ketone mixtures mix, be transferred in the cutter equipped with zigzag shearing disk, shear velocity be 3000 turns/
Under conditions of min, shearing dispersion 2h, after be transferred in planetary ball mill, rotating speed be 2500 turns/min, abrasive media be oxidation
Zirconium pearl, grain size are grinding distribution 4h under conditions of 1mm, obtain black dispersion liquid；
Step 2.2）, at 15 DEG C, by 1.3 kilograms of flatting silica and 1.0 kilograms of titanium dioxide and 10.3 kilograms of N, N- dimethyl
Acetamide and 10.4 kilograms of N- crassitude alcohol/ketone mixtures mixing, are then added 0.05 kilogram of anti-settling agent M-5 and are uniformly mixed,
It is transferred in the cutter equipped with zigzag shearing disk, shearing dispersion 1h, obtains white dispersion liquid under conditions of 1800 turns/min；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 5h, obtains a kind of filler dispersion liquid of stabilization, dispersion liquid solid content is under conditions of 1000 turns/min
10%。
Embodiment 9
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 87.72% polyamides according to weight percent hundred
Imine polymer and 12.28% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
33.5 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 30nm,
Using 5 μm of silica of grain size that vapor phase method produces as 2.0 kilograms of flatting silica, the rutile type titanium white 1.0 thousand of 0.4 μm of grain size
Gram, 0.2 kilogram of N20 anti-settling agents, 29.3 kilograms of the DMAC N,N' dimethyl acetamide used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diaminos
Yl diphenyl ether is dissolved in 120 kilograms of gamma-butyrolactons, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h obtains 150,000
Gram polyamic acid resin；Its solid content is 20%, viscosity 15000mpas；
Step 2）, take 33.5 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in sand mill,
It is 2500 turns/min in rotating speed, abrasive media is zirconium pearl, and grain size is grinding distribution 4h under conditions of 0.1mm, obtains black dispersion
Liquid；
Step 2.2）, at 15 DEG C, 2.0 kilograms of flatting silica and 1.0 kilograms of titanium dioxide and 20.3 kilograms of polarity is organic
Solvent mixes, and 0.2 kilogram of anti-settling agent N20 is then added and is uniformly mixed, is transferred in ultrasonic disperse equipment, ultrasonic disperse 2h is obtained
White dispersion liquid；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 4h, obtains a kind of filler dispersion liquid of stabilization, dispersion liquid solid content is under conditions of 2000 turns/min
12%。
Embodiment 10
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 90.91% polyamides according to weight percent hundred
Imine polymer and 9.09% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
30 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 30nm, with
The silica that vapor phase method production grain size is 6 μm is as 1.3 kilograms of flatting silica, the rutile type titanium white 0.7 that grain size is 1.0 μm
Kilogram, 0.1 kilogram of PTG anti-settling agents, using DMAC N,N' dimethyl acetamide as 27.0 kilograms of polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diaminos
Yl diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
To 150 kilograms of polyamic acid resins；Its solid content is 20%, viscosity 15000mpas；
Step 2）, take 30.0 kilograms of filler dispersion liquid and step 1）System is mixed in 150 kilograms of obtained polyamic acid resins
It obtains black polyamic acid resin to defoam black polyamic acid resin, casting film-forming according to conventional biaxial tension method, then through double
To stretching, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in sand mill,
It is 2500 turns/min in rotating speed, abrasive media is zirconium pearl, and grain size is grinding distribution 4h under conditions of 0.8 μm, obtains black dispersion
Liquid；
Step 2.2）, at 15 DEG C, 1.3 kilograms of flatting silica and 0.7 kilogram of titanium dioxide and 18.0 kilograms of polarity is organic
Solvent mixes, and 0.1 kilogram of anti-settling agent PTG is then added and is uniformly mixed, is transferred to mulser, under the conditions of rotating speed is 2000 turns/min
Emulsion dispersion 4h obtains white dispersion liquid；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 4h, obtains a kind of filler dispersion liquid of stabilization, dispersion liquid solid content is under conditions of 2000 turns/min
10%。
Embodiment 11
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 91.46% polyamides according to weight percent hundred
Imine polymer and 8.54% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
28 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 30nm, with
6 μm of silica of grain size of precipitation method production are as 1.3 kilograms of flatting silica, the rutile type titanium white 0.5 thousand of 0.4 μm of grain size
Gram, 0.1 kilogram of M-5 anti-settling agents, 25.2 kilograms of the DMAC N,N' dimethyl acetamide used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diaminos
Yl diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
To 150 kilograms of polyamic acid resins；Its solid content is 20%, viscosity 12000mpas；
Step 2）, take 28.0 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in sand mill,
It is 2500 turns/min in rotating speed, abrasive media is zirconium pearl, and grain size is grinding distribution 4h under conditions of 1.2 mm, obtains black dispersion
Liquid；
Step 2.2）, at 15 DEG C, 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 16.2 kilograms of polarity is organic
Solvent mixes, and 0.1 kilogram of anti-settling agent M-5 is then added and is uniformly mixed, is transferred to homogenizer, under the conditions of rotating speed is 1200 turns/min
Emulsion dispersion 4h obtains white dispersion liquid；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 4h, obtains a kind of filler dispersion liquid of stabilization, dispersion liquid solid content is under conditions of 2000 turns/min
10%。
Embodiment 12
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 82.54% polyamides according to weight percent hundred
Imine polymer and 17.46% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
56.4 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 20nm,
The rutile titanium dioxide of 6 μm of .3 kilograms of silica 1s used as flatting silica of grain size, 0.6 μm of grain size for being produced using vapor phase method
0.5 kilogram of powder, 0.36 kilogram of V15 anti-settling agents, 53.2 kilograms of the DMAC N,N' dimethyl acetamide used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, prepares by the following method：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 4.0 kilograms of 4,4- diamino
Diphenyl ether and 2.2 kilograms of p-phenylenediamine are dissolved in 135 kilograms of n,N-dimethylacetamide, add 8.8 kilograms of equal benzene tetramethyls
Acid dianhydride, reaction 5h obtain polyamic acid resin；Its solid content is 10%, viscosity 15000mpas；
Step 2）, take 56.4 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, step 1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of rotating speed is 3000 turns/min, shearing dispersion 2h, after be transferred to sand
It is 2500 turns/min in rotating speed, abrasive media is zirconium pearl, and grain size is grinding distribution 4h under conditions of 3 mm, is obtained black in grinding machine
Color dispersion liquid；
Step 2.2）, at 15 DEG C, 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 44.2 kilograms of polarity is organic
Solvent mixes, and 0.36 kilogram of anti-settling agent V15 is then added and is uniformly mixed, is transferred in magnetic stirring apparatus, rotating speed be 1200 turns/
It is dispersed with stirring 4h under the conditions of min, obtains white dispersion liquid；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 4h under conditions of 2000 turns/min, obtains a kind of filler dispersion liquid of stabilization, and dispersion liquid solid content is 5%.
Embodiment 13
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 87.6% polyamides according to weight percent hundred
Imine polymer and 12.4% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
35.4 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 20nm,
The rutile titanium dioxide of 6 μm of .3 kilograms of silica 1s used as flatting silica of grain size, 1.0 μm of grain size for being produced using the precipitation method
0.5 kilogram of powder, 0.42 kilogram of MS-55 anti-settling agents, 32.2 kilograms of the DMAC N,N' dimethyl acetamide used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, prepares by the following method：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 9.9 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 127.5 kilograms of n,N-dimethylacetamide, adds 5.4 kilograms of pyromellitic acid anhydrides and 7.2 kilograms
Biphenyl acid acid anhydride, reaction 5h obtain 150 kilograms of polyamic acid resins；Its solid content is 15%, viscosity 15000mpas；
Step 2）, take 35.4 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 3000 turns/min under conditions of, shearing dispersion 2h, after be transferred in ball mill,
It is 2500 turns/min in rotating speed, abrasive media is zirconium pearl, and grain size is grinding distribution 4h under conditions of 4 mm, obtains black dispersion
Liquid；
Step 2.2）, at 15 DEG C, 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 23.2 kilograms of polarity is organic
Solvent mixes, and 0.42 kilogram of anti-settling agent MS-55 is then added and is uniformly mixed, is transferred in the cutter equipped with zigzag shearing disk,
Shearing dispersion 1h, obtains white dispersion liquid under conditions of 1800 turns/min；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 4h under conditions of 2000 turns/min, obtains a kind of filler dispersion liquid of stabilization, and dispersion liquid solid content is 8%.
Embodiment 14
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 91.72% polyamides according to weight percent hundred
Imine polymer and 8.28% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
23.3 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 20nm,
The rutile titanium dioxide of 6 μm of .3 kilograms of silica 1s used as flatting silica of grain size, 3.0 μm of grain size for being produced using the precipitation method
0.18 kilogram of 0.5 kilogram of powder, MS-55 anti-settling agents 20.5 kilograms of gamma-butyrolacton used as polar organic solvent.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 15.8 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 117 kilograms of n,N-dimethylacetamide, adds 17.2 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
150 kilograms of polyamic acid resins；Its solid content is 22%, viscosity 12000mpas；
Step 2）, take 23.3 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained polyamic acid resin, which is mixed, is made black
Color polyamic acid resin defoams black polyamic acid resin, casting film-forming according to conventional biaxial tension method, then through two-way drawing
It stretches, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, shear velocity be 5000 turns/min under conditions of disperse 1h, after be transferred to containing grinding medium
In the milling apparatus of matter, disperses 4h under the conditions of grinding rate is 500 turns/min, obtain black dispersion liquid；Milling apparatus is row
Planetary ball mill, abrasive media are zirconium oxide bead, and the abrasive media particle size is 1mm.
Step 2.2）, at 15 DEG C, by 1.3 kilograms of flatting silica and 0.5 kilogram of titanium dioxide and 11.5 kilograms of polarity
Organic solvent mixes, and 0.18 kilogram of anti-settling agent MS-55 is then added and is uniformly mixed, is transferred to the cutter equipped with zigzag shearing disk
In, shearing dispersion 1h, obtains white dispersion liquid under conditions of 1800 turns/min；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 4h, obtains a kind of filler dispersion liquid of stabilization, dispersion liquid solid content is under conditions of 2000 turns/min
12%。
Comparative example 1
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 88.93% polyamides according to weight percent hundred
Imine polymer and 11.07% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
28.8 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 20nm,
Produced using the precipitation method grain size 6 μm of .3 kilograms of silica 1s used as flatting silica, the N that is used as polar organic solvent,
26.5 kilograms of N- dimethylacetylamides.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, prepares by the following method：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 4.0 kilograms of 4,4- diamino
Diphenyl ether and 2.2 kilograms of p-phenylenediamine are dissolved in 135 kilograms of n,N-dimethylacetamide, add 8.8 kilograms of equal benzene tetramethyls
Acid dianhydride, reaction 5h obtain polyamic acid resin；Its solid content is 15%, viscosity 15000mpas；
Step 2）, take 28.8 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained polyamic acid resin, which is mixed, is made black
Color polyamic acid resin defoams black polyamic acid resin, casting film-forming according to conventional biaxial tension method, then through two-way drawing
It stretches, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, step 1）, at 15 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of rotating speed is 3000 turns/min, shearing dispersion 2h, after be transferred to pearl
It is 2500 turns/min in rotating speed, abrasive media is zirconium pearl, and grain size is grinding distribution 4h under conditions of 4 mm, is obtained black in grinding machine
Color dispersion liquid；
Step 2.2）, at 15 DEG C, 1.3 kilograms of flatting silica is mixed with 17.5 kilograms of polar organic solvent, is transferred to and is furnished with
In the cutter of zigzag shearing disk, shearing dispersion 1h, obtains white dispersion liquid under conditions of 1800 turns/min；
Step 2.3）, at 15 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：75）In,
Shearing dispersion 4h under conditions of 2000 turns/min, obtains a kind of filler dispersion liquid of stabilization, and dispersion liquid solid content is 8%.
Comparative example 2
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 93.75% polyamides according to weight percent hundred
Imine polymer and 6.25% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
20 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：1.0 kilograms of the low conductive black of grain size 50nm, with
5 μm of .0 kilograms of silica 1s used as flatting silica of grain size of precipitation method production, the N, N- that are used as polar organic solvent
18 kilograms of dimethylacetylamide.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, temperature be 25 DEG C under conditions of, according to conventional polyamide acid synthetic method, by 14.4 kilograms of 4,4- diamino
Diphenyl ether is dissolved in 120 kilograms of n,N-dimethylacetamide, adds 15.6 kilograms of pyromellitic acid anhydrides, and reaction 5h is obtained
Polyamic acid resin；Polyamic acid resin solid content is 20%, viscosity 15000mpas；
Step 2）, take 20.0 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, step 1）, at 20 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents,
Be transferred in the cutter equipped with zigzag shearing disk, under conditions of rotating speed is 1200 turns/min, shearing dispersion 6h, after be transferred to row
It is 4000 turns/min in rotating speed, abrasive media is zirconium oxide bead, and grain size is grinding distribution under conditions of 1mm in planetary ball mill
2h obtains black dispersion liquid
Step 2）, at 20 DEG C, 1.0 kilograms of flatting silica is mixed with 9.0 kilograms of polar organic solvent, is transferred to equipped with sawtooth
In the cutter of shape shearing disk, shearing dispersion 4h, obtains white dispersion liquid under conditions of 800 turns/min；
Step 3）, at 20 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid mixing,
It is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：100）In,
Shearing dispersion 2h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid content is under conditions of 2500 turns/min
10%。
Comparative example 3
A kind of micro-nano inorganic particle hybrid modified black matt polyimide film, is by 93.46% polyamides according to weight percent hundred
Imine polymer and 6.54% inorganic filler composition, particularly polyamic acid resin is 150 kilograms, and inorganic filler dispersion liquid is
21 kilograms.Inorganic filler dispersion liquid is the component according to following weight grams：Grain size be 10nm 1.0 kilograms of low conductive black,
Using the silica of 3 μm of the grain size of vapor phase method production as 1.0 kilograms of flatting silica, the mixed-crystal titanium pigment 0.1 thousand of 0.1 μm of grain size
Gram, polar organic solvent be 18.9 kilograms of n,N-Dimethylformamide.
A kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, makes by the following method
It is standby：
Step 1）, under conditions of temperature is 0 DEG C, according to conventional polyamide acid synthetic method, by 14.4 kilogram 4,4 '-diaminos
Yl diphenyl ether is dissolved in 120 kilograms of n,N-Dimethylformamide, adds 15.6 kilograms of pyromellitic acid anhydride, reaction time
In 3h, polyamic acid resin, solid content 20%, viscosity 1000mpas are obtained；
Step 2）, take 21.0 kilograms of filler dispersion liquid and above-mentioned steps 1）Obtained 150 kilograms of polyamic acid resins mixing is stirred
Mixing obtains black polyamic acid resin, according to conventional biaxial tension method, black polyamic acid resin is defoamed, casting film-forming, then
Through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
Wherein, filler dispersion liquid is to be prepared in accordance with the following steps：
Step 2.1）, at 10 DEG C, 1.0 kilograms of low conductive black is mixed with 9.0 kilograms of polar organic solvents, is transferred to and is furnished with
In the cutter of zigzag shearing disk, rotating speed be 500 turns/min under conditions of, shearing dispersion 10h, after be transferred to planetary type ball-milling
It is 5000 turns/min in rotating speed, abrasive media is zirconium oxide bead, and grain size is grinding distribution 0.5h under conditions of 1mm, is obtained in machine
Black dispersion liquid；
Step 2.2）, at 10 DEG C, 1.0 kilograms of flatting silica and 0.1 kilogram of titanium dioxide and 9.9 kilograms of polarity is organic molten
Agent mixes, and is transferred in the cutter equipped with zigzag shearing disk, and shearing dispersion 5h, obtains white under conditions of 500 turns/min
Dispersion liquid；
Step 2.3）, at 10 DEG C, by above-mentioned steps 1）Obtained black dispersion liquid and step 2）Obtained white dispersion liquid is mixed
It closes, is transferred to the cutter equipped with zigzag shearing disk（Reaction kettle diameter：Shear disk diameter：Liquid level is 100：50：110）
In, shearing dispersion 0.5h, obtains a kind of filler dispersion liquid of stabilization, wherein dispersion liquid solid contains under conditions of 3000 turns/min
Amount is 10%.
The black matt polyimide film that micro-nano inorganic particle hybrid prepared by embodiment 1-12 and comparative example 1-3 is modified
Can as shown in table 2, comparative example and comparative example, after anti-settling agent is added, the elasticity modulus of black polyamide thin film has
It improves, it was confirmed that Ti-O-Ti network structures increase, and physical crosslinking point increases in system, limits the movement of PI strands, reduces
Plastic deformation.It further illustrates when polyimides of the addition containing micro-and nano-particles can inhibit the plasticity shape of Kapton
Become, improves its elasticity modulus.
2 film performance of table
Claims (9)
1. a kind of micro-nano inorganic particle hybrid modified black matt polyimide film, including polyimide polymer and inorganic
Filler, which is characterized in that inorganic filler includes that the group of following parts by weight is grouped as：1.0 parts of low conductive black, flatting silica 0.4
~2.0 parts, 0.1~1.2 part of titanium dioxide, 0.014~0.8 part of anti-settling agent.
2. micro-nano inorganic particle hybrid modified black matt polyimide film according to claim 1,
It is characterized in that, calculate in percentage by weight, it is inorganic with polyimide polymer and the total amount of inorganic filler for 100%
Filler accounts for 4.25 ~ 25%.
3. micro-nano inorganic particle hybrid modified black matt polyimide film according to claim 1,
It is characterized in that, the raw material for preparing polyimide polymer includes that aromatic diamine, aromatic dianhydride and polarity are organic molten
Agent, wherein aromatic diamine are 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), connection
Any one in phenylenediamine or two kinds of mixtures；Aromatic dianhydride is pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracids
Dianhydride, any one in 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracid dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides or two
Kind of any of the above than mixture；Polar organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl Asia
The combination of the arbitrary ratio of one or more of sulfone, N- methyl pyrrolidones and gamma-butyrolacton；Polyimide polymer
Synthesis is using conventional synthetic methods in industry, using any one in in-situ polymerization, solution polycondensation, random copolymerization and block polymerization,
The aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1, ensure synthesized polyamides according to mass percent
Amino acid resin solid content is 10~22%, and synthesis temperature is controlled at 0~40 DEG C, and the reaction time is 3~10h after dianhydride adds,
Polyamic acid resin viscosity is with rotational viscometer observing and controlling system in the mpas of 1000mpas ~ 150,000.
4. micro-nano inorganic particle hybrid modified black matt polyimide film according to claim 1, which is characterized in that
The low conductive black is sheet resistance >=10 of 10~500nm of ecosystem grain size8The low electrical-conductive nanometer carbon black of nanometer；It is described to disappear
Light powder is vapor phase method and any one silica that the precipitation method produce, preferably fumed silica, and grain size is 1~8 μm；
The titanium dioxide is any one of rutile-type, Detitanium-ore-type and mixed crystal type, preferably rutile-type, grain size is 0.1~
3.0μm。
5. micro-nano inorganic particle hybrid modified black matt polyimide film according to claim 1, which is characterized in that
The anti-settling agent is aerosil, specifically Cabot Cabots CAB-O- SIL aerosils M-5, PTG, MS-
55, M-7D, WACKER watts grams of aerosils N20, V15, T4, and both at home and abroad in the aerosil of other models
Any one.
6. a kind of preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film, which is characterized in that according to
It is prepared by following steps system：
Step 1）, temperature be 0~40 DEG C under conditions of, according to conventional polyamide acid synthetic method, aromatic diamine is dissolved
In polar organic solvent, aromatic dianhydride is added, the reaction time between 3~10h, obtains polyamic acid resin, and
Ensure that its solid content is 10~22% according to mass percent, viscosity is controlled in the mpas of 1000mpas ~ 150,000；It is wherein described
Aromatic dianhydride and the molar ratio of aromatic diamine are 0.9~1.1:1；
Step 2）, take according to parts by weight 19.514~58.2 parts of filler dispersion liquid and above-mentioned steps 1）150 parts of polyamide
Acid resin is mixed obtained black polyamic acid resin and defoams black polyamic acid resin according to conventional biaxial tension method,
Casting film-forming, then through biaxial tension, high temperature imidization obtains micro-nano inorganic particle hybrid modified black matt polyimide film.
7. the preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film according to claim 6,
It is characterized in that, the filler dispersion liquid is prepared in accordance with the following steps：
Step 2.1）, at 10~40 DEG C, 1.0 parts of low conductive blacks and 9.0 parts of polar organic solvents are mixed according to parts by weight
Close, be transferred in cutter, shear velocity be 500~5000 turns/min under conditions of disperse 1~10h, after be transferred to milling apparatus
In, 0~4h is disperseed under the conditions of grinding rate is 500~5000 turns/min, obtains black dispersion liquid；
Step 2.2）, at 10~40 DEG C, according to parts by weight by 0.4~2.0 part of grain size be 1~8 μm of flatting silica and 0.1~
1.2 parts of grain sizes are that 0.1~3.0 μm of titanium dioxide mix with 9.0~44.2 parts of polar organic solvents, then addition grain size for 7~
0.014~3.6 portion of anti-settling agent of 100nm is uniformly mixed, and is transferred to that shearing, ultrasound, emulsification, homogeneous dissipates, magnetic force divides in dispersing apparatus
Any one in, rate be 500 ~ 5000 turns/min under conditions of disperse 1~5h, obtain white dispersion liquid；
Step 2.3）, at 10~40 DEG C, by above-mentioned steps 2.1）Obtained black dispersion liquid and step 2.2）Obtained white
Dispersion liquid mixes, and is transferred in cutter, 0.5~10h of shearing dispersion under conditions of shear velocity is 500~5000 turns/min,
Obtain filler dispersion liquid.
8. the preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film according to claim 7,
It is characterized in that, in step 2.1）In milling apparatus be ball mill, sand mill, planetary ball mill or three-roll grinder in appoint
Meaning is a kind of, and wherein ball mill, sand mill, planetary ball mill are zirconium oxide bead, zirconium pearl, ceramic bead, glass equipped with abrasive media
Any one in pearl and stainless shot, the abrasive media particle size are 0.1~5mm.
9. the preparation method of micro-nano inorganic particle hybrid modified black matt polyimide film according to claim 7,
It is characterized in that, above-mentioned steps 2.1）To step 2.3）Involved in cutter equipped with shearing disk material be stainless steel, polytetrafluoro
The edge of any one of material, preferably stainless steel shearing disk, the shearing disk is zigzag, and the cutter being related to is mating to be cut
The unit sizes of cutting disc, reactor and liquid level follow following ratio：Reaction kettle diameter：Shear disk diameter：Liquid level is
100:（25~75）:（50~100）.
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