CN108034062A - A kind of Black extinction-type polyimide film preparation method - Google Patents
A kind of Black extinction-type polyimide film preparation method Download PDFInfo
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- CN108034062A CN108034062A CN201711352463.4A CN201711352463A CN108034062A CN 108034062 A CN108034062 A CN 108034062A CN 201711352463 A CN201711352463 A CN 201711352463A CN 108034062 A CN108034062 A CN 108034062A
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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Abstract
The present invention is a kind of Black extinction-type polyimide film preparation method, key step:Ith, polyamic acid resin solution is routinely prepared.IIth, black paste is prepared, black pigment amount is 2~20wt% of polyamic acid resin solution solid content M.IIIth, delustring agent dispersing liquid is prepared, delustring dosage is 2~20wt% of M.IVth, black polyamic acid resin solution is prepared, above-mentioned polyamic acid resin solution, black paste and delustring agent dispersing liquid blending and stirring, defoam spare.Vth, black polyamic acid solution routinely salivates, and gained polyamide acid film is first sent into high-temperature solvent pond, and applies ultrasonic wave to it and carry out hot solvent ultrasound reunion processing, post-tensioning, imidization and sizing, Black extinction-type polyimide film is made.The black pigment and delustering agent average grain diameter of the present invention is moderate, increases hot solvent ultrasound reunion processing after resin solution salivation, gained film light transmittance, glossiness and physico mechanical characteristic have clear improvement.
Description
Technical field
The present invention relates to Kapton manufacturing technology, is specially a kind of Black extinction-type polyimide film preparation side
Method.
Background technology
Flexible printed wiring board (FPC) is widely used in 3C Product, optical lens module, liquid crystal display (LCD) module
And the product such as solar cell, and Kapton (Polyimide Film, abbreviation PI film) is commonly used for its base material or covering
Membrane material, since traditional PI film is respectively provided with high surface flatness in application process, film surface reflects most incident ray
And produce high gloss.The dazzle or astigmatism that the film surface of high gloss is produced there are light reflection, cause the uncomfortable of vision, when long
Between watch when easily make eye fatigue.Especially there is the high gloss PI films polyamides Asia of the colors such as black, white, blueness, red
Amine film, influence of the reflected light that its surface produces to vision are more notable.
On the other hand, when the larger and transparent higher PI films of surface gloss are applied to FPC, the circuit design point of FPC
Cloth is easy to understand and plagiarized by the same trade.
So the existing market demand possesses the PI films of the characteristics such as low-luster, low light transmission and high insulation resistance.Low-luster
The high insulation resistance and low light transmission of black PI films can protect internal circuit design, while component facade can be made to have more texture and U.S.
See.
The production technology of Kapton is using the polyamic acid resin solution by polycondensation reaction synthesis as original at present
Material, on slobbering machine salivation obtain the polyamic acid thick film with self-supporting, then by heating stretching, imidization, sizing at
Reason obtains Kapton.Obtain having concurrently the Kapton of low-luster, low light transmission and high insulation resistance, poly-
Must be added in imide membrane preparation process in colour additive (such as：Colorant, dyestuff etc.) and delustering agent.General technique is
Colour additive is used to reduce the light transmittance of Kapton, or addition delustering agent causes Kapton surface shape
Into concave-convex micro-structure to reduce the glossiness of Kapton.
The delustering agent of micron-level particle size is generally used in the prior art, because of the filtration system filter core aperture of existing extrusion die
Smaller, delustering agent frequently results in filtration system and blocks during extrusion salivates, and can not realize the serialization film of long period.
If the foreign matters such as the impurity that increase filtration system filter core aperture is be easy to cause in resin solution, gel are embedded in film again, cause thin
Film surface quality declines.
In black polyamide thin film manufacturing process, when inorganic particle (delustering agent) or carbon powder material (being in colour additive)
Particle diameter is too big or too small, and or adding too much or it is too low can be caused for the physical property of Kapton it is undesirable
Influence.If the particle diameter of inorganic particle or carbon powder material is larger, manufactured film surface is excessively coarse, is not suitable for electronic product
In；If the particle diameter of inorganic particle or carbon powder material is smaller, powder clustering phenomena is easily produced, causes additive in film to disperse
Non-uniform problem, and the operation of manufacturing process is difficult to control.It is dispersed in Kapton to influence additive, removes
The particle diameter of inorganic particle or carbon powder material, also has the content of inorganic particle or carbon powder material.If in film inorganic particle or
The content of carbon powder material is very few, and film glossiness and light transmittance can not just reduce and reach requirement.And content it is larger when, can equally produce
Raw additive disperses non-uniform problem；A large amount of addition delustering agents also result in Kapton performance degradation, easy embrittlement,
And a large amount of additives easily occur sedimentation and reunite in polyamic acid resin, can also increase the production cost of film.
The material of delustering agent can be divided into inorganic compound and organic compound.Wherein inorganic compound includes silica, oxygen
Change aluminium, calcium carbonate, barium sulfate, titanium dioxide etc., inorganic particulate has higher bulk density, if adding substantial amounts of inorganic particulate
It is may result in polyimide matrix to reunite and disperse inequality, so that the uniformity of film electrical insulating property is reduced, it is unfavorable
In subsequent applications.And the organic compound for being used for delustering agent includes poly- carbonic acid vinegar (PC), polystyrene (PS), polymethylacrylic acid
Methyl esters (PMMA), polyethylene (PE), polypropylene (PP), two vinegar of poly terephthalic acid second (PET), epoxy resin etc..Due to poly-
In the preparation process of imide membrane, chemical conversion temperature must be more than 250 DEG C, but above-mentioned organic compound can not all bear 250
DEG C or higher temperature.Made an addition to when using such organic compound as delustering agent in Kapton, film can occur
Crackle or hole, or because melt it is uneven produce color inconsistent patch the defects of.
At present, the main production technology of delustring black PI films is divided into two classes:One kind is to add black pigment in PI resins
With delustering agent filler, then there is the PI films of low-transmittance and low-luster by chemical imidization or hot imidization, synthesis,
This method is easy to operate, and positive effect, but due to the addition of mass filler, significantly reduces the mechanical property of PI films
Energy；Another kind of is one layer of PI film containing black pigment and photoextinction of coating on the single or double of PI basement membranes.Although this
Kind method can preferably make Kapton that desirable black effect be presented, and can ensure that Kapton is certain
Mechanical performance, but the black resin being additionally coated with would generally increase manufacturing process and cost, and to Kapton
Matter adversely affects.In addition, also Kapton can be caused to be exposed to hot adverse circumstance because resin coated layer heat resistance is poor
When performance degradation easily occurs.Existing many patent applications in relation to manufacturing low gloss black polyamide thin film, but because of manufacture
Complex process, production control accuracy requirement is higher and manufactures the defects such as cost height, it is difficult to implements.
Such as Chinese invention patent CN104742461A " the double-deck polyimide films and its system of low-luster of application in 2015
Make method " blending is inserted between levels polyimide film there is black pigment and form recess and hole in the thickness direction of film
The polyimide film in hole, obtains having high screening optical activity, the double-deck Kapton of low-luster concurrently.The China of application in 2015
Patent of invention CN 104830058A " polyimide film of low-k and low-luster and preparation method thereof ", film main structure
It is monofilm or multilayer for the fluoro containing polymers of polyimides, the carbon black of 0.5wt% to 5wt% and 15wt% to 40wt%
Film.Chinese invention patent " delustering agent, the polyimides containing the delustering agent being made of polyimides powder of application in 2012
Film and preparation method thereof " is disclosed the organic matting agent that polyimides powder is formed being uniformly distributed in Kapton and made
The Kapton of good film characteristics and low-luster must be had concurrently.The Chinese invention patent CN of application in 2012
103561953A " polyimide film " on the single or double of the polyimide layer (A) containing black organic pigment have comprising
Inorganic or organic filler polyimide layer (B), electrical insulating property, the electricity of the film are excellent in reliability.
The content of the invention
The purpose of the present invention is designing a kind of Black extinction-type polyimide film preparation method, using with such film one
As the delustering agent that uses prepare polyamic acid resin solution compared to the less inorganic filler delustering agent of average grain diameter, extrusion salivation into
There is type self-supporting polyamide acid film first to carry out hot solvent ultrasound reunion processing, then carry out biaxial tension, high temperature imidization
And heat treatment.Kapton product glossiness obtained by this law and light transmittance substantially reduce, film roll profile pattern
Increase, appearance substantially improve.
A kind of Black extinction-type polyimide film preparation method provided by the invention, including following key step:
Ith, the preparation of polyamic acid resin solution
Prepare polyamic acid resin solution according to a conventional method, in an inert atmosphere, control synthetic system temperature for 12 DEG C~
Aromatic diamine is added into solvent under conditions of 75 DEG C and be stirred dissolving, after aromatic diamine is completely dissolved, divide 3~8 times at the uniform velocity
It is (0.9~1.1) to add with aromatic diamine molar ratio：1 aromatic dianhydride, and stirred with 120r/ minutes~1200r/ minutes,
Synthesize to obtain polyamic acid resin solution through 3~24h of polycondensation reaction.
In view of cost, inert atmosphere is generally realized with nitrogen.
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides
(DMAC), N, N'- dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), tetramethyl sulfone, N,
N'- dimethyl-N, N'- acrylic urea (DMPU), N, any one in N dialkyl group Carboxylamides or any a variety of combination.
The polyamic acid resin solution that the dosage control of the aromatic diamine, aromatic dianhydride and solvent is formed for this step
In the ratio of solid content M be 10wt%~50wt%.
The aromatic diamine is 3,4'- diaminodiphenyl ethers, 1,3- bis--(4- amino-benzene oxygens) benzene, 4,4'- diaminourea two
Phenylate (4,4'-ODA), 1,3- diaminobenzenes, 2,2'- bis- (trifluoromethyl) benzidine, 4,4'- benzidines and p-phenylenediamine
(p-PDA) any one in or any a variety of combination.
The aromatic dianhydride is Pyromellitic Acid diacid (PMDA), 3,3', and 4,4'- biphenyl four completes acid diacid acid anhydride
(BPDA), 2,2', 3,3'- biphenyl four completes acid diacid acid anhydride (BPDA), diphenyl ether tetraformic dicarboxylic anhydride (ODPA), Benzophenone and completes acid two
Double (the 3,4- dicarboxylic acids phenyl) hexafluoropropane dianhydrides (6FDA) of acid anhydrides (BTDA), 2,2-, the double phthalic anhydrides of 4,4'- oxygen
(ODPA), 3,4,3', 4'- diphenyl thio-ether tetrformate dianhydride (3,4,3', 4'-TDPA), 2,3,2', 3'- diphenyl thio-ether tetrformates
It is any one in dianhydride (2,3,2', 3'-TDPA) and 2,3,3', 4'- diphenyl thio-ether tetrformate dianhydride (2,3,3', 4'-TDPA)
Kind or any a variety of combination.
IIth, prepared by black paste
Take black pigment to add in solvent to be mixed evenly to obtain black paste；The amount for adding black pigment is step I
2wt%~20wt% of solid content M in the polyamic acid resin solution, 0.01~0.8 μ of black pigment average grain diameter
m。
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides
(DMAC), N, N'- dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), tetramethyl sulfone, N,
N'- dimethyl-N, N'- acrylic urea (DMPU), N, any one in N dialkyl group Carboxylamides or any a variety of combination.
The solvent dosage control of the black paste be black pigment content ratio in black paste be 10wt%~
30wt%.
The amount of the black pigment added is preferably 6wt%~10wt% of M.
The average grain diameter for the black pigment that preferred version is added for O.015 μm~0.4 μm, be preferably average grain diameter O.02
μm~0.1 μm.If the particle diameter of black pigment is smaller, the phenomenon of aggregation is easily produced, causes to disperse non-uniform ask in the film
Topic, and be difficult to control in process operations.If the particle diameter of black pigment is larger, manufactured film surface is excessively coarse, does not apply to
In electronic product；If the additive amount of filler is too small, the same light-proofness effect that suppresses reduces；If excessive, polyamides Asia is damaged
Amine film physical property.
The mixing after black pigment is added in the solvent first to mix shear agitation, afterwards high speed dispersion mulser
Emulsification pretreatment processing, then handled through high pressure homogenizing, black paste is made.
IIIth, prepared by delustring agent dispersing liquid
Cancel after photo etching is added in solvent and be mixed evenly to obtain delustring agent dispersing liquid, the delustring dosage of addition is step
2wt%~20wt% of solid content M in the I polyamic acid resin solution, the delustering agent average grain diameter are 0.01~0.8
μm。
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides
(DMAC), N, N'- dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), tetramethyl sulfone, N,
N'- dimethyl-N, N'- acrylic urea (DMPU), N, any one in N dialkyl group Carboxylamides or any a variety of combination.
The delustering agent is any one in silica, polyimides, aluminium oxide and titanium dioxide or any a variety of
Combination.
The solvent dosage control of the delustring agent dispersing liquid is that the dulling agent content ratio in delustring agent dispersing liquid is
10wt%~30wt%.
Preferred version is 8wt%~12wt% that the amount of the delustering agent added is M.
The delustering agent average grain diameter that preferred version is added for O.05 μm~0.6 μm, the delustering agent preferably added is averaged
Particle diameter O.08 μm~0.3 μm.
If the average grain diameter of delustering agent is too small relative to Kapton thickness to be prepared, suppress glossiness effect
Reduce；If excessive, can not be sufficiently secured within Kapton.It is same to suppress gloss if the additive amount of filler is too small
Spending effect reduces；If excessive, Kapton physical property is damaged.
The mixing added in the solvent after delustering agent is mixing shear agitation to be first, afterwards high speed dispersion mulser
Emulsification pretreatment processing, then ground machine milled processed, and further carry out ultrasonic disperse processing and delustring agent dispersing liquid is made.
The step I prepares polyamic acid resin solution, step II prepares black paste and step III prepares delustering agent
Solvent used in dispersion liquid is identical.
IVth, prepared by black polyamic acid resin solution
Take polyamic acid resin solution obtained by step I, black paste obtained by step II and the delustering agent obtained by step III
Dispersion liquid blending and stirring, is made black polyamic acid resin solution, and defoams spare；
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, and thickness 20~
520 μm, the then dry solvent for removing 60wt%~35wt% at 100~250 DEG C, obtain with can self-supporting polyamides
Amino acid film, gained polyamide acid film is peeled off from ring steel belt, is sent into the solvent cell that temperature is 50 DEG C~180 DEG C, and right
It applies supersonic frequency 20KHZ~150KHZ, the ultrasonic wave of ultrasonic power 0.5KW~3.6KW, and the hot solvent in solvent cell surpasses
Acoustic agglomeration processing time is 10s~180s.
The hot solvent ultrasound reunion processing makes delustering agent, the black pigment carry out table contained by polyamide acid film upper and lower surface
Face migration, wriggle and uniform aggregation (particularly delustering agent inorganic filler aggregation is obvious and uniform) occur, and filler passes through self assembly
Behavior generation (micron order) is coarse and irregular molding modified surface, reduces film glossiness.If solvent temperature mistake during processing
It is low, extinction effect unobvious；Temperature is excessive, be easy to cause Film Fractionation, causes film to be broken, and influences the serialization of film production；
The processing time too short same unobvious of its extinction effect, processing time is long also to be easy to cause Film Fractionation, causes film continuous
The problem of metaplasia production is abnormal.
The solvent that the hot solvent ultrasound is reunited in the high-temperature solvent pond handled is aprotic polar solvent low molecular weight
Carboxylamide, specially N, N'- dimethylacetylamides (DMAC), N, N'- dimethylformamides (DMF), 1-methyl-2-pyrrolidinone
(NMP), dimethyl sulfoxide (DMSO), tetramethyl sulfone, N, N'- dimethyl-N, N'- acrylic urea (DMPU), N, N dialkyl group carboxyl acyls
Any one in amine or any a variety of combination.
The temperature of hot solvent ultrasound reunion processing is 60 DEG C~150 DEG C described in preferred version, and the time is 20s~120s.
The temperature of hot solvent ultrasound reunion processing is 80 DEG C~120 DEG C described in preferred solution, and the time is 30s~60s.
Further, the ultrasonic frequency applied is 60KHZ~100KHZ, power is 1.8KW~2.8KW.
By the hot solvent ultrasound reunite processing polyamide acid film be delivered in length and breadth on biaxial orientation stretching machine carry out 0.8~
2.2 times of stretchings, 180 DEG C~500 DEG C high temperature imidization processing, after last 180 DEG C~360 DEG C sizings, winding, is made thickness 2.5
~50 μm of Black extinction-type polyimide film.
Compared with prior art, it is the advantages of a kind of Black extinction-type polyimide film preparation method of the invention：1st, often
It is micron order to advise delustering agent median particle size, and delustering agent granularity of the invention is only 0.01~0.8 μm, and extrusion salivation is molding to be had
Self-supporting polyamide acid film first carries out hot solvent ultrasound reunion processing, and polyamide acid film is ultrasonically treated in hot solvent,
Delustering agent, black pigment is reunited, reduce film surface glossiness；2nd, prepared Black extinction-type polyimide film is visible
Light light transmittance is less than 0.1%, 60 ° of gloss value ＜ 25, elongation ＞ 60%, tensile strength >=230MPa, elastic modulus G T.GT.GT
3.5GPa, and maintain the insulation performance and mechanical property of Kapton itself；3rd, prepared black matt type polyamides is sub-
Amine film has shading, photoextinction, and the processing that ultrasound is reunited in hot solvent also enhances the tear resistance of film；4、
Increased hot solvent ultrasound reunite the solvent cell of processing, after existing slobbering machine, before biaxial orientation stretching machine, debugging is held
Easily, and it can ensure that producing continuous, technique is simple and convenient to operate；5th, the black matt type polyimides prepared by this method is thin
Film is suitable for basement membrane or cover layer, electronic tag basement membrane of flexible print circuit board etc..
Embodiment
Embodiment 1
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, synthetic system temperature is controlled as 12 DEG C, to 45kg N, N'- dimethylacetylamides (DMAC) solvent
Middle addition 2.39kg aromatic diamines 4,4'- diaminodiphenyl ethers (4,4'-ODA) are stirred dissolving, and 4,4'-ODA are completely dissolved
Afterwards, it is 1 to divide 8 at the uniform velocity addition and aromatic diamine molar ratios:1 2.61kg aromatic dianhydride Pyromellitic Acid diacid (PMDA),
And stirred with 1200r/ minutes, synthesize to obtain solid content M=5kg through polycondensation reaction 12h, i.e. solid content ratio is the poly- of 10wt%
Amic acid resin solution；
IIth, prepared by black paste
The 20wt% of the solid content M in polyamic acid resin solution as obtained by step I takes carbon black 1kg to add solvent N,
It is mixed evenly to obtain the black paste of content of carbon black 30% in N'- dimethylacetylamides (DMAC) 2.33kg；This example carbon black
0.01 μm of average grain diameter.
The black pigment of this step can also use black titanium, bone black (bone black), Cyanine Black (cyanine black), second
Acetylene black, lampblack, graphite, iron oxide black, nigrosine and Hua Jing it is black in any one or any a variety of combination.
The mixing added in this example N, N'- dimethylacetylamide (DMAC) solvent after black pigment carbon black exists to be first
Shear agitation 30 minutes is mixed under the conditions of 120r/ minutes, after through high speed dispersion mulser emulsification pretreatment processing in 3600r/ minute
240 minutes, then through the high-pressure homogeneous processing of high pressure homogenizer 180MPa 30 minutes, black paste is made.
IIIth, prepared by delustring agent dispersing liquid
The 2wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching silica 0.1kg
It is mixed evenly to obtain dioxide-containing silica ratio 20% after adding in solvent N, N'- dimethylacetylamide (DMAC) 0.5kg
Delustring agent dispersing liquid, this example silica average grain diameter be 0.8 μm.
The delustering agent of this step can also use any one in polyimides, aluminium oxide and titanium dioxide or any a variety of
Combination.
The mixing added in this example solvent N, N'- dimethylacetylamide (DMAC) after delustering agent silica exists to be first
Shear agitation 30 minutes is mixed under the conditions of 1200r/ minutes, after through high speed dispersion mulser emulsification pretreatment processing in 1200r/ minute
30 minutes, then ground machine milled processed 30 minutes, and further carry out that delustering agent point is made after ultrasonic disperse is handled 240 minutes
Dispersion liquid.
IVth, prepared by black polyamic acid resin solution
Take polyamic acid resin solution obtained by step I, black paste, the delustering agent of step III gained disperse obtained by step II
Liquid blending and stirring, is made black polyamic acid resin solution, and defoams spare.
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, 20 μ of thickness
M, the then dry solvent for removing 35wt% at 100 DEG C, obtain with can self-supporting polyamide acid film, this example is by gained
Polyamide acid film is peeled off from ring steel belt, is sent into temperature as 50 DEG C of N, in N'- dimethylacetylamides (DMAC) solvent cell, and
Apply supersonic frequency 20KHZ, the ultrasonic wave of ultrasonic power 0.5KW to it, when the hot solvent ultrasound reunion in solvent cell is handled
Between be 180s.
The polyamide acid film handled of reuniting by above-mentioned hot solvent ultrasound is delivered to carries out 2.2 times in length and breadth on biaxial orientation stretching machine
Stretching, 500 DEG C of high temperature imidizations processing, then after carrying out 360 DEG C of sizings, finally wind, the black matt type of 2.5 μm of thickness is made
Kapton.
Embodiment 2
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, to control synthetic system temperature be 22 DEG C, to 37.5kg N, in N'- dialkyl group Carboxylamide solvents
Add 6.38kg aromatic diamines 2, double (trifluoromethyl) benzidine of 2'- are stirred dissolving, after it is completely dissolved, divide 3 times it is even
It is 0.98 that speed, which is added with aromatic diamine molar ratio,:1 5.99kg aromatic dianhydrides 3,3', 4,4'- biphenyl four completes acid diacid acid anhydride
(BPDA), and with 1000r/ minutes stir, synthesize to obtain solid content M=12.4kg through polycondensation reaction 8h, i.e. solid content ratio is
The polyamic acid resin solution of 25wt%；
IIth, prepared by black paste
The 16wt% of the solid content M in polyamic acid resin solution as obtained by step I takes iron black 2kg to add solvent N,
It is mixed evenly to obtain the black paste of iron black content 10% in N'- dimethyl sulfoxides (DMSO) 18kg；The iron black average grain of this example
0.8 μm of footpath.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 20wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching silica 2.5kg
It is mixed evenly to obtain disappearing for dioxide-containing silica ratio 30% after adding in solvent N-methyl pyrilidone (NMP) 5.8kg
Photo etching dispersion liquid, this example silica average grain diameter are 0.01 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, 520 μ of thickness
M, the then dry solvent for removing 60wt% at 250 DEG C, obtain with can self-supporting polyamide acid film, this example is by gained
Polyamide acid film is peeled off from ring steel belt, is sent into temperature as 180 DEG C of N, in N'- dimethylacetylamides (DMAC) solvent cell,
And apply supersonic frequency 150KHZ, the ultrasonic wave of ultrasonic power 3.6KW to it, the hot solvent ultrasound reunion processing in solvent cell
Time is 10s.
The polyamide acid film handled of reuniting by above-mentioned hot solvent ultrasound is delivered to carries out 0.8 times in length and breadth on biaxial orientation stretching machine
Stretching, 180 DEG C of high temperature imidizations processing, then after carrying out 180 DEG C of sizings, finally wind, the black matt type of 50 μm of thickness is made
Kapton.
Embodiment 3
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, synthetic system temperature is controlled to add for 50 DEG C into 25kg 1-methyl-2-pyrrolidinones (NMP) solvent
Enter 7.92kg aromatic diamines 3,4'- diaminodiphenyl ethers (3,4'-ODA) are stirred dissolving, after it is completely dissolved, divide 5 times
It is 1.02 at the uniform velocity to add with aromatic diamine molar ratio:1 17.23kg aromatic dianhydrides 2, double (3, the 4- dicarboxylic acids phenyl) hexafluoros of 2-
Propane dianhydride (6FDA), and stirred with 1000r/ minutes, synthesize to obtain solid content M=25.15kg through polycondensation reaction 8h, i.e., contain admittedly
Amount ratio is the polyamic acid resin solution of 50wt%；
IIth, prepared by black paste
The 4wt% of the solid content M in polyamic acid resin solution as obtained by step I takes acetylene black 1kg to add solvent N-
It is mixed evenly to obtain the black paste of acetylene black content 15% in methyl pyrrolidone (NMP) 5.6kg；This example acetylene black is put down
Equal 0.02 μm of particle diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 16wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching aluminium oxide 4.04kg
It is mixed evenly to obtain the delustering agent of alumina content ratio 20% after adding in solvent N, N'- dimethyl sulfoxide (DMSO) 16kg
Dispersion liquid, this example aluminium oxide average grain diameter are 0.3 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, 250 μ of thickness
M, the then dry solvent for removing 50wt% at 180 DEG C, obtain with can self-supporting polyamide acid film, this example is by gained
Polyamide acid film is peeled off from ring steel belt, is sent into temperature as 150 DEG C of N, in N'- dimethylacetylamides (DMAC) solvent cell,
And apply supersonic frequency 100KHZ, the ultrasonic wave of ultrasonic power 2.8KW to it, the hot solvent ultrasound reunion processing in solvent cell
Time is 20s.
The polyamide acid film handled of reuniting by above-mentioned hot solvent ultrasound is delivered to carries out 1.2 times in length and breadth on biaxial orientation stretching machine
Stretching, 380 DEG C of high temperature imidizations processing, then after carrying out 250 DEG C of sizings, finally wind, the black matt type of 25 μm of thickness is made
Kapton.
Embodiment 4
Ith, the preparation of polyamic acid resin solution
In argon gas atmosphere, synthetic system temperature is controlled as 60 DEG C, to 42.5kg N, N'- dimethyl-N, N'- acrylic urea
(DMPU) 2.22kg aromatic diamines p-phenylenediamine (p-PDA) is added in solvent and is stirred dissolving, after p-PDA is completely dissolved, divide 5
Secondary at the uniform velocity add with aromatic diamine molar ratio is 1.1:1 5.48kg aromatic dianhydrides biphenyl four completes acid diacid acid anhydride (BPDA), and
Stirred with 800r/ minutes, synthesize to obtain solid content M=7.70kg through polycondensation reaction 3h, i.e. solid content ratio is the poly- of 15wt%
Amic acid resin solution；
IIth, prepared by black paste
The 6wt% of the solid content M in polyamic acid resin solution as obtained by step I takes the black 0.47kg of titanium to add solvent N,
It is mixed evenly to obtain the black paste of the black content 10% of titanium in N'- dialkyl group Carboxylamides 4.23kg；This example titanium is black average
0.1 μm of particle diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 5wt% of the solid content M in polyamic acid resin solution as obtained by step I takes TITANIUM DIOXIDE DELUSTRANT 0.39kg
It is mixed evenly to obtain disappearing for content of titanium dioxide ratio 12% after adding in solvent N, N'- dialkyl group Carboxylamide 2.86kg
Photo etching dispersion liquid, this example titanium dioxide average grain diameter are 0.08 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, 360 μ of thickness
M, the then dry solvent for removing 40wt% at 150 DEG C, obtain with can self-supporting polyamide acid film, this example is by gained
Polyamide acid film is peeled off from ring steel belt, is sent into temperature as 120 DEG C of N, in N'- dimethylformamides (DMF) solvent cell, and
Apply supersonic frequency 60KHZ, the ultrasonic wave of ultrasonic power 1.8KW to it, when the hot solvent ultrasound reunion in solvent cell is handled
Between be 30s.
The polyamide acid film handled of reuniting by above-mentioned hot solvent ultrasound is delivered to carries out 1.4 times in length and breadth on biaxial orientation stretching machine
Stretching, 450 DEG C of high temperature imidizations processing, then after carrying out 300 DEG C of sizings, finally wind, the black matt type of 36 μm of thickness is made
Kapton.
Embodiment 5
Ith, the preparation of polyamic acid resin solution
In argon gas atmosphere, control synthetic system temperature to be 15 DEG C, to 40kg N, add in N'- Dimethyl Asian Maple (DMSO) solvent
Enter 2.49kg aromatic diamines p-phenylenediamine (p-PDA) and be stirred dissolving, after it is completely dissolved, point 4 at the uniform velocity additions and virtue
Race's diamines molar ratio is 0.9:1 7.51kg 3,4,3', 4'- diphenyl thio-ether tetrformates dianhydride (3,4,3', 4'-TDPA), and with
Stir within 800r/ minutes, synthesize to obtain solid content M=10kg through polycondensation reaction 8h, i.e. solid content ratio is the polyamide of 20wt%
Acid resin solution；
IIth, prepared by black paste
The 2wt% of the solid content M in polyamic acid resin solution as obtained by step I takes nigrosine 0.2kg to add solvent
In N, N'- Dimethyl Asian Maple (DMSO) 0.64kg, it is mixed evenly to obtain the black paste of nigrosine content 30%；This example aniline
Black 0.4 μm of average grain diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 8wt% of the solid content M in polyamic acid resin solution as obtained by step I takes TITANIUM DIOXIDE DELUSTRANT 0.8kg
It is mixed evenly to obtain disappearing for content of titanium dioxide ratio 30% after adding in solvent N, N'- Dimethyl Asian Maple (DMSO) 1.86kg
Photo etching dispersion liquid, this example titanium dioxide average grain diameter are 0.05 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, 400 μ of thickness
M, the then dry solvent for removing 30wt% at 200 DEG C, obtain with can self-supporting polyamide acid film, this example is by gained
Polyamide acid film is peeled off from ring steel belt, temperature is sent into as 80 DEG C of N, in N'- Dimethyl Asian Maple (DMSO) solvent cell, and to it
Apply supersonic frequency 90KHZ, the ultrasonic wave of ultrasonic power 2.2KW, the processing time of reuniting of the hot solvent ultrasound in solvent cell is
60s。
The polyamide acid film handled of reuniting by above-mentioned hot solvent ultrasound is delivered to carries out 1 times of drawing in length and breadth on biaxial orientation stretching machine
Stretch, 250 DEG C of high temperature imidizations processing, then after carrying out 220 DEG C of sizings, finally wind, the black matt type that 40 μm of thickness is made gathers
Imide membrane.
Embodiment 6
Ith, the preparation of polyamic acid resin solution
In argon gas atmosphere, synthetic system temperature is controlled as 72 DEG C, to 40kg N, N'- dimethylacetylamides (DMAC) solvent
Middle addition 4.79kg aromatic diamines 4,4'- diaminodiphenyl ethers (4,4'-ODA) are stirred dissolving, and 4,4'-ODA are completely dissolved
Afterwards, it is 1 to divide 8 at the uniform velocity addition and aromatic diamine molar ratios:1 5.21kg aromatic dianhydride Pyromellitic Acid diacid (PMDA),
And stirred with 800r/ minutes, synthesize to obtain solid content M=10kg through polycondensation reaction 12h, i.e. solid content ratio is the poly- of 20wt%
Amic acid resin solution；
IIth, prepared by black paste
The 2wt% of the solid content M in polyamic acid resin solution as obtained by step I takes graphite 1kg to add solvent N, N'-
It is mixed evenly to obtain the black paste of content of graphite 30% in dimethylacetylamide (DMAC) 2.33kg；This example graphite is averaged
0.015 μm of particle diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 12wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching polyimides 1.2kg
It is mixed evenly to obtain polyimide content ratio 30% after adding in solvent N, N'- dimethylacetylamide (DMAC) 2.8kg
Delustring agent dispersing liquid, this example polyimides average grain diameter be 0.6 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, 100 μ of thickness
M, the then dry solvent for removing 55wt% at 220 DEG C, obtain with can self-supporting polyamide acid film, this example is by gained
Polyamide acid film is peeled off from ring steel belt, is sent into temperature as 60 DEG C of N, in N'- dimethylacetylamides (DMAC) solvent cell, and
Apply supersonic frequency 120KHZ, the ultrasonic wave of ultrasonic power 3.2KW to it, when the hot solvent ultrasound reunion in solvent cell is handled
Between be 120s.
The polyamide acid film handled of reuniting by above-mentioned hot solvent ultrasound is delivered to carries out 2 times of drawings in length and breadth on biaxial orientation stretching machine
Stretch, 300 DEG C of high temperature imidizations processing, then after carrying out 260 DEG C of sizings, finally wind, the black matt type that 10 μm of thickness is made gathers
Imide membrane.
Comparative example is 1.
Step I to IV same as Example 1,
When prepared by step V Kapton, no hot solvent ultrasound reunion processing, carries out only according to conventional filming technology
Black polyamide thin film is made in coating, dry solidification, stretching, imidization, heat treatment.
Comparative example is 2.
It is step I, II and step IV, V same as Example 1,
When prepared by step III delustring agent dispersing liquid, the average grain diameter of delustering agent silica is 2 μm, more than 1 μm.Still by step
The 2wt% of solid content M in the polyamic acid resin solution of rapid I gained takes 0.1kg silica to add solvent N, N'- dimethyl
It is mixed evenly to obtain the delustring agent dispersing liquid of dioxide-containing silica ratio 20% after in acetamide (DMAC) 0.5kg.
Comparative example is 3.
It is step I, II and step IV, V same as Example 1,
When prepared by step III delustring agent dispersing liquid, the average grain diameter of delustering agent silica is 0.008 μm, less than 0.01 μ
m。
Other preparation methods are identical with 1 step III of embodiment.
Comparative example is 4.
It is step I, III and step IV, V same as Example 1,
When prepared by step II black paste, 1.8 μm of carbon black average grain diameter, the black pigment more than application claims is averaged grain
0.8 μm of the footpath upper limit.
Other preparation methods are identical with 1 step II of embodiment.
Comparative example is 5.
It is step I, III and step IV, V same as Example 1,
When prepared by step II black paste, 0.008 μm of carbon black average grain diameter, the black pigment less than application claims is averaged
0.01 μm of particle diameter limit.
Other preparation methods are identical with 1 step II of embodiment.
Comparative example is 6.
Step I to IV same as Example 1,
When prepared by step V Black extinction-type polyimide film, gained polyamide acid film is peeled off from ring steel belt,
Temperature is sent into as 30 DEG C of N, in N'- dimethylacetylamides (DMAC) solvent cell, and applies supersonic frequency 180KHZ, ultrasound to it
The ultrasonic wave of power 0.2KW, the hot solvent ultrasound reunion processing time in solvent cell is 300s.The other processes of this step
It is identical with 1 step V of embodiment.
Comparative example is 7.
Step I to IV same as Example 1,
When prepared by step V Black extinction-type polyimide film, gained polyamide acid film is peeled off from ring steel belt,
Temperature is sent into as 250 DEG C of N, in N'- dimethylacetylamides (DMAC) solvent cell, and applies supersonic frequency 10KHZ, ultrasound to it
The ultrasonic wave of power 4.8KW, the hot solvent ultrasound reunion processing time in solvent cell is 5s.The other processes of this step with
1 step V of embodiment is identical.
It is swollen to detect the light transmittance of black polyamide thin film made from the various embodiments described above and each comparative example, glossiness, heat
Swollen coefficient (CTE), tensile strength, elongation, modulus, tearing strength and show the performances such as quality, the results are shown in Table 1：
1 embodiment of the present invention of table and the performance table of comparisons of film obtained by comparative example
As shown in table 1, embodiment 1 to 6 prepare Black extinction-type polyimide film have relatively low glossiness,
The excellent optical property such as light transmittance and mechanical property (tensile strength, elongation and modulus are of a relatively high), while also show
High resistance to tearing (tearing strength) and good thermal property (such as CTE, shrinking percentage is relatively low).
And 1. black polyamide thin film that the comparative example handled is prepared of reuniting without hot solvent ultrasound does not have desired light
Learn performance, thermal property and mechanical property.Comparative example is 2. in 5., the average grain diameter mistake of used black pigment and delustering agent
Big or too small, the black polyamide thin film optical property of preparation, thermal property and mechanical property are substantially poor.Comparative example is 6.
In, hot solvent ultrasound reunion treatment temperature is excessive to cause polyamide acid film to dissolve, can not continuous film forming.Comparative example 7. in, thermosol
Agent ultrasound reunion treatment temperature is too low, supersonic frequency is too small, and processing time is shorter, film surface delustering agent, black pigment etc.
Filler reunion unobvious, cause film glossiness still higher.
Above-described embodiment, is only further described the purpose of the present invention, technical solution and beneficial effect specific
A example, the present invention are not limited to this.All any modifications made within the scope of disclosure of the invention, equivalent substitution, change
Into etc., it is all contained within protection scope of the present invention.
Claims (10)
1. a kind of Black extinction-type polyimide film preparation method, including following key step:
Ith, the preparation of polyamic acid resin solution
Polyamic acid resin solution is prepared according to a conventional method, and in an inert atmosphere, it is 12 DEG C~75 DEG C to control synthetic system temperature
Under conditions of add aromatic diamine into solvent and be stirred dissolving, after aromatic diamine is completely dissolved, divides and at the uniform velocity add for 3~8 times
It is (0.9~1.1) with aromatic diamine molar ratio：1 aromatic dianhydride, and stirred with 120r/ minutes~1200r/ minutes, through contracting
3~24h of poly- reaction synthesizes to obtain polyamic acid resin solution；
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides, N, N'-
Dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, tetramethyl sulfone, N, N'- dimethyl-N, N'- acrylic urea, N, N bis-
Any one in alkyl carboxyl acid amides or any a variety of combination；
In the polyamic acid resin solution that the dosage control of the aromatic diamine, aromatic dianhydride and solvent is formed for this step
The ratio of solid content M is 10wt%~50wt%；
The aromatic diamine is 3,4'- diaminodiphenyl ethers, 1,3- bis--(4- amino-benzene oxygens) benzene, 4,4'- diaminourea hexichol
Any one in ether, 1,3- diaminobenzenes, 2,2'- bis- (trifluoromethyl) benzidine, 4,4'- benzidines and p-phenylenediamine
Or any a variety of combination；
The aromatic dianhydride is Pyromellitic Acid diacid, 3,3', and 4,4'- biphenyl four completes acid diacid acid anhydride, 2,2', 3,3'- biphenyl
Four, which complete acid diacid acid anhydride, diphenyl ether tetraformic dicarboxylic anhydride, Benzophenone, completes double (the 3,4- dicarboxylic acids phenyl) hexafluoros third of acid diacid acid anhydride, 2,2-
Alkane dianhydride, 4,4'- oxygen double phthalic anhydride, 3,4,3', 4'- diphenyl thio-ether tetrformates dianhydride, 2,3,2', 3'- diphenyl sulfides
Any one in tetracarboxylic acid dianhydride and 2,3,3', 4'- diphenyl thio-ether tetrformate dianhydride or any a variety of combination；
IIth, prepared by black paste
Take black pigment to add in solvent to be mixed evenly to obtain black paste；The amount of black pigment is added as described in step I
2wt%~20wt% of solid content M in polyamic acid resin solution, 0.01~0.8 μm of the black pigment average grain diameter；
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides, N, N'-
Dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, tetramethyl sulfone, N, N'- dimethyl-N, N'- acrylic urea, N, N bis-
Any one in alkyl carboxyl acid amides or any a variety of combination；
The solvent dosage control of the black paste is that the black pigment content ratio in black paste is 10wt%~30wt%；
IIIth, prepared by delustring agent dispersing liquid
Cancel after photo etching is added in solvent and be mixed evenly to obtain delustring agent dispersing liquid, the delustring dosage of addition is step I institute
2wt%~20wt% of the solid content M in polyamic acid resin solution is stated, the delustering agent average grain diameter is 0.01~0.8 μm；
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides, N, N'-
Dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, tetramethyl sulfone, N, N'- dimethyl-N, N'- acrylic urea, N, N bis-
Any one in alkyl carboxyl acid amides or any a variety of combination；
The delustering agent is any one or any a variety of group in silica, polyimides, aluminium oxide and titanium dioxide
Close；
The solvent dosage control of the delustring agent dispersing liquid be dulling agent content ratio in delustring agent dispersing liquid be 10wt%~
30wt%；
IVth, prepared by black polyamic acid resin solution
Polyamic acid resin solution obtained by step I, black paste obtained by step II and the delustering agent obtained by step III is taken to disperse
Liquid blending and stirring, is made black polyamic acid resin solution, and defoams spare；
Vth, prepared by Black extinction-type polyimide film
Black polyamic acid solution prepared by step IV by extrusion molding mould coated on ring steel belt, thickness for 20~
520 μm, the then dry solvent for removing 60wt%~35wt% at 100~250 DEG C, obtain with can self-supporting polyamides
Amino acid film, gained polyamide acid film is peeled off from ring steel belt and is sent into the solvent cell that temperature is 50 DEG C~180 DEG C, and right
It applies supersonic frequency 20KHZ~150KHZ, the ultrasonic wave of ultrasonic power 0.5KW~3.6KW, and the hot solvent in solvent cell surpasses
Acoustic agglomeration processing time is 10s~180s；
The solvent that the hot solvent ultrasound is reunited in the high-temperature solvent pond handled is aprotic polar solvent low molecular weight carboxyl
Acid amides, specially N, N'- dimethylacetylamides, N, N'- dimethylformamides, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, tetramethyl
Sulfone, N, N'- dimethyl-N, N'- acrylic urea, N, any one in N dialkyl group Carboxylamides or any a variety of combination；
The polyamide acid film handled of reuniting by hot solvent ultrasound is delivered to carries out 0.8~2.2 in length and breadth on biaxial orientation stretching machine
Stretch again, 180 DEG C~500 DEG C high temperature imidizations processing, after last 180 DEG C~360 DEG C sizings, winding, obtained 2.5 μm of thickness~
50 μm of Black extinction-type polyimide film.
2. Black extinction-type polyimide film preparation method according to claim 1, it is characterised in that：
The amount that the black pigment that black paste is added is prepared in the step II is 6wt%~10wt% of M.
3. Black extinction-type polyimide film preparation method according to claim 1, it is characterised in that：
Prepared in the step II average grain diameter of the black pigment that black paste is added O.02 μm~0.1 μm.
4. Black extinction-type polyimide film preparation method according to claim 1, it is characterised in that：
8wt%~12wt% that the amount that the step III prepares the delustering agent entered added by delustring agent dispersing liquid is M.
5. Black extinction-type polyimide film preparation method according to claim 1, it is characterised in that：
The step III prepare the average grain diameter of the delustering agent entered added by delustring agent dispersing liquid for O.05 μm~0.6 μm.
6. Black extinction-type polyimide film preparation method according to claim 1, it is characterised in that：
The step III prepare the average grain diameter of the delustering agent entered added by delustring agent dispersing liquid for O.08 μm~0.3 μm.
7. Black extinction-type polyimide film preparation method according to any one of claim 1 to 6, its feature exist
In：
The step I prepares polyamic acid resin solution, step II prepares black paste and step III prepares delustering agent and disperses
Solvent used in liquid is identical.
8. Black extinction-type polyimide film preparation method according to claim 1, it is characterised in that：
The ultrasonic temperature handled of reuniting of the hot solvent is during the step V prepares Black extinction-type polyimide film
60 DEG C~150 DEG C, the time is 20s~120s.
9. Black extinction-type polyimide film preparation method according to claim 1, it is characterised in that：
The ultrasonic temperature handled of reuniting of the hot solvent is during the step V prepares Black extinction-type polyimide film
80 DEG C~120 DEG C, the time is 30s~60s.
10. Black extinction-type polyimide film preparation method according to claim 8 or claim 9, it is characterised in that：
The ultrasonic frequency applied is 60KHZ~100KHZ, power is 1.8KW~2.8KW.
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