CN107987529A - A kind of sub- black Kapton preparation method - Google Patents
A kind of sub- black Kapton preparation method Download PDFInfo
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention is a kind of sub- black Kapton preparation method, key step:Ith, polyamic acid resin solution is prepared according to a conventional method.IIth, black paste, 2~20wt% that the amount of black pigment is the solid content M in above-mentioned polyamic acid resin solution are prepared.IIIth, black polyamic acid resin solution is prepared, above-mentioned polyamic acid resin solution, black paste and agglomerator are blended, and are stirred under low-temperature condition, and defoaming is spare.IVth, conveyance conduit heats after the filtered system of black polyamic acid solution, and resin solution completes preheating reunion processing, then sub- black Kapton is routinely made.Also the delustring agent dispersing liquid for 2~20wt% that delustring dosage is M can be added in step III.0.01~0.8 μm of the black pigment average grain diameter of the present invention, and agglomerator is added during polyamic acid resin polycondensation synthesis, 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 sub- black Kapton preparation 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, salivates on slobbering machine and obtains the polyamic acid thick film with self-supporting, then fixed by heating stretching, imidization, cooling
Type handles to obtain Kapton.Obtain having concurrently the Kapton of low-luster, low light transmission and high insulation resistance,
Must be added in Kapton preparation process in colour additive (such as：Colorant, dyestuff etc.) and delustering agent.General work
Skill is the light transmittance for using colour additive to reduce Kapton, or addition delustering agent causes Kapton table
Face forms 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.
At present, the main production technology of black matt 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.Early stage also once attempted to directly prepare the PI of black low gloss using the large-sized pigment of micron order
Film, but bulky grain pigment is easier to block filtration system, leads to not continuously be film-made, has to abandon attempting.It is existing many related
The patent application of low gloss black polyamide thin film is manufactured, but because manufacturing process is complicated, production control accuracy requirement is higher
And the defect such as manufacture cost height, it is difficult to implement.
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 a kind of sub- black Kapton preparation method of design, it is molten to prepare black polyamic acid resin
Liquid, without delustering agent, agglomerator is added during polyamic acid resin polycondensation synthesis and is preheated after filtration system
Reunion is handled, and finally carries out salivation film forming, and preferable Extinction Characteristic is presented in film surface in the black pigment particles of homopolymerization.This law
Obtained Kapton product glossiness and light transmittance substantially reduce, and film roll profile pattern increase, appearance changes significantly
It is kind.
A kind of sub- black Kapton preparation method provided by the invention, 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 0 DEG C~50 to control synthetic system temperature
Aromatic diamine is added into solvent under conditions of DEG C and be stirred dissolving, after aromatic diamine is completely dissolved, divides 3~8 times and at the uniform velocity add
It is (0.9~1.1) to enter with aromatic diamine molar ratio：1 aromatic dianhydride, and stirred with 120r/min~1200r/min, through contracting
3~12h of poly- reaction synthesizes to obtain polyamic acid resin solution.
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 (3, the 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 for the black pigment that preferred version is added is 6wt%~10wt% of M.
The average grain diameter for the black pigment that preferred version is added for O.02 μm~0.1 μm.If the particle diameter of black pigment compared with
It is small, the phenomenon of aggregation is easily produced, causes to disperse non-uniform problem in the film, and is difficult to control in process operations.If
The particle diameter of black pigment is larger, and manufactured film surface is excessively coarse, is not suitable in electronic product；If the additive amount mistake of filler
Small, then equally suppressing light-proofness effect reduces；If excessive, Kapton physical property is damaged.
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 black polyamic acid resin solution
Polyamic acid resin solution obtained by step I, black paste obtained by step II and agglomerator blending are taken, keeps polymerization
System is under 0~20 DEG C of low-temperature condition and stirs, and black polyamic acid resin solution is made, disappears under 0~20 DEG C of low-temperature condition
Steep spare；
The agglomerator dosage be M 0.2wt%-2wt%, preferred version agglomerator dosage be M 0.3wt%~
1wt%, is preferably 0.4wt%~0.6wt% that polyimides weight is M.If the additive amount of agglomerator is too small, suppress gloss
Spending effect reduces；If excessive, Kapton physical property is damaged.
The agglomerator is inorganic or organic agglomerator, it is mainly realized by charge neutralization, bridging action is added
Black pigment is added uniformly to reunite in polyimide matrix.The preferred macromolecule organic flocculating agent carboxymethyl cellulose of agglomerator
Sodium (CMC), polyacrylamide (PAM), hydrolysed polyacrylic, Sodium Polyacrylate, calcium polyacrylate (CPA), acrylic acid and methacrylic acid
Copolymer, polydimethyl diallyl ammonium chloride, konjak glucomannan (KGM), xanthans (XTG) and sodium alginate (SA)
In any one or any a variety of combination.
IVth, prepared by sub- black Kapton
Black polyamic acid solution prepared by step III in course of conveying after filtered system, resin supplying channel into
The black polyamic acid resin solution completion preheating reunion processing that row heats, keeps 75~120 DEG C of temperature to make in it.Afterwards
Self-supporting Polyamic Acid Film is made into slobbering machine in black polyamic acid resin solution, then through biaxial tension, high temperature imidization
And heat treatment, obtain sub- black polyamide thin film.
The step III can also add delustring agent dispersing liquid when preparing black polyamic acid resin solution.The step III is made
During standby black polyamic acid resin solution, take polyamic acid resin solution obtained by step I, black paste obtained by step II and disappear
Photo etching dispersion liquid blending and stirring, is made black polyamic acid resin solution, and defoams spare.
Preparing for the delustring agent dispersing liquid is as follows：
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 delustering agent is any one in silica, polyimides, aluminium oxide and titanium dioxide or any a variety of
Combination.
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 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 prepares delustring agent dispersing liquid
Solvent used is identical.
Compared with prior art, it is the advantages of a kind of black Kapton preparation method in Asia of the present invention：1st, in polyamide
Agglomerator is added during acid resin polycondensation synthesis, and preheating group is carried out after the filtration system during by resin transfer
Poly- processing, resin is acted in preheating treatment procedure, inside it by agglomerator triggers black pigment to be migrated, wriggled and occurred
Preferable Extinction Characteristic is presented in film surface in uniformly aggregation, the homopolymerization black pigment particles formed, and the pigment of reunion meets
The requirement of film low gloss；Also delustering agent can be added, to improve extinction effect；At the same time because reunion is carried out after filtration apparatus,
Therefore traditional filtering precision can be kept, and filter efficiency is greatly improved, reduce filtration apparatus and replace number, realize long continuous
Production；2nd, prepared sub- black Kapton visible light transmittance rate is less than 0.1%, 60 ° of gloss value ＜ 30, elongation
＞ 65%, tensile strength >=230MPa, elastic modulus G T.GT.GT 3GPa, and maintain the insulation characterisitic and power of Kapton itself
Learn characteristic；3rd, the prepared black Kapton in Asia has shading, photoextinction, and because the introducing of agglomerator enhances film
Tear resistance；4th, this law realizes matt performance by adding agglomerator, and ensures continuous production, and technique is simple, easy to operate.
Embodiment
Embodiment 1
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, synthetic system temperature is controlled as 10 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/min, 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) 2kg；This example carbon black is averaged
0.01 μm of particle 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
Under the conditions of 120r/min mix shear agitation 30min, after through 3600r/min high speed dispersion mulsers emulsification pretreatment handle
240min, then through the high-pressure homogeneous processing 30min of high pressure homogenizer 180MPa, black paste is made.
IIIth, prepared by black polyamic acid resin solution
Take black paste obtained by polyamic acid resin solution obtained by step I and step II, and the polyamide as obtained by step I
The 0.2wt% of solid content M in acid resin solution takes agglomerator polyacrylamide 0.01kg to be blended, and keeps polymerization system to be in 20
DEG C low-temperature condition under stir, black polyamic acid resin solution is made, is defoamed under 10 DEG C of low-temperature conditions spare.
IVth, prepared by sub- black Kapton
In course of conveying after filtered system, resin supplying channel adds black polyamic acid solution obtained by step III
75 DEG C of heat and holding, make black polyamic acid resin solution complete preheating reunion processing.Resin is made certainly into slobbering machine afterwards
Polyamic Acid Film is supported, then through biaxial tension, high temperature imidization and heat treatment, obtains sub- black 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/min stir, synthesize to obtain solid content M=12.40kg 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.
This example also prepares 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
Under the conditions of 1200r/min mix shear agitation 30min, after through 1200r/min high speed dispersion mulsers emulsification pretreatment handle
30min, then ground machine milled processed 30min, and further carry out obtained delustering agent after ultrasonic disperse handles 240min and disperse
Liquid.
IIIth, prepared by black polyamic acid resin solution
Black paste and delustring agent dispersing liquid obtained by polyamic acid resin solution obtained by step I and step II are taken, and by step
The 2wt% of solid content M in the polyamic acid resin solution of rapid I gained takes agglomerator calcium polyacrylate (CPA) 0.25kg to be blended, and keeps
Polymerization system is under 0 DEG C of low-temperature condition and stirs, and black polyamic acid resin solution is made, is defoamed under 5 DEG C of low-temperature conditions standby
With.
IVth, prepared by sub- black Kapton
After filtration system, resin supplying channel heats and keeps 75 DEG C, remaining processing procedure of this step and 1 phase of embodiment
Together.
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/min, 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.
This example also prepares delustring agent dispersing liquid.
The 20wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching aluminium oxide 2.5kg and adds
It is mixed evenly to obtain the delustering agent of alumina content ratio 10% after entering in solvent N-methyl pyrilidone (NMP) 22.5kg
Dispersion liquid, this example aluminium oxide average grain diameter are 0.01 μm.
The mixing added in this example solvent after delustering agent is similar to Example 2.
IIIth, prepared by black polyamic acid resin solution
Black paste and delustring agent dispersing liquid obtained by polyamic acid resin solution obtained by step I and step II are taken, and by step
The 0.3wt% of solid content M in the polyamic acid resin solution of rapid I gained takes agglomerator Sodium Polyacrylate 0.08kg to be blended, and protects
Hold polymerization system to stir under 15 DEG C of low-temperature condition, black polyamic acid resin solution is made, disappears under 15 DEG C of low-temperature conditions
Steep spare.
IVth, prepared by sub- black Kapton
After filtration system, resin supplying channel heats and keeps 90 DEG C, remaining processing procedure of this step and 1 phase of embodiment
Together.
Embodiment 4
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, synthetic system temperature is controlled as 0 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 8
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/min, synthesize to obtain solid content M=7.7kg through polycondensation reaction 3h, i.e. solid content ratio is the polyamides of 15wt%
Amino 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.
This example also prepares 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 2.
IIIth, prepared by black polyamic acid resin solution
Take black paste obtained by polyamic acid resin solution obtained by step I and step II, and the polyamide as obtained by step I
The 1wt% of solid content M in acid resin solution takes agglomerator konjak glucomannan (KGM) 0.08kg to be blended, and keeps condensate
System stirs under 12 DEG C of low-temperature condition, and black polyamic acid resin solution is made, is defoamed under 3 DEG C of low-temperature conditions spare.
IVth, prepared by sub- black Kapton
After filtration system, resin supplying channel heats and keeps 80 DEG C, remaining processing procedure of this step and 1 phase of embodiment
Together.
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 1:1 7.51kg 3,4,3', 4'- diphenyl thio-ether tetrformates dianhydride (3,4,3', 4'-TDPA), and with
800r/min is stirred, and synthesizes to obtain solid content M=10kg through polycondensation reaction 8h, i.e. solid content ratio is the polyamic acid of 20wt%
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-N, N'- acrylic urea (DMPU) 0.64kg, it is mixed evenly to obtain the black of nigrosine content 30%
Slurry；0.4 μm of this example nigrosine average grain diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
This example also prepares 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 2kg and adds
It is mixed evenly to obtain the delustering agent of polyimide content ratio 25% after entering in solvent N-methyl pyrilidone (NMP) 6kg
Dispersion liquid, this example polyimides average grain diameter are 0.6 μm.
The mixing added in this example solvent after delustering agent is similar to Example 2.
IIIth, prepared by black polyamic acid resin solution
Take black paste obtained by polyamic acid resin solution obtained by step I and step II, and the polyamide as obtained by step I
The 0.4wt% of solid content M in acid resin solution takes agglomerator sodium alginate 0.07kg to be blended, and keeps polymerization system to be in 18 DEG C
Low-temperature condition under stir, black polyamic acid resin solution is made, is defoamed under 8 DEG C of low-temperature conditions spare.
IVth, prepared by sub- black Kapton
After filtration system, resin supplying channel heats and keeps 100 DEG C, remaining processing procedure of this step and embodiment 1
It is identical.
Embodiment 6
Ith, the preparation of polyamic acid resin solution
In argon gas atmosphere, synthetic system temperature is controlled as 22 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 6 at the uniform velocity addition and aromatic diamine molar ratios:1 5.21kg aromatic dianhydride Pyromellitic Acid diacid (PMDA),
And stirred with 800r/min, 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 10wt% of the solid content M in polyamic acid resin solution as obtained by step I takes carbon black 1.0kg to add solvent N,
It is mixed evenly to obtain the black paste of content of carbon black 20% in N'- dimethylformamides (DMF) 4kg；This example carbon black is averaged
0.4 μm of particle diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
This example also prepares 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 content of titanium dioxide ratio 30% after adding in solvent N, N'- dimethylformamide (DMF) 1.86kg
Delustring agent dispersing liquid, this example titanium dioxide average grain diameter be 0.3 μm.
The mixing added in this example solvent after delustering agent is similar to Example 2.
IIIth, prepared by black polyamic acid resin solution
Take black paste obtained by polyamic acid resin solution obtained by step I and step II, and the polyamide as obtained by step I
The 0.6wt% of solid content M in acid resin solution takes agglomerator polydimethyl diallyl ammonium chloride 0.10kg to be blended, and keeps poly-
Zoarium system stirs under 12 DEG C of low-temperature condition, and black polyamic acid resin solution is made, is defoamed under 10 DEG C of low-temperature conditions standby
With.
IVth, prepared by sub- black Kapton
After filtration system, resin supplying channel heats and keeps 110 DEG C, remaining processing procedure of this step and embodiment 1
It is identical.
Embodiment 7
Ith, the preparation of polyamic acid resin solution
In argon gas atmosphere, synthetic system temperature is controlled as 15 DEG C, to 40kg N, N'- dimethylacetylamides (DMAC) solvent
Middle addition 3.31kg aromatic diamines p-phenylenediamine (p-PDA) is stirred dissolving, after 4,4'-ODA are completely dissolved, divides 4 times at the uniform velocity
It is 1 to add with aromatic diamine molar ratio:1 6.69kg aromatic dianhydride Pyromellitic Acid diacid (PMDA), and with 800r/min
Stirring, synthesizes to obtain solid content M=10kg, i.e. solid content ratio is that the polyamic acid resin of 20wt% is molten through polycondensation reaction 12h
Liquid；
IIth, prepared by black paste
The 10wt% of the solid content M in polyamic acid resin solution as obtained by step I takes carbon black 1.0kg to add solvent N,
It is mixed evenly to obtain the black paste of content of carbon black 30% in N'- dimethylformamides (DMF) 2.33kg；This example carbon black is put down
Equal 0.4 μm of particle diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
This example also prepares 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 content of titanium dioxide ratio 30% after adding in solvent N, N'- dimethylformamide (DMF) 1.86kg
Delustring agent dispersing liquid, titanium dioxide average grain diameter used in this example be 0.05 μm.
The mixing added in this example solvent after delustering agent is similar to Example 2.
IIIth, prepared by black polyamic acid resin solution
Take black paste obtained by polyamic acid resin solution obtained by step I and step II, and the polyamide as obtained by step I
The 0.6wt% of solid content M in acid resin solution takes agglomerator polydimethyl diallyl ammonium chloride 0.10kg to be blended, and keeps poly-
Zoarium system stirs under 12 DEG C of low-temperature condition, and black polyamic acid resin solution is made, is defoamed under 10 DEG C of low-temperature conditions standby
With.
IVth, prepared by sub- black Kapton
After filtration system, resin supplying channel heats and keeps 110 DEG C, remaining processing procedure of this step and embodiment 1
It is identical.
Comparative example is 1.
Step I, II and step IV are same as Example 1,
When prepared by step III black polyamic acid resin solution, without agglomerator, polyamic acid resin obtained by step I is only taken
Black paste blending obtained by solution, step II, keeps polymerization system to be under 20 DEG C of low-temperature condition and stirs, black polyamides is made
Amino acid resin solution, defoams under 10 DEG C of low-temperature conditions spare.
Comparative example is 2.
Step I, III and step IV are 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 3.
Step I, III and step IV are 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.
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, the sub- black Kapton that prepared by embodiment 1 to 7 has relatively low glossiness, light transmittance
Etc. excellent optical property and mechanical property (tensile strength, elongation and modulus are of a relatively high), while also show high resistance to
Lancinating (tearing strength) and good thermal property (such as CTE, shrinking percentage is relatively low).
Black polyamide thin film without the 1. middle preparation of the comparative example using agglomerator is without desired optical
Energy, thermal property and mechanical property.Comparative example 2. and 3. in, the average grain diameter of used black pigment is excessive or too small, system
Standby black polyamide thin film optical property, thermal property and mechanical property are substantially poor.
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 sub- black Kapton preparation method, including following key step:
Ith, the preparation of polyamic acid resin solution
In an inert atmosphere, control synthetic system temperature be 0 DEG C~50 DEG C under conditions of into solvent add aromatic diamine carry out
Stirring and dissolving, after aromatic diamine is completely dissolved, point 3~8 at the uniform velocity addition and aromatic diamine molar ratios are (0.9~1.1)：1
Aromatic dianhydride, and stirred with 120r/min~1200r/min, synthesize to obtain polyamic acid resin through 3~12h of polycondensation reaction molten
Liquid；
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 dosage control of the aromatic diamine, aromatic dianhydride and solvent is consolidating in finally formed polyamic acid resin solution
Content M ratios are 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'- double (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 (3, the 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 four
Formic acid dianhydride, 2,3,3', any one in 4'- diphenyl thio-ether tetrformate dianhydrides 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 black polyamic acid resin solution
Polyamic acid resin solution obtained by step I, black paste obtained by step II and agglomerator blending are taken, keeps polymerization system
Stirred under 0~20 DEG C of low-temperature condition, black polyamic acid resin solution is made, is defoamed under 0~20 DEG C of low-temperature condition standby
With；
The agglomerator dosage is the 0.2wt%-2wt% of M；
The agglomerator is macromolecule organic flocculating agent sodium carboxymethylcellulose, polyacrylamide, hydrolysed polyacrylic, polypropylene
Sour sodium, calcium polyacrylate (CPA), copolymer, polydimethyl diallyl ammonium chloride, the konjac mannan of acrylic acid and methacrylic acid
Any one in glycan, xanthans and sodium alginate or any a variety of combination；
IVth, prepared by sub- black Kapton
After filtered system, resin supplying channel carries out at heating the step III gained black polyamic acid resin solution
Reason, keeps 75~120 DEG C of temperature, and self-supporting Polyamic Acid Film is made into slobbering machine in black polyamic acid solution afterwards, then
Through biaxial tension, high temperature imidization and heat treatment, sub- black Kapton is obtained.
2. the black Kapton preparation method in Asia 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. the black Kapton preparation method in Asia 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. the black Kapton preparation method in Asia according to claim 1, it is characterised in that：
0.3wt%~1wt% that the amount that the step III prepares agglomerator used in black polyamic acid resin solution is M.
5. the black Kapton preparation method in Asia according to claim 1, it is characterised in that：
0.4wt%~0.6wt% that the amount that the step III prepares agglomerator used in black polyamic acid resin solution is M.
6. the black Kapton preparation method in Asia according to any one of claim 1 to 5, it is characterised in that：
The step III is additionally added delustring agent dispersing liquid when preparing black polyamic acid resin solution；The step III prepares black
During polyamic acid resin solution, polyamic acid resin solution obtained by step I, black paste obtained by step II and delustering agent point are taken
Dispersion liquid blending and stirring, is made black polyamic acid resin solution, and defoams spare；
Preparing for the delustring agent dispersing liquid is as follows：
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 delustering agent is any one or any a variety of group in silica, polyimides, aluminium oxide and titanium dioxide
Close；
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 delustring agent dispersing liquid be dulling agent content ratio in delustring agent dispersing liquid be 10wt%~
30wt%.
7. the black Kapton preparation method in Asia according to claim 6, it is characterised in that：
The amount for the delustering agent that the delustring agent dispersing liquid adds when preparing is 8wt%~12wt% of M.
8. the black Kapton preparation method in Asia according to claim 6, it is characterised in that：
The delustering agent average grain diameter that the delustring agent dispersing liquid adds when preparing for O.05 μm~0.6 μm.
9. the black Kapton preparation method in Asia according to claim 6, it is characterised in that：
The delustering agent average grain diameter that the delustring agent dispersing liquid adds when preparing O.08 μm~0.3 μm.
10. the black Kapton preparation method in Asia according to claim 6, it is characterised in that：
The step I prepares polyamic acid resin solution, step II prepares black paste and prepares used in delustring agent dispersing liquid
Solvent it is identical.
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