CN108892792A - A kind of black polyamide thin film and preparation method thereof - Google Patents

A kind of black polyamide thin film and preparation method thereof Download PDF

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CN108892792A
CN108892792A CN201810333314.1A CN201810333314A CN108892792A CN 108892792 A CN108892792 A CN 108892792A CN 201810333314 A CN201810333314 A CN 201810333314A CN 108892792 A CN108892792 A CN 108892792A
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paa
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phase silica
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CN108892792B (en
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刘萍
张双庆
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GUANGDONG DANBOND TECHNOLOGY Co Ltd
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GUANGDONG DANBOND TECHNOLOGY Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2289—Oxides; Hydroxides of metals of cobalt
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

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Abstract

A kind of black polyamide thin film and preparation method thereof is provided, this method comprises the following steps：(1) under inert atmosphere and certain temperature, fragrant four carboxylic acid's dianhydride of predetermined molar ratio and aromatic diamine compound is reacted in the first solvent and obtain PAA solution；(2) non-carbon black black pigment is added in the second solvent, non-carbon black black pigment slurry is made in dispersion after mixing evenly；(3) disperse that gas-phase silica slurry is made after mixing third solvent and gas-phase silica powder；(4) the PAA solution, non-carbon black black pigment slurry and gas-phase silica slurry are thoroughly mixed, obtain PAA composite solution；The PAA composite solution, catalyst and acid anhydrides dehydrating agent are mixed to get mixture solution, obtain black polyamide thin film through curtain coating, painting, drying, stretching etc..Black polyamide film of the invention has preferable physical and chemical performance, and two sides has the appearance of black of uniform coloring simultaneously, and light-shading effect is good, and products application is extensive.

Description

A kind of black polyamide thin film and preparation method thereof
Technical field
The present invention relates to Kapton class materials, and in particular to a kind of black polyamide thin film and its preparation side Method.
Background technique
Flexible printed wiring board FPC is widely used in computer, communication, consumer electronics product, optical lens module, liquid The products such as crystal display (LCD) module and solar battery, and polyimides (PI) film is commonly used for its substrate or covering membrane material Expect, it is dizzy caused by existing because of light reflection since the surface gloss of traditional PI film is larger and transparent higher in application process Light or astigmatism and route design distribution is easy to interpret and by the same trade plagiarize the problem of, so require PI film have low-luster, The characteristics such as low light transmission and insulating properties, low-luster can make element appearance have more texture and beauty, and insulating properties and low light transmission are then Internal circuit design can be protected.Black PI film has the performances such as good light-proofness, antistatic property, thermal conductivity, meets above-mentioned Demand is widely used in the fields such as optics, electronics, aerospace.
Preparation has both the black PI film of low-luster, low light transmission and insulating properties, needs to add colour generation in PI film processing procedure Additive and delustering agent, usually by have colour additive reduce PI film light transmittance, or addition delustering agent make PI film surface Concave-convex micro-structure is formed to reduce the glossiness of PI film.In black PI film manufacturing processes, due to inorganic particle or carbon powder material Partial size it is too big or too small can cause undesirable influence for PI thin film physics performance.If inorganic particle or carbon powder material Partial size is larger, and manufactured film surface is excessively coarse, is not suitable in electronic product；If the grain of inorganic particle or carbon powder material The phenomenon that diameter is smaller, is easy to produce aggregation is caused to disperse non-uniform problem in the film, and is operationally difficult to control.It removes The partial size of inorganic particle or carbon powder material will affect that its dispersibility in the PI film is outer, and inorganic particle or carbon powder material contain Amount can also have an impact, if the content of inorganic particle or carbon powder material is larger, can equally generate the non-uniform phenomenon of dispersion；But Content is smaller, then the glossiness of film and light transmittance can be made excessively high, there are problems that atomized surface effect is bad and light transmission.
Summary of the invention
The purpose of the present invention is to provide a kind of black polyamide thin film and preparation method thereof, the black PI that is prepared Film has preferable physical and chemical performance simultaneously, while two sides has the appearance of black of uniform coloring, and light-shading effect is good, synthesis technology letter Single, yields is high, and products application is extensive.
In order to achieve the above objectives, the present invention uses following technical scheme：
A kind of preparation method of black polyamide thin film, includes the following steps：
(1) preparation of polyamic acid (PAA) solution：Under inert atmosphere and certain temperature, by the fragrance of predetermined molar ratio Tetracarboxylic dianhydride and aromatic diamine compound react in the first solvent obtains PAA solution；
(2) preparation of non-carbon black black pigment slurry：Non- carbon black black pigment is added in the second solvent, after mixing evenly Non- carbon black black pigment slurry is made in dispersion；
(3) preparation of gas-phase silica slurry：Disperse that gas phase is made after third solvent and gas-phase silica powder are mixed White carbon black slurry；
(4) chemical imidization：The PAA solution, non-carbon black black pigment slurry and gas-phase silica slurry are sufficiently stirred Mixing is mixed, PAA composite solution is obtained；It is molten that the PAA composite solution, catalyst and acid anhydrides dehydrating agent are mixed to get mixture Liquid, curtain coating coat the mixture solution, the gel mould formed after drying are stretched at room temperature, then add under tension Heat abstraction solvent, defoaming, the dry section in the hot imidization furnace of anaerobic of inert gas shielding by film Jing Guo different temperatures continuously rise Temperature is dry, and black polyamide thin film is made through curtain coating-biaxial tension.
Preferably, aromatic diamine compound described in step (1) is 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] At least one of propane (BAPP), p-phenylenediamine and 4,4 '-diamino-diphenyl ethers.
Preferably, fragrant four carboxylic acid's dianhydride described in step (1) is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides (BTDA), one of pyromellitic acid anhydride or both combines.
Preferably, the molar ratio of fragrant four carboxylic acid's dianhydride and aromatic diamine compound described in step (1) is 1-1.01: 1；The content of PAA is 18-28wt% in the PAA solution being prepared；The reaction temperature is 0~50 DEG C, reaction time 2-6 Hour.
Preferably, non-carbon black black pigment described in step (2) is cobalt oxide, black iron oxide, ferrochrome oxide, aniline At least one of black, partial size is 0.1-10 μm；In the black polyamide thin film, the content of non-carbon black black pigment is 10-30wt%.
Preferably, ultrasonic disperse is separated into described in step (2), the time of dispersion is 10-30 minutes, and dispersion temperature is 0-50℃；It is separated into shearing dispersion in step (3), the revolving speed of the shearing dispersion is 2500r/min, and the processing time is 1- 3h, dispersion temperature are 0-50 DEG C.
Preferably, the median particle diameter of gas-phase silica powder described in step (3) is 3.2-3.5 μm, density 3-5g/ cm3；In the black polyamide thin film, the content of gas-phase silica powder is 1.5wt%-10wt%.
Preferably, described in the first solvent described in step (1), the second solvent described in step (2) and step (3) Third solvent be each independently N,N-dimethylformamide, DMAC N,N' dimethyl acetamide (DMAC), N- methyl -2- pyrrolidines At least one of ketone, sulfolane, tetramethylurea, dimethyl sulfone.
Preferably, catalyst described in step (4) is pyridine, α-methylpyridine, beta-picoline, 3,4- dimethyl pyrazole Pyridine, 3,5- lutidines, 4- picoline, 4- isopropyl pyridine, N, N- dimethyl benzylamine, isoquinolin, 4- benzyl pyridine, N, At least one of N- dimethyl dodecylamine and triethylamine；The dosage of the catalyst is relative to 1 mole of step (1) In PAA in PAA solution obtained amount, be 0.1-0.5 moles.
Preferably, acid anhydrides dehydrating agent described in step (4) be benzoyl oxide, acetic anhydride, propionic andydride and butyric anhydride in extremely Few one kind；Amount of the dosage of the acid anhydrides dehydrating agent relative to the PAA in PAA solution obtained in 1 mole of step (1), It is 0.2-0.6 moles.
Catalyst described in step (4) is pyridine, α-methylpyridine, beta-picoline, 3,4- lutidines, 3,5- bis- Picoline, 4- picoline, 4- isopropyl pyridine, N, N- dimethyl benzylamine, isoquinolin, 4- benzyl pyridine, N, N- dimethyl At least the two in lauryl amine and triethylamine mixes；Acid anhydrides dehydrating agent described in step (4) is acetic anhydride, propionic andydride It is mixed at least one of butyric anhydride with benzoyl oxide.
Preferably, the dry temperature of dry section continuous warming described in step (4) by film Jing Guo different temperatures be 80 DEG C- 300 DEG C, the dry section continuous warming for being divided into 4 different temperatures is dry, and the temperature in the firstth area [80 DEG C, 120 DEG C), the temperature in the secondth area Degree [120 DEG C, 185 DEG C), and the temperature in third area [185 DEG C, 260 DEG C), the temperature [260 DEG C, 300 DEG C] in the 4th area, each drying Area controllably sets ± 2, and guarantees that hot wind air capacity cannot be less than 10m on the upside of hot warm cleannes and drying tunnel3/ minute, downside hot wind Air capacity cannot be less than 20m3/ minute, each warm area equal length and drying time 25-60 minutes total.
A kind of black polyamide thin film is made of polyimides, non-carbon black black pigment and gas-phase silica, wherein The weight content of non-carbon black black pigment is 10-30wt%, and the weight content of gas-phase silica is 1.5wt%-10wt%, surplus For polyimides.
Compared with prior art, the invention has the advantages that：
The present invention uses and adds non-carbon black black pigment, gas-phase silica (delustering agent) in polyimide resin and pass through The black polyamide thin film surface black uniformity that chemical imidization method is prepared is high, and two sides glossiness is consistent, gloss Spend it is low, OD value be greater than 2.5, good shading effect；The preparation process of research and development is easy to operate, and yields is high.Chemical imines The black thin film for changing preparation is higher than black thin film dielectric strength prepared by hot imidization method, good physical and chemical.Chemical imidization Even if the black polyamide film of preparation is cast on smooth surface, two sides is all lacklustre (matt effect), favorably In the either side that any extra play is applied to black polyamide film, usage range is expanded.The polyamides of hot imines method preparation Imines precursor film is in thermal transition and when being cast on smooth surface, and only air surface matt effect is preferable.Chemical imines preparation Film has higher dielectric strength, dielectric strength > 144kv/mm than film prepared by hot imidization method.In general, dielectric is strong Degree is reduced with the increase of delustring dosage.Therefore, by the processing of hot imidization, although can achieve low 60 degree of gloss Degree, but increase the amount of delustering agent, dielectric strength will reduce.
Specific embodiment
With embodiment, the invention will be further described below, but the invention is not limited to these embodiments.
A kind of preparation method of black polyamide thin film, includes the following steps：
(1) preparation of polyamic acid (PAA) solution：Under inert atmosphere and certain temperature, by the fragrance of predetermined molar ratio Tetracarboxylic dianhydride and aromatic diamine compound react in the first solvent obtains PAA solution；
(2) preparation of non-carbon black black pigment slurry：Non- carbon black black pigment is added in the second solvent, after mixing evenly Non- carbon black black pigment slurry is made in dispersion；
(3) preparation of gas-phase silica slurry：Disperse that gas phase is made after third solvent and gas-phase silica powder are mixed White carbon black slurry；
(4) chemical imidization：The PAA solution, non-carbon black black pigment slurry and gas-phase silica slurry are sufficiently stirred Mixing is mixed, PAA composite solution is obtained；It is molten that the PAA composite solution, catalyst and acid anhydrides dehydrating agent are mixed to get mixture Liquid, curtain coating coat the mixture solution, the gel mould formed after drying are stretched at room temperature, then add under tension Heat abstraction solvent, defoaming, the dry section in the hot imidization furnace of anaerobic of inert gas shielding by film Jing Guo different temperatures continuously rise Temperature is dry, and black polyamide thin film is made through curtain coating-biaxial tension.
In some preferred embodiments, one of following optimum condition or in the absence of conflict can choose Any combination：
Aromatic diamine compound described in step (1) is 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] propane (BAPP), at least one of p-phenylenediamine and 4,4 '-diamino-diphenyl ethers.
Fragrant four carboxylic acid's dianhydride described in step (1) is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides (BTDA), One of pyromellitic dianhydride or both combination.
The molar ratio of fragrant four carboxylic acid's dianhydride described in step (1) and aromatic diamine compound is 1-1.01:1.Into one It step ground during the reaction can be using following operation：First by the fragrant four carboxylic acid of the amount less than aromatic diamine compound Dianhydride and aromatic diamine compound, which are dissolved in the first solvent, to be reacted, and after reacting a period of time, is supplemented that fragrance is added (molar ratio of the fragrant four carboxylic acid's dianhydride and aromatic diamine compound that are added in total is 1-1.01 to tetracarboxylic dianhydride:1), simultaneously Solution viscosity is monitored, stops addition fragrant four carboxylic acid's dianhydride when viscosity reaches 2000-3000 pool, obtains PAA solution.It can incite somebody to action The temperature of PAA solution be maintained at 20-30 DEG C it is spare.For example, can be by the aromatic diamine of 40-60 parts by volume and 35-55 volume Fragrant four carboxylic acid's dianhydride (and the parts by volume for the fragrant four carboxylic acid's dianhydride being added at this time is less than parts by volume of aromatic diamine) of part It is reacted in the first solvent, after reacting a period of time, is supplemented that fragrant four carboxylic acid's dianhydride of 6-8 parts by volume is added.
The content of PAA is 18-28wt% in the PAA solution being prepared.The reaction temperature of step (1) is 0~50 DEG C, instead It is 2-6 hours between seasonable.
Non- carbon black black pigment described in step (2) is cobalt oxide, in black iron oxide, ferrochrome oxide, nigrosine At least one, partial size are 0.1-10 μm.In the black polyamide thin film, the content of non-carbon black black pigment is 10- 30wt%.
Ultrasonic disperse is separated into described in step (2), the time of dispersion is 10-30 minutes, and dispersion temperature is 0-50 DEG C.
It being separated into shearing dispersion in step (3), the revolving speed of the described shearing dispersion is 2500r/min, and the processing time is 1-3h, dispersion temperature are 0-50 DEG C.
The median particle diameter of gas-phase silica powder described in step (3) is 3.2-3.5 μm, density 3-5g/cm3；Institute It states in black polyamide thin film, the content of gas-phase silica powder is 1.5wt%-10wt%.
Third described in first solvent described in step (1), the second solvent described in step (2) and step (3) Solvent is each independently N,N-dimethylformamide, DMAC N,N' dimethyl acetamide (DMAC), n-methyl-2-pyrrolidone, ring At least one of fourth sulfone, tetramethylurea, dimethyl sulfone.
Catalyst described in step (4) is pyridine, α-methylpyridine, beta-picoline, 3,4- lutidines, 3,5- bis- Picoline, 4- picoline, 4- isopropyl pyridine, N, N- dimethyl benzylamine, isoquinolin, 4- benzyl pyridine, N, N- dimethyl At least one of lauryl amine and triethylamine.
The dosage of step (4) described catalyst is relative to the PAA's in PAA solution obtained in 1 mole of step (1) Amount is 0.1-0.5 moles.
Further, catalyst described in step (4) is pyridine, α-methylpyridine, beta-picoline, 3,4- dimethyl pyrazole Pyridine, 3,5- lutidines, 4- picoline, 4- isopropyl pyridine, N, N- dimethyl benzylamine, isoquinolin, 4- benzyl pyridine, N, At least the two in N- dimethyl dodecylamine and triethylamine mixes.More preferably, catalyst is triethylamine and pyridine etc. It mole mixes, the catalyst of formation can improve the production efficiency of polyimides, and improve the mechanical-physical of polyimides Energy, tensile strength and film quality.
Acid anhydrides dehydrating agent described in step (4) is at least one of benzoyl oxide, acetic anhydride, propionic andydride and butyric anhydride.
The dosage of acid anhydrides dehydrating agent described in step (4) is relative in PAA solution obtained in 1 mole of step (1) PAA amount, be 0.2-0.6 moles.
Further, acid anhydrides dehydrating agent described in step (4) be at least one of acetic anhydride, propionic andydride and butyric anhydride with Benzoyl oxide is mixed.More preferably, acid anhydrides dehydrating agent is that acetic anhydride is mixed with benzoyl oxide equimolar, formation Mixed dehydration agent dehydration rate with higher.Dry section continuous warming described in step (4) by film Jing Guo different temperatures is dry Temperature be 80 DEG C -300 DEG C, the dry section continuous warming for being divided into 4 different temperatures is dry, the temperature in the firstth area [80 DEG C, 120 DEG C), the temperature in the secondth area [120 DEG C, 185 DEG C), the temperature in third area [185 DEG C, 260 DEG C), the temperature in the 4th area [260 DEG C, 300 DEG C], each dry section controllably sets ± 2, and guarantees that hot wind air capacity cannot be less than on the upside of hot warm cleannes and drying tunnel 10m3/ minute, downside hot wind air capacity cannot be less than 20m3/ minute, each warm area equal length and total drying time 25-60 Minute.
Room temperature herein refers to 20-30 DEG C.
Embodiment 1
(1) under room temperature, 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] 25 liters of propane (BAPP) are dissolved in DMAC With 4,25 liters of 4 '-diamino-diphenyl ethers (4,4 '-ODA), and add 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides (BTDA) 30 liters, 15 liters of two acid dianhydride of Pyromellitic Acid (PMDA) is added after dissolution and is gathered before stirring 2 hours formation thermoplastic polyimide Body prepolymer；It is supplemented that 6-8 liter (being 6 liters in this example) BTDA and/or pyromellitic acid anhydride, prison is added after reaction a period of time Solution viscosity is controlled, stops addition when viscosity reaches 3000 pool (thus final actually aromatic diamine compound and fragrance four Carboxylic acid dianhydride substantially equimolar), stir within 2 hours PAA content be 20wt% PAA solution, temperature be maintained at 20 DEG C it is standby With.
(2) 7.5g cobalt oxide is dispersed in 38.9 grams of DMAC, with ultrasonic processor ultrasonic disperse 10 minutes, makes pigment Depolymerization.
(3) the gas-phase silica powder of the DMAC of 75.4g and 15.0g (its median particle diameter is 3.2-3.5 μm) is cut in height It cuts in rotor-stator mixer and is sufficiently mixed, gas-phase silica slurry is made.
(4) in a mixer, by 170.5 grams of PAA solution, 6.1 grams of gas-phase silica slurries and 36.6 grams of non-carbon black black Pigment slurry is sufficiently mixed to obtain PAA mixed solution.Under the protection of nitrogen stream, the PAA obtained by every 100 moles is added 10 Mole acetic anhydride and mixture, 20 moles of triethylamine and the pyridine equimolar of benzoyl oxide equimolar mixing mixed Mixed catalyst, and be cast in 600mm width, application of mixture solution, with a thickness of 50 μm, the gel mould that will be formed after drying It stretches at room temperature, then heating removes solvent, defoaming, in the hot imidization furnace of anaerobic of inert gas shielding under tension 4 dry section continuous warmings by film Jing Guo different temperatures are dry, 80 DEG C of the temperature in the firstth area, 120 DEG C of the temperature in the secondth area, the 185 DEG C of the temperature in 3rd area, 260 DEG C of the temperature in the 4th area, every dry section controllably sets ± 2, and guarantees hot warm cleannes and drying tunnel Upside hot wind air capacity cannot be less than 10m3/ minute, downside hot wind air capacity cannot be less than 20m3/ minute, the identical length of each warm area Degree and total 25 minutes drying times, about 50 μm of black polyamide thin film is made through curtain coating-biaxial tension.
The black pigment of final black polyamide the film gas-phase silica comprising 2.5wt% and 15wt% obtained, it is remaining Amount is polyimides.
Embodiment 2
Embodiment 2 the difference from embodiment 1 is that：The content for changing non-carbon black black pigment is 10wt%.It is final to be made Black polyamide film include 2.5wt% gas-phase silica and 10wt% black pigment.
Embodiment 3
Embodiment 3 the difference from embodiment 1 is that：The content for changing non-carbon black black pigment is 30%.It is final obtained Black polyamide film includes the gas-phase silica of 2.5wt% and the black pigment of 30wt%.
Embodiment 4
Embodiment 4 the difference from embodiment 1 is that：The content for changing gas-phase silica is 5wt%.Final black obtained Polyimide film includes the gas-phase silica of 5wt% and the black pigment of 15wt%.
Embodiment 5
Embodiment 5 the difference from embodiment 1 is that：The content for changing gas-phase silica is 10wt%.It is final obtained black Color polyimide film includes the gas-phase silica of 10wt% and the black pigment of 15wt%.
Comparative example
Comparative example is identical as (1)-(3) the step of embodiment 1, and step (4) uses hot imidization method.
(4) hot imidization：The degassed PAA mixed solution being prepared is cast to glass using stainless steel cast rod On plate.Glass plate containing wet cast membrane is placed on 80-100 DEG C of hot plate, dry 30-45 minutes partially dried to be formed , the film of part imidization.Black film is peeled from glass, is placed in baking oven；Oven temperature increases in 60-75min To 320 DEG C, constant temperature 10 minutes, 400 DEG C are then warming up to, keeps 5min, then taking-up and cooling from baking oven.
Final black polyamide film obtained includes the gas-phase silica of 2.5wt% and the black pigment of 15wt%.
Film performance made from each embodiment and comparative example is as follows：
Embodiment 1-5 proves, the black polyamide thin film prepared by chemical imidization, 60 degree of glossiness on two sides Value reaches general well below 60 degree of gloss value of the Kapton for being not added with filler less than 5 (matt appearances) The requirement of black polyamide thin film glossiness≤50.
Optical density (optical density, OD) is defined as the characterization of material light shielding ability.It is measured, is indicated with transmissive mirror The optical density that detected material sponges.Optical density is the logarithm of incident light and transmitted light ratio or pair of light penetration inverse Number.Calculation formula is OD=lg (incident light/transmitted light) or OD=lg (1/ light transmittance)
With the increase of compounded mix, the significant increase of optical density of PI film of the film than being not added with compounded mix shows material The light shielding ability of material enhances.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that Specific implementation of the invention is only limited to these instructions.For those skilled in the art to which the present invention belongs, it is not taking off Under the premise of from present inventive concept, several equivalent substitute or obvious modifications can also be made, and performance or use is identical, all answered When being considered as belonging to protection scope of the present invention.

Claims (10)

1. a kind of preparation method of black polyamide thin film, which is characterized in that include the following steps：
(1) preparation of polyamic acid (PAA) solution：Under inert atmosphere and certain temperature, by the fragrant tetracarboxylic acid of predetermined molar ratio Acid dianhydride and aromatic diamine compound react in the first solvent obtains PAA solution；
(2) preparation of non-carbon black black pigment slurry：Non- carbon black black pigment is added in the second solvent, is dispersed after mixing evenly Non- carbon black black pigment slurry is made；
(3) preparation of gas-phase silica slurry：Disperse that gas phase hard charcoal is made after third solvent and gas-phase silica powder are mixed Black wash material；
(4) chemical imidization：The PAA solution, non-carbon black black pigment slurry and gas-phase silica slurry are sufficiently stirred mixed It closes, obtains PAA composite solution；The PAA composite solution, catalyst and acid anhydrides dehydrating agent are mixed to get mixture solution, flowed Prolong the coating mixture solution, the gel mould formed after drying is stretched at room temperature, then heating is gone under tension Except solvent, defoaming, the dry section continuous warming in the hot imidization furnace of anaerobic of inert gas shielding by film Jing Guo different temperatures is done It is dry, black polyamide thin film is made through curtain coating-biaxial tension.
2. preparation method according to claim 1, it is characterised in that：Aromatic diamine compound described in step (1) For at least one in 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] propane, p-phenylenediamine and 4,4 '-diamino-diphenyl ethers Kind；And/or fragrant four carboxylic acid's dianhydride described in step (1) is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, equal benzene tetramethyl One of acid dianhydride or both combination.
3. preparation method according to claim 1, it is characterised in that：Fragrant four carboxylic acid's dianhydride described in step (1) and virtue The molar ratio of fragrant race's diamine compound is 1-1.01:1；The content of PAA is 18-28wt% in the PAA solution being prepared；It is described Reaction temperature is 0~50 DEG C, and the reaction time is 2-6 hours.
4. preparation method according to claim 1, it is characterised in that：Non- carbon black black pigment described in step (2) is oxygen Change at least one of cobalt, black iron oxide, ferrochrome oxide, nigrosine, partial size is 0.1-10 μm；The black polyamide In film, the content 10-30wt% of non-carbon black black pigment.
5. preparation method according to claim 1, it is characterised in that：Gas-phase silica powder described in step (3) Median particle diameter is 3.2-3.5 μm, density 3-5g/cm3；In the black polyamide thin film, gas-phase silica powder contains Amount is 1.5wt%-10wt%.
6. preparation method according to claim 1, it is characterised in that：Catalyst described in step (4) is pyridine, Alpha-Methyl Pyridine, beta-picoline, 3,4- lutidines, 3,5- lutidines, 4- picoline, 4- isopropyl pyridine, N, N- bis- Methylbenzylamine, isoquinolin, 4- benzyl pyridine, N, at least one of N- dimethyl dodecylamine and triethylamine；The catalysis Amount of the dosage of agent relative to the PAA in PAA solution obtained in 1 mole of step (1) is 0.1-0.5 moles.
7. preparation method according to claim 1, it is characterised in that：Acid anhydrides dehydrating agent described in step (4) is benzoic acid At least one of acid anhydride, acetic anhydride, propionic andydride and butyric anhydride；The dosage of the acid anhydrides dehydrating agent is relative to 1 mole of step (1) amount of the PAA in PAA solution obtained is 0.2-0.6 moles.
8. preparation method according to claim 1, it is characterised in that：Catalyst described in step (4) is pyridine, Alpha-Methyl Pyridine, beta-picoline, 3,4- lutidines, 3,5- lutidines, 4- picoline, 4- isopropyl pyridine, N, N- bis- Methylbenzylamine, isoquinolin, 4- benzyl pyridine, N, both at least mixing in N- dimethyl dodecylamine and triethylamine； Acid anhydrides dehydrating agent described in step (4) is that at least one of acetic anhydride, propionic andydride and butyric anhydride are mixed with benzoyl oxide It forms.
9. preparation method according to claim 1, it is characterised in that：By film by different temperatures described in step (4) The dry temperature of dry section continuous warming is 80 DEG C -300 DEG C, and the dry section continuous warming for being divided into 4 different temperatures is dry, first Area temperature [80 DEG C, 120 DEG C), the temperature in the secondth area [120 DEG C, 185 DEG C), the temperature in third area [185 DEG C, 260 DEG C), the 4th The temperature [260 DEG C, 300 DEG C] in area, each dry section controllably sets ± 2, and guarantees that hot wind is empty on the upside of hot warm cleannes and drying tunnel Tolerance cannot be less than 10m3/ minute, downside hot wind air capacity cannot be less than 20m3It/minute, each warm area equal length and always does Dry time 25-60 minutes.
10. a kind of black polyamide thin film, which is characterized in that by polyimides, non-carbon black black pigment and gas-phase silica Composition, wherein the weight content of non-carbon black black pigment is 10-30wt%, and the weight content of gas-phase silica is 1.5wt%- 10wt%, surplus are polyimides.
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KR101156084B1 (en) * 2011-09-19 2012-06-20 에스케이씨코오롱피아이 주식회사 Black polyimide film and method for preparing the same
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KR101156084B1 (en) * 2011-09-19 2012-06-20 에스케이씨코오롱피아이 주식회사 Black polyimide film and method for preparing the same
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