CN102093558A - Polyimide film material capable of serving as flexible transparent conducting film substrate and preparation method thereof - Google Patents
Polyimide film material capable of serving as flexible transparent conducting film substrate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyimide film material capable of serving as a flexible transparent conducting film substrate and a preparation method thereof. Polyimide is obtained by undergoing a low-temperature solution condensation reaction between alicyclic dianhydride and fluorine diphenyl ether-containing aromatic diamine, and aminating hot imide. The polyimide film material has the glass-transition temperature between 250 DEG C and 300 DEG C, a very light film color, the ultraviolet cutoff wavelength between 280 nanometers and 330 nanometers, high transparency in a visible light region (between 400 nanometers and 700 nanometers), the light transmission rate of over 90 percent at the position of 450 nanometers and high machining performance, so that the film material can be taken as a substrate material of a flexible transparent conducting film.
Description
Technical field
The present invention relates to a kind of polyimide film material that can be used as the flexible transparent conducting film substrate and preparation method thereof.
Background technology
Polyimide (polyimides of the present invention, PI) be a kind of by alicyclic ring dianhydride and fluorine-containing phenylate type aromatic diamine monomer through cryogenic fluid polycondensation and hot-imide and the polyimide that obtains, this polyimide has high temperature resistant and water white characteristics, can be used as the flexible transparent conducting film substrate material, this flexible transparent conducting film material can be used for solar cell, flat-panel monitor, thin film transistor (TFT), gas sensor, antistatic coating and semiconductor/insulator/semi-conductor (SIS) heterojunction, the high-technology fields such as window of modern opportunity of combat and cruise missile, so this polyimide has special application background.
Substrate material as flexible transparent conducting film need satisfy following condition: 1. film must have good light transmittance, and the transmittance of the above wavelength of 500nm surpasses 90%; 2. good thermotolerance will be arranged, for satisfying the needs of processing condition such as magnetron sputtering, second-order transition temperature should be more than 250 ℃, and can keep excellent mechanical intensity; 3. bright and clean, smooth, the free of pinholes of film surface, spots take place to prevent short circuit or breaking phenomena.In present available material, polyester (PET), polycarbonate (PC) etc. are arranged, but because UV resistant not, rate of moisture absorption is too high, can not satisfy high temperature process technology etc. and be restricted, so polyimide (PI) should be a preferred material.PI with water white transparency and high-temperature stability can be widely used in high-tech sectors such as microelectronics and photoelectron.For example in the optical communication field, be used as optical waveguide material, spectral filter, optical fiber, optoelectronic package material, second-order non-linear optical materials, photorefractive material, photochromics and photoelectric material etc.Be used as aligning film material, the plastic base of negativity compensate film, flexible organic electro-luminescence indicating meter etc. in field of liquid crystal display.As the baseplate material of solar battery array and antenna-reflected/collector material etc., also can be used as the colourless coating material that big area does not have seam welding at aerospace field.Owing to can have higher specific refractory power and in visible-range, have the good transparency, also can be used as lens material.But general PI is a Huang-brown transparent material, and the formation that reduces charge transfer complex (CTC) by reduction intramolecularly and Intermolecular Forces is the main path of design water white transparency PI.
At present, adopt following means usually for the transparency that increases the PI film: (1) is introduced in the PI molecular structure and is contained fluoro substituents or side group, utilizes the bigger electronegativity of fluorine atom, cuts off the conjugation of electronic cloud, suppresses the formation of CTC; (2) reduce the content of aromatic structure in the PI molecular structure, have the dianhydride or the diamine monomer of alicyclic structure, reduce the probability that CTC forms as employing; (3) introduce non-coplanar structure, can reduce the formation of CTC; (4) in the PI molecular structure, introduce between the position replace the diamines of structure.This be since between the position replace a structure and can hinder along the flow of charge of molecular chain fragrance, reduce divide between conjugation; (5) introduce the sulfuryl structure, utilize the formation of the strong electrophilic effect minimizing CTC of sulfuryl.
In the document of exercise question " preparation of fluorine-containing half alicyclic ring clear polyimides film and performance (investigation of materials journal; 2008; 22 (6): 615-618) ", the author is respectively with alicyclic dianhydride monomer 1,2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA), 1,2,4,5-pentamethylene tetracarboxylic dianhydride (CPDA) and 1,2,4,5-hexanaphthene tetracarboxylic dianhydride (CHDA) and aromatic series fluorinated diamine 1, the fluorine-containing half alicyclic polyimide of two two series of (4-amido-2-4-trifluoromethylphenopendant) benzene (6FAPB) and 4,4 '-two (4-amido-2-4-trifluoromethylphenopendant) biphenyl (6FBAB) prepared in reaction of 4-, these PI films have good thermostability, initial heat decomposition temperature is above 450 ℃ in nitrogen, second-order transition temperature is above 250 ℃, (400-700nm) has the good transparency in visible-range, and the transmitance at 450nm place surpasses 88%, and the ultraviolet cut-on wavelength is at 295～319nm.Therefore, will can keep the intrinsic heat-resistant stability of PI in alicyclic structure and the fluoro-containing group introducing PI molecular structure, and significantly reduce its absorption in the ultraviolet-visible light zone.
In the document of exercise question " Effects of internal linkage groups of fluorinated diamine on the optical and dielectricproperties of polyimide thin films (Polymer 2007; 48; 2130-2143) ", the author has compared fluorinated diamine link group to the PI Effect on Performance, three kinds of fluorinated diamines respectively with BTDA, ODPA and 6FDA reaction obtain polyimide, result of study shows, the ultraviolet cut-on wavelength of polyimide is at 339～399nm, initial heat decomposition temperature is above 530 ℃, 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa and 4 of 2-, 4 '-two (4-amino-2-4-trifluoromethylphenopendant) phenyl ether is than 4, and 4 '-two (4-amino-2-4-trifluoromethylphenopendant) biphenyl (6FBAB) has more shallow color and the transmitance of Geng Gao; Have-CF
3Phenylate type diamines more help improving the solvability and the optical transparency of polyimide, and can keep higher thermostability.
In the document of exercise question " is the synthetic and performance (Shanghai Communications University's journal 2005; 39 (11): 1821-1823; 1832) of monomeric alicyclic polyimide with CBTDA ", the author has synthesized 1,2,3,4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2 one dimethyl methyl acid anhydrides) (CBTDA), then with aromatic diamines 4,4 '-diamino-3,3 '-dimethyl diphenylmethane (DADMDPM) and 4,4 '-diamino-diphenyl ether (DADPE) reacts respectively, has synthesized two kinds of alicyclic polyimide by chemical imidization and hot imidization method. and institute's synthetic polyimide has the high second-order transition temperature (＞290 ℃) and the higher transparency, and the ultraviolet cut-on wavelength is respectively 330 and 335nm.
Therefore, the present invention combines the alicyclic ring dianhydride with fluorine-containing phenylate type aromatic diamines, when improving the polyimide light transmission rate, improve its thermotolerance, make it can satisfy water white transparency and durothermic double requirements simultaneously, can be as the substrate material of flexible transparent conducting film.
Summary of the invention
The present invention carries out the cryogenic fluid polycondensation by dianhydride and the fluorine-containing phenylate type aromatic diamines that contains alicyclic structure, prepare the good and water white polyimide film material of temperature tolerance through the hot-imide process, make it can be used as the substrate material of flexible transparent conducting film.
The feature chemical structural formula that can be used as the polyimide of flexible transparent conducting film substrate:
In the formula
The typical synthetic method that can be used as the polyimide film material of flexible transparent conducting film substrate:
1. earlier a kind of fluorine-containing phenylate type aromatic diamine is dissolved in a certain amount of polar aprotic solvent;
2. treat under agitation to act on after diamines dissolves fully, a kind of alicyclic dianhydride of mol ratios such as adding, temperature of reaction is about 0～25 ℃, and the reaction times is 15～25 hours, obtains having the even heavy-gravity polyamic acid solution of certain solid content;
3. above-mentioned polyamic acid solution is coated on the clean slick sheet glass, adopts the hot-imide method under the nitrogen protection environment, to make the Kapton that can be used for the flexible conductive film substrate.
Described alicyclic dianhydride is selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,4,5-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3:5, the 6-tetracarboxylic dianhydride, dicyclo [2.2.2] octane-2,3:5,6-tetracarboxylic dianhydride and 1,2,3, and 4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2-dimethyl methyl acid anhydrides) in a kind of.
Described fluorine-containing phenylate type aromatic diamine is selected from: 2, and two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa and 4 of 2-, a kind of in 4 '-two (4-amino-2-4-trifluoromethylphenopendant) phenyl ether.
Described polar aprotic solvent is selected from N, dinethylformamide, a kind of in N,N-dimethylacetamide and the N-N-methyl-2-2-pyrrolidone N-.
Mol ratios such as alicyclic ring dianhydride and fluorine-containing phenylate type aromatic diamine are are reacted.
The solid content of described polyamic acid is 10～25%.
Described imidization method is the hot-imide method, and carries out in the nitrogen protection environment.
Described final imidization temperature is 200～350 ℃, and the imidization time is 0.1～1 hour.
The chemical equation that is prepared the polyimide that can be used as the flexible transparent conducting film substrate by alicyclic dianhydride and fluorine-containing phenylate type aromatic diamine monomer is as follows:
In the formula
The typical heat imidization technology that the present invention adopts is: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.According to the difference of polyimide molecule structure, needed final imide temperature difference, generally between 200～350 ℃, the imidization time is 0.1～1 hour.
Beneficial effect: its molecular rigidity of dianhydride monomer with alicyclic structure is stronger, and the polyimide for preparing based on their all has better heat-resisting and mechanical property, and alicyclic structure seldom or not contains-and CH
2Deng the extinction group, and reduce conjugated structure, therefore given polyimide the higher transparency again.In the fluorine-containing phenylate type aromatic diamine-CF
3The introducing of group and ehter bond can improve the solvability and the thermostability of polyimide, reduce the specific inductivity and the water absorbability of polyimide, and can increase the transparency of polyimide, therefore polyimide of the present invention combines the high-temperature stability of PI, highlights its superior optical property again.The ultraviolet cut-on wavelength of polyimide is at 280～330nm, and the light transmission rate at 450nm place surpasses 90%, and second-order transition temperature is between 250～300 ℃.
Embodiment
Embodiment 1
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g (0.01mol) of 2-are dissolved in the DMAc solvent of 51.38ml, stir to make solution becomes get clear.Disposable adding 1 in this solution then; 2; 3; 4-tetramethylene tetracarboxylic dianhydride (CBDA) 1.9611g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate, and solid content is 15wt%, and limiting viscosity is 1.25dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 288 ℃, and the ultraviolet cut-on wavelength is 293nm, and the light transmission rate at 450nm place is 94%.
Embodiment 2
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g (0.01mol) of 2-are dissolved in the DMAc solvent of 52.23ml, stir to make solution becomes get clear.Disposable adding 1 in this solution then; 2; 4; 5-pentamethylene tetracarboxylic dianhydride (CPDA) 2.1014g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate, and solid content is 15wt%, and limiting viscosity is 1.06dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 251 ℃, and the ultraviolet cut-on wavelength is 303nm, and the light transmission rate at 450nm place is 90%.
Example 3
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g (0.01mol) of 2-are dissolved in the DMAc solvent of 53.08ml, stir to make solution becomes get clear.Disposable adding 1 in this solution then; 2; 4; 5-hexanaphthene tetracarboxylic dianhydride (CHDA) 2.2417g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate, and solid content is 15wt%, and limiting viscosity is 1.00dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 279 ℃, and the ultraviolet cut-on wavelength is 305nm, and the light transmission rate at 450nm place is 90%.
Embodiment 4
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the phenyl ether 5.2042g (0.01mol) of 2-are dissolved in the DMAc solvent of 43.29ml, stir to make solution becomes get clear.Disposable adding 1 in this solution then; 2; 3; 4-tetramethylene tetracarboxylic dianhydride (CBDA) 1.9611g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate, and solid content is 15wt%, and limiting viscosity is 1.16dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 286 ℃, and the ultraviolet cut-on wavelength is 295nm, and the light transmission rate at 450nm place is 95%.
Embodiment 5
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the phenyl ether 5.2042g (0.01mol) of 2-are dissolved in the DMAc solvent of 44.13ml, stir to make solution becomes get clear.Disposable adding 1 in this solution then; 2; 4; 5-pentamethylene tetracarboxylic dianhydride (CPDA) 2.1014g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate, and solid content is 15wt%, and limiting viscosity is 1.05dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 252 ℃, and the ultraviolet cut-on wavelength is 306nm, and the light transmission rate at 450nm place is 91%.
Example 6
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the phenyl ether 5.2042g (0.01mol) of 2-are dissolved in the DMAc solvent of 44.98ml, stir to make solution becomes get clear.Disposable adding 1 in this solution then; 2; 4; 5-hexanaphthene tetracarboxylic dianhydride (CHDA) 2.2417g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate, and solid content is 15wt%, and limiting viscosity is 1.02dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 275 ℃, and the ultraviolet cut-on wavelength is 310nm, and the light transmission rate at 450nm place is 92%.
Example 7
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g (0.01mol) of 2-are dissolved in the DMF solvent of 53.41ml, stir to make solution becomes get clear.Disposable adding dicyclo [2.2.1] heptane-2 in this solution then; 3:5; 6-tetracarboxylic dianhydride 2.3618g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate; solid content is 15wt%, and limiting viscosity is 1.07dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 269 ℃, and the ultraviolet cut-on wavelength is 286nm, and the light transmission rate at 450nm place is 93%.
Example 8
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the HFC-236fa 6.5445g (0.01mol) of 2-are dissolved in the DMF solvent of 54.28ml, stir to make solution becomes get clear.Disposable adding dicyclo [2.2.2] octane-2 in this solution then; 3:5; 6-tetracarboxylic dianhydride 2.5020g (0.01mol); stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment; the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate; solid content is 15wt%, and limiting viscosity is 1.05dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 267 ℃, and the ultraviolet cut-on wavelength is 288nm, and the light transmission rate at 450nm place is 92%.
Example 9
In the three neck reaction flasks that are equipped with agitator, thermometer and nitrogen feeding mouth, with 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] the phenyl ether 5.2042g (0.01mol) of 2-are dissolved in the DMF solvent of 51.13ml, stir to make solution becomes get clear.Disposable adding 1,2,3 in this solution then; 4-tetramethylene-symmetry (3; 6-oxo bridge-1,2,3; 6-tetrahydrochysene benzene-1; 2-dimethyl methyl acid anhydrides (CBTDA) 3.3226g (0.01mol), stirring makes it to dissolve fully the back and continue reaction 15～25 hours under the nitrogen protection environment, and the transparent thick liquid that obtains is the presoma-polyamic acid of the polyimide that can be used as the flexible transparent conducting film substrate; solid content is 15wt%, and limiting viscosity is 1.18dL/g.This polyamic acid solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up according to following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, then this polyimide film is placed 100 ℃ of loft drier dried for standby.
This Kapton is the water white transparency shape, its salient features: second-order transition temperature is 283 ℃, and the ultraviolet cut-on wavelength is 280nm, and the light transmission rate at 450nm place is 95%.
Claims (10)
1. polyimide film material that can be used as the flexible transparent conducting film substrate, it is characterized in that: described polyimide has following chemical structural formula:
In the formula
2. polyimide film material that can be used as the flexible transparent conducting film substrate as claimed in claim 1, it is characterized in that: Ar is selected from:
Ar ' is selected from:
3. one kind as the described preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate of claim 1～2, it is characterized in that described method comprises the steps:
1. earlier a kind of fluorine-containing phenylate type aromatic diamine is dissolved in a certain amount of polar aprotic solvent;
2. treat under agitation to act on after diamines dissolves fully, a kind of alicyclic dianhydride of mol ratios such as adding, temperature of reaction is about 0～25 ℃, and the reaction times is 15～25 hours, obtains having the even heavy-gravity polyamic acid solution of certain solid content;
3. above-mentioned polyamic acid solution is coated on the clean slick sheet glass, adopts the hot-imide method under the nitrogen protection environment, to make the Kapton that can be used for the flexible conductive film substrate.
4. preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate as claimed in claim 3, it is characterized in that: described alicyclic dianhydride is selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,4,5-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3:5, the 6-tetracarboxylic dianhydride, dicyclo [2.2.2] octane-2,3:5,6-tetracarboxylic dianhydride and 1,2,3,4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2-dimethyl methyl acid anhydrides) a kind of in.
5. preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate as claimed in claim 3, it is characterized in that: described fluorine-containing phenylate type aromatic diamine is selected from: 2, two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa and 4 of 2-, a kind of in 4 '-two (4-amino-2-4-trifluoromethylphenopendant) phenyl ether.
6. preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate as claimed in claim 3, it is characterized in that: described polar aprotic solvent is selected from N, dinethylformamide, a kind of in N,N-dimethylacetamide and the N-N-methyl-2-2-pyrrolidone N-.
7. preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate as claimed in claim 3 is characterized in that: alicyclic ring dianhydride and fluorine-containing phenylate type aromatic diamine are etc. that mol ratio is reacted.
8. preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate as claimed in claim 3, it is characterized in that: the solid content of described polyamic acid is 10～25%.
9. preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate as claimed in claim 3, it is characterized in that: described imidization method is the hot-imide method, and carries out in the nitrogen protection environment.
10. preparation method who can be used as the polyimide film material of flexible transparent conducting film substrate as claimed in claim 3, it is characterized in that: described final imidization temperature is 200～350 ℃, and the imidization time is 0.1～1 hour.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898644A (en) * | 2011-07-28 | 2013-01-30 | 苏州华辉材料科技有限公司 | Soluble fluorine-containing aromatic semi-alicyclic polyimide film material and preparation method thereof |
| CN104193993A (en) * | 2014-08-13 | 2014-12-10 | 南京理工大学 | Polyamide acid copolymer and polyimide film prepared from polyamide acid copolymer |
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| CN102898644A (en) * | 2011-07-28 | 2013-01-30 | 苏州华辉材料科技有限公司 | Soluble fluorine-containing aromatic semi-alicyclic polyimide film material and preparation method thereof |
| CN110028666B (en) * | 2014-02-14 | 2021-11-09 | 旭化成株式会社 | Polyimide precursor and resin composition containing same |
| CN110028666A (en) * | 2014-02-14 | 2019-07-19 | 旭化成株式会社 | Polyimide precursor and resin combination containing it |
| CN104193993A (en) * | 2014-08-13 | 2014-12-10 | 南京理工大学 | Polyamide acid copolymer and polyimide film prepared from polyamide acid copolymer |
| CN104804188B (en) * | 2015-04-26 | 2018-03-02 | 威海新元科盛新材料有限公司 | A kind of preparation method of Kapton |
| CN104804188A (en) * | 2015-04-26 | 2015-07-29 | 荣成市科盛化工有限公司 | Method for preparing polyimide film |
| CN104898325A (en) * | 2015-05-18 | 2015-09-09 | 深圳市华星光电技术有限公司 | Liquid crystal display panel and device |
| CN105037727A (en) * | 2015-09-16 | 2015-11-11 | 苏州华辉材料科技有限公司 | Polyimide film material capable of serving as conducting film substrate and preparing method of polyimide film material |
| CN107293353A (en) * | 2016-04-01 | 2017-10-24 | 律胜科技股份有限公司 | Flexible transparent polyimide laminate and process for producing the same |
| CN109762335A (en) * | 2018-12-29 | 2019-05-17 | 山东华夏神舟新材料有限公司 | Flexible Displays high transparency low bulk Kapton and preparation method thereof |
| CN109762335B (en) * | 2018-12-29 | 2020-12-22 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film for flexible display and preparation method thereof |
| CN109896753A (en) * | 2019-04-08 | 2019-06-18 | 拓米(成都)应用技术研究院有限公司 | A kind of foldable ultra-thin glass cover board and its modified CPI are coated with preparation method |
| CN110408064A (en) * | 2019-08-06 | 2019-11-05 | 苏州大学 | A kind of preparation method of colorless polyimide film |
| CN112500567A (en) * | 2020-12-21 | 2021-03-16 | 奥克控股集团股份公司 | High-modulus transparent polyimide film material containing amide structure and preparation method thereof |
| CN112500567B (en) * | 2020-12-21 | 2023-03-14 | 奥克控股集团股份公司 | High-modulus transparent polyimide film material containing amide structure and preparation method thereof |
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