CN102382303B - Colorless and transparent polyimide resin material and preparation method thereof - Google Patents
Colorless and transparent polyimide resin material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a colorless and transparent polyimide resin material. 1,2,3,4-cyclohexanetetracarboxylic dianhydride is chosen as dianhydride monomer or comonomer to carry out polycondensation reaction with primary diamine, so that the polyimide resin material is prepared. Because the 1,2,3,4-cyclohexanetetracarboxylic dianhydride comonomer has a distorted molecular structure, a large free volume exists between polymer molecular chains, and thereby the formation of charge transfer complex (CTC) in and between polyimide molecules is inhibited; and meanwhile, because of the introduction of a lipid structure, the electron-stimulated transition mode in the polyimide molecular chains is changed, the absorption of the aromatic polyimide in the visible light region is remarkably weakened, and thereby the transparency of the polymer is greatly increased. The ultraviolet light transmission cutoff wavelength of a produced polyimide film is 280nm to 380nm, the light transmissivity at 450nm is 86 to 94 percent, moreover, the glass-transition temperature is 250 DEG C to 400 DEG C, and the polyimide resin material has a good application prospect in the fields of flexible substrate materials for solar cells, flexible transparent conducting film substrate materials, liquid crystal display materials and the like.
Description
Technical field
The present invention relates to the polyimide material technical field, be specifically related to water white polyimide resin material and preparation method thereof.
Background technology
Polyimide is the polymkeric substance of a class excellent combination property, have characteristics such as good thermotolerance, lower temperature resistance, solvent resistance and flame retardant resistance, have superior dielectric properties and mechanical property simultaneously concurrently, therefore, be widely used in fields such as electronics, microelectronics, aerospace, laser, photoelectricity.
High optical transparency can enlarge the application of polyimide aspect photoelectric material, for example, be used for solar cell flexible substrate, be used for the optical waveguide material that communication connects, the alignment films that is used for liquid-crystal display, and the light half-wave plate etc. that is used for planar lightwave circuit.But, traditional Kapton presents pale brown look or brown usually, to the 500nm light penetration less than 40%, seriously limited its application at photoelectric field, its major cause is to be present in the electrophilic effect of carbonyl in the dianhydride residue that alternately occurs in the main polymer chain and the intramolecularly and the intermolecular charge transfer complex (CTC) that produce to electronic action of diamines residue.Therefore, light color even colourless Kapton be obtained, the formation of CTC will be reduced or eliminate.
Begin from the eighties in last century, the method of the reduction polyimide color that people take mainly comprises: (1) is introduced in the polyimide molecule structure and is contained fluoro substituents, because fluorine atom has very big electronegativity, can cut off the conjugation of electronic cloud, suppress the formation of CTC; (2) adopt the conjugation that has big side group or have unsymmetrical structure unit obstruction electronic cloud, suppress the formation of CTC; (3) obtain to have the polyimide of fat units with the dianhydride of lipid structure or diamine monomer, reduce the content of aromatic structure unit in the polyimide molecule chain, change the mode of being excited of electronics in the polyimide molecule chain, fundamentally suppress the formation of CTC.
At present, generally adopt aforesaid method (1) to obtain light Kapton, two (3, the 4-dicarboxylic acid) hexafluoropropane dianhydrides of 2,2-commonly used obtain a series of energy as dianhydride monomer and satisfy different light color even the colorless polyimide films that require.But, because 2, two (3, the 4-dicarboxylic acid) hexafluoropropane dianhydrides of 2-are very expensive, limited the large-scale application of such Kapton.Simultaneously, in the method (2) owing to have big side group or have the synthetic relatively difficulty of the monomer of unsymmetrical structure, can't large-scale application.Therefore, method (3) has obtained numerous investigators' concern, for example, and in 1. Liu J.G. of document, Nakamura Y.et al., Chem.Mater., 2008,20,273; 2. application number is the U.S. Patent application document of US6245881; 3. publication number is the Chinese invention patent Shen Qing Publication specification sheets of CN101084254A; 4. publication number is all to have reported in the documents such as Chinese invention patent Shen Qing Publication specification sheets of CN101831074A with the synthetic polyimide of alicyclic dianhydride monomer, this polyimide has high transparent and lower cutoff wavelength, possess higher thermostability and excellent solvability simultaneously, caused that people pay attention to widely.
Summary of the invention
Technical purpose of the present invention is at above-mentioned prior art, water white polyimide resin novel material is provided, this polyimide resin material has high transparent, high heat resistance and excellent solvability and lower advantages such as water-intake rate, has application promise in clinical practice in association areas such as the flexible substrate material of solar cell, flexible transparent conducting film substrate material, liquid crystal display materials.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: water white polyimide resin material has following structural formula:
Wherein, n
1And n
2All be the integer more than or equal to 1, A1 and A2 are the residues of binary primary amine, and A1 and A2 are separate, uncorrelated mutually.The said structure formula represented 1,2,3, the residue of 4-hexanaphthene tetracarboxylic dianhydride can be following two kinds of isomerization unit:
Cis-1,2,3, the residual body of 4-hexanaphthene tetracarboxylic dianhydride
Anti-form-1, the residual body of 2,3,4-hexanaphthene tetracarboxylic dianhydride
In the mixture of any one or two kinds.
As preferably, the n in the said structure formula
1Value and n
2Value is the integer between 10 to 10000.
As preferably, above-mentioned A1 and A2 are selected from one or more in the following groups:
The present invention also provides another kind of water white polyimide resin material, has following structural formula:
Wherein, n
1And n
2All be the integer more than or equal to 1, B refers to the residue except other tetracarboxylic dianhydride beyond 1,2,3, the 4-hexanaphthene tetracarboxylic dianhydride residue, and A1 and A2 are the residues of binary primary amine, and A1 and A2 are separate, uncorrelated mutually.The said structure formula represented 1,2,3, the residue of 4-hexanaphthene tetracarboxylic dianhydride can be following two kinds of isomerization unit:
Cis-1,2,3, the residual body of 4-hexanaphthene tetracarboxylic dianhydride
Anti-form-1, the residual body of 2,3,4-hexanaphthene tetracarboxylic dianhydride
In the mixture of any one or two kinds.
As preferably, the n in the said structure formula
1Value and n
2Value is the integer between 10 to 10000.
As preferably, A1 and A2 are selected from one or more in the following groups:
As preferably, the B in the said structure formula is selected from
In any one or multiple.
Two kinds of polyimide resin materials provided by the invention all present the water white transparency shape, and its second-order transition temperature is 250 ℃～400 ℃, and the uv-absorbing cutoff wavelength is 280nm～380nm, and the light transmission rate at the 450nm place is 86%～94%.
Two kinds of water white polyimide resin materials provided by the invention all are to adopt polycondensation synthetic.
Have structural formula:
Water white polyimide resin preparation methods be: obtained by polycondensation by 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and a kind of binary primary amine monomer; Perhaps obtained by polycondensation by 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and two kinds and two or more binary primary amine monomers.
Have structural formula:
Water white polyimide resin preparation methods be: the mixture of other tetracarboxylic dianhydride that is referred to by 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and B obtains by polycondensation with a kind of binary primary amine monomer; The perhaps mixture of other tetracarboxylic dianhydride that is referred to by 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and B obtains by polycondensation with two kinds and two or more binary primary amine monomer.
In polymer arts, the content of each structural unit generally can be controlled by the feed ratio of raw material in the polymkeric substance, and the content of each structural unit also can be controlled by the feed ratio of raw material in the described transparent polyimide resin material.
Concrete polycondensation can be adopted one-step synthesis and two step synthesis methods.
One-step synthesis is in the environment that is full of rare gas element (as nitrogen, argon gas etc.), tetracarboxylic dianhydride and binary primary amine monomer fed intake according to the equivalent ratio add in the phenol solvent (as meta-cresol, para-chlorophenol etc.), perhaps add polar aprotic solvent (as N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, gamma-butyrolactone etc.) and benzene kind solvent (as dimethylbenzene, orthodichlorobenzene etc.) in the mixed solvent, be warming up to certain temperature, then by directly obtaining polyimide solution except the water that generates in the dereaction.
The two step method synthesis method comprises two stages, at first be in the environment that is full of rare gas element (as nitrogen, argon gas etc.), tetracarboxylic dianhydride and binary primary amine are fed intake the adding polar aprotic solvent (as N according to the equivalent ratio, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, gamma-butyrolactone etc.) in, reaction at a certain temperature, generate polyamic acid precursor, carry out imidization with elevated temperature heat imidization method or with catalyst chemical imidization method then, be transformed into polyimide.
With trans 1,2,3, two (4-aminophenyl) HFC-236fa of 4-hexanaphthene tetracarboxylic dianhydride and 2,2-are example by polycondensation synthesis of polyimides resin material, and the polymerization route of one-step synthesis and two-step synthesis respectively as depicted in figs. 1 and 2.
Among above-mentioned two kinds of preparation methods, binary primary amine can be selected from 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 1, the 3-phenylenediamine, 3,3 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, 3,3 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-the diamino benzophenone, 4,4 '-the diamino benzophenone, 2,2 '-two (trifluoromethyl) benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-diaminodiphenyl oxide, 2,2 '-two (trifluoromethyl)-4,4 '-diaminodiphenyl sulfide, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two (3-aminophenyl) HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-, 1, two (5-amino-3-4-trifluoromethylphenopendant) benzene of 3-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (3-trifluoromethyl-5-amino-benzene oxygen) phenylfluoroforms of 6-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] propane of 2-, 2, in two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-and two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-one or more.
Among above-mentioned two kinds of preparation methods, other tetracarboxylic dianhydride that B refers to can be selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid dianhydride, dicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride, dicyclo [2.2.2] suffering-7-alkene-2,3,5,6-tetracarboxylic acid dianhydride, 1,2,3,4-connects pyromellitic dianhydride, 1,2,4,5-pyromellitic dianhydride, 2,2 ', 3,3 '-the biphenyl tetracarboxylic acid anhydrides, 2,3,3 ', 4 '-the biphenyl tetracarboxylic acid anhydrides, 3,3 ', 4,4 '-the biphenyl tetracarboxylic acid anhydrides, 2,2 ', 3,3 '-the diphenyl ether tetraformic acid anhydride, 2,3,3 ', 4 '-the diphenyl ether tetraformic acid anhydride, 3,3 ', 4,4 '-the diphenyl ether tetraformic acid anhydride, 2,2 ', 3,3 '-the diphenyl thio-ether tetrformate acid anhydride, 2,3,3 ', 4 '-the diphenyl thio-ether tetrformate acid anhydride, 3,3 ', 4,4 '-the diphenyl thio-ether tetrformate acid anhydride, 1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 1,3-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-in two (3,4-di carboxyl phenyloxy) phenyl ether dianhydride one or more.
Compared with prior art, water white polyimide resin material provided by the present invention adopts asymmetric fatty dianhydride, and namely 1,2,3,4-hexanaphthene tetracarboxylic dianhydride obtains polyimide as dianhydride monomer or comonomer with the aromatic diamine reaction.Because 1,2,3,4-hexanaphthene tetracarboxylic dianhydride monomer is a cycloaliphatic ring dianhydride, and resulting polymers is subjected to light activated mode and is transformed into n → π * transition by the π → π * transition of conventional fragrant polyimide, needs higher energy, thereby show lower cutoff wavelength, transmittance preferably; Simultaneously, because 1,2,3,4-hexanaphthene tetracarboxylic dianhydride monomer has the molecular structure of distortion, and the polymkeric substance that obtains has bigger free volume, has suppressed charge transfer complex (CTC) in polyimide molecule and intermolecular formation.Both actings in conjunction, significantly weakened the absorption of aromatic polyimide in the visible region, thereby improved the transparency of polyimide resin material greatly, obtaining UV-light is 280nm～380nm through cutoff wavelength, the light transmission rate at 450nm place is 86%～94%, and second-order transition temperature is 250 ℃～400 ℃ polyimide resin material.In addition, because the introducing of cycloaliphatic ring makes the polyimide resin material of gained have good solubility and lower water-intake rate.Therefore, polyimide resin material of the present invention has that the transparency is high, second-order transition temperature is high, good heat resistance, favorable solubility, and advantage such as water-intake rate is low, in association areas such as the flexible substrate material of solar cell, flexible transparent conducting film substrate material, liquid crystal display materials application promise in clinical practice is arranged.At last, one of main raw material of the present invention, 1,2,3,4-hexanaphthene tetracarboxylic dianhydride is synthetic simple, and raw materials cost is lower.
As novel polyimide resin material, its avatar comprises multiple, for example, polyimide resin material of the present invention can be made film, plastics, fiber etc., is applied in various association areas.
Description of drawings
Fig. 1 utilizes one-step synthesis to prepare the example polymerization route example of polyimide resin material of the present invention;
Fig. 2 utilizes two-step synthesis to prepare the example polymerization route example of polyimide resin material of the present invention;
Fig. 3 is that the Kapton that uses the polyimide resin material in embodiment 1 and the comparing embodiment 1 to obtain is the transmittance curve figure of the light of 200nm～800nm to wavelength.
Embodiment
Describe in further detail below in conjunction with accompanying drawing and the present invention of embodiment.
Embodiment 1:
In the present embodiment, water white polyimide resin material has following structural formula:
Concrete preparation method is: under the room temperature, with 2,2 of 16.0 grams (0.05 mole) '-two (trifluoromethyl) benzidines and 200 milliliters of meta-cresols join in the reactor of being furnished with agitator and nitrogen protection being arranged.Treat 2,2 '-after two (trifluoromethyl) benzidine dissolves fully, add the cis-1,2 of 5.6 grams (0.025 mole), the anti-form-1 of 3,4-hexanaphthene tetracarboxylic dianhydride and 5.6 grams (0.025 mole), 2,3,4-hexanaphthene tetracarboxylic dianhydride continues to stir and dissolves fully until the two.Be warming up to 180 ℃ of reaction 5h then.To react the water that generates with de-watering apparatus simultaneously in reaction process gets rid of from reaction system and obtains polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains the polyimide powder resin.Wherein the second-order transition temperature of polymer powder is 358 ℃.
With the polyimide powder N that obtains, it is 10% solution that dinethylformamide is configured to concentration expressed in percentage by weight, with casting method this solution is coated on the clean sheet glass, sheet glass is placed in the loft drier that has nitrogen protection, heats up according to follow procedure: at first be to keep 4h down at 80 ℃; Be warming up to 150 ℃ then, insulation 1h; Then be warming up to 200 ℃, insulation 1h; Be warming up to 240 ℃ at last, insulation 0.5h.This heating schedule can be abbreviated as: 80 ℃, and 4h; 150 ℃, 1h; 200 ℃, 1h; 240 ℃, 0.5h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain the film that water white polyimide resin material constitutes, the thickness of this film is 15 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 288nm, the light transmission rate at the 450nm place is 91.4%.
Comparing embodiment 1:
Present embodiment is the comparative example of embodiment 1.
In the present embodiment, the polyimide resin material has following structural formula:
Concrete preparation method is: under the room temperature, with 2,2 of 16.0 grams (0.05 mole) '-two (trifluoromethyl) benzidines and 280 milliliters of meta-cresols join in the reactor of being furnished with agitator and nitrogen protection being arranged.Fully stir, treat 2,2 '-after two (trifluoromethyl) benzidine dissolves fully, add 2,3,3 of 16.3 grams (0.05 mole) ', 4 '-the diphenyl thio-ether tetrformate dianhydride, continue to stir and dissolve fully until the two.Be warming up to 180 ℃ of reaction 5h then.To react the water that generates with de-watering apparatus simultaneously in reaction process gets rid of from reaction system and obtains polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains the polyimide powder resin.Wherein the second-order transition temperature of polymer powder is 285 ℃.
With the polyimide powder N that obtains, it is 10% solution that the N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, with casting method its solution is coated on the clean sheet glass, and sheet glass is positioned in the loft drier that has nitrogen protection, heat up according to follow procedure: 80 ℃, 4h; 150 ℃, 1h; 200 ℃, 1h; 240 ℃, 0.5h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain Kapton, thickness is 15 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 408nm, the light transmission rate at the 450nm place is 81.5%.
Fig. 3 is that the polyimide resin film in embodiment 1 and the comparing embodiment 1 is the light penetration graphic representation of 200nm～800nm to wavelength.As can be seen from Figure 1, under the condition of same thin film thickness, adopt 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and 2,2 '-polyimide resin material that the polymerization of two (trifluoromethyl) benzidine obtains, than adopting other tetracarboxylic dianhydride, for example 2,3,3 ', 4 '-the diphenyl thio-ether tetrformate dianhydride, with 2,2 '-two (trifluoromethyl) benzidine polyreaction after synthetic polyimide resin material, its film improves greatly in the long transmitance of all-wave, and cutoff wavelength reduces significantly.
Embodiment 2:
In the present embodiment, water white polyimide resin material has following structural formula:
Concrete preparation method is: under the room temperature, and with 2 of 16.7 grams (0.05 mole), two (4-aminophenyl) HFC-236fa of 2-and 160 milliliters of N, dinethylformamide joins in the reactor of being furnished with agitator.Treat 2,2 '-after two (4-aminophenyl) HFC-236fa is dissolved fully, at room temperature add the cis-1,2,3 of 11.2 grams (0.05 mole), 4-hexanaphthene tetracarboxylic dianhydride.After dissolving fully etc. system, be warming up to 50 ℃, and continuously stirring 3h, make the polyamic acid solution of thickness.
This polyamic acid solution is coated on the clean sheet glass, sheet glass is positioned in the loft drier that has nitrogen protection, heat up according to follow procedure: 80 ℃, 4h; 150 ℃, 1h; 200 ℃, 1h; 250 ℃, 1h; 300 ℃, 0.5h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 18 μ m.Wherein the second-order transition temperature of this film is 328 ℃.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 292nm, the light transmission rate at the 450nm place is 90.2%.
Embodiment 3:
In the present embodiment, water white polyimide resin material has following structural formula:
Concrete preparation method is: under the room temperature, with 2 of 16.7 grams (0.05 mole), two (4-aminophenyl) HFC-236fa of 2-and 100 milliliters of N-Methyl pyrrolidone join in the reactor of being furnished with agitator.Treat 2,2 '-after two (4-aminophenyl) HFC-236fa is dissolved fully, at room temperature add anti-form-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and 50 milliliters of orthodichlorobenzenes of 11.2 grams (0.05 mole).Continue to stir and dissolve fully until the two.Be warming up to 180 ℃ of reaction 10h then.To react the water that generates with de-watering apparatus simultaneously in reaction process gets rid of from reaction system and obtains polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains polyimide powder.Wherein the second-order transition temperature of polymer powder is 323 ℃.
With the polyimide powder N that obtains, it is 10% solution that dinethylformamide is configured to concentration expressed in percentage by weight, with casting method its solution is coated on the clean sheet glass, and sheet glass is positioned in the loft drier that has nitrogen protection, heat up according to follow procedure: 80 ℃, 4h; 150 ℃, 1h; 200 ℃, 1h; 220 ℃, 0.5h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 16 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 294nm, the light transmission rate at the 450nm place is 90.3%.
Embodiment 4:
In the present embodiment, water white polyimide resin material has following structural formula:
Concrete preparation method is: under the room temperature, with 2,2 of 16.8 grams (0.05 mole) '-two (trifluoromethyl)-4 and 200 milliliters of meta-cresols join in the reactor of being furnished with agitator and nitrogen protection being arranged.Treat 2,2 '-after two (trifluoromethyl)-4 dissolve fully, adding the anti-form-1 of 11.2 grams (0.05 mole), 2,3,4-hexanaphthene tetracarboxylic dianhydride continues to stir and dissolves fully until the two.Be warming up to 180 ℃ of reaction 5h then.To react the water that generates with de-watering apparatus simultaneously in reaction process gets rid of from reaction system and obtains polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains the polyimide powder resin.Wherein the second-order transition temperature of polymer powder is 308 ℃.
With the polyimide powder N that obtains, it is 12% solution that the N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, with casting method its solution is coated on the clean sheet glass, sheet glass is positioned in the loft drier, 80 ℃, 10h, take out then and put into vacuum drying oven and heat up according to follow procedure: 80 ℃, 1h; 100 ℃, 1h; 140 ℃, 1h; 180 ℃, 1h; 230 ℃, 1h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 18 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 297nm, the light transmission rate at the 450nm place is 90.0%.
Embodiment 5:
In the present embodiment, water white polyimide resin material has following structural formula, wherein in reactant feeds intake, and 2,2 '-two (trifluoromethyl) benzidines and 4,4 '-ratio of the amount of substance of two (3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide is 7/3:
Concrete preparation method is: under the room temperature; with 2 of 11.2 grams (0.035 mole); 2 '-two (trifluoromethyl) benzidine, 8.5 grams (0.015 mole) 4,4 '-two (3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzides and 230 milliliters of meta-cresols join in the reactor of being furnished with agitator and nitrogen protection being arranged.Fully stir, treat that two kinds of diamines dissolve fully after, at room temperature add the anti-form-1 of 11.2 grams (0.05 mole), 2,3,4-hexanaphthene tetracarboxylic dianhydride continues to stir and dissolves fully until dianhydride.Be warming up to 180 ℃ of reaction 5h then.To react the water that generates with de-watering apparatus simultaneously in reaction process gets rid of from reaction system and obtains polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains polyimide powder.Wherein the second-order transition temperature of polymer powder is 299 ℃.
With the polyimide powder N that obtains, it is 12% solution that dinethylformamide is configured to concentration expressed in percentage by weight, with casting method its solution is coated on the clean sheet glass, and sheet glass is positioned in the loft drier that has nitrogen protection, heat up according to follow procedure: 80 ℃, 4h; 150 ℃, 1h; 200 ℃, 1h; 220 ℃, 0.5h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 14 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 295nm, the light transmission rate at the 450nm place is 90.2%.
Embodiment 6:
In the present embodiment, water white polyimide resin material has following structural formula, wherein in reactant feeds intake, and cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and 2,3,3 ', 4 '-ratio of the amount of substance of diphenyl ether tetraformic acid anhydride is 9/1:
Concrete preparation method is: under the room temperature, and with 1 of 21.4 grams (0.05 mole), two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-and 210 milliliters of N, dinethylformamide joins in the reactor of being furnished with agitator and nitrogen protection being arranged.After treating that two (4-amino-2-4-trifluoromethylphenopendant) benzene of 1,3-dissolve fully, add 2,3 of 1.6 grams (0.005 mole), 3 ', 4 '-the diphenyl ether tetraformic acid anhydride and 10.1 the gram (0.045 mole) cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride continues to stir and dissolves fully until the two.After dissolving fully etc. system, continuously stirring is reacted 3h at normal temperatures, makes the polyamic acid solution of thickness.
This polyamic acid solution is coated on the clean sheet glass, sheet glass is positioned in the loft drier that has nitrogen protection, heat up according to follow procedure: 80 ℃, 4h; 150 ℃, 1h; 200 ℃, 1h; 250 ℃, 0.5h; 290 ℃, 0.5h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 18 μ m.Wherein the second-order transition temperature of this film is 296 ℃.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 306nm, the light transmission rate at the 450nm place is 89.2%.
Embodiment 7:
In the present embodiment, water white polyimide resin material has following structural formula, wherein in reactant feeds intake, and cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and 2,3,3 ', 4 '-ratio of the amount of substance of diphenyl ether tetraformic dianhydride is 1/1:
Concrete preparation method is: under the room temperature, with 2,2 of 16.0 grams (0.05 mole) '-two (trifluoromethyl) benzidines and 250 milliliters of meta-cresols join in the reactor of being furnished with agitator and nitrogen protection being arranged.Treat 2,2 '-after two (trifluoromethyl) benzidine dissolves fully, add the cis-1,2 of 5.6 grams (0.025 mole), 2,3 of 3,4-hexanaphthene tetracarboxylic dianhydride and 7.8 grams (0.025 mole), 3 ', 4 '-diphenyl ether tetraformic dianhydride, continue to stir and dissolve fully until the two.Be warming up to 190 ℃ of reaction 8h then.The water that will generate in will reacting with de-watering apparatus simultaneously in reaction process is got rid of from reaction system and is obtained polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains polyimide powder.Wherein the second-order transition temperature of polymer powder is 322 ℃.
It is 10% solution that the polyimide powder that obtains is configured to concentration expressed in percentage by weight with N-Methyl pyrrolidone, with casting method its solution is coated on the clean sheet glass, sheet glass is positioned in the loft drier, 80 ℃, 10h, take out then and put into vacuum drying oven and heat up according to follow procedure: 80 ℃, 1h; 100 ℃, 1h; 140 ℃, 1h; 180 ℃, 1h; 230 ℃, 1h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 19 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 353nm, the light transmission rate at the 450nm place is 87.1%.
Embodiment 8:
In the present embodiment, water white polyimide resin material has following structural formula, wherein in reactant feeds intake, and anti-form-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and 2,3,3 ', 4 '-ratio of the amount of substance of diphenyl ether tetraformic dianhydride is 1/4:
Concrete preparation method is: under the room temperature, with 2,2 of 16.0 grams (0.05 mole) '-two (trifluoromethyl) benzidines and 250 milliliters of meta-cresols join in the reactor of being furnished with agitator and nitrogen protection being arranged.Treat 2,2 '-after two (trifluoromethyl) benzidine dissolves fully, add the anti-form-1 of 2.2 grams (0.01 mole), 2,2,3 of 3,4-hexanaphthene tetracarboxylic dianhydride and 12.4 grams (0.04 mole), 3 ', 4 '-diphenyl ether tetraformic dianhydride, continue to stir and dissolve fully until the two.Be warming up to 190 ℃ of reaction 8h then.The water that will generate in will reacting with de-watering apparatus simultaneously in reaction process is got rid of from reaction system and is obtained polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains polyimide powder.Wherein the second-order transition temperature of polymer powder is 312 ℃.
It is 13% solution that the polyimide powder that obtains is configured to concentration expressed in percentage by weight with N-Methyl pyrrolidone, with casting method its solution is coated on the clean sheet glass, sheet glass is positioned in the loft drier, 80 ℃, 10h, take out then and put into vacuum drying oven and heat up according to follow procedure: 80 ℃, 1h; 100 ℃, 1h; 140 ℃, 1h; 180 ℃, 1h; 230 ℃, 1h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 22 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 360nm, the light transmission rate at the 450nm place is 86.3%.
Embodiment 9:
In the present embodiment, water white polyimide resin material has following structural formula, wherein in reactant feeds intake, and cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and 3,3 ', 4,4 '-ratio of the amount of substance of biphenyl tetracarboxylic dianhydride is 9/1:
Concrete preparation method is: under the room temperature, with 2,2 of 16.0 grams (0.05 mole) '-two (trifluoromethyl) benzidines and 250 milliliters of meta-cresols join in the reactor of being furnished with agitator and nitrogen protection being arranged.Treat 2,2 '-after two (trifluoromethyl) benzidine dissolves fully, add the cis-1,2 of 10.1 grams (0.045 mole), 3,3 of 3,4-hexanaphthene tetracarboxylic dianhydride and 1.5 grams (0.005 mole) ', 4,4 '-bibenzene tetracarboxylic dianhydride, continue to stir and dissolve fully until the two.Be warming up to 190 ℃ of reaction 8h then.The water that will generate in will reacting with de-watering apparatus simultaneously in reaction process is got rid of from reaction system and is obtained polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains polyimide powder.Wherein the second-order transition temperature of polymer powder is 324 ℃.
With the polyimide powder N that obtains, it is 10% solution that the N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, with casting method its solution is coated on the clean sheet glass, sheet glass is positioned in the loft drier, 80 ℃, 10h, take out then and put into vacuum drying oven and heat up according to follow procedure: 80 ℃, 1h; 100 ℃, 1h; 140 ℃, 1h; 180 ℃, 1h; 200 ℃, 1h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 14 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 352nm, the light transmission rate at the 450nm place is 88.0%.
Embodiment 10:
In the present embodiment, water white polyimide resin material has following structural formula, wherein in reactant feeds intake, and anti-form-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and 3,3 ', 4,4 '-ratio of triphen bis ether tetracarboxylic dianhydride's amount of substance is 1/1:
Concrete preparation method is: under the room temperature, with 2,2 of 16.8 grams (0.05 mole) '-two (trifluoromethyl)-4 and 120 milliliters of N-Methyl pyrrolidone join in the reactor of being furnished with agitator and nitrogen protection being arranged.Treat 2,2 '-after two (trifluoromethyl)-4 dissolve fully, add the anti-form-1 of 5.6 grams (0.025 mole), 2,3,4-hexanaphthene tetracarboxylic dianhydride, 10.1 gram (0.025 moles) 1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride and 50 milliliters of orthodichlorobenzenes continue to stir and dissolve fully until the two.Be warming up to 180 ℃ of reaction 10h then.To react the water that generates with de-watering apparatus simultaneously in reaction process gets rid of from reaction system and obtains polyimide solution.Reaction solution splashed into obtain fibrous polyimide precipitation in the ethanol, oven dry obtains polyimide powder.Wherein the second-order transition temperature of polymer powder is 304 ℃.
With the polyimide powder N that obtains, it is 10% solution that the N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, with casting method its solution is coated on the clean sheet glass, sheet glass is positioned in the loft drier, 80 ℃, 10h, take out then and put into vacuum drying oven and heat up according to follow procedure: 80 ℃, 1h; 100 ℃, 1h; 140 ℃, 1h; 180 ℃, 1h; 200 ℃, 1h.Treat to take out sheet glass after temperature is down to room temperature, be placed on demoulding in the warm water, then film is placed 120 ℃ of dry 2h of loft drier, obtain water white Kapton, its thickness is 21 μ m.
Film by ultraviolet-visual spectrometer test method for preparing see through curve, the uv-absorbing cutoff wavelength of this film is 366nm, the light transmission rate at the 450nm place is 88.1%.
Claims (14)
1. water white polyimide resin material, it is characterized in that: described polyimide resin material has following chemical formula:
Wherein,
Be the residue of 1,2,3,4-hexanaphthene tetracarboxylic dianhydride, its structure is cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride residue
And anti-form-1,2,3,4-hexanaphthene tetracarboxylic dianhydride residue
In a kind of, or the mixture of two kinds of structures;
n
1And n
2All be the integer more than or equal to 1, A1 and A2 are the residues of binary primary amine, and A1 and A2 are separate, uncorrelated mutually;
The uv-absorbing cutoff wavelength of described polyimide resin material is 280nm～380nm, and the light transmission rate at the 450nm place is 86%～94%.
2. water white polyimide resin material according to claim 1, it is characterized in that: described A1 and A2 are one or more in the following groups:
3. water white polyimide resin material according to claim 1 and 2 is characterized in that: described n
1Value and n
2Value is between 10 to 10000.
4. water white polyimide resin material according to claim 1 and 2, it is characterized in that: the second-order transition temperature of described polyimide resin material is 250 ℃～400 ℃.
5. water white polyimide resin material preparation method according to claim 1 and 2, it is characterized in that, by 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and a kind of binary primary amine monomer obtain by polycondensation, perhaps by 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and two kinds and two or more binary primary amine monomers obtain by polycondensation;
Wherein, described 1,2,3,4-hexanaphthene tetracarboxylic dianhydride is cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and anti-form-1, any one in two kinds of dianhydride monomers of 2,3,4-hexanaphthene tetracarboxylic dianhydride or both mixtures.
6. the preparation method of transparent polyimide resin material according to claim 5, it is characterized in that: described binary primary amine is selected from 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 1, the 3-phenylenediamine, 3,3 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, 3,3 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-the diamino benzophenone, 4,4 '-the diamino benzophenone, 2,2 '-two (trifluoromethyl) benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-diaminodiphenyl oxide, 2,2 '-two (trifluoromethyl)-4,4 '-diaminodiphenyl sulfide, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two (3-aminophenyl) HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-, 1, two (5-amino-3-4-trifluoromethylphenopendant) benzene of 3-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (3-trifluoromethyl-5-amino-benzene oxygen) phenylfluoroforms of 6-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] propane of 2-, 2, in two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-and two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-one or more.
7. water white polyimide resin material, it is characterized in that: described polyimide resin material has following chemical formula:
Wherein,
Be the residue of 1,2,3,4-hexanaphthene tetracarboxylic dianhydride, its structure is cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride residue
And anti-form-1,2,3,4-hexanaphthene tetracarboxylic dianhydride residue
In a kind of, or the mixture of two kinds of structures;
n
1And n
2All be the integer more than or equal to 1, B refers to except four of other tetracarboxylic dianhydride beyond 1,2,3, the 4-hexanaphthene tetracarboxylic dianhydride and replaces residues, and A1 and A2 are the binary primary amine residues, and A1 and A2 are separate, uncorrelated mutually;
The uv-absorbing cutoff wavelength of described polyimide resin material is 280nm～380nm, and the light transmission rate at the 450nm place is 86%～94%.
8. water white polyimide resin material according to claim 7, it is characterized in that: described A1 and A2 are one or more in the following groups:
9. according to claim 7 or 8 described water white polyimide resin materials, it is characterized in that: described B is selected from any one or a few in the following groups:
10. according to claim 7 or 8 described water white polyimide resin materials, it is characterized in that: described n
1Value and n
2Value is between 10 to 10000.
11. according to claim 7 or 8 described water white polyimide resin materials, it is characterized in that: the second-order transition temperature of described polyimide resin material is 250 ℃～400 ℃.
12. according to claim 7 or 8 described water white polyimide resin preparation methods, it is characterized in that: described transparent polyimide material is by 1,2,3, the mixture of other tetracarboxylic dianhydride that 4-hexanaphthene tetracarboxylic dianhydride and B refer to obtains by polycondensation with a kind of binary primary amine monomer; The perhaps mixture of other tetracarboxylic dianhydride that is referred to by 1,2,3,4-hexanaphthene tetracarboxylic dianhydride and B obtains by polycondensation with two kinds and two or more binary primary amine monomer;
Wherein, described 1,2,3,4-hexanaphthene tetracarboxylic dianhydride is cis-1,2,3,4-hexanaphthene tetracarboxylic dianhydride and anti-form-1, any one in two kinds of dianhydride monomers of 2,3,4-hexanaphthene tetracarboxylic dianhydride or both mixtures.
13. water white polyimide resin preparation methods according to claim 12, it is characterized in that: described binary primary amine is selected from 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 1, the 3-phenylenediamine, 3,3 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, 3,3 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-the diamino benzophenone, 4,4 '-the diamino benzophenone, 2,2 '-two (trifluoromethyl) benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-diaminodiphenyl oxide, 2,2 '-two (trifluoromethyl)-4,4 '-diaminodiphenyl sulfide, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two (3-aminophenyl) HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 3-, 1, two (5-amino-3-4-trifluoromethylphenopendant) benzene of 3-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (3-trifluoromethyl-5-amino-benzene oxygen) phenylfluoroforms of 6-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] propane of 2-, 2, in two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-and two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-one or more.
14. water white polyimide resin preparation methods according to claim 12 is characterized in that: other tetracarboxylic dianhydride that described B refers to is selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid dianhydride, dicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride, dicyclo [2.2.2] suffering-7-alkene-2,3,5,6-tetracarboxylic acid dianhydride, 1,2,3,4-pyromellitic dianhydride, 1,2,4,5-pyromellitic dianhydride, 2,2 ', 3,3 '-the biphenyl tetracarboxylic acid anhydrides, 2,3,3 ', 4 '-the biphenyl tetracarboxylic acid anhydrides, 3,3 ', 4,4 '-the biphenyl tetracarboxylic acid anhydrides, 2,2 ', 3,3 '-the diphenyl ether tetraformic acid anhydride, 2,3,3 ', 4 '-the diphenyl ether tetraformic acid anhydride, 3,3 ', 4,4 '-the diphenyl ether tetraformic acid anhydride, 2,2 ', 3,3 '-the diphenyl thio-ether tetrformate acid anhydride, 2,3,3 ', 4 '-the diphenyl thio-ether tetrformate acid anhydride, 3,3 ', 4,4 '-the diphenyl thio-ether tetrformate acid anhydride, 1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 1,3-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-in two (3,4-di carboxyl phenyloxy) phenyl ether dianhydride one or more.
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| CN102634021B (en) * | 2012-03-30 | 2013-12-25 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic polyimide resin and preparation method thereof |
| CN102807675A (en) * | 2012-08-19 | 2012-12-05 | 南京依麦德光电材料科技有限公司 | Flexible transparent polyimide film material and preparation method thereof |
| CN102911359B (en) * | 2012-10-19 | 2014-04-23 | 中国科学院宁波材料技术与工程研究所 | Transparent polyimide and preparation method thereof |
| CN102993750A (en) * | 2012-12-12 | 2013-03-27 | 中国科学院长春应用化学研究所 | Polyimide film and preparation method thereof |
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| CN104151823B (en) * | 2014-09-02 | 2019-02-26 | 长春聚明光电材料有限公司 | Kapton and preparation method thereof |
| CN106795283B (en) * | 2014-09-02 | 2020-07-10 | 东丽株式会社 | Resin and photosensitive resin composition |
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| KR20210075665A (en) * | 2019-12-13 | 2021-06-23 | 주식회사 두산 | Polyimide film having high yield strain |
| CN114008110A (en) * | 2020-05-14 | 2022-02-01 | 律胜科技股份有限公司 | Polyimide film and method for producing same |
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| CN117551295A (en) * | 2024-01-12 | 2024-02-13 | 宁波长阳科技股份有限公司 | Colorless transparent polyimide film with low phase difference and preparation method thereof |
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| WO2006068096A1 (en) * | 2004-12-24 | 2006-06-29 | Mitsubishi Gas Chemical Company, Inc. | Low water-absorptive polyimide resin and method for producing same |
| CN101580637B (en) * | 2009-06-12 | 2011-08-31 | 东华大学 | Alicyclic-containing polyimide film and preparation method thereof |
| CN101831074A (en) * | 2010-04-30 | 2010-09-15 | 辽宁科技大学 | New type fluorine-containing copolyimide and preparation method thereof |
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