CN111073283A - Cross-linked polyimide film, optical film and preparation method thereof - Google Patents
Cross-linked polyimide film, optical film and preparation method thereof Download PDFInfo
- Publication number
- CN111073283A CN111073283A CN201911191881.9A CN201911191881A CN111073283A CN 111073283 A CN111073283 A CN 111073283A CN 201911191881 A CN201911191881 A CN 201911191881A CN 111073283 A CN111073283 A CN 111073283A
- Authority
- CN
- China
- Prior art keywords
- polyimide film
- group
- cross
- film
- diamine monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a cross-linking type polyimide film, the transmissivity of light with 400nm wavelength is more than 80%, and the solvent resistance index is within 1%. Meanwhile, the invention also provides the application of the polyimide film in photoelectric display devices and other products and parts with high requirements on light transmission and solvent resistance.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to a cross-linked polyimide film, an optical film and a preparation method thereof.
Background
In the field of optoelectronics, polymer materials, especially colorless and transparent polymer materials, are used in products such as light sensors, flexible displays, solar cells, and the like. The main requirements for polymer materials used in the field of optoelectronics are optical transparency, mechanical properties and heat resistance, and the most common one to meet this requirement is a polyimide material, and the most typical polyimide material is a linear polyimide synthesized from pyromellitic dianhydride and 4, 4' -diaminodiphenyl ether. The polyimide has the advantages of high main chain rigidity, good heat resistance and good mechanical properties at high and low temperatures, but the rigid structure of the main chain makes the polyimide insoluble, thereby bringing certain difficulty to product processing; and the charge transfer complex in or among molecules can bring certain color, thereby limiting the application in the optical field.
In recent years, colorless transparent polyimide films have been developed, but there is a problem that the original solvent resistance of polyimide is lowered, and therefore, when the film is used as a substrate, an optical coating layer or a film and exposed to a developing solution such as a polar solvent or an acid or alkali or other coating solution or the like, the surface thereof is dissolved, swelled or shrunk, and the form thereof is changed, so that the film cannot be used alone without a protective layer.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a cross-linked polyimide film, wherein the transmittance of light with wavelength of 400nm is more than 80%, and the solvent resistance index is within 1%. Meanwhile, the invention also provides the application of the polyimide film in photoelectric display devices and other products and parts with high requirements on light transmission and solvent resistance.
The invention provides a cross-linking type polyimide film, which comprises diamine monomers and tetracarboxylic dianhydride monomers as raw materials, wherein at least one of the diamine monomers is a diamine monomer containing a benzimidazole group structure.
Preferably, the synthetic raw material also comprises a cross-linking agent, and the cross-linking agent is preferably dihalo-aromatic hydrocarbon.
Preferably, the diamine monomer containing a benzimidazole group structure is 10 to 20 mol% of the total amount of the diamine monomer.
Preferably, at least one of the diamine monomers is an aromatic diamine monomer containing at least one substituent of an oxy group, a sulfone group or a fluorine group; preferably, the aromatic diamine monomer having at least one substituent group of an oxy group, a sulfone group or a fluorine group is 80 to 90 mol% of the total amount of the diamine monomer.
Preferably, the first and second electrodes are formed of a metal,
the tetracarboxylic dianhydride monomer is selected from any one or combination of the following compounds:
the diamine monomer containing the benzimidazole group structure is selected from any one or combination of the following compounds:
the aromatic diamine monomer containing at least one substituent of an oxygen group, a sulfone group or a fluorine group is selected from any one or more of the following compounds:
the cross-linking agent is selected from any one or combination of more of the following compounds:
preferably, the glass transition temperature of the film is 330 ℃ or more, and the tensile strength is 120MPa or more; preferably, the film has a 400nm wavelength light transmittance of 80% or more and a solvent resistance index of 1% or less.
The invention also provides a preparation method of the cross-linked polyimide film, which comprises the following steps:
s1, dissolving diamine monomers in an organic solvent, adding tetracarboxylic dianhydride monomers to carry out polycondensation reaction to obtain a polyamic acid solution, adding a cross-linking agent into the polyamic acid solution, and uniformly mixing to obtain an intermediate solution;
and S2, diluting the intermediate solution obtained in the step S1 with an organic solvent, coating the diluted intermediate solution on a carrier to form a film, and heating the film to perform imidization and crosslinking reaction to obtain the crosslinked polyimide film.
Preferably, in step S1, the polycondensation reaction is performed under the protection of inert gas, the temperature of the polycondensation reaction is preferably 5 ℃, the reaction time is preferably 8 hours, and the organic solvent is preferably at least one of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide;
preferably, in step S2, the organic solvent is at least one of an amide solvent, a ketone solvent and an ether solvent, the diluted concentration of the polyamic acid solution is preferably 10 wt% of solid content, the coating method is preferably a casting method, and the support is preferably a glass plate;
preferably, the heating for imidization and crosslinking specifically comprises: drying the carrier coated with the film at 70-80 ℃ for 1-2h, cooling to room temperature, then heating to 150-.
The invention provides an optical film which is made of the cross-linked polyimide film.
The invention provides a photoelectric display device which comprises the optical film.
According to the invention, the cross-linked polyimide film is obtained by adopting a diamine monomer containing a benzimidazole group to perform polycondensation with tetracarboxylic dianhydride, introducing aromatic diamine containing an oxygen group, a sulfone group or a fluorine group to participate in copolymerization, then adding a cross-linking agent, and performing imidization and cross-linking reaction under a heating condition, wherein in the cross-linked polyimide film, the main chain structure contains the benzimidazole group structure, so that the molecular chain spacing is favorably increased, and the charge transfer in molecules and among molecules is inhibited; meanwhile, imidazole groups and a cross-linking agent are cross-linked, and after thermal imidization, the finally obtained polyimide has good solvent resistance, colorless transparency, excellent heat resistance and excellent mechanical property; furthermore, if a fluorine-containing group and/or a sulfone group and an oxy group with strong electron withdrawing property are introduced into the main chain structure, the electron donating property of the diamine part can be destroyed, and the conjugated property of the main chain can be destroyed, so that the effect of improving the light transparency of the polyimide film is further achieved.
The cross-linked polyimide film finally obtained by the invention has high glass transition temperature, colorless transparency and excellent solvent resistance, and can be used as a flexible transparent substrate material to be applied to the manufacturing process of optical devices such as solar cells, image displays, transparent substrates and the like.
Detailed Description
The cross-linking type polyimide film is formed by cross-linking polyimide copolymerized by diamine monomers and tetracarboxylic dianhydride monomers, wherein at least one of the diamine monomers is a diamine monomer containing a benzimidazole group.
In order to improve the solvent resistance of the polyimide film during the synthesis of the cross-linked polyimide film, the solvent resistance of the polyimide film is improved by including a diamine monomer having a benzimidazole group and including the diamine monomer in a predetermined amount, particularly selected from the group consisting of: at least one of 2- (3-aminophenyl) -5-aminobenzimidazole and 2- (4-aminophenyl) -5-aminobenzimidazole, which can provide a crosslinking site, and thereby the present invention has been completed.
Meanwhile, in order to further improve the light transmittance of the polyimide film, the polyimide film is synthesized by including the following tetracarboxylic dianhydride monomers, particularly selected from: 4, 4'- (hexafluoroisopropylene) diphthalic anhydride, 4' -oxydiphthalic anhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride, 2, 3, 5-tricarboxycyclopentaneacetic dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1] hept-2, 3, 5, 6-tetracarboxylic dianhydride, 3, 4, 6-tricarboxybicyclo [2.2.2] heptaneacetic dianhydride, bicyclo [2.2.2] hept-2, 3, 5, 6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3, 5, 6-tetracarboxylic dianhydride, decahydro-1, 4, 5, 8-dimethylenenaphthalene-2, 3, 6, 7-tetracarboxylic dianhydride or decahydro-biphenyl-3, at least one of 3', 4, 4' -tetracarboxylic dianhydrides can provide a polyimide film having high light transmittance, and the present invention has been completed.
In addition, in order to further improve the light transmittance of the polyimide by incorporating a tetracarboxylic dianhydride monomer, an aromatic diamine monomer containing at least one substituent group of an oxy group, a sulfone group or a fluoro group may be incorporated, and particularly, at least one member selected from the group consisting of 4, 4 '-diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, α '-bis (4-aminophenyl) -1, 4-diisopropylbenzene, 4' -bis (2-trifluoromethyl-4-aminophenoxy) benzene, 3 '-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 4' -bis (2-methyl-4-aminophenoxy) benzene, 3 '-bis (2-methyl-4-aminophenoxy) benzene, 4' -bis (2-trifluoromethyl-4-aminophenoxy) biphenyl, 4 '-bis (2-methyl-4-aminophenoxy) biphenyl, 2' -bis (4-aminophenoxy) phenyl, 2, 4 '-bis (4-hexafluoropropane, 2, 4' -bis (4-trifluoromethylphenoxy) sulfone, 2, 4 '-bis (4-aminophenyl) propane and 2, 4' -bis (trifluoromethyl-4-aminophenoxy) propane may be incorporated.
In addition, the crosslinking agent used for crosslinking is dihalogenated aromatic hydrocarbon, especially selected from at least one of o-dichlorobenzyl, m-dichlorobenzyl, 1, 4-p-dichlorobenzyl, 4 '-dichloromethyl biphenyl, o-dibrombenzyl, m-dibrombenzyl, 1, 4-p-dibrombenzyl, 4' -dibromomethyl biphenyl.
In the present invention, the preparation of the polyimide film comprises the following steps:
(1) dissolving diamine monomers in an organic solvent, adding tetracarboxylic dianhydride monomers to carry out polycondensation reaction to obtain a polyamic acid solution, adding a cross-linking agent into the polyamic acid solution, and uniformly mixing to obtain an intermediate solution;
(2) diluting the intermediate solution obtained in the step (1) with an organic solvent, coating a carrier to form a film, and heating to perform imidization and crosslinking reaction to obtain the crosslinked polyimide film.
The polyamic acid obtained by polycondensation of the tetracarboxylic dianhydride monomer and the diamine monomer can be obtained under conventionally known conditions, and the order of addition or method of addition of the tetracarboxylic dianhydride and the diamine monomer is not particularly limited. For example, the diamine-based monomer may be dissolved in an organic solvent, and a tetracarboxylic dianhydride-based monomer may be added thereto to perform a polymerization reaction at an appropriate reaction temperature, thereby obtaining a polyamic acid solution; wherein the amount of the diamine-based monomer added is usually 0.8mol or more and 1.2mol or less based on 1mol of the tetracarboxylic dianhydride; the reaction temperature is not particularly limited as long as it is a temperature at which the reaction can proceed, and is usually 0 ℃ or higher, preferably 5 ℃; the reaction time is usually 5 hours or more, preferably 8 hours; the reaction environment may be under air, preferably under an inert gas atmosphere; the organic solvent for the reaction is not particularly limited as long as it can dissolve the polyamic acid, and amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.
Further, when the polyamic acid solution is formed into a polyimide film, the polyamic acid solution is applied to a support and subjected to imidization to form a film, preferably, the polyamic acid solution is diluted with an organic solvent and then applied to a clean and smooth glass plate by a casting method, and the imidization reaction may be performed by a known method such as thermal imidization, chemical imidization, or a combination of thermal imidization and chemical imidization; the invention preferentially adopts thermal imidization, and in order to improve the solvent resistance of the polyimide, the invention also comprises the step of crosslinking the polyimide, preferably adding a crosslinking agent into a polyamic acid solution, then performing thermal imidization and thermal crosslinking reaction, specifically adding the crosslinking agent into the polyamic acid solution under the condition of low temperature, rapidly stirring and uniformly mixing, then coating the polyamic acid solution on a glass plate to form a film, placing the glass plate coated with the film into a forced air drying box at 70-80 ℃ for 1-4h, placing the glass plate in a tubular furnace after the temperature is reduced to room temperature, heating to 150-, and then drying and dewatering in a drying oven at the temperature of 80-100 ℃ to obtain the cross-linked polyimide film.
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of a cross-linked polyimide film comprises the following steps:
s1, under the nitrogen atmosphere, dissolving 8mmol of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl and 2mmol of 2- (3-aminophenyl) -5-aminobenzimidazole which are used as diamine monomer raw materials in 30ml of N, N-dimethylacetamide solvent, stirring until the diamine monomer raw materials are completely dissolved, adding 10mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride which is used as tetracarboxylic dianhydride monomer raw material, continuing stirring until the diamine monomer raw materials are completely dissolved to obtain a homogeneous solution with a solid content of 20 wt%, reacting for 8 hours at 5 ℃ to obtain a viscous polyamic acid solution, adding 4mmol of o-dichlorobenzyl which is used as a crosslinking agent into the polyamic acid solution, and stirring for 2 hours to obtain a polyamic acid solution containing the crosslinking agent;
s2, diluting the polyamic acid solution containing the cross-linking agent obtained in the step S1 into a solution with the concentration of 10 wt% by using N, N-dimethylacetamide, uniformly coating the diluted polyamic acid solution on a clean and smooth glass plate by using a tape casting method, drying the glass plate coated with the polyamic acid solution in a drying oven at 70 ℃ for 1h for curing, cooling to 25 ℃, taking out, placing in a tube furnace, heating to 150 ℃, drying for 1h, heating to 350 ℃, drying for 0.5h, heating to 400 ℃, drying for 0.5h, cooling to 25 ℃, taking out, placing in water for demoulding to obtain a film, and placing the obtained film in a drying oven at 100 ℃ for drying and removing water to obtain the cross-linked polyimide film with the thickness of 50 micrometers. The results of the performance test on the polyimide film are shown in table 1.
Example 2
A cross-linked polyimide film was prepared in the same manner as in example 1, except that 10mmol of 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride was added as a tetracarboxylic dianhydride monomer and 4mmol of dichlorom-benzyl was added as a cross-linking agent in the synthesis of polyamic acid in step S1, and the results of the performance test on the polyimide film thus obtained are shown in table 1.
Example 3
A crosslinked polyimide film was prepared in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 10mmol of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride was added as a raw material for the tetracarboxylic dianhydride monomer, and 4mmol of 1, 4-p-dichlorobenzyl was added as a crosslinking agent. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Example 4
A crosslinked polyimide film was prepared in the same manner as in example 1, except that 10mmol of decahydrobiphenyl-3, 3', 4, 4' -tetracarboxylic dianhydride was added as a raw material of the tetracarboxylic dianhydride monomer and 4mmol of 4, 4' -dichloromethylbiphenyl was added as a crosslinking agent in the synthesis of polyamic acid in step S1. The results of the relevant performance tests of the polyimide films thus obtained are shown in table 1.
Example 5
A crosslinked polyimide film was obtained in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 8mmol of 4, 4 '-bis (2-trifluoromethyl-4-aminophenoxy) benzene and 2mmol of 2- (4-aminophenyl) -5-aminobenzimidazole as the starting diamine monomer, 10mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride as the starting tetracarboxylic dianhydride monomer, and 4mmol of o-dibromide as the crosslinking agent were added. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Example 6
A crosslinked polyimide film was prepared in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 8mmol of 4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) benzene and 2mmol of 2- (4-aminophenyl) -5-aminobenzimidazole as the starting diamine monomer, 10mmol of 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride as the starting tetracarboxylic dianhydride monomer, and 4mmol of m-dibromobenzyl as the crosslinking agent were added. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Example 7
A crosslinked polyimide film was prepared in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 8mmol of 4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) benzene and 2mmol of 2- (4-aminophenyl) -5-aminobenzimidazole as the starting diamine monomer, 10mmol of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride as the starting tetracarboxylic dianhydride monomer, and 4mmol of 1, 4-p-dibromide benzyl as the crosslinking agent were added. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Example 8
A crosslinked polyimide film was obtained in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 8mmol of 4, 4 '-bis (2-trifluoromethyl-4-aminophenoxy) benzene and 2mmol of 2- (4-aminophenyl) -5-aminobenzimidazole as diamine monomer raw materials, 10mmol of decahydrobiphenyl-3, 3', 4, 4 '-tetracarboxylic dianhydride as tetracarboxylic dianhydride monomer raw materials, and 4mmol of 4, 4' -dibromomethylbiphenyl as a crosslinking agent were added. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Example 9
A crosslinked polyimide film was obtained in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 8mmol of 2, 2' -bis (trifluoromethyl) diaminobiphenyl and 2mmol of 2- (3-aminophenyl) -5-aminobenzimidazole as diamine monomer raw materials, 5mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride and 5mmol of 4, 4' -oxybisphthalic anhydride as tetracarboxylic dianhydride monomer raw materials, and 4mmol of 1, 4-p-dichlorobenzyl as a crosslinking agent were added. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Example 10
A crosslinked polyimide film was obtained in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 8mmol of 2, 2 '-bis (trifluoromethyl) diaminobiphenyl and 2mmol of 2- (4-aminophenyl) -5-aminobenzimidazole as diamine monomer raw materials, 5mmol of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride and 5mmol of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride monomer raw materials, and 4mmol of 1, 4-p-dichlorobenzyl as a crosslinking agent were added. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Example 11
A crosslinked polyimide film was prepared in the same manner as in example 1, except that 8mmol of 4, 4' -diaminodiphenyl ether and 2mmol of 2- (3-aminophenyl) -5-aminobenzimidazole were added as the diamine monomer raw materials in the synthesis of polyamic acid in step S1. The results of the relevant performance tests of the polyimide films thus obtained are shown in table 1.
Comparative example 1
A polyimide film was obtained in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 10mmol of 2, 2' -bis (trifluoromethyl) -4, 4' -diaminobiphenyl was added as the starting diamine monomer, and 10mmol of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride was added as the starting tetracarboxylic dianhydride monomer. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Comparative example 2
A polyimide film was obtained in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 10mmol of 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl was added as the starting diamine monomer, and 10mmol of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride was added as the starting tetracarboxylic dianhydride monomer. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
Comparative example 3
A polyimide film was obtained in the same manner as in example 1, except that in the synthesis of polyamic acid in step S1, 10mmol of 2, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl was added as the starting diamine monomer, and 5mmol of 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride and 5mmol of 4, 4' -oxydiphthalic anhydride were added as the starting tetracarboxylic dianhydride monomer. The results of the relevant property tests of the polyimide film thus obtained are shown in table 1.
The polyimide films obtained in examples and comparative examples were subjected to the performance tests shown in the following methods, and the results are shown in Table 1.
Glass transition temperature of polyimide film: DSC measurement was performed under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min using a differential scanning calorimeter, and the glass transition temperature was determined.
The mechanical properties of the polyimide film were measured by a universal material testing machine in accordance with GB/T1040.3-2006.
The solvent resistance index of the polyimide film is obtained from the thickness of the film after being immersed in a polar solvent for 10min and the thickness deviation before being immersed in the solvent, and is calculated according to formula 1:
in the above formula, t0Is the thickness of the film before it is immersed in the solvent, t1The thickness of the film was measured after immersing the film in a solvent for 10 min. The thickness of the film was measured using a micrometer screw at any of 5 points on the film.
The optical properties of the polyimide film were measured using an ultraviolet-visible absorption spectrometer.
The haze of the polyimide film was judged by dropping a drop of 100% DMAC on the film and observing the film.
●, generating fog phenomenon, ○, not generating fog phenomenon.
TABLE 1 test results of crosslinked polyimide films obtained in examples 1 to 11 and comparative examples 1 to 3
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The cross-linked polyimide film is characterized in that the synthetic raw materials comprise diamine monomers and tetracarboxylic dianhydride monomers, wherein at least one of the diamine monomers is a diamine monomer containing a benzimidazole group structure.
2. The cross-linked polyimide film according to claim 1, wherein the raw material for synthesis further comprises a cross-linking agent, and the cross-linking agent is preferably a dihalo-aromatic hydrocarbon.
3. The crosslinked polyimide film according to claim 1 or 2, wherein the diamine monomer having a benzimidazole group structure is 10 to 20 mol% based on the total amount of the diamine monomer.
4. The cross-linked polyimide film according to any one of claims 1 to 3, wherein at least one of the diamine monomers is an aromatic diamine monomer containing at least one substituent group selected from an oxy group, a sulfone group and a fluoro group; preferably, the aromatic diamine monomer having at least one substituent group of an oxy group, a sulfone group or a fluorine group is 80 to 90 mol% of the total amount of the diamine monomer.
5. The crosslinked polyimide film according to any one of claims 1 to 4,
the tetracarboxylic dianhydride monomer is selected from any one or combination of the following compounds:
the diamine monomer containing the benzimidazole group structure is selected from any one or combination of the following compounds:
the aromatic diamine monomer containing at least one substituent of an oxygen group, a sulfone group or a fluorine group is selected from any one or more of the following compounds:
the cross-linking agent is selected from any one or combination of more of the following compounds:
6. the crosslinked polyimide film according to any one of claims 1 to 5, wherein the film has a glass transition temperature of 330 ℃ or higher and a tensile strength of 120MPa or higher; preferably, the film has a 400nm wavelength light transmittance of 80% or more and a solvent resistance index of 1% or less.
7. A method for producing a crosslinked polyimide film according to any one of claims 1 to 6, comprising the steps of:
s1, dissolving diamine monomers in an organic solvent, adding tetracarboxylic dianhydride monomers to carry out polycondensation reaction to obtain a polyamic acid solution, adding a cross-linking agent into the polyamic acid solution, and uniformly mixing to obtain an intermediate solution;
and S2, diluting the intermediate solution obtained in the step S1 with an organic solvent, coating the diluted intermediate solution on a carrier to form a film, and heating the film to perform imidization and crosslinking reaction to obtain the crosslinked polyimide film.
8. The method of claim 7, wherein in step S1, the polycondensation reaction is performed under inert gas atmosphere, the polycondensation reaction temperature is preferably 5 ℃, the reaction time is preferably 8 hours, and the organic solvent is preferably at least one of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide;
preferably, in step S2, the organic solvent is at least one of an amide solvent, a ketone solvent and an ether solvent, the diluted concentration of the polyamic acid solution is preferably 10 wt% of solid content, the coating method is preferably a casting method, and the support is preferably a glass plate;
preferably, in step S2, the heating for imidization and crosslinking specifically includes: drying the carrier coated with the film for 1-2h at 70-80 ℃, then heating to 150-.
9. An optical film comprising the crosslinked polyimide film according to any one of claims 1 to 6.
10. An electro-optic display device comprising the optical film of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911191881.9A CN111073283B (en) | 2019-11-28 | 2019-11-28 | Cross-linked polyimide film, optical film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911191881.9A CN111073283B (en) | 2019-11-28 | 2019-11-28 | Cross-linked polyimide film, optical film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111073283A true CN111073283A (en) | 2020-04-28 |
| CN111073283B CN111073283B (en) | 2022-05-31 |
Family
ID=70312003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911191881.9A Active CN111073283B (en) | 2019-11-28 | 2019-11-28 | Cross-linked polyimide film, optical film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111073283B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354815A (en) * | 2021-05-18 | 2021-09-07 | 深圳市华星光电半导体显示技术有限公司 | Flexible substrate, manufacturing method thereof and display panel |
| CN114702671A (en) * | 2022-03-14 | 2022-07-05 | 江苏环峰电工材料有限公司 | Carboxylated crosslinked polyimide prepolymer and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080305379A1 (en) * | 2006-02-17 | 2008-12-11 | Cheil Industries Inc. | Polymer Electrolyte Membrane for Fuel Cell and Membrane-Electrode Assembly and Fuel Cell Including the Same |
| CN101375444A (en) * | 2006-02-17 | 2009-02-25 | 第一毛织株式会社 | High molocular electrolyte membrane for fuel cell, and membrane-electrode assembly thereby, fuel cell |
| CN102911595A (en) * | 2012-11-02 | 2013-02-06 | 东华大学 | Benzimidazole-type humidity-sensitive high-molecular coating material and preparation method and application thereof |
| CN103571500A (en) * | 2012-07-18 | 2014-02-12 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| TW201425473A (en) * | 2012-10-16 | 2014-07-01 | Nissan Chemical Ind Ltd | Composition for heat-resistant substrate |
| CN104629081A (en) * | 2015-01-28 | 2015-05-20 | 同济大学 | Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base |
| CN107722268A (en) * | 2016-08-10 | 2018-02-23 | 新日铁住金化学株式会社 | The manufacture method of polyimide precursor, polyimides and transparent polyimide film |
| CN109705799A (en) * | 2018-12-21 | 2019-05-03 | 东华大学 | A kind of YASI epoxy organic imides silica gel and preparation method thereof |
| CN109722212A (en) * | 2018-12-21 | 2019-05-07 | 福建省海钛智能科技有限公司 | A kind of acid imide epoxy organic silica gel and preparation method thereof |
| CN110092932A (en) * | 2019-05-13 | 2019-08-06 | 东华大学 | A kind of preparation method of self-cross linking type Kapton |
| CN110105570A (en) * | 2019-05-22 | 2019-08-09 | 四川大学 | A kind of high-fire resistance, low thermal expansion coefficient polyimide material and preparation method thereof |
-
2019
- 2019-11-28 CN CN201911191881.9A patent/CN111073283B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080305379A1 (en) * | 2006-02-17 | 2008-12-11 | Cheil Industries Inc. | Polymer Electrolyte Membrane for Fuel Cell and Membrane-Electrode Assembly and Fuel Cell Including the Same |
| CN101375444A (en) * | 2006-02-17 | 2009-02-25 | 第一毛织株式会社 | High molocular electrolyte membrane for fuel cell, and membrane-electrode assembly thereby, fuel cell |
| CN103571500A (en) * | 2012-07-18 | 2014-02-12 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| TW201425473A (en) * | 2012-10-16 | 2014-07-01 | Nissan Chemical Ind Ltd | Composition for heat-resistant substrate |
| CN102911595A (en) * | 2012-11-02 | 2013-02-06 | 东华大学 | Benzimidazole-type humidity-sensitive high-molecular coating material and preparation method and application thereof |
| CN104629081A (en) * | 2015-01-28 | 2015-05-20 | 同济大学 | Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base |
| CN107722268A (en) * | 2016-08-10 | 2018-02-23 | 新日铁住金化学株式会社 | The manufacture method of polyimide precursor, polyimides and transparent polyimide film |
| CN109705799A (en) * | 2018-12-21 | 2019-05-03 | 东华大学 | A kind of YASI epoxy organic imides silica gel and preparation method thereof |
| CN109722212A (en) * | 2018-12-21 | 2019-05-07 | 福建省海钛智能科技有限公司 | A kind of acid imide epoxy organic silica gel and preparation method thereof |
| CN110092932A (en) * | 2019-05-13 | 2019-08-06 | 东华大学 | A kind of preparation method of self-cross linking type Kapton |
| CN110105570A (en) * | 2019-05-22 | 2019-08-09 | 四川大学 | A kind of high-fire resistance, low thermal expansion coefficient polyimide material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354815A (en) * | 2021-05-18 | 2021-09-07 | 深圳市华星光电半导体显示技术有限公司 | Flexible substrate, manufacturing method thereof and display panel |
| CN114702671A (en) * | 2022-03-14 | 2022-07-05 | 江苏环峰电工材料有限公司 | Carboxylated crosslinked polyimide prepolymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111073283B (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| USRE48141E1 (en) | Transparent polyamide-imide resin and film using same | |
| KR102417428B1 (en) | Polyamic acid composition comprising alicyclic monomer and trasparent polyimide film using the same | |
| KR101928598B1 (en) | Polyimide film and process for preparing same | |
| EP3266808A1 (en) | Composition for polyimide film for flexible substrate of optoelectronic device | |
| CN105637016A (en) | Polyimide-based solution and polyimide-based film prepared by using same | |
| CN113227206B (en) | Imide-amic acid copolymer, process for producing the same, varnish, and polyimide film | |
| CN110317339B (en) | Polyimide precursor, polyimide film, and display device including the same | |
| US20110178266A1 (en) | Polyimide film | |
| CN110099946B (en) | Transparent polyimide film | |
| JP6257302B2 (en) | POLYIMIDE PRECURSOR, RESIN COMPOSITION CONTAINING THE SAME, POLYIMIDE FILM AND ITS MANUFACTURING METHOD, AND LAMINATE AND ITS MANUFACTURING METHOD | |
| CN110606949B (en) | Colorless transparent polyimide film containing fluorine and Cardo structure and preparation method thereof | |
| EP3257888B1 (en) | Polyamic acid, polyimide resin and polyimide film | |
| KR101760555B1 (en) | Polyimide-based solution and polyimide-based film prepared by using same | |
| CN111073282B (en) | Solvent-resistant colorless transparent cross-linked polyimide film and preparation method thereof | |
| CN111073283B (en) | Cross-linked polyimide film, optical film and preparation method thereof | |
| CN114621436B (en) | High heat-resistant transparent polyimide film, preparation method and application | |
| KR101797806B1 (en) | Polyimide-based solution and polyimide-based film prepared by using same | |
| JP7349253B2 (en) | A polyamic acid, a polyamic acid solution, a polyimide, a polyimide film, a laminate, a flexible device, and a method for producing a polyimide film. | |
| CN111040156B (en) | Solvent-resistant and high-dimensional-stability cross-linked polyimide film | |
| KR102040355B1 (en) | High strength transparent polyamide-imide and process for preparing same | |
| CN112500570B (en) | Flexible display device, polyamic acid varnish for display, and polyimide film | |
| CN110372899B (en) | High-hydrophobicity colorless transparent heat-resistant polyimide film and preparation method thereof | |
| US11697710B2 (en) | Colorless polyimide film containing fluorine and cardo structure and preparation method thereof | |
| KR102288303B1 (en) | A laminate structure for manufacturing flexible display and a process for manufacturing a flexible display using same | |
| KR102003772B1 (en) | Composition for preparinig polyimide-based film and transparent polyimide-based film prepared by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220803 Address after: Light Film Town, Lanxi Economic Development Zone, Lanjiang Street, Lanxi City, Jinhua City, Zhejiang Province, 321000 Patentee after: Zhejiang Zhongke Jiuyuan New Material Co.,Ltd. Address before: Building a, Jiatai garden, No. 52, Binhe East Road, Taiyuan City, Shanxi Province Patentee before: Li Nanwen Patentee before: Zhejiang Zhongke Jiuyuan New Material Co.,Ltd. |
|
| TR01 | Transfer of patent right |