CN112625291B - High-hardness and high-transparency polyimide flexible cover plate and preparation method thereof - Google Patents
High-hardness and high-transparency polyimide flexible cover plate and preparation method thereof Download PDFInfo
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- CN112625291B CN112625291B CN202011372277.9A CN202011372277A CN112625291B CN 112625291 B CN112625291 B CN 112625291B CN 202011372277 A CN202011372277 A CN 202011372277A CN 112625291 B CN112625291 B CN 112625291B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 101
- 239000004642 Polyimide Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 48
- 238000002834 transmittance Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 38
- 239000012948 isocyanate Substances 0.000 claims description 31
- 150000002513 isocyanates Chemical class 0.000 claims description 31
- 238000002791 soaking Methods 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical group CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 3
- -1 alcohol compound Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 70
- 238000003756 stirring Methods 0.000 description 33
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000001035 drying Methods 0.000 description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 229920005575 poly(amic acid) Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000012024 dehydrating agents Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- 229920001621 AMOLED Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- 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
Abstract
The invention provides a polyimide flexible cover plate with high hardness and high transparency and a preparation method thereof, wherein the polyimide flexible cover plate comprises a polyimide film and an inorganic oxide film attached to the surface of the polyimide film; the surface hardness of the polyimide flexible cover plate is more than 5H, and the light transmittance of 550nm is more than 80%. According to the high-hardness and high-transparency polyimide flexible cover plate and the preparation method thereof, the inorganic oxide film is attached to the surface of the polyimide film, so that the hardness of the cover plate is effectively improved on the basis of ensuring the light transmission.
Description
Technical Field
The invention relates to the technical field of polyimide, in particular to a polyimide flexible cover plate with high hardness and high transparency and a preparation method thereof.
Background
The flexible foldable AMOLED display screen is used as a next generation display terminal device, related products are successively released in recent years along with important manufacturers of the display screen, and rapid development of related technologies is initiated.
The flexible display has the characteristics of flexibility, high definition and high color gamut saturation, however, in practical application, the substrate of the flexible screen has the defects of low hardness and poor external force damage resistance, so that the service life and the comfort degree of the flexible screen are determined by the stable and reliable cover plate material. How to improve the comprehensive properties such as hardness of the flexible cover plate material is a difficult problem in the field.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the high-hardness and high-transparency polyimide flexible cover plate and the preparation method thereof.
The invention provides a polyimide flexible cover plate with high hardness and high transparency, which comprises a polyimide film and an inorganic oxide film attached to the surface of the polyimide film;
the surface hardness of the polyimide flexible cover plate is more than 5H, and the light transmittance of 550nm is more than 80%.
Preferably, the inorganic oxide film is SiO2ZnO or TiO2At least one of the inorganic oxide films of (1).
The invention also provides a preparation method of the high-hardness and high-transparency polyimide flexible cover plate, which comprises the following steps:
s1, carrying out coupling reaction on the inorganic oxide and a coupling agent containing isocyanate to obtain an isocyanate functionalized inorganic oxide;
s2, adding the polyimide film with the molecular chain containing hydroxyl into a solution containing isocyanate functionalized inorganic oxide for soaking, taking out, heating and curing to obtain the polyimide film with the surface attached with the inorganic oxide film, namely the flexible cover plate.
Preferably, the inorganic oxide is nano-SiO2Nano ZnO or nano TiO2At least one of;
preferably, the particle size of the inorganic oxide is 10 to 300 nm.
Preferably, the isocyanate-containing coupling agent is isocyanatopropyltriethoxysilane;
preferably, the mass ratio of the inorganic oxide to the isocyanatopropyltriethoxysilane is 1: 0.05-0.3.
Preferably, the polyimide film containing hydroxyl in the molecular chain is obtained by polymerizing tetracarboxylic dianhydride and diamine containing phenolic hydroxyl;
preferably, the tetracarboxylic dianhydride is 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride and the phenolic hydroxyl group-containing diamine is 3, 3' -dihydroxybenzidine.
Preferably, the soaking temperature is 50-70 ℃, and the soaking time is 1-3 h.
Preferably, the temperature for heating and curing is 100-300 ℃, and the time is 0.5-2 h.
Preferably, the solution containing the isocyanate functional inorganic oxide has an isocyanate functional inorganic oxide content of 10 to 50 wt%.
Preferably, in the solution containing the isocyanate functionalized inorganic oxide, the solvent is an alcohol compound.
According to the high-hardness and high-transparency polyimide flexible cover plate provided by the invention, the polyimide film with the hydroxyl group on the molecular chain is soaked in the solution of the isocyanate functional inorganic oxide, and the isocyanate group modified on the surface of the isocyanate functional inorganic oxide can form bonding with the polyimide with the hydroxyl group on the molecular chain, so that the polyimide film and the inorganic oxide form effective combination after soaking, and finally a layer of uniform and firm inorganic oxide film is formed on the surface of the polyimide film.
Therefore, the defect that peeling is easy to occur due to the interfacial tension between the polyimide film and the inorganic oxide film is effectively overcome, the surface hardness of the obtained flexible cover plate can reach more than 5H on the basis of ensuring the light transmission, and the technical effect of external force damage resistance is improved.
Detailed Description
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 high-hardness and high-transparency polyimide flexible cover plate is prepared by the following steps:
s1, dissolving 0.2g of isocyanatopropyl triethoxysilane in 30mL of ethanol, heating to 60 ℃, stirring for 10min, and adding 2g of nano SiO2(the average particle size is 40nm), heating to 120 ℃, and stirring for 3 hours to obtain an ethanol solution containing the isocyanate functionalized inorganic oxide;
s2, under the nitrogen atmosphere, adding 1.08g (5mmol) of 3, 3 '-dihydroxybenzidine and 1.00g (5mmol) of 4, 4' -diaminodiphenyl ether into 30mL of anhydrous N, N-dimethylacetamide, uniformly stirring, adding 2.24g (10mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, and stirring at room temperature for reaction for 3 hours to obtain a polyamic acid solution; adding 0.76mL of pyridine into the polyamic acid solution as an imidizing agent, adding 2.05mL of acetic anhydride as a dehydrating agent after complete dispersion, heating to 80 ℃, stirring for reaction for 6 hours, adding the obtained reaction solution into ethanol for precipitation, filtering and drying to obtain polyimide; adding the polyimide into N, N-dimethylacetamide to prepare a solution with the solid content of 20 wt%, coating the solution on a glass substrate, and heating the solution at 100 ℃ to volatilize an organic solvent to obtain a self-supporting dry film, namely a polyimide film with a hydroxyl group in a molecular chain, wherein the film thickness is 100 micrometers;
s2, adding the polyimide film with the molecular chain containing hydroxyl obtained in the step S2 into the ethanol solution containing the isocyanate functionalized inorganic oxide obtained in the step S1, soaking, performing ultrasonic oscillation (with ultrasonic power of 300W) for 2 hours at 60 ℃ to complete soaking, taking out the polyimide film, placing the polyimide film in a drying oven to dry and remove ethanol, finally treating at 150 ℃ for 1 hour, and heating to 260 ℃ for 1 hour to obtain the high-hardness and high-transparency polyimide flexible cover plate.
Example 2
A high-hardness and high-transparency polyimide flexible cover plate is prepared by the following steps:
s1, dissolving 0.2g of isocyanatopropyl triethoxysilane in 30mL of ethanol, heating to 60 ℃, stirring for 10min, and adding 2g of nano SiO2(the average particle size is 40nm), heating to 120 ℃, and stirring for 3 hours to obtain an ethanol solution containing the isocyanate functionalized inorganic oxide;
s2, under the nitrogen atmosphere, adding 1.08g (5mmol) of 3, 3 '-dihydroxybenzidine and 1.84g (5mmol) of 4, 4' -bis (4-aminophenoxy) biphenyl into 30mL of anhydrous N, N-dimethylacetamide, uniformly stirring, adding 2.24g (10mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, and stirring at room temperature for reaction for 3 hours to obtain a polyamic acid solution; adding 0.95mL of pyridine into the polyamic acid solution as an imidizing agent, adding 2.2mL of acetic anhydride as a dehydrating agent after complete dispersion, heating to 80 ℃, stirring for reaction for 6 hours, adding the obtained reaction solution into ethanol for precipitation, filtering and drying to obtain polyimide; adding the polyimide into N, N-dimethylacetamide to prepare a solution with the solid content of 20 wt%, coating the solution on a glass substrate, and heating the solution at 100 ℃ to volatilize an organic solvent to obtain a self-supporting dry film, namely a polyimide film with a hydroxyl group in a molecular chain, wherein the film thickness is 100 micrometers;
s2, adding the polyimide film with the molecular chain containing hydroxyl obtained in the step S2 into the ethanol solution containing the isocyanate functionalized inorganic oxide obtained in the step S1, soaking, performing ultrasonic oscillation (with ultrasonic power of 300W) for 2 hours at 60 ℃ to complete soaking, taking out the polyimide film, placing the polyimide film in a drying oven to dry and remove ethanol, finally treating at 150 ℃ for 1 hour, and heating to 260 ℃ for 1 hour to obtain the high-hardness and high-transparency polyimide flexible cover plate.
Example 3
A high-hardness and high-transparency polyimide flexible cover plate is prepared by the following steps:
s1, dissolving 0.2g of isocyanatopropyltriethoxysilane in 30mL of ethanol, heating to 60 ℃, stirring for 10min, adding 2g of nano ZnO (average particle size of 40nm), heating to 100 ℃, and stirring for 3h to obtain an ethanol solution containing isocyanate functionalized inorganic oxide;
s2, under the nitrogen atmosphere, adding 1.08g (5mmol) of 3, 3 '-dihydroxybenzidine and 1.00g (5mmol) of 4, 4' -diaminodiphenyl ether into 30mL of anhydrous N, N-dimethylacetamide, uniformly stirring, adding 2.24g (10mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, and stirring at room temperature for reaction for 3 hours to obtain a polyamic acid solution; adding 0.76mL of pyridine into the polyamic acid solution to serve as an imidizing agent, adding 2.05mL of acetic anhydride to serve as a dehydrating agent after complete dispersion, heating to 80 ℃, stirring for reaction for 6 hours, adding the obtained reaction solution into ethanol for precipitation and precipitation, filtering and drying to obtain polyimide; adding the polyimide into N, N-dimethylacetamide to prepare a solution with the solid content of 20 wt%, coating the solution on a glass substrate, and heating at 100 ℃ to volatilize an organic solvent to obtain a self-supporting dry film, namely a polyimide film with a hydroxyl group in a molecular chain, wherein the film thickness is 100 micrometers;
s2, adding the polyimide film with the molecular chain containing hydroxyl obtained in the step S2 into the ethanol solution containing the isocyanate functionalized inorganic oxide obtained in the step S1, soaking, performing ultrasonic oscillation (with ultrasonic power of 300W) for 2 hours at 60 ℃ to complete soaking, taking out the polyimide film, placing the polyimide film in a drying oven to dry and remove ethanol, finally treating at 150 ℃ for 1 hour, and heating to 260 ℃ for 1 hour to obtain the high-hardness and high-transparency polyimide flexible cover plate.
Example 4
A high-hardness and high-transparency polyimide flexible cover plate is prepared by the following steps:
s1, dissolving 0.2g of isocyanatopropyl triethoxysilane in 30mL of ethanol, heating to 60 ℃, stirring for 10min, and then adding 2g of nano TiO2(the average particle size is 40nm), heating to 120 ℃, and stirring for 3 hours to obtain an ethanol solution containing the isocyanate functionalized inorganic oxide;
s2, under the nitrogen atmosphere, adding 1.08g (5mmol) of 3, 3 '-dihydroxybenzidine and 1.00g (5mmol) of 4, 4' -diaminodiphenyl ether into 30mL of anhydrous N, N-dimethylacetamide, uniformly stirring, adding 2.24g (10mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, and stirring at room temperature for reaction for 3 hours to obtain a polyamic acid solution; adding 0.76mL of pyridine into the polyamic acid solution as an imidizing agent, adding 2.05mL of acetic anhydride as a dehydrating agent after complete dispersion, heating to 80 ℃, stirring for reaction for 6 hours, adding the obtained reaction solution into ethanol for precipitation, filtering and drying to obtain polyimide; adding the polyimide into N, N-dimethylacetamide to prepare a solution with the solid content of 20 wt%, coating the solution on a glass substrate, heating at 100 ℃ to volatilize an organic solvent, and obtaining a self-supporting dry film, namely a polyimide film with a molecular chain containing hydroxyl, wherein the film thickness is 100 micrometers;
s2, adding the polyimide film with the molecular chain containing hydroxyl groups obtained in the step S2 into the ethanol solution containing the isocyanate functionalized inorganic oxide obtained in the step S1, soaking, performing ultrasonic oscillation (with ultrasonic power of 300W) for 2 hours at 60 ℃ to complete soaking, taking out the polyimide film, drying in a drying oven to remove ethanol, finally treating at 150 ℃ for 1 hour, and heating to 260 ℃ for 1 hour to obtain the high-hardness and high-transparency polyimide flexible cover plate.
Comparative example 1
A polyimide flexible cover plate is prepared by the following steps:
s1, mixing 2g of nanoSiO2(average particle diameter of 40nm) in 30mL of ethanol to obtain a dispersion containing nano SiO2The ethanol solution of (a);
s2, under the nitrogen atmosphere, adding 1.08g (5mmol) of 3, 3 '-dihydroxybenzidine and 1.00g (5mmol) of 4, 4' -diaminodiphenyl ether into 30mL of anhydrous N, N-dimethylacetamide, uniformly stirring, adding 2.24g (10mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, and stirring at room temperature for reaction for 3 hours to obtain a polyamic acid solution; adding 0.76mL of pyridine into the polyamic acid solution as an imidizing agent, adding 2.05mL of acetic anhydride as a dehydrating agent after complete dispersion, heating to 80 ℃, stirring for reaction for 6 hours, adding the obtained reaction solution into ethanol for precipitation, filtering and drying to obtain polyimide; adding the polyimide into N, N-dimethylacetamide to prepare a solution with the solid content of 20 wt%, coating the solution on a glass substrate, and heating at 100 ℃ to volatilize an organic solvent to obtain a self-supporting dry film, namely a polyimide film with a hydroxyl group in a molecular chain, wherein the film thickness is 100 micrometers;
s2, adding the polyimide film containing hydroxyl on molecular chain obtained in the step S2 to the polyimide film containing nano SiO obtained in the step S12Soaking in the ethanol solution, performing ultrasonic oscillation (ultrasonic power is 300W) for 2 hours at 60 ℃ to complete soaking, taking out the polyimide film, drying in a drying oven to remove ethanol, finally treating at 150 ℃ for 1 hour, and heating to 260 ℃ for 1 hour to obtain the polyimide flexible cover plate.
Comparative example 2
A polyimide flexible cover plate is prepared by the following steps:
s1, dissolving 0.2g of isocyanatopropyl triethoxysilane in 30mL of ethanol, heating to 60 ℃, stirring for 10min, and then adding 2g of nano SiO2(the average particle size is 40nm), heating to 120 ℃, and stirring for 3 hours to obtain an ethanol solution containing the isocyanate functionalized inorganic oxide;
s2, under the nitrogen atmosphere, adding 2.16g (10mmol) of 3, 3' -dihydroxybenzidine into 30mL of anhydrous N, N-dimethylacetamide, uniformly stirring, adding 2.24g (10mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, and stirring at room temperature for reaction for 3 hours to obtain a polyamic acid solution; adding 0.76mL of pyridine into the polyamic acid solution as an imidizing agent, adding 2.05mL of acetic anhydride as a dehydrating agent after complete dispersion, heating to 80 ℃, stirring for reaction for 6 hours, adding the obtained reaction solution into ethanol for precipitation, filtering and drying to obtain polyimide; adding the polyimide into N, N-dimethylacetamide to prepare a solution with the solid content of 20 wt%, coating the solution on a glass substrate, and heating the solution at 100 ℃ to volatilize an organic solvent to obtain a self-supporting dry film, namely a polyimide film with a hydroxyl group in a molecular chain, wherein the film thickness is 100 micrometers;
s2, adding the polyimide film with the molecular chain containing hydroxyl group obtained in the step S2 into the ethanol solution containing the isocyanate functionalized inorganic oxide obtained in the step S1, soaking, performing ultrasonic oscillation (with ultrasonic power of 300W) for 2 hours at 60 ℃ to complete soaking, taking out the polyimide film, drying in a drying box to remove ethanol, finally treating at 150 ℃ for 1 hour, and heating to 260 ℃ for 1 hour to obtain the polyimide flexible cover plate.
Comparative example 3
A polyimide flexible cover plate is prepared by the following steps:
s1, dissolving 0.2g of isocyanatopropyl triethoxysilane in 30mL of ethanol, heating to 60 ℃, stirring for 10min, and adding 2g of nano SiO2(the average particle size is 40nm), heating to 120 ℃, and stirring for 3 hours to obtain an ethanol solution containing the isocyanate functionalized inorganic oxide;
s2, under the nitrogen atmosphere, adding 2.00g (10mmol) of 4, 4' -diaminodiphenyl ether into 30mL of anhydrous N, N-dimethylacetamide, uniformly stirring, adding 2.24g (10mmol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, and reacting for 3 hours at room temperature by stirring to obtain a polyamic acid solution; adding 0.76mL of pyridine into the polyamic acid solution as an imidizing agent, adding 2.05mL of acetic anhydride as a dehydrating agent after complete dispersion, heating to 80 ℃, stirring for reaction for 6 hours, adding the obtained reaction solution into ethanol for precipitation, filtering and drying to obtain polyimide; adding the polyimide into N, N-dimethylacetamide to prepare a solution with the solid content of 20 wt%, coating the solution on a glass substrate, and heating the solution at 100 ℃ to volatilize an organic solvent to obtain a dry film with self-supporting property, namely a polyimide film, wherein the film thickness is 100 micrometers;
s2, adding the polyimide film obtained in the step S2 into the ethanol solution containing the isocyanate functionalized inorganic oxide obtained in the step S1, soaking, performing ultrasonic oscillation (ultrasonic power 300W) for 2 hours at 60 ℃ to complete soaking, taking out the polyimide film, drying in a drying oven to remove ethanol, finally treating at 150 ℃ for 1 hour, and heating to 260 ℃ for 1 hour to obtain the polyimide flexible cover plate.
The polyimide flexible cover sheets obtained in examples and comparative examples were subjected to performance tests as shown in the following method, and the results are referred to table 1.
Surface hardness, measured using a pencil hardness meter according to ASTM D3363 film hardness test (pencil method);
the light transmittance at the wavelength of 550nm is tested by an ultraviolet-visible spectrometer.
Table 1 test results of polyimide flexible cover sheets obtained in correspondence with examples 1 to 4 and comparative examples 1 to 2
| Surface hardness (H) | Light transmittance T550 (%) | |
| Example 1 | 6 | 87.1 |
| Example 2 | 6 | 88.3 |
| Example 3 | 5 | 88.9 |
| Example 4 | 5 | 86.2 |
| Comparative example 1 | 2 | 80.5 |
| Comparative example 2 | 3 | 81.6 |
| Comparative example 3 | 2 | 72.1 |
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 (9)
1. A high-hardness and high-transparency polyimide flexible cover plate is characterized by comprising a polyimide film and an inorganic oxide film attached to the surface of the polyimide film;
the surface hardness of the polyimide flexible cover plate is more than 5H, and the light transmittance at 550nm is more than 80%;
the polyimide flexible cover plate is prepared by the following method:
carrying out coupling reaction on an inorganic oxide and a coupling agent containing isocyanate to obtain an isocyanate functionalized inorganic oxide;
adding a polyimide film with a molecular chain containing hydroxyl into a solution containing isocyanate functionalized inorganic oxide for soaking, taking out the polyimide film, and heating and curing to obtain the polyimide film with the surface attached with the inorganic oxide film, namely the flexible cover plate;
the polyimide film with the molecular chain containing hydroxyl is obtained by carrying out polymerization reaction on 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, 3 '-dihydroxybenzidine and 4, 4' -diaminodiphenyl ether;
the inorganic oxide is nano SiO2Nano ZnO or nano TiO2At least one of (1).
2. A preparation method of a polyimide flexible cover plate with high hardness and high transparency is characterized by comprising the following steps:
s1, carrying out coupling reaction on the inorganic oxide and a coupling agent containing isocyanate to obtain an isocyanate functionalized inorganic oxide;
s2, adding a polyimide film with a molecular chain containing hydroxyl into a solution containing isocyanate functionalized inorganic oxide for soaking, taking out, heating and curing to obtain a polyimide film with an inorganic oxide film attached to the surface, namely the flexible cover plate;
the polyimide film with the molecular chain containing hydroxyl is obtained by carrying out polymerization reaction on 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, 3 '-dihydroxybenzidine and 4, 4' -diaminodiphenyl ether;
the inorganic oxide is nano SiO2Nano ZnO or nano TiO2At least one of (1).
3. The method for preparing a high-hardness, high-transparency polyimide flexible cover sheet according to claim 2, wherein the particle size of the inorganic oxide is 10 to 300 nm.
4. The method for preparing a high-hardness and high-transparency polyimide flexible cover plate according to claim 2, wherein the isocyanate-containing coupling agent is isocyanatopropyltriethoxysilane.
5. The method for preparing the high-hardness and high-transparency polyimide flexible cover plate according to claim 4, wherein the mass ratio of the inorganic oxide to the isocyanatopropyltriethoxysilane is 1: 0.05-0.3.
6. The method for preparing the polyimide flexible cover plate with high hardness and high transparency according to claim 2, wherein the soaking temperature is 50-70 ℃ and the soaking time is 1-3 h.
7. The method for preparing a polyimide flexible cover plate with high hardness and high transparency according to claim 2, wherein the temperature for heating and curing is 100-300 ℃ and the time is 0.5-2 h.
8. The method for preparing a high-hardness, high-transparency polyimide flexible cover sheet according to any one of claims 2 to 7, wherein the solution containing the isocyanate functional inorganic oxide has an isocyanate functional inorganic oxide content of 1 to 15 wt%.
9. The method for preparing a high-hardness and high-transparency polyimide flexible cover plate according to any one of claims 2 to 7, wherein the solvent in the solution containing the isocyanate functionalized inorganic oxide is an alcohol compound.
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| KR101688173B1 (en) * | 2011-12-26 | 2016-12-21 | 코오롱인더스트리 주식회사 | Plastic substrate |
| KR101537845B1 (en) * | 2012-12-12 | 2015-07-17 | 코오롱인더스트리 주식회사 | Transparent Polyimide Substrate and method for producing the same |
| KR102147330B1 (en) * | 2019-09-30 | 2020-08-24 | 에스케이이노베이션 주식회사 | Antistatic polyimide film and flexible display panel using same |
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Denomination of invention: A high hardness, high transparency polyimide flexible cover plate and its preparation method Effective date of registration: 20231114 Granted publication date: 20220712 Pledgee: China Merchants Bank Co.,Ltd. Jinhua Branch Pledgor: Zhejiang Zhongke Jiuyuan New Material Co.,Ltd. Registration number: Y2023980065179 |