WO2023221605A1 - 一种聚酰胺-酰亚胺膜及其制备方法和柔性显示器 - Google Patents

一种聚酰胺-酰亚胺膜及其制备方法和柔性显示器 Download PDF

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WO2023221605A1
WO2023221605A1 PCT/CN2023/080130 CN2023080130W WO2023221605A1 WO 2023221605 A1 WO2023221605 A1 WO 2023221605A1 CN 2023080130 W CN2023080130 W CN 2023080130W WO 2023221605 A1 WO2023221605 A1 WO 2023221605A1
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polyamide
aromatic
imide
imide film
dicarbonyl compound
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PCT/CN2023/080130
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English (en)
French (fr)
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张群
祝春才
胡涛
刘国隆
徐哲
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浙江中科玖源新材料有限公司
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Priority to US18/036,653 priority Critical patent/US20240101822A1/en
Publication of WO2023221605A1 publication Critical patent/WO2023221605A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/14—Polyamide-imides
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • 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

Definitions

  • the present application relates to the technical field of optical materials, and in particular to a polyamide-imide film, its preparation method and a flexible display.
  • Thin displays such as liquid crystal displays or organic light-emitting diode displays are realized in the form of touch screen panels and are widely used not only in smartphones and tablets but also in various smart devices characterized by portability such as various wearable devices.
  • the basic structure of a flexible display can be divided into three main layers: substrate, intermediate display medium and packaging.
  • the flexible substrate as the support and protection component of the entire flexible display, not only has an important impact on the display quality of the display, but also is directly related to the service life of the device.
  • polyimide film has good thermal stability and low coefficient of linear thermal expansion (CTE), so it is considered the preferred substrate material for flexible displays.
  • CTE coefficient of linear thermal expansion
  • the conventional polyimide film is colored yellow or brown due to its high aromatic ring density, and therefore has low transmittance in the visible light region and exhibits a yellow color.
  • this application proposes a polyamide-imide film and a preparation method thereof.
  • the polyamide-imide film can obtain extremely low yellowness index and birefringence, and is suitable for For substrate production of flexible displays.
  • This application proposes a polyamide-imide film, which is obtained by copolymerizing aromatic dianhydrides, aromatic dicarbonyl compounds and aromatic diamines;
  • aromatic dicarbonyl compounds include fluorinated aromatic dicarbonyl compounds and non-fluorinated aromatic dicarbonyl compounds.
  • the aromatic dicarbonyl compounds are specifically selected to include fluorinated aromatic dicarbonyl compounds and non-fluorinated aromatic dicarbonyl compounds, so that the molecular chain of the resulting polyamide-imide film also has fluorine-substituted amides.
  • Repeating units and non-fluorine-substituted amide repeating units the existence of these two repeating units helps to destroy the regularity of molecules, improve the degree of freedom of molecular chains and enhance flexibility, achieving high light transmittance and low yellowness index At the same time, the synergistic effect of reducing birefringence can also be achieved.
  • the fluorinated aromatic dicarbonyl compound is tetrafluoroterephthaloyl chloride.
  • the non-fluorinated aromatic dicarbonyl compound is terephthaloyl chloride, isophthalyl At least one of chlorine or 4,4'-biphenyldicarboxylic acid chloride.
  • the molar ratio of the fluorinated aromatic dicarbonyl compound and the non-fluorinated aromatic dicarbonyl compound is 1-1.5:1.
  • the molar ratio of the fluorinated aromatic dicarbonyl compound and the non-fluorinated aromatic dicarbonyl compound is limited to appropriately control the content of imide repeating units and amide repeating units in the molecular chain, thereby further improving the polyamide- Yellowness index and birefringence of imide films.
  • the aromatic dianhydride is pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-hexafluoroisopropylphthalic anhydride, 3 , at least one of 3',4,4'-benzophenone tetracarboxylic dianhydride or 4,4'-oxydiphthalic anhydride.
  • the aromatic diamine is p-phenylenediamine, m-phenylenediamine, 4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)diaminobiphenyl or 4,4' -At least one of diaminodiphenyl ethers.
  • the molar ratio of the aromatic dianhydride and the aromatic dicarbonyl compound is 1:1-4.
  • the molar ratio of the aromatic dianhydride to the aromatic dicarbonyl compound is limited to further improve the properties of the polyamide-imide film while ensuring that the inherent mechanical properties of the polyamide-imide film are not deteriorated. Yellowness index and birefringence.
  • This application proposes a preparation method of polyamide-imide membrane, including:
  • the aromatic dianhydride and the aromatic diamine are polymerized, they are sequentially polymerized with the non-fluorinated aromatic dicarbonyl compound and the fluorinated aromatic dicarbonyl compound.
  • the resulting polyamic acid is imidized and then cast into film to obtain the polyamide-imide film.
  • the imidization is carried out under the conditions of a catalyst and a dehydrating agent;
  • the catalyst is at least one of pyridine, picoline, quinoline or isoquinoline, and the dehydrating agent is acetic anhydride or propionic anhydride. Or at least one of trifluoroacetic anhydride.
  • This application also proposes a flexible display, which includes the above-mentioned polyamide-imide film.
  • This application proposes a polyamide-imide film and its preparation method, which uses fluorinated aromatic dicarbonyl compounds and non-fluorinated aromatic dicarbonyl compounds as starting materials of aromatic dicarbonyl compounds to obtain polyamide -Imide film, which can achieve extremely low birefringence properties while maintaining colorless transparency, so it can be effectively used in flexible displays.
  • This application proposes a polyamide-imide membrane, which is obtained by copolymerizing aromatic dianhydrides, aromatic dicarbonyl compounds and aromatic diamines.
  • aromatic dicarbonyl compound is a mixture of a fluorinated aromatic dicarbonyl compound and a non-fluorinated aromatic dicarbonyl compound
  • the resulting polyamide-imide film exhibits effective improvements in yellowness index and birefringence.
  • Fluorinated aromatic dicarbonyl compounds have better solubility than non-fluorinated aromatic dicarbonyl compounds. Therefore, the combination of the two as aromatic dicarbonyl compounds can ensure the high transparency of the resulting polyamide-imide film. Effectively improve yellowness index and birefringence.
  • aromatic dianhydride is a fluorinated aromatic dianhydride and/or the aromatic diamine is a fluorinated aromatic diamine
  • the resulting polyamide-imide film does not show a response to yellowness index and diamine. Improvement of refractive index.
  • Aromatic dianhydrides and/or aromatic diamines have relatively good solubility regardless of whether they are fluorinated or not. Therefore, the aromatic dianhydrides and/or aromatic diamines have relatively good solubility only when the aromatic dianhydrides are fluorinated aromatic dianhydrides and/or aromatic diamines. Fluorination of aromatic diamines does not show improvements in yellowness index and birefringence.
  • the fluorinated aromatic dicarbonyl compound is preferably tetrafluoroterephthaloyl chloride or monofluoroterephthalyl chloride. At least one of acid chloride, 2-fluoro-isophthaloyl chloride or 4-fluoro-isophthaloyl chloride; the non- The fluorinated aromatic dicarbonyl compound is preferably at least one of terephthaloyl chloride, isophthaloyl chloride or 4,4'-biphenyl dicarbonyl chloride.
  • the aromatic dianhydride is preferably pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, At least one of 4,4'-hexafluoroisopropyl phthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride or 4,4'-oxydiphthalic anhydride
  • the aromatic diamine is preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)diaminobiphenyl or 4, At least one of 4'-diaminodiphenyl ethers.
  • the polyamide-imide film proposed in this application is obtained by polymerizing aromatic dianhydrides, aromatic dicarbonyl compounds and aromatic diamines, imidizing them and casting them into films; during the polymerization process, it is preferably The aromatic dianhydride and the aromatic diamine are polymerized first, and then the non-fluorinated aromatic dicarbonyl compound and the fluorinated aromatic dicarbonyl compound are sequentially added for polymerization, so that the required yellowness index and birefringence can be obtained at the same time Improved polyamide-imide.
  • the above-mentioned polymerization reaction is preferably carried out in an inert atmosphere at 0 to 60°C for 1 to 24 hours; the solvents used in the reaction are N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl acetamide (DMAc) or dimethyl sulfoxide (DMSO).
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMAc dimethyl acetamide
  • DMSO dimethyl sulfoxide
  • a polyamide-imide film the preparation method of which includes:
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • DMAc N,N-dimethylacetamide
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C and dry for 1 hour, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane, and control the polyamide-imide
  • the thickness of the film is 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • Phthaloyl chloride continue stirring and reacting at room temperature for 6 hours to obtain a polyamic acid solution; add 1.58g pyridine and 2.04g acetic anhydride to the polyamic acid solution, stir and react at room temperature for 30min, 70°C Continue stirring the reaction for 1 hour, cool to room temperature, use excess methanol to precipitate the polymer, filter, rinse with a large amount of methanol, and dry to obtain polyamide-imide resin;
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • DMAc N,N-dimethylacetamide
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C and dry for 1 hour, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane, and control the polyamide-imide
  • the thickness of the film is 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • Tetrafluoroterephthaloyl chloride continue stirring and reacting at room temperature for 6 hours to obtain a polyamic acid solution; add 1.58g pyridine and 2.04g acetic anhydride to the polyamic acid solution, stir and react at room temperature for 30 minutes, and continue stirring at 70°C React for 1 hour, cool to room temperature, use excess methanol to precipitate the polymer, filter, rinse with a large amount of methanol, and dry to obtain polyamide-imide resin;
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C for 1 hour, continue to raise the temperature to 200 °C, dry for 1 hour, then raise the temperature to 300 °C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane. Control the polyamide-imide membrane.
  • the thickness of the amide-imide film was 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • DMAc N,N-dimethylacetamide
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C and dry for 1 hour, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane, and control the polyamide-imide
  • the thickness of the film is 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • DMAc N,N-dimethylacetamide
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C and dry for 1 hour, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane, and control the polyamide-imide
  • the thickness of the film is 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • DMAc N,N-dimethylacetamide
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C and dry for 1 hour, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane, and control the polyamide-imide
  • the thickness of the film is 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • IPC isophthaloyl chloride
  • the polyamide-imide resin was added to N,N-dimethylacetamide (DMAc) and re-dissolved completely to obtain a solution with a solid content of 10wt%.
  • the resulting solution was cast on a stainless steel plate. Raise the temperature to 120°C and dry for 1 hour in the air, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, and dry for 0.5h. After cooling to room temperature, the membrane is separated to obtain the polyamide-imide membrane. Control the polyamide-imide membrane. The thickness of the amide-imide film was 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • DMAc N,N-dimethylacetamide
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C and dry for 1 hour, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane, and control the polyamide-imide
  • the thickness of the film is 50 ⁇ m.
  • a polyamide-imide film the preparation method of which includes:
  • the polyamideimide resin was added to N,N-dimethylacetamide (DMAc) and redissolved completely to obtain a solution with a solid content of 10wt%.
  • DMAc N,N-dimethylacetamide
  • the resulting solution was cast on a stainless steel plate and heated to 120°C under vacuum. °C and dry for 1 hour, continue to raise the temperature to 200°C, dry for 1 hour, then raise the temperature to 300°C, dry for 0.5 hours, and then separate the membrane after cooling to room temperature to obtain the polyamide-imide membrane, and control the polyamide-imide
  • the thickness of the film is 50 ⁇ m.
  • T550 Light transmittance: Use a UV spectrophotometer (X-rite Ci7800) to measure the light transmittance at 550nm;
  • Yellowness Index According to ASTM E313 standard, use a UV spectrophotometer (X-rite Ci7800) to measure the yellowness index at 550nm;
  • Birefringence wavelength measured at 594nm using prism coupler (Metricon 2010/M) below, the TE (transverse electric wave) mode and TM (transverse magnetic wave) mode are used to measure the refractive index, and the difference between the two is used as the birefringence;
  • Elastic modulus according to ASTM D882 standard, use a film tensile testing machine to measure the elastic modulus at room temperature 25°C.
  • the polyamide-imide film described in the embodiment of the present application exhibits high light transmittance and simultaneously has a low yellowness index and low birefringence.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

本申请提出了一种聚酰胺-酰亚胺膜及柔性显示器，该聚酰胺-酰亚胺膜是由芳香族二酐和芳香族二羰基化合物与芳香族二胺共聚得到；其中，所述芳香族二羰基化合物包括氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物。本申请的聚酰胺-酰亚胺膜能够获得极低的黄度指数和双折射率，适用于柔性显示器的基板制作。

Description

一种聚酰胺-酰亚胺膜及其制备方法和柔性显示器
本申请要求于2022年5月17日提交中国专利局、申请名称为一种聚酰胺-酰亚胺膜及柔性显示器、申请号为202210536326.0的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及光学材料技术领域，尤其涉及一种聚酰胺-酰亚胺膜及其制备方法和柔性显示器。
背景技术
液晶显示器或有机发光二极管显示器等薄型显示器以触摸屏面板形式实现，不仅广泛用于智能电话和平板电脑，而且还用于各种可穿戴设备等以便携性为特征的各种智能设备。
柔性显示器的基本构造可以分为基板、中间显示介质与封装等三层主要结构。这其中，柔性基板作为整个柔性显示器的支撑与保护组件，不仅对于显示器的显示品质有着重要的影响，而且会直接关系到器件的使用寿命。
综合而言，聚酰亚胺膜具有较好的热稳定性和较低的线性热膨胀系数(CTE)，所以被认为是用于柔性显示器的首选基板材料。但是，现有的聚酰亚胺膜由于高的芳香族环密度被着色成黄色或褐色，因而在可见光区域中的透过率低，并显示出黄色系的颜色。
因此，为了能够用于柔性显示器，研究人员正在研究将聚酰亚胺的黄色转化为无色透明的各种方法。但是，一方面，现有的透明聚酰亚胺普遍具有较大的双折射，而较大的双折射会使光线发生延迟，从而降低显示器的黑白对比度，增加不同视角的色彩偏移；另一方面，聚酰亚胺膜的黄色指数依旧相对较高，不足以满足市场上柔性显示器所需的性能。
申请内容
基于背景技术中存在的技术问题，本申请提出了一种聚酰胺-酰亚胺膜及其制备方法，所述聚酰胺酰-亚胺膜能够获得极低的黄度指数和双折射率，适用于柔性显示器的基板制作。
本申请提出了一种聚酰胺-酰亚胺膜，所述聚酰胺-酰亚胺膜是将芳香族二酐和芳香族二羰基化合物与芳香族二胺共聚得到；
其中，所述芳香族二羰基化合物包括氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物。
本申请中，芳香族二羰基化合物具体选择为包括氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物，如此使所得聚酰胺-酰亚胺膜的分子链中同时具有氟取代的酰胺重复单元和非氟取代的酰胺重复单元，这两种重复单元的存在有助于破坏分子的规整度，提高分子链的自由度和增强柔韧性，实现了高透光率和低黄度指数的同时，还可以取得降低双折射率的协同效果。
其中，所述氟化芳香族二羰基化合物为四氟对苯二甲酰氯。
其中，所述非氟化芳香族二羰基化合物为对苯二甲酰氯、间苯二甲酰 氯或4，4'-联苯二甲酰氯中的至少一种。
其中，所述氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物的摩尔比为1-1.5:1。
本申请中，氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物的摩尔比的限定，可以适当控制分子链中酰亚胺重复单元和酰胺重复单元的含量，从而进一步改善聚酰胺-酰亚胺膜的黄度指数和双折射率。
其中，所述芳香族二酐为均苯四甲酸二酐、3，3'，4，4'-联苯四甲酸二酐、4，4'-六氟异丙基邻苯二甲酸酐、3，3'，4，4'-二苯甲酮四甲酸二酐或4，4'-氧双邻苯二甲酸酐中的至少一种。
其中，所述芳香族二胺为对苯二胺、间苯二胺、4，4'-二氨基联苯、2，2'-二(三氟甲基)二氨基联苯或4，4'-二氨基二苯醚中的至少一种。
其中，所述芳香族二酐和芳香族二羰基化合物的摩尔比为1:1-4。
本申请中，芳香族二酐与芳香族二羰基化合物的摩尔比的限定，可以在保证聚酰胺-酰亚胺膜的固有机械性能不被劣化情况下，进一步改善聚酰胺-酰亚胺膜的黄度指数和双折射率。
本申请提出了一种聚酰胺-酰亚胺膜的制备方法，包括：
将芳香族二酐与芳香族二胺进行聚合后，再依次与非氟化芳香族二羰基化合物以及氟化芳香族二羰基化合物进行聚合，所得聚酰胺酸进行酰亚胺化后，再浇铸成膜，即得到所述聚酰胺-酰亚胺膜。
其中，所述酰亚胺化是在催化剂和脱水剂条件下进行；所述催化剂为吡啶、甲基吡啶、喹啉或异喹啉中的至少一种，所述脱水剂为乙酸酐、丙酸酐或三氟乙酸酐中的至少一种。
本申请还提出一种柔性显示器，其包括上述的聚酰胺-酰亚胺膜。
本申请提出的一种聚酰胺-酰亚胺膜及其制备方法，其将氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物作为芳香族二羰基化合物的起始原料来得到聚酰胺-酰亚胺膜，如此可以在保持无色透明的基础上，获得极低的双折射性能，因此可有效应用于柔性显示器。
具体实施方式
本申请提出的一种聚酰胺-酰亚胺膜，由芳香族二酐和芳香族二羰基化合物与芳香族二胺共聚得到。在所述芳香族二羰基化合物为氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物的混合物时，所得聚酰胺酰亚胺膜表现出对黄度指数和双折射率的有效改善。氟化芳香族二羰基化合物相对非氟化芳香族二羰基化合物溶解性好，因此，二者复配作为芳香族二羰基化合物，在保证所得聚酰胺-酰亚胺膜高透明性的同时，可以有效地改善黄度指数和双折射率。
但是，仅在芳香族二酐为氟化芳香族二酐和/或芳香族二胺为氟化芳香族二胺时，所得聚酰胺-酰亚胺膜却并不能表现出对黄度指数和双折射率的改善。芳香族二酐和/或芳香族二胺无论是否为含氟取代，其都具有相对良好的溶解性，因此，仅在芳香族二酐为氟化芳香族二酐和/或芳香族二胺为氟化芳香族二胺时，并不能表现出对黄度指数和双折射率的改善。
本申请中，为了获得对黄度指数和双折射率协同改善的聚酰胺-酰亚胺膜，所述氟化芳香族二羰基化合物优选为四氟对苯二甲酰氯、单氟对苯二甲酰氯、2-氟-间苯二甲酰氯或4-氟-间苯二甲酰氯中的至少一种；所述非 氟化芳香族二羰基化合物优选为对苯二甲酰氯、间苯二甲酰氯或4，4'-联苯二甲酰氯中的至少一种。
本申请中，为了保持聚酰胺-酰亚胺膜的固有机械性能，所述芳香族二酐优选为均苯四甲酸二酐、3，3'，4，4'-联苯四甲酸二酐、4，4'-六氟异丙基邻苯二甲酸酐、3，3'，4，4'-二苯甲酮四甲酸二酐或4，4'-氧双邻苯二甲酸酐中的至少一种；所述芳香族二胺优选为对苯二胺、间苯二胺、4，4'-二氨基联苯、2，2'-二(三氟甲基)二氨基联苯或4，4'-二氨基二苯醚中的至少一种。
本申请中所提出的聚酰胺-酰亚胺膜，将芳香族二酐和芳香族二羰基化合物与芳香族二胺进行聚合、酰亚胺化后浇铸成膜后得到；聚合过程中，优选为将芳香族二酐与芳香族二胺先进行聚合，再依次加入非氟化芳香族二羰基化合物和氟化芳香族二羰基化合物进行聚合，如此可以获得所需要的黄度指数和双折射率同时改善的聚酰胺-酰亚胺。
本申请中，上述聚合反应优选为在惰性气氛下在0至60℃下进行1至24h反应；反应所用的溶剂为N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)或二甲基亚砜(DMSO)。
下面，通过具体实施例对本申请的技术方案进行详细说明，但是应该明确提出这些实施例用于举例说明，但是不解释为限制本申请的范围。
实施例1
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将3.2023g(10mmol)2，2'-二(三氟甲基)二氨基 联苯(TFDB)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入1.3327g(3mmol)4，4'-六氟异丙基邻苯二甲酸酐(6FDA)搅拌溶解反应，再加入0.6091g(3mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入1.0999g(4mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
实施例2
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将1.8423g(10mmol)4，4'-二氨基联苯(MSDS)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入0.8827g(3mmol)3，3'，4，4'-联苯四甲酸二酐(6FDA)搅拌溶解反应，再加入0.6091g(3mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入1.0999g(4mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃ 下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
实施例3
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将2.0024g(10mmol)4，4'-二氨基二苯醚(ODA)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入0.9667g(3mmol)3，3'，4，4'-二苯甲酮四甲酸二酐(BTDA)搅拌溶解反应，再加入0.6091g(3mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入1.0999g(4mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚 酰胺-酰亚胺膜的厚度为50μm。
实施例4
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将3.2023g(10mmol)2，2'-二(三氟甲基)二氨基联苯(TFDB)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入1.3327g(3mmol)4，4'-六氟异丙基邻苯二甲酸酐(6FDA)搅拌溶解反应，再加入0.6091g(3mmol)间苯二甲酰氯(IPC)搅拌溶解反应，接着加入1.0999g(4mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
实施例5
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将3.2023g(10mmol)2，2'-二(三氟甲基)二氨基 联苯(TFDB)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入2.2211g(5mmol)4，4'-六氟异丙基邻苯二甲酸酐(6FDA)搅拌溶解反应，再加入0.4060g(2mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入0.8249g(3mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
实施例6
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将3.2023g(10mmol)2，2'-二(三氟甲基)二氨基联苯(TFDB)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入0.8885g(2mmol)4，4'-六氟异丙基邻苯二甲酸酐(6FDA)搅拌溶解反应，再加入0.8121g(4mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入1.0999g(4mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐， 室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
对比例1
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将3.2023g(10mmol)2，2'-二(三氟甲基)二氨基联苯(TFDB)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入1.3327g(3mmol)4，4'-六氟异丙基邻苯二甲酸酐(6FDA)搅拌溶解反应，再加入0.6091g(3mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入0.8121g(4mmol)间苯二甲酰氯(IPC)，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真 空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
对比例2
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将3.2023g(10mmol)2，2'-二(三氟甲基)二氨基联苯(TFDB)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入1.3327g(3mmol)4，4'-六氟异丙基邻苯二甲酸酐(6FDA)搅拌溶解反应，再加入0.8121g(4mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入0.8249g(3mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
对比例3
一种聚酰胺-酰亚胺膜，其制备方法包括：
在氮气保护下，将3.2023g(10mmol)2，2'-二(三氟甲基)二氨基联苯(TFDB)加入50mL N，N-二甲基乙酰胺(DMAc)中搅拌溶解完全，加入1.3327g(6mmol)4，4'-六氟异丙基邻苯二甲酸酐(6FDA)搅拌溶解反应，再加入0.3451g(1.7mmol)对苯二甲酰氯(TPC)搅拌溶解反应，接着加入0.6324g(2.3mmol)四氟对苯二甲酰氯，室温下继续搅拌反应6h，得到聚酰胺酸溶液；向所述聚酰胺酸溶液中加入1.58g吡啶和2.04g乙酸酐，室温下搅拌反应30min，70℃下继续搅拌反应1h，冷却至室温后用过量甲醇将聚合物沉淀析出，过滤后用大量甲醇冲洗，干燥后得到聚酰胺酰亚胺树脂；
将所述聚酰胺酰亚胺树脂加入到N，N-二甲基乙酰胺(DMAc)中重新溶解完全，得到固含量为10wt％的溶液，所得溶液浇铸在不锈钢板上，真空下升温至120℃干燥1h，继续升温至200℃，干燥1h，再升温至300℃，干燥0.5h，降至室温后分离出膜，得到所述聚酰胺-酰亚胺膜，控制该聚酰胺-酰亚胺膜的厚度为50μm。
性能测试：
光透射率(T550)：使用紫外分光光度计(X-rite Ci7800)测量在550nm处的光透射率；
黄度指数(YI)：根据ASTM E313标准，使用紫外分光光度计(X-rite Ci7800)测量在550nm处的黄度指数；
双折射率：使用棱镜耦合器(Metricon 2010/M)，在594nm测量波长 下，采用TE(横电波)模式和TM(横磁波)模式测量折射率，并将二者差值作为双折射率；
弹性模量，按照ASTMD882标准，使用薄膜拉力试验机在室温25℃下测量其弹性模量。
上述实施例和对比例所得聚酰胺-酰亚胺膜的性能测试结果如下表1所示：
表1实施例和对比例所述聚酰胺-酰亚胺膜的性能测试结果
从上表1可知，本申请实施例所述聚酰胺-酰亚胺膜显示出高的透光率，并同时具有低的黄度指数和低双折射率。
以上所述，仅为本申请较佳的具体实施方式，但本申请的保护范围并 不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，根据本申请的技术方案及其申请构思加以等同替换或改变，都应涵盖在本申请的保护范围之内。

Claims (10)

  1. 一种聚酰胺-酰亚胺膜，将芳香族二酐和芳香族二羰基化合物与芳香族二胺共聚得到；所述芳香族二羰基化合物包括氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物。
  2. 根据权利要求1所述的聚酰胺-酰亚胺膜，其中，所述氟化芳香族二羰基化合物为四氟对苯二甲酰氯。
  3. 根据权利要求1所述的聚酰胺-酰亚胺膜，其中，所述非氟化芳香族二羰基化合物为对苯二甲酰氯、间苯二甲酰氯或4，4'-联苯二甲酰氯中的至少一种。
  4. 根据权利要求1所述的聚酰胺-酰亚胺膜，其中，所述氟化芳香族二羰基化合物和非氟化芳香族二羰基化合物的摩尔比为1-1.5:1。
  5. 根据权利要求1所述的聚酰胺-酰亚胺膜，其中，所述芳香族二酐为均苯四甲酸二酐、3，3'，4，4'-联苯四甲酸二酐、4，4'-六氟异丙基邻苯二甲酸酐、3，3'，4，4'-二苯甲酮四甲酸二酐或4，4'-氧双邻苯二甲酸酐中的至少一种。
  6. 根据权利要求1所述的聚酰胺-酰亚胺膜，其中，所述芳香族二胺为对苯二胺、间苯二胺、4，4'-二氨基联苯、2，2'-二(三氟甲基)二氨基联苯或4，4'-二氨基二苯醚中的至少一种。
  7. 根据权利要求1所述的聚酰胺-酰亚胺膜，其中，所述芳香族二酐和芳香族二羰基化合物的摩尔比为1:1-4。
  8. 一种聚酰胺-酰亚胺膜的制备方法，包括：
    将芳香族二酐与芳香族二胺进行聚合后，再依次与非氟化芳香族二羰基化合物以及氟化芳香族二羰基化合物进行聚合，所得聚酰胺酸进行酰亚胺化后，再浇铸成膜，即得到所述聚酰胺-酰亚胺膜。
  9. 根据权利要求8所述的聚酰胺-酰亚胺膜的制备方法，其中，所述酰亚胺化是在催化剂和脱水剂条件下进行；所述催化剂为吡啶、甲基吡啶、喹啉或异喹啉中的至少一种，所述脱水剂为乙酸酐、丙酸酐或三氟乙酸酐中的至少一种。
  10. 一种柔性显示器，其包括权利要求1所述的聚酰胺-酰亚胺膜。
PCT/CN2023/080130 2022-05-17 2023-03-07 一种聚酰胺-酰亚胺膜及其制备方法和柔性显示器 WO2023221605A1 (zh)

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