WO2021120427A1 - 聚酰亚胺薄膜及其制备方法、显示装置 - Google Patents
聚酰亚胺薄膜及其制备方法、显示装置 Download PDFInfo
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- polyimide film
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- hydroxyphenol
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 50
- 239000010409 thin film Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000004642 Polyimide Substances 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 125000004185 ester group Chemical group 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 14
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 229920005575 poly(amic acid) Polymers 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000010408 film Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000006159 dianhydride group Chemical group 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- -1 tetracarboxylic dianhydride derivative Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 claims 3
- HGMQPWXYDSTESW-UHFFFAOYSA-N anthracene-1,2,3-tricarboxylic acid Chemical class C1=CC=C2C=C(C(C(O)=O)=C(C(C(=O)O)=C3)C(O)=O)C3=CC2=C1 HGMQPWXYDSTESW-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 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 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 2
- 229920002647 polyamide Polymers 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- 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
- C08G73/1003—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
- C08G73/1067—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
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to the field of display technology, in particular to a polyimide film, a preparation method thereof, and a display device.
- plastic base material is superior to the current inorganic glass base material in terms of flexibility and film formability, but has poor heat resistance and thermal dimensional stability. Therefore, it is very necessary to improve the heat resistance of flexible substrate materials.
- the purpose of the present invention is to provide a polyimide film, a preparation method thereof, and a display device, which can effectively improve the heat resistance and deformation resistance of the polyimide film.
- the present invention provides a polyimide film, the molecular structure of which is:
- n 1000 ⁇ 3500.
- the present invention also provides a method for preparing a polyimide film, which includes the following steps: preparing a first compound having a dianhydride structure; adding the first compound and a first solvent to the first round bottom protected by argon The second compound with fluorodiamine structure is added to the first round-bottom flask, and the mixture is continuously stirred and fully reacted at room temperature for 24 to 96 hours to obtain a polyamic acid containing an ester group structure.
- the step of preparing the first compound having a dianhydride structure specifically includes: providing chlorinated trimethylenetricarboxylic acid anhydride and hydroxyphenol; adding the chlorinated trimethylenetricarboxylic acid anhydride, the hydroxyphenol and a catalyst to In the second round-bottom flask, continuously stir and dissolve; heat the round-bottom flask to 40-60°C, fully react for 3-9h and cool to form a second mixed solution; add absolute ethanol to the second mixed solution and wash for 4 ⁇ After 6 times, the filter cake was suction filtered and stored, and placed in a vacuum drying oven at 50-100°C for 24 to 48 hours to obtain the first compound.
- the first compound includes a bisanthracene tetracarboxylic dianhydride derivative; the first solvent includes N-methylpyrrolidone; the second compound includes a diamine monomer; the second solvent includes toluene .
- the molar ratio of the first compound to the second compound is 1:3 to 3:1.
- the catalyst includes N,N-dimethylformamide; the hydroxyphenol includes phenyl; after adding the chlorinated trimethylene tricarboxylic acid anhydride, the hydroxyphenol and the catalyst to the second round bottom flask In the step, the stirring speed is 200 ppm to 340 ppm.
- the molar ratio of the chlorinated trimanthracene tricarboxylic acid anhydride to the hydroxyphenol is 1:2 to 1:1.
- the present invention also provides a display device including the polyimide film.
- the display device includes: a flexible substrate, a material of the flexible substrate is a polyimide film; and a display panel arranged on the flexible substrate.
- the display panel is an OLED display panel.
- the invention provides a polyimide film, a preparation method thereof, and a display device.
- a polyamic acid containing an ester group structure is prepared.
- the polyamic acid is prepared by a two-step method.
- the introduction of dianhydride containing ester group structure into polyimide increases the content of benzene ring.
- the introduction of ester group is conducive to the realization of flexibility. It not only improves its heat resistance components, but also introduces longer flexible chain components. This way, on the one hand, the regularity of macromolecules can be effectively destroyed, thereby improving the flexibility of the material, on the other hand, the introduction of rigid aromatic ring groups is conducive to the realization of its heat resistance.
- the ester bond is introduced into the dianhydride through the esterification reaction, and then participates in the preparation of the polyimide material.
- Fig. 1 is a graph of temperature baking of a polyimide film in Example 1 provided by the present invention
- Example 2 is a graph of temperature baking of the polyimide film in Example 2 provided by the present invention.
- Example 3 is a graph of temperature baking of the polyimide film in Example 3 provided by the present invention.
- Example 4 is a graph of temperature baking of the polyimide film in Example 4 provided by the present invention.
- Fig. 5 is a graph showing the weight loss curve of the polyimide film prepared by the present invention.
- Figure 6 is the fluorescence spectrum of the electrochromic polyamic acid material of the present invention in N,N'-dimethylacetamide solution
- FIG. 7 is a schematic diagram of the structure of the display device of the present invention.
- the invention provides a polyimide film, the molecular structure of which is:
- n ranges from 1000 to 3500, and the corresponding molecular weight of the polyimide film is from 200,000 to 400,000.
- the preparation method of the polyimide film of the present invention is described in detail by taking the preparation of the target compound (a polyimide film of the present invention) as an example.
- the preparation method of the electrochromic polyamic acid material of the present invention includes the following steps S1 to S8.
- the second solvent is added to the polyamic acid, and the temperature is raised to 150-250° C. under an argon atmosphere to fully react for 4-6 hours to obtain the first mixed solution.
- the specific cross-linking curing process of polyimide film lasts for 3 to 5 hours; the heating rate is 4-10°C/min, the highest temperature is 420°C to 500°C, and the baking stage is divided into two methods: hard baking and soft baking ; Hard bake is to directly heat up to the highest temperature and keep the temperature at a constant temperature for about 1h to cool down, as shown in Figure 1 and Figure 2, the difference between the schemes is that the highest temperature rise is different, the highest temperature of the scheme in Figure 1 is 450 °C, the highest temperature of the scheme in Figure 2 It is 475°C.
- Soft drying is a constant temperature platform that is divided into two or more times, and finally the temperature is lowered. As shown in Figure 3 and Figure 4, the process passes through the constant temperature platform three times.
- the temperature is 180 °C for 20 minutes, 350 Constant temperature at °C for 20 minutes, constant temperature at 450 °C for 40 minutes; in the scheme of Fig. 4, constant temperature at 180 °C for 25 minutes, constant temperature at 250 °C for 20 minutes, and constant temperature at 470 °C for 23 minutes.
- the method used in this patent includes but is not limited to the baking method and time interval of FIGS. 1 to 4.
- the present invention simply verifies the polyimide film.
- the polyimide film prepared by the polyamic acid containing ester structure as monomer unit has a weight loss of 1% and a temperature of about 590°C. This is mainly due to the introduction of large The use of aromatic ring and ester structure in the current OLED field is very beneficial.
- the polyimide film of the present invention has good thermal stability, and the deformation rate at 50-350°C is less than 2ppm/K, which provides the use of a stacked structure with inorganic materials.
- the idea, especially as an OLED substrate material provides a good solution to withstand the temperature rise and decrease in multiple manufacturing processes.
- the present invention also provides a display device including the polyimide film.
- the display device includes: a flexible substrate and a display panel, the material of the flexible substrate is a polyimide film; the display panel is provided on the flexible substrate, so The display panel is an OLED display panel.
- the flexible substrate of the display device provided by this embodiment has thermal stability and flexibility, which improves the stability of the display device.
- the invention provides a polyimide film, a preparation method thereof, and a display device.
- a polyamic acid containing an ester group structure is prepared.
- the polyamic acid is prepared by a two-step method.
- the introduction of dianhydride containing ester group structure into polyimide increases the content of benzene ring.
- the introduction of ester group is conducive to the realization of flexibility. It not only improves its heat resistance components, but also introduces longer flexible chain components. This way, on the one hand, the regularity of macromolecules can be effectively destroyed, thereby improving the flexibility of the material, on the other hand, the introduction of rigid aromatic ring groups is conducive to the realization of its heat resistance.
- the ester bond is introduced into the dianhydride through the esterification reaction, and then participates in the preparation of the polyimide material.
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- 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)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
提供一种聚酰亚胺薄膜及其制备方法、显示装置。具体为制备一种含有酯基结构的聚酰胺酸,通过两步法制备聚酰胺酸。在聚酰亚胺中引入含有酯基结构的二酸酐,提高苯环含量的同时引入酯基有利于柔性实现,这不仅提高了其耐热性成分。由引入更长的柔性链成分,这样一方面可以有效的破坏大分子的规整度,从而提高材料的柔韧性,另一方面引入刚性的芳环基团,有利于其耐热性的实现。通过酯化反应将酯键引入到二酐,再来参与制备聚酰亚胺材料。
Description
本发明涉及显示技术领域,尤其涉及一种聚酰亚胺薄膜及其制备方法、显示装置。
国内的柔性OLED衬底材料越来越趋向于使用光学透明的耐热聚酰亚胺材料,然而,由于难以同时获得高水平的综合性能,即光学透明性,耐热性,对设备制造过程中的热循环的尺寸稳定性(热尺寸稳定性)以及膜柔韧性等。所以在OLED领域的现阶段,其柔性性能的实现成为一个难以实现的核心。
因为塑料基底材料在柔韧性和薄膜成形性方面优于目前的无机玻璃基材,但耐热性和热尺寸稳定性差。所以,对柔性衬底材料的耐热性能的提高是非常必要的。
本发明的目的在于,提供一种聚酰亚胺薄膜及其制备方法、显示装置,可以有效的提高聚酰亚胺薄膜的耐热性以及耐形变能力。
为解决上述技术问题,本发明提供一种聚酰亚胺薄膜,其分子结构式为:
,其中,n的数值范围为1000~3500。
本发明还提供一种聚酰亚胺薄膜的制备方法,包括如下步骤:制备具有二酐结构的第一化合物;将所述第一化合物以及第一溶剂加入到有氩气保护的第一圆底烧瓶中并充分溶解;将具有氟二胺结构的第二化合物加入至所述第一圆底烧瓶中,在常温下不断的搅拌并充分反应24~96h后,得到含酯基结构的聚酰胺酸;将第二溶剂加入至所述聚酰胺酸中,在氩气的氛围下升温到150~250℃充分反应4~6h得到第一混合溶液;使用有机滤膜对所述第一混合溶液进行过滤,将得到的滤液悬涂在玻璃基板上;在50~100℃真空环境下恒温0.5~1h,除去所述滤液的第一溶剂;烘烤所述玻璃基板上的滤液形成一薄膜,并将整块玻璃基板以及薄膜浸泡在去离子水中72~96h后揭下玻璃基板上的薄 膜;取出所述薄膜并再次置入80℃真空干燥,得到所述聚酰亚胺薄膜。
进一步地,在所述制备具有二酐结构的第一化合物步骤中,具体包括:提供氯化偏蒽三甲酸酐以及羟基苯酚;将所述氯化偏蒽三甲酸酐、所述羟基苯酚以及催化剂加入至第二圆底烧瓶中,不断搅拌溶解;加热所述圆底烧瓶至40~60℃,充分反应3~9h冷却形成第二混合溶液;加入无水乙醇至所述第二混合溶液中洗涤4~6次后抽滤保存滤饼,并放入50~100℃℃真空干燥箱中干燥24~48h,得到所述第一化合物。
进一步地,所述第一化合物包括双蒽型四羧酸二酐衍生物;所述第一溶剂包括N-甲基吡咯烷酮;所述第二化合物包括二胺单体;所述第二溶剂包括甲苯。
进一步地,所述第一化合物与所述第二化合物的摩尔比为:1:3~3:1。
进一步地,所述催化剂包括N,N-二甲基甲酰胺;所述羟基苯酚包括苯基;在将所述氯化偏蒽三甲酸酐、所述羟基苯酚以及催化剂加入至第二圆底烧瓶的步骤中,所述搅拌速度为200ppm~340ppm。
进一步地,所述氯化偏蒽三甲酸酐与所述羟基苯酚的摩尔比为1:2~1:1。
本发明还提供一种显示装置,包括所述聚酰亚胺薄膜。
进一步地,所述显示装置包括:柔性衬底,所述柔性衬底的材料为聚酰亚胺薄膜;显示面板,设于所述柔性衬底上。
进一步地,所述显示面板为OLED显示面板。
本发明提供了聚酰亚胺薄膜及其制备方法、显示装置。具体为制备一种含有酯基结构的聚酰胺酸。通过两步法制备聚酰胺酸。首先,在聚酰亚胺中引入含有酯基结构的二酸酐,提高苯环的含量,同时引入酯基有利于柔性实现,不仅提高了其耐热性成分,由引入更长的柔性链成分,这样一方面可以有效的破坏大分子的规整度,从而提高材料的柔韧性,另一方面引入刚性的芳环基团,有利于其耐热性的实现。通过酯化反应将酯键引入到二酐,再来参与制备聚酰亚胺材料。
下面结合附图,通过对本申请的具体实施方式详细描述,将使本申请的技术方案及其它有益效果显而易见。
图1为本发明提供的实施例1聚酰亚胺薄膜温度烘烤的曲线图;
图2为本发明提供的实施例2聚酰亚胺薄膜温度烘烤的曲线图;
图3为本发明提供的实施例3聚酰亚胺薄膜温度烘烤的曲线图;
图4为本发明提供的实施例4聚酰亚胺薄膜温度烘烤的曲线图;
图5为本发明制备的聚酰亚胺薄膜的失重曲线图;
图6为本发明电致变色聚酰胺酸材料在N,N'-二甲基乙酰胺溶液的荧光光谱;
图7为本发明显示装置的结构示意图;
显示装置10
柔性衬底11;显示面板10。
本申请提供一种实体键盘输入系统、键盘输入方法及存储介质,为使本申请的目的、技术方案及效果更加清楚、明确,以下参照附图并举实施例对本申请进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本申请,并不用于限定本申请。
本发明提供一种聚酰亚胺薄膜,其分子结构式为:
其中,n的数值范围为1000~3500,对应的所述聚酰亚胺薄膜的分子量在200000~400000万。
为了更加清楚的解释本发明,下面结合本发明的聚酰亚胺薄膜的制备方法对所述聚酰亚胺薄膜进行进一步解释。
在本发明一实施例中,以制备目标化合物(本发明的一种聚酰亚胺薄膜)为例,详细说明本发明的聚酰亚胺薄膜的制备方法。
本发明的电致变色聚酰胺酸材料制备方法,包括以下步骤S1~S8。
S1)制备具有二酐结构的第一化合物;在所述制备具有二酐结构的第一化合物步骤中,具体包括S11~S14。
S11)提供氯化偏蒽三甲酸酐以及羟基苯酚。所述羟基苯酚包括苯基,还可以由如下化合物的分子结构式中任意一种代替,如下分子式并未画出两侧的二醇结构。
S12)将所述氯化偏蒽三甲酸酐、所述羟基苯酚以及催化剂加入至第二圆底烧瓶中,不断搅拌溶解。
S13)加热所述圆底烧瓶至50~100℃,充分反应3~9h冷却形成第二混合溶液。
S14)加入无水乙醇至所述第二混合溶液中洗涤4~6次后抽滤保存滤饼,并放入50~100℃真空干燥箱中干燥24~48h,得到所述第一化合物,所述第一化合物的分子结构式如下:
S2)将所述第一化合物以及第一溶剂加入到有氩气保护的第一圆底烧瓶中并充分溶解。
S3)将具有氟二胺结构的第二化合物加入至所述第一圆底烧瓶中,在常温下不断的搅拌并充分反应24~96h后,得到含酯基结构的聚酰胺酸,其分子结构式如下:
S4)将第二溶剂加入至所述聚酰胺酸中,在氩气的氛围下升温到150~250℃充分反应4~6h得到第一混合溶液。
S5)使用有机滤膜对所述第一混合溶液进行过滤,将得到的滤液悬涂在玻璃基板上。
S6)在80℃真空环境下恒温0.5~1h,除去所述滤液的第一溶剂。
S7)烘烤所述玻璃基板上的滤液形成一薄膜,并将整块玻璃基板以及薄膜浸泡在去离子水中72~96h后揭下玻璃基板上的薄膜。
S8)取出所述薄膜并再次置入80℃真空干燥,得到所述聚酰亚胺薄膜。
具体的聚酰亚胺薄膜的交联固化过程持续3~5h;升温速度为4-10℃/分钟,升温的最高温度420℃~500℃,烘烤阶段分为硬烘和软烘两种方式;硬烘为直接升温到最高温度并且恒温1h左右降温,如图1和图2所示,方案区别在于升高的最高温度不同,图1的方案最高温度为450℃,图2的方案最高温度为475℃。
软烘则是分2次及2次以上的恒温平台,最后再降温,如图3以及图4所示,过程中经过了三次恒温平台,图3方案中,分别是180℃恒温20分钟,350℃恒温20分钟,450℃恒温40分钟;在图4方案中,分别是180℃恒温25分钟,250℃恒温20分钟,470℃恒温23分钟。
通过软硬烘烤的不同温度的控制,从而实现材料在不同恒温阶段的交联和溶剂去除。本专利使用的方法包含不限于图1~图4的烘烤方式及时间区间。
为了将所述聚酰亚胺薄膜的性能进一步阐述,本发明对所述聚酰亚胺薄膜进行简单验证。
如图5所述,所述含有酯基结构的聚酰胺酸作为单体单元制备的聚酰亚胺薄膜,其失重质量的1%,温度大约在590℃左右,这主要是得益于引入大芳香环和酯基结构,在目前OLED领域的材料的使用是非常有益的。如图6所示,可以看出本发明聚酰亚胺薄膜具有良好的热稳定性,在50-350℃的变形率达到2ppm/K以下,这为其与无机材料进行堆叠结构的使用提供了思路,尤其是作为OLED衬底材料其在多道制程中承受升温和降低提供了很好的解决办法。
经实验证明所述聚酰亚胺薄膜具有较高的耐热性以及柔韧性。为了将所述聚酰亚胺薄膜运用至发光装置中,本发明还提供了一种显示装置,包括所述的聚酰亚胺薄膜。
具体的,如图7所示,所述显示装置包括:柔性衬底以及显示面板,所述柔性衬底的材料为聚酰亚胺薄膜;所述显示面板设于所述柔性衬底上,所述显示面板为OLED显示面板。
本实施例提供的显示装置的柔性衬底具有热稳定性以及柔韧性,提高了所述显示装置的稳定性。
本发明提供了聚酰亚胺薄膜及其制备方法、显示装置。具体为制备一种含有酯基结构的聚酰胺酸。通过两步法制备聚酰胺酸。首先,在聚酰亚胺中引入含有酯基结构的二酸酐,提高苯环的含量,同时引入酯基有利于柔性实现,不仅提高了其耐热性成分,由引入更长的柔性链成分,这样一方面可以有效的破坏大分子的规整度,从而提高材料的柔韧性,另一方面引入刚性的芳环基团,有利于其耐热性的实现。通过酯化反应将酯键引入到二酐,再来参与制备聚酰亚胺材料。
可以理解的是,对本领域普通技术人员来说,可以根据本申请的技术方案及其发明构思加以等同替换或改变,而所有这些改变或替换都应属于本申请所附的权利要求的保护范围。
Claims (10)
- 一种聚酰亚胺薄膜的制备方法,其特征在于,包括如下步骤;制备具有二酐结构的第一化合物;将所述第一化合物以及第一溶剂加入到有氩气保护的第一圆底烧瓶中并充分溶解;将具有氟二胺结构的第二化合物加入至所述第一圆底烧瓶中,在常温下不断的搅拌并充分反应24~96h后,得到含酯基结构的聚酰胺酸;将第二溶剂加入至所述聚酰胺酸中,在氩气的氛围下升温到150~250℃充分反应4~6h得到第一混合溶液;使用有机滤膜对所述第一混合溶液进行过滤,将得到的滤液悬涂在玻璃基板上;在50~100℃真空环境下恒温0.5~1h,除去所述滤液的第一溶剂;烘烤所述玻璃基板上的滤液形成一薄膜,并将整块玻璃基板以及薄膜浸泡在去离子水中72~96h后揭下玻璃基板上的薄膜;取出所述薄膜并再次置入50~100℃真空干燥,得到所述聚酰亚胺薄膜。
- 根据权利要求2所述的聚酰亚胺薄膜的制备方法,其中,在所述制备具有二酐结构的第一化合物步骤中,具体包括:提供氯化偏蒽三甲酸酐以及羟基苯酚;将所述氯化偏蒽三甲酸酐、所述羟基苯酚以及催化剂加入至第二圆底烧瓶中,不断搅拌溶解;加热所述圆底烧瓶至40~60℃,充分反应3~9h冷却形成第二混合溶液;加入无水乙醇至所述第二混合溶液中洗涤4~6次后抽滤保存滤饼,并放入50~100℃的真空干燥箱中干燥24~48h,得到所述第一化合物。
- 根据权利要求2所述的聚酰亚胺薄膜的制备方法,其中,所述第一化合物包括双蒽型四羧酸二酐衍生物;所述第一溶剂包括N-甲基吡咯烷酮;所述第二化合物包括二胺单体;所述第二溶剂包括甲苯。
- 根据权利要求2所述的聚酰亚胺薄膜的制备方法,其中,所述第一化合物与所述第二化合物的摩尔比为:1:3~3:1。
- 根据权利要求3所述的聚酰亚胺薄膜的制备方法,其中,所述催化剂包括N,N-二甲基甲酰胺;所述羟基苯酚包括苯基;在将所述氯化偏蒽三甲酸酐、所述羟基苯酚以及催化剂加入至第二圆底烧瓶的步骤中,所述搅拌速度为200ppm~340ppm。
- 根据权利要求3所述的聚酰亚胺薄膜的制备方法,其中,所述氯化偏蒽三甲酸酐与所述羟基苯酚的摩尔比为1:2~1:1。
- 一种显示装置,其中,包括权利要求1所述聚酰亚胺薄膜。
- 根据权利要求8所述的显示装置,其中,所述显示装置包括:柔性衬底,所述柔性衬底的材料为聚酰亚胺薄膜;显示面板,设于所述柔性衬底上。
- 根据权利要求9所述的显示装置,其中,所述显示面板为OLED显示面板。
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