WO2021056790A1 - 一种聚酰亚胺材料、制备方法及其应用 - Google Patents

一种聚酰亚胺材料、制备方法及其应用 Download PDF

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WO2021056790A1
WO2021056790A1 PCT/CN2019/120216 CN2019120216W WO2021056790A1 WO 2021056790 A1 WO2021056790 A1 WO 2021056790A1 CN 2019120216 W CN2019120216 W CN 2019120216W WO 2021056790 A1 WO2021056790 A1 WO 2021056790A1
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compound
polyimide material
material according
solution
polyimide
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PCT/CN2019/120216
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French (fr)
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汪亚民
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武汉华星光电半导体显示技术有限公司
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Priority to US16/649,855 priority Critical patent/US20210403751A1/en
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • 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
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • 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

  • This application relates to the technical field of display panels, and in particular to a polyimide material, a preparation method and its application.
  • HCI Human-Computer Interaction
  • the traditional PI material has a relatively low thermal expansion coefficient because of its strong rigid linear structure, it also often brings about problems in mechanical properties, permeability and other aspects on the other hand.
  • the industry's research on this area is in a state of application bottleneck.
  • the application research of PI has begun to be directed: to reduce the thermal expansion coefficient as much as possible, while achieving good transparency. Transient and mechanical properties.
  • the PI material as a thermal expansion coefficient is within a hundred orders of magnitude, and the current inorganic materials such as glass and silicon have basically achieved a smaller order of magnitude difference.
  • various types of functional layers need to be provided on it, which makes it inevitably necessary to bond with various types of metals, Si and other materials. During this period, it is required to bond materials to each other.
  • the CTE values are similar.
  • the CTE value of Cu is about 18ppm/K
  • the CTE value of Si is about 3ppm/K.
  • the range of CTE values between the two varies greatly; moreover, the bonding material itself needs to have a sufficiently high Parameters such as mechanical support strength and high insulation.
  • One aspect of the present invention is to provide a polyimide material, which incorporates a diamine structure by introducing a dianhydride structure containing fluorine and a benzene ring in a new molecular structure, so that the designed target polyimide material compound , It can not only achieve its own highly regular arrangement, but also promote the coordinated arrangement of diamine molecules to make the molecular chain of the target compound closer, realize the close packing between the molecular chains, and then achieve the target compound by having a more regular molecular chain structure Low CTE value performance parameters of the material.
  • a kind of polyimide material, its molecular structure general formula is:
  • the polyimide material compound involved in the present invention is derived from its precursor polyamic acid (PAA) through dehydration cyclization treatment, wherein the precursor polymer
  • PAA polyamic acid
  • amic acid is:
  • the raw materials used for the preparation of the polyamic acid include 3,5-trifluoromethyl-p-1,3-diether-diphthalic anhydride (for the convenience of subsequent description, it is denoted as Compound A), 2,4-trifluoromethyl-p-aniline (denoted as compound B for the convenience of subsequent description) and phthalic anhydride (denoted as compound C for the convenience of subsequent description).
  • the general structural formula adopted by the compound A is:
  • the general structural formula adopted by the compound B is:
  • the general structural formula adopted by the compound C is:
  • the specific ratio between the two can be but not limited to 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1 And 10:0 and so on.
  • the polyimide material involved in the present invention may be used to prepare the raw material for the precursor polyamide, which is only one of the compound B or the compound C, and both are not required. mixture.
  • it is preferable to include both the compound B and the compound C in the preparation raw materials, that is, the content of the compound B and the compound C is greater than 0 at the same time, for example, compound B: compound C a :b, where 0 ⁇ a ⁇ 10, 0 ⁇ b ⁇ 10.
  • Another aspect of the present invention is to provide a method for preparing the polyimide material of the present invention, which includes the following steps:
  • Step S1. Add compound A: 3,5-trifluoromethyl p-1,3-diether-diphthalic anhydride and compound B: 2,4-trifluoromethyl p-aniline in the raw materials to N , N-dimethylhexanamide and N-methylpyrrolidone mixture to form a first mixed solution, and then start stirring; in the preparation of the raw material compound C: phthalic anhydride is added to the above-mentioned stirring A second mixed solution is formed in a mixed solution, and it is continuously stirred for 24 to 96 hours at 20 to 40 degrees to make it fully dissolved;
  • Step S2 Perform suction filtration on the second mixed solution in a vacuum environment, vacuum the solution obtained after suction filtration for 0.8-1.5h to remove bubbles in the solution, and then remove all the extracted solution.
  • the solution is allowed to stand at room temperature for 2 to 4 hours to obtain a solution containing the precursor polyamic acid;
  • Step S3 subjecting the solution containing the precursor polyamic acid to dehydration and cyclization treatment to obtain the polyimide material related to the present invention.
  • another aspect of the present invention is to provide an application of the polyimide material related to the present invention, which is used to form a polyimide film layer disposed on a substrate, wherein the substrate is generally It is a glass substrate, but not limited to.
  • Another aspect of the present invention is to provide a method for preparing a polyimide film layer on a glass substrate using the polyimide material of the present invention, which includes the following steps:
  • Step S1 providing the precursor polyamic acid solution obtained by the preparation method of the polyimide material related to the present invention, and coating it on a glass substrate;
  • Step S2 H-VCD process is performed on the glass substrate at a temperature range of 110-130°C to remove 55-75% of the solvent in the polyamic acid solution coated thereon, and then the temperature is raised and the highest
  • a constant temperature process (Recipe) at a temperature in the range of 400 to 500°C causes the polyamic acid coated on the glass substrate to undergo a dehydration cyclization reaction, thereby crosslinking and curing, and finally obtains the resin formed on the glass substrate Polyimide film layer.
  • the constant temperature process for the polyamic acid is about 3 to 5 hours, that is, the crosslinking and curing process of the polyamic acid lasts for 3 to 5 hours, and the temperature rise rate involved is 4 hours. ⁇ 10°C, the highest temperature is in the range of 420°C ⁇ 500°C.
  • another aspect of the present invention is to provide an application of the polyimide material related to the present invention, which is used as a constituent material of a substrate layer on a PI substrate.
  • the PI substrate involved in the present invention can be used on various devices that require a substrate layer composed of a polyimide film layer, such as, but not limited to, optoelectronic devices.
  • another aspect of the present invention is to provide an application of the substrate layer related to the present invention, which is used on a display panel.
  • the display panel includes the substrate layer involved in the present invention, and a device function layer is provided on the substrate layer.
  • the display panel may be an OLED display panel, but is not limited.
  • a polyimide material related to the present invention uses a newly introduced 2,4-trifluoromethyl dianhydride with a benzene ring and a fluorine-containing pair Phenylenediamine, the simplest combination structure of p-phenylenediamine is used to design the molecular structure of the target polyimide material compound; wherein the fluorine-containing group introduced in the molecular structure design of the target compound can not only reduce The intermolecular force can also destroy the close packing of the polymer and reduce its crystallization performance, thereby effectively improving its permeability; on the other hand, it can also be used to adjust the rigid structure of the main chain.
  • diamine structures with different degrees of compactness are obtained, and the relationship between the thermal expansion coefficient and the molecular main chain structure of the target compound is obtained.
  • the correlation between the thermal expansion coefficient of the target compound and the rigid molecular chain structure not only the highly regular arrangement of the target compound itself can be realized, but also the coordinated arrangement of two diamine molecules can be promoted to make the molecular chain closer.
  • the more regular molecular chain structure of this target compound will make the material itself exhibit a relatively low CTE value in terms of CTE parameter performance.
  • the target compound material involved in the present invention selects dianhydrides containing fluorine and benzene rings as raw materials to make the final material to achieve good transparency, and improve its mechanical properties, which can make it better
  • the substrate layer for OLED but it needs to be clear that the polyimide material involved in this case is not limited to the substrate used for OLED, it can be used in a variety of suitable scene applications, as long as the performance of the target compound is obtained according to different raw material ratios. The parameters only need to meet the requirements of the scene application.
  • FIG. 1 is a schematic structural diagram of a PI substrate provided in an embodiment of the present invention
  • FIG. 2 is a schematic diagram of a constant temperature manufacturing process provided in an embodiment of the present invention.
  • FIG. 3 is a schematic diagram of a constant temperature manufacturing process provided in another embodiment of the present invention.
  • FIG. 4 is a schematic diagram of a constant temperature process provided in another embodiment of the present invention.
  • FIG. 5 is a schematic diagram of a constant temperature manufacturing process provided in another embodiment of the present invention.
  • Fig. 6 is a thermal expansion coefficient curve of different target compounds of the polyimide material related to the present invention obtained by different raw material ratios in another embodiment of the present invention.
  • FIG. 7 is a stress-strain curve of different target compounds of the polyimide material according to the present invention obtained from different raw material ratios shown in FIG. 6.
  • the present invention relates to a compound structure of a polyimide material and its preparation method, in order to avoid unnecessary repetition of description and clearer description, the preparation method will be mainly used for all aspects of the present invention.
  • the compound structure of the polyimide material is described in detail.
  • One embodiment of the present invention provides a method for preparing the polyimide material of the present invention, which includes the following steps:
  • Step S2 Perform suction filtration on the second mixed solution in a vacuum environment, and treat the solution obtained by suction filtration with a vacuum pump for about 1 hour to remove bubbles in the second mixed solution, and then remove the evacuated
  • the solution is allowed to stand at room temperature for 2 to 4 hours to further reduce the bubbles in it, until there are no bubbles visible to the naked eye, and then obtain a solution containing the precursor polyamic acid (wherein the precursor polyamic acid is denoted as compound D);
  • Step S3 Perform dehydration and cyclization treatment on the precursor polyamic acid solution to obtain the polyimide material target compound (denoted as compound E) related to the present invention.
  • a polyimide film layer (PI layer) on a glass substrate with the polyimide material of the present invention can be used to perform dehydration and cyclization of the precursor polyamic acid solution.
  • the process is described in further detail.
  • the precursor polyamic acid solution obtained in step S2 is spin-coated on a glass substrate 100 in the manner of a slit coater, and then the glass substrate is subjected to H-treatment at a temperature range of 110 to 130°C.
  • VCD process to remove about 70% of the solvent in the polyamic acid solution coated on it, and then heat it up and perform a constant temperature process (Recipe) with a maximum temperature in the range of 400-500°C, so that the glass substrate
  • Recipe constant temperature process
  • the polyamic acid coated on 100 undergoes dehydration and cyclization reaction to crosslink and solidify, and finally a polyimide film layer 12 formed on the glass substrate 10 is obtained.
  • the constant temperature process for the polyamic acid is about 3 to 5 hours, that is, the crosslinking and curing process of the polyamic acid lasts for 3 to 5 hours, and the temperature rise rate involved is 4 to 10°C.
  • the highest temperature is in the range of 420°C ⁇ 500°C.
  • the baking stage in the constant temperature process is divided into two ways: hard baking and soft baking. Hard baking means directly heating up to the highest temperature and keeping the temperature at a constant temperature for about 1 hour before cooling down; while soft baking is divided into 2 times and more than 2 times.
  • the constant temperature of the constant temperature platform of each constant temperature platform rises sequentially, that is, the constant temperature temperature of the second constant temperature platform is higher than the constant temperature temperature of the first constant temperature platform, and finally the temperature is lowered, so as to realize that the precursor polyamic acid is at a different constant temperature Stage cross-linking and solvent removal.
  • Figures 2 to 5 illustrate 4 different constant temperature platforms, but not limited to.
  • Figure 6 illustrates the thermal expansion coefficient curves of different compounds E obtained by the preparation schemes of the compound B and compound C in different proportions.
  • the ratio between the compound B and the compound C is closely related to the thermal expansion coefficient of the compound E that is finally produced.
  • the compound E selects the scheme with the ratio of compound B and compound C as (0:10) and (10:0), that is, from a single compound B or compound C and the compound
  • the specific curve shown in the figure is PI (10:0) and PI (0:10).
  • a single component has a greater influence on the thermal expansion coefficient of the target compound E formed. It shows that the ternary system has a better effect on reducing the thermal expansion coefficient of the final formed material, that is, it is preferable to include both the compound B and the compound C in the preparation raw materials.
  • FIG. 7 illustrates the stress-strain curve of the target compound E prepared under the six different raw material ratio schemes of the compound B and the compound C in the above example.
  • the elongation at break of the synthesized target compound E can be achieved above 15% under the above six different raw material ratio schemes.
  • This value indicates that the target compound E is in This parameter can meet the requirements of the OLED flexible substrate in this index.
  • the present invention relates to a polyimide material, which uses newly introduced 2,4-trifluoromethyl dianhydride with benzene ring and fluorine-containing p-phenylenediamine, the simplest combination structure of p-benzene Diamine carries out the molecular structure design of the target polyimide material compound; wherein the fluorine-containing group introduced in the molecular structure design of the target compound can not only reduce the intermolecular force, but also destroy the polymer Closely packed to reduce its crystallization performance, thereby effectively improving its permeability; on the other hand, it can also be used to adjust the rigid structure of the main chain.
  • diamine structures with different degrees of compactness are obtained, and the relationship between the thermal expansion coefficient and the molecular main chain structure of the target compound is obtained.
  • the correlation between the thermal expansion coefficient of the target compound and the rigid molecular chain structure not only the highly regular arrangement of the target compound itself can be realized, but also the coordinated arrangement of two diamine molecules can be promoted to make the molecular chain closer.
  • the more regular molecular chain structure of this target compound will make the material itself exhibit a relatively low CTE value in terms of CTE parameter performance.
  • the target compound material involved in the present invention selects dianhydrides containing fluorine and benzene rings as raw materials to make the final material to achieve good transparency, and improve its mechanical properties, which can make it better
  • the substrate layer for OLED display panels but it needs to be clear that the polyimide material involved in this case is not limited to the substrate used for OLED display panels. It can be used in various suitable scene applications, as long as the target compound is obtained according to different raw material ratios. The performance parameters can meet the requirements of the scene application.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

一种聚酰亚胺材料，其采用引入带有苯环的2,4-三氟甲基的二酐和含氟对苯二胺，再结合结构上最为简单的对苯二胺进行目标聚酰亚胺材料化合物的分子结构设计，使得设计得出的目标聚酰亚胺材料具有较低的CTE值性能参数。

Description

一种聚酰亚胺材料、制备方法及其应用
本申请要求于2019年09月24日提交中国专利局、申请号为201910902459.3、发明名称为“一种聚酰亚胺材料、制备方法及其应用”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
本申请涉及显示面板技术领域，尤其涉及一种聚酰亚胺材料、制备方法及其应用。
背景技术
已知，目前OLED面板、太阳能电池板等越来越多的新型光电器件正在朝着柔性、轻薄的方向发展。
其中柔性电子产品的出现有可能带来Human-Computer Interaction(HCI)的一场伟大变革。但是在这之前，仍然有众多技术障碍需要逐一攻克。器件的柔性与否，很大程度上要取决于所用的衬底材料。例如，在OLED领域，柔性衬底是业界已知的和蒸镀技术并列的两个难以攻克的核心之一。
其中传统的PI材料虽然是因为具有强刚性直链结构从而使其拥有了较低的热膨胀系数，但是这在另一方面往往也会带来机械性能、透过性能等方面的问题。目前业界对于这一块的研究正处于应用瓶颈状态，从2015年人们设想将PI材料作为柔性衬底材料开始，对PI的应用研究开始朝向：尽可能的降低热膨胀系数的同时，实现其良好的透过性及机械性能。
进一步的，PI材料作为热膨胀系数在百级以内与目前的玻璃、硅等无机材料基本实现了较小的数量级差距。但是作为柔性衬底材料，其上需要设置各种类型的功能层，这也就使得其不可避免的需要与各种类型的金属、Si等材料进行贴合，这期间就要求相互贴合材料间的CTE值相接近。
具体来讲，例如Cu的CTE值为18ppm/K左右，而Si的CTE值为3ppm/K左右，这两者间的CTE数值范围变化较大；而且，还需要贴合材料本身具有足够高的力学支撑强度和高绝缘性等参数指标。
技术问题
本发明的一个方面是提供一种聚酰亚胺材料，其通过引入全新的分子结构中含有氟和 苯环的二酐结构，在结合二胺结构，使得设计出的目标聚酰亚胺材料化合物，不仅可以实现自身的高规整排列还可以促进二胺分子的协同排列进而使得所在目标化合物分子链更紧密，实现分子链之间的紧密堆砌，进而通过具有更规整的分子链结构实现所在目标化合物材料的低CTE值性能参数。
技术解决方案
本发明采用的技术方案如下：
一种聚酰亚胺材料，其采用的分子结构通式为：
Figure PCTCN2019120216-appb-000001
进一步的，在不同实施方式中，其中本发明涉及的所述聚酰亚胺材料化合物是由其前驱体聚酰胺酸(polyamic acid，PAA)通过脱水环化处理而来，其中所述前驱体聚酰胺酸采用的结构通式为：
Figure PCTCN2019120216-appb-000002
进一步的，在不同实施方式中，其中所述聚酰胺酸采用的制备原料包括3,5-三氟甲基对1,3-二醚-二邻苯二甲酸酐(为便于后续描述，记为化合物A)、2,4-三氟甲基对苯胺(为便于后续描述，记为化合物B)和邻苯二甲酸酐(为便于后续描述，记为化合物C)。
进一步的，在不同实施方式中，其中所述化合物A采用的结构通式为：
Figure PCTCN2019120216-appb-000003
进一步的，在不同实施方式中，其中所述化合物B采用的结构通式为：
Figure PCTCN2019120216-appb-000004
进一步的，在不同实施方式中，其中所述化合物C采用的结构通式为：
Figure PCTCN2019120216-appb-000005
进一步的，在不同实施方式中，其中所述化合物A、化合物B和化合物C之间的摩尔比为化合物A＝化合物B+化合物C。
进一步的，在不同实施方式中，其中所述化合物B和化合物C之间的摩尔比a:b＝(0:10)～(10:0),其中0≤a≤10，0≤b≤10，a+b＝10。两者间的具体比例可以是但不限于0:10、1:9、2:8、3:7、4:6、5:5、6:4、7:3、8:2、9:1以及10:0等等。
也就是说，在一些情况下，本发明涉及的所述聚酰亚胺材料其前驱体聚酰氨酸的制备原料可以只是所述化合物B或是化合物C中的一种，而不需要两者的混合物。但在另一些情况下，所述制备原料中还是优选同时包括所述化合物B和化合物C，即所述化合物B和化合物C的含量是同时大于0的含量，例如，化合物B：化合物C＝a:b，其中0<a<10，0<b<10。
进一步的，本发明的又一方面是提供一种本发明涉及的所述聚酰亚胺材料的制备方法，包括以下步骤：
步骤S1、将制备原料中的化合物A：3,5-三氟甲基对1,3-二醚-二邻苯二甲酸酐、化合物B：2,4-三氟甲基对苯胺加入到N,N－二甲基己酰胺与N－甲基吡咯烷酮的混合物中形 成第一混合溶液，然后开始搅拌；在将制备原料中的化合物C：邻苯二甲酸酐加入到上述搅拌中的所述第一混合溶液中形成第二混合溶液，在20～40度下继续揽拌24～96h，使其充分溶解；
步骤S2、在真空环境下对所述第二混合溶液进行抽滤，将通过抽滤后得到的溶液真空抽气处理0.8～1.5h，除去所述溶液中的气泡，然后将抽气过后的所述溶液在室温下静置2～4h，进而得到含有前驱体聚酰胺酸的溶液；以及
步骤S3、对所述含有前驱体聚酰胺酸的溶液进行脱水环化处理，进而得到本发明涉及的所述聚酰亚胺材料。
进一步的，在不同实施方式中，在所述步骤S1中，其中所述N,N－二甲基乙酰胺胺与N-甲基吡咯烷酮的混合物之间的体积比为0.2～2。即DMAC/NMP＝v/v＝0.2～2。
进一步的，本发明的又一方面是提供一种本发明涉及的所述聚酰亚胺材料的应用，其为用于构成设置在一基板上的聚酰亚胺膜层，其中所述基板一般为玻璃基板，但不限于。
进一步的，本发明的又一方面是提供一种使用本发明涉及的所述聚酰亚胺材料在一玻璃基板上制备聚酰亚胺膜层的制备方法，包括以下步骤：
步骤S1、提供经由本发明涉及的所述聚酰亚胺材料制备方法获得的所述前驱体聚酰胺酸溶液，并将其涂布在一玻璃基板上；
步骤S2、在110～130℃温度范围下对所述玻璃基板进行H-VCD制程，以除去其上涂布的所述聚酰胺酸溶液中55～75％的溶剂，然后对其升温并进行最高温度在400～500℃范围下的恒温制程(Recipe)，使得所述玻璃基板上涂布的所述聚酰胺酸发生脱水环化反应从而交联固化，进而最终得到形成在所述玻璃基板上的聚酰亚胺膜层。
进一步的，在所述步骤S2中，其中对所述聚酰胺酸进行的恒温制程在3～5h左右，即所述聚酰胺酸的交联固化过程持续3～5h，其中涉及的升温速度为4～10℃，最高温度在420℃～500℃范围内。
进一步的，本发明的又一方面是提供一种本发明涉及的所述聚酰亚胺材料的应用，其为用作一种PI基板上的衬底层的构成材料。进一步的，本发明涉及的所述PI基板，可以用于各种需要由聚酰亚胺膜层构成的衬底层的器件上，例如，光电器件，但不限于。
进一步的，本发明的又一方面是提供一种本发明涉及的所述衬底层的应用，其为用于一种 显示面板上。其中所述显示面板包括本发明涉及的所述衬底层，所述衬底层上设置有器件功能层。具体来讲，所述显示面板可以是OLED显示面板，但不限于。
有益效果
相对于现有技术，本发明的有益效果是：本发明涉及的一种聚酰亚胺材料，其采用全新引入的带有苯环的2,4-三氟甲基的二酐和含氟对苯二胺，在结合结构上最为简单的对苯二胺进行目标聚酰亚胺材料化合物的分子结构设计；其中所述目标化合物分子结构设计中引入的含氟基团，一方面不仅可以减小分子间的作用力，同时还可以破坏聚合物的紧密堆积，降低其结晶性能，从而有效提高其透过性能；另一方面还可用于调节主链的刚性结构。
进一步的，通过实施制备原料中六种不同含量的二胺配比方案，获得了不同紧密程度的二胺结构，进而得出热膨胀系数与目标化合物分子主链结构的关系。这其中通过获知目标化合物的热膨胀系数与具有刚直性的分子链结构间的相关性，不仅可以实现目标化合物自身的高规整排列，还可以促进两个二胺分子的协同排列使得分子链更紧密，从而实现分子链之间的紧密堆砌，而这种目标化合物所具有的更规整的分子链结构，即会使其所在材料本身在CTE参数性能上表现出相对较低的CTE值。
综上所述，本发明涉及的所述目标化合物材料选用含氟和苯环的二酐作为制备原料，使得最终所在材料实现了良好的透明度，并且提高了其机械性能，可使得其能更好的用于OLED的衬底层。但需要明确的是，本案涉及的所述聚酰亚胺材料并不限于用于OLED的衬底，其可以用于各种适合的场景应用，只要其根据不同原料配比获得的目标化合物的性能参数符合场景应用要求即可。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明的一个实施方式中提供的一种PI基板的结构示意图；
图2为本发明的一个实施方式中提供的一种恒温制程的过程示意图；
图3为本发明的又一个实施方式中提供的一种恒温制程的过程示意图；
图4为本发明的又一个实施方式中提供的一种恒温制程的过程示意图；
图5为本发明的又一个实施方式中提供的一种恒温制程的过程示意图；
图6为本发明的又一个实施方式中，不同原料配比获得的不同本发明涉及的所述聚酰亚胺材料目标化合物的热膨胀系数曲线；以及
图7为图6所示的由不同原料配比获得的不同本发明涉及的所述聚酰亚胺材料目标化合物的应力应变曲线。
本发明的实施方式
以下将结合附图和实施例，对本发明涉及的一种聚酰亚胺材料、其制备方法及其应用的技术方案作进一步的详细描述。
其中由于本发明涉及了一种聚酰亚胺材料的化合物结构及其制备方法，为了避免不必要的重复描述，以及更为清晰的说明，以下将以所述制备方法为主对本发明涉及的所述聚酰亚胺材料的化合物结构进行细节说明。
其中本发明涉及的一个实施方式提供了一种制备本发明涉及的所述聚酰亚胺材料的方法，其包括以下步骤：
步骤S1、将制备原料中的化合物A：3,5-三氟甲基对1,3-二醚-二邻苯二甲酸酐、化合物B：2,4-三氟甲基对苯胺加入到N,N－二甲基己酰胺与N－甲基吡咯烷酮的混合物(DMAC/NMP＝v/v＝0.2～2)中形成一第一混合溶液，然后开始搅拌；在将原料中的化合物C：邻苯二甲酸酐加入到上述搅拌中的所述第一混合溶液中，在室温20～40度下继续揽拌24～96h，使其充分溶解进而形成一第二混合溶液；
步骤S2、在真空环境下对所述第二混合溶液进行抽滤，将通过抽滤得到的溶液用真空泵抽气处理1h左右，除去所述第二混合溶液中的气泡，然后将抽气过后的溶液在室温下静置2～4h使其中的气泡进一步减少，直到肉眼所见无气泡，进而得到一含有前驱体聚酰胺酸的溶液(其中所述前驱体聚酰胺酸记为化合物D)；
步骤S3、对所述前驱体聚酰胺酸溶液进行脱水环化处理，进而得到本发明涉及的所述聚酰亚胺材料目标化合物(记为化合物E)。
这其中，可以结合本发明涉及的所述聚酰亚胺材料在一玻璃基板上形成聚酰亚胺膜层(PI层)的过程，来对上述前驱体聚酰胺酸溶液进行脱水环化处理的过程做进一步的细节说明。
具体可以是，将所述步骤S2获得的所述前驱体聚酰胺酸溶液以slit coater的方式旋涂在一玻璃基板100上，然后在110～130℃温度范围下对所述玻璃基板进行H-VCD制程，以除去其上涂布的所述聚酰胺酸溶液中70％左右的溶剂，然后对其升温并进行最高温度在400～500℃范围下的恒温制程(Recipe)，使得所述玻璃基板100上涂布的所述聚酰胺酸发生脱水环化反应从而交联固化，进而最终得到形成在所述玻璃基板10上的聚酰亚胺膜层12，其最终结构图示请参阅图1所示。
这其中，对所述聚酰胺酸进行的恒温制程在3～5h左右，即所述聚酰胺酸的交联固化过程持续3～5h，其中涉及的升温速度为4～10℃，恒温过程中的最高温度在420℃～500℃范围内。进一步的，所述恒温过程中的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恒温1h左右后降温；而软烘则是分成2次及2次以上的恒温平台，每次恒温平台的恒温温度依次上升，即第二次恒温平台的恒温温度高于第一次恒温平台的恒温温度，最后再降温，从而实现所述前驱体聚酰胺酸在不同恒温阶段的交联和其中的溶剂去除。其中，请参阅图2～5所示，其图示了4种不同的恒温平台，但不限于。
进一步的，根据本发明的创作构思可知，其中作为所述前驱体聚酰胺酸制备原料中的所述化合物B和化合物C之间是存在一个配比的，通过不同的配比方案可以获知本案涉及的所述聚酰亚胺材料目标化合物的热膨胀系数与具有刚直性的分子链结构间的相关性。
具体来讲，请参阅图6所示，其图示了采用由不同配比的所述化合物B和化合物C的制备方案获得的不同所述化合物E的热膨胀系数曲线，从图中可以看出所述化合物B和化合物C配比关系与最终生成的所述化合物E的热膨胀系数存在较大的关系。
例如，所述化合物E在选用所述化合物B和化合物C的配比为(0：10)及(10：0)的方案时，即由单一的所述化合物B或是化合物C和所述化合物A合成所述目标化合物E时，具体如图中的PI(10:0)和PI(0:10)所示曲线，其单一组分对形成的目标化合物E的热膨胀系数的影响较大，这说明还是三元体系对降低最终形成材料的热膨胀系数具有较好的作用，即制备原料中优选同时包括所述化合物B和化合物C。其中当所述化合物B与化合物C的配比比例为5:5＝1的时候，具体如图中的PI(5:5)所示曲线，两者的协同作用最强，导致所述目标化合物E的直链的规整性更强，自由体积难以改变，从而实现了其低热膨胀系数。
进一步的，请参阅图7所示，其图示了上述举例中由6种不同所述化合物B和化合物C原料配比方案下制备得到的目标化合物E的应力应变曲线。如图7中所示，可以看出在上述这6种不同原料配比方案下，其合成的目标化合物E的断裂伸长率都能实现在15％以上，这一数值表明这些目标化合物E在这一参数上均能满足OLED柔性衬底在该指标上的要求。
如此可知，同时引入三元的体系一方面不仅有利于热膨胀系数性能的提升，另一个方面也有利于其机械性能，这进一步说明了规整性的直链对其交联点密度具有促进作用，从而实现更紧密的交联达到更好的机械性能。另外，还有一个关键因素就是其透过性参数，由于这一性能参数不便于图示展示，因此未有图示；但可以明确的是，所述化合物E的透过率参数是超过75％的，其符合当前业界所有柔性面板衬底，对于透过性的要求。
本发明涉及的一种聚酰亚胺材料，其采用全新引入的带有苯环的2,4-三氟甲基的二酐和含氟对苯二胺，在结合结构上最为简单的对苯二胺进行目标聚酰亚胺材料化合物的分子结构设计；其中所述目标化合物分子结构设计中引入的含氟基团，一方面不仅可以减小分子间的作用力，同时还可以破坏聚合物的紧密堆积，降低其结晶性能，从而有效提高其透过性能；另一方面还可用于调节主链的刚性结构。
进一步的，通过实施制备原料中六种不同含量的二胺配比方案，获得了不同紧密程度的二胺结构，进而得出热膨胀系数与目标化合物分子主链结构的关系。这其中通过获知目标化合物的热膨胀系数与具有刚直性的分子链结构间的相关性，不仅可以实现目标化合物自身的高规整排列，还可以促进两个二胺分子的协同排列使得分子链更紧密，从而实现分子链之间的紧密堆砌，而这种目标化合物所具有的更规整的分子链结构，即会使其所在材料本身在CTE参数性能上表现出相对较低的CTE值。
综上所述，本发明涉及的所述目标化合物材料选用含氟和苯环的二酐作为制备原料，使得最终所在材料实现了良好的透明度，并且提高了其机械性能，可使得其能更好的用于OLED显示面板的衬底层。但需要明确的是，本案涉及的所述聚酰亚胺材料并不限于用于OLED显示面板的衬底，其可以用于各种适合的场景应用，只要其根据不同原料配比获得的目标化合物的性能参数符合场景应用要求即可。
本发明的技术范围不仅仅局限于上述说明中的内容，本领域技术人员可以在不脱离本发明技术思想的前提下，对上述实施例进行多种变形和修改，而这些变形和修改均应当属于本发明的范围内。

Claims (9)

  1. 一种聚酰亚胺材料，其化合物采用的结构通式为：
    Figure PCTCN2019120216-appb-100001
  2. 根据权利要求1所述的聚酰亚胺材料，其中所述聚酰亚胺材料化合物是由其前驱体聚酰胺酸(polyamicacid，PAA)通过脱水环化处理而来，其中所述前驱体聚酰胺酸采用的结构通式为：
    Figure PCTCN2019120216-appb-100002
  3. 根据权利要求2所述的聚酰亚胺材料，其中所述聚酰胺酸采用的制备原料包括3,5-三氟甲基对1,3-二醚-二邻苯二甲酸酐(化合物A)、2,4-三氟甲基对苯胺(化合物B)和邻苯二甲酸酐(化合物C)。
  4. 根据权利要求3所述的聚酰亚胺材料，其中所述化合物A采用的结构通式为：
    Figure PCTCN2019120216-appb-100003
    其中所述化合物B采用的结构通式为：
    Figure PCTCN2019120216-appb-100004
  5. 根据权利要求3所述的聚酰亚胺材料，其中所述化合物A、化合物B和化合物C之间的摩尔比为化合物A＝化合物B+化合物C。
  6. 根据权利要求5所述的聚酰亚胺材料，其中所述化合物B和化合物C之间的摩尔比a:b＝(0:10)～(10:0),其中0≤a≤10，0≤b≤10，a+b＝10。
  7. 根据权利要求6所述的聚酰亚胺材料，其中所述化合物B和化合物C的摩尔比a:b中，其中0<a<10，0<b<10，a+b＝10。
  8. 一种制备根据权利要求1所述聚酰亚胺材料的制备方法，包括以下步骤：
    步骤S1、将制备原料中的化合物A：3,5-三氟甲基对1,3-二醚-二邻苯二甲酸酐、化合物B：2,4-三氟甲基对苯胺加入到N,N－二甲基己酰胺与N－甲基吡咯烷酮的混合物中形成第一混合溶液，然后开始搅拌；在将制备原料中的化合物C：邻苯二甲酸酐加入到上述搅拌中的所述第一混合溶液中形成第二混合溶液，在20～40度下继续揽拌24～96h，使其充分溶解；
    步骤S2、在真空环境下对所述第二混合溶液进行抽滤，将通过抽滤后得到的溶液真空抽气处理0.8～1.5h，除去所述溶液中的气泡，然后将抽气过后的所述溶液在室温下静置2～4h，进而得到含有前驱体聚酰胺酸的溶液；以及
    步骤S3、对所述含有前驱体聚酰胺酸的溶液进行脱水环化处理，进而得到本发明涉及的所述聚酰亚胺材料。
  9. 一种PI基板，其包括基板和其上设置的聚酰亚胺膜层，其中所述聚酰亚胺膜层选用的构成材料包括根据权利要求1所述的聚酰亚胺材料。
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