WO2021031924A1 - 含氟和Cardo结构的无色透明聚酰亚胺薄膜及其制备方法 - Google Patents

含氟和Cardo结构的无色透明聚酰亚胺薄膜及其制备方法 Download PDF

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WO2021031924A1
WO2021031924A1 PCT/CN2020/108384 CN2020108384W WO2021031924A1 WO 2021031924 A1 WO2021031924 A1 WO 2021031924A1 CN 2020108384 W CN2020108384 W CN 2020108384W WO 2021031924 A1 WO2021031924 A1 WO 2021031924A1
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chemical formula
polyimide film
polyamic acid
acid solution
diamine
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PCT/CN2020/108384
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English (en)
French (fr)
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江艳艳
王振中
任茜
张维
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深圳瑞华泰薄膜科技股份有限公司
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Publication of WO2021031924A1 publication Critical patent/WO2021031924A1/zh

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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
    • C08G73/1003—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
    • C08G73/1067—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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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

Definitions

  • the invention provides a polyamic acid solution and a transparent polyimide film prepared from the polyamic acid solution that can improve heat resistance.
  • polyimide Compared with other polymer materials, polyimide has better stability during high temperature processing. However, the traditional polyimide film is dark brown or yellow, which is formed because of the charge transfer complex (CTC) interaction between the aromatic rings in the polyimide main chain structure.
  • CTC charge transfer complex
  • linking groups such as thioketone ( —SO 2 ), hexafluoroisopropyl, ether (—O—) or side groups of large substituents capable of imparting larger free volume, or alicyclic structure.
  • the present invention introduces fluorine-containing substituents and Cardo structure into the polymer skeleton structure, and optimizes the ratio of these groups to prepare a transparent polyimide film with higher thermal stability.
  • the transparent polyimide film has high application value as an optical film in the fields of display substrates, liquid crystal displays (LCD) and organic light emitting diodes (OLED).
  • the object of the present invention is to provide a polyamic acid solution which is formed by copolymerization of tetracarboxylic dianhydride and diamine.
  • the repeating unit structure of the above polyamic acid contains at least one fluorine-containing substituent and a Cardo structure.
  • the polyamic acid solution is to make the diamine including the chemical formula 1 or the chemical formula 1 and the chemical formula 2 and the polymerization component of the tetracarboxylic dianhydride including the chemical formula 3, the chemical formula 4 or the chemical formula 3, the chemical formula 4 and the chemical formula 5 are carried out in an organic solvent Manufactured by reaction.
  • the diamine includes chemical formula 1 or a combination of chemical formula 1 and chemical formula 2;
  • the tetracarboxylic dianhydride includes a combination of Chemical Formula 3, Chemical Formula 4, or a combination of Chemical Formula 3, Chemical Formula 4, and Chemical Formula 5.
  • Q 1 , Q 2 , Q 3 and Q 4 are each independently selected from hydrogen, halogen atoms, such as —F, —Cl, —Br, —I or hydroxyl (—OH), thiol (—SH), nitro (—NO 2 ), C 1-10 alkyl, C 1-4 haloalkoxy, C 1-10 haloalkyl, cyano and C 6-20 aryl, as preferred, Q 1 , Q 2 , Q 3 and Q 4 may be a substituent selected from a halogen atom, a hydroxyl group, a halogenated alkyl group, an alkyl group, an aryl group, and a cyano group.
  • halogen atoms such as —F, —Cl, —Br, —I or hydroxyl (—OH), thiol (—SH), nitro (—NO 2 ), C 1-10 alkyl, C 1-4 haloalkoxy, C 1-10 haloalky
  • the halogen atom may be fluorine (-F), and the halogen alkyl group may be a C 1-10 fluoroalkyl group containing fluoromethyl, perfluoroethyl, trifluoromethyl, etc., wherein the alkyl group is from methyl, ethyl , Propyl, isopropyl, tert-butyl, pentyl and naphthyl. More preferably, the substituent may be a fluorine-containing fluorine atom-containing substituent.
  • Ar can be selected from any of the following groups:
  • the molar ratio of the total amount of diamine to the total amount of tetracarboxylic dianhydride is 1:0.98 to 1:1.1, preferably 1:1 to 1:1.05, and the reaction is continued under a nitrogen or argon atmosphere 4 ⁇ 48h, the reaction temperature is controlled at -20°C ⁇ 60°C.
  • the organic solvent used in the present invention can be selected from amide solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc) and dimethylsulfoxide (DMSO); Cyclic ester solvents such as ⁇ -valerolactone, ⁇ -butyrolactone and ⁇ -methyl- ⁇ -butyrolactone; phenol solvents, such as m-cresol and p-cresol; sulfolane, acetophenone, dimethyl sulfoxide And one or more of other solvents with low boiling point.
  • the solvent used in the present invention is not limited to the above-mentioned solvents.
  • the solid content of the polyamic acid solution is 10 to 40 wt%, preferably 15 to 35 wt% relative to the total amount of the polyamic acid and the solvent.
  • the diamine in the composition of the polyamic acid solution, is a combination of Chemical Formula 1 and Chemical Formula 2, and the molar percentage of Chemical Formula 1 is not less than 60%;
  • the mole percentage of the chemical formula 3 in the dianhydride is 10%-40%, the mole percentage of the chemical formula 4 is 30%-80%, and the mole percentage of the chemical formula 5 is 0-50%.
  • the diamine in the composition of the polyimide solution, is 60%-95% mol% of Chemical Formula 1 and 5%-40% mol% of Chemical Formula 2, and
  • the dianhydride is chemical formula 3 with a percentage content of 10%-40% and chemical formula 4 with a molar percentage content of 60%-90%.
  • the diamine is chemical formula 1
  • the dianhydride is chemical formula 3 with a molar percentage of 10%-30%, 30%-80% Chemical formula 4 with molar percentage content and Chemical formula 5 with molar percentage content of 5% to 50%.
  • Another object of the present invention is to provide a transparent polyimide film, which is made from the above polyamic acid solution.
  • the glass transition temperature (Tg) is not less than 360°C
  • the second measurement of the thermal expansion coefficient (CTE) in the range of 50 ⁇ 250°C is not more than 50ppm/°C
  • the birefringence is not more than 0.06
  • b* is not more than 5.
  • the yellowness index is not more than 8, and the modulus is not less than 4.0 Gpa; the transmittance of the polyimide film at 550 nm is not less than 88%, and the haze is not more than 0.5%.
  • the transparent polyimide film has a higher glass transition temperature (Tg) and a lower coefficient of thermal expansion (CTE). With excellent heat resistance and good optical properties, it can be used as a substrate for display or semiconductor fields.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polyimide film.
  • the specific steps can be the following methods: 1 Mix the polyamic acid solution with the imidization catalyst, and coat the mixture on On the substrate, heat in an oven to remove the solvent to form a pre-coated film, peel off the pre-coated film, and fix it on a steel support for imidization (dehydration and ring closure) by heat treatment, or cast the above-mentioned mixture on the glass
  • the polyimide film can be obtained directly by heat treatment to remove the solvent and imidize it;
  • 2It can also be directly coated on the substrate with the polyamic acid solution, and then the polyimide film is obtained in the same manner.
  • the polyamic acid solution can be mixed with the imidization catalyst and dehydrating agent, and then the polyimide film can be obtained in the same manner.
  • mode 1 is preferred.
  • the heat treatment conditions are as follows but not limited to this: the above-mentioned mixed liquid is dried in the range of 50°C to 180°C, preferably 80°C to 150°C, and then further heated at a maximum temperature of 300°C to 500°C. To complete imidization, the temperature is preferably 300°C to 400°C.
  • the heat treatment is performed in an air atmosphere or a nitrogen atmosphere, preferably in a nitrogen atmosphere.
  • the polyamic acid solution mixture may include an imidization catalyst, and the catalyst may be selected from imidazole compounds, benzimidazole compounds, quinolones, pyridine and isoquinoline compounds, etc. .
  • the imidization catalyst may be used alone, or may be used in combination of two or more types. Relative to the total mass of the polyamic acid polymer, the amount of the imidization catalyst is preferably 0.1-10 wt%, more preferably 0.9-7 wt%.
  • the thickness of the polyimide film is not particularly limited, but is preferably 5 to 250 ⁇ m, and more preferably 10 to 60 ⁇ m.
  • CBDA Cyclobutane-1,2,3,4-tetracarboxylic dianhydride
  • the film performance test method is as follows:
  • the light transmittance, b value, haze and yellowness index of the film in the embodiment of the present invention and the comparative example are all measured with an ultraviolet spectrophotometer (X-rite Ci7800), and the obtained values are all averaged.
  • the birefringence of the film in the embodiment of the present invention and the comparative example is measured using a prism coupler (Metricon 2010/M), the measurement wavelength is 637 nm, and TE (transverse electric wave) mode and TM (transverse magnetic wave) mode are used.
  • the glass transition temperature of the film in the examples and comparative examples of the present invention was measured using a dynamic mechanical analyzer (DMA850).
  • the test conditions are as follows: load is 0.05N, heating rate is 3°C/min, and under nitrogen atmosphere at 200-500 Measure in the temperature range of °C, and record the inflection point of the curve with the maximum value as the glass transition temperature.
  • the coefficient of thermal expansion (CTE) of the film in the examples of the present invention and the comparative example was measured twice using a thermomechanical analyzer (TMA 7100C) at a temperature of 50-250°C.
  • TMA 7100C thermomechanical analyzer
  • the test conditions are as follows: the load is 20mN, and the heating rate of the first test It is 10°C/min, and the heating rate for the second test is 5°C/min.
  • the film after heat treatment may have residual stress, but it can be completely eliminated after the first scan. Therefore, the second test value will be taken as the CTE measurement value in this manual.
  • the polyimide films of Examples 1 to 9 of the present invention have high transparency, and the glass transition temperature is above 360°C, even reaching close to 390°C.
  • the polyimide film of the invention has a coefficient of thermal expansion (CTE) of 50 ppm/°C or less, a modulus of 4.0 GPa or more, and a yellowness index less than 8.
  • CTE coefficient of thermal expansion
  • Comparative Example 1 to Comparative Example 4 in Table 2 show that the polyimide film incorporating the Cardo structure exhibits an increased glass transition temperature.
  • Examples 1 to 9 of Table 1 and Table 2 show that the polyimide film with a higher content of fluorinated substituents exhibits higher transmittance.
  • the polyimide film of the present invention can optimize the film performance by adjusting the content of fluorinated substituents and Cardo structure, so that the film has high heat resistance, transparency and high modulus at the same time.
  • the polyimide film of the present invention can optimize the film performance by adjusting the content of fluorinated substituents and Cardo structure, so that the film has high heat resistance, transparency and high modulus at the same time.

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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)
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Abstract

一种含氟取代基和Cardo结构的聚酰亚胺薄膜及其制备方法。该聚酰亚胺薄膜具有优异的耐热性、透明度和力学性能。所述透明聚酰亚胺薄膜的玻璃化转变温度(Tg)为360℃以上，热膨胀系数(CTE)为50ppm/℃以下，模量为4.0GPa以上，b*不大于5，黄度指数不大于8。该透明聚酰亚胺薄膜可用作显示基板或液晶显示器(LCD)、有机发光二极管(OLED)等领域的光学薄膜及其他领域的基材。

Description

[根据细则37.2由ISA制定的发明名称]　含氟和Cardo结构的无色透明聚酰亚胺薄膜及其制备方法 技术领域
本发明提供一种聚酰胺酸溶液及由所述聚酰胺酸溶液制备的可提高耐热性的透明聚酰亚胺薄膜。
背景技术
在过去几年中，玻璃是用作制造光电器件基材的第一选择。但目前光电器件的发展正趋向于柔性化，这就意味着玻璃会因其易碎的性质而难以适应这种新的趋势。此时，聚合材料将会是玻璃的良好替代品。众所周知，许多聚合材料都能够表现出如玻璃一般良好的光学性能及优异的柔韧性。但柔性基材因其在器件制造的过程中需经历高温加工的过程，柔性显示，包括OLED显示屏，往往需要在高温条件下制造例如，氧化物TFT和低温多晶硅(LTPS)的工艺温度通常在350℃以上，有时甚至达到500℃。因此，其应用除了需要良好的光学性能和柔韧性外，还需要具备一定的热稳定性和尺寸稳定性。
因此，研制出具有优良的耐热性能、光学透明性和力学性能的聚酰亚胺具有重要意义。
与其它聚合物材料相比，聚酰亚胺在高温处理过程中具有更优异的稳定性。但传统的聚酰亚胺薄膜是深棕色或黄色的，这是因为聚酰亚胺主链结构中的芳香环之间存在着电荷转移复合化(CTC)的相互作用而形成的。
在一些研究工作中，为了能使分子间或分子内电荷转移相互作用最小化以制造出无色透明的聚酰亚胺，研究者在分子的主链结构中引入了连接基团，例如硫酮(—SO 2)、六氟异丙基、醚(—O—)或能够赋予较大自由体积的大取代基侧基，或者脂环族结构。
然而，在大部分情况下，这些官能团的引入会大大牺牲薄膜的热稳定性，研制出高玻璃化转变温度的透明聚酰亚胺具有重要的作用。因此，本发明将含氟取代基和Cardo结构引入到聚合物骨架结构中，并通过优化这些基团的配比，以制备出具有较高热稳定性的透明聚酰亚胺薄膜。该透明聚酰亚胺薄膜作为显示基片、液晶显示器(LCD)和有机发光二极管(OLED)等领域的光学薄膜有很高的应用价值。
发明内容
本发明的目的是提供一种聚酰胺酸溶液，所述聚酰胺酸溶液是由四羧酸二酐和二胺共聚而成。上述聚酰胺酸的重复单元结构中至少含有一种含氟取代基和Cardo结构。
所述聚酰胺酸溶液是使包括化学式1或者化学式1和化学式2的二胺与包括化学式3、化学式4或者化学式3、化学式4和化学式5的四羧酸二酐的聚合成分在有机溶剂中进行反应而制造的。其中，所述二胺包括化学式1或者化学式1和化学式2的组合；
所述四羧酸二酐包括化学式3、化学式4的组合或者化学式3、化学式4和化学式5的组合。
Figure PCTCN2020108384-appb-000001
上述化学式2中，
Q 1、Q 2、Q 3和Q 4各自独立地选自氢、卤素原子，例如—F、—Cl、—Br、—I或羟基(—OH)、硫醇基(—SH)、硝基(—NO 2)、C 1-10烷基、C 1-4卤代烷氧基、C 1-10卤代烷基、氰基及C 6-20芳基，作为优选，Q 1、Q 2、Q 3和Q 4可以是选自卤素原子、羟基、卤代烷基、烷基、芳基和氰基的取代基。例如，卤素原子可以是氟(—F)，卤素烷基可以是含氟甲基、全氟乙基、三氟甲基等C 1-10的氟烷基，其中烷基从甲基、乙基、丙基、异丙基、叔丁基、戊基和萘基中选择。更优选地，所述取代基可以是含氟原子的氟基取代基。
Figure PCTCN2020108384-appb-000002
Figure PCTCN2020108384-appb-000003
上述化学式4中，Ar可以选自下述基团中的任意一种：
Figure PCTCN2020108384-appb-000004
Figure PCTCN2020108384-appb-000005
上述化学式4和化学式5中，
Q 5、Q 6和Q 7各自独立地选自单键、—O—、—S—、—SO 2—、—C(＝O)—、—C(＝O)O—、—C(＝O)NH—、亚苯基及它们的组合。
根据一实施例，所述二胺总量与四羧酸二酐总量的摩尔比为1:0.98～1:1.1，优选为1:1～1:1.05，于氮气或氩气氛围下持续反应4～48h，反应温度控制在-20℃～60℃。
本发明所用有机溶剂可选自N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)和二甲基亚砜(DMSO)等酰胺溶剂；γ-戊内酯、γ-丁内酯和α-甲基-γ-丁内酯等环酯溶剂；苯酚溶剂，如间甲苯酚和对甲苯酚；环丁砜、苯乙酮、二甲基亚砜及其他具有低沸点溶剂中的一种或多种。本发明所用溶剂不局限于上述几种溶剂。
相对于聚酰胺酸和溶剂的总量，聚酰胺酸溶液的固含量为10～40wt％，优选为15～35wt％。
在优选实施方案中，聚酰胺酸溶液的组成中，所述二胺是化学式1和化学式2的组合且其中化学式1的摩尔百分含量不小于60％；
所述二酐中化学式3的摩尔百分含量为10％～40％，化学式4的摩尔百分含量为30％～80％、化学式5的摩尔百分含量为0～50％。
在另一优选的实施方案中，聚酰亚胺溶液的组成中，所述二胺为60％～95％摩尔百分含量的化学式1和5％～40％摩尔百分含量的化学式2，并且所述二酐为10％～40％百分含量的化学式3和60％～90％摩尔百分含量的化学式4。
根据又一优选的实施方案中，聚酰亚胺溶液的组成中，所述二胺为化学式1，并且所述二酐为10％～30％摩尔百分含量的化学式3、30％～80％摩尔百分含量的化学式4以及5％～50％摩尔百分含量的化学式5。
本发明另一目的是提供一种透明聚酰亚胺薄膜，该聚酰亚胺薄膜是由上述聚酰胺酸溶液制得。其玻璃化转变温度(Tg)不低于360℃，热膨胀系数(CTE)在50～250℃范围内测量第二次的结果不大于50ppm/℃，双折射不大于0.06，b*不大于5，黄度指数不大于8，模量不低于4.0Gpa；所述聚酰亚胺薄膜在550nm处的透过率不小于88％，雾度不大于0.5％。该透明聚酰亚胺薄膜具有较高的玻璃化转变温度(Tg)和较低的热膨胀系数(CTE)。具有优异的耐热性和良好的光学性能，可作为基材用于显示或半导体领域。
本发明的又一目的是提供制备上述聚酰亚胺薄膜的方法，具体步骤可为以下几种方式：①将所述聚酰胺酸溶液与亚胺化催化剂混合，并将其混合液涂布在基板上，于烘箱内加热以去除溶剂形成预涂膜，将所述预涂膜剥离，并固定在钢支架上通过热处理进行亚胺化(脱水和环关闭)，或者将上述混合液浇铸在玻璃板上，直接通过热处理以去除溶剂并使其亚胺化从而获得聚酰亚胺薄膜；②也可以是将所述聚酰胺酸溶液直接涂布在基板上，然后以相同处理方式获得聚酰亚胺薄膜；③又或者是可以将所述聚酰胺酸溶液与亚胺化催化剂和脱水剂混合，然后以相同处理方式获得聚酰亚胺薄膜。本发明以方式①作为优选。其中，所述热处理条件如下但并不局限于此：将上述混合液于50℃～180℃范围内进行干燥，优选为80℃～150℃，然后在最高温度为300℃～500℃进一步加热以完成亚胺化，优选为300℃～400℃。通常，热处理是在空气气氛或氮气气氛中进行，优选为氮气气氛中进行。
根据本发明一实施例，所述聚酰胺酸溶液混合液可包含亚胺化催化剂，所述催化剂可选自咪唑类化合物、苯并咪唑类化合物、喹诺酮类化合物、吡啶和异喹啉类化合物等。其中，所述亚胺化催化剂可单独使用，或者可以以两种或多种类型的组合使用。相对聚酰胺酸聚合 物总质量而言，所述的亚胺化催化剂量优选为0.1～10wt％，更优选为0.9～7wt％。
此外，聚酰亚胺薄膜的厚度没有特殊限制，但优选为5～250μm，更优选为10～60μm。
具体实施方式
下面，将对本发明的实施例进行更详细地描述，但本发明的范围并不局限于以下实施例。
实施例中使用的聚合物组分如下所述，均为市售产品：
TFMB：2,2'-二(三氟甲基)二氨基联苯
BAFL：9,9'-双(4-氨基苯基)芴
FFDA：9,9'-双(4-氨基-3-氟苯基)芴
6FDA：六氟二酐
s-BPDA：3,3',4,4'-联苯四甲酸二酐
BPAF：9,9'-双(邻苯二甲酸酐)芴
CBDA：环丁烷-1,2,3,4-四羧酸二酐
异喹啉
薄膜性能测试方法如下所述：
透光率、b*、雾度、黄度指数
本发明实施例和对比例中薄膜的透光率、b值、雾度和黄度指数均使用紫外分光光度计(X-rite Ci7800)测量，所得数值均取平均值。
双折射
本发明实施例和对比例中薄膜的双折射使用棱镜耦合器(Metricon 2010/M)测量，测量波长为637nm，采用TE(横电波)模式和TM(横磁波)模式。
玻璃化转变温度(Tg)
本发明实施例和对比例中薄膜的玻璃化转变温度使用动态机械分析仪(DMA850)测量，其测试条件如下：负载为0.05N、加热速率为3℃/min、于氮气气氛下在200～500℃温度范围内进行测量，将具有最大值的曲线的拐点记录为玻璃化转变温度。
热膨胀系数(CTE)
本发明实施例和对比例中薄膜的热膨胀系数(CTE)使用热机械分析仪(TMA 7100C)于50～250℃范围下测量两次，其测试条件如下：负载为20mN，第一次测试升温速率为10℃/min，第二次测试升温速率为5℃/min。经热处理后的薄膜可能存在着残余应力，但经第一次扫描后可完全消除，因此，本说明书中将取第二次测试数值作为CTE测量值。
<实施例1>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入230.49g二甲基乙酰胺(DMAc)作为溶剂。随后加入25.618g(0.08mol)TFMB和6.969g(0.02mol)BAFL并匀速搅拌得到澄清的二胺溶液。然后，将8.885g(0.02mol)的6FDA和23.538g(0.08mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.25g(0.0252mol)，并搅拌1小时得到聚酰胺酸混合液。在进行脱气后，通过涂布机将聚酰胺酸混合液涂布在基板上并于100℃下干燥10min得到预涂膜，随后将其剥离，固定在钢支架上，从150℃至300℃加热30min，并在300℃下保持15min完成亚胺化，待其缓慢冷却后从支架上分离得到聚酰亚胺薄膜。
<实施例2>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入229.49g二甲基乙酰胺(DMAc)作为溶剂。随后加入28.821g(0.09mol)TFMB和3.484g(0.01mol)BAFL并匀速搅拌得到澄清的二胺溶液。然后，将8.885g(0.02mol)的6FDA和23.538g(0.08mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.24g(0.0251mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<实施例3>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入234.80g二甲基乙酰胺(DMAc)作为溶剂。随后加入28.821g(0.09mol)TFMB和3.484g(0.01mol)BAFL并匀速搅拌得到澄清的二胺溶液。然后，将13.327g(0.03mol)的6FDA和20.595g(0.07mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.31g(0.0256mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<实施例4>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入241.13g二甲基乙酰胺(DMAc)作为溶剂。随后加入25.618g(0.08mol)TFMB和6.969g(0.02mol)BAFL并匀速搅拌得到澄清的二胺溶液。然后，将17.770g(0.04mol)的6FDA和17.653g(0.06mol) 的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.40g(0.0263mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<实施例5>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入241.40g二甲基乙酰胺(DMAc)作为溶剂。随后加入28.821g(0.09mol)TFMB和3.844g(0.01mol)FFDA并匀速搅拌得到澄清的二胺溶液。然后，将17.770g(0.04mol)的6FDA和17.653g(0.06mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.40g(0.0263mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<实施例6>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入243.68g二甲基乙酰胺(DMAc)作为溶剂。随后加入25.618g(0.08mol)TFMB和7.688g(0.02mol)FFDA并匀速搅拌得到澄清的二胺溶液。然后，将17.770g(0.04mol)的6FDA和17.653g(0.06mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.44g(0.0266mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<实施例7>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入240.13g二甲基乙酰胺(DMAc)作为溶剂。随后加入32.023g(0.1mol)TFMB并匀速搅拌得到澄清的二胺溶液。然后，将9.169g(0.02mol)BPAF、8.885g(0.02mol)的6FDA和17.653g(0.06mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.39g(0.0262mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<实施例8>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入239.63g二甲基乙酰胺 (DMAc)作为溶剂。随后加入32.023g(0.1mol)TFMB并匀速搅拌得到澄清的二胺溶液。然后，将4.584g(0.01mol)BPAF、13.327g(0.03mol)的6FDA和17.653g(0.06mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.38g(0.0262mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<实施例9>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入238.36g二甲基乙酰胺(DMAc)作为溶剂。随后加入32.023g(0.1mol)TFMB并匀速搅拌得到澄清的二胺溶液。然后，将22.922g(0.05mol)的BPAF、4.442g(0.01mol)的6FDA和7.844g(0.04mol)CBDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.36g(0.026mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<对比例1>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入228.49g二甲基乙酰胺(DMAc)作为溶剂。随后加入32.023g(0.1mol)TFMB并匀速搅拌得到澄清的二胺溶液。然后，将8.885g(0.02mol)的6FDA和23.538g(0.08mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.22g(0.0249mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<对比例2>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入306.573g二甲基乙酰胺(DMAc)作为溶剂。随后加入32.023g(0.1mol)TFMB并匀速搅拌得到澄清的二胺溶液。然后，将17.77g(0.04mol)的6FDA和17.653g(0.06mol)的s-BPDA依次加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.37g(0.0261mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<对比例3>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入221.85g二甲基乙酰胺 (DMAc)作为溶剂。随后加入19.214g(0.06mol)TFMB和13.938g(0.04mol)BAFL并匀速搅拌得到澄清的二胺溶液。然后，将29.422g(0.1mol)的s-BPDA加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.13g(0.0242mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
<对比例4>
在装有搅拌器、氮气保护和温度控制器的500mL反应器中，加入271.04g二甲基乙酰胺(DMAc)作为溶剂。随后加入32.023g(0.1mol)TFMB匀速搅拌得到澄清的二胺溶液。然后，将44.424g(0.1mol)的6FDA加入到上述二胺溶液中。所得混合液于室温下反应12～24小时，得到固体含量为22wt％的聚酰胺酸溶液。
在聚酰胺酸溶液中加入异喹啉3.82g(0.0296mol)，并搅拌1小时得到聚酰胺酸混合液。随后将以与实施例1相同的方式形成聚酰亚胺薄膜。
表1.
Figure PCTCN2020108384-appb-000006
Figure PCTCN2020108384-appb-000007
表2.
Figure PCTCN2020108384-appb-000008
根据上述表1和表2的结果，本发明实施例1至实施例9的聚酰亚胺薄膜均具有较高的透明度，且玻璃化转变温度在360℃以上，甚至达到接近390℃，同时本发明的聚酰亚胺薄膜热膨胀系数(CTE)为50ppm/℃以下，模量为4.0GPa以上，黄度指数小于8。其中，表2的比较例1至比较例4显示引入Cardo结构的聚酰亚胺薄膜表现出提高的玻璃化转变温度。此外，表1和表2的实施例1至实施例9显示具有较高氟化取代基含量的聚酰亚胺薄膜表现出更高的透过率。通过实施例1、2和对比例1的比较可见，当在对比例1的基础上引入Cardo结构，可明显提高玻璃化转变温度。对比例3显示，当二胺中的Cardo结构比重过高，会导致薄膜的力学性能，及光学性能的下降(如黄度指数升高)。因此，本发明所述的聚酰亚胺薄膜可以通过调整氟化取代基和Cardo结构的含量对薄膜性能进行优化，从而使薄膜同时兼有较高的耐热性、透明性和高模量等特性，可用作显示基板或液晶显示器(LCD)、有机发光二极管(OLED)等领域的光学薄膜及其他领域基材。

Claims (14)

  1. 一种聚酰胺酸溶液，其特征在于，所述聚酰胺酸是由四羧酸二酐和二胺在有机溶剂中进行反应而制得，
    其中，所述二胺总量与四羧酸二酐总量的摩尔比为1:0.98～1:1.1；
    其中，所述二胺具有下述化学式1或者化学式1和化学式2两种单体组合的结构，所述四羧酸二酐具有选自化学式3和化学式4两种单体的组合或者化学式3，化学式4和化学式5三种单体组合的结构；
    当所述二胺是化学式1和化学式2的组合时，其中化学式1在该组合中的摩尔百分含量不小于60％；
    所述二酐中化学式3的摩尔百分含量为10％～40％、化学式4的摩尔百分含量为30％～80％、化学式5的摩尔百分含量为0～50％；
    [化学式1]
    Figure PCTCN2020108384-appb-100001
    [化学式2]
    Figure PCTCN2020108384-appb-100002
    上述化学式2中，
    Q 1、Q 2、Q 3和Q 4各自独立地选自氢、卤素原子、羟基、硫醇基、硝基、C 1-10烷基、C 1-4卤代烷氧基、C 1-10卤代烷基、氰基及C 6-20芳基；
    [化学式3]
    Figure PCTCN2020108384-appb-100003
    [化学式4]
    Figure PCTCN2020108384-appb-100004
    上述化学式4中，Ar可以选自下述基团中的任意一种：
    Figure PCTCN2020108384-appb-100005
    [化学式5]
    Figure PCTCN2020108384-appb-100006
    上述化学式4和化学式5中，
    Q 5、Q 6和Q 7各自独立地选自单键、—O—、—S—、—SO 2—、—C(＝O)—、—C(＝O)O—、—C(＝O)NH—、亚苯基及它们的组合。
  2. 根据权利要求1所述的聚酰胺酸溶液，其特征在于，所述二胺为60％～95％摩尔百分含量的化学式1和5％～40％摩尔百分含量的化学式2，并且所述二酐为10％～40％摩尔百分含量的化学式3和60％～90％摩尔百分含量的化学式4。
  3. 根据权利要求1所述的聚酰胺酸溶液，其特征在于，所述二胺为化学式1，并且所述二酐为10％～30％摩尔百分含量的化学式3、30％～80％摩尔百分含量的化学式4以及5％～50％ 摩尔百分含量的化学式5。
  4. 根据权利要求1所述的聚酰胺酸溶液，其特征在于，所述Q 1、Q 2、Q 3和Q 4是选自氢、氟或C 1-10的氟烷基的取代基，其中烷基从甲基、乙基、丙基、异丙基、叔丁基、戊基和萘基中选择。
  5. 根据权利要求1所述的聚酰胺酸溶液，其中，所述有机溶剂选自间甲苯酚、二甲基甲亚胺、N-甲基-2-吡咯烷酮、二甲基乙酰胺、二甲亚砜、丙酮中的一种或多种。
  6. 根据权利要求1所述的聚酰胺酸溶液，其特征在于聚酰胺酸溶液的固含量为15～35wt％。
  7. 一种透明聚酰亚胺薄膜，其特征在于，其由权利要求1所述的聚酰胺酸溶液制备。
  8. 根据权利要求7所述的聚酰亚胺薄膜，具有以下特征：
    其玻璃化转变温度(Tg)不低于360℃，热膨胀系数(CTE)在50～250℃范围内测量第二次的结果不大于50ppm/℃，双折射不大于0.06，b*不大于5，黄度指数不大于8，模量不低于4.0Gpa；所述聚酰亚胺薄膜在550nm处的透过率不小于88％，雾度不大于0.5％。
  9. 据权利要求7所述的聚酰亚胺薄膜，其制备方法包含下述步骤：
    将权利要求1所述的聚酰胺酸溶液中加入亚胺化催化剂并搅拌1～6小时混合均匀，得到混合液；
    然后将混合液涂布在基板上，干燥并去除溶剂，得到膜层，将该膜层亚胺化以制得透明聚酰亚胺薄膜。
  10. 据权利要求9所述的聚酰亚胺薄膜的制备方法，其特征在于，所述的膜层是在80～150℃的温度下加热5～60min制得。
  11. 据权利要求9所述的聚酰亚胺薄膜的制备方法，其特征在于，所述的透明聚酰亚胺薄膜是将所述膜层再次直接高温处理制得。
  12. 据权利要求9所述的聚酰亚胺薄膜的制备方法，其特征在于，所述的透明聚酰亚胺薄膜也可以通过将所述膜层从基板上分离下来并固定在钢支架上，然后于300～400℃的高温条件下再次加热10～60min制得。
  13. 据权利要求9所述的聚酰亚胺薄膜制备方法，其特征在于，所述亚胺化催化剂选自叔胺、咪唑类化合物、苯并咪唑类化合物、喹诺酮类化合物、吡啶类、异喹啉类化合物中的一种或多种。
  14. 权利要求7所述的无色透明聚酰亚胺薄膜作为基材应用于显示或半导体领域。
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