CN110606949B - Colorless transparent polyimide film containing fluorine and Cardo structure and preparation method thereof - Google Patents
Colorless transparent polyimide film containing fluorine and Cardo structure and preparation method thereof Download PDFInfo
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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
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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
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- 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
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- 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
Abstract
The invention provides a polyimide film containing a fluorine substituent and a Cardo structure and a preparation method thereof. The polyimide film has excellent heat resistance, transparency and mechanical properties. The transparent polyimide film has a glass transition temperature (Tg) of 360 ℃ or higher, a Coefficient of Thermal Expansion (CTE) of 50 ppm/DEG C or lower, a modulus of 4.0GPa or higher, b x not greater than 5, and a yellowness index of 8 or lower. The transparent polyimide film can be used as a display substrate or a base material in optical films in the fields of Liquid Crystal Displays (LCDs), Organic Light Emitting Diodes (OLEDs), and the like, and in other fields.
Description
Technical Field
The invention provides a polyamic acid solution and a transparent polyimide film prepared from the polyamic acid solution and capable of improving heat resistance.
Background
In the past few years, glass has been the first choice for use as a substrate for fabricating optoelectronic devices. However, the development of optoelectronic devices is tending to be flexible, which means that glass is difficult to adapt to this new trend due to its fragile nature. In this case, the polymeric material would be a good substitute for glass. It is well known that many polymeric materials can exhibit good optical properties, as well as excellent flexibility, as glass. However, flexible substrates, including OLED displays, are often subjected to high temperature processing during device fabrication, and the process temperature required to fabricate, for example, oxide TFTs and Low Temperature Polysilicon (LTPS) under high temperature conditions is typically above 350 c and sometimes even up to 500 c. Therefore, in addition to good optical properties and flexibility, some thermal and dimensional stability is required for its application.
Therefore, the development of polyimide with excellent heat resistance, optical transparency and mechanical properties is of great significance.
Polyimide has superior stability during high temperature processing compared to other polymer materials. However, the conventional polyimide film is dark brown or yellow due to the Charge Transfer Complex (CTC) interaction between aromatic rings in the main chain structure of polyimide.
In some research work, to enable intermolecular or intramolecular charge transfer interactions to be optimizedMiniaturization to produce colorless and transparent polyimides has led researchers to the introduction of linking groups, such as thione (-SO), into the backbone structure of the molecule2) Hexafluoroisopropyl, ether (-O-) or bulky pendant substituents capable of imparting large free volume, or cycloaliphatic structures.
However, in most cases, the introduction of these functional groups greatly sacrifices the thermal stability of the film, and the development of transparent polyimide with high glass transition temperature plays an important role. Therefore, the invention introduces the fluorine-containing substituent and the Cardo structure into the polymer skeleton structure, and prepares the transparent polyimide film with higher thermal stability by optimizing the proportion of the groups. The transparent polyimide film has high application value as an optical film in the fields of display substrates, Liquid Crystal Displays (LCDs), Organic Light Emitting Diodes (OLEDs) and the like.
Disclosure of Invention
The invention aims to provide a polyamic acid solution which is prepared by copolymerizing tetracarboxylic dianhydride and diamine. The repeat unit structure of the polyamic acid contains at least one fluorine-containing substituent and a Cardo structure.
The polyamic acid solution is manufactured by reacting a diamine including chemical formula 1 or chemical formula 1 and chemical formula 2 with a polymerization component including tetracarboxylic dianhydride of chemical formula 3, chemical formula 4 or chemical formula 3, chemical formula 4 and chemical formula 5 in an organic solvent. Wherein 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.
[ chemical formula 1]
[ chemical formula 2]
In the chemical formula 2 described above, the,
Q1、Q2、Q3and Q4Each independently of the others, selected from hydrogen, halogen atoms, e.g. -F, — Cl, — Br, — I or hydroxy (-OH), thiol (-SH), nitro (-NO)2)、C1-10Alkyl radical, C1-4Haloalkoxy, C1-10Haloalkyl, cyano and C6-20Aryl, preferably, Q1、Q2、Q3And Q4May be a substituent selected from the group consisting of a halogen atom, a hydroxyl group, a haloalkyl group, an alkyl group, an aryl group and a cyano group. For example, the halogen atom may be fluorine (-F), and the haloalkyl group may be a C group such as a fluoromethyl group, perfluoroethyl group, trifluoromethyl group, etc1-10Wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl and naphthyl. More preferably, the substituent may be a fluoro substituent containing a fluorine atom.
[ chemical formula 3]
[ chemical formula 4]
In the above chemical formula 4, Ar may be selected from any one of the following groups:
[ chemical formula 5]
In the above-described chemical formulas 4 and 5,
Q5、Q6and Q7Each independently selected from the group consisting of a single bond, — O-, -S-, -SO2- (O) -, -C (═ O) O-, -C (═ O) NH-, phenylene, and combinations thereof.
According to one embodiment, the molar ratio of the total amount of diamine to the total amount of tetracarboxylic dianhydride is 1: 0.98-1: 1.1, preferably 1: 1-1: 1.05, and the reaction is continued for 4-48 hours in a nitrogen or argon atmosphere, and the reaction temperature is controlled at-20 ℃ to 60 ℃.
The organic solvent used in the present invention may be selected from amide solvents such as N-methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc), and Dimethylsulfoxide (DMSO); cyclic ester solvents such as γ -valerolactone, γ -butyrolactone and α -methyl- γ -butyrolactone; phenol solvents such as m-cresol and p-cresol; one or more of sulfolane, acetophenone, dimethyl sulfoxide and other solvents having a 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 35wt%, with respect to the total amount of the polyamic acid and the solvent.
In a preferred embodiment, in the composition of the polyamic acid solution, the diamine is a combination of chemical formula 1 and chemical formula 2 and wherein the mole percentage content of chemical formula 1 is not less than 60%;
the dianhydride comprises 10-40 mol% of chemical formula 3, 30-80 mol% of chemical formula 4 and 0-50 mol% of chemical formula 5.
In another preferred embodiment, the composition of the polyimide solution is such that the diamine is 60 to 95% by mole of formula 1 and 5 to 40% by mole of formula 2, and the dianhydride is 10 to 40% by mole of formula 3 and 60 to 90% by mole of formula 4.
According to still another preferred embodiment, the composition of the polyimide solution is such that the diamine is of formula 1 and the dianhydride is of formula 3 in a molar percentage of 10% to 30%, of formula 4 in a molar percentage of 30% to 80%, and of formula 5 in a molar percentage of 5% to 50%.
The invention also aims to provide a transparent polyimide film, which is prepared from the polyamic acid solution. The glass transition temperature (Tg) is not lower than 360 ℃, the second measurement result of the Coefficient of Thermal Expansion (CTE) in the range of 50-250 ℃ is not higher than 50 ppm/DEG C, the birefringence is not higher than 0.06, b is not higher than 5, the yellowness index is not higher than 8, and the modulus is not lower than 4.0 Gpa; the transmittance of the polyimide film at 550nm is not less than 88%, and the haze is not more than 0.5%. The transparent polyimide film has a relatively high glass transition temperature (Tg) and a relatively low Coefficient of Thermal Expansion (CTE). Has excellent heat resistance and good optical performance, and can be used as a base material in the display or semiconductor field.
The invention also aims to provide a method for preparing the polyimide film, which can be implemented by the following specific steps: mixing the polyamic acid solution with an imidization catalyst, coating the mixed solution on a substrate, heating in an oven to remove a solvent to form a pre-coated film, peeling the pre-coated film, fixing the pre-coated film on a steel support, and imidizing (dehydrating and ring closing) through heat treatment, or casting the mixed solution on a glass plate, directly removing the solvent through heat treatment and imidizing the mixed solution to obtain a polyimide film; or directly coating the polyamic acid solution on a substrate, and then obtaining a polyimide film in the same processing mode; and thirdly, or mixing the polyamic acid solution with an imidization catalyst and a dehydrating agent, and then obtaining the polyimide film in the same processing mode. The present invention is preferably (i). Wherein, the heat treatment conditions are as follows but not limited thereto: the mixture is dried at a temperature in the range of 50 ℃ to 180 ℃, preferably 80 ℃ to 150 ℃, and then further heated at a maximum temperature of 300 ℃ to 500 ℃ to complete imidization, preferably 300 ℃ to 400 ℃. The heat treatment is usually carried out in an air atmosphere or a nitrogen atmosphere, and preferably in a nitrogen atmosphere.
According to an embodiment of the present invention, the polyamic acid solution mixture solution may include an imidization catalyst, and the catalyst may be selected from imidazole compounds, benzimidazole compounds, quinolone compounds, pyridine compounds, isoquinoline compounds, and the like. Among them, the imidization catalyst may be used alone, or may be used in combination of two or more types. The amount of the imidization catalyst is preferably 0.1 to 10 wt%, and more preferably 0.9 to 7 wt%, based on the total mass of the polyamic acid polymer.
The thickness of the polyimide film is not particularly limited, but is preferably 5 to 250 μm, and more preferably 10 to 60 μm.
Detailed Description
Hereinafter, examples of the present invention will be described in more detail, but the scope of the present invention is not limited to the following examples.
The polymer components used in the examples are as follows, all commercially available products:
TFMB: 2,2' -bis (trifluoromethyl) diaminobiphenyl
BAFL: 9,9' -bis (4-aminophenyl) fluorene
FFDA: 9,9' -bis (4-amino-3-fluorophenyl) fluorene
6 FDA: hexafluoro dianhydride
s-BPDA: 3,3',4,4' -Biphenyltetracarboxylic dianhydride
BPAF: 9,9' -bis (phthalic anhydride) fluorene
CBDA: cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride
Isoquinoline derivatives
The film performance test method is as follows:
transmittance, b, haze, yellowness index
The light transmittance, b-value, haze and yellowness index of the films of the examples and comparative examples of the present invention were measured using an ultraviolet spectrophotometer (X-rite Ci7800), and the obtained values were averaged.
Double refraction
The birefringence of the films in the examples of the present invention and the comparative examples was measured using a prism coupler (Metricon 2010/M), with a measurement wavelength of 637nm, using a TE (transverse electric wave) mode and a TM (transverse magnetic wave) mode.
Glass transition temperature (Tg)
The glass transition temperatures of the films in the examples and comparative examples of the present invention were measured using a dynamic mechanical analyzer (DMA850) under the following test conditions: the load was 0.05N, the heating rate was 3 ℃/min, the measurement was performed at a temperature range of 200 to 500 ℃ under a nitrogen atmosphere, and the inflection point of the curve having the maximum value was recorded as the glass transition temperature.
Coefficient of Thermal Expansion (CTE)
The Coefficient of Thermal Expansion (CTE) of the films in the examples and comparative examples of the present invention was measured twice using a thermomechanical analyzer (TMA 7100C) at a temperature ranging from 50 to 250 ℃, under the following test conditions: the load is 20mN, the first test heating rate is 10 ℃/min, and the second test heating rate is 5 ℃/min. The film after heat treatment may have residual stress, but it is completely eliminated after the first scan, and therefore the second test value is taken as the CTE measurement in this specification.
< example 1>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 230.49g of dimethylacetamide (DMAc) was added as a solvent. 25.618g (0.08mol) of TFMB and 6.969g (0.02mol) of BAFL were then added and stirred at a constant speed to give a clear diamine solution. Then, 8.885g (0.02mol) of 6FDA and 23.538g (0.08mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.25g (0.0252mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. After degassing, the polyamic acid mixture was coated on a substrate by a coater and dried at 100 ℃ for 10min to obtain a pre-coated film, which was then peeled off, fixed on a steel support, heated from 150 ℃ to 300 ℃ for 30min, and kept at 300 ℃ for 15min to complete imidization, and after it was slowly cooled, it was separated from the support to obtain a polyimide film.
< example 2>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 229.49g of dimethylacetamide (DMAc) was added as a solvent. 28.821g (0.09mol) of TFMB and 3.484g (0.01mol) of BAFL were then added and stirred at a constant speed to give a clear diamine solution. Then, 8.885g (0.02mol) of 6FDA and 23.538g (0.08mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.24g (0.0251mol) of isoquinoline, and stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< example 3>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 234.80g of dimethylacetamide (DMAc) was added as a solvent. 28.821g (0.09mol) of TFMB and 3.484g (0.01mol) of BAFL were then added and stirred at a constant speed to give a clear diamine solution. Then, 13.327g (0.03mol) of 6FDA and 20.595g (0.07mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.31g (0.0256mol) of isoquinoline, and stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< example 4>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 241.13g of dimethylacetamide (DMAc) was added as a solvent. 25.618g (0.08mol) of TFMB and 6.969g (0.02mol) of BAFL were then added and stirred at a constant speed to give a clear diamine solution. Then, 17.770g (0.04mol) of 6FDA and 17.653g (0.06mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.40g (0.0263mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< example 5>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 241.40g of dimethylacetamide (DMAc) was added as a solvent. 28.821g (0.09mol) of TFMB and 3.844g (0.01mol) of FFDA were then added and stirred at a constant speed to give a clear diamine solution. Then, 17.770g (0.04mol) of 6FDA and 17.653g (0.06mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.40g (0.0263mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< example 6>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 243.68g of dimethylacetamide (DMAc) was added as a solvent. 25.618g (0.08mol) of TFMB and 7.688g (0.02mol) of FFDA were then added and stirred at a constant speed to give a clear diamine solution. Then, 17.770g (0.04mol) of 6FDA and 17.653g (0.06mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.44g (0.0266mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< example 7>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 240.13g of dimethylacetamide (DMAc) was added as a solvent. 32.023g (0.1mol) of TFMB were then added and stirred at a constant speed to give a clear diamine solution. Then, 9.169g (0.02mol) of BPAF, 8.885g (0.02mol) of 6FDA and 17.653g (0.06mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.39g (0.0262mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< example 8>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 239.63g of dimethylacetamide (DMAc) was added as a solvent. 32.023g (0.1mol) of TFMB were then added and stirred at a constant speed to give a clear diamine solution. Then, 4.584g (0.01mol) of BPAF, 13.327g (0.03mol) of 6FDA and 17.653g (0.06mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.38g (0.0262mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< example 9>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 238.36g of dimethylacetamide (DMAc) was added as a solvent. 32.023g (0.1mol) of TFMB were then added and stirred at a constant speed to give a clear diamine solution. Then, 22.922g (0.05mol) of BPAF, 4.442g (0.01mol) of 6FDA and 7.844g (0.04mol) of CBDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.36g (0.026mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< comparative example 1>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 228.49g of dimethylacetamide (DMAc) was added as a solvent. 32.023g (0.1mol) of TFMB were then added and stirred at a constant speed to give a clear diamine solution. Then, 8.885g (0.02mol) of 6FDA and 23.538g (0.08mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.22g (0.0249mol) of isoquinoline, and stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< comparative example 2>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 306.573g of dimethylacetamide (DMAc) was added as a solvent. 32.023g (0.1mol) of TFMB were then added and stirred at a constant speed to give a clear diamine solution. Then, 17.77g (0.04mol) of 6FDA and 17.653g (0.06mol) of s-BPDA were added to the above diamine solution in this order. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.37g (0.0261mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< comparative example 3>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 221.85g of dimethylacetamide (DMAc) was added as a solvent. 19.214g (0.06mol) of TFMB and 13.938g (0.04mol) of BAFL were then added and stirred at a constant speed to give a clear diamine solution. 29.422g (0.1mol) of s-BPDA were then added to the diamine solution. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.13g (0.0242mol) of isoquinoline, and the mixture was stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
< comparative example 4>
In a 500mL reactor equipped with a stirrer, nitrogen blanket and temperature controller, 271.04g of dimethylacetamide (DMAc) was added as a solvent. 32.023g (0.1mol) of TFMB were then added and stirred at a constant speed to give a clear diamine solution. Then, 44.424g (0.1mol) of 6FDA was added to the above diamine solution. And reacting the obtained mixed solution at room temperature for 12-24 hours to obtain a polyamic acid solution with the solid content of 22 wt%.
To the polyamic acid solution was added 3.82g (0.0296mol) of isoquinoline, and stirred for 1 hour to obtain a polyamic acid mixture. A polyimide film was then formed in the same manner as in example 1.
TABLE 1
TABLE 2
According to the results of the above tables 1 and 2, the polyimide films of examples 1 to 9 of the present invention all had high transparency and glass transition temperature of 360 ℃ or more, even up to nearly 390 ℃, while the Coefficient of Thermal Expansion (CTE) of the polyimide film of the present invention was 50 ppm/c or less, modulus was 4.0GPa or more, and yellowness index was less than 8. Among them, comparative examples 1 to 4 of table 2 show that the polyimide film introduced with the Cardo structure exhibits an increased glass transition temperature. In addition, examples 1 to 9 of tables 1 and 2 show that the polyimide films having higher fluorinated substituent contents exhibit higher transmittance. As can be seen from comparison of examples 1 and 2 with comparative example 1, when a Cardo structure is introduced on the basis of comparative example 1, the glass transition temperature can be significantly increased. Comparative example 3 shows that when the Cardo structure specific gravity in the diamine is too high, it results in a decrease in the mechanical properties of the film, as well as in the optical properties (e.g., an increase in the yellowness index). Therefore, the polyimide film disclosed by the invention can optimize the film performance by adjusting the content of the fluorinated substituent and the Cardo structure, so that the film has the characteristics of high heat resistance, transparency, high modulus and the like, and can be used as a display substrate or an optical film in the fields of Liquid Crystal Displays (LCDs), Organic Light Emitting Diodes (OLEDs) and the like and a substrate in other fields.
Claims (12)
1. A polyamic acid solution is characterized in that the polyamic acid is prepared by the reaction of tetracarboxylic dianhydride and diamine in an organic solvent,
wherein the molar ratio of the total amount of diamine to the total amount of tetracarboxylic dianhydride is 1: 0.98-1: 1.1;
wherein the diamine has a structure of the following chemical formula 1 or a combination of two monomers of chemical formula 1 and chemical formula 2, and the tetracarboxylic dianhydride has a structure selected from a combination of two monomers of chemical formula 3 and chemical formula 4 or a combination of three monomers of chemical formula 3, chemical formula 4 and chemical formula 5;
when the diamine accounts for 60-95 mol% of the chemical formula 1 and 5-40 mol% of the chemical formula 2, the tetracarboxylic dianhydride accounts for 10-40 mol% of the chemical formula 3 and 60-90 mol% of the chemical formula 4;
when the diamine is a chemical formula 1, the tetracarboxylic dianhydride is 10-30% of a chemical formula 3, 30-80% of a chemical formula 4 and 5-50% of a chemical formula 5 in mol percentage;
[ chemical formula 1]
[ chemical formula 2]
In the chemical formula 2 described above, the,
Q1、Q2、Q3and Q4Each independently selected from hydrogen, halogen atom, hydroxyl, thiol, nitro, and C1-10Alkyl radical, C1-4Haloalkoxy, C1-10Haloalkyl, cyano and C6-20An aryl group;
[ chemical formula 3]
[ chemical formula 4]
In the above chemical formula 4, Ar may be selected from any one of the following groups:
[ chemical formula 5]
In the above-described chemical formulas 4 and 5,
Q5、Q6and Q7Each independently selected from the group consisting of a single bond, — O-, -S-, -SO2-, -C (= O) -, -C (= O) O-, -C (= O) NH-, phenylene, and combinations thereof.
2. The polyamic acid solution according to claim 1, wherein Q is1、Q2、Q3And Q4Is selected from hydrogen, fluorine or C1-10Wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl and naphthyl.
3. The polyamic acid solution according to claim 1, wherein said organic solvent is selected from one or more of m-cresol, dimethyl methyl imine, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone.
4. The polyamic acid solution according to claim 1, wherein the polyamic acid solution has a solid content of 15 to 35 wt%.
5. A transparent polyimide film produced from the polyamic acid solution according to claim 1.
6. The polyimide film according to claim 5, having the following features:
the glass transition temperature (Tg) of the high-strength high-modulus thermoplastic elastomer is not lower than 360 ℃, the second measurement result of the Coefficient of Thermal Expansion (CTE) in the range of 50-250 ℃ is not more than 50 ppm/DEG 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 lower than 4.0 Gpa; the transmittance of the polyimide film at 550nm is not less than 88%, and the haze is not more than 0.5%.
7. The polyimide film according to claim 5, which is prepared by a method comprising the steps of:
adding an imidization catalyst into the polyamic acid solution of claim 1, stirring for 1-6 hours, and uniformly mixing to obtain a mixed solution;
and then coating the mixed solution on a substrate, drying and removing the solvent to obtain a film layer, and imidizing the film layer to obtain the transparent polyimide film.
8. The polyimide film according to claim 7, wherein the film is prepared by heating at 80-150 ℃ for 5-60 min.
9. The polyimide film according to claim 7, wherein the transparent polyimide film is obtained by directly subjecting the film layer to a high temperature treatment again.
10. The polyimide film according to claim 7, wherein the transparent polyimide film is prepared by separating the film layer from the substrate, fixing the film layer on a steel support, and then heating the film layer again at 300-400 ℃ for 10-60 min.
11. The polyimide film according to claim 7, wherein the imidization catalyst is one or more selected from the group consisting of tertiary amines, imidazoles, benzimidazoles, quinolones, pyridines, and isoquinolines.
12. The transparent polyimide film according to claim 5 is used as a substrate for display or semiconductor applications.
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| KR102489446B1 (en) * | 2020-11-30 | 2023-01-19 | 주식회사 넥스플렉스 | Composition for manufacturing polyimide film and polyimide film for flexible metal clad laminate manufactured using the same |
| CN112708132B (en) * | 2020-11-30 | 2022-05-13 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film containing benzimidazole structure and preparation method thereof |
| KR20220167506A (en) * | 2021-06-14 | 2022-12-21 | 에스케이이노베이션 주식회사 | Polyimide based film and film for cover window and display device comprising the same |
| KR20220168256A (en) * | 2021-06-16 | 2022-12-23 | 에스케이이노베이션 주식회사 | Composition for forming polyimide film for cover window, a process for preparing same and uses thereof |
| WO2023200025A1 (en) * | 2022-04-13 | 2023-10-19 | 주식회사 넥스플렉스 | Composition for producing polyimide film and polyimide film for flexible metal clad laminate produced using same |
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| KR101870341B1 (en) * | 2013-12-26 | 2018-06-22 | 코오롱인더스트리 주식회사 | Colorless Polyamide―imide Resin and Film Thereof |
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