CN106947080B - Composition for preparing polyimide film, preparation method thereof and preparation method of polyimide film using composition - Google Patents

Composition for preparing polyimide film, preparation method thereof and preparation method of polyimide film using composition Download PDF

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CN106947080B
CN106947080B CN201611223753.4A CN201611223753A CN106947080B CN 106947080 B CN106947080 B CN 106947080B CN 201611223753 A CN201611223753 A CN 201611223753A CN 106947080 B CN106947080 B CN 106947080B
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bis
anhydride
polyamic acid
dianhydride
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CN106947080A (en
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车荣哲
朴势周
安民石
李承埈
边滋勋
洪宇成
朴圣然
郑载勋
裴珉英
梁奇锡
李相准
金东敏
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Dongjin Semichem Co Ltd
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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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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

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  • Manufacturing & Machinery (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

The present invention relates to a polyimide precursor, a method for preparing the same, and a method for preparing a polyimide film using the polyimide precursor.

Description

Composition for preparing polyimide film, preparation method thereof and preparation method of polyimide film using composition
Technical Field
The present invention relates to a composition for producing a polyimide film containing a polyimide precursor, a method for producing the same, and a method for producing a polyimide film using the polyimide precursor.
Background
Polyimide raw materials are excellent in heat resistance and chemical resistance, and are highly likely to be used as a substrate for flexible displays.
Polyimide substrate raw materials are generally prepared into a sheet type by a high-temperature thermal imide reaction after a polyamide acid (PAA) is coated on a glass slide (carrier glass) using an applicator or a flat coater. However, the throughput of the curing process (i.e., the thermal imidization process) that can be performed in a convection oven is limited by a batch type process rather than a continuous process, and a long process time is required for a high temperature process of 400 ℃.
In order to increase the process speed, a coated substrate is put into a convection oven at a high temperature of 120 ℃ or higher, which is not completely cooled by the oven, to perform thermal imidization, depending on the capacity of the curing process (CAPA). In this case, the solvent rapidly volatilizes, and thus the leveling (leveling) property of the film surface is reduced. Thus, many related studies are being conducted in order to improve such problems using a crosslinking agent (korean patent No. 10-0889910).
Disclosure of Invention
The present invention has been made to solve the problems occurring in the prior art described above, and has been accomplished by the present invention by improving the surface characteristics of a polyimide film even if imidization is performed at a high temperature using a polyimide precursor containing a specific content of a crosslinking agent.
An embodiment of the present invention provides a method for preparing a polyimide precursor, including: a step of adding an anhydride (anhydride) monomer to a polymerization solvent containing a diamine monomer to perform a reaction; a step of synthesizing a polyamic acid by adding a blocking agent (end capping agent) to the reaction solution and then reacting the resultant; and a step of adding a crosslinking agent to the polyamic acid to mix the polyamic acid and the crosslinking agent.
Another embodiment of the present invention provides a method for preparing a polyimide film, including: a step of adding an anhydride monomer to a polymerization solvent containing a diamine monomer to perform a reaction; a step of synthesizing a polyamic acid by adding a blocking agent to the reaction solution and then reacting the resultant solution; a step of adding a crosslinking agent to the polyamic acid and mixing the same; a step of applying a composition containing a polyamic acid to which the above-mentioned crosslinking agent is added to a support; and a step of thermally imidizing the polyimide precursor coated on the support at a temperature of 100 ℃ or higher.
The polyimide precursor of the present invention is formed by adding a specific amount of a crosslinking agent to a polyamic acid, and can improve the surface properties of a polyimide film even when imidized at a high temperature. In particular, the surface leveling (leveling) property of the polyimide film can be improved, and the transmittance loss can be reduced.
Drawings
Fig. 1 is an image of a polyimide film according to an embodiment of the present invention.
Fig. 2 is an image of a polyimide film according to an embodiment of the present invention.
FIG. 3 is an image of a polyimide film according to an embodiment of the present invention.
Fig. 4 is an image of a polyimide film of a comparative example of the present invention.
Fig. 5 is an image of a polyimide film of the comparative example of the present invention.
Fig. 6 is an image of a polyimide film of a comparative example of the present invention.
Fig. 7 is an image of a polyimide film of a comparative example of the present invention.
Detailed Description
Examples and embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily implement the present invention.
However, the present invention can be realized in many different forms and is not limited to the examples and embodiments described herein. In order to clearly explain the present invention, portions not related to the description are omitted in the drawings, and like reference numerals are given to like portions throughout the specification.
An embodiment of the present invention provides a method for preparing a polyimide precursor, including: a step of adding an anhydride monomer to a polymerization solvent containing a diamine monomer to perform a reaction; a step of synthesizing a polyamic acid by adding a blocking agent (end capping agent) to the reaction solution and then reacting the resultant; and a step of adding a crosslinking agent to the polyamic acid to mix the polyamic acid and the crosslinking agent.
In one embodiment of the present invention, the diamine monomer may comprise a diamine monomer selected from the group consisting of p-phenylene diamine (PPDA), 4-diaminodiphenyl ether (ODA, 4' -Oxydianiline), 4-diaminodiphenyl methane (MDA, 4,4' -methylethylenimine), m-tolidine (2, 2' -Dimethyl-4,4' -Diaminobiphenyl) (4, 4' - (2, 2' -Dimethyl-4,4' -Diaminobiphenyl)), 1,3-BIS (4 ' -Aminophenoxy) benzene (TPE-R, 1,3-BIS (4 ' -amp-phenoxyl) benzone), 2' -BIS (trifluoromethyl) benzidine (TFMB, 2,2' -Bis (trifluoromethyl) benzodine), 2-BIS [4- (4-Aminophenoxy) Phenyl ] Hexafluoropropane (HFBAPP, 2-BIS [4- (4-amino-phenoxy) Phenyl ] Hexafluorofluoropropane), 2-BIS (3-amino-4-hydroxyphenyl) Hexafluoropropane (BIS-AP-AF, 2,2-BIS (3-amino-4-hydroxyphenoyl) Hexafluoropropane), 1,3-Diamino 2,4,5,6-Tetrafluorobenzene (DRFB, 1,3-Diamino 2,4,5, 6-Tetrafluorobenzene), 3' -Diamino diphenyl sulfone (DDS, 3' -Diaminodiphenyl Sulfone), 4' -Diamino diphenyl sulfone (ASD, 4' -Diaminodiphenyl Sulfide), BIS [4- (4-Aminophenoxy) Phenyl ] sulfone (BAPS, the component of Bis [4- (4-Aminophenoxy) phenyl ] sulfolane), 2-Bis [4- (3-Aminophenoxy) phenyl ] Sulfone) (mBAPS, 2-Bis [4- (3-Aminophenoxy) Benzene ] sulfolane), and combinations thereof, may preferably be p-phenylenediamine (PPDA). The p-phenylenediamine (PPDA) is an aromatic monomer and provides high heat resistance.
In one embodiment of the present invention, the anhydride monomer may be an aromatic dianhydride monomer, for example, may include a monomer selected from the group consisting of 3,3', 4' -benzophenone tetracarboxylic dianhydride (BTDA, 3', 4' -benzopheno netetracarboxylicdianhydride), pyromellitic dianhydride (PMDA, pyromellit icdianhydride), 3', 4' -biphenyltetracarboxylic dianhydride (BPDA, 3',4,4' -biphenyl tetracarboxylicaciddianhydride), 2'-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (6 fda, 2-bis (3, 4-anhydrodicarbadoxyphenyl) -hexafluoropropanedi anhydride), a-biphenyl tetracarboxylic dianhydride (a-BPDA, 2, 3',4biphenyl tetracar boxylicaciddianhydride), 4 '-oxydiphthalic anhydride (ODPA, 4,4' -oxydi phthalic anhydride), 3', 4' -diphenyl sulfone tetracarboxylic dianhydride (DSDA, 3',4,4' -diphenylsulfone-tetracarboxylic dianhydride), 2-bis [4 (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride) (BPADA, 2-bis [4 (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride), hydroquinone diphthalic anhydride (HQDA, hydro quinone diphthalic anhydride) and combinations thereof. More than one aromatic dianhydride monomer may be used, and for example, at least two monomers may be used.
In one embodiment of the present invention, the polymerization solvent may be any solvent used in the art, and may include, for example, a component selected from the group consisting of an amide-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, a symmetrical glycol diether-based solvent, an ether-based solvent, and a combination thereof. The amide-based solvent may include Dimethylformamide (DMF), dimethylacetamide (DMAC), n-methylpyrrolidone (NMP), etc., and the ketone-based solvent may include acetone, methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, etc. The ether solvent may include Tetrahydrofuran (THF), 1, 3-dioxolane, 1, 4-dioxane, etc., and the ester solvent may include methyl acetate, ethyl acetate, butyl acetate, gamma-butyrolactone, alpha-acetolactone, beta-propiolactone, delta-valerolactone, etc. The symmetric ethylene glycol diether solvent may include methyl ethylene glycol monomethyl ether (1, 2-dimethoxyethane), methyl diethylene glycol dimethyl ether (bis (2-methoxyethyl) ether), methyl triethylene glycol dimethyl ether (1, 2-bis (2-methoxyethoxy) ethane), methyl tetraethylene glycol dimethyl ether (bis [2- (2-methoxyethoxyethyl) ] ether), ethyl ethylene glycol monomethyl ether (1, 2-dimethoxyethane), ethyl diethylene glycol dimethyl ether (bis (2-ethoxyethyl) ether), butyl diethylene glycol dimethyl ether (bis (2-butoxyethyl) ether, and the like, and the ether solvent may include ethylene glycol diether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1, 3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and the like. The polymerization solvent is preferably one or more solvents, and for example, n-methylpyrrolidone (NMP) may be used.
In one embodiment of the present invention, the capping agent is used to regulate the polymerization reaction, and monomers in the form of anhydrides may be used. The monomer in the form of anhydride may be selected from the group consisting of phthalic anhydride (PA, phthallic anhydride), tetradecyl succinic anhydride (TSA, tetradecyl succinic anhydride), hexadecyl succinic anhydride (HAS, hexadecyl succinic anhydride), octadecyl succinic anhydride (OSA, octadecyl succinic anhydride), and combinations thereof, and preferably Phthalic Anhydride (PA) may be used. The blocking agent adjusts the molecular weight of the polymer in the form of mono-anhydride, reduces the content of unreacted materials, and improves storage stability.
In one embodiment of the present invention, the method may further comprise the steps of: after the synthesis of the above polyamic acid, a step of adding a solid in accordance with the standard of the product to be produced and a solvent for adjusting the viscosity. The solvent may be the same as the synthetic solvent, and other solvents may be used to improve physical properties.
In one embodiment of the present invention, the crosslinking agent may comprise 4,4' -methylenebis (N, N-dicyclohexyl aniline). The above-mentioned crosslinking agent is preferably 4,4' -methylenebis (N, N-diglycidyl aniline) having the following chemical formula:
in one embodiment of the invention, the above-described crosslinking agent may be added in an amount of about 2000 to about 4000ppm relative to the monomer. When the above-mentioned crosslinking agent is added at a content of less than 2000ppm, the surface of the polyimide film may be poor, and when it is added at a content of more than 4000ppm, the transmittance of the polyimide film may be lowered.
Another embodiment of the present invention provides a composition for producing a polyimide film, which contains a polyimide precursor produced by the method for producing a polyimide precursor of the present application.
In one embodiment of the present invention, the polyimide precursor may comprise a polyamic acid polymer form.
In one embodiment of the present invention, the polyimide precursor is formed by adding a specific amount of a crosslinking agent to a polyamic acid, and the surface properties of the polyimide film can be improved even by imidization at a high temperature. In particular, the surface homogenization (leve rolling) property of the polyimide film can be improved, and the transmittance loss can be reduced.
Yet another embodiment of the present invention provides a method for preparing a polyimide film, including: a step of adding an anhydride monomer to a polymerization solvent containing a diamine monomer to perform a reaction; a step of synthesizing a polyamic acid by adding a blocking agent to the reaction solution and then reacting the resultant solution; a step of adding a crosslinking agent to the polyamic acid and mixing the same; a step of applying a composition containing a polyamic acid to which the above-mentioned crosslinking agent is added to a support; and a step of thermally imidizing the polyimide precursor coated on the support at a temperature of 100 ℃ or higher.
In one example of the present application, the thermal imidization may be performed at, for example, about 100 ℃ to about 500 ℃, about 100 ℃ to about 400 ℃, about 100 ℃ to about 300 ℃, about 100 ℃ to about 200 ℃, about 200 ℃ to about 500 ℃, about 300 ℃ to about 500 ℃, about 400 ℃ to about 500 ℃, but is not limited thereto.
Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to the examples.
Examples (example)
Example 1
After 21.62g (0.2 mol) of p-phenylenediamine (PPDA) was completely dissolved in 529.2g of n-methylpyrrolidone (NMP) which was kept at room temperature, 52.96g (0.18 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 4.36g (0.02 mol) of pyromellitic dianhydride (PMDA) were sequentially charged. After 1 hour from the completion of the dissolution, 0.43g (0.0029 mol) of Phthalic Anhydride (PA) was charged and reacted for 16 hours to terminate the polymerization of polyamide acid (PAA). Then, 2000ppm of 4,4' -methylenebis (N, N-dicyclohexyl aniline) (0.15874 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in the same reaction solvent N-methylpyrrolidone (NMP), and then added to the polyamide acid (PAA) to mix.
Example 2
After 21.62g (0.2 mol) of p-phenylenediamine (PPDA) was added to 529.2g of n-methylpyrrolidone (NMP) which was kept at room temperature and dissolved completely, 52.96g (0.18 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 4.36g (0.02 mol) of pyromellitic dianhydride (PMDA) were added in this order. After 1 hour from the completion of the dissolution, 0.43g (0.0029 mol) of Phthalic Anhydride (PA) was charged. After 16 hours of reaction, 3000ppm of 4,4' -methylenebis (N, N-dicyclohexyl aniline) (0.23811 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in the same reaction solvent N-methylpyrrolidone (NMP), and then added to the polyamide acid (PAA) for additional mixing.
Example 3
After 21.62g (0.2 mol) of p-phenylenediamine (PPDA) was completely dissolved in 529.2g of n-methylpyrrolidone (NMP) which was kept at room temperature, 52.96g (0.18 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 4.36g (0.02 mol) of pyromellitic dianhydride (PMDA) were sequentially charged. After 1 hour from the completion of the dissolution, 0.43g (0.0029 mol) of Phthalic Anhydride (PA) was charged. After 16 hours of reaction, 4000ppm of 4,4' -methylenebis (N, N-dicyclohexyl aniline) (0.31748 g) having reached the content of monomers (PPDA, BPDA and PMDA) was dissolved in the solvent, and then the resultant mixture was added to the polyamide acid (PAA) after the completion of the reaction.
Comparative example 1
After 21.62g (0.2 mol) of p-phenylenediamine (PPDA) was completely dissolved in 529.2g of n-methylpyrrolidone (NMP) which was kept at room temperature, 52.96g (0.18 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 4.36g (0.02 mol) of pyromellitic dianhydride (PMDA) were sequentially charged. After 1 hour from the completion of the dissolution, 0.43g (0.0029 mol) of Phthalic Anhydride (PA) was charged and reacted for 16 hours to terminate the polymerization of polyamide acid (PAA). Then, the same amount of solvent n-methylpyrrolidone (NMP) as in example 1 was added to the polyamic acid (PAA) after the completion of the reaction, and the mixture was further mixed.
Comparative example 2
After 21.62g (0.2 mol) of p-phenylenediamine (PPDA) was added to 529.2g of n-methylpyrrolidone (NMP) which was kept at room temperature and dissolved completely, 52.96g (0.18 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 4.36g (0.02 mol) of pyromellitic dianhydride (PMDA) were added in this order. After 1 hour from the completion of the dissolution, 0.43g (0.0029 mol) of Phthalic Anhydride (PA) was charged and reacted for 16 hours to terminate the polymerization of polyamide acid (PAA). Then, after 1000ppm of 4,4' -methylenebis (N, N-dicyclohexyl aniline) (0.07937 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in the same reaction solvent N-methylpyrrolidone (NMP), the mixture was put into the polyamide acid (PAA) and mixed.
Comparative example 3
After 21.62g (0.2 mol) of p-phenylenediamine (PPDA) was added to 529.2g of n-methylpyrrolidone (NMP) which was kept at room temperature and dissolved completely, 52.96g (0.18 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 4.36g (0.02 mol) of pyromellitic dianhydride (PMDA) were added in this order. After 1 hour from the completion of the dissolution, 0.43g (0.0029 mol) of Phthalic Anhydride (PA) was charged and reacted for 16 hours to terminate the polymerization of polyamide acid (PAA). Then, 1500ppm of 4,4' -methylenebis (N, N-dicyclohexyl aniline) (0.119055 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in the same reaction solvent N-methylpyrrolidone (NMP), and then the mixture was put into the polyamide acid (PAA) to be mixed.
Comparative example 4
After 21.62g (0.2 mol) of p-phenylenediamine (PPDA) was added to 529.2g of n-methylpyrrolidone (NMP) which was kept at room temperature and dissolved completely, 52.96g (0.18 mol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 4.36g (0.02 mol) of pyromellitic dianhydride (PMDA) were added in this order. After 1 hour from the completion of the dissolution, 0.43g (0.0029 mol) of Phthalic Anhydride (PA) was charged. After 16 hours of reaction, 5000ppm of 4,4' -methylenebis (N, N-dicyclohexyl aniline) (0.39685 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in the same reaction solvent N-methylpyrrolidone (NMP), and then the resultant mixture was added to the polyamide acid (PAA) after the completion of the reaction and mixed.
Experimental example 1
The polyimide precursors of examples 1 to 3 and comparative examples 1 to 4 were coated on LCD Glass SM TECH, new glass (200×200×0.63) with a wet film (wet) thickness of 400 μm using an applicator (Baker), and then placed in a convection oven heated at 120 ℃ to perform a thermal imide reaction. Then, the temperature was raised to 3℃per minute, and after maintaining the temperature below 450℃at maximum for 1 hour, the temperature was slowly cooled. After cooling, the film was collected, and the film was analyzed for external morphology, optical properties, and the like, and the results thereof are shown in fig. 1 to 4 and tables 1 and 2.
TABLE 1
TABLE 2
As shown in fig. 1 to 7, it was confirmed that the homogenized state of the film surface was good when 4,4 '-methylenebis (N, N-dicyclohexyl aniline) was added at a content of 2000ppm to 4000ppm (fig. 1 to 3), but the homogenized state of the film surface was poor when 4,4' -methylenebis (N, N-dicyclohexyl aniline) was not added (fig. 4) and when it was added at a content of 1000ppm or 5000ppm (fig. 5 to 7).
As shown in tables 1 and 2, it was confirmed that the transmittance rapidly decreased when the amount of the catalyst was less than 2000ppm or 5000ppm or more.
The above description of the present invention is for illustration, and it will be understood by those skilled in the art that the present invention can be easily modified in various specific forms without changing the technical spirit or essential features of the present invention. Accordingly, it should be understood that the various embodiments described above are illustrative in all respects, and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, a plurality of components described in a distributed manner may be implemented in a combined manner.
The scope of the invention is indicated by the appended claims rather than by the foregoing detailed description, and all changes and modifications that come within the meaning and range of equivalency of the claims and are therefore intended to be embraced therein.

Claims (9)

1. A polyimide precursor composition comprising:
a polyamic acid;
a crosslinking agent in an amount of 2000 to 4000ppm relative to the polyamide acid; and
a polymerization solvent comprising a component selected from the group consisting of an amide-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, a symmetrical glycol diether-based solvent, an ether-based solvent, and combinations thereof,
the crosslinking agent comprises 4,4' -methylenebis (N, N-dicyclohexyl aniline).
2. A method of preparing the polyimide precursor composition according to claim 1, comprising:
a step of adding an anhydride monomer to a polymerization solvent containing a diamine monomer to perform a reaction;
a step of synthesizing polyamic acid by adding a blocking agent to the reaction solution and then performing a reaction;
a step of adding a crosslinking agent to the polyamic acid in an amount of 2000 to 4000ppm with respect to the polyamic acid to perform mixing;
the crosslinking agent comprises 4,4' -methylenebis (N, N-dicyclohexyl aniline).
3. The method of claim 2, wherein the step of determining the position of the substrate comprises, the diamine monomer is selected from p-phenylenediamine, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane, m-tolidine, 1,3-bis (4 '-aminophenoxy) benzene, 2' -bis (trifluoromethyl) benzidine, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-diamino 2,4,5,6-tetrafluorobenzene, 3'-diamino diphenyl sulfone, 4' -diamino diphenyl sulfone, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2-bis [4- (3-aminophenoxy) phenyl ] sulfone, and combinations thereof.
4. The method of claim 2 wherein said anhydride monomer is an aromatic dianhydride monomer.
5. The method according to claim 4, wherein the aromatic dianhydride monomer comprises a compound selected from the group consisting of 3,3', 4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, 2'-bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride, a-biphenyltetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, 3', 4' -diphenylsulfone tetracarboxylic dianhydride, 2-bis [4 (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, hydroquinone diphthalic anhydride, and combinations thereof.
6. The method according to claim 2, wherein at least 2 anhydride monomers are added.
7. The method according to claim 2, wherein the polymerization solvent comprises a component selected from the group consisting of an amide-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, a symmetrical glycol diether-based solvent, an ether-based solvent, and combinations thereof.
8. The method of claim 2, wherein the capping agent is selected from the group consisting of phthalic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, and combinations thereof.
9. The preparation method of the polyimide film is characterized by comprising the following steps:
a step of adding an anhydride monomer to a polymerization solvent containing a diamine monomer to perform a reaction;
a step of synthesizing polyamic acid by adding a blocking agent to the reaction solution and then performing a reaction;
a step of adding a crosslinking agent to the polyamic acid in an amount of 2000 to 4000ppm with respect to the polyamic acid to perform mixing;
a step of applying a composition containing a polyamic acid to which the above-mentioned crosslinking agent is added to a support; and
a step of thermally imidizing the polyimide precursor coated on the support at a temperature of 100 ℃ or higher,
the crosslinking agent comprises 4,4' -methylenebis (N, N-dicyclohexyl aniline).
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