CN106928707B - Polyimide polymer composition, method for producing same, and polyimide film - Google Patents
Polyimide polymer composition, method for producing same, and polyimide film 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
- C08G73/1067—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
- 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 present invention relates to a polyimide polymer composition, a method for producing the same, and a polyimide film using the polyimide polymer composition. The polyimide polymer composition includes dimethylpropionamide and a polyamic acid-polyimide copolymer of chemical formula 1, and thus can provide a polyimide film having improved physical properties such as a Coefficient of Thermal Expansion (CTE) and transmittance compared to a conventional polar solvent. In the following chemical formula 1, R1Is a fluoro group or aromatic anhydride monomer, R is a diamine monomer, n is an integer of 1 to 1000, and m is an integer of 1 to 1000. [ chemical formula 1]
Description
Technical Field
The present invention relates to a polyimide polymer composition, a method for producing the same, and a polyimide film using the polyimide polymer composition.
Background
Polyimide resins are excellent in electrical, thermal, chemical, and mechanical properties as compared with other polymers, and thus are widely used in the fields of heat-resistant advanced materials and electronic materials. In particular, in the field of displays, attention is being paid to a material for manufacturing a flexible substrate because of its high heat resistance.
For the synthesis of polyimide, a diamine monomer, a dianhydride monomer, and a polar solvent are generally used. According to the imidization method, a thermal imidization method, a chemical imidization method, and the like are often used, and in order to apply the chemical imidization method, a chemical imidization reaction is also performed using a catalyst and a dehydrating agent.
In order to synthesize a polyimide resin having excellent heat resistance, a monomer having an aromatic structure is used, but the film has a brown or yellow color due to the high density of the aromatic ring, and thus has a low transmittance in the visible light region. Such polyimide resins are limited in the field where transparency is required, and other compositions and structural designs are required in order to be used instead of glass substrate materials. However, since one of the properties is improved and the other property is degraded, it is actually required to develop a polyamic acid (polyamide acid) composition in order to produce a transparent flexible substrate satisfying all of transparency, thermal properties, and mechanical properties of polyimide.
Most of the solvents used for synthesizing polyimide are polar solvents and are environmentally limited (japanese patent No. 5201155). However, the resin composition cannot obtain desired physical properties, and thus, it is still used.
Disclosure of Invention
Problems to be solved
In order to solve the above-mentioned problems in the prior art, the present invention has been completed by manufacturing a polyamic acid-polyimide copolymer using Dimethylpropionamide (DMPA) as a synthesis solvent or a dispersion solvent.
Means for solving the problems
An aspect of the present invention provides a polyimide polymer composition, which is produced by using dimethylpropionamide as a synthesis solvent or a dispersion solvent, and includes a polyamic acid-polyimide copolymer represented by the following chemical formula 1:
[ chemical formula 1]
In the above chemical formula 1, R1Is a fluoro group or aromatic anhydride monomer, R is a diamine monomer, n is an integer of 1 to 1000, and m is an integer of 1 to 1000.
Another aspect of the present invention is to provide a method for producing a polyimide polymer composition for producing a transparent polyimide film, including: a step of adding an acid anhydride monomer to a synthesis solvent containing a diamine monomer to carry out a reaction; a step of adding a catalyst and a dehydrating agent to the reaction solution to carry out a reaction and then curing; and dispersing the cured product in dimethylpropionamide.
Still another aspect of the present invention provides a method for producing a polyimide polymer composition, including: a step of adding an acid anhydride monomer to a dimethylpropionamide solution containing a diamine monomer to carry out a reaction; a step of adding a terminal capping agent to the reaction solution and then reacting the mixture to synthesize polyamic acid; and a step of adding a crosslinking agent to the polyamic acid and mixing the polyamic acid and the crosslinking agent.
Still another aspect of the present invention is to provide a transparent or colored polyimide film formed from the polyimide polymer composition of the above aspect of the present invention.
Effects of the invention
In the present invention, dimethylpropionamide is used for synthesis or dispersion instead of a polar solvent conventionally used for synthesis of polyimide, and thus, the compound can be used instead of a polar solvent subject to environmental restrictions. The present invention can provide a polyimide film having improved physical properties such as a Coefficient of Thermal Expansion (CTE) and transmittance compared to those of a conventional polyimide film using a polar solvent, by using DMPA.
Detailed Description
An aspect of the present invention provides a polyimide polymer composition which is produced by using dimethylpropionamide as a synthesis solvent or a dispersion solvent, and includes a polyamic acid-polyimide copolymer represented by the following chemical formula 1:
[ chemical formula 1]
In the above chemical formula 1, R1Is a fluoro group or aromatic anhydride monomer, R is a diamine monomer, n is an integer of 1 to 1000, and m is an integer of 1 to 1000.
In one embodiment of the present invention, the polyimide polymer composition can be used for producing a transparent or colored polyimide film.
In one embodiment of the present invention, the diamine monomer may include a diamine monomer selected from the group consisting of p-Phenylenediamine (PPD A, p-Phenylenediamine), 4, 4-diaminodiphenyl ether (ODA, 4,4'-Oxydianiline), 4, 4-diaminodiphenylmethane (MDA, 4,4' -methylideneindoline), m-toluidine (2,2'-Dimethyl-4,4' -diaminodiphenol), 1,3-BIS (4 '-Aminophenoxy) benzene (R, 1,3-BIS (4' -Aminophenoxy) benzene), 2,2'-BIS (trifluoromethyl) benzidine (TFMB, 2,2' -BIS (trifluoromethylphenoxy) benzidine), 2,2-BIS [4- (4-Aminophenoxy) Phenyl ] Hexafluoropropane (HFPP, 2,2-BIS [4- (4-Aminophenoxy) TPE), and 2,2-BIS [4- (4-Aminophenoxy) Phenyl ] Hexafluoropropane (HFPP, 2-BIS [4- (4-Aminophenoxy) TPE), 2-BIS (3-amino-4-hydroxyphenyl) hexafluoropropane (BIS-AP-AF, 2,2-BIS (3-amino-4-hydroxyphenyl) hexafluoro-propane), 1,3-Diamino-2,4,5,6-Tetrafluorobenzene (DRFB, 1,3-Diamino-2,4,5,6-Tetrafluorobenzene), 3,3'-Diaminodiphenyl Sulfone (DDS, 3,3' -Diaminodiphenyl Sulfone), 4,4'-Diaminodiphenyl Sulfide (ASD, 4,4' -Diaminodiphenyl Sulfide), Bis [4- (4-Aminophenoxy) phenyl ] Sulfone (BAPS, Bis [4- (4-Aminophenoxy) phenyl ] Sulfone), 2,2-Bis [4- (3-Aminophenoxy) phenyl ] Sulfone (mBAPS, 2,2-Bis [4- (3-Aminophenoxy) Benzene ] Sulfone), and combinations thereof. The diamine monomer can be suitably selected and used according to the physical properties required in the field of application of polyimide. In order to produce a polyimide film having high heat resistance and a low thermal expansion coefficient, an aromatic diamine monomer can be selected and used, and when a colored polyimide which does not require transparency is synthesized, a PPDA monomer is suitably used. In addition, for synthesizing transparent polyimide, a fluorine-based monomer, for example, a TFMB monomer may be used.
In one embodiment of the present invention, the acid anhydride monomer may be an aromatic dianhydride monomer, and may include a monomer selected from the group consisting of 3,3',4,4' -benzophenone tetracarboxylic dianhydride (BTDA, 3,3',4,4' -benzophenone ethylene diamine), pyromellitic dianhydride (PMDA), 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA, 3,3',4,4' -biphenyltetracarboxylic dianhydride), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA, 2,2-bis (3, 4-phthalic anhydride), 2, 3', 4'-biphenyl tetracarboxylic dianhydride (a-BPDA, 2,3,3', 4-biphenyltetracarboxylic dianhydride), and 4,4 '-diphenylsulfone dianhydride (3, 4' -diphenylsulfone dianhydride), 3,4 '-diphenylsulfone dianhydride (3, 4' -diphenylsulfone dianhydride), 3,3',4,4' -di (phenylsulfone-tetrahydroxy) phenyl propane dianhydride), 2,2-bis [4(3,4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA, 2,2-bis [4(3,4-dicarboxyphenoxy) phenyl ] propane dianhydride), hydroquinone diphthalic anhydride (HQDA), and combinations thereof. One or more aromatic dianhydride monomers may be used, and for example, at least two monomers may be used. The acid anhydride monomer can be suitably selected and used according to the physical properties required in the field of application of polyimide. When synthesizing a colored polyimide film that exhibits high heat resistance characteristics and does not require transparency, BP DA and PMDA monomers can be used. In addition, 6FDA monomer is preferably used for synthesizing transparent polyimide, and BPDA monomer is preferably used for improving heat resistance and mechanical properties.
Another aspect of the present invention provides a method for producing a polyimide polymer composition, including: a step of adding an acid anhydride monomer to a synthesis solvent containing a diamine monomer to carry out a reaction; a step of adding a catalyst and a dehydrating agent to the reaction solution to carry out a reaction and then curing; and dispersing the cured product in dimethylpropionamide.
Still another aspect of the present invention provides a method for producing a polyimide polymer composition, including: a step of adding an acid anhydride monomer to a dimethylpropionamide solution containing a diamine monomer to carry out a reaction; a step of adding an end-capping agent to the reaction solution to perform a reaction to synthesize a polyamic acid; and a step of adding a crosslinking agent to the polyamic acid and mixing the polyamic acid and the crosslinking agent.
In one embodiment of the present invention, the polyimide polymer composition can be used for producing a transparent or colored polyimide film.
In one embodiment of the present invention, the diamine monomer may comprise a diamine monomer selected from the group consisting of p-phenylenediamine, 4-diaminodiphenyl ether, 4-diaminodiphenylmethane, 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'-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide, bis [4- (4-aminophenoxy) phenyl ] sulfone, 2-bis [4- (3-aminophenoxy) phenyl ] sulfone, and combinations thereof. The diamine monomer can be suitably selected and used according to the physical properties required in the field of application of polyimide. In order to produce a polyimide film having high heat resistance and a low thermal expansion coefficient, an aromatic diamine monomer can be selected and used, and when a colored polyimide which does not require transparency is synthesized, a PPDA monomer is suitably used. In addition, for synthesizing transparent polyimide, a fluorine-based monomer, for example, a TFMB monomer may be used.
In one embodiment of the present invention, the acid anhydride monomer may be an aromatic dianhydride monomer, and for example, may include a material selected from the group consisting of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 2,3,3', 4-biphenyl tetracarboxylic dianhydride, 4,4' -oxydiphthalic anhydride, 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride, 2-bis [4(3,4-dicarboxyphenoxy) phenyl ] propane dianhydride, hydroquinone diphthalic anhydride, and a combination thereof. One or more aromatic dianhydride monomers may be used, and for example, at least two monomers may be used. The acid anhydride monomer can be suitably selected and used according to the physical properties required in the field of application of polyimide. When synthesizing a colored polyimide film that exhibits high heat resistance characteristics and does not require transparency, BPDA and PMDA monomers may be used. In addition, 6FDA monomer is preferably used for synthesizing transparent polyimide, and BPDA monomer is preferably used for improving heat resistance and mechanical properties.
In one embodiment of the present invention, the synthetic solvent may be used without limitation as long as it is a solvent used in the art, and may include, for example, one 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 solvent may include Dimethylformamide (DMF), Dimethylacetamide (DMAC), n-methylpyrrolidone (NMP), and the ketone solvent may include acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, and the like. The ether solvent may comprise Tetrahydrofuran (THF), 1, 3-dioxolane and 1, 4-dioxane
And an alkane, and the ester solvent may include methyl acetate, ethyl acetate, butyl acetate, γ -butyrolactone, α -acetolactone, β -propiolactone, δ -valerolactone, and the like. The symmetric glycol diether solvent may comprise methyl monoethylene glycol dimethyl 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) ethyl)]Ether), ethyl monoethylene glycol dimethyl ether (1, 2-diethoxyethane), ethyl diethylene glycol dimethyl ether (bis (2-ethoxyethyl) ether), butyl diethylene glycol dimethyl ether (bis (2-butoxyethyl) ether)) And the ether solvent may include ethylene glycol ethers, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl 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.
In one embodiment of the present invention, the synthetic solvent may be dimethylpropionamide.
In one embodiment of the present invention, the capping agent may be selected from the group consisting of Phthalic Anhydride (PA), Tetradecyl Succinic Anhydride (TSA), hexadecyl succinic anhydride (HAS), octadecyl succinic anhydride (OS a), and a combination thereof, and preferably, may be P A. The end-capping agent is used for controlling the polymerization reaction, and can control the molecular weight of a polymer in the form of a mono-acid anhydride, reduce the content of unreacted materials, and improve the storage stability.
In one embodiment of the present invention, the step of adding an acid anhydride monomer to a synthesis solvent containing a diamine monomer to perform a reaction may be followed by a step of adding a capping agent.
In one embodiment of the present invention, when the polyimide polymer composition is synthesized in the polyamic acid polymer solution, the imidization reaction may be parallel to the thermal imidization reaction and the chemical imidization reaction. In the case of paralleling the two imidization reactions, the following advantages are obtained: when the thermal imidization reaction is performed, the reaction temperature may be reduced, and an unreacted phase remaining at the time of synthesis may be removed in advance through a precipitation process.
In one embodiment of the present invention, the dehydrating agent and the catalyst may be used for chemical imidization, the dehydrating agent may include an acid anhydride such as acetic anhydride, and the catalyst may include a tertiary amine such as pyridine, isoquinoline, and β -picoline.
In one embodiment of the present invention, the crosslinking agent may comprise 4,4' -methylenebis (N, N-diglycidylaniline). The above-mentioned 4,4' -methylenebis (N, N-diglycidylaniline) may have the following structure:
in one embodiment of the present invention, the polyimide polymer composition may further comprise a step of adding a crosslinking agent to the polyimide polymer composition.
Still another aspect of the present invention is to provide a transparent or colored polyimide film formed from the polyimide polymer composition of the present invention.
In one embodiment of the present invention, the polyimide film may be produced by: a step of coating the polyimide polymer composition on a substrate; and heating and drying the substrate coated with the polyimide polymer.
In one embodiment of the present invention, a transparent or colored polyimide film can be produced depending on the kinds of the diamine monomer and the acid anhydride monomer used in the production of the polyimide polymer composition.
Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to the examples.
Examples
Example 1: production of polyimide Polymer solution for producing transparent polyimide film
While nitrogen was passed through a temperature-adjustable stirred reactor connected to a nitrogen injection device and a dropping funnel, 704.2g of DMAC was charged at normal temperature, and then 32.02g (0.1mol) of TFMB as a fluorine-based diamine monomer was dissolved. 8.83g (0.03mol) of an aromatic monomer BPDA as an acid anhydride monomer and 31.1g (0.07mol) of a fluorine-based monomer 6FDA were put therein to carry out a reaction. After 1 hour had elapsed after complete dissolution, pyridine and acetic anhydride were added as a catalyst and a dehydrating agent, and after the temperature was raised to 70 ℃, the reaction was carried out for 1 hour, and the reaction mixture was cooled to normal temperature.
Thereafter, the precipitate was solidified in a mixed solution of MeOH and distilled water (3: 1). After thorough washing in MeOH, thorough drying was performed in a vacuum oven at 80 ℃ for 6 hours, thereby obtaining a polyimide polymer solid.
The obtained polyimide solid was dispersed in a DMPA solution, sufficiently stirred until no solid remained, and then filtered to remove foreign matters and an unreacted phase, thereby obtaining a polyimide polymer solution.
Comparative example 1
While nitrogen was passed through a temperature-adjustable stirred reactor connected to a nitrogen injection device and a dropping funnel, 704.2g of DMAC was charged at normal temperature, and then 32.02g (0.1mol) of TFMB as a fluorine-based diamine monomer was completely dissolved. To this mixture were added 8.83g (0.03mol) of an aromatic monomer BPDA and 31.1g (0.07mol) of a fluorine-based monomer 6FDA as acid anhydride monomers to carry out a reaction. After 1 hour had elapsed after complete dissolution, pyridine and acetic anhydride were added as a catalyst and a dehydrating agent, and after the temperature was raised to 70 ℃, the reaction was carried out for 1 hour, and the reaction mixture was cooled to normal temperature.
Thereafter, the precipitate was solidified in a mixed solution of MeOH and distilled water. After thorough washing in MeOH, thorough drying was performed in a vacuum oven at 80 ℃ for 6 hours, thereby obtaining a polyimide solid.
The obtained polyimide solid was dispersed in a DMAC solution, sufficiently stirred until no solid remained, and filtered to remove foreign matters and an unreacted phase, thereby obtaining a polyimide polymer solution.
Comparative example 2
While nitrogen was passed through a temperature-adjustable stirred reactor connected to a nitrogen injection device and a dropping funnel, 704.2g of DMPA was charged at room temperature, and then 32.02g (0.1mol) of TFMB as a fluorine-based diamine monomer was completely dissolved. To this mixture were added 8.83g (0.03mol) of an aromatic monomer BPDA and 31.1g (0.07mol) of a fluorine-based monomer 6FDA as acid anhydride monomers to carry out a reaction. After 1 hour had elapsed after complete dissolution, pyridine and acetic anhydride were added as a catalyst and a dehydrating agent, and after the temperature was raised to 70 ℃, the reaction was carried out for 1 hour, and the reaction mixture was cooled to normal temperature.
Thereafter, the precipitate was solidified in a mixed solution of MeOH and distilled water. After thorough washing in MeOH, thorough drying was performed in a vacuum oven at 80 ℃ for 6 hours, thereby obtaining a polyimide solid.
The obtained polyimide solid was dispersed in a DMPA solution, sufficiently stirred until no solid remained, and filtered to remove foreign matters and an unreacted phase, thereby obtaining a polyimide polymer solution.
Example 2: production of transparent polyimide film
The polyimide polymer solutions obtained in the above examples 1, comparative examples 1 and comparative examples 2 were coated on a glass substrate at a wet film thickness of 400 μm using an applicator (applicator), and then dried to 280 ℃ by heating in a convection oven (convection oven), thereby producing a polyimide film having a thickness of 30 μm.
Example 3: production of polyimide Polymer solution for producing colored polyimide film
242.45g of DMPA was charged into a temperature-controlled stirred reactor connected to a nitrogen injection device and a dropping funnel while passing nitrogen through the reactor, 10.91g of PPDA was completely dissolved, and 26.48g of BPDA and 2.18g of PMDA were sequentially charged. After complete dissolution and 1 hour had elapsed, 0.2g of PA was charged, and a reaction was performed for 16 hours, whereby Polyacrylamide (PA a, polyacylamide) was synthesized. Thereafter, 4' -methylenebis (N, N-diglycidylaniline) having a monomer content of 4000pp m (DMPA, BPDA and PMDA) was dissolved in the same solvent as the reaction solvent, added to PAA after the reaction, and mixed.
Comparative example 3
242.45g of NMP was charged at room temperature while passing nitrogen through a temperature-adjustable stirred reactor connected to a nitrogen injection device and a dropping funnel, 10.91g of PPDA was completely dissolved, and 26.48g of BPDA and 2.18g of PMDA were sequentially charged. After complete dissolution and 1 hour had elapsed, 0.2g of PA was charged and a reaction was carried out for 16 hours, whereby PAA was synthesized. Thereafter, 4000ppm of 4,4' -methylenebis (N, N-diglycidylaniline) based on the content of the monomers (PP DA, BPDA and PMDA) was dissolved in a solvent, added to PAA after the reaction, and mixed.
Example 4: production of colored polyimide film
The polyimide polymer solutions obtained in the above example 3 and comparative example 3 were coated on a glass substrate with a wet film thickness of 350 μm using a coater, and then dried by heating to 450 ℃ in a convection oven, thereby producing a polyimide film having a thickness of 20 μm.
Experimental example 1
The physical properties of the polyimide films synthesized in the above examples 2 and 4 were evaluated by the following methods, and the results thereof are shown in the following tables 1 to 3.
Determination of the coefficient of thermal expansion
The linear thermal expansion coefficient was measured by the TMA-method using a static thermomechanical analyzer (TMA) (TA instruments, Q400). The temperature rise rate is measured at 5 ℃ per minute, the cooling rate is measured at 20 ℃ per minute, and stress may remain in the film, so that the temperature is measured at a temperature of 30 ℃ to 300 ℃ at a temperature of Tg or lower. The coefficient of thermal expansion values were determined from the slopes upon cooling.
Measurement of transmittance
The average value was measured after 5 measurements in the visible light region using an optical measuring device (Nippon Denshoku Co., Ltd., COH-400).
Determination of the yellowness
The yellowness was measured by an optical measuring instrument (CoH-400, Japan Electrochrome).
The above results of the measurement are shown in tables 1 to 3.
[ Table 1]
Production of transparent polyimide (film thickness of 30 μm)
[ Table 2]
Production of colored polyimide (film thickness of 20 μm)
[ Table 3]
Comparison of physical Properties of synthetic solvents: DMPA, DMAC, NMP
As can be seen from tables 1 to 3, when DMPA (dimethylpropionamide) is used, physical properties such as a thermal expansion coefficient and a transmittance are more excellent than DMAC (N, N-dimethylacetamide) or NMP (N-methyl 2 pyrrolidone) which is a polar solvent used in the conventional production of a polyimide film. In addition, the monomer is more easily dissolved in DMPA, thereby exhibiting high solubility.
The above description of the present invention is intended to be illustrative, and it will be readily apparent to those skilled in the art that the present invention may be modified into other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all respects and not restrictive. For example, the respective components described in the overall form may be implemented in a dispersed manner, and similarly, the components described in the dispersed manner may be implemented in a combined form.
The scope of the present invention is indicated by the appended claims, rather than the foregoing detailed description, and all changes and modifications that come within the meaning and range of equivalency of the claims are to be construed as being included therein.
Claims (13)
1. A polyimide polymer composition comprising N, N-dimethylpropionamide as a dispersion solvent and a polyamic acid-polyimide copolymer of chemical formula 1,
the synthetic solvent used in the method for producing a polyimide polymer composition comprises a substance selected from the group consisting of an amide solvent, a ketone solvent, an ether solvent, an ester solvent, and a combination thereof,
the amide solvent is dimethylformamide, dimethylacetamide or N-methylpyrrolidone,
[ chemical formula 1]
In the chemical formula 1, the metal oxide is represented by,
R1is a fluoro group or a 4-valent organic group derived from an aromatic acid anhydride monomer,
r is a 2-valent organic group derived from a diamine monomer,
n is an integer of 1 to 1000,
m is an integer of 1 to 1000.
2. The polyimide polymer composition according to claim 1, wherein the ether solvent is a symmetric glycol diether solvent.
3. The polyimide polymer composition according to claim 1, wherein the diamine monomer is selected from the group consisting of p-phenylenediamine, 4'-diaminodiphenyl ether, 4' -diaminodiphenylmethane, 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'-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, and combinations thereof.
4. The polyimide polymer composition according to claim 1, wherein the acid anhydride monomer comprises a material selected from the group consisting of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 4,4' -oxydiphthalic anhydride, 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride, 2-bis [4- (3,4-dicarboxyphenoxy) phenyl ] propane dianhydride, 4,4' -terephthal-oxydiphthalic anhydride, and a combination thereof.
5. The polyimide polymer composition according to claim 1, further comprising 4,4' -methylenebis (N, N-diglycidylaniline).
6. A method for producing a polyimide polymer composition, comprising:
a step of adding an acid anhydride monomer to a synthesis solvent containing a diamine monomer to carry out a reaction;
adding a catalyst and a dehydrating agent to the reaction solution to react and then curing; and
a step of dispersing the cured product in N, N-dimethylpropionamide as a dispersion solvent,
the synthetic solvent comprises a substance selected from the group consisting of an amide-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, and a combination thereof,
the amide solvent is dimethylformamide, dimethylacetamide or N-methylpyrrolidone.
7. The method for producing a polyimide polymer composition according to claim 6, wherein the ether solvent is a symmetric glycol diether solvent.
8. The method for producing a polyimide polymer composition according to claim 6, wherein the diamine monomer is selected from the group consisting of p-phenylenediamine, 4'-diaminodiphenyl ether, 4' -diaminodiphenylmethane, m-tolidine, 1,3-bis (4 '-aminophenoxy) benzene, 2' -bis (trifluoromethyl) benzidine, and 2,2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-diamino-2,4,5,6-tetrafluorobenzene, 3'-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, and combinations thereof.
9. The method for producing a polyimide polymer composition according to claim 6, wherein the acid anhydride monomer is an aromatic dianhydride monomer.
10. The method for producing a polyimide polymer composition according to claim 9, wherein the aromatic dianhydride monomer comprises a substance selected from the group consisting of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 4,4' -oxydiphthalic anhydride, 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride, 2-bis [4- (3,4-dicarboxyphenoxy) phenyl ] propane dianhydride, 4,4' -terephthal-thalic anhydride, and a combination thereof.
11. The method for producing a polyimide polymer composition according to claim 6, wherein at least one acid anhydride monomer is added.
12. The method for producing a polyimide polymer composition according to claim 6, wherein the dehydrating agent comprises an acid anhydride, and the catalyst comprises a tertiary amine.
13. A transparent or colored polyimide film formed from the polyimide polymer composition of claim 1.
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| KR20190017527A (en) * | 2017-08-11 | 2019-02-20 | 주식회사 동진쎄미켐 | Polyimide precursor composition and method for producing polyimide film using the same |
| KR20190017524A (en) * | 2017-08-11 | 2019-02-20 | 주식회사 동진쎄미켐 | Polyimide precursor composition and method for producing polyimide film using the same |
| KR101840978B1 (en) | 2017-09-14 | 2018-03-21 | 주식회사 엘지화학 | Polyimide copolymer and polyimide film manufactured by using same |
| KR101840977B1 (en) * | 2017-09-14 | 2018-03-21 | 주식회사 엘지화학 | Polyimide precursor composition and polyimide film manufactured by using same |
| KR102117151B1 (en) | 2017-09-29 | 2020-05-29 | 주식회사 엘지화학 | Polyimide precursor solution and polyimide film prepared by using same |
| WO2019066204A1 (en) * | 2017-09-29 | 2019-04-04 | 주식회사 엘지화학 | Polyimide precursor solution and polyimide film produced using same |
| CN109651630A (en) * | 2017-10-11 | 2019-04-19 | 达迈科技股份有限公司 | The manufacturing method of transparent polyimide film |
| KR101906394B1 (en) * | 2017-11-10 | 2018-10-11 | 에스케이씨코오롱피아이 주식회사 | Ultra Thin Black Polyimide Film and Method For Preparing The Same |
| KR102281613B1 (en) * | 2017-11-21 | 2021-07-23 | 주식회사 엘지화학 | Polyimide film for display substrates |
| KR102285023B1 (en) * | 2018-01-02 | 2021-08-02 | 동우 화인켐 주식회사 | Precursor polymer containing benzyl alcohol group, insulation layer formed from the same and method of forming insulation layer using the same |
| KR102350095B1 (en) | 2018-01-03 | 2022-01-11 | 주식회사 엘지화학 | Poly(amide-imide) copolymer film and preparation method of the same |
| KR102566319B1 (en) * | 2018-06-19 | 2023-08-16 | 주식회사 동진쎄미켐 | Polyimide varnish composition and method for producing film using the same |
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| US11535709B2 (en) * | 2019-03-05 | 2022-12-27 | Promerus, Llc | Reactive end group containing polyimides and polyamic acids and photosensitive compositions thereof |
| CN110885443B (en) * | 2019-12-11 | 2022-04-22 | 万华化学集团股份有限公司 | Thermoplastic polyimide and preparation method thereof |
| CN111704735B (en) * | 2020-06-24 | 2023-05-26 | 中国科学院光电技术研究所 | Polyimide optical film material with ultralow thermal expansion coefficient and high strength and preparation method thereof |
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| JP2017119868A (en) | 2017-07-06 |
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