KR20170079896A - Polyimidepolymer composition, method for producing thereof and method for producing polyimide film using the same - Google Patents

Abstract

The present invention relates to a polyimide polymer composition, a process for producing the same, and a process for producing a polyimide film using the same.

Description

TECHNICAL FIELD The present invention relates to a polyimide polymer composition, a process for producing the same, and a process for producing a polyimide film using the same. BACKGROUND ART [0002]

The present invention relates to a polyimide polymer composition, a process for producing the same, and a process for producing a polyimide film using the same.

The polyimide resin has various electrical, thermal, chemical and mechanical properties as compared with other polymers, and thus has been widely applied to heat-resistant materials and electronic materials. Particularly in the display field, attention is being paid to the high heat resistance properties of materials for making flexible substrates.

To synthesize the polyimide, a diamine monomer, a dianhydride monomer and a polar solvent are generally used. According to the imide method, a thermal imide method and a chemical imide method are widely used. In order to apply a chemical imide method, a chemical imide reaction is carried out using a catalyst and a dehydrating agent.

 In order to synthesize a polyimide resin having excellent heat resistance, an aromatic structure monomer should be used, but the film color is brown or yellow due to the high density of the aromatic ring, so that the transmittance in the visible light region is lowered. Such a polyimide resin has limitations in areas where transparency is required, and other compositions and structure design are required to replace glass substrate materials. However, when one physical property is improved, other properties are deteriorated, and thus it is necessary to develop a polyamic acid composition in order to produce a transparent flexible substrate satisfying all the transparency, thermal properties, and mechanical properties of polyimide.

Most of the solvents used for synthesizing polyimide are substances which are environmentally regulated by a polar solvent (Japanese Patent No. 5201155). However, when I replace it, I can not get the desired property, and I use it as it is.

The present invention has been accomplished to solve the problems of the prior art by preparing a polyamic acid-polyimide copolymer using dimethylpropionamide (DMPA) as a synthetic solvent or a dispersion solvent.

One aspect of the present invention provides a polyimide polymer composition comprising a polyamic acid-polyimide copolymer, which is produced by using dimethylpropionamide (DMPA) as a synthetic solvent or a dispersion solvent, and is represented by the following Chemical Formula 1:

[Chemical Formula 1]

In Formula 1,

R ₁ is a fluorine group or an aromatic anhydride monomer,

R is a diamine monomer,

n is an integer of 1 to 1,000,

and m is an integer of 1 to 1,000.

According to another aspect of the present invention, there is provided a process for producing a polyimide resin, comprising the steps of: adding an anhydride monomer to a synthetic solvent containing a diamine monomer and reacting; Adding a catalyst and a dehydrating agent to the reaction solution to react and solidify the catalyst; And dispersing the solidified material in DMPA (dimethylpropionamide). The present invention also provides a method for producing a polyimide polymer composition for producing a transparent polyimide film.

According to another aspect of the present invention, there is provided a method for producing a polymer electrolyte membrane comprising the steps of: adding an anhydride monomer to a dimethylpropionamide (DMPA) solution containing a diamine monomer and reacting; Adding a terminal-capping agent to the reaction solution, and then reacting to synthesize a polyamic acid; And a step of adding a cross-linking agent to the polyamic acid and mixing the polyimide polymer composition.

Another aspect of the present invention provides a transparent or colored polyimide film formed from the polyimide polymer composition according to the above aspect of the present invention.

The present invention can replace a polar solvent to be environmentally controlled by using DMPA (dimethylpropionamide) instead of the polar solvent used for the synthesis of polyimide. By using DMPA, the present invention can provide a polyimide film improved in physical properties such as CTE and transmittance as compared with a conventional polar solvent.

Hereinafter, embodiments and embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art.

The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments and examples described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

One aspect of the present invention provides a polyimide polymer composition comprising a polyamic acid-polyimide copolymer, which is produced by using dimethylpropionamide (DMPA) as a synthetic solvent or a dispersion solvent, and is represented by the following Chemical Formula 1:

[Chemical Formula 1]

In Formula 1,

R ₁ is a fluorine group or an aromatic anhydride monomer,

R is a diamine monomer,

n is an integer of 1 to 1,000,

and m is an integer of 1 to 1,000.

In one embodiment of the present invention, the polyimide polymer composition may be one for producing a transparent or colored polyimide film.

In one embodiment of the present invention, the diamine monomer is selected from the group consisting of PPDA (p-Phenylenediamine), ODA (4,4'-Oxydianiline), MDA (4,4'-Methylenedianiline), m- Dimethyl-4,4'-Diaminobiphenyl), TPE-R (1,3-BIS (4'-Aminophenoxyl) benzene), TFMB (2,2'-Bis (trifluoromethyl) benzidine), HFBAPP (2,2- 4- (4-Aminophenoxy) Phenyl] hexafluoropropane), BIS-AP-AF (2,2-Bis (4,4'-Diaminodiphenyl Sulfide), BAPS (Bis [4- (4-aminophenoxy) phenyl] sulfone), m-BAPS (2,2- Bis [4- (3-Aminophenoxy) Benzene] Sulfone), and combinations thereof. Appropriate diamine monomers may be selected depending on the required properties in the application field of polyimide. In order to produce a polyimide film exhibiting a low thermal expansion coefficient with a high heat resistance property, a diamine monomer having an aromatic structure can be selected and used. It is appropriate to use a PPDA monomer in the synthesis of a colored polyimide which does not require transparency. Further, in order to synthesize a transparent polyimide, fluorine-based monomers can be used. For example, TFMB monomers can be used.

In one embodiment of the present invention, the anhydride monomer may be an aromatic dianhydride monomer, such as, for example, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, PMDA (pyromellitic dianhydride), BPDA 3,3 ', 4,4'-biphenyl tetracarboxylic acid hydrides, 6-di (3,4-anhydrodicarboxyphenyl) -hexafluoropropanediohydride, 6,3'4-biphenyl tetracarboxylic acid hydrides, 4,4'-oxydiphthalic anhydride, DSDA (3,3 ', 4,4'-diphenylsulfone-tetracarboxylic dianhydride), BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) , Hydroquinone diphthalic anhydride (HQDA), and combinations thereof. The aromatic dianhydride monomer may use one or more, for example, at least two monomers. Suitable anhydride monomers can be selected and used according to the requirements of the polyimide application field. BPDA and PMDA monomers can be used in the synthesis of colored polyimide films which exhibit high heat resistance and do not require transparency. Further, in order to synthesize a transparent polyimide, the use of a 6FDA monomer is appropriate, and in order to improve heat resistance and mechanical properties, it is appropriate to use a BPDA monomer.

According to another aspect of the present invention, there is provided a process for producing a polyimide resin, comprising the steps of: adding an anhydride monomer to a synthetic solvent containing a diamine monomer and reacting; Adding a catalyst and a dehydrating agent to the reaction solution to react and solidify the catalyst; And dispersing the solidified material in dimethylpropionamide (DMPA). The present invention also provides a method for producing a polyimide polymer composition.

According to another aspect of the present invention, there is provided a method for producing a polymer electrolyte membrane comprising the steps of: adding an anhydride monomer to a dimethylpropionamide (DMPA) solution containing a diamine monomer and reacting; Adding a terminal-capping agent to the reaction solution, and then reacting to synthesize a polyamic acid; And a step of adding a cross-linking agent to the polyamic acid and mixing the polyimide polymer composition.

In one embodiment of the present invention, the polyimide polymer composition may be one for producing a transparent or colored polyimide film.

In one embodiment of the present invention, the diamine monomer is selected from the group consisting of PPDA (p-Phenylenediamine), ODA (4,4'-Oxydianiline), MDA (4,4'-Methylenedianiline), m- Dimethyl-4,4'-Diaminobiphenyl), TPE-R (1,3-BIS (4'-Aminophenoxyl) benzene), TFMB (2,2'-Bis (trifluoromethyl) benzidine), HFBAPP (2,2- 4- (4-Aminophenoxy) Phenyl] hexafluoropropane), BIS-AP-AF (2,2-Bis (4,4'-Diaminodiphenyl Sulfide), BAPS (Bis [4- (4-aminophenoxy) phenyl] sulfone), m-BAPS (2,2- Bis [4- (3-Aminophenoxy) Benzene] Sulfone), and combinations thereof. Appropriate diamine monomers may be selected depending on the required properties in the application field of polyimide. In order to produce a polyimide film exhibiting a low thermal expansion coefficient with a high heat resistance property, a diamine monomer having an aromatic structure can be selected and used. It is appropriate to use a PPDA monomer in the synthesis of a colored polyimide which does not require transparency. Further, in order to synthesize a transparent polyimide, fluorine-based monomers can be used. For example, TFMB monomers can be used.

In one embodiment of the present invention, the anhydride monomer may be an aromatic dianhydride monomer, such as, for example, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, PMDA (pyromellitic dianhydride), BPDA 3,3 ', 4,4'-biphenyl tetracarboxylic acid hydrides, 6-di (3,4-anhydrodicarboxyphenyl) -hexafluoropropanediohydride, 6,3'4-biphenyl tetracarboxylic acid hydrides, 4,4'-oxydiphthalic anhydride, DSDA (3,3 ', 4,4'-diphenylsulfone-tetracarboxylic dianhydride), BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) , Hydroquinone diphthalic anhydride (HQDA), and combinations thereof. The aromatic dianhydride monomer may use one or more, for example, at least two monomers. Suitable anhydride monomers can be selected and used according to the requirements of the polyimide application field. BPDA and PMDA monomers can be used in the synthesis of colored polyimide films which exhibit high heat resistance and do not require transparency. Further, in order to synthesize a transparent polyimide, the use of a 6FDA monomer is appropriate, and in order to improve heat resistance and mechanical properties, it is appropriate to use a BPDA monomer.

In one embodiment of the present invention, the synthetic solvent may be any solvent that is used in the art without limitation, and examples thereof include amide solvents, ketone solvents, ether solvents, ester solvents, symmetric glycol diethers A solvent, a solvent, an ether solvent, and combinations thereof. The amide solvent may include dimethylformamide (DMF), dimethylacetamide (DMAC), n-methylpyrrolidone (NMP), etc. The ketone solvent may include acetone, methyl ethyl ketone (MEK), methyl Isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, and the like. The ether solvent may include tetrahydrofuran (THF), 1,3-dioxolane and 1,4-dioxane, and the ester solvent may include methyl acetate, ethyl acetate, butyl acetate, Lactone,? -Acetolactone,? -Propiolactone,? -Valerolactone, and the like. The symmetrical glycol diether solvents include methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyltriglyme (1,2- Methoxyethoxy) ethane), methyl tetraglyme (bis [2- (2-methoxyethoxyethyl) ether], ethyl monoglyme (1,2-diethoxyethane), ethyl diglyme (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2-butoxyethyl) ether), and the ether solvents include glycol diethers, 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, tripylene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether , 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol No-ethyl ether, di, and the like ethylene glycol monobutyl ether, ethylene glycol monoethyl ether.

In one embodiment of the present invention, the synthetic solvent may be dimethylpropionamide (DMPA).

In one embodiment of the invention, the end-capping agent is selected from the group consisting of phthalic anhydride, tetradecyl succinic anhydride (TSA), hexadecyl succinic anhydride (HAS), octadecyl succinic anhydride (OSA) It may be selected, and preferably it may be PA. The end-capping agent is for controlling the polymerization reaction, and can control the molecular weight of the polymer in the mono-anhydride form, reduce the content of the unreacted material, and improve the storage stability.

In one embodiment of the present invention, the step of adding an anhydride monomer to a synthetic solvent containing a diamine monomer, followed by the step of reacting, may further include the step of adding an end-capping agent.

In one embodiment of the present invention, in the synthesis of the polyimide polymer composition in the polyamic acid polymer solution, the imidization reaction may be performed in parallel with the thermal imide reaction and the chemical imide reaction. When the two imidization reactions are carried out simultaneously, the reaction temperature can be reduced during the thermal imidization reaction, and the unreacted phase remaining in the synthesis can be removed in advance through the precipitation process.

In one embodiment of the present invention, the dehydrating agent and the catalyst are used for a chemical imidization reaction, and the dehydrating agent includes an acid anhydride such as acetic anhydride, and the catalyst is selected from the group consisting of pyridine, isoquinoline, And may contain the same tertiary amines.

In one embodiment of the present invention, the crosslinking agent may include 4,4'-methylenebis (N, N-diglycidylaniline). The 4,4'-methylenebis (N, N-diglycidylaniline) may have the following structure:

In one embodiment of the present invention, a step of adding a crosslinking agent to the polyimide polymer composition may be further included.

Another aspect of the present invention provides a transparent or colored polyimide film formed from the polyimide polymer composition according to the present invention.

In one embodiment of the present invention, the polyimide film comprises: 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 may be produced depending on the kind of the diamine monomer and the anhydride monomer used in the production of the polyimide polymer composition.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited by these Examples.

[ Example ]

Example  1: Preparation of Polyimide Polymer Solution for the Production of Transparent Polyimide Film

(DMF) was charged with 704.2 g of DMAC at room temperature, and then 32.02 g (0.1 mol) of TFMB, which is a fluorine-based diamine monomer, was dissolved in a temperature-controlled stirring reactor connected to a nitrogen injection apparatus and a dropping funnel. 8.83 g (0.03 mol) of the aromatic monomer BPDA and 31.1 g (0.07 mol) of the fluorine-based monomer 6FDA were reacted as anhydride monomers. After 1 hour, pyridine and acetic anhydride were added as a catalyst and dehydrating agent, and the mixture was heated to 70 ° C, reacted for 1 hour, and cooled to room temperature.

It was then solidified by precipitation in a mixture of MeOH and distilled water (3: 1). Sufficiently washed with MeOH, and sufficiently dried in a vacuum oven at 80 DEG C for 6 hours to obtain a polyimide polymer solid.

 The polyimide solids obtained were dispersed in a DMPA solution, stirred sufficiently to avoid the remaining solids, and then filtered to remove the foreign substances and unreacted phases to obtain a polyimide polymer solution.

Comparative Example  One

The DMF was charged with 704.2 g of DMAC at room temperature while passing nitrogen through a temperature-controlled stirring reactor connected to a nitrogen injection device and a dropping funnel, and then 32.02 g (0.1 mol) of TFMB as a fluorine-based diamine monomer was completely dissolved. 8.83 g (0.03 mol) of BPDA, which is an aromatic monomer, and 31.1 g (0.07 mol) of 6FDA as a fluorine monomer were added as anhydride monomers and reacted. After 1 hour, pyridine and acetic anhydride were added as a catalyst and dehydrating agent, and the mixture was heated to 70 ° C, reacted for 1 hour, and cooled to room temperature.

Then, it was precipitated in a mixed solution of MeOH and distilled water, and solidified. Sufficiently washed with MeOH, and dried thoroughly in a vacuum oven at 80 캜 for 6 hours to obtain a polyimide solid.

 The resulting polyimide solid was dispersed in a DMAC solution, filtered sufficiently to remove foreign matters and unreacted phases to obtain a polyimide polymer solution.

Comparative Example  2

A nitrogen-introducing reactor and a dropping funnel were connected to a thermostatable stirring reactor. While nitrogen was passed through the reactor, 704.2 g of DMPA was charged at room temperature, and 32.02 g (0.1 mol) of TFMB as a fluorine-based diamine monomer was completely dissolved. 8.83 g (0.03 mol) of BPDA, which is an aromatic monomer, and 31.1 g (0.07 mol) of 6FDA as a fluorine monomer were reacted as anhydride monomers. After 1 hour, pyridine and acetic anhydride were added as a catalyst and dehydrating agent, and the mixture was heated to 70 ° C, reacted for 1 hour, and cooled to room temperature.

Then, it was precipitated in a mixed solution of MeOH and distilled water, and solidified. Sufficiently washed with MeOH, and dried thoroughly in a vacuum oven at 80 캜 for 6 hours to obtain a polyimide solid.

 The resulting polyimide solid was dispersed in a DMPA solution, and sufficiently stirred to eliminate remaining solids and filtered to remove foreign matter and unreacted phases to obtain a polyimide polymer solution.

Example  2: Preparation of transparent polyimide film

The polyimide polymer solution obtained in Example 1 and Comparative Examples 1 and 2 was coated on a glass substrate with an applicator at a wet thickness of 400 μm and then heated and dried in a convection oven at 280 ° C. A polyimide film having a thickness of 탆 was prepared.

Example  3: Preparation of polyimide polymer solution for the production of colored polyimide film

In a temperature-controlled stirred reactor equipped with a nitrogen inlet and a dropping funnel, 242.45 g of DMPA was charged at room temperature while nitrogen was passed through. Then 10.91 g of PPDA was completely dissolved and 26.48 g of BPDA and 2.18 g of PMDA were added in turn. After 1 hour from complete dissolution, 0.2 g of PA was added and reacted for 16 hours to synthesize PAA. Then, 4,4'-methylenebis (N, N-diglycidylaniline) of 4000 ppm of the contents of monomers (DMPA, BPDA and PMDA) was dissolved in the same solvent as the reaction solvent, Respectively.

Comparative Example  3

Nitrogen was injected into a stirred reactor equipped with a nitrogen inlet and a dropping funnel. NMP (242.45 g) was charged at room temperature while passing nitrogen through the reactor. Then, 10.91 g of PPDA was completely dissolved and 26.48 g of BPDA and 2.18 g of PMDA were introduced. After 1 hour of complete dissolution, PAA was synthesized by adding 0.2 g of PA and reacting for 16 hours. Then, 4,4'-methylenebis (N, N-diglycidylaniline) of 4000 ppm of the monomer (PPDA, BPDA and PMDA) contents was dissolved in the solvent and added to the PAA after the reaction.

Example  4: Preparation of colored polyimide film

The polyimide polymer solution obtained in Example 3 and Comparative Example 3 was coated on a glass substrate with an applicator using a wet thickness of 350 占 퐉 and then heated to 450 占 폚 in a convention oven to prepare a polyimide film having a thickness of 20 占 퐉.

Experimental Example  One

The properties of the polyimide films synthesized in Examples 2 and 4 were evaluated by the following methods, and the results are shown in Tables 1 to 3 below.

Measurement of thermal expansion coefficient

The linear thermal expansion coefficient was measured according to TMA-method using TMA (TA instrument, Q400). The heating rate was measured at 5 ° C per minute and the cooling rate at 20 ° C per minute. Since the stress in the film may remain, the temperature was measured from 30 ° C to 300 ° C at a temperature below Tg. CTE values were measured at slope during cooling.

Permeability measurement

The average value was measured five times in the visible region using an optical measuring instrument (Nippon Denshoku Co., COH-400).

Yellowness measurement

The yellowness was measured using an optical measuring instrument (Nippon Denshoku, COH-400).

The measurement results are shown in Tables 1 to 3.

Transparent polyimide preparation (30 탆 film thickness) No. Classification Amine Anhydride catalyst menstruum CTE T YI Example 1 synthesis F-based monomer Aromatic structure monomer Catalyst and dehydrating agent DMAC 20.8 90.1 2.7 Dispersion After precipitation, drying, redispersing DMPA 17.6 90.3 3.1 Comparative Example 1 synthesis F-based monomer Aromatic structure monomer Catalyst and dehydrating agent DMAC 21.1 89.8 2.6 Dispersion After precipitation, drying, redispersing DMAC 20.5 89.7 4.5 Comparative Example 2 synthesis F-based monomer Aromatic structure monomer Catalyst and dehydrating agent DMPA 22.49 89.5 3.9 Dispersion After precipitation, drying, redispersing DMPA 21.05 89.72 4.1

Preparation of colored polyimide (20 탆 film thickness) Classification Amine Anhydride menstruum CTE T YI Example 3 synthesis Aromatic structure monomer Aromatic structure monomer DMPA 3.12 55.8 - Comparative Example 3 synthesis Aromatic structure monomer Aromatic structure monomer NMP 3.54 51.3 -

Comparison of synthetic solvent properties: DMPA, DMAC, NMP division DMPA DMAC NMP N, N-Dimethylpropionamide N, N-Dimethylacetamide 1-Methyl-2-pyrrolidinone CAS No. 758-96-3 127-19-5 872-50-4 confiscation 101.15 87.12 99.13 B.P 174-176 [deg.] C 165.1 DEG C. 202 ° C Refractive index 1.438 1.439 1.479 Dielectric constant 33.08 37.78 32.20 Dipole Moment 3.78D 3.72D 4.09D rescue

As can be seen from Tables 1 to 3, DMPA (dimethylpropionamide) was used in comparison with DMAC (N, N-Dimethylacetamide) or NMP (n-Methyl 2 pyrrolidone) which are conventionally used in the production of polyimide films. , It can be confirmed that the physical properties such as CTE and permeability are superior. Also, the monomers were more soluble in DMPA and showed high solubility.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the foregoing description, and all changes or modifications derived from the meaning and scope of the claims and the equivalents thereof are included in the scope of the present invention. .

Claims (14)

A polyimide polymer composition comprising a polyamic acid-polyimide copolymer, which is produced by using dimethylpropionamide (DMPA) as a synthesis solvent or a dispersion solvent and represented by Formula (1)
[Chemical Formula 1]

In Formula 1,
R ₁ is a fluorine group or an aromatic anhydride monomer,
R is a diamine monomer,
n is an integer of 1 to 1,000,
and m is an integer of 1 to 1,000.

The method according to claim 1,
The diamine monomer may be at least one selected from the group consisting of PPDA (p-phenylenediamine), ODA (4,4'-Oxydianiline), MDA (4,4'-Methylenedianiline), 2,2'- , TPE-R (1,3-BIS (4'-Aminophenoxy) benzene), TFMB (2,2'-Bis (trifluoromethyl) benzidine), HFBAPP (2,2- (1,3-diamino-2,4,5,6-tetrafluorobenzene), DDS (3,3-diamino-4-hydroxyphenyl) hexafluoropropane) (4-aminophenoxy) phenyl sulfone), m-BAPS (2,2-Bis [4- (3-Aminophenoxy) Benzene] Sulfone), and combinations thereof.
The method according to claim 1,
The anhydride monomer may be selected from the group consisting of BTDA (3,3 ', 4,4'-benzophenonetetracarboxylic dihydride), PMDA (pyromellitic dianhydride), BPDA (3,3', 4,4'-biphenyl tetracarboxylic acid hydrides), 6FDA 3,4-anhydrodicarboxyphenyl) -hexafluoropropanedianhydride), a-BPDA (2,3,3 ', 4-biphenyl tetracarboxylic acid dihydride), 4,4'- oxydiphthalic anhydride, DSDA (3,3', 4,4'- diphenylsulfone-tetracarboxylic dianhydride), BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, HQDA (hydroquinone diphthalic anhydride), and combinations thereof. , Polyimide polymer composition.
Adding an anhydride monomer to a synthetic solution containing a diamine monomer and reacting;
Adding a catalyst and a dehydrating agent to the reaction solution to react and solidify the catalyst; And
Dispersing the solidified product in DMPA (dimethylpropionamide)
≪ / RTI >
Adding an anhydride monomer to a dimethylpropionamide (DMPA) solution containing a diamine monomer and reacting;
Adding a terminal-capping agent to the reaction solution, and then reacting to synthesize a polyamic acid; And
Adding a cross-linking agent to the polyamic acid and mixing
≪ / RTI >
The method according to claim 4 or 5,
The diamine monomer may be at least one selected from the group consisting of PPDA (p-phenylenediamine), ODA (4,4'-Oxydianiline), MDA (4,4'-Methylenedianiline), 2,2'- , TPE-R (1,3-BIS (4'-Aminophenoxy) benzene), TFMB (2,2'-Bis (trifluoromethyl) benzidine), HFBAPP (2,2- (1,3-diamino-2,4,5,6-tetrafluorobenzene), DDS (3,3-diamino-4-hydroxyphenyl) hexafluoropropane) (4-aminophenoxy) phenyl sulfone), m-BAPS (2,2-Bis [4- (3-Aminophenoxy) Benzene] sulfone), and combinations thereof. ≪ Desc / Clms Page number 13 >
The method according to claim 4 or 5,
Wherein the anhydride monomer is an aromatic dianhydride monomer.
8. The method of claim 7,
The aromatic dianhydride monomer may be selected from the group consisting of BTDA (3,3 ', 4,4'-benzophenonetetracarboxylic dihydride), PMDA (pyromellitic dianhydride), BPDA (3,3', 4,4'-biphenyl tetracarboxylic acid hydydride), 6FDA (3,4-anhydrodicarboxyphenyl) -hexafluoropropanedianhydride), a-BPDA (2,3,3 ', 4-biphenyl tetracarboxylic acid dihydride), 4,4'- oxydiphthalic anhydride, DSDA (3,3' -diphenylsulfone-tetracarboxylic dianhydride), BPADA (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride), HQDA (hydroquinone diphthalic anhydride) and combinations thereof ≪ / RTI > by weight of the polyimide polymer composition.
The method according to claim 4 or 5,
Wherein at least one anhydride monomer is added to the polyimide polymer composition.
5. The method of claim 4,
Wherein the synthetic solvent is selected from the group consisting of an amide solvent, a ketone solvent, an ether solvent, an ester solvent, a symmetric glycol diether solvent, an ether solvent and combinations thereof. ≪ / RTI >
5. The method of claim 4,
Wherein the dehydrating agent comprises an acid anhydride, and the catalyst is selected comprising tertiary amines.
6. The method of claim 5,
Wherein the end-capping agent is selected from the group consisting of phthalic anhydride, tetradecyl succinic anhydride (TSA), hexadecyl succinic anhydride (HAS), octadecyl succinic anhydride (OSA), and combinations thereof. Gt;
6. The method of claim 5,
Wherein the cross-linking agent comprises 4,4'-methylenebis (N, N-diglycidylaniline).
A transparent or colored polyimide film formed from the polyimide polymer composition of claim 1.