TW201736442A - 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 preparation method thereof, and a method of producing a polyimide film using the same.

Description

Polyimine polymer composition, preparation method thereof and method for preparing polyimine film using same

Cross-references to related applications.

The present application claims priority to Korean Patent Application No. 10-2015-0190927, filed on Dec. 31, 2015, to the Korean Intellectual Property Office, the entire disclosure of which is hereby incorporated by reference.

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

Polyimine resins have excellent electrical, thermal, chemical and mechanical properties compared to other polymer resins and are therefore used in a variety of applications, including advanced materials and electronic materials that are resistant to heat. In particular, polyimine resins have attracted attention as flexible substrate materials in the field of displays due to their high heat resistance.

In order to synthesize polyimine, a diamine monomer, a dianhydride monomer, and a polar solvent are usually used. The imidization is often carried out by a method such as a thermal imidization method or a chemical imidization method. When a chemical oxime imidation method is used, a catalyst and a dehydrating agent can be used for the chemical hydrazine imidization reaction.

In order to synthesize a polyimide resin having excellent heat resistance, an aromatic monomer should be used. In this case, the film made using the polyimide resin is brown or yellow, and thus has low transmittance in the visible light region. Since the use of such a polyimide resin is limited in the field where transparency is required, other compositions and structural designs are required to replace the glass substrate material. However, if one property is improved, other properties are lowered. Therefore, in order to manufacture a transparent flexible substrate that satisfies all transparency, thermal properties, and mechanical properties, it is necessary to develop a polyamic acid composition.

The solvent used for the synthesis of the polyimine is mostly a polar solvent which adversely affects the environment (Japanese Patent No. 5201155). However, since the desired properties cannot be obtained when these solvents are replaced with other solvents, it is still necessary to use these solvents.

The present inventors have made extensive efforts to solve the problems existing in the prior art, and as a result, a polyglycine/polyimine copolymer has been prepared by using dimethylpropionamine as a synthetic solvent or a dispersion solvent, thereby completing the present invention. .

In one aspect, the present invention provides a polyilylimine polymer composition comprising a poly-proline/polyimine copolymer represented by the following formula 1, wherein the poly-proline/polyimine copolymer is used in two Methylpropionamide is prepared as a synthetic solvent or dispersion solvent:

Formula 1

among them

R ₁ is a fluoro group or an aromatic anhydride monomer;

R is a diamine monomer;

n is an integer from 1 to 1,000; and,

m is an integer of 1 to 1,000.

In another aspect, the present invention provides a process for preparing a polyiminoimine polymer composition for preparing a transparent polyimide film, the method comprising the steps of: adding an anhydride monomer and allowing an anhydride monomer Reacting with a synthetic solvent containing a diamine monomer to obtain a reaction solution; reacting the reaction solution in the presence of a catalyst and a dehydrating agent, followed by solidification to obtain a solid matter; and dispersing the solid substance in dimethylpropanamide (DMPA) in.

In another aspect, the present invention provides a process for preparing a polyiminoimine polymer composition comprising the steps of: adding an anhydride monomer and reacting the anhydride monomer with a solution of a diamine monomer in dimethylpropionamide To obtain a reaction solution; to add an end-capping agent to the reaction solution, and then react the reaction solution to synthesize poly-proline; and to add a crosslinking agent and to make the crosslinking agent and poly-proline mixing.

In another aspect, the invention provides a clear or colored polyimide film formed from the polyimine polymer composition of the invention.

Hereinafter, the embodiments and examples of the present invention will be described in detail so that those skilled in the art can easily implement the present invention.

However, the invention may be embodied in a variety of different forms and is not limited to the embodiments and examples described herein.

In one aspect, the present invention provides a polyilylimine polymer composition comprising a poly-proline/polyimine copolymer represented by the following formula 1, wherein the poly-proline/polyimine copolymer is used Preparation of dimethylpropionamide (DMPA) as a synthetic solvent or dispersion solvent:

Formula 1:

among them

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

R is a diamine monomer;

n is an integer from 1 to 1,000;

m is an integer of 1 to 1,000.

In one embodiment of the invention, the polyimine polymer composition can be used to prepare a clear or colored polyimide film.

In an exemplary embodiment of the invention, the diamine monomer may comprise selected from PPDA (p-phenylenediamine), ODA (4,4'-oxydianiline). ), MDA (4,4'-methylenediphenylamine (4,4'-methylenedianiline)), m-toluidine (2,2'-dimethyl-4,4'-diaminobiphenyl (2, 2'-dimethyl-4,4'-diaminobiphenyl)), TPE-R (1,3-bis(4'-aminophenoxyl)benzene), TFMB (2,2'-bis(trifluoromethyl)benzidine), HFBAPP (2,2-bis[4-(4-aminophenoxy)benzene) 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane), BIS-AP-AF(2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro Propane (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), DRFB (1,3-diamino-2,4,5,6-tetrafluorobenzene (1,3-diamino-2, 4,5,6-tetrafluorobenzene ), DDS (3,3'-diaminodiphenyl sulfone), ASD (4,4'-diaminodiphenyl sulfide) (4,4'-diaminodiphenyl sulfide)), BAPS (bis[4-(4-aminophenoxy)phenyl]sulfonate), m-BAPS ( 2,2-bis[4-(3-amine The group consisting of phenoxy) phenyl] sulfone (2,2-bis [4- (3-aminophenoxy) benzene] sulfone)) and combinations of one. Suitable diamine monomers can be selected depending on the properties desired in the field of using polyimine. In order to produce a polyimide film having high heat resistance and a low coefficient of thermal expansion, a diamine monomer having an aromatic structure may be selected and used, and in order to synthesize a colored polyimide film having no transparency requirement, PPDA monomer is preferably used. . Further, in order to synthesize a transparent polyimine, a fluorine-based monomer such as a TFMB monomer may be used.

In one embodiment of the invention, the anhydride monomer may be an aromatic dianhydride monomer. For example, the anhydride monomer may include a solvent selected from the group consisting of BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride), PMDA (homobenzene tetra) Pyromellitic dianhydride, BPDA (3,3',4,4'-biphenyl tetracarboxylic acid dianhydride), 6FDA (2, 2-Bis (3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride (), a-BPDA (2,3,3', 4-(3,3',4-biphenyl tetracarboxylic acid dianhydride), ODPA (4,4'-oxydiphthalic anhydride) , DSDA (3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride), BPADA (2,2-double [4- (2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride), HQDA (hydroquinone diphthalic anhydride) One of a group consisting of hydroquinone diphthalic anhydride) and combinations thereof. One or more, for example, two or more monomers may be used as the aromatic dianhydride monomer. Suitable anhydride monomers are used depending on the properties required in the field of using polyimine. In order to synthesize a colored polyimide film exhibiting high heat resistance and high transparency, BPDA and PMDA monomers can be used. In order to synthesize a transparent polyimine, it is preferred to use a 6FDA monomer, and in order to improve the heat resistance and mechanical properties of the polyimide film, it is preferred to use a BPDA monomer.

In another aspect, the present invention provides a process for preparing a polyiminoimine polymer composition for preparing a transparent polyimide film, the method comprising the steps of: adding an anhydride monomer and allowing the anhydride monomer to contain a diamine The synthesis solvent of the monomer is reacted to obtain a reaction solution; the reaction solution is reacted in the presence of a catalyst and a dehydrating agent, followed by solidification to obtain a solid substance; and the solid substance is dispersed in dimethylpropionamide (DMPA). .

In another aspect, the present invention provides a process for preparing a polyiminoimine polymer composition comprising the steps of: adding an anhydride monomer and allowing the anhydride monomer to be combined with dimethylpropanamide (DMPA) containing a diamine monomer. The solution is reacted to obtain a reaction solution; an end-capping agent is added to the reaction solution, and then the reaction solution is reacted to synthesize polylysine; then a crosslinking agent is added and the polyamine is added The acid is mixed with the crosslinking agent.

In one embodiment of the invention, the polyimine polymer composition can be used to prepare a clear or colored polyimide film.

In one embodiment of the invention, the diamine monomer may comprise a substrate selected from the group consisting of PPDA (p-phenylenediamine), ODA (4,4'-oxydiphenylamine), MDA (4,4'-methylenediphenylamine). , m-toluidine (2,2'-dimethyl-4,4'-diaminobiphenyl), TPE-R (1,3-bis(4'-aminophenoxy)benzene), TFMB ( 2,2'-bis(trifluoromethyl)benzidine), HFBAPP (2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane), BIS-AP-AF (2 , 2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), DRFB (1,3-diamino-2,4,5,6-tetrafluorobenzene), DDS (3,3' -diaminodiphenylphosphonium), ASD (4,4'-diaminodiphenyl sulfide), BAPS (bis[4-(4-aminophenoxy)phenyl]anthracene), m- One of a group consisting of BAPS (2,2-bis[4-(3-aminophenoxy)benzene]indole) and combinations thereof. Suitable diamine monomers can be selected depending on the properties desired in the field of using polyimine. In order to produce a polyimide film having high heat resistance and a low coefficient of thermal expansion, a diamine monomer having an aromatic structure may be selected and used, and in order to synthesize a colored polyimide film having no transparency requirement, PPDA single is preferably used. body. Further, in order to synthesize a transparent polyimine, a fluorine-based monomer such as a TFMB monomer may be used.

In one embodiment of the invention, the anhydride monomer may be an aromatic dianhydride monomer. For example, the anhydride monomer may include a solvent selected from the group consisting of BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride), PMDA (pyromellitic dianhydride), BPDA (3,3', 4 , 4'-biphenyltetracarboxylic dianhydride), 6FDA (2,2-bis(3,4-dehydrated dicarboxyphenyl)-hexafluoropropane dianhydride), a-BPDA (2,3,3', 4-biphenyltetracarboxylic dianhydride), ODPA (4,4'-oxydiphthalic anhydride), DSDA (3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride), BPADA (2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, HQDA (hydroquinone diphthalic anhydride), and combinations thereof 1. One or more, for example two or more, monomers may be used as the aromatic dianhydride monomer. Suitable anhydride monomers may be used depending on the properties required in the field of using polyimides. BPDA and PMDA monomers can be used for the high-heat-resistance and non-transparent color-sensitive polyimide film. In addition, in order to synthesize the transparent polyimide, it is preferred to use 6FDA monomer, and in order to improve the heat resistance of the polyimide film For sexual and mechanical properties, it is preferred to use a BPDA monomer.

In one embodiment of the present invention, the synthetic solvent is not particularly limited as long as it is a solvent used in the art. For example, the synthetic solvent may include one selected from the group consisting of amide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and symmetry. One of a group consisting of a symmetric glycol diether solvent, an ether solvent, and combinations thereof. The guanamine solvent may include dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.; the ketone solvent may include acetone. (acetone), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, and the like. Ether-based solvents may include tetrahydrofuran (THF), 1,3-dioxolane and 1,4-dioxane; esters Ester-based solvents may include methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, α-lactone ( --acetolactone), β-propiolactone, δ-valerolactone, etc. (δ-valerolactone). The symmetric glycol diether solvent may include methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (double) (2-methoxyethyl)ether), methyl diglyme (bis(2-methoxyethyl)ether), methyl diglyme (1,2-bis(2-methoxyethoxy)B (methyl triglyme (1,2-bis(2-methoxyethoxy)ethane)), methyltetraglyme dimethyl ether 2-(2-methoxyethoxyethyl)] ether) (methyl tetraglyme (bis) [2-(2-methoxyethoxyethyl)]ether)), ethyl monoglyme (1,2-diethoxyethane), ethyl diethylene glycol Diethyl ether (bis(2-ethoxyethyl)ether), butyl diglyme (bis(2-butoxyethyl)ether) (butyl diglyme (bis(2-butoxyethyl)ether), etc., and ether solvents may include glycol diether, dipropylene glycol methyl ether, tripropylene glycol methyl ether (tripropylene glycol methyl ether), propylene glycol-n-propyl ether, dipropylene glycol n-propyl ether (diprop Gylene glycol-n-propyl ether), propylene glycol-n-butyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol-n-propyl ether Glycol-n-propyl ether), propylene glycol phenyl ether, dipropylene glycol methyl ether, 1,3-dioxolane, ethylene glycol Ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether Wait.

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

In one embodiment of the invention, the capping agent may be selected from the group consisting of PA (phthalic anhydride), TSA (tetradecyl succinic anhydride), HAS (hexadecyl amber). A group consisting of hexadecyl succinic anhydride, OSA (octadecyl succinic anhydride), and combinations thereof, and preferably may be PA. The blocking agent is used to control the polymerization reaction, and can control the molecular weight of the polymer in the form of monoanhydride, reduce the content of unreacted substances, and improve storage stability.

In one embodiment of the invention, the method may further comprise the step of adding a capping agent after the step of adding the anhydride monomer and reacting the anhydride monomer with a synthetic solvent containing the diamine monomer.

In one embodiment, the quinone imidization reaction in the polyimine polymer composition synthesized from the poly-proline solution may be a thermal imidation reaction and a chemical imidization reaction (chemical Combination of imidation reaction). When the two oxime imidization reactions are carried out in combination, there is a temperature which can lower the heat oxime imidization reaction, and the advantage of the unreacted phase remaining during the synthesis can be removed in advance by the precipitation method.

In one embodiment of the invention, a dehydrating agent and a catalyst can be used in the oxime imidization reaction. The dehydrating agent may include an acid anhydride such as acetic anhydride, and the catalyst may include a tert-amine such as pyridine, isoquinoline or β-picoline.

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

In one embodiment of the invention, the method may further comprise the step of adding a crosslinking agent to the polyamidene polymer composition.

In another aspect, the present invention provides a transparent or colored polyimide film formed from a polyimide composition of the present invention.

In one embodiment of the present invention, the polyimide film may be prepared by a method comprising the steps of: coating a polyimide composition on a substrate; and heating and drying the polyimide coated with polyimine. The substrate of the composition.

In one embodiment of the present invention, a transparent or colored polyimide film can be prepared according to the kind of the diamine monomer and the anhydride monomer used in the preparation of the polyimide pigment polymer composition.

In the following, the invention will be described in further detail with reference to examples, but the scope of the invention is not limited by the examples.

Example

Example 1: Preparation of a Polyimine Polymer Solution for Preparing a Transparent Polyimine Film

While nitrogen was passed through the reactor, 704.2 g of DMAC was charged to a temperature-controlled reactor equipped with a stirrer, a nitrogen inlet, and a dropping funnel at room temperature. Then, 32.02 g (0.1 mol) of the fluorodiamine monomer TFMB was dissolved in DMAC. To the solution, 8.83 g (0.03 mol) of an aromatic monomer BPDA and 31.1 g (0.07 mol) of a fluorine-based monomer 6FDA which are an anhydride monomer were added and reacted. About 1 hour after complete dissolution, pyridine as a catalyst and acetic anhydride as a dehydrating agent were added to the reaction solution. Next, the reaction solution was heated to 70 ° C, allowed to react at this temperature for 1 hour, and then cooled to room temperature.

Then, the reaction solution was precipitated and solidified in a mixed solution of MeOH and distilled water (3:1).

The formed solid was sufficiently washed with MeOH, and then sufficiently dried in a vacuum oven at 80 ° C for 6 hours to obtain a solid polyimine polymer.

The obtained solid polyimine was dispersed in a DMPA solution and stirred well to dissolve the residual solid. Next, the stirred solution was filtered to remove foreign matter and an unreacted phase, thereby obtaining a polyilylimine polymer solution.

Comparative example 1

While nitrogen was passed through the reactor, 704.2 g of DMAC was charged to a temperature-controlled reactor equipped with a stirrer, a nitrogen inlet, and a dropping funnel at room temperature. Then, 32.02 g (0.1 mol) of the fluorodiamine monomer TFMB was dissolved in DMAC. To the solution, 8.83 g (0.03 mol) of an aromatic monomer BPDA which is an anhydride monomer and 31.1 g (0.07 mol) of a fluorine-based monomer 6FDA were added and reacted. About 1 hour after complete dissolution, pyridine as a catalyst and acetic anhydride as a dehydrating agent were added to the reaction solution. Next, the reaction solution was heated to 70 ° C, allowed to react at this temperature for 1 hour, and then cooled to room temperature.

Then, the resulting solution was precipitated in a mixed solution of MeOH and distilled water, and then solidified.

The obtained solid substance was sufficiently washed with MeOH, and then sufficiently dried in a vacuum oven at 80 ° C for 6 hours to obtain a solid polyimine.

The obtained solid polyimine was dispersed in a DMAC solution and thoroughly stirred to dissolve the residual solid. Next, the stirred solution was filtered to remove foreign matter and an unreacted phase, thereby obtaining a polyilylimine polymer solution.

Comparative example 2

While nitrogen was passed through the reactor, 704.2 g of DMPA was charged to a temperature-controlled reactor equipped with a stirrer, a nitrogen inlet, and a dropping funnel at room temperature. Then, 32.02 g (0.1 mol) of the fluorodiamine monomer TFMB was dissolved in DMAC. To the solution, 8.83 g (0.03 mol) of an aromatic monomer BPDA which is an anhydride monomer and 31.1 g (0.07 mol) of a fluorine-based monomer 6FDA were added and reacted. About 1 hour after complete dissolution, pyridine as a catalyst and acetic anhydride as a dehydrating agent were added to the reaction solution. Next, the reaction solution was heated to 70 ° C, allowed to react at this temperature for 1 hour, and then cooled to room temperature.

Then, the resulting solution was precipitated in a mixed solution of MeOH and distilled water, and then solidified.

The obtained solid substance was sufficiently washed with MeOH, and then sufficiently dried in a vacuum oven at 80 ° C for 6 hours to obtain a solid polyimine.

The obtained solid polyimine was dispersed in a DMPA solution and stirred well to dissolve the residual solid. Next, the stirred solution was filtered to remove foreign matter and an unreacted phase, thereby obtaining a polyilylimine polymer solution.

Example 2: Preparation of a transparent polyimide film

The polyimine polymer solution obtained in Example 1 and Comparative Examples 1 and 2 was coated on a glass substrate to a thickness of 400 μm (on a wet basis) using an applicator, and then heated to 280 in a convection oven. °C, thereby preparing a polyimide film having a thickness of 30 μm.

Example 3: Preparation of a Polyimine Polymer Solution for Preparing a Colored Polyimine Film

While nitrogen was passed through the reactor, 242.45 g of DMPA was charged to a temperature-controlled reactor equipped with a stirrer, a nitrogen inlet, and a dropping funnel at room temperature. Then, 10.91 g of PPDA was completely dissolved in DMPA, and 26.48 g of BPDA and 2.18 g of PMDA were sequentially added thereto. One hour after complete dissolution, 0.2 g of PA was added to the solution, which was then allowed to react for 16 hours to synthesize PAA. Then, based on the content of the monomers (PPDA, BPDA, and PMDA), 4000 ppm of a 4,4'-methylenebis(N,N-diepoxypropylaniline) solution in the same solvent as the reaction solvent was added. It is mixed with the reaction product PAA.

Comparative Example 3: Preparation of Polyimine Polymer Solution for Preparing Colored Polyimine Films

While nitrogen was passed through the reactor, 242.45 g of NMP was charged to a temperature-controlled reactor equipped with a stirrer, a nitrogen inlet, and a dropping funnel at room temperature. Then, 10.91 g of PPDA was completely dissolved in NMP, and 26.48 g of BPDA and 2.18 g of PMDA were sequentially added thereto. One hour after complete dissolution, 0.2 g of PA was added to the solution, which was then allowed to react for 16 hours to synthesize PAA. Then, based on the content of the monomers (PPDA, BPDA and PMDA), 4000 ppm of a 4,4'-methylenebis(N,N-bis-epoxypropylaniline) solution in a solvent is added and mixed with the reaction product PAA. .

Example 4: Preparation of Colored Polyimine Film

The polyimine polymer solution obtained in Example 3 and Comparative Example 3 was coated on a glass substrate to a thickness of 350 μm (on a wet basis) using an applicator, and then heated to 450 ° C in a convection oven. Thus, a polyimide film having a thickness of 20 μm was prepared.

Test example 1

The physical properties of the polyimide film prepared in the above Examples 2 and 4 were evaluated in the following manner, and the evaluation results are shown in the following Tables 1 to 3.

Measurement of thermal expansion coefficient

The linear thermal expansion coefficient of each polyimide film was measured according to the TMA method using TMA (Q400, TA Instrument). The measurement was carried out at a heating rate of 5 ° C / min and a cooling rate of 20 ° C / min. Further, since the stress in the film may remain, the measurement is performed at a temperature range of 30 ° C to 300 ° C which is lower than the glass transition temperature (Tg) of the film. The coefficient of thermal expansion (CTE) of each film was measured with a gradient during cooling.

Transmittance measurement

The light transmittance of each film was measured five times with an optical measuring device (COH-400, Nippon Denshoku), and the measured values were averaged.

Measurement of yellowness index

The yellowing of each film was measured using an optical measuring device (COH-400, Nippon Denshoku).

The measurement results are shown in Table 1, Table 2, and Table 3. Table 1: Preparation of transparent polyimine (film thickness: 30 μm) Table 2: Preparation of colored polyimine (film thickness: 20 μm) Table 3: Comparison of physical properties of synthetic solvents (DMPA, DMAC and NMP)

As can be seen from Tables 1 to 3 above, with the use of DMAC (N,N-dimethylacetamide) or NMP (n-methyl-2-pyrrolidone) which is a polyimine film of the conventional art. Compared to the polar solvent used in the manufacture, DMPA (dimethylpropionamide) is used to exhibit better physical properties such as CTE and transmittance. In addition, the monomer shows higher solubility in DMPA.

As described above, according to the present invention, dimethylpropionamide is used in synthesis or dispersion instead of the polar solvent used in the conventional art for synthesizing polyimine, and thus it is possible to avoid the use of a polar solvent which adversely affects the environment. The use of the DMPA according to the present invention provides a polyimide film having improved properties such as coefficient of thermal expansion (CTE) and transmittance compared to the use of a conventional polar solvent.

The above-described embodiments of the present invention are for illustrative purposes only, and it is understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention. Therefore, the embodiments are to be understood in all respects only illustrative and not restrictive. For example, each component described in a single form can be executed in a distributed fashion, and similarly, components described in a distributed form can be executed in combination.

While the invention has been described with reference to the various embodiments of the present invention, it will be understood by those of ordinary skill in the art that the invention may be practiced without departing from the spirit and scope of the disclosure and the equivalents thereof. Various changes in form and detail.

no.

no.

no.

Claims (14)

A polyimine polymer composition comprising dimethyl propylamine (DMPA) and a poly phthalic acid/polyimine copolymer represented by the following formula 1: Formula 1 Wherein R ₁ is a fluorine group or an aromatic anhydride monomer; R is a diamine monomer; n is an integer of from 1 to 1,000; and m is an integer of from 1 to 1,000. The polyimine polymer composition according to claim 1, wherein the diamine single system is selected from the group consisting of PPDA (p-phenylenediamine), ODA (4,4'-oxydiphenylamine), MDA (4) , 4'-methylenediphenylamine), m-toluidine (2,2'-dimethyl-4,4'-diaminobiphenyl), TPE-R (1,3-bis(4'-amine) Phenoxy group) phenyl), TFMB (2,2'-bis(trifluoromethyl)benzidine), HFBAPP (2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane), BIS-AP-AF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), DRFB (1,3-diamino-2,4,5,6-four Fluorobenzene), DDS (3,3'-diaminodiphenylphosphonium), ASD (4,4'-diaminodiphenyl sulfide), BAPS (bis[4-(4-aminophenoxy) Group of phenyl] fluorene), m-BAPS (2,2-bis[4-(3-aminophenoxy)benzene]indole), and combinations thereof. The polyimine polymer composition according to claim 1, wherein the anhydride single system is selected from the group consisting of BTDA (3,3',4,4'-benzophenonetetracarboxylic dianhydride), PMDA (pyromellitic dianhydride), BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride), 6FDA (2,2-bis(3,4-dehydrodicarboxyphenyl)-hexa Fluoropropane dianhydride), a-BPDA (2,3,3',4-biphenyltetracarboxylic dianhydride), ODPA (4,4'-oxydiphthalic anhydride), DSDA (3,3' , 4,4'-diphenylphosphonium tetracarboxylic dianhydride), BPDA (2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride), HQDA (hydroquinone) Group of diphthalic anhydride) and combinations thereof. A method for preparing a polyimine polymer composition for preparing a transparent polyimide film, the method comprising the steps of: adding an anhydride monomer and reacting the anhydride monomer with a synthetic solvent containing a diamine monomer Obtaining a reaction solution; reacting the reaction solution in the presence of a catalyst and a dehydrating agent, followed by solidification to obtain a solid substance; and dispersing the solid substance in dimethylpropanamide (DMPA). A method for preparing a polyilylimine polymer composition, comprising the steps of: adding an anhydride monomer and reacting an anhydride monomer with dimethylpropanamide (DMPA) containing a diamine monomer to obtain a reaction solution; To the reaction solution, a terminal agent is added, and then the reaction solution is reacted to synthesize poly-proline; and a crosslinking agent is added and the crosslinking agent is mixed with poly-proline. The method of claim 4, wherein the diamine monosystem is selected from the group consisting of PPDA (p-phenylenediamine), ODA (4,4'-oxydiphenylamine), MDA (4, 4' -methylenediphenylamine), m-toluidine (2,2'-dimethyl-4,4'-diaminobiphenyl), TPE-R (1,3-bis(4'-aminophenoxy) Benzene), TFMB (2,2'-bis(trifluoromethyl)benzidine), HFBAPP (2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane), BIS-AP-AF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), DRFB (1,3-diamino-2,4,5,6-tetrafluorobenzene) , DDS (3,3'-diaminodiphenylphosphonium), ASD (4,4'-diaminodiphenyl sulfide), BAPS (bis[4-(4-aminophenoxy)benzene) a group consisting of m-BAPS (2,2-bis[4-(3-aminophenoxy)benzene]indole) and combinations thereof. The method of claim 4, wherein the anhydride monomer is an aromatic dianhydride monomer. The method of claim 7, wherein the aromatic dianhydride monomer comprises a monomer selected from the group consisting of BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride), PMDA (isophenylene) Acid dianhydride), BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride), 6FDA (2,2-bis(3,4-dehydrated dicarboxyphenyl)-hexafluoropropane dianhydride ), a-BPDA (2,3,3',4-biphenyltetracarboxylic dianhydride), ODPA (4,4'-oxydiphthalic anhydride), DSDA (3,3',4,4 '-Diphenylphosphonium tetracarboxylic dianhydride), BPADA (2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride), HQDA (hydroquinone diphenylene) Group of anhydrides and combinations thereof. The method of claim 4, wherein the anhydride monomer added comprises one or more anhydride monomers. The method of claim 4, wherein the synthetic solvent comprises a solvent selected from the group consisting of a guanamine solvent, a ketone solvent, an ether solvent, an ester solvent, a symmetric glycol diether solvent, an ether solvent, and combinations thereof. One of the groups. The method of claim 4, wherein the dehydrating agent comprises an acid anhydride, and the catalyst comprises a tertiary amine. The method of claim 5, wherein the blocking agent is selected from the group consisting of PA (phthalic anhydride), TSA (tetradecyl succinic anhydride), HAS (cetyl succinic anhydride), OSA a group consisting of (octadecyl succinic anhydride) and combinations thereof. The method of claim 5, wherein the crosslinking agent comprises 4,4'-methylenebis(N,N-diepoxypropylaniline). A transparent or colored polyimide film formed from the polyimide composition described in claim 1 of the patent application.