KR101907320B1 - Polyimide film for flexible display device substrate - Google Patents

Abstract

The present invention relates to a polyimide film for flexible display device substrates. To this end, diamine p-PDA is added in an excessive proportion compared to s-BPDA which is an acid anhydride to provide polyimide which is polymerized with a polymerization factor added with a terminal encapsulant comprising a phthalic anhydride (PA), thereby enabling production of substrates for flexible display devices having positive CTE without deteriorating heat resistance even at a temperature of 350°C or higher. In addition, by applying the production method to produce the polyimide film having higher permeability than a polyimide film produced via simply compositions of diamine in an excessive amount, TFT devices can be produced more easily through align keys when producing devices on the polyimide substrates.

Description

POLYIMIDE FILM FOR FLEXIBLE DISPLAY DEVICE SUBSTRATE BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a polyimide film for a flexible display element substrate having improved residual stress and transmittance and a method of manufacturing the same.

Polyimide (PI) is a polymer having a relatively low crystallinity or mostly noncrystalline structure. It is easy to synthesize and can produce a thin film film. It also has advantages of not requiring a crosslinking agent for curing, transparency, rigid chain structure Is a polymer material with excellent heat resistance, chemical resistance, excellent mechanical properties, electrical properties and dimensional stability. It is widely used in electric and electronic materials such as automobile, aerospace, flexible circuit board, liquid crystal alignment film for LCD, have.

In particular, polyimide is a high-performance polymer material having high thermal stability, mechanical properties, chemical resistance, and electrical properties, and is growing as a substrate material for flexible display. In order to use it for display purposes, There is a problem that the thermal expansion coefficient should not be negative at a temperature of 350 DEG C or more in order to lower the defect rate due to the residual stress of the substrate in the heat treatment process. Therefore, many researches have been carried out to minimize changes in optical characteristics and thermal history while maintaining the basic characteristics of polyimide.

Flexible displays are increasingly in demand in the marketplace due to their free form factor, lightweight and thin features and unbreakable characteristics. In order to realize such a flexible display, polyimide composed of polyimide BPDA (3,3 ', 4,4'-biphenyltetracarboxylic dianhydride) -PDA (phenylene diamine) having excellent heat resistance is used.

It is known that when the diamine, which is a monomer in the polymerization of a polyimide for a substrate, and the diamine in a dianhydride are polymerized in an excess amount, it is advantageous in terms of viscosity and molecular weight stability. However, the substrate using polyimide polymerized with excess of diamine exhibits a shrinkage at high temperature due to a negative thermal expansion coefficient (CTE) at a high temperature of 350 ° C or higher. In addition, when cured at a temperature of 450 ° C or higher, There is a problem of deterioration. When the CTE is negative, residual stress is induced in the heat treatment process of the TFT process, resulting in various defects such as cracking of the inorganic film and lifting of the film.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polyimide film having improved transparency without causing shrinkage even in a high temperature process.

The present invention also provides a method for producing the polyimide film.

The present invention also provides a flexible display device comprising the polyimide film as a substrate.

In order to solve the above-described problems,

From polymerization components comprising less than 1 mole of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) per mole of 4,4'-para-phenylenediamine (pPDA) And polyimide film for a flexible display element substrate characterized in that a thermal expansion coefficient (CTE) is a positive value at a temperature of 350 ° C or higher by adding a phthalic anhydride (PA) to seal the terminal.

According to one embodiment, the 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) and 4,4'-paraphenylenediamine (pPDA) have a molar ratio of 0.98: 1. ≪ / RTI >

According to one embodiment, the transmittance of the polyimide substrate made of the polyimide composition may be 70% or more.

According to one embodiment, the end-cap comprising the PA may be polymerized in a 0.02 to 0.025 mole ratio to 1 mole of pPDA.

According to one embodiment, the polyimide film that has been cooled after the first temperature increase may be a positive temperature at a temperature of 350 DEG C or higher, where the CTE measured at the second temperature increase from 100 deg. C to 460 deg.

According to one embodiment, the CTE measured when the polyimide film cooled after the first temperature increase is subjected to the second temperature increase from 100 ° C to 460 ° C may have a value of 0 or more and 7 ° C / ppm or less.

In order to solve the other problems of the present invention, it has been proposed that in a polymerization solvent, 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s- BPDA) and a phthalic anhydride (PA) to produce a polyimide precursor;

Preparing a polyimide precursor solution comprising the polyimide precursor and an organic solvent;

Applying the polyimide precursor solution onto a substrate; And

And drying and heating the coated polyimide precursor solution to produce a polyimide film. The present invention also provides a method for producing a polyimide film for a flexible display device substrate.

According to one embodiment, in the curing process by drying and heating the polyimide precursor solution, the final curing temperature may be 450 캜 or higher.

In order to solve still another problem of the present invention, there is provided a flexible display device comprising the polyimide film.

The present invention provides a polyimide polymerized with polymerization initiator added with a terminal endblock containing a phthalic anhydride (PA) by adding an excess of p-PDA, which is a diamine, to s-BPDA, which is an acid anhydride, , It is possible to provide a substrate for a flexible display device having a positive CTE without deteriorating the heat resistance even at a temperature of 350 DEG C or more. Also, by manufacturing a polyimide film having a higher transmittance than that of a polyimide film prepared by simply preparing a diamine-excess composition through such a manufacturing method, it is possible to more easily manufacture a TFT device through an align key when a device is manufactured on a polyimide substrate.

Fig. 1 shows changes in thermal expansion of polyimide films according to Examples and Comparative Examples at 100 to 460 占 폚.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The present invention relates to a process for the preparation of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) comprising less than 1 mole of 3,3', 4,4'-biphenylcarboxylic dianhydride (s- Characterized in that the polyimide film for a flexible display element substrate is polymerized from a polymerization component and has a positive thermal expansion coefficient (CTE) at a temperature of 350 DEG C or more by encapsulating the terminal by adding phthalic anhydride (PA) .

In general, efforts have been made to improve the physical properties of a polyimide film by focusing on the stability of the viscosity and the molecular weight of the polyimide precursor solution by reacting the diamine excessively in the process of preparing the polyimide. However, A thermal stability problem such as a thermal expansion coefficient of the polyimide film indicating negative water at a high temperature may occur.

In particular, when a diamine excess amount of polyimide substrate is prepared by using NMP (N-methyl-2-pyrrolidone) solvent, CTE at a high temperature shows negative (shrinking behavior) The permeability may be lowered due to the amine terminal group. In the case of the polyimide film using NMP, a negative CTE may be generated at a temperature of 350 ° C or higher in the TMA measurement, which may induce residual stress on the substrate during the heat treatment process of the substrate device TFT applying the high temperature process temperature And may cause various defects such as cracks in the inorganic film and lifting of the film.

Accordingly, the present invention provides a polyimide having improved mechanical properties while improving thermal stability by adding an excess of diamine, endcapping the main chain with phthalic anhydride (PA) , A polyimide film having a positive thermal expansion coefficient even at a high temperature of 350 DEG C or more can be provided. That is, the shrinkage due to the high temperature was not caused.

The present invention relates to a process for producing a polyimide precursor composition comprising the above 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) and 4,4'-para-phenylenediamine (pPDA) in a ratio of 0.98: Can be polymerized in a molar ratio of 0.9875: 1 to 0.9890: 1.

In addition, the present invention can improve both heat resistance and permeability by adding phthalic anhydride together with s-BPDA and pPDA, and the phthalic anhydride can be used in a molar ratio of 0.02 to 0.025 relative to 1 mole of pPDA 0.022 to 0.025 molar ratio can be added and polymerized.

The polyimide film according to the present invention has a positive thermal expansion coefficient at a temperature of 350 ° C or higher, more specifically, a CTE measurement method using TMA, wherein the polyimide film cooled after the first heating is heated at 100 ° C to 460 ° C. The CTE value measured at the second temperature increase may be a positive value at a temperature of 350 ° C or higher, preferably 0 to 7 ppm / ° C, and preferably 0 to 6 ppm / Or less.

Examples of the method for encapsulating the terminal of the polyimide obtained from the diamine and the tetracarboxylic acid dianhydride using the terminal sealing agent include a method of reacting the tetracarboxylic acid dianhydride and the diamine followed by continuing the reaction by adding the terminal sealing agent, A method in which an end-capping agent is added to the diamine to react with the tetracarboxylic acid dianhydride, followed by further reaction with tetracarboxylic acid dianhydride, a method in which tetracarboxylic acid dianhydride, diamine and the terminal endblock agent are simultaneously added and reacted .

From the above reaction, the polyimide precursor having end-capped groups can be polymerized.

The polymerization reaction of the polyimide precursor can be carried out according to a usual polyimide precursor polymerization method such as solution polymerization.

The reaction may be carried out under anhydrous conditions, and the temperature during the polymerization may be -75 to 50 ° C, preferably 0 to 40 ° C. The diamine and the acid dianhydride may be contained in an amount of about 10 to 30% by weight in the polymerization solvent, and the polymerization time and the reaction temperature The molecular weight can be controlled accordingly.

Specific examples of the organic solvent that can be used in the polymerization reaction include gamma-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy- Ketones such as methyl-2-pentanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Examples of the solvent include ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propylene glycol, (DMF), diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-methylpyrrolidone N, N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylurea, N, N-dimethylacetamide, N, Dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) Ethane, bis [2- (2-methoxyethoxy)] ether, and mixtures thereof May be used.

Preferably, sulfoxide-based solvents such as dimethyl sulfoxide and diethyl sulfoxide; Formaldehyde type solvents such as N, N-dimethylformamide and N, N-diethylformamide; Acetamide-based solvents such as N, N-dimethylacetamide and N, N-diethylacetamide; Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone may be used alone or as a mixture. However, the present invention is not limited thereto. Further, aromatic hydrocarbons such as xylene and toluene may be further used.

The method for producing a polyimide film using the polyimide precursor is characterized in that the polyimide precursor composition comprising the polyimide precursor and the organic solvent is coated on one side of the substrate and separated from the substrate after the imidation and curing process .

Specifically, the polyimide precursor composition may be in the form of a solution in which a polyimide precursor is dissolved in an organic solvent. When the polyimide precursor composition has such a shape, for example, when a polyimide precursor is synthesized in an organic solvent, May be obtained by adding the polyimide precursor solution itself or the same solution obtained after the polymerization or diluting the polyimide precursor solution obtained after the polymerization with another solvent.

The polyimide precursor composition preferably contains a solid content in an amount such that the polyimide precursor composition has an appropriate viscosity in view of processability such as coating properties in the film forming step. The solid content is preferably 5 to 20 wt% based on the total weight of the polyimide precursor composition, ≪ / RTI > Alternatively, it may be desirable to adjust the polyimide precursor composition to have a viscosity of 400 to 50,000 cP. The viscosity of the polyimide precursor composition may be less than 400 cP, and when the viscosity of the polyimide precursor composition is more than 50,000 cP, the flowability of the display substrate using the polyimide precursor composition may be reduced during coating, It is possible to cause problems in the manufacturing process.

Next, the polyimide film can be produced by applying the polyimide precursor composition prepared above to one surface of the substrate, thermally imidizing and curing the polyimide precursor composition at a temperature of 80 ° C to 500 ° C, and then separating from the substrate.

In this case, the substrate may be glass, metal substrate, plastic substrate, or the like without any particular limitation. Among these, the polyimide precursor is excellent in thermal and chemical stability during the imidation and curing process, A glass substrate that can be easily separated without damage to the subsequently formed polyimide-based film may be desirable.

Specific examples of the coating method include a spin coating method, a bar coating method, a roll coating method, an air-knife method, a gravure method, a reverse roll method, a kiss roll method, a doctor blade method, A spray method, a dipping method, a brushing method, or the like may be used. Of these, it is more preferable to carry out the continuous process and to perform the casting method which can increase the imidization rate of the polyimide.

The polyimide precursor composition may also be applied over the substrate to a thickness range such that the polyimide film to be finally prepared has a thickness suitable for the display substrate.

Specifically, it may be applied in an amount such that the thickness is 10 to 30 mu m. After the application of the polyimide precursor composition, a drying process for removing the solvent present in the polyimide precursor composition prior to the curing process may be further optionally performed.

The drying process may be carried out according to a conventional method, specifically at a temperature of 140 ° C or lower, or 80 ° C to 140 ° C. If the drying temperature is lower than 80 캜, the drying process becomes longer. If the drying temperature is higher than 140 캜, the imidization rapidly proceeds to make it difficult to form a polyimide film having a uniform thickness.

Then, the curing process may be carried out by heat treatment at a temperature of 80 ° C to 500 ° C. The curing process may be carried out by a multi-stage heat treatment at various temperatures within the above-mentioned temperature range. The curing time in the curing step is not particularly limited and can be, for example, 3 to 60 minutes.

Further, a subsequent heat treatment step may be further optionally performed to increase the imidization ratio of the polyimide in the polyimide film after the curing step to form the polyimide-based film having the above-mentioned physical properties.

The subsequent heat treatment step is preferably performed at 200 ° C or higher, or 200 ° C to 500 ° C for 1 minute to 30 minutes. The subsequent heat treatment process may be performed once or may be performed in two or more stages. Specifically, it may be carried out in three stages including a first heat treatment at 200 to 220 캜, a second heat treatment at 300 캜 to 380 캜, and a third heat treatment at 400 to 500 캜, And curing at a temperature of 450 ° C or higher for 30 minutes or more.

Thereafter, the polyimide film formed on the substrate can be produced from the substrate by a conventional method to produce a polyimide film.

The polyimide according to the present invention may have a glass transition temperature of about 360 DEG C or higher. Since the polyimide film has such excellent heat resistance, the polyimide film can maintain excellent heat resistance and mechanical properties against high temperature heat added during the device manufacturing process.

The polyimide film according to the present invention may have a thermal decomposition temperature (Td 1%) of 1% or less, which is 550 ° C or more.

The polyimide film according to the present invention has excellent mechanical properties. For example, the elongation may be 20% or more, preferably 25% or more, and the tensile strength may be 500 MPa or more, preferably 520 MPa or more, more preferably 530 MPa or more, and the tensile modulus may be 10 GPa or more.

The present invention provides a polyimide film encapsulated with a terminal end-capping agent comprising a phthalic anhydride, thereby exhibiting a positive CTE value even at a high temperature and causing a negative CTE (contraction occurrence) It is possible to provide a polyimide film having high transmittance characteristics, preferably a polyimide film having a transmittance of 70% or more. In the case of manufacturing an element on the polyimide substrate, the align key The fabrication of the TFT device can be facilitated.

The polyimide according to the present invention can be used as a substrate for a device, a cover substrate for a display, an optical film, an IC (integrated circuit) package, an adhesive film, a multilayer flexible printed circuit (FPC) Protective films for optical discs, and the like.

The present invention provides a flexible display device including the polyimide film. For example, the display device may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), and the like. In particular, a low temperature polycrystalline silicon (LTPS) ) ≪ / RTI > process, although the present invention is not limited thereto.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Example 1 BPDA-pPDA / PA (98.9: 100: 2.2) polyimide polymerization

(57.259 mmol) of paraphenylenediamine (p-PDA) in a state where the reactor temperature was maintained at 25 占 폚, ≪ / RTI > 16.661 g (56.629 mmol) of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) and 56.96 g of NMP were added to the p-PDA solution at the same temperature, After that, polyamic acid was polymerized. Then, 0.187 g (1.260 mmol) of phthalic anhydride (PA) was added to the polyamic acid solution and stirred for a predetermined time to prepare a polyimide precursor.

The polyimide precursor solution was prepared by adding the organic solvent so that the solid concentration of the polyimide precursor solution prepared from the reaction was 12.8 wt%.

The polyimide precursor solution was spin-coated on a glass substrate. The glass substrate coated with the polyimide precursor solution was placed in an oven, heated at a rate of 6 ° C / min, and cured at 120 ° C for 10 minutes and at 460 ° C for 55 minutes. After completion of the curing process, the glass substrate was immersed in water to remove the film formed on the glass substrate and dried at 100 DEG C in an oven to prepare a polyimide film having a thickness of 10 mu m.

≪ Comparative Example 1 > BPDA-pPDA (98.9: 100) polyimide polymerization

(NMP) (N-methyl-2-pyrrolidone) was charged into a stirrer through which nitrogen gas flow was conducted. Then, 6.243 g (57.726 mmol) of paraphenylenediamine (p-PDA) ≪ / RTI > 16.797 g (57.091 mmol) of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) and 56.96 g of NMP were added to the above p-PDA solution at the same temperature, To prepare a polyimide precursor.

The polyimide precursor solution prepared from the reaction was prepared by adding the organic solvent so that the solid concentration of the polyimide precursor was 12.8 wt%.

The polyimide precursor solution was spin-coated on a glass substrate. The glass substrate coated with the polyimide precursor solution was placed in an oven, heated at a rate of 6 ° C / min, and cured at 120 ° C for 10 minutes and at 460 ° C for 55 minutes. After completion of the curing process, the glass substrate was immersed in water to remove the film formed on the glass substrate and dried at 100 DEG C in an oven to prepare a polyimide film having a thickness of 10 mu m.

Comparative Example 2 BPDA-PMDA-pPDA (88.9: 10: 100) polyimide polymerization

100 g of NMP (N-methyl-2-pyrrolidone) was charged into an agitator through which nitrogen gas flowed. 6.364 g (58.849 mmol) of paraphenylenediamine (p-PDA) ≪ / RTI > 15.393 g (52.316 mmol) of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) and 1.289 g (5.885 mmol) of pyromellitic dianhydride (PMDA) And 56.96 g of NMP were added at the same temperature and dissolved for a certain period of time and stirred to prepare a polyimide precursor.

The polyimide precursor solution prepared from the reaction was prepared by adding the organic solvent so that the solid concentration of the polyimide precursor was 12.8 wt%.

The polyimide precursor solution was spin-coated on a glass substrate. The glass substrate coated with the polyimide precursor solution was placed in an oven, heated at a rate of 6 ° C / min, and cured at 120 ° C for 10 minutes and at 460 ° C for 55 minutes. After completion of the curing process, the glass substrate was immersed in water to remove the film formed on the glass substrate and dried at 100 DEG C in an oven to prepare a polyimide film having a thickness of 10 mu m.

COMPARATIVE EXAMPLE 3 BPDA-PMDA-pPDA / PA (88.9: 10: 100: 2.2) polyimide polymerization

(P-PDA) (6.33 g, 58.363 mmol) while maintaining the temperature of the reactor at 25 占 폚, ≪ / RTI > 15.265 g (51.885 mmol) of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) and 1.273 g (5.836 mmol) of pyromellitic dianhydride (PMDA) were added to the p- And 56.96 g of NMP were added at the same temperature and dissolved for a certain period of time and stirred to prepare a polyimide precursor. Then, 0.190 g (1.284 mmol) of phthalic anhydride (PA) was added to the polyamic acid solution and stirred for a predetermined time to prepare a polyimide precursor.

The polyimide precursor solution prepared from the reaction was prepared by adding the organic solvent so that the solid concentration of the polyimide precursor was 12.8 wt%.

The polyimide precursor solution was spin-coated on a glass substrate. The glass substrate coated with the polyimide precursor solution was placed in an oven, heated at a rate of 6 ° C / min, and cured at 120 ° C for 10 minutes and at 460 ° C for 55 minutes. After completion of the curing process, the glass substrate was immersed in water to remove the film formed on the glass substrate and dried at 100 DEG C in an oven to prepare a polyimide film having a thickness of 10 mu m.

<Experimental Example 1>

The CTE, the thermal decomposition temperature, the mechanical properties and the permeability of each of the polyimide films prepared above were measured in the following manner and are shown in Table 1.

<Measurement of thermal expansion coefficient>

For each of the polyimide films prepared in Example 1 and Comparative Example 1, a film was prepared to have a size of 5 x 20 mm, and then the sample was loaded into a Q400 instrument of TA using an accessory. The actual measured film length was equal to 16 mm. The film was pulled up at a rate of 4 [deg.] C / min in a temperature range of 100 [deg.] C to 460 [deg.] C with 0.02 N, and then cooled at 4 [deg.] C / min in a temperature range of 460 [ Cooled at a rate of.

Then, each of the cooled samples was heated at a heating rate of 5 ° C / min at a temperature of 100 ° C to 460 ° C, and the change in thermal expansion of the sample was measured by TMA. The dimensional change of the sample according to the temperature change by the heating is shown in FIG. 1, and the thermal expansion coefficient measured in the temperature range is shown in Table 1 below.

<Measurement of thermal decomposition temperature>

Discovery TGA from TA instruments was used to measure the temperature at 1% weight reduction of the polymer in a nitrogen atmosphere.

&Lt; Measurement of mechanical properties &

Three to four dumbbell specimens were prepared in accordance with ASTM D 412, and then the elongation (%) and tensile strength (tensile strength) of each resin film were measured at a rate of 30 mm and 10 mm / (MPa) and tensile modulus (GPa) were measured.

<Transmittance>

The transmittance was measured according to JIS K 7105 using a transmittance meter (Model 8453 UV-visible Spectrophotometer, manufactured by Agilent Technologies) and the average transmittance was measured at a wavelength of 380 to 780 nm.

As shown in Table 1 and FIG. 1, Comparative Example 1, which is a polyimide film produced by mixing an excess of diamine, showed a negative CTE at a temperature of 350 ° C or higher and Comparative Example 2 having a BPDA-PMDA-pPDA skeleton And 3, the heat resistance was lowered by further including PMDA, and it was confirmed that the CTE appeared to be negative at a temperature of 350 ° C or higher. In addition, it can be seen that Comparative Example 3 shows a decrease in heat resistance as PMDA is added even though it is encapsulated with PA. Also, in Comparative Examples 2 and 3, the transmittance was also significantly reduced compared with the polyimide film of the present invention.

On the other hand, the polyimide film of Example 1, which is a polyimide film according to the present invention, is prepared by addition of a terminal blocking agent such as PA to the BPDA-pPDA backbone, thereby maintaining the mechanical properties and permeability, Can be seen. That is, the present invention can provide a polyimide film in which the CTE shrinkage property at high temperature is maintained while maintaining excellent mechanical properties derived from an excess amount of the polyimide film, and the heat resistance is remarkably improved, And it is possible to provide a more transparent and rigid polyimide film even in a high-temperature process.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (9)

Is polymerized from a polymerization component comprising 0.98 to 0.99 mole of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) relative to 1 mole of 4,4'-paraphenylenediamine (pPDA) (CTE) at a temperature of 350 ° C or higher to have positive (+) values. When the temperature is higher than 350 ° C, the thermal expansion coefficient (CTE) Wherein the polyimide film has a CTE of not less than 0 and not more than 7 ppm / 占 폚 measured when the polyimide film is cooled at a second temperature elevation from 100 占 폚 to 460 占 폚. delete The method according to claim 1,
Wherein the film has a transmittance of 70% or more. The method according to claim 1,
Wherein the end-capping agent comprising the PA is polymerized in a 0.02 to 0.025 molar ratio relative to 1 mole of pPDA. delete delete The polymerization solvent was added with 0.98 to 0.99 mole of 3,3 ', 4,4'-biphenylcarboxylic dianhydride (s-BPDA) relative to 1 mole of 4,4'-para-phenylenediamine (pPDA) And adding a phthalic anhydride (PA) as a terminal endblock to produce a polyimide precursor;
Preparing a polyimide precursor solution comprising the polyimide precursor and an organic solvent;
Applying the polyimide precursor solution onto a substrate; And
The method for manufacturing a polyimide film for a flexible display substrate according to claim 1, wherein the applied polyimide precursor solution is cured by drying and heating, and the final curing temperature is 450 ° C or higher. delete 5. A flexible display device comprising the polyimide film according to any one of claims 1, 3, and 4 as a substrate.

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