WO2016108675A1 - Polyamide-imide precursor, polyamide-imide film, and display device comprising same - Google Patents

Abstract

The present invention relates to: a polyamide-imide precursor, comprising, in a molecular structure, a first block obtained by copolymerizing monomers including dianhydride and diamine, a second block obtained by copolymerizing monomers including an aromatic dicarbonyl compound and diamine, and a third block obtained by copolymerizing monomers including an aromatic dicarbonyl compound and aromatic diamine, wherein the dianhydride for forming the first block contains 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), and wherein the diamine for forming the first and second blocks contains 9,9-bis(3-fluoro-4-aminophenyl)fluorene (FFDA); a polyamide-imide obtained by imidizing the precursor; a polyamide-imide film; and an image display device comprising the film.

Description

Polyamide-imide precursor, polyamide-imide film and display device comprising the same

The present invention relates to a polyamide-imide precursor, a polyamide-imide film imidized thereto, and a display device including the polyamide-imide film.

In general, a polyimide (PI) film is a film of a polyimide resin, and a polyimide resin is a solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by ring closure dehydration at a high temperature. The high heat resistant resin manufactured by imidation is called. Since such polyimide films have excellent mechanical, heat resistance, and electrical insulation properties, they are used in a wide range of fields for electronic materials such as semiconductor insulating films, TFT-LCD electrode protective films, and flexible printed circuit boards.

However, polyimide resins are usually colored brown and yellow due to their high aromatic ring density, which results in low transmittance in the visible range and yellowish color. As a result, the light transmittance is lowered, and a large birefringence is exhibited, which makes it difficult to use the optical member.

In order to solve this limitation, a method of purifying and polymerizing monomers and a solvent has been attempted in the past, but the improvement of the transmittance was not large. On the other hand, US Patent No. 5053480 uses a method of using an aliphatic ring-based dianhydride component instead of an aromatic dianhydride, thereby improving transparency and color in solution or film formation. However, this was only an improved effect compared to the purification method, ultimately there is a limit to improve the permeability, high permeability was not achieved, but rather resulted in thermal and mechanical degradation.

In addition, U.S. Pat.Nos. 4,595,548,4603061, 4,464,824,4895972, 52,18083, 5,345,3, 52,18077, 53,670,46,533,826. No. 5986036, 6262328 and Korea Patent Publication No. 2003-0009437 have a substituent such as -CF ₃ , or the p-position by a linking group such as -O-, -SO _2- , CH _2- The use of aromatic dianhydride dianhydrides and aromatic diamine monomers having a bent structure connected to m-positions has led to the disclosure of novel polyimide structures having improved transmittance and clarity of color as long as the thermal properties are not significantly reduced. However, this also has a limitation in terms of mechanical properties, heat resistance, birefringence, it was confirmed that it is insufficient to use as a display device material such as OLED, TFT-LCD, flexible display.

Accordingly, the present invention is to provide a polyamide-imide precursor for forming a film having a low birefringence and colorless transparency and excellent mechanical properties and heat resistance. In addition, the present invention provides a polyamide-imide film prepared by imidating the polyamide-imide precursor and an image display device including the same.

A first preferred embodiment of the present invention for solving the above problems is a first block copolymerized monomers comprising dianhydride and diamine; A second block copolymerized with monomers comprising an aromatic dicarbonyl compound and a diamine; And a polyamide-imide precursor comprising in the molecular structure a third block copolymerized with monomers comprising an aromatic dicarbonyl compound and an aromatic diamine. Provided that the dianhydride forming the first block includes 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and forms the first block and the second block. Diamines include 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA).

In addition, a second preferred embodiment of the present invention is a polyamide-imide resin having a structure obtained by imidizing the polyamide-imide precursor of the first embodiment, and the third embodiment is a polyamide- of the first embodiment. It is a polyamide-imide film manufactured by imidating an imide precursor.

Furthermore, a fourth preferred embodiment of the present invention is an image display device comprising the polyamide-imide film of the third embodiment.

When the polyamide-imide precursor of the present invention is imidized, it is possible to form a film or a film having low birefringence and colorless transparency and excellent mechanical properties and heat resistance. In particular, the polyamide-imide film of the present invention can be usefully used in various fields such as semiconductor insulating film, TFT-LCD insulating film, passivation film, liquid crystal alignment film, optical communication material, solar cell protective film, flexible display substrate and the like.

1 is an example in which the polyamide-imide precursor of the present invention is imidized, wherein a first block (A) in which 6FDA and FFDA are polymerized, a second block (B) in which TPC and FFDA are polymerized, and TPC and TFBD are polymerized Molecular structural formulas showing the molecular structure of the polyamide-imide comprising the third block (C).

The present invention comprises a first block copolymerized with monomers comprising dianhydride and diamine; A second block copolymerized with monomers comprising an aromatic dicarbonyl compound and a diamine; And it provides a polyamide-imide precursor comprising a third block copolymerized with monomers comprising an aromatic dicarbonyl compound and an aromatic diamine in the molecular structure. Provided that the dianhydride forming the first block includes 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and forms the first block and the second block. Diamines include 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA).

More specifically, the present invention provides a dianhydride including 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA); A first block copolymerized with a diamine comprising 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA); A second block copolymerized with an aromatic dicarbonyl compound and a diamine comprising 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA); And it provides a polyamide-imide precursor comprising a third block copolymerized with an aromatic dicarbonyl compound and an aromatic diamine in the molecular structure.

When the polyamide-imide precursor of the present invention is filmed for use as a substrate or a protective layer of an image display device, the first block including an imide bond may be excellent in optical as well as thermal and mechanical properties. The second block and the third block including an amide bond and a polymerized so as to exist simultaneously in the molecular structure. That is, by securing the mechanical properties that may be insufficient in the case of the conventional imide structure only through the second block and the third block having the amide bond structure, the thermal stability, mechanical properties, low birefringence and optical properties are finally improved in a balanced manner. It can be done.

In particular, in the present invention, by using 6FDA as the dianhydride forming the first block, birefringence improvement and heat resistance can be ensured, and above all, the bulk bond in the molecular structure as the diamine forming the first block and the second block. Optical use by aromatic dicarbonyl compounds introduced into the second and third blocks by using 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA) containing a benzene ring of structure The deterioration of a characteristic can be prevented effectively.

In this case, the first block and the second block in the present invention is preferably included so that the sum is 20 to 80 mol% with respect to the total block copolymer 100 mol in order to improve the yellowness and birefringence, side to prevent mechanical properties deterioration It may be more preferably included to be from 40 to 60 mol%. When the sum of the first block and the second block is less than 20 mol%, since the molar ratio of the third block is relatively high, the mechanical properties may be improved, but the optical properties such as yellowness and yellowness may decrease rapidly. When the sum of the first block and the second block exceeds 80 mole%, the improvement of the mechanical properties may be insignificant, such that distortion and tearing may occur in the display manufacturing process.

In addition, in the present invention, the first block and the second block preferably has a molar ratio of 2: 8 to 8: 2. If the content of the first block does not fall within the above range, thermal stability and mechanical properties may be improved, but optical properties such as yellowness or transmittance may be deteriorated and birefringence may be high, and thus may not be suitable for use as an optical device. On the other hand, if the content of the second block does not fall within the above range, the effect of improving the thermal stability and mechanical properties may not meet the expectations.

In the present invention, the aromatic dicarbonyl compound forming the second block and the third block includes terephthaloyl chloride (pPC), terephthalic acid, and isophthaloyl dichloride (Iso). -phthaloyl dichloirde) and 4,4'-benzoyl dichloride (4,4'-benzoyl chloride) may be one or more selected from the group consisting of, more preferably terephthaloyl chloride (p-Terephthaloyl chloride, TPC) And isophthaloyl dichloride (Iso-phthaloyl dichloirde) may be used at least one selected from.

As the aromatic diamine forming the third block, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (HFBAPP) and bis (4- (4-aminophenoxy) phenyl Sulfone (BAPS), bis (4- (3-aminophenoxy) phenyl) sulfone (BAPSM), 4,4'-diaminodiphenylsulfone (4DDS), 3,3'-diaminodiphenylsulfone (3DDS) ), 2,2-bis (4- (4-aminophenoxy) phenyl propane) (6HMDA), 4,4'-diaminodiphenylpropane (6HDA), 4,4'-diaminodiphenylmethane (MDA ), 4,4'-diaminodiphenylsulfide (4,4'-Thiodianiline), 4,4'-diaminodiphenyl diethylsilane, 4,4'-diaminodiphenylsilane (44DDS), 4,4'-diaminodiphenyl N-methylamine, 4,4'-diaminodiphenyl N-phenylamine (4,4'-diaminodiphenyl N-phenylamine), 1,3-diaminobenzene (m-PDA), 1,2-diaminobenzene (o-PDA), 4,4'-oxydianiline (44'ODA), 3,3'- Oxydianiline (33 'ODA), 2,4-oxydianiline (24'ODA), 3,4'-oxydianiline ( 34 'ODA), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 4,4'-bis (3- Diamines having at least one soft group selected from the group consisting of aminophenoxy) biphenyl (M-Tolidine) and 4,4'-bis (4-aminophenoxy) biphenyl (BAPB) can be used.

In the present invention, the aromatic diamine forming the third block is distinguished from 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA) which is the diamine forming the first block and the second block. It may be. If FFDA is also included in the third block, the structure may be the same as that of the second block, and thus sufficient mechanical properties according to the three-component structure may be difficult to express. Similarly, if the aromatic diamine forming the third block is replaced with FFDA in the first and second blocks, the structure of the second block and the third block is the same, and thus the optical properties and birefringence are increased. Can come. That is, the first and second blocks preferably include FFDA, a Cardo-based diamine containing a benzene ring of bulk structure, and the third block uses the aromatic diamine to secure mechanical properties. It is preferable.

In addition, when a structure derived from an aromatic dicarbonyl compound is included in the molecular structure, it may be easy to implement high thermal stability and mechanical properties, but birefringence may be high due to benzene ring in the molecular structure. Therefore, in the present invention, it may be more preferable to use the aromatic diamine forming the third block having a flexible group introduced into the molecular structure in order to prevent birefringence reduction caused by the aromatic dicarbonyl compound. In particular, bis (4- (3-aminophenoxy) phenyl) sulfone (BAPSM), 4,4'-diaminodiphenylsulfone (4DDS) and 2, in which the length of the flexible group is long and the position of the substituent is in the meta position At least one aromatic diamine selected from, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (HFBAPP) may be advantageous for achieving good birefringence.

Dianhydrides comprising 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) polymerizing the monomers; A first block copolymerized with a diamine comprising 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA); A second block copolymerized with an aromatic dicarbonyl compound and a diamine comprising 9,9-bis (3-fluoro-4-aminophenyl) fluoroene (FFDA); And a polyamide-imide precursor of the present invention comprising a third block copolymerized with an aromatic dicarbonyl compound and an aromatic diamine in a molecular structure, measured by gel permeation chromatography (GPC) in a solid concentration range of about 20 to 25 wt%. One weight average molecular weight is 60,000 to 70,000, and the viscosity is preferably 400ps to 600ps.

On the other hand, the present invention may provide a polyamide-imide film prepared by imidating a polyamide-imide resin having a structure in which the polyamide-imide precursor is dehydrated, that is, imidized. In this case, in order to manufacture a polyamide-imide resin or a polyamide-imide film by using the polyamide-imide precursor, the following imidization step may be performed.

First, a polyamide-imide precursor solution is prepared by copolymerizing <dianhydride and aromatic dicarbonyl compound> and <diamine and aromatic diamine> satisfying the above-described conditions of the present invention in an equivalent ratio of 1: 1 based on the total monomer molar ratio. do. At this time, the polymerization conditions are not particularly limited, but may be preferably performed in an inert atmosphere such as nitrogen or argon at -10 to 80 ℃ for 2 to 48 hours.

In this case, a solvent may be used for the solution polymerization of the monomers, and the solvent is not particularly limited as long as it is a known reaction solvent. Preferably, m-cresol and N-methyl-2-pyrrolidone (NMP) are used. One or more polar solvents selected from dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate and the like can be used. In addition, a low boiling point solution such as tetrahydrofuran (THF), chloroform or the like or a low absorbing solvent such as γ-butyrolactone may be used.

In addition, the content of the solvent is not particularly limited, but in order to obtain the molecular weight and viscosity of the appropriate polyamide-imide precursor solution, the content of the solvent is preferably 50 to 95% by weight of the total polyamide-imide precursor solution. And it may be more preferable that it is 70 to 90% by weight.

The obtained polyamide-imide precursor solution can then be appropriately selected and imidized by a known imidization method, and examples thereof include thermal imidization, chemical imidization, thermal imidization and chemical imidization. It can be applied in combination.

In the chemical imidization method, a polyamide-imide precursor solution is reacted by adding an imidization catalyst represented by a dehydrating agent represented by an acid anhydride such as acetic anhydride and tertiary amines such as isoquinoline, β-picolin, and pyridine. The thermal imidization method is a method in which the polyamide-imide precursor solution is gradually heated in a temperature range of 40 to 300 ° C. and heated and reacted for 1 to 8 hours.

In this invention, the composite imidation method which used together the thermal imidation method and the chemical imidation method is applicable as an example of manufacturing a polyamide-imide film. In the complex imidization method, more specifically, a dehydrating agent and an imidization catalyst are added to a polyamide-amide precursor solution, and cast on a support, followed by heating at 80 to 200 ° C, preferably 100 to 180 ° C, to dehydrate and imidize. The catalyst may be activated, partially cured and dried, followed by a series of processes heating at 200 to 400 ° C. for 5 to 400 seconds.

In addition, in the present invention, after the obtained polyamide-imide precursor solution is imidized, the imidized solution is added to a second solvent, precipitated, filtered and dried to obtain a solid content of the polyamide-imide resin. It is also possible to produce a polyamide-imide film by dissolving the obtained polyamide-imide resin solid content in a 1st solvent and forming into a film. The polyamide-imide resin solid content is filtered and dried under conditions of boiling point of the second solvent, the temperature is preferably 50 to 120 ° C, and the time is 3 to 24 hours, and the film forming process is cast to 40 to 400 It may be performed by heating for 1 minute to 8 hours while gradually increasing the temperature in the temperature range of ℃.

In addition, the same solvent as the solvent used in the polymerization of the polyamide-imide precursor solution may be used as the first solvent, and the second solvent may be more polar than the first solvent in order to obtain a solid content of the polyamide-imide resin. One or more of these low solvents, namely, water, alcohols, ethers and ketones can be used. At this time, the content of the second solvent is not particularly limited, but is preferably 5 to 20 times by weight based on the weight of the polyamide-imide precursor solution.

In the present invention, the polyamide-imide film obtained can be heat treated once more to solve the thermal history and residual stress remaining in the film. At this time, the temperature of the additional heat treatment process is preferably 300 to 500 ℃, the heat treatment time is preferably 1 minute to 3 hours, the residual volatile content of the film after the heat treatment may be 5% or less, preferably 3% or less. . As a result, the thermally treated film finally exhibits very stable thermal characteristics.

Although the thickness of the said polyamide-imide film in this invention is not specifically limited, It is preferable that it is the range of 5-100 micrometers, More preferably, it is 9-15 micrometers.

The polyamide-imide film according to the present invention has a birefringence (n) defined as Transeverse Elictric (TE) -TM (Transverse magnetic) based on a film thickness of 10 to 50 µm of 0.030 or less, and a transmittance measured at 550 nm. It is 88% or more and exhibits optical characteristics with yellowness of 5 or less, so that it can be usefully used as an optical element such as a substrate or a protective layer of a display.

In addition, the polyimide film according to the present invention has a linear thermal expansion coefficient (CTE) of 60 ppm measured twice at 50 to 250 ° C. by TMA-Method based on a film thickness of 10 to 50 μm. It is less than / ℃, and the elongation at break measured based on ASTM D882 is 5% or more, so it can exhibit excellent yield because it does not bend or deform easily even in the severe process temperature or rapid temperature change during display fabrication.

Furthermore, the present invention can provide an image display device having excellent optical and physical properties and high manufacturing yield by including the aforementioned polyimide film.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention more specifically, and the present invention is not limited thereto.

Example 1

The reactor was filled with 398.628 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler. 49.207 g (0.128 mol) of fluoro-4-aminophenyl) fluoroene (FFDA) were dissolved. Then, 10.247 g (0.032 mol) of 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) was added thereto, followed by reaction for 2 hours, and 10.247 g of bis trifluoromethylbenzidine (TFDB). 0.032 mol) was added. After maintaining the temperature of the solution below 10 ℃ and 25.987 g (0.128 mol) of terephthaloyl chloride (TPC) was added and then reacted at low temperature for 1 hour and then heated to room temperature and reacted for 18 hours. A polyamide-amide precursor solution having a concentration of solids of 20% by weight and a viscosity of 120 poise was obtained.

After the reaction was completed, the obtained solution was applied to a stainless plate, cast at 10 to 20 μm, dried at 80 ° C. for 20 minutes, at 120 ° C. for 20 minutes, and at 300 ° C. for 10 minutes of isothermal hot air, and then gradually cooled. The polyamide-imide film having a thickness of 20 μm was prepared by separating from the plate.

Example 2

FFDA 30.754 g (0.08 mol) was charged after filling 386.301 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler as a reactor. Dissolved. Thereafter, 14.216 g (0.032 mol) of 6FDA was added thereto and reacted for 2 hours, and TFDB 25.618 g (0.08 mol) was added thereto. After the temperature of the solution was maintained at 10 ℃ or less, TPC 25.987g (0.128mol) was added and reacted for 1 hour at low temperature, then the temperature was raised to room temperature and reacted for 18 hours. As a result, the concentration of solid content was 20 weight %, A polyamide-amide precursor solution having a viscosity of 640 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Example 3

After filling 401.714 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler as a reactor, 19.606 g (0.051 mol) of FFDA was added. Dissolved. Thereafter, 15.105 g (0.034 mol) of 6FDA was added thereto and reacted for 2 hours, and 38.107 g (0.119 mol) of TFDB was added thereto. After maintaining the temperature of the solution to 10 ℃ or less, TPC 27.611g (0.136mol) was added and then reacted for 1 hour at low temperature, the temperature was raised to room temperature and reacted for 18 hours, as a result the concentration of solid content 20 weight %, A polyamide-amide precursor solution having a viscosity of 1100 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Example 4

The reactor was filled with 390.410 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler, followed by 36.905 g (0.096 mol) of FFDA. Dissolved. Thereafter, 14.216 g (0.032 mol) of 6FDA was added thereto, followed by reaction for 2 hours, and 20.495 g (0.064 mol) of TFDB was added thereto. After the temperature of the solution was maintained at 10 ℃ or less, TPC 25.987g (0.128mol) was added and reacted for 1 hour at low temperature, then the temperature was raised to room temperature and reacted for 18 hours. As a result, the concentration of solid content was 20 weight %, A polyamide-amide precursor solution having a viscosity of 610 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Example 5

The reactor was filled with 405.849 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler, followed by 36.905 g (0.096 mol) of FFDA. Dissolved. Thereafter, 21.324 g (0.048 mol) of 6FDA was added thereto and reacted for 2 hours, and 20.495 g (0.064 mol) of TFDB was added thereto. After the temperature of the solution was maintained at 10 ℃ or less, TPC 22.738g (0.112mol) was added and then reacted at low temperature for 1 hour and then heated to room temperature and reacted for 18 hours. As a result, the concentration of solid content was 20 weight %, A polyamide-amide precursor solution having a viscosity of 590 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Example 6

After filling with 394.957 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler as a reactor, 34.599 g (0.09 mol) of FFDA was added. Dissolved. Thereafter, 26.655 g (0.06 mol) of 6FDA was added thereto and reacted for 2 hours, and 12.914 g (0.06 mol) of TFDB was added thereto. Thereafter, the temperature of the solution was maintained at 10 ° C. or lower, and then 18.272 g (0.09 mol) of TPC was added thereto, followed by reaction at low temperature for 1 hour, and then heated to room temperature for 18 hours. As a result, the concentration of solids was 20 weight. %, A polyamide-amide precursor solution having a viscosity of 550 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Example 7

As a reactor, 398.288 g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler, followed by 31.139 g (0.081 mol) of FFDA. Dissolved. Thereafter, 23.99 g (0.054 mol) of 6FDA was added thereto, followed by reaction for 2 hours, and 27.999 g (0.054 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (HFBAPP) was added thereto. Thereafter, the temperature of the solution was maintained at 10 ° C. or lower, and then TPC 16.445g (0.081 mol) was added thereto, followed by reaction at low temperature for 1 hour, and then heated to room temperature for 18 hours. As a result, the concentration of solids was 20 weight. %, A polyamide-amide precursor solution having a viscosity of 420 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 1

After filling 338.101 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler as a reactor, 39.212 g (0.102 mol) of FFDA was added. Dissolved. Thereafter, after maintaining the temperature of the solution at room temperature, 6FDA 45.314g (0.102mol) was added thereto and reacted for 18 hours to obtain a polyamide-amide precursor solution having a solid content of 20 wt% and a viscosity of 120 poise.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 2

The reactor was filled with 399.466 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler, followed by 65.353 g (0.17 mol) of FFDA. After maintaining the temperature of the solution to 10 ℃ or less, TPC 34.513g (0.17mol) was added and then reacted for 1 hour at low temperature, the temperature was raised to room temperature and reacted for 18 hours. Polyamide-amide precursor solution having a weight of 20 wt.% And a viscosity of 150 poise.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 3

As a reactor, 397.530 g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler, followed by 41.630 g (0.13 mol) of TFDB. Dissolved. Thereafter, after maintaining the temperature of the solution at room temperature, 6FDA 57.753 g (0.13 mol) was added thereto and reacted for 18 hours to obtain a polyamide-amide precursor solution having a solid content of 20 wt% and a viscosity of 1750 poise.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 4

The reactor was filled with 397.670 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler, followed by 60.844 g (0.19 mol) of TFDB. Dissolved. After maintaining the temperature of the solution below 10 ℃, TPC 38.574g (0.19mol) was added and then reacted for 1 hour at low temperature, the temperature was raised to room temperature and reacted for 18 hours, as a result the concentration of solid content 20 weight %, A polyamide-amide precursor solution having a viscosity of 2100 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 5

The reactor was filled with 388.660 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler, followed by 9.611 g (0.025 mol) of FFDA. Dissolved. Then, after maintaining the temperature of the solution at room temperature, TFDB 32.023g (0.1mol) was added and 2 hours later 6FDA 55.531g (0.125mol) was added. The reaction was carried out for 18 hours. As a result, a polyamide-amide precursor solution having a concentration of solids of 20% by weight and a viscosity of 1100 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 6

As a reactor, 398.290 g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler, followed by FFDA 24.027 g (0.0625 mol). Dissolved. Then, after maintaining the temperature of the solution at room temperature, 20.014g (0.0625mol) of TFDB was added, and 55.531g (0.125mol) of 6FDA was added after 2 hours. The reaction was carried out for 18 hours, and as a result, a polyamide-amide precursor solution having a concentration of solids of 20% by weight and a viscosity of 550 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 7

FFDA 38.443 g (0.1 mol) was charged after filling 407.920 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler as a reactor. Dissolved. After the solution was maintained at room temperature, TFDB 8.006g (0.025mol) was added, and 2 hours later, 6FDA 55.531g (0.125mol) was added thereto. The reaction was carried out for 18 hours. As a result, a polyamide-amide precursor solution having a concentration of solids of 20% by weight and a viscosity of 110poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 8

After filling with 438.887 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 26.141 g (0.068 mol) of FFDA was added. Dissolved. Thereafter, 30.209 g (0.068 mol) of 6FDA was added and reacted for 2 hours, and 32.663 g (0.102 mol) of TFDB was added thereto. Thereafter, the temperature of the solution was maintained at 10 ° C. or lower, and then 20.708 g (0.102 mol) of TPC was added thereto, followed by reaction at low temperature for 1 hour, and then heated to room temperature for 18 hours. As a result, the concentration of solids was 20 weight. %, A polyamide-amide precursor solution having a viscosity of 920 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 9

After filling with 421.425 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, TFDB 54.439 g (0.17 mol) was charged. Dissolved. Then, 6FDA 30.209g (0.068mol) was added and reacted for 2 hours, the temperature of the solution was maintained at 10 ℃ or less, TPC 20.708g (0.102mol) was added and then reacted at low temperature for 1 hour and then at room temperature It heated up and reacted for 18 hours, As a result, the polyamide-amide precursor solution which is 20 weight% of solid content, and the viscosity is 710poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 10

The reactor was filled with 465.081 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler, followed by 65.353 g (0.17 mol) of FFDA. Dissolved. Then, 6FDA 30.209g (0.068mol) was added and reacted for 2 hours, the temperature of the solution was maintained at 10 ℃ or less, TPC 20.708g (0.102mol) was added and then reacted at low temperature for 1 hour and then at room temperature It heated up and reacted for 18 hours, As a result, the polyamide-amide precursor solution which is 20 weight% of solid content, and is 220 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 11

FFDA 29.217g (0.076mol) was charged after filling 417.187g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler as a reactor. Dissolved, and 36.506 g (0.114 mol) of TFDB was dissolved while maintaining the temperature. Then, after maintaining the temperature of the solution to 10 ℃ or less, TPC 38.574g (0.190mol) was added and reacted for 1 hour at low temperature, the reaction was raised to room temperature for 18 hours, the result was a solid concentration of 20 A polyamide-amide precursor solution having a weight percentage of 530 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 12

After filling with 420.722 g of N-methyl-2-pyrrolidone (NMP) while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler as a reactor, 46.113 g (0.144 mol) of TFDB was added. Dissolved. Thereafter, 15.993 g (0.036 mol) of 6FDA was added thereto and reacted for 2 hours, and 13.839 g (0.036 mol) of FFDA was added thereto. After maintaining the temperature of the solution below 10 ℃, TPC 29.235g (0.144mol) was added and then reacted at low temperature for 1 hour and then heated to room temperature and reacted for 18 hours, as a result the concentration of solid content 20 weight %, A polyamide-amide precursor solution having a viscosity of 325 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Comparative Example 13

As a reactor, 450.566 g of N-methyl-2-pyrrolidone (NMP) was charged while passing nitrogen through a 500 ml reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller, and a cooler, followed by 58.433 g (0.152 mol) of FFDA. Dissolved. Thereafter, 11.180 g (0.038 mol) of BPDA was added thereto, followed by reaction for 6 hours, and 12.169 g (0.038 mol) of TFDB was added thereto. Thereafter, the temperature of the solution was maintained at 10 ° C. or lower, and then 30.859 g (0.152 mol) of TPC was added thereto. The reaction was carried out at low temperature for 1 hour, and then heated to room temperature for 18 hours. %, A polyamide-amide precursor solution having a viscosity of 280 poise was obtained.

Thereafter, a polyamide-imide film was prepared in the same manner as in Example 1.

Measurement Example

The physical properties of the polyamide-imide films prepared in Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.

(1) Viscosity: 6 times or 7 times at 25 rpm using a Brookfield viscometer (RVDV-II + P) and twice at 50 rpm using a scandal to measure the average value.

(2) Measurement of transmittance: The transmittance was measured three times at 550 nm using a UV spectrometer (Cotica Minolta CM-3700d), and the average values are shown in Table 1.

(3) Yellowness (Y.I.) measurement: The yellowness was measured by ASTM E313 standard using a UV spectrometer (Konita Minolta, CM-3700d).

(4) birefringence measurement: using a birefringence analyzer (Prism Coupler, Sairon SPA4000) measured the average value by measuring three times in each of the TE (Transeverse Elictric) and TM (Transverse magnetic) mode at 532nm, (TE mode)-( TM mode) is reflected in the birefringence value.

(5) Measurement of coefficient of thermal expansion (CTE): The linear coefficient of thermal expansion at 50 to 250 was measured twice according to the TMA-Method using TMA (TA Instrument, Q400). The size of the specimen was 4 mm x 24 mm, the load was 0.02 N, and the temperature increase rate was 10 / min. At this time, since the residual stress may remain in the film through the film formation and heat treatment, the second value was presented as a real measurement after the residual stress was completely removed in the first run.

(6) Elongation at break (%) measurement: Measurement was made according to the standard of ASTM-D882 using Instron 5967. Specimen size was measured at 15mm × 100mm, Load cell 1KN, and tension rate at 10mm / min.

Table 1 division Component ¹⁾ Molar ratio A / B / C ²⁾ Viscosity 550nm transmittance (%) YI Example 1 (FFDA: TFDB) :( 6FDA: TPC) (8: 2) :( 2: 8) 0.2 / 0.6 / 0.2 120 90.00 1.65 Example 2 (FFDA: TFDB) :( 6FDA: TPC) (5: 5) :( 2: 8) 0.2 / 0.3 / 0.5 640 90.70 1.35 Example 3 (FFDA: TFDB) :( 6FDA: TPC) (3: 7) :( 2: 8) 0.2 / 0.1 / 0.7 1100 88.70 3.46 Example 4 (FFDA: TFDB) :( 6FDA: TPC) (6: 4) :( 2: 8) 0.2 / 0.4 / 0.4 610 90.65 1.41 Example 5 (FFDA: TFDB) :( 6FDA: TPC) (6: 4) :( 3: 7) 0.3 / 0.3 / 0.4 590 90.72 1.52 Example 6 (FFDA: TFDB) :( 6FDA: TPC) (6: 4) :( 4: 6) 0.4 / 0.2 / 0.4 550 90.68 1.48 Example 7 (FFDA: HFBAPP) :( 6FDA: TPC) (6: 4) :( 4: 6) 0.4 / 0.2 / 0.4 420 90.20 1.62 Comparative Example 1 FFDA: 6FDA 10:10 1/0/0 120 89.79 1.09 Comparative Example 2 FFDA: TPC 10:10 0/1/0 150 88.65 0.98 Comparative Example 3 TFDB: 6FDA 10:10 1/0/0 1750 90.34 1.37 Comparative Example 4 TFDB: TPC 10:10 0/0/1 2100 76.87 23.9 Comparative Example 5 (FFDA: TFDB): 6FDA (2: 8): 10 1/0/0 1100 90.97 1.09 Comparative Example 6 (FFDA: TFDB): 6FDA (5: 5): 10 1/0/0 550 90.75 0.73 Comparative Example 7 (FFDA: TFDB): 6FDA (8: 2): 10 1/0/0 110 90.24 0.74 Comparative Example 8 (FFDA: TFDB) :( 6FDA: TPC) (4: 6) :( 4: 6) 0.4 / 0 / 0.6 920 88.53 3.52 Comparative Example 9 TFDB: 6FDA: TPC 10: 4: 6 0.4 / 0 / 0.6 710 89.21 3.07 Comparative Example 10 FFDA: 6FDA: TPC 10: 4: 6 0.4 / 0.6 / 0 220 90.11 1.78 Comparative Example 11 FFDA: TFDB: TPC 4: 6: 10 0 / 0.4 / 0.6 530 88.72 3.34 Comparative Example 12 (TFDB: FFDA) :( 6FDA: TPC) (8: 2) :( 2: 8) 0.2 / 0.6 / 0.2 325 90.17 2.03 Comparative Example 13 (FFDA: TFDB) :( BPDA: TPC) (8: 2) :( 2: 8) 0.2 / 0.6 / 0.2 280 87.11 5.17

1) In the case of the same monomer, the order of description corresponds to the order of input.

2) A = first block, B = second block, C = third block

TABLE 2 division Prism coupler Linear thermal expansion coefficient (ppm / ℃) Elongation at Break (%) Transverse electric mode Transverse magnetic mode Birefringence Example 1 1.6609 1.6436 0.0173 50.91 3.92% Example 2 1.6494 1.6304 0.0190 34.40 5.31% Example 3 1.6551 1.6223 0.0328 36.68 5.02% Example 4 1.6482 1.6300 0.0182 37.12 5.11% Example 5 1.6517 1.6364 0.0153 39.99 4.98% Example 6 1.6544 1.6395 0.0149 40.37 5.03% Example 7 1.6714 1.6583 0.0121 44.50 6.11% Comparative Example 1 1.6090 1.6014 0.0076 62.22 3.40% Comparative Example 2 1.6958 1.6811 0.0147 47.25 4.01% Comparative Example 3 1.5604 1.5520 0.0084 54.04 3.84% Comparative Example 4 1.6621 1.5461 0.1160 28.81 6.29% Comparative Example 5 1.5757 1.5593 0.0164 63.28 3.38% Comparative Example 6 1.5769 1.5663 0.0106 63.76 2.61% Comparative Example 7 1.6086 1.5998 0.0088 66.70 2.58% Comparative Example 8 1.6581 1.6109 0.0472 31.21 5.41% Comparative Example 9 1.6614 1.6189 0.0425 34.37 4.99% Comparative Example 10 1.6522 1.6430 0.0092 61.78 3.22% Comparative Example 11 1.6417 1.5999 0.0418 33.42 4.52% Comparative Example 12 1.6618 1.6490 0.0128 59.43 3.28% Comparative Example 13 1.5432 1.5195 0.0237 42.17 4.78%

As shown in Table 1 and Table 2, Examples 1 to 7 have the same level of transmittance, yellowness, and birefringence as those of Comparative Examples 1, 3, and 5 to 7, which are conventional polyimide substrates, but have a low coefficient of thermal expansion. The optical properties and heat resistance were excellent, and at the same time, the elongation at break was greater than or equal to that of Comparative Examples 2 and 4, which are polyamides, indicating that the mechanical properties were excellent. In particular, in the case of adding HFBAPP, a diamine having a long length of the flexible group as in Example 7, it can be seen that the birefringence and elongation at break more improved.

In addition, when the second block in which the FFDA and the aromatic dicarbonyl compound were copolymerized was not included in the molecular structure as in Comparative Examples 8 and 9, there was a limit of optical characteristics (decreased transmittance and increase in birefringence difference). When the 1st block or the 2nd block is not formed like 10 and 11, heat resistance (comparative example 10) or birefringence (comparative example 11) fell according to the case of the block which is not formed. In addition, when FFDA was not included as the diamine forming the first block and the second block, the heat resistance was not sufficient as in Comparative Example 12, and when 6FDA was not included as the dianhydride forming the first block, the comparison was performed. As in Example 13, the yellowness value was found to be undesirable.

 The present invention relates to a polyamide-imide precursor, and is applicable to an imide-ized polyamide-imide, polyamide-imide film, and an image display device including the film.

Claims (12)

A first block copolymerized with monomers comprising dianhydride and diamine; A second block copolymerized with monomers comprising an aromatic dicarbonyl compound and a diamine; And A third block copolymerized with monomers comprising an aromatic dicarbonyl compound and an aromatic diamine in a molecular structure, The dianhydride forming the first block includes 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), and the diamine forming the first block and the second block. Is a 9,9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) polyamide-imide precursor. The method of claim 1, wherein the aromatic dicarbonyl compounds forming the second block and the third block are terephthaloyl chloride (TPC), terephthalic acid, isophthaloyl dichloride ( Iso-phthaloyl dichloirde) and polyamide-imide precursor, characterized in that at least one member selected from the group consisting of 4,4'-benzoyl dichloride. The method of claim 1, wherein the aromatic diamine forming the third block is 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (HFBAPP), bis (4- (4-aminophenoxy). Phenyl) sulfone (BAPS), bis (4- (3-aminophenoxy) phenyl) sulfone (BAPSM), 4,4'-diaminodiphenylsulfone (4DDS), 3,3'-diaminodiphenyl Sulfone (3DDS), 2,2-bis (4- (4-aminophenoxy) phenyl propane) (6HMDA), 4,4'-diaminodiphenylpropane (6HDA), 4,4'-diaminodiphenyl Methane (MDA), 4,4'-Thiodianiline, 4,4'-diaminodiphenyl diethylsilane, 4,4'-diamino Diphenylsilane (44DDS), 4,4'-diaminodiphenyl N-methylamine (4,4'-diaminodiphenyl N-methyl amine), 4,4'-diaminodiphenyl N-phenylamine (4,4 '-diaminodiphenyl N-phenylamine), 1,3-diaminobenzene (m-PDA), 1,2-diaminobenzene (o-PDA), 4,4'-oxydianiline (44'ODA), 3, 3'-oxydianiline (33 'ODA), 2,4-oxydianiline (24'ODA), 3,4'-oxy Dianiline (34 'ODA), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 4,4'-bis Polyamide-imide, characterized in that at least one member selected from the group consisting of (3-aminophenoxy) biphenyl (M-Tolidine) and 4,4'-bis (4-aminophenoxy) biphenyl (BAPB) Precursor. The polyamide-imide precursor of claim 1, wherein the first block and the second block comprise 30 to 80 mole% of the sum of the total block copolymers. The polyamide-imide precursor of claim 1, wherein the first block and the second block have a molar ratio of 8: 2 to 2: 8. The polyamide-imide resin which has a structure which imidated the polyamide-imide precursor of any one of Claims 1-5. The polyamide-imide film manufactured by imidating the polyamide-imide precursor of any one of Claims 1-5. 8. The polyamide-imide film of claim 7, wherein the polyamide-imide film has a birefringence (n) defined as Transeverse Elictric (TE) -TM (Transverse magnetic) of 0.030 or less. According to claim 7, wherein the polyamide-imide film is linear thermal expansion coefficient (CTE) measured by repeating twice at 50 to 250 ℃ by thermal deformation analysis (TMA-Method) based on the film thickness of 10 to 50㎛ Is 60 ppm / degrees C or less, The polyamide-imide film characterized by the above-mentioned. The polyamide-imide film of claim 7, wherein the polyamide-imide film has a transmittance of 88% or more and a yellowness of 5 or less, measured at 550 nm based on a film thickness of 10 to 50 µm. The polyamide-imide film of claim 7, wherein the polyimide film has an elongation at break of 5% or more based on ASTM D882 (film thickness of 10 to 50 µm). An image display device comprising the polyimide film of claim 7.

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