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WO2016108675A1 - Précurseur de polyamide-imide, film de polyamide-imide, et dispositif d'affichage le comprenant - Google Patents

Précurseur de polyamide-imide, film de polyamide-imide, et dispositif d'affichage le comprenant Download PDF

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Publication number
WO2016108675A1
WO2016108675A1 PCT/KR2015/014593 KR2015014593W WO2016108675A1 WO 2016108675 A1 WO2016108675 A1 WO 2016108675A1 KR 2015014593 W KR2015014593 W KR 2015014593W WO 2016108675 A1 WO2016108675 A1 WO 2016108675A1
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polyamide
imide
block
film
bis
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PCT/KR2015/014593
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English (en)
Korean (ko)
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양종원
정학기
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코오롱인더스트리 주식회사
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Priority claimed from KR1020150190313A external-priority patent/KR102227672B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to CN201580076508.2A priority Critical patent/CN107250213B/zh
Priority to JP2017534993A priority patent/JP6410946B2/ja
Priority to US15/540,803 priority patent/US11130844B2/en
Priority to EP21153237.9A priority patent/EP3848403A1/fr
Priority to EP15875769.0A priority patent/EP3241860B1/fr
Publication of WO2016108675A1 publication Critical patent/WO2016108675A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyamide-imide precursor, a polyamide-imide film imidized thereto, and a display device including the polyamide-imide film.
  • a polyimide (PI) film is a film of a polyimide resin
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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
  • the third embodiment is a polyamide- of the first embodiment. It is a polyamide-imide film manufactured by imidating an imide precursor.
  • a fourth preferred embodiment of the present invention is an image display device comprising the polyamide-imide film of the third embodiment.
  • the polyamide-imide precursor of the present invention 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.
  • 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.
  • 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).
  • 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.
  • 6FDA 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride
  • FFDA 9,9-bis (3-fluoro-4-aminophenyl) fluoroene
  • FFDA 9,9-bis (3-fluoro-4-
  • the first block including an imide bond may be excellent in optical as well as thermal and mechanical properties.
  • 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.
  • FFDA 9,9-bis (3-fluoro-4-aminophenyl) fluoroene
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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)
  • isophthaloyl dichloride (Iso-phthaloyl dichloirde) may be used at least one selected from.
  • 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'-d
  • 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.
  • FFDA 9,9-bis (3-fluoro-4-aminophenyl) fluoroene
  • BAPSM bis (4- (3-aminophenoxy) phenyl) sulfone
  • DDS 4,4'-diaminodiphenylsulfone
  • HFBAPP 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane
  • 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%.
  • GPC gel permeation chromatography
  • 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.
  • the following imidization step may be performed.
  • 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.
  • 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 °C for 2 to 48 hours.
  • 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.
  • 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.
  • a low boiling point solution such as tetrahydrofuran (THF), chloroform or the like or a low absorbing solvent such as ⁇ -butyrolactone may be used.
  • 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.
  • 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, ⁇ -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.
  • 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.
  • 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.
  • 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 °C.
  • 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.
  • these low solvents namely, water, alcohols, ethers and ketones can be used.
  • 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.
  • the polyamide-imide film obtained can be heat treated once more to solve the thermal history and residual stress remaining in the film.
  • the temperature of the additional heat treatment process is preferably 300 to 500 °C
  • 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.
  • the thermally treated film finally exhibits very stable thermal characteristics.
  • 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 ⁇ m 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.
  • TE Transeverse Elictric
  • TM Transverse magnetic
  • 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 ⁇ m. It is less than / °C, 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.
  • CTE linear thermal expansion coefficient
  • 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.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 49.207 g (0.128 mol) of fluoro-4-aminophenyl) fluoroene (FFDA) were dissolved.
  • 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.
  • TPC terephthaloyl chloride
  • the obtained solution was applied to a stainless plate, cast at 10 to 20 ⁇ m, 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 ⁇ m was prepared by separating from the plate.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • concentration of solid content was 20 weight %
  • a polyamide-amide precursor solution having a viscosity of 590 poise was obtained.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • 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 °C 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.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • 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 °C, 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.
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 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 °C 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.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • 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.
  • Yellowness (Y.I.) measurement The yellowness was measured by ASTM E313 standard using a UV spectrometer (Konita Minolta, CM-3700d).
  • 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.
  • TE Transeverse Elictric
  • TM Transverse magnetic
  • CTE coefficient of thermal expansion
  • A first block
  • B second block
  • C third block
  • 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 3.3
  • 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.
  • Comparative Examples 2 and 4 which are polyamides
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne : un précurseur de polyamide-imide, comprenant, dans une structure moléculaire, un premier bloc obtenu par copolymérisation de monomères comprenant un dianhydride et une diamine, un deuxième bloc obtenu par copolymérisation de monomères comprenant un composé dicarbonyle aromatique et une diamine, et un troisième bloc obtenu par copolymérisation de monomères comprenant un composé dicarbonyle aromatique et une diamine aromatique, le dianhydride pour former le premier bloc contenant du dianhydride de 2-bis(3,4-dicarboxyphényl)hexafluoropropane (6FDA), et la diamine pour former les premier et deuxième blocs contenant du 9,9-bis(3-fluoro-4-aminophényl)fluorène (FFDA) ; un polyamide-imide obtenu par imidation du précurseur ; un film de polyamide-imide ; et un dispositif d'affichage d'image comprenant le film.
PCT/KR2015/014593 2014-12-31 2015-12-31 Précurseur de polyamide-imide, film de polyamide-imide, et dispositif d'affichage le comprenant WO2016108675A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201580076508.2A CN107250213B (zh) 2014-12-31 2015-12-31 聚酰胺-酰亚胺前体、聚酰胺-酰亚胺薄膜以及包括该薄膜的显示装置
JP2017534993A JP6410946B2 (ja) 2014-12-31 2015-12-31 ポリアミド−イミド前駆体、ポリアミド−イミドフィルム及びこれを含む表示素子
US15/540,803 US11130844B2 (en) 2014-12-31 2015-12-31 Polyamide-imide precursor, polyamide-imide film, and display device comprising same
EP21153237.9A EP3848403A1 (fr) 2014-12-31 2015-12-31 Précurseur de polyamide-imide, film de polyamide-imide, et dispositif d'affichage le comprenant
EP15875769.0A EP3241860B1 (fr) 2014-12-31 2015-12-31 Précurseur de polyamide-imide, film de polyamide-imide, et dispositif d'affichage le comprenant

Applications Claiming Priority (4)

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KR20140195670 2014-12-31
KR10-2014-0195670 2014-12-31
KR1020150190313A KR102227672B1 (ko) 2014-12-31 2015-12-30 폴리아마이드-이미드 전구체, 폴리아마이드-이미드 필름 및 이를 포함하는 표시소자
KR10-2015-0190313 2015-12-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018123319A (ja) * 2017-02-01 2018-08-09 住友化学株式会社 ポリイミドフィルム
JP2019506479A (ja) * 2016-09-13 2019-03-07 エルジー・ケム・リミテッド ポリイミド系ブロック共重合体及びこれを含むポリイミド系フィルム

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130029129A (ko) * 2011-05-18 2013-03-22 삼성전자주식회사 폴리(아미드-이미드) 블록 코폴리머, 이를 포함하는 성형품 및 상기 성형품을 포함하는 디스플레이 장치
KR20130035691A (ko) * 2011-09-30 2013-04-09 코오롱인더스트리 주식회사 공중합 폴리아마이드-이미드 필름 및 공중합 폴리아마이드-이미드의 제조방법
KR20130110589A (ko) * 2012-03-29 2013-10-10 코오롱인더스트리 주식회사 폴리이미드 필름
WO2014003210A1 (fr) * 2012-06-25 2014-01-03 Kolon Industries, Inc. Film de copolymère de polyamide-imide et procédé de préparation d'un copolymère de polyamide-imide
KR20140012270A (ko) * 2012-07-19 2014-02-03 삼성전자주식회사 폴리이미드 전구체 조성물, 이를 사용하여 제조된 성형품 및 상기 성형품을 포함하는 디스플레이 장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130029129A (ko) * 2011-05-18 2013-03-22 삼성전자주식회사 폴리(아미드-이미드) 블록 코폴리머, 이를 포함하는 성형품 및 상기 성형품을 포함하는 디스플레이 장치
KR20130035691A (ko) * 2011-09-30 2013-04-09 코오롱인더스트리 주식회사 공중합 폴리아마이드-이미드 필름 및 공중합 폴리아마이드-이미드의 제조방법
KR20130110589A (ko) * 2012-03-29 2013-10-10 코오롱인더스트리 주식회사 폴리이미드 필름
WO2014003210A1 (fr) * 2012-06-25 2014-01-03 Kolon Industries, Inc. Film de copolymère de polyamide-imide et procédé de préparation d'un copolymère de polyamide-imide
KR20140012270A (ko) * 2012-07-19 2014-02-03 삼성전자주식회사 폴리이미드 전구체 조성물, 이를 사용하여 제조된 성형품 및 상기 성형품을 포함하는 디스플레이 장치

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019506479A (ja) * 2016-09-13 2019-03-07 エルジー・ケム・リミテッド ポリイミド系ブロック共重合体及びこれを含むポリイミド系フィルム
US10800882B2 (en) 2016-09-13 2020-10-13 Lg Chem, Ltd. Polyimide-based block copolymers and polyimide-based film comprising the same
JP2018123319A (ja) * 2017-02-01 2018-08-09 住友化学株式会社 ポリイミドフィルム
JP2020125485A (ja) * 2017-02-01 2020-08-20 住友化学株式会社 ポリイミドフィルム
JP7005680B2 (ja) 2017-02-01 2022-01-21 住友化学株式会社 ポリイミドフィルム

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