WO2008072914A1 - Résine polyimide et couche d'alignement de cristaux liquides et film polyimide utilisant cette résine - Google Patents

Résine polyimide et couche d'alignement de cristaux liquides et film polyimide utilisant cette résine Download PDF

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Publication number
WO2008072914A1
WO2008072914A1 PCT/KR2007/006512 KR2007006512W WO2008072914A1 WO 2008072914 A1 WO2008072914 A1 WO 2008072914A1 KR 2007006512 W KR2007006512 W KR 2007006512W WO 2008072914 A1 WO2008072914 A1 WO 2008072914A1
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Prior art keywords
bis
polyimide
transmittance
aminophenoxy
film
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PCT/KR2007/006512
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English (en)
Inventor
Hak Gee Jung
Sang Wook Park
Hyo Jun Park
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Kolon Industries, Inc.
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Priority claimed from KR1020060129005A external-priority patent/KR101142692B1/ko
Priority claimed from KR1020060129009A external-priority patent/KR101167341B1/ko
Priority claimed from KR1020060128978A external-priority patent/KR101167337B1/ko
Application filed by Kolon Industries, Inc. filed Critical Kolon Industries, Inc.
Priority to JP2009541229A priority Critical patent/JP4891411B2/ja
Priority to US12/518,258 priority patent/US20100048861A1/en
Publication of WO2008072914A1 publication Critical patent/WO2008072914A1/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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a polyimide resin that is colorless and transparent, and to a liquid crystal alignment layer and a polyimide film using the same.
  • polyimide (PI) resin refers to highly heat-resistant resin obtained by ring closure and dehydration of polyamic acid at high temperature, which is obtained by solution polymerization of aromatic dianhydride and aromatic diamine or aromatic diisocyanate.
  • the aromatic dianhydride includes, for example, pyromellitic dianhydride (PMDA) or biphenyl tetracarboxylic dianhydride (BPDA)
  • the aromatic diamine includes, for example, oxydianiline (ODA) , p-phenylene diamine (p-PDA) , m-phenylene diamine (m- PDA) , methylene dianiline (MDA) , and bisaminophenylhexafluoropropane (HFDA) .
  • polyimide resin which is insoluble, infusible and super high heat resistant, has superior properties, including heat and oxidation resistance, radiation resistance, cryogenic resistance properties, and chemical resistance, it has been used in various fields, including advanced heat resistant materials, such as automobile materials, aircraft materials, or spacecraft materials, and electronic materials, such as insulation coating agents, insulating films, semiconductors, or electrode protective films of TFT-LCDs .
  • advanced heat resistant materials such as automobile materials, aircraft materials, or spacecraft materials
  • electronic materials such as insulation coating agents, insulating films, semiconductors, or electrode protective films of TFT-LCDs .
  • polyimide resin has been used as display materials, such as optical fibers or liquid crystal alignment layers, and transparent electrode films, which are constructed by mixing conductive fillers with polymers or applying conductive fillers to the surface of polymer films .
  • US Patent No. 5053480 discloses a method of using an alicyclic dianhydride component instead of the aromatic dianhydride. Although this method improves transparency and color in a solution phase or a film phase compared to the purification methods, the improvement in transmittance is limited, and therefore high transmittance is not realized, and also, the thermal and mechanical properties thereof are deteriorated.
  • the present invention provides a polyimide resin, which is colorless and transparent and has superior properties, including mechanical properties and heat stability, and also provides a liquid crystal alignment layer and a polyimide film using the same.
  • a polyimide resin which is prepared from a polymer of aromatic dianhydride and aromatic diamine, the aromatic dianhydride comprising 2,2'- bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6- FDA) and 4- (2, 5-dioxotet.rahydrofuran-3-yl) -1, 2, 3, 4- tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), and the aromatic diamine comprising one or a mixture of two or more selected from among 2, 2' -bis (trifluoromethyl) -4, 4' - diaminobiphenyl (2,2'-TFDB), 3, 3' -bis (trifluoromethyl) - 4, 4' -diaminobiphenyl (3,3'-TFDB), 4, 4' -bis (3- aminophenoxy) diphenylsulfone (
  • the aromatic diamine may further comprise one or a mixture of two or more selected from among 2,2'- bis [4 (4-aminophenoxy) phenyl] hexafluoropropane (4-BDAF) , 2,2' -bis [3 (3-aminophenoxy) phenyl 1 hexafluoropropane (3- BDAF), 1,3-bis (3-aminophenoxy) benzene (APB-133), l,3-bis(4- aminophenoxy) benzene (APB-134), l,4-bis(4- aminophenoxy) benzene (APB-144), and 2, 2-bis [4- (4- aminophenoxy) phenyl] propane (6-HMDA) .
  • 2,2'- bis [4 (4-aminophenoxy) phenyl] hexafluoropropane (4-BDAF)
  • the 2, 2-bis (3,4- dicarboxyphenyl) hexafluoropropane dianhydride may be used in an amount of 1-99 mol%, based on the total amount of the aromatic dianhydride.
  • DBSDA bis (3-aminophenyl)sulfone (3-DDS) , and bis (4- aminophenyl) sulfone (4-DDS) may be used in an amount of
  • a liquid crystal alignment layer comprising the polyimide resin mentioned above ⁇ s provided.
  • the liquid crystal alignment layer according to the second embodiment may have a pretilt angle of 0-2°.
  • a polyimide film comprising the polyimide resin mentioned above is provided.
  • the polyimide film according to the third embodiment may have average transmittance of 85% or more at 380 ⁇ 780 nm and average transmittance of 88% or more at 551-780 nm, according to measurement of transmittance using a UV spectrophotometer, based on a film thickness of 50-100 ⁇ m.
  • the polyimide film according to the third embodiment may have transmittance of 88% or more at 550 nm, transmittance of 85% or more at 500 nm, and transmittance of 50% or more at 420 nm, according to the measurement of transmittance using a UV spectrophotometer, based on the film thickness of 50-100 ⁇ m.
  • the polyimide film according to the third embodiment may have a yellow index of 15 or less based on the film thickness of 50-100 ⁇ m.
  • the polyimide film according to the third embodiment may have a dielectric constant of 3.0 or less at 1 GHz based on the film thickness of 50-100 ⁇ m.
  • the polyimide film according to the third embodiment may have an average coefficient of thermal expansion of 50 ppm or less at 50-200 ° C, based on the film thickness of 50-100 ⁇ m.
  • the polyimide film according to the third embodiment may have a modulus of 3.0 GPa or more, based on the film thickness of 50-100 ⁇ m-
  • the polyimide film according to the third embodiment may have a 50% UV cut-off wavelength of 400 nm or less, based on the film thickness of 50-100 ⁇ m.
  • the present invention can provide a polyimide resin that is colorless and transparent and has superior properties, including mechanical properties and heat stability, and that can thus be used in various fields, including semiconductor insulating films, TFT-LCD insulating films, passivation films, liquid crystal alignment layers, optical communication materials, protective films for solar cells, and flexible display substrates, and also provide a liquid crystal alignment layer and a polyimide film using the same.
  • FIG. 1 illustrates a liquid crystal alignment layer manufactured using the polyimide resin of the present invention.
  • the present invention is directed to a polyimide resin, which is composed of a copolymer of diamine and dianhydride, and a liquid crystal alignment layer and a polyimide film using the same, and, in particular, to a colorless transparent polyimide resin and a liquid crystal alignment layer and a polyimide film using the same.
  • the aromatic dianhydride used in the present invention essentially includes 2,2-bis(3,4- dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA) and 4- (2, 5-dioxotetrahydrofuran-3-yl) -1, 2, 3, 4- tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA).
  • the FDA is used in an amount of 1 ⁇ 99 mol%, and preferably 10-90 mol%, based on the total amount of the dianhydride.
  • polyamic acid that is transparent and has high visible light transmittance, a low UV absorption and yellow index, and a high viscosity.
  • the aromatic diamine used in the present invention essentially includes one or a mixture of two or more selected from among 2, 2' -bis (trifluoromethyl) -4, 4' - diaminobiphenyl (2,2'-TFDB), 3, 3' -bis (trifluoromethyl) -
  • aromatic diamine may further include one or a mixture of two or more: selected from among 2,2'- bis [4 (4-aminophenoxy) phenyl] hexaEluoropropane (4-BDAF) , 2, 2' -bis [3 (3-aminophenoxy) phenyl] hexafluoropropane (3-
  • BDAF 1,3-bi s (3-aminophenoxy) benzene
  • APIB-133 1,3-bi s (3-aminophenoxy) benzene
  • APIB-134 1,3-bis(4- aminophenoxy) benzene
  • APIB-144 1,3-bis(4- aminophenoxy) benzene
  • 6-HMDA 2, 2-bis [4- (4- aminophenoxy) phenyl] propane
  • DBSDA bis (3-aminophenyl)sulfone (3-DDS) , and bis (4- aminophenyl) sulfone (4-DDS)
  • DBSDA bis (3-aminophenyl)sulfone
  • 4- aminophenyl) sulfone (4-DDS) may be used in an amount of 10-90 mol%, and preferably 20-80 mol%, based on the total amount of the diamine.
  • the dianhydride and the diamine are dissolved in equivalent molar amounts in an organic solvent and are then reacted, thus preparing a polyamic acid solution.
  • the reaction conditions are not particularly limited, but include a reaction temperature of -20 ⁇ 80 ° C and a reaction time of 2 ⁇ 48 hours. Furthermore, the reaction is preferably conducted in an inert atmosphere of argon or nitrogen.
  • the organic solvent that is used for the solution polymerization of the monomers is not particularly limited, as long as polyamic acid can be dissolved therein.
  • reaction solvents useful are one or more polar solvents selected from among m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) , dimethylacetamide (DMAc) , dimethylsulfoxide (DMSO), acetone, and diethylacetate.
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethylsulfoxide
  • acetone and diethylacetate
  • a low-boiling-point solvent such as tetrahydrofuran (THF) or chloroform
  • a low-absorbing- solvent such as ⁇ -butyrolactone
  • the amount of the organic solvent is not particularly limited, but is preferably 50-95 wt%, and more preferably 70-90 wt%, based on the total amount of the polyamic acid solution, in order to realize appropriate molecular weight and viscosity of a polyamic acid solution.
  • the polyamic acid solution thus obtained is imidized to thus prepare a polyimide resin having a glass transition temperature of 200-350TC.
  • the polyamic acid is subjected to spin coating or roll coating on a glass substrate (e.g., ITO glass), and then to thermal curing at 80 ° C for 5min and 250 ° C for 20 min, thus realizing polyimidization during the removal of the solvent. Thereby, a thin film (having a thickness of about 10-1000 run) is formed on the glass substrate.
  • the polyamic acid solution is used in a state of being diluted to have an appropriate coating solution viscosity of 10-50 cps.
  • the solvent used for dilution is not limited to the solvent for polymerization.
  • the known dilution solvent is exemplified by polar solvents, such as N-methyl-2-pyrrolidone (NMP) , dimethylformamide (DMF) , dimethylacetamide (DMAc) , ⁇ - butyrolactone, and 2-n-butoxyethanol, which may be used alone or in mixtures thereof.
  • a coating solution of the polyamic acid prepared from the above monomers may be prepared through one or more processes selected from among the coating solution preparation processes below:
  • the coating solutions prepared through the above processes may be subjected to two or more steps of filtration using filters having a pore size selected within the range of 0.1-5 ⁇ m and an ion filter just before the coating process.
  • pretilt angle indicates an angle by which liquid crystals are previously tilted in order to increase a speed of response to voltage, when voltage is applied to liquid crystals to arrange the liquid crystals in a predetermined orientation.
  • the liquid crystal alignment layer including the polyimide resin of the present invention shows a stable pretilt angle of 0-2°, and may thus be applied to an alignment layer for IPS (En-Plane Switching) modes requiring a pretilt angle of less than 2°.
  • a filler may be added to the polyamic acid solution so as to improve various properties of the polyimide film, including sliding properties, heat conductivity, electrical conductivity, and corona resistance.
  • the filler is not particularly limited, but specific examples thereof include silica, titanium oxide, layered silica, carbon nanotubes, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
  • the particle size of the filler may vary depending on the properties of the film to be modified and the type of filler to be added, and is not particularly limited.
  • the average particle size thereof is preferably set within 0.001-50 jMii, more preferably 0.005-25 ⁇ m, and still more preferably 0.01-10 ⁇ m.
  • the polyimide film may be easily and effectively modified and may also exhibit good surfaces properties, electrical conductivity, and mechanical properties .
  • the amount of the filler may vary depending on the properties of the film to be modified and the particle size of the filler, and is not particularly limited.
  • the filler is added in an amount of 0.001-20 parts by weight, and preferably 0., 01-10 parts by weight, based on 100 parts by weight of the polyamic acid solution.
  • the method of adding the filler is not particularly limited, but includes, for instance, adding the filler to the polyamic acid solution before or after polymerization, kneading the filler using a 3 roll mill after completion of the polymerization of polyamic acid, or mixing a dispersion solution containing the filler with the polyamic acid solution.
  • the method of manufacturing the polyimide film from the polyamic acid solution thus obtained is not particularly limited, and any conventionally known methods may be used.
  • the imidization of the polyamic acid solution includes, for example, thermal imidization and chemical imidization. Particularly useful is chemical imidization. Chemical imidization is conducted by adding a dehydrating agent, including acid anhydride, such as acetic anhydride, and an imidization catalyst, including tertiary amine, such as isoquinoline, ⁇ -picoline, or pyridine, to the polyamic acid solution. The chemical imidization may be conducted along with the thermal imidization, and heating conditions may vary depending on the type of polyamic acid solution and the thickness of the film.
  • a dehydrating agent including acid anhydride, such as acetic anhydride
  • an imidization catalyst including tertiary amine, such as isoquinoline, ⁇ -picoline, or pyridine
  • the polyimide film is obtained by heating the polyamic acid solution on a substrate at 80 ⁇ 200 ° C, and preferably 100 ⁇ 180 ° C to activate the dehydrating agent and the imidization catalyst, performing partial curing and drying to obtain a polyamic acid film in a gel state, separating the polyamic acid film from the substrate, and heating the film in a gel state at 200 ⁇ 400 ° C for 5-400 sec.
  • the thickness of the polyimide film thus obtained is not particularly limited, but is preferably set within 10-250 ⁇ m, and more preferably 25-150 IM, in consideration of the application field thereof.
  • the polyimide film manufactured in the present invention has transmittance of 88% or more at 550 nm, 85% or more at 500 nm, and 50% or more at 420 nm, according to measurement of transmittance using a UV spectrophotometer, based on a film thickness of 50-100 ⁇ m. Further, the average transmittance thereof is 85% or more at 380-780 run, and is 88% or more at 551-780 nm.
  • the polyimide film has a yellowing index of 15 or less based on the film thickness of 50-100 ⁇ m.
  • the polyimide film of the present invention satisfying the aforementioned transmittance and yellowing index, may be used in fields requiring transparency, in which it is difficult to apply a conventional polyimide film due to the yellow color thereof, including protective films, or diffusion sheets and coating films of TFT-LCDs, for example, interlayers, gate insulators, and liquid crystal alignment layers of TFT-LCDs.
  • protective films, or diffusion sheets and coating films of TFT-LCDs for example, interlayers, gate insulators, and liquid crystal alignment layers of TFT-LCDs.
  • the transparent polyimide When the transparent polyimide is applied to the liquid crystal alignment layer, it contributes to an increase in porosity, thus enabling the fabrication of a TFT-LCD having a high contrast ratio, and may also be used for flexible display substrates.
  • the polyimide film of the present invention has a dielectric constant of 3.0 or less at 1 GHz, and may thus be used as a semiconductor passivation film.
  • the polyimide film of the present invention has an average coefficient of thermal expansion (average CTE) of
  • the polyimide film may shrink or expand, depending on the variation in process temperatures, when applied to a TFT array process for placing a TFT on the film, resulting in unrealized alignment in an electrode doping process. Further, the film does not remain flat, and thus may warp. Hence, as the CTE is decreased, the TFT process may be more accurately conducted.
  • the polyimide film of the present invention has a modulus of 3.0 GPa or more. In this case, the polyimide film may be more easily applied to a roll-to-roll process for a flexible display substrate. When the polyimide film is used as a substrate film for flexible displays and FCCLs, a roll-to-roll process is conducted. At this time, because the film is subjected to tension when it is wound on and released from the rolls, a film having a modulus of less than 3.0 GPa may break down.
  • the polyimide film of the present invention has a 50% cut-off wavelength of 400 nm or less according to the measurement of transmittance using a UV spectrophotometer. Therefore, the polyimide film of the present invention may be used as a surface protective film for solar cells.
  • Example 1 While nitrogen was passed through a 100 ml three-neck round bottom flask reactor equipped with a stirrer, a nitrogen inlet, a dropping funnel, a temperature controller and a condenser, 33.5386 g of N,N-dimethylacetamide (DMAc) was loaded thereto, and the temperature of the reactor was decreased to 0 ° C. 3.62922 g (0.007 mol) of 4-BDAF and 0.7449 g (0.003 mol) of 3-DDS was dissolved therein. This solution was maintained at 0 ° C.
  • DMAc N,N-dimethylacetamide
  • the polyamic acid solution was spread 500 ⁇ 1000 (M thick on a glass substrate using a doctor blade, and was then dried in a vacuum oven at 40 ° C for 1 hour and at 60 ° C for 2 hours, thus affording a self-supporting film.
  • the film was then cured in a high-temperature oven at 80 ° C for 3 hours, 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 30 min at a heating rate of 5 ° C/min, thereby affording polyimide films having a thickness of 50 ⁇ m and 100 ⁇ xa.
  • Example 2 As in Example 1, 2.04631 g (0.007 mol) of APB-133 and 0.7449 g (0.003 mol) of 4-DDS were completely dissolved in 27.20696 g of DMAc. To the solution, 3.10975 g (0.007 mol) of ⁇ -FDA and 0.90078 g (0.003 mol) of TDA were sequentially added and the mixture was stirred for 1 hour till the 6-FDA and TDA were completely dissolved. The solid content of the resulting solution was thus 20 wt%. The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1950 cps at 23 ° C. Thereafter, polyimide films were manufactured in the same manner as in Example 1.
  • Example 6 As in Example 1, 2.24161 g (0.007 mol) of 2,2'-TFDB and 0.7449 g (0.003 mol) of 4-DDS were completely dissolved in 27.98796 g of DMAc. To the solution, 3.1097 g (0.007 mol) of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added and the solubion was stirred for 1 hour till the 6-FDA and TDA were completely dissolved. The solid content was thus 20 wt% . The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 2000 cps at 23 ° C. Thereafter, polyimide films were manufactured in the same manner as in Example 1.
  • Example 2 As in Example 1, 5.1846 g (0.01 mol) of 4-BDAF was dissolved in 38.5084 g of DMAc, after which 4.4425 g (0.01 mol) of 6-FDA was added thereto. The solution was stirred for 1 hour till the 6-FDA was completely dissolved. The solid content was thus 20 wt%. The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1300 cps at
  • polyimide films were manufactured in the same manner as in Example 1, and the thicknesses thereof were 25 ⁇ m, 50 ⁇ m, and 100 ⁇ m.
  • Example 2 As in Example 1, 2.9233 g (0.01 mol) of APB-133 was dissolved in 29.4632 g of DMAc, after which 4.4425 g (0.01 mol) of 6-FDA was added thereto. The solution was stirred for 1 hour till the 6-FDA was completely dissolved. The solid content was thus 20 wt%. The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1200 cps at 23 ° C.
  • Example 2 As in Example 1, 2.4830 g (0.01 mol) of 3-DDS was dissolved in 27.702 g of DMAc, after which 4.4425 g (0.01 mol) of 6-FDA was added thereto. The solution was stirred for 1 hour till the 6-FDA was completely dissolved. The solid content was thus 20 wt%. The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1300 cps at 23 ° C.
  • Example 4 As in Example 1, 2.4830 g (0.01 mol) of 4-DDS was dissolved in 27.702 g of DMAc, after which 4.4425 g (0.01 mol) of 6-FDA was added thereto. The solution was stirred for 1 hour till the 6-FDA was completely dissoved. The solid content was thus 20 wt%. The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1400 cps at
  • Example 2.0024 g (0.01 mol) of 3,3'-ODA was dissolved in 25.7796 g of DMAc, after which 4.4425 g (0.01 mol) of 6-FDA was added thereto and the resulting solution was stirred for 1 hour till 6-FDA was completely dissoved. The solid content was thus 20 wt% .
  • the solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1600 cps at 23 ° C.
  • Example 2.0024 g (0.01 mol) of 4,4'-ODA was dissolved in 16.7344 g of DMAc, after which 2.1812 g (0.01 mol) of PMDA was added thereto and the resulting solution was stirred for 1 hour till the PMDA was completely dissoved. The solid content was thus 20 wt%.
  • the solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 2500 poises at 23°C. Thereafter, polyimide films were manufactured in the same manner as in Comparative Example 1.
  • Each of the polyimide films was measured for visible light transmittance and 50% cut-off wavelength using a UV spectrophotometer (Varian, CarylOO) .
  • the yellowing index was measured according to ASTM E313.
  • modulus was measured according to JIS K 6301 using a universal testing machine, Model 1000, available from Instron.
  • the glass transition temperature was measured using a differential scanning calorimeter (DSC, TA Instrument, Q200) .
  • DSC differential scanning calorimeter
  • Q200 TA Instrument, Q200
  • CTE Coefficient of Thermal Expansion
  • the CTE was measured at 50 ⁇ 200 ° C according to a TMA method using a TMA (TA Instrument, Q400) .
  • the polyamic acid solution of each of the examples and comparative examples was diluted to have a solution viscosity of 10-50 cps using ⁇ -butyrolactone as a dilution solvent, filtered using filters having sizes of 2 ⁇ m, 0.45 /zm, and 0.2 /im and then an ion filter, applied on a glass substrate (ITO glass) (application conditions: spin coating, 400-4,000 rpm, 10-40 sec).
  • ITO glass application conditions: spin coating, 400-4,000 rpm, 10-40 sec.
  • Each polyamic solution on the glass substrate was thermally cured at 80 ° C for 5 min and then 250 ° C for 20 min, thus realizing polyimidization during the removal of the solvent. Thereby, a thin film (having a thickness of 100 nm) was formed on the glass substrate.
  • the glass substrate 1, 2 thus coated were positioned for use as upper and lower substrate respectively , after which liquid crystal molecules 4 were introduced into the space between the glass substrate 1, 2, thus affording liquid crystal cells including a liquid crystal layer 5 (FIG. 1) .
  • the pretilt angle of each of the liquid crystal cells was measured through a crystal rotation method. The results are shown in Table 5, below. TABLE 1
  • the polyimide films of the present invention had transmittance of 88% or more at 550 nm, 85% or more at 500 nm, and 50% or more at 420 nm in the visible light range, even though they were 50 ⁇ m or 100 ⁇ m thick. Furthermore, the average transmittance thereof was 85% or more at 380-780 nm and 88% or more at 551-780 nm, and the yellow index thereof was consistently low. Thereby, the polyimide film of the present invention was confirmed to be very transparent .
  • the average transmittance of the film was 85% or more in the visible light range of 380 ⁇ 780 nm, regardless of the thickness thereof.
  • a polyimide film having a thickness of 90 ⁇ m or more could not be manufactured.
  • the polyimide films manufactured in the examples of the present invention had a wavelength of 400 nm or less, at which transmittance was 50%, ultimately realizing a colorless transparent polyimide film having superior visible light transmittance.
  • the polyimide film of the present invention can be used as a surface protective film for solar cells.
  • the polyimide film has an average CTE of 50 ppm or less, it can exhibit high dimensional stability, and furthermore, can manifest film properties, necessary for application to a roll-to- roll process, thanks to the modulus of 3.0 GPa or more thereof.
  • the polyimide film of the present invention can be applied to a TFT process for fabricating flexible display substrates and active displays, and also has a dielectric constant of 3.0 or less, thus enabling it to be used as a semiconductor passivation film.
  • the liquid crystal alignment layer manufactured using the polyimide resin of the present invention has a pretilt angle of 2° or less, and thus can be used as an alignment layer for IPS modes .

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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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une résine polyimide, incolore et transparente qui possède des propriétés supérieures, comprenant des propriétés mécaniques et une stabilité à la chaleur, et qui peut donc être utilisée dans différents domaines, notamment dans des films isolants semi-conducteurs, des films isolants TFT-LCD, des films électrode transparents, des films de passivation, des couches d'alignement de cristaux liquides, des matériaux de communication optique, des films de protection pour cellules solaires, et des substrats d'afficheur souples. L'invention concerne aussi une couche d'alignement de cristaux liquides et un film polyimide utilisant cette résine polyimide.
PCT/KR2007/006512 2006-12-15 2007-12-13 Résine polyimide et couche d'alignement de cristaux liquides et film polyimide utilisant cette résine WO2008072914A1 (fr)

Priority Applications (2)

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JP2009541229A JP4891411B2 (ja) 2006-12-15 2007-12-13 ポリイミド樹脂とこれを用いた液晶配向膜およびポリイミドフィルム
US12/518,258 US20100048861A1 (en) 2006-12-15 2007-12-13 Polyimide resin and liquid crystal alignment layer and polyimide film using the same

Applications Claiming Priority (6)

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KR1020060129005A KR101142692B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름
KR1020060129009A KR101167341B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름
KR10-2006-0129009 2006-12-15
KR1020060128978A KR101167337B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름
KR10-2006-0129005 2006-12-15
KR10-2006-0128978 2006-12-15

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WO2008072914A1 true WO2008072914A1 (fr) 2008-06-19

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JP2010100698A (ja) * 2008-10-22 2010-05-06 Nissan Chem Ind Ltd ポリアミック酸およびポリイミドフィルム
JP2010102886A (ja) * 2008-10-22 2010-05-06 Tokyo Kogei Univ 画像表示装置およびフレキシブル透明有機エレクトロルミネッセンス素子
JP2010209334A (ja) * 2009-03-10 2010-09-24 Lg Chem Ltd ポリイミド系重合体とこれらの共重合体、並びにこれを含むポジ型感光性樹脂組成物
JP2012503299A (ja) * 2008-09-23 2012-02-02 コーロン インダストリーズ インク 透明電極
JP2012503701A (ja) * 2008-09-26 2012-02-09 コーロン インダストリーズ インク ポリイミドフィルム
CN111212868A (zh) * 2017-10-11 2020-05-29 株式会社钟化 聚酰亚胺树脂及其制造方法、聚酰亚胺溶液、以及聚酰亚胺薄膜及其制造方法
US10858482B2 (en) 2015-02-12 2020-12-08 Samsung Electronics Co., Ltd. Composition of preparing poly(imide-benzoxazole) copolymer, poly(imide-benzoxazole) copolymer, article containing poly(imide-benzoxazole) copolymer, and display device including same
CN112062961A (zh) * 2020-09-21 2020-12-11 华东理工大学 一种无色透明聚酰亚胺液晶取向膜的制备方法

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KR102145141B1 (ko) 2012-04-27 2020-08-14 우베 고산 가부시키가이샤 폴리아믹산 용액 조성물, 및 폴리이미드
CN107428934B (zh) 2015-03-31 2020-10-02 旭化成株式会社 聚酰亚胺膜、聚酰亚胺清漆、使用了聚酰亚胺膜的制品、以及层积体
KR102097431B1 (ko) * 2019-05-13 2020-04-07 에스케이씨코오롱피아이 주식회사 폴리이미드 및 이의 제조 방법
KR102224505B1 (ko) * 2019-07-05 2021-03-09 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조 방법, 이를 포함하는 폴리이미드 및 이를 포함하는 피복물
KR102224506B1 (ko) * 2019-07-05 2021-03-09 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조 방법 및 이를 포함하는 폴리이미드
KR102224504B1 (ko) * 2019-07-05 2021-03-09 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조 방법 및 이를 포함하는 폴리이미드
KR102224503B1 (ko) * 2019-07-05 2021-03-09 피아이첨단소재 주식회사 폴리아믹산 조성물, 폴리아믹산 조성물의 제조 방법, 이를 포함하는 폴리이미드 및 이를 포함하는 피복물

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JP2012503299A (ja) * 2008-09-23 2012-02-02 コーロン インダストリーズ インク 透明電極
TWI493571B (zh) * 2008-09-23 2015-07-21 Kolon Inc 透明電極
JP2012503701A (ja) * 2008-09-26 2012-02-09 コーロン インダストリーズ インク ポリイミドフィルム
JP2010100698A (ja) * 2008-10-22 2010-05-06 Nissan Chem Ind Ltd ポリアミック酸およびポリイミドフィルム
JP2010102886A (ja) * 2008-10-22 2010-05-06 Tokyo Kogei Univ 画像表示装置およびフレキシブル透明有機エレクトロルミネッセンス素子
JP2010209334A (ja) * 2009-03-10 2010-09-24 Lg Chem Ltd ポリイミド系重合体とこれらの共重合体、並びにこれを含むポジ型感光性樹脂組成物
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US10858482B2 (en) 2015-02-12 2020-12-08 Samsung Electronics Co., Ltd. Composition of preparing poly(imide-benzoxazole) copolymer, poly(imide-benzoxazole) copolymer, article containing poly(imide-benzoxazole) copolymer, and display device including same
CN111212868A (zh) * 2017-10-11 2020-05-29 株式会社钟化 聚酰亚胺树脂及其制造方法、聚酰亚胺溶液、以及聚酰亚胺薄膜及其制造方法
CN111212868B (zh) * 2017-10-11 2022-09-16 株式会社钟化 聚酰亚胺树脂及其制造方法、聚酰亚胺溶液、以及聚酰亚胺薄膜及其制造方法
CN112062961A (zh) * 2020-09-21 2020-12-11 华东理工大学 一种无色透明聚酰亚胺液晶取向膜的制备方法
CN112062961B (zh) * 2020-09-21 2021-12-14 华东理工大学 一种无色透明聚酰亚胺液晶取向膜的制备方法

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