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WO2008072916A1 - Film poyimide - Google Patents

Film poyimide Download PDF

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Publication number
WO2008072916A1
WO2008072916A1 PCT/KR2007/006514 KR2007006514W WO2008072916A1 WO 2008072916 A1 WO2008072916 A1 WO 2008072916A1 KR 2007006514 W KR2007006514 W KR 2007006514W WO 2008072916 A1 WO2008072916 A1 WO 2008072916A1
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Prior art keywords
bis
solution
polyimide film
mol
transmittance
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PCT/KR2007/006514
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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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Kolon Industries Inc
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Priority claimed from KR1020060128978A external-priority patent/KR101167337B1/ko
Priority claimed from KR1020060128999A external-priority patent/KR101167339B1/ko
Priority claimed from KR1020060128992A external-priority patent/KR101211857B1/ko
Priority claimed from KR1020060129009A external-priority patent/KR101167341B1/ko
Priority claimed from KR1020060129011A external-priority patent/KR101167483B1/ko
Priority claimed from KR1020060129005A external-priority patent/KR101142692B1/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Publication of WO2008072916A1 publication Critical patent/WO2008072916A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide film that is colorless and transparent.
  • 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 ODA
  • p-PDA p-phenylene diamine
  • 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 .
  • 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 film, which is colorless and transparent and exhibits superior properties, including mechanical properties and heat stability.
  • a polyimide film which is manufactured from a polymer of aromatic dianhydride and aromatic diamine, and has average transmittance of 85% or more at 380-780 run according to measurement of transmittance using a UV spectrophotometer, and a yellowing index of 15 or less, based on a film thickness of 50-100 IM.
  • the polyimide film according to the embodiment may have average transmittance of 88% or more at 551-780 nm, transmittance of 88% or more at 550 nm, transmittance of
  • the polyimide film according to the embodiment may have an optical density of less than 50 at 420 nm, based on the film thickness of 50-100 ⁇ m.
  • the aromatic dianhydride may comprise one or a mixture of two or more selected from among 2,2-bis(3,4- dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA), 4-
  • the aromatic diamine may comprise one or a mixture of two or more selected from among oxydianiline (ODA), l,3-bis(3- aminophenoxy) benzene (APB-133) , l,3-bis(4- aminophenoxy) benzene (APB-134), l,4-bis(4- aminophenoxy) benzene (APB-144), bis (3-aminophenyl) sulfone
  • 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 /an.
  • 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 is a photograph of the polyimide film of Example 1 placed on a piece of paper;
  • FIG. 2 is a photograph of the polyimide film of Comparative Example 1 placed on a piece of paper .
  • the polyimide film of the present invention is a film of polyimide resin prepared from a copolymer of diamine and dianhydride, and in particular, is a colorless transparent polyimide film.
  • the polyimide film manufactured in the present invention has average transmittance of 85% or more at 380-780 nm according to measurement of transmittance using a UV spectrophotometer based on a film thickness of 50 ⁇ 100 ⁇ m, and has a yellowing index of 15 or less based on the film thickness of 50-100 ⁇ m.
  • the polyimide film preferably has average transmittance of 88% or more at 551-780 nm, 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 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 a 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 an optical density of less than 50 at 420 nm based on the film thickness of 50-100 ⁇ m.
  • the polyimide film satisfying the aforementioned optical density and transmittance decreases the refractive index, which indicates the degree of scattering of light passed through the film, and thus, as the distortion of the color, size, or position of a target through the film is decreased, birefringence and retardation are reduced. Therefore, the polyimide film of the present invention may be applied in fields requiring transparency.
  • the aromatic dianhydride used in the present invention is not particularly limited, but includes one or a mixture of two or more selected from among 2,2- bis (3, 4-dicarboxyphenyl)hexafluoropropane dianhydride (6- FDA) , 4- (2, 5-dioxotetrahydrofuran-3-yl) -1, 2, 3, 4- tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), and 4, 4' - (4, 4' -isopropylidenediphenoxy)bis (phthalic anhydride) (HBDA) .
  • the aromatic diamine used in the present invention is not particularly limited but includes one or a mixture of two or more selected from among oxydianiline
  • ODA OAA
  • l,3-bis(3-aminophenoxy) benzene APB-133
  • l,3-bis(4- aminophenoxy) benzene APB-134
  • l,4-bis(4- aminophenoxy) benzene APB-144
  • bis (3-aminophenyl) sulfone (3-DDS)
  • bis (4-aminophenyl) sulfone (4-DDS) 2,2'- bis (trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-TFDB)
  • 3, 3' -bis (trifluoromethyl) -4, 4' -diaminobiphenyl 3, 3' -TFDB)
  • 2, 2' -bis [4 ( 4-aminophenoxy) phenyl] hexafluoropropane (4- BDAF)
  • 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.
  • 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 ⁇ m, more preferably 0.005-25 (M 1 and still more preferably 0.01-10 ⁇ m.
  • the polyimide film may be easily and effectively modified and may also exhibit good surface properties, e Lectrical 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.
  • a dehydrating agent including acid anhydride, such as acetic anhydride
  • an imidization catalyst including tertiary amine, such as isoquinoline, ⁇ -picoline, or pyridine
  • 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.
  • 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
  • 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.
  • the polyimide film may be more easily applied to a roll-to-roll process for a flexible display substrate.
  • a roll-to-roll process is conducted.
  • the polyimide film of the present invention has a 50% cut-off wavelength of 400 run 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.
  • 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 JM.
  • Example 2 As in Example 1, 4.1051 g (0.01 mol) of 6-HMDA was dissolved in 31.3106 g of DMAc, and this solution was maintained at 0 ° C. To the solution 2.2215 g (0.005 mol) of ⁇ -FDA and 1.5013 g (0.005 mol) of TDA were sequentially added thereto and the solution stirred for 1 hour the 6-FDA and TDA were completely dissolved. The solid content of the solution was 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.
  • Example 2 As in Example 1, 2.87357 g (0.007 mol) of 6-HMDA was dissolved in 30.5158 g of DMAc, and 0.7449 g (0.003 mol) of 3-DDS was added thereto and completely dissolved. To the solution 3.1097 g (0.007 mol) of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added the solution was stirred for 1 hour till the 6-FDA and TDA were completely dissolved. The solid content of the solution was 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, 2.87357 g (0.007 mol) of 6-HMDA was dissolved in 30.5158 g of DMAc, and 0.7449 g (0.003 mol) of 4-DDS was added thereto and completely dissolved. To the solution 3.1097 g (0.007 mol) of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added the solution was stirred for 1 hour till the ⁇ -FDA and TDA were completely dissolved. The solid content of the solution was 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.
  • Example 2 As in Example 1, 2.24161 g (0.007 mol) of 2,2'-TFDB and 0.7449 g (0.003 mol) of 3-DDS were dissolved in 27.98796 g of DMAc. To the mixture, 3.1097 g (0.007 mol) of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added and then the solution 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.
  • Example 2 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 solution 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.
  • Example 2 As in Example 1, 3.62922 g (0.007 mol) of 4-BDAF was dissolved in 33.5386 g of DMAc, and 0.7449 g (0.003 mol) of 3-DDS was added thereto and completely dissolvedTo the solution, 3.1097 g (0.007 molj of 6-FDA and 0.90078 g (0.003 mol) of TDA were sequentially added and the solution 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 2200 cps at 23 ° C. Thereafter, polyimide films were manufactured in the same manner as in Example 1.
  • Example 9 As in Example 1, 3.62922 g (0.007 mol) of 4-BDAF was dissolved in 33.5386 g of DMAc, and 0.7449 g (0.003 mol) of 4-DDS was added thereto and completely dissolved. To the solution 3.1097 g (0.007 mol) of ⁇ -FDA and 0.90078 g (0.003 mol) of TDA were sequentially added and the solution was stirred for 1 hour till the 6-FDA and TDA were completely dissolved. The solid content of the solution was 20 wt% . The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 2100 cps at 23 ° C. Thereafter, polyimide films were manufactured in the same manner as in Example 1.
  • 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 6-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
  • Example 2 As in Example 1, 3.2023 g (0.01 ml) of 2,2'-TFDB was completely dissolved in 30.986 g of DMAc. This solution was maintained at 0°C. To the solution , 3.64355 g (0.007 mol) of 6-HBDA and 0.90078 g (0.003 mol) of TDA were sequentially added and the mixture was stirred for 1 hour till the ⁇ -HBDA 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 2000 cps at 23 ° C. Thereafter, polyimide films were manufactured in the same manner as in Example 1.
  • Example 13 As in Example 1, 2.483 g (0.01 mol) of 4-DDS was dissolved in 28.1093 g of DMAc, and this solution was maintained at 0 ° C. To the solution 3.64355 g (0.007 mol) of 6-HBDA and 0.90078 g (0.003 mol) of TDA were sequentially added and the solution was stirred for 1 hour till the 6- HBDA and TDA were completely dissolved. The solid content of the solution was 20 wt% . The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1800 cps at 23 ° C.
  • Example 2 As in Example 1, 5.1846 g (0.01 mol) of 4-BDAF was dissolved in 38.9157 g of DMAc, and this solution was maintained at 0 ° C. To the solution 3.64355 g (0.007 mol) of 6-HBDA and 0.90078 g (0.003 mol) of TDA were sequentially added the solution was stirred for 1 hour till the 6-HBDA and TDA were completely dissolved. The solid content of the solution was 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.
  • Example 15 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 30.3628 g of DMAc. This solution was maintained at 0 ° C. To the solution 3.6435 g (0.007 mol) of 6-HBDA and 0.96069 g (0.003 mol) of TDA were sequentially added thereto and stirred for 1 hour till the 6-HBDA and TDA were completely dissolved. The solid content of the solution was 20 wt%. The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1700 cps at 23 ° C. Thereafter, polyimide films were manufactured in the ' same manner as in Example 1.
  • Example 2 As in Example 1, 2.24161 g (0.007 mol) of 2,2'-TFDB and 1.55538 g (0.003 mol) of 3-BDAF was added thereto and completely dissolved in 33.60472 g of DMAc. This solution was maintained at 0 ° C. To the solution, 3.6435 g (0.007 mol) of 6-HBDA and 0.96069 g (0.003 mol) of TDA were sequentially added thereto and stirred for 1 hour till the 6-HBDA and TDA were completely dissolved. The solid content of the solution was 20 wt% . The solution was then stirred at room temperature for 8 hours, thus affording a polyamic acid solution having a viscosity of 1800 cps at 23 ° C. Thereafter, polyimide films were manufactured in the same manner as in Example 1.
  • Example 1 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 moi) of ⁇ -FDA was added thereto. The solution was stirred for 1 hour till the 6-FDA was completely dissolved. The so Lid 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.
  • polyimide fi lnas were manufactured in the same manner as in Example 1, and the thicknesses thereof were 25 ⁇ m, 50 ⁇ m r 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 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. Thereafter, polyimide films were manufactured in the same manner as in Comparative Example 1.
  • 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
  • Comparative Example 6 having a thickness of 50 ⁇ m, was placed on a piece of paper having yellow letters and lines printed thereon, and photographed. The results are shown in
  • Equation 1 The optical density was calculated according to Equation 1 below: Equation 1
  • OD, A. _ --11 « w r [ - -L ic £ W (A) ] wherein 1 is the thickness of the film, Ax is absorbance at a wavelength of ⁇ , T is transmittance, I 0 is intensity of incident light, and I is intensity of transmitted light.
  • Modulus The 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) .
  • the CTE was measured at 50 ⁇ 200 ° C according to a TM ⁇ method using a TMA (TA Instrument, Q400) .
  • the polyimide films of the present invention having a thickness of 50 ⁇ m and 100 ⁇ m, had average transmittance of 85% or more at 380-780 nm, a yellowing index of 15 or less, and an optical density of less than 50 at 420 nm.
  • the polyimide film satisfying the aforementioned transmittance, yellowing index and optical density was transparent to the extent that yellow letters and lines printed on paper placed therebeneath could be seen.
  • 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.

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Abstract

L'invention concerne un film polyimide, incolore et transparent 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.
PCT/KR2007/006514 2006-12-15 2007-12-13 Film poyimide Ceased WO2008072916A1 (fr)

Applications Claiming Priority (12)

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KR1020060128978A KR101167337B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름
KR1020060128999A KR101167339B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름
KR10-2006-0129005 2006-12-15
KR10-2006-0128992 2006-12-15
KR10-2006-0129009 2006-12-15
KR1020060128992A KR101211857B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 필름
KR10-2006-0128999 2006-12-15
KR10-2006-0129011 2006-12-15
KR10-2006-0128978 2006-12-15
KR1020060129009A KR101167341B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름
KR1020060129011A KR101167483B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름
KR1020060129005A KR101142692B1 (ko) 2006-12-15 2006-12-15 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및필름

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WO2010093013A1 (fr) * 2009-02-13 2010-08-19 学校法人東京工芸大学 Dispositif d'affichage d'image et élément électroluminescent organique
US20110178266A1 (en) * 2008-09-26 2011-07-21 Han Moon Cho Polyimide film
US8859715B2 (en) 2010-12-23 2014-10-14 Industrial Technology Research Institute Polyimide polymer solution, polyimide polymer, transparent film, displaying device and solar cell
WO2014168423A1 (fr) * 2013-04-10 2014-10-16 Kolon Industries, Inc. Substrat de couvercle en polyimide
EP3290461A4 (fr) * 2015-04-28 2019-01-02 Kolon Industries, Inc. Résine de polyimide et film utilisant celle-ci
CN111205643A (zh) * 2020-03-20 2020-05-29 无锡创彩光学材料有限公司 一种透明聚酰亚胺薄膜及其制备方法

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US6232428B1 (en) * 1999-01-19 2001-05-15 I.S.T. Corporation Essentially colorless, transparent polyimide coatings and films
JP2004006735A (ja) * 2002-03-22 2004-01-08 Ube Ind Ltd 半導体パッケ−ジ内部絶縁用ポリイミドフィルムおよび積層基板
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US5338826A (en) * 1987-07-15 1994-08-16 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administation Structures from low dielectric polyimides
US5986036A (en) * 1997-06-27 1999-11-16 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Substrate material for holographic emulsions utilizing fluorinated polyimide film
US6232428B1 (en) * 1999-01-19 2001-05-15 I.S.T. Corporation Essentially colorless, transparent polyimide coatings and films
US20040063898A1 (en) * 2001-02-23 2004-04-01 Masaru Nishinaka Polymide film and process for producing the same
JP2004006735A (ja) * 2002-03-22 2004-01-08 Ube Ind Ltd 半導体パッケ−ジ内部絶縁用ポリイミドフィルムおよび積層基板

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Publication number Priority date Publication date Assignee Title
US20110178266A1 (en) * 2008-09-26 2011-07-21 Han Moon Cho Polyimide film
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
WO2010093013A1 (fr) * 2009-02-13 2010-08-19 学校法人東京工芸大学 Dispositif d'affichage d'image et élément électroluminescent organique
CN102273318A (zh) * 2009-02-13 2011-12-07 学校法人东京工芸大学 图像显示装置及有机电致发光元件
CN102273318B (zh) * 2009-02-13 2015-03-04 学校法人东京工芸大学 图像显示装置及有机电致发光元件
JP5682956B2 (ja) * 2009-02-13 2015-03-11 学校法人東京工芸大学 画像表示装置および有機エレクトロルミネッセンス素子
US8859715B2 (en) 2010-12-23 2014-10-14 Industrial Technology Research Institute Polyimide polymer solution, polyimide polymer, transparent film, displaying device and solar cell
WO2014168423A1 (fr) * 2013-04-10 2014-10-16 Kolon Industries, Inc. Substrat de couvercle en polyimide
KR20140122385A (ko) * 2013-04-10 2014-10-20 코오롱인더스트리 주식회사 폴리이미드 커버기판
KR101579645B1 (ko) 2013-04-10 2015-12-22 코오롱인더스트리 주식회사 폴리이미드 커버기판
EP3290461A4 (fr) * 2015-04-28 2019-01-02 Kolon Industries, Inc. Résine de polyimide et film utilisant celle-ci
CN111205643A (zh) * 2020-03-20 2020-05-29 无锡创彩光学材料有限公司 一种透明聚酰亚胺薄膜及其制备方法

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TW200900431A (en) 2009-01-01

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