WO2017111300A1 - Solution d'acide polyamique sur laquelle un monomère diamine ayant une nouvelle structure est appliqué, et film de polyimide comprenant la solution - Google Patents

Solution d'acide polyamique sur laquelle un monomère diamine ayant une nouvelle structure est appliqué, et film de polyimide comprenant la solution Download PDF

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WO2017111300A1
WO2017111300A1 PCT/KR2016/012829 KR2016012829W WO2017111300A1 WO 2017111300 A1 WO2017111300 A1 WO 2017111300A1 KR 2016012829 W KR2016012829 W KR 2016012829W WO 2017111300 A1 WO2017111300 A1 WO 2017111300A1
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diamine
mol
compound
polyamic acid
polyimide film
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PCT/KR2016/012829
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English (en)
Korean (ko)
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안경일
김동연
이재훈
김선영
오현석
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주식회사 두산
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Priority to CN201680075839.9A priority Critical patent/CN108431088B/zh
Priority to JP2018533188A priority patent/JP6899830B2/ja
Publication of WO2017111300A1 publication Critical patent/WO2017111300A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • 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
    • 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 diamine monomer having a novel structure, a polyamic acid composition for producing a transparent polyimide resin including such a diamine monomer, and a transparent polyimide resin prepared from the composition and applicable to a flexible display substrate or a protective film.
  • a transparent plastic substrate manufactured by film-forming a polymer resin such as polyethylene terephthalate (PET) or polyether sulfone (PES) has been developed.
  • the transparent plastic substrate using a polymer resin such as PET or PES has a good ductility compared to the glass substrate, but has a low heat resistance because the glass transition temperature (Tg) is low.
  • Tg glass transition temperature
  • CTE coefficient of thermal expansion
  • a technique for producing a transparent plastic substrate using a polyimide resin having excellent heat resistance and a relatively low coefficient of thermal expansion has attracted attention.
  • Polyimide resin (PI) has a limitation in showing high transparency like a glass substrate because it is colored in brown or yellow due to the effect of a charge transfer complex (CTC) and thus has low transmittance in the visible region. . Therefore, a lot of research is in progress to solve this problem.
  • a polyimide (PI) resin refers to a high heat-resistant resin prepared by solution polymerization of an aromatic acid dianhydride and an aromatic diamine or an aromatic diisocyanate to produce a polyamic acid derivative, and then imidization by ring closure dehydration at a high temperature.
  • pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) is used, and as the aromatic diamine component, oxydianiline (ODA) ), p-phenylene diamine (p-PDA), m-methylene diamine (m-MDA), methylene diamine (MDA), bisaminophenylhexafluoropropane (HFDA), etc.
  • ODA oxydianiline
  • p-PDA p-phenylene diamine
  • m-MDA m-methylene diamine
  • MDA methylene diamine
  • HFDA bisaminophenylhexafluoropropane
  • the acid dianhydride or diamine component has a trade-off relationship between optical properties, thermal properties, and mechanical properties, it is necessary to develop a compound of a component suitable for each property, that is, a monomer for transparent PI. Accordingly, development of a transparent polyamic acid composition for a flexible display having high transparency, excellent heat resistance, low thermal expansion coefficient, and excellent mechanical properties is required.
  • the present invention is directed to the introduction of a monomer having a specific chemical structure and substituents improve the optical, mechanical and thermal properties compared to the conventional.
  • a polyimide resin having high transparency, excellent mechanical and thermal properties it is judged to be effective to introduce a rigid chemical monomer, and a diamine monomer derivative having a specific chemical structure Designed and synthesized, by adjusting the content of the new diamine monomer synthesized in a specific range, a transparent polyamic acid composition and a polyimide film that can simultaneously implement a low YI (high Yellow Index), high light transmittance, mechanical and thermal properties For the purpose of manufacturing.
  • YI high Yellow Index
  • the present invention is a transparent polyamic acid applicable to a plastic transparent substrate, a TFT substrate, a flexible printed circuit board, a flexible OLED surface lighting substrate, and an electronic paper substrate material for LCD and OLED flexible displays. It is to provide a composition and a transparent polyimide film.
  • the present invention provides a compound represented by the following formula (1).
  • Y is a C 6 ⁇ C 40 arylene group, the C 6 ⁇ C 40 arylene group may be substituted with a halogen or a C 1 ⁇ C 6 alkyl group substituted with a halogen atom,
  • X 1 and X 2 are the same or different, are each independently selected from hydrogen, halogen, the group consisting of an alkyl group of C 1 ⁇ C 6 alkyl, and C 1 ⁇ in which one or more hydrogen substituted with halogen atoms C 6, the Provided that at least one of X 1 , X 2 and Y has a halogen or a C 1 to C 6 alkyl group substituted with a halogen atom,
  • n is an integer of 0-3.
  • each of X 1 and X 2 is an electron-withdrawing group (EWG) which is independently F or CF 3 .
  • EWG electron-withdrawing group
  • the present invention (a) a diamine containing a compound of the formula (1); (b) acid dianhydrides; And (c) an organic solvent, wherein the compound represented by Chemical Formula 1 provides a polyamic acid composition that is included in the range of 10 to 90 mol% based on 100 mol% of the total diamine.
  • the diamine is fluorinated first diamine; It may further comprise one or more selected from the group consisting of sulfone-based second diamine, hydroxy-based third diamine, ether-based fourth diamine and alicyclic fifth diamine.
  • the content of the fluorinated first diamine, sulfone-based second diamine, hydroxy-based third diamine, ether-based fourth diamine and cycloaliphatic fifth diamine are each 10 to 90 mol based on 100 mol% total diamine May be%.
  • the acid dianhydride may include one or more selected from the group consisting of fluorinated aromatic first acid dianhydride, alicyclic diacid dianhydride and non-fluorinated aromatic tertiary dianhydride.
  • the content of the at least one compound selected from the group consisting of the first acid dianhydride, the second acid dianhydride and the third acid dianhydride may be in the range of 10 to 100 mol% based on 100 mol% of the total acid dianhydride.
  • the ratio (a / b) of the number of moles of the diamine (a) and the acid dianhydride (b) may range from 0.7 to 1.3.
  • the present invention provides a transparent polyimide film prepared by imidizing the polyamic acid composition described above.
  • the transparent polyimide film may satisfy the physical property conditions of the following (i) to (v), more specifically (i) the glass transition temperature (Tg) is 320 to 400 °C range, (ii ) The light transmittance of wavelength 550nm is 88% or more based on film thickness of 50 ⁇ m, (iii) Yellowness is 4.0 or less according to ASTM E313 standard, (iv) Tensile strength is 110 MPa or more, and (v) Tensile modulus is May be at least 3.5 GPa.
  • Tg glass transition temperature
  • iii Yellowness is 4.0 or less according to ASTM E313 standard
  • Tensile strength is 110 MPa or more
  • Tensile modulus is May be at least 3.5 GPa.
  • the transparent imide film may be used as a substrate and / or protective film for a flexible display.
  • a polyamic acid composition having excellent optical properties, mechanical properties, thermal properties, etc. by adopting a diamine monomer having a specific structure and a substituent and adjusting the weight percentage thereof.
  • the polyamic acid composition having excellent optical properties, mechanical properties, thermal properties and the like as a substrate, it is possible to provide a flexible display substrate exhibiting excellent physical properties and product reliability.
  • the present invention provides a compound represented by Chemical Formula 1, preferably a diamine compound.
  • Y is a C 6 ⁇ C 40 arylene group, the C 6 ⁇ C 40 arylene group may be substituted with a halogen or a C 1 ⁇ C 6 alkyl group substituted with a halogen atom,
  • X 1 and X 2 are the same or different, are each independently selected from hydrogen, halogen, the group consisting of an alkyl group of C 1 ⁇ C 6 alkyl, and C 1 ⁇ in which one or more hydrogen substituted with halogen atoms C 6, the Provided that at least one of X 1 , X 2 and Y has a halogen or a C 1 to C 6 alkyl group substituted with a halogen atom,
  • n is an integer of 0-3.
  • the compound represented by Formula 1 is a conventional 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,4'- Basic structure is similar to Diaminobiphenyl (hereinafter referred to as TFDB), but has a more rigid structure as a divalent arylene linker is introduced between the diamine-substituted moieties in the compound. . Therefore, since it is not decomposed by heat or light and is more stable against external impact, optical properties, thermal properties, and mechanical properties (Modulus, Strength) of the polyamic acid composition including the same may be significantly improved.
  • TFDB Diaminobiphenyl
  • the polyimide film is dark brown rather than colorless because of the Charge Transfer Complex (CTC) of ⁇ electrons present in the imide chain. Since -F, -CF 3 and the like introduced in Chemical Formula 1 are strong electron withdrawing groups, the CT-Complex does not occur through the movement between ⁇ electrons, thereby exhibiting high transparency of polyimide.
  • EWG electron-withdrawing group
  • CTC Charge Transfer Complex
  • X 1 and X 2 may be a conventional electron withdrawing group (EWG) known in the art, each independently fluorine (F) or CF 3 It is preferred.
  • EWG electron withdrawing group
  • the Y may be a conventional C 6 ⁇ C 40 arylene group known in the art, specific examples thereof include phenylene, biphenylene, triphenylenyl and the like.
  • the Y is preferably selected from the group of substituents represented by the following formula.
  • R 1 to R 3 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, F, and CF 3 .
  • R 1 to R 3 are each independently F or CF 3 .
  • the compound represented by Formula 1 according to the present invention may be more specific to any one of a compound group consisting of Compound 1 to Compound 26, but is not particularly limited thereto.
  • the transparent polyamic acid composition of the present invention is for producing a transparent polyimide film, characterized in that it comprises a compound represented by the formula (1) as a diamine (diamine) component.
  • the polyamic acid composition comprises (a) a diamine containing the compound of Formula 1; (b) acid dianhydrides; And (c) an organic solvent.
  • the diamine (a) monomer used in the preparation of the transparent polyamic acid of the present invention may include a compound represented by Chemical Formula 1, and may be mixed with a conventional diamine compound known in the art.
  • the amount of the diamine monomer represented by Chemical Formula 1 is not particularly limited, and may be, for example, in the range of 10 to 90 mol% based on 100 mol% of the total acid dianhydride, and preferably in the range of 20 to 80 mol%. .
  • the diamine compound mixed with the compound of Formula 1 may be used without particular limitation as long as the compound has a diamine structure in the molecule.
  • An example is an aromatic, alicyclic, or aliphatic compound having a diamine structure.
  • Diamines usable in the present invention include optical properties such as high transmittance, low Y.I, low haze, and the like; Thermal properties such as high glass transition temperature (High Tg) and low coefficient of thermal expansion (Low CTE); Considering mechanical properties such as high modulus and high surface hardness, linear structures having fluorinated substituents or sulfone based, hydroxy based, ether based, etc. Appropriate combinations of structures to include are required. Accordingly, in the present invention, as the diamine compound, fluorinated aromatic first diamine, sulphonated second diamine, hydroxy third diamine, ether fourth diamine and alicyclic fifth diamine each having a fluorine substituent introduced therein alone. It may be used or in a form in which two or more thereof are mixed.
  • Non-limiting examples of diamine monomer (a) that can be used include oxydianiline (ODA), 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB ), 2,2'-bis (trifluoromethyl) -4,3'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,3'-Diaminobiphenyl), 2,2'-bis ( Trifluoromethyl) -5,5'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -5,5'-Diaminobiphenyl), 2,2'-bis (trifluoromethyl) -4,4 '-Diaminophenyl ether (2,2'-Bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 6-FODA), bis aminohydroxy phenyl hexafluoropropane (DBOH), bis amino
  • the fluorinated first diamine is a 2,2'-bis (trifluoromethyl) -4,4'-dia which may lead to linear polymerisation.
  • Preference is given to using minobiphenyl (2,2'-TFDB).
  • the hydroxy tertiary diamine is 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane (2,2-Bis (3-amino-4-methylphenyl) -hexafluoropropane, BIS-AT- AF) is preferred.
  • BIS-AT- AF 2,2-bis (3-amino-4-methylphenyl) -hexafluoropropane
  • the content of the fluorinated first diamine, sulfonated second diamine, hydroxy third diamine, ether fourth diamine, alicyclic fifth diamine, and the like are not particularly limited. It may be 10 to 90 mol% based on 100 mol% of the total diamine, preferably in the range of 20 to 80 mol%.
  • Acid dianhydride (b) monomers used in the preparation of the transparent polyamic acid of the present invention can be used without limitation, acid dianhydrides such as fluorinated, non-fluorinated, alicyclic and the like known in the art having an acid dianhydride structure in the molecule.
  • acid dianhydrides such as fluorinated, non-fluorinated, alicyclic and the like known in the art having an acid dianhydride structure in the molecule.
  • the fluorinated first acid dianhydride, alicyclic diacid dianhydride, and non-fluorinated triacid dianhydride may be used alone or in a mixed form of two or more thereof.
  • the fluorinated first acid dianhydride monomer is not particularly limited as long as it is an aromatic acid dianhydride into which a fluorine substituent is introduced.
  • fluorinated first dianhydrides examples include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydrid, 6-FDA), 4- (trifluoromethyl) pyromellitic dianhydride (4- (trifluoromethyl) pyromellitic dianhydride, 4-TFPMDA). These may be used alone or in combination of two or more thereof.
  • 6-FDA is a very suitable compound for clearing due to its very high property of limiting the formation of change transfer complexes (CTCs) between and within molecular chains.
  • the alicyclic diacid dianhydride that can be used in the present invention is not particularly limited as long as it is a compound having an acid dianhydride structure having an alicyclic ring instead of an aromatic ring in the compound.
  • Examples of the alicyclic second dianhydride usable in the present invention include cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA) , Bicyclo [2,2,2] -7-octene-2,3,5,6-tetracarboxylic dianhydride (BCDA), or mixtures of one or more thereof, but are not particularly limited thereto. .
  • CBDA cyclobutane tetracarboxylic dianhydride
  • CPDA 1,2,3,4-cyclopentane tetracarboxylic dianhydride
  • BCDA Bicyclo [2,2,2] -7-octene-2,3,5,6-tetracarboxylic dianhydride
  • the non-fluorinated tertiary acid dianhydride monomer is not particularly limited as long as it is a non-fluorinated aromatic acid dianhydride to which a fluorine substituent is not introduced.
  • Non-limiting examples of non-fluorinated tertiary dianhydride monomers that can be used include pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (3, 3 ′, 4,4′-Biphenyl tetracarboxylic acid dianhydride (BPDA). These may be used alone or in combination of two or more thereof.
  • PMDA pyromellitic dianhydride
  • BPDA 4,4'-biphenyltetracarboxylic acid dianhydride
  • the content of at least one compound selected from the group consisting of the first acid dianhydride, the second acid dianhydride and the third acid dianhydride is not particularly limited. In one example, they may each range from 10 to 100 mole percent, based on 100 mole percent total acid dianhydride, preferably in the range from 10 to 90 mole percent, more preferably 20 to 80 mole percent.
  • the ratio thereof when the fluorinated first acid dianhydride and the non-fluorinated third acid dianhydride are mixed as the acid dianhydride (b), the ratio thereof may be 40 to 90: 60 to 10 mol%.
  • the ratio thereof when the fluorinated first acid dianhydride and alicyclic second acid dianhydride are mixed as the acid dianhydride (b), the ratio thereof may be 30 to 70:70 to 30 mol%. have.
  • the ratio of their use is 40 to 90: 60 to 10 mol% ratio. Can be.
  • the ratio (a / b) of the number of moles of the diamine component (a) to the number of moles of the dianhydride component (b) may be 0.7 to 1.3, preferably 0.8 to 1.2. And more preferably 0.9 to 1.1.
  • the solvent (c) for solution polymerization of the aforementioned monomers included in the polyamic acid composition of the present invention may use any organic solvent known in the art without limitation.
  • solvents examples include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • acetone diethyl
  • polar solvents selected from acetate, and dimethyl phthalate (DMP) can be used.
  • low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such as ⁇ -butyrolactone may be used.
  • the content of the solvent is not particularly limited, but in order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, the content of the solvent for polymerization (the first solvent) may range from 50 to 95 wt% based on the total weight of the polyamic acid composition. It is preferably in the range of 70 to 90% by weight, more preferably in the range of 75 to 85% by weight.
  • the polyamic acid composition of the present invention may be prepared by adding the above-described acid dianhydride and diamine into an organic solvent and reacting.
  • the diamine of Formula 1 at least one or more diamine components of the first to fifth diamine, and acid dianhydride, diamine (a) and acid dianhydride (b) to improve the glass transition temperature and yellowness Transparent polyamic acid compositions can be formed with an equivalent ratio of approximately 1: 1.
  • the composition of the polyamic acid composition is not particularly limited, and for example, based on 100% by weight of the total weight of the polyamic acid composition, 2.5 to 25.0% by weight of the acid dianhydride, 2.5 to 25.0% by weight of diamine, and the remaining amount to satisfy 100% by weight of the composition It may be configured to include an organic solvent of. In one example, the content of the organic solvent may be 75 to 85% by weight. Meanwhile, in the composition of the polyamic acid composition according to the present invention, based on 100% by weight of solids, the acid dianhydride may be in the range of 30 to 70% by weight, and diamine 30 to 70% by weight. However, this is not particularly limited.
  • Such transparent polyamic acid compositions of the present invention may have a viscosity in the range of about 1,000 to 50,000 cps, preferably about 3,000 to 15,000 cps.
  • the viscosity of the polyamic acid solution falls within the above-described range, the thickness of the polyamic acid solution may be easily adjusted when the solution is coated, and the coating surface may be uniformly exhibited.
  • the polyamic acid solution of the present invention may contain a small amount of additives such as plasticizers, antioxidants, flame retardants, dispersants, viscosity regulators, leveling agents and the like within the range that does not significantly impair the object and effect of the present invention if necessary. .
  • the present invention provides a polyimide film prepared by imidizing and heat treating the polyamic acid solution described above at high temperature.
  • the polyimide resin is a polymer material containing an imide ring, and is excellent in heat resistance, chemical resistance, abrasion resistance, and electrical properties.
  • the polyimide resin may be in the form of a random copolymer or a block copolymer.
  • a polyimide resin film in order to apply a polyimide resin film to a flexible display, it should basically have characteristics such as high transparency, low thermal expansion coefficient, and high glass transition temperature. More specifically, a light transmittance of 550 nm is 90% or more based on a film thickness of 10 ⁇ m, a yellowness value of 550 nm is 3 or less, a glass transition temperature (Tg) of 300 ° C. or more is required.
  • the polyimide film of the present invention prepared by imidizing the polyamic acid composition described above has a rigid chemical structure in a repeating unit and exhibits high transparency while having low yellowness, thermal expansion coefficient, and high glass transition temperature. (Tg), high tensile strength and elastic modulus.
  • the polyimide film has a physical property condition of the following (i) to (v), such as (i) the glass transition temperature (T g ) is in the range of 320 to 400 °C, (ii) the film thickness 50 ⁇ m reference
  • T g glass transition temperature
  • the film thickness 50 ⁇ m reference The light transmittance of 500 nm is 88% or more, (iii) the yellowness according to ASTM E313 standard is 4.0 or less (50 micrometers basis), (iv) tensile strength is 110-150 MPa, (v) tensile elasticity modulus is 3.5-
  • the 5.0 GPa range can all be met.
  • the polyimide film according to the present invention may be prepared by exothermic solution polymerization of a transparent polyamic acid solution according to conventional methods known in the art.
  • the transparent polyamic acid composition may be prepared by coating (casting) a glass substrate and inducing an imide cyclization reaction (Imidazation) for 0.5 to 8 hours while gradually raising the temperature in the range of 30 to 350 ° C. It is preferable to react in inert atmosphere, such as argon and nitrogen at this time.
  • the coating method may be used without limitation conventional methods known in the art, for example, spin coating (dip coating), dip coating (Dip coating), solvent casting (Solvent casting), slot die coating (Slot die coating) ) And at least one method selected from the group consisting of spray coating.
  • the colorless transparent polyimide layer may be coated at least once with a transparent polyamic acid composition such that the thickness of the colorless and transparent polyimide layer is several hundreds of micrometers.
  • the thickness of the polyimide film thus formed is not particularly limited and may be appropriately adjusted according to the field to be applied. For example, it may be in the range of 10 to 150 ⁇ m, preferably in the range of 10 to 80 ⁇ m.
  • the transparent polyimide film manufactured as described above may be used in various fields, and particularly, displays for organic EL devices (OLEDs), displays for liquid crystal devices, TFT substrates, flexible printed circuit boards that require high transparency and heat resistance. It can be used as a flexible display substrate and a protective film such as a flexible OLED surface lighting substrate, a substrate material for electronic paper.
  • OLEDs organic EL devices
  • TFT substrates TFT substrates
  • flexible printed circuit boards that require high transparency and heat resistance.
  • a protective film such as a flexible OLED surface lighting substrate, a substrate material for electronic paper.
  • CBDA cyclobutane-1,2,3,4-tetracarboxylic dianhydride
  • 6FDA cyclobutane-1,2,3,4-tetracarboxylic dianhydride
  • compositions of the polyamic acid composition prepared in Examples 1 to 20 and Comparative Examples 1 to 6 are as shown in Table 1 below. At this time, mol% represents the mole ratio of each monomer in diamine and the whole acid dianhydride.
  • Measurement was performed using a UV-Vis NIR Spectrophotometer (Shimadzu, model name: UV-3150) at a wavelength of 550 nm.
  • Yellowness was measured according to ASTM E313 using a spectrophotometer (Konica Minolta, model name: CM-3700d).
  • Tensile strength (MPa) and elastic modulus (GPa) were measured according to ISO 527-3 using UTM (Instron, Model Name: 5942).
  • the thickness of the film was measured by a thickness gauge (Mitutoyo, model name: 293-140).
  • Example 1 52 90 3.2 340 129 4.2 Example 2 50 90 2.9 345 144 4.6 Example 3 51 90 3.3 339 128 4.0 Example 4 49 90 3.1 342 141 4.4 Example 5 51 90 2.7 330 137 4.6 Example 6 52 91 2.5 337 142 4.8 Example 7 50 90 2.9 329 140 4.7 Example 8 50 90 2.8 331 144 4.9 Example 9 49 91 2.7 321 127 3.9 Example 10 51 91 2.5 336 132 4.2 Example 11 49 91 2.9 327 129 4.0 Example 12 50 91 2.7 339 136 4.4 Example 13 52 90 2.9 341 133 4.3 Example 14 48 90 2.9 338 129 4.1 Example 15 50 90 3.2 349 128 3.9 Example 16 51 90 3.7 347 124 3.7 Example 17 51 90 2.9 330 135 4.5 Example 18 50 91 2.9 3
  • the polyimide film of the present invention improves the optical, thermal, and mechanical properties of the conventional polyimide film, and the polyimide film is usefully applied as a transparent plastic substrate instead of a glass substrate when manufacturing a flat panel display. It could be confirmed.

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Abstract

La présente invention concerne : un nouveau monomère utilisé comme composant diamine d'un acide polyamique; une composition d'acide polyamique contenant celui-ci; et un polyimide préparé à partir de la composition. La composition d'acide polyamique selon l'invention présente d'excellentes caractéristiques optiques, thermiques et mécaniques, et peut être appliquée en tant que matériau pour écran souple.
PCT/KR2016/012829 2015-12-24 2016-11-09 Solution d'acide polyamique sur laquelle un monomère diamine ayant une nouvelle structure est appliqué, et film de polyimide comprenant la solution WO2017111300A1 (fr)

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US20210214501A1 (en) * 2019-02-01 2021-07-15 Lg Chem, Ltd. Polyimide-based polymer film, substrate for display device, and optical device using the same
CN113698594A (zh) * 2021-09-08 2021-11-26 湖南工业大学 一种聚酰胺树脂及其制备方法
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CN110938220A (zh) * 2018-09-21 2020-03-31 达迈科技股份有限公司 透明聚酰亚胺膜的制备方法
KR102188949B1 (ko) * 2018-10-15 2020-12-09 주식회사 엘지화학 폴리이미드 전구체 및 이를 이용하는 폴리이미드 필름
KR102260540B1 (ko) * 2019-01-02 2021-06-08 주식회사 대림 폴리아믹산 조성물의 제조방법, 폴리아믹산 조성물, 이를 이용한 폴리이미드 필름의 제조방법 및 그 제조방법을 통해 제조된 폴리이미드 필름.
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KR20220067390A (ko) * 2020-11-17 2022-05-24 주식회사 엘지화학 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 회로 기판, 광학 장치 및 전자 장치
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CN109423047A (zh) * 2017-08-28 2019-03-05 苏州聚萃材料科技有限公司 耐热聚酰亚胺薄膜及其制备的显示器基板
JP7414011B2 (ja) 2019-02-01 2024-01-16 エルジー・ケム・リミテッド ポリイミド系樹脂フィルム、およびこれを利用したディスプレイ装置用基板ならびに光学装置
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JP2022518984A (ja) * 2019-02-01 2022-03-18 エルジー・ケム・リミテッド ポリイミド前駆体組成物およびそれから製造されたポリイミドフィルム、ディスプレイ装置用基板、および光学装置
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KR20200096100A (ko) * 2019-02-01 2020-08-11 주식회사 엘지화학 폴리이미드 전구체 조성물 및 이로부터 제조된 폴리이미드 필름, 디스플레이 장치용 기판, 및 광학 장치
US20210214501A1 (en) * 2019-02-01 2021-07-15 Lg Chem, Ltd. Polyimide-based polymer film, substrate for display device, and optical device using the same
US20210230368A1 (en) * 2019-02-01 2021-07-29 Lg Chem, Ltd. Polyimide-based polymer film, substrate for display device, and optical device using the same
US12060456B2 (en) 2019-02-01 2024-08-13 Lg Chem, Ltd. Polyimide precursor composition and polyimide film, substrate for display device, and optical device prepared by using same
WO2020159174A1 (fr) * 2019-02-01 2020-08-06 주식회사 엘지화학 Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, chacun utilisant celui-ci
WO2020159184A1 (fr) * 2019-02-01 2020-08-06 주식회사 엘지화학 Film polymère à base de polyimide, substrat pour appareil d'affichage l'utilisant, et appareil optique
US11999823B2 (en) 2019-02-01 2024-06-04 Lg Chem, Ltd. Polyimide-based polymer film, substrate for display device, and optical device using the same
KR102465430B1 (ko) * 2019-02-01 2022-11-10 주식회사 엘지화학 폴리이미드 전구체 조성물 및 이로부터 제조된 폴리이미드 필름, 디스플레이 장치용 기판, 및 광학 장치
JP7364140B2 (ja) 2019-02-01 2023-10-18 エルジー・ケム・リミテッド ポリイミド前駆体組成物およびそれから製造されたポリイミドフィルム、ディスプレイ装置用基板、および光学装置
JP7414010B2 (ja) 2019-02-01 2024-01-16 エルジー・ケム・リミテッド ポリイミド系樹脂フィルム、およびこれを利用したディスプレイ装置用基板ならびに光学装置
WO2020159193A1 (fr) * 2019-02-01 2020-08-06 주식회사 엘지화학 Composition de précurseur de polyimide et film de polyimide, substrat pour dispositif d'affichage, et dispositif optique, chacun fabriqué à partir de celle-ci
JP7414013B2 (ja) 2019-02-01 2024-01-16 エルジー・ケム・リミテッド ポリイミド系樹脂フィルム、およびこれを利用したディスプレイ装置用基板ならびに光学装置
US20220325045A1 (en) * 2019-04-23 2022-10-13 Dupont Electronics, Inc. Polymers for use in electronic devices
CN113698594B (zh) * 2021-09-08 2023-08-04 湖南工业大学 一种聚酰胺树脂及其制备方法
CN113698594A (zh) * 2021-09-08 2021-11-26 湖南工业大学 一种聚酰胺树脂及其制备方法

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