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WO2018143583A2 - Polyimide et film de polyimide préparé à partir de celui-ci destiné à un écran flexible - Google Patents

Polyimide et film de polyimide préparé à partir de celui-ci destiné à un écran flexible Download PDF

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Publication number
WO2018143583A2
WO2018143583A2 PCT/KR2018/000810 KR2018000810W WO2018143583A2 WO 2018143583 A2 WO2018143583 A2 WO 2018143583A2 KR 2018000810 W KR2018000810 W KR 2018000810W WO 2018143583 A2 WO2018143583 A2 WO 2018143583A2
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Prior art keywords
group
polyimide
formula
carbon atoms
diamine
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PCT/KR2018/000810
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English (en)
Korean (ko)
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WO2018143583A3 (fr
Inventor
정혜원
구기철
김경준
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020170167165A external-priority patent/KR101989028B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP20198866.4A priority Critical patent/EP3812415B1/fr
Priority to EP18748750.9A priority patent/EP3578589A4/fr
Priority to CN201880003834.4A priority patent/CN109803995B/zh
Priority to JP2019512727A priority patent/JP7048020B2/ja
Priority to US16/461,601 priority patent/US11319409B2/en
Publication of WO2018143583A2 publication Critical patent/WO2018143583A2/fr
Publication of WO2018143583A3 publication Critical patent/WO2018143583A3/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
    • 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
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present invention relates to a polyimide having improved heat resistance and thermal stability and a polyimide film for flexible display including the same.
  • Polyimide (PI) is a polymer with relatively low crystallinity or mostly amorphous structure. It is easy to synthesize, can make thin film, and does not need a crosslinker for curing. It is a polymer material that has excellent heat resistance, chemical resistance, excellent mechanical properties, electrical properties and dimensional stability. It is widely used in electric and electronic materials such as automotive, aerospace, flexible circuit boards, liquid crystal alignment films for LCDs, adhesives and coating agents. have.
  • polyimide is a high-performance polymer material with high thermal stability, mechanical properties, chemical resistance, and electrical properties, it does not satisfy the colorless and transparent property, which is a basic requirement for the display field, and also requires a lower coefficient of thermal expansion.
  • Kapton's coefficient of thermal expansion sold by DuPont, has a low coefficient of thermal expansion of about 30 ppm / ° C, but this also does not meet the requirements of plastic substrates. Therefore, many studies have been conducted to minimize optical characteristics and thermal hysteresis while maintaining basic characteristics of polyimide.
  • An object of the present invention is to provide a polyimide with improved heat resistance and thermal stability.
  • Another object of the present invention is to provide a polyimide film containing the polyimide.
  • the present invention also provides a diamine with a novel structure comprising a spiro or cardo group in its molecular structure.
  • the present invention to solve the above technical problem
  • polyimide prepared from a polymerization component comprising tetracarboxylic dianhydride and at least one diamine selected from the following formulas (1a) to (1e).
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, and a carbon number It is a substituent selected from the halogenoalkoxy of 1-4, the halogenoalkyl of 1-10, C6-C20, and the aryl group,
  • the diamine of Formula 1 may be included in an amount of 30 to 100 mol% with respect to the total content of the diamine.
  • the coefficient of thermal expansion (CTE) of the polyimide may be 50ppm / °C or less.
  • the glass transition temperature (Tg) of the polyimide may be 330 °C or more.
  • the polyimide film for flexible displays containing the said polyimide is provided.
  • the present invention also provides a diamine represented by any one of the following Formulas 1a to 1e.
  • R 1, R 2 each independently represent a hydrogen atom, -F, -Cl, -Br, and a halogen atom, is selected from -I hydroxyl group (-OH), thiol (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy having 1 to 4 carbon atoms, a halogenoalkyl having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • the polyimide according to the present invention may be prepared from diamines containing spiro or cardo groups in which two or more phenyl groups are linked and fixed, thereby improving dimensional stability against heat as well as high glass transition temperature.
  • the polyimide film made of the polyimide according to the present invention has excellent thermal stability, and is a flexible device with high temperature process, in particular OLED (organic light) using an oxide TFT (thin film transistor) and LTPS (low temperature polysilicon) process. emitting diode) device.
  • substituted means that at least one hydrogen contained in the compound or the organic group is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a hydroxy group And substituted with a substituent selected from the group consisting of alkoxy groups, carboxylic acid groups, aldehyde groups, epoxy groups, cyano groups, nitro groups, amino groups, sulfonic acid groups and derivatives thereof having 1 to 10 carbon atoms.
  • a single bond, a double bond, a triple bond, an alkylene group having 1 to 10 carbon atoms for example, methylene group (-CH 2- ), an ethylene group (-CH 2 CH 2 -), etc.
  • the present invention provides an ultrahigh temperature resistant polyimide made from diamines having a novel structure.
  • Another object of the present invention to provide a polyimide film containing the polyimide.
  • the present invention provides a diamine represented by one selected from the following Chemical Formulas 1a to 1e.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, and a carbon number It is a substituent chosen from the halogeno alkoxy of 1-4, the halogenoalkyl of 1-10 carbon atoms, and the aryl group of 6-20 carbon atoms.
  • the diamine of the general formula (1) may be included in the content of 30 to 100 mol% with respect to the total content of the diamine in the polymerization component, preferably it may be included in a content of 50 to 100 mol%.
  • the diamine according to the present invention has a structure including a spiro group or a cardo group in which two or more phenyl groups are connected and fixed, and a polyimide comprising a group in which a phenyl group is not fixed.
  • a polyimide having a high thermal transition and a decrease in the CTE is reduced by fixing a phenyl group, thereby obtaining a polyimide having excellent thermal stability. Can provide.
  • the glass transition temperature of the polyimide may be 330 °C or more, preferably 350 °C or more.
  • the CTE of the polyimide may be 50 ppm / ° C. or less, preferably 30 ppm / ° C. or less, for example, 10 to 30 ppm / ° C.
  • the CTE is set to be pulled with a force of 0.02N after a sample of a thickness of 10 ⁇ m, width 5mm, length 5cm to the jig so that the measurement length is 16mm, and the temperature increase rate to 5 °C / min to rise to 300 °C ( After the first temperature rise) and then cooled to 50 ° C (primary cooling), and the temperature is increased to 450 ° C (secondary temperature increase) in the step of measuring the value in the 100 ⁇ 250 °C section.
  • the molar ratio of the total content of the tetracarboxylic dianhydride and the content of the diamine may be preferably 1: 0.99 to 0.99: 1, preferably 1: 0.98 to 0.98: 1.
  • the tetracarboxylic dianhydride may be used as long as it is generally used for the production of polyimide.
  • tetracarboxylic dianhydrides usable in the production of polyimides are tetravalent organic groups of aromatic, cycloaliphatic, or aliphatic in the molecule, or combinations thereof, and aliphatic, cycloaliphatic, or aromatic tetravalent organic groups.
  • It may be tetracarboxylic dianhydride including tetravalent organic groups connected to each other via a crosslinked structure.
  • it may be a tetracarboxylic dianhydride including a tetravalent organic group structure selected from the group consisting of tetravalent organic groups of Formulas 2a to 2e and combinations thereof.
  • R 11 to R 17 each independently represent a hydrogen atom, a halogen atom (selected from -F, -Cl, -Br, and -I), a hydroxyl group (-OH), and a thiol group (-SH ), A nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy having 1 to 4 carbon atoms, a halogenoalkyl having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms Can,
  • A1 is an integer of 0 to 2
  • a2 is an integer of 0 to 4
  • a3 is an integer of 0 to 8
  • a4 and a5 may each independently represent an integer of 0 to 3
  • a6 and a9 may each independently represent an integer of 0 to 3
  • a7 and a8 may each independently represent an integer of 0 to 9
  • tetracarboxylic dianhydride used in the present invention may be used in the structure, but tetracarboxylic dianhydride including a tetravalent organic group selected from the group consisting of 3a to 3r, but is not limited thereto.
  • At least one hydrogen atom present in the tetravalent organic group of 3a to 3r may be selected from the group consisting of -F, -Cl, -Br and -I, a halogen atom, a hydroxyl group (-OH), a thiol group ( -SH), a nitro group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy having 1 to 4 carbon atoms, a halogenoalkyl having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms It may be substituted with a substituent.
  • diamines may be used in addition to the diamine of Chemical Formula 1, and the diamine may be used as long as it is generally used for preparing polyimide, and specifically, an aliphatic, alicyclic or aromatic divalent compound.
  • an organic group or a combination group thereof an aliphatic, alicyclic or aromatic divalent organic group may be directly connected or a divalent organic group connected to each other through a crosslinking structure, for example, 2 of Formulas 4a to 4g It may be a diamine containing a divalent organic group structure selected from the group consisting of a divalent organic group and a combination thereof.
  • R 21 to R 28 each independently represent an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, etc.), halogen group and hydroxy group
  • a cyclohexylene group, etc. a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms (e.g., a phenylene group, a naphthalene group, a fluorenylene group, etc.), and combinations thereof may be selected.
  • a cyclohexylene group, etc. a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms (e.g., a phenylene group, a naphthalene group, a fluorenylene group, etc.), and combinations thereof may be selected.
  • b 1 , b 4 and b 5 are each independently an integer from 0 to 4
  • b 2 is an integer from 0 to 6
  • b 3 is an integer from 0 to 3
  • b 6 and b 9 are each independently 0 or is an integer of 1
  • b 7, and 8 b are each independently an integer of 0 to 10.
  • the diamine used in the present invention may further be a diamine including a divalent organic group selected from the group consisting of the formulas 5a to 5t in the structure, but is not limited thereto.
  • the at least one hydrogen atom present in the divalent organic group of 5a to 5t is a halogen atom selected from -F, -Cl, -Br and -I, hydroxyl group (-OH), thiol group (-SH), nitro Or a substituent selected from a group (-NO 2 ), a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy having 1 to 4 carbon atoms, a halogenoalkyl having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • a halogen atom selected from -F, -Cl, -Br and -I
  • hydroxyl group -OH
  • thiol group -SH
  • a cyano group an alkyl group having 1 to 10 carbon atoms
  • a halogenoalkoxy having
  • the polymerization component may further include a diamine of the following Chemical Formula 6 together with the diamine selected from Chemical Formulas 1a to 1e.
  • R 31 and R 32 are each independently a halogen atom selected from -F, -Cl, -Br and -I, a hydroxyl group (-OH), a thiol group (-SH), a nitro group (-NO 2 ), A substituent selected from a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenoalkoxy having 1 to 4 carbon atoms, a halogenoalkyl having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms,
  • n and m are each independently an integer of 0-4.
  • the method for reacting the tetracarboxylic dianhydride with the diamine can be carried out according to a conventional polyimide precursor polymerization production method such as solution polymerization. Specifically, after dissolving diamine in an organic solvent, tetracarboxylic dianhydride is added to the resulting mixed solution and polymerized to produce a polyamic acid as a polyimide precursor.
  • the reaction can be carried out under an inert gas or nitrogen stream and can be carried out in anhydrous conditions.
  • the polymerization temperature may be carried out at -20 to 60 °C, preferably 0 to 45 °C. If the reaction temperature is too high, the reactivity may be increased to increase the molecular weight, it may be disadvantageous in terms of the process by increasing the viscosity of the precursor composition.
  • sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • formamide solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide
  • Acetamide solvents such as N, N-diethylacetamide
  • pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone
  • phenol, o-, m- or p Phenol solvents such as cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, ⁇ -butyrolactone, and the like, and these may be used alone or as a mixture, more preferably N, N-diethylacetamide (N, N-diethylacetamide, DEAc), N, N-diethylformamide (DEF), N-ethylpyrrolidone (NE
  • the organic solvent may further use an aromatic hydrocarbon such as xylene, toluene, and also up to about 50% by weight of alkali metal salt or alkaline earth in the solvent to promote dissolution of the polymer. Further metal salts may be added.
  • aromatic hydrocarbon such as xylene, toluene
  • alkali metal salt or alkaline earth in the solvent to promote dissolution of the polymer. Further metal salts may be added.
  • the polyimide precursor solution manufactured by the above-mentioned manufacturing method contains solid content in the quantity which makes the said composition have appropriate viscosity in consideration of processability, such as applicability
  • the content of the composition may be adjusted such that the total polyimide precursor is 5 to 20% by weight, preferably 8 to 18% by weight, more preferably 8 to 12% by weight. have.
  • the polyimide precursor solution may be adjusted to have a viscosity of 2,000 cP or more, or 3,000 cP or more, and the viscosity of the polyimide precursor solution may be 10,000 cP or less, preferably 9,000 cP or less, and more preferably 8,000 cP. It is preferable to adjust so that it may have the following viscosity.
  • the viscosity of the polyimide precursor solution exceeds 10,000 cP, the efficiency of degassing during the processing of the polyimide film is lowered. As a result, not only the efficiency of the process but also the resulting film has poor surface roughness due to foaming, resulting in electrical, optical and mechanical properties. Can be degraded.
  • the polyimide according to the present invention may have a weight average molecular weight of 10,000 to 200,000 g / mol, or 20,000 to 100,000 g / mol, or 30,000 to 100,000 g / mol. It is preferable that molecular weight distribution (Mw / Mn) is 1.1-2.5. If the weight average molecular weight or molecular weight distribution of the polyimide is out of the above range, it may be difficult to form a film or the characteristics of the polyimide film such as permeability, heat resistance and mechanical properties may be deteriorated.
  • the polyimide precursor obtained as a result of the polymerization reaction is imidated, whereby a transparent polyimide film can be produced.
  • the imidization process may specifically include a chemical imidization method or a thermal imidization method.
  • a dehydrating agent and an imidization catalyst are added to the polymerized polyimide precursor solution, and then heated to a temperature of 50 to 100 ° C. to imidize by chemical reaction, or the alcohol is removed while refluxing the solution.
  • Polyimide can be obtained by the method of drawing.
  • pyridine, triethylamine, picoline, or quinoline may be used as the imidization catalyst, and in addition, N- of substituted or unsubstituted nitrogen-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds
  • acid anhydrides such as acetic anhydride can be used.
  • the polyimide precursor solution may be imidized by applying a heat treatment on a substrate.
  • the polyimide precursor solution may be in the form of a solution dissolved in an organic solvent, and in the case of having such a form, for example, when a polyimide precursor is synthesized in an organic solvent, the solution may be the reaction solution itself obtained. The reaction solution may be diluted with another solvent. Moreover, when a polyimide precursor is obtained as a solid powder, it may be made to melt
  • the present invention comprises the steps of applying the polyimide precursor solution on a substrate;
  • It provides a method for producing a polyimide film comprising the step of heat-treating the applied polyimide precursor solution.
  • the polyimide precursor solution is applied to a substrate and heat-treated on an IR oven, a hot air oven or a hot plate, wherein the heat treatment temperature may be in the range of 300 to 500 ° C, preferably 320 to 480 ° C, and the temperature range It can also be carried out in a multistage heating process.
  • the heat treatment process may be carried out for 20 to 70 minutes, preferably for 20 to 60 minutes.
  • the organic solvent contained in the polyimide precursor solution of the present invention may be the same as the organic solvent used in the synthesis reaction.
  • this invention is a range which does not impair an effect, you may add an imidation promoter etc. for the purpose of advancing a silane coupling agent, a crosslinkable compound, and imidation efficiently.
  • the polyimide-based film has a haze value of 1 or less, preferably 0.9 or less, or 0.7 or less, and more preferably 0.5 or less, thereby providing a polyimide film having improved transparency.
  • the thickness of the polyimide film may be 8 to 15 ⁇ m, preferably 10 to 12 ⁇ m.
  • the transmittance of light with a wavelength of 380 to 760 nm in the film thickness range of 5 to 30 ⁇ m is 80% or more, and the yellowness (YI) is about 25 or less, preferably about 20 or less, and more preferably about 16 or less. Or a colorless transparent polyimide film having a value of 15 or less.
  • the polyimide film has an in-plane retardation value R in of about 0 to 100 nm, and an absolute value of the retardation value R th in the thickness direction is about 1500 nm or less, or 0 to 1000 nm or less, preferably 30 to 800 nm. Or less, more preferably, 50 to 700 nm or less. Visibility suitable for a display may be expressed in the phase difference range in the thickness direction, and when the thickness direction phase difference is 1500 nm or more, a phase difference occurs in the polyimide film so that light is distorted and thus visibility may be significantly reduced.
  • an article including the polyimide copolymer is provided.
  • the molded article may be a film, a fiber, a coating material, an adhesive material, but is not limited thereto.
  • the molded article may be formed by a dry wet method, a dry method, a wet method, etc. using the composite composition of the copolymer and the inorganic particles, but is not limited thereto.
  • the molded article may be an optical film, in which case, the composition comprising the polyimide copolymer is applied to the substrate by a method such as spin coating, and then easily dried and cured. Can be prepared.
  • the polyimide according to the present invention may exhibit excellent heat resistance against thermal changes that may occur in a high temperature process, such as an element substrate, a display cover substrate, an optical film, an integrated circuit (IC) package, and an adhesive film.
  • adhesive film multilayer FPC (flexible printed circuit), tape, a touch panel, a protective film for an optical disk, etc. can be used in various fields.
  • the display device may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), and the like, and in particular, a low temperature polysilicon (LTPS) process requiring a high temperature process It may be suitable for an OLED device using, but is not limited thereto.
  • LCD liquid crystal display device
  • OLED organic light emitting diode
  • LTPS low temperature polysilicon
  • Diamine compound of formula 10 (Compound 10) was prepared as follows.
  • the diamine compound of formula 11 (Compound 11) was prepared as follows.
  • BPDA 3,3,4,4'-biphenyltetracarboxylic dianhydride
  • TFDB 2,2'-bis (trifluoromethyl)-[1,1 ' -biphenyl] -4,4'-diamine
  • a polyamic acid resin prepared by polymerizing 0.5mol and 0.5mol of the diamine of Formula 10 prepared in Synthesis Example 1 and 80% by weight of DMAc (dimethylacetamide) as a solvent.
  • DMAc dimethylacetamide
  • a composition comprising 20% by weight of polyamic acid-based resin prepared by polymerizing 1 mol of BPDA and 0.99 mol of the diamine of Formula 11 prepared in Synthesis Example 2 and 80% by weight of DMAc as a solvent. After drying, the coating was applied to a thickness of 10 ⁇ m, and the resulting coating film was continuously subjected to a drying step at 100 ° C. and a curing step at 300 ° C. for 60 minutes to form a polyimide film for forming a polymer layer of the flexible substrate. It was.
  • an alkali-free glass As a carrier substrate, 20% by weight of a polyamic acid-based resin prepared by polymerizing 1 mol of BPDA, 0.5 mol of TFDB, and 0.5 mol of the diamine of Formula 12 prepared in Synthesis Example 3, and 80% by weight of DMAc as a solvent
  • the composition was coated to have a thickness of 10 ⁇ m, and the resulting coating film was continuously subjected to a drying step at 100 ° C. and a curing step at 300 ° C. for 60 minutes to form a polymer for forming a polymer layer of the flexible substrate.
  • the mid film was formed.
  • a composition containing 20% by weight of a polyamic acid resin prepared by polymerizing 1 mol of BPDA and 0.99 mol of TFDB and 80% by weight of DMAc as a solvent was applied so as to have a thickness of 10 ⁇ m.
  • the resulting coating film was continuously subjected to a drying step at a temperature of 100 ° C. and a curing step at 300 ° C. for 60 minutes to form a polyimide film for forming a polymer layer of a flexible substrate including a polyimide resin. .
  • a polyimide film for forming a layer of the flexible substrate was prepared in the same manner as in Example 1, except that diamine (SBF) of the following formula was used.
  • a sample with a thickness of 10 ⁇ m, a width of 5 mm, and a length of 5 cm is set to be pulled by a jig so that the measuring length becomes 16 mm, and then pulled with a force of 0.02 N, and the temperature rising rate is 5 ° C./min.
  • the thermal expansion value in the range of 100 to 250 ° C. was measured by TMA (Q400 of TA). At this time, the inflection point seen in the temperature increase section in the first temperature increase step was set to Tg.
  • Thickness direction retardation (Rth) of the film having a thickness of 10 ⁇ m, a width of 5 cm, and a length of 5 cm was measured by Axoscan.
  • the polyimide film according to the present invention has a lower CTE value and a higher glass transition temperature than the polyimide of Comparative Examples 1 and 2. Especially in the case of Example 2, the CTE value is similar to that of Comparative Example 1, but has a much higher glass transition temperature.
  • the present invention by including two phenyl groups fixed and spiro or cardo group fixed in the molecular structure, it is possible to limit the movement of the phenyl group even if the temperature rises, thereby improving the dimensional stability against heat.

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Abstract

L'invention concerne un polyimide préparé à partir d'une diamine contenant un groupe spiro ou cardo dans une structure moléculaire, la stabilité dimensionnelle du polyimide pouvant être améliorée à une température élevée, le polyimide permettant ainsi d'obtenir un film de polyimide utile pour un substrat flexible.
PCT/KR2018/000810 2017-01-31 2018-01-17 Polyimide et film de polyimide préparé à partir de celui-ci destiné à un écran flexible Ceased WO2018143583A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP20198866.4A EP3812415B1 (fr) 2017-01-31 2018-01-17 Polyimide et film de polyimide préparé à partir de celui-ci destiné à un écran flexible
EP18748750.9A EP3578589A4 (fr) 2017-01-31 2018-01-17 Polyimide et film de polyimide préparé à partir de celui-ci destiné à un écran flexible
CN201880003834.4A CN109803995B (zh) 2017-01-31 2018-01-17 聚酰亚胺和由其制备的用于柔性显示器的聚酰亚胺膜
JP2019512727A JP7048020B2 (ja) 2017-01-31 2018-01-17 ポリイミド及びこれより製造されたフレキシブルディスプレイ用ポリイミドフィルム
US16/461,601 US11319409B2 (en) 2017-01-31 2018-01-17 Polyimide and polyimide film, prepared therefrom, for flexible display

Applications Claiming Priority (4)

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KR20170013726 2017-01-31
KR10-2017-0013726 2017-01-31
KR10-2017-0167165 2017-12-07
KR1020170167165A KR101989028B1 (ko) 2017-01-31 2017-12-07 폴리이미드 및 이로부터 제조된 플렉시블 디스플레이용 폴리이미드 필름

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JP2004182962A (ja) * 2002-10-09 2004-07-02 Hitachi Chem Co Ltd トリプチセン骨格を有するポリイミド樹脂及び光部品
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