WO2020159183A1 - Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, l'utilisant chacun - Google Patents

Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, l'utilisant chacun Download PDF

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Publication number
WO2020159183A1
WO2020159183A1 PCT/KR2020/001263 KR2020001263W WO2020159183A1 WO 2020159183 A1 WO2020159183 A1 WO 2020159183A1 KR 2020001263 W KR2020001263 W KR 2020001263W WO 2020159183 A1 WO2020159183 A1 WO 2020159183A1
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Prior art keywords
polyimide
functional group
based resin
resin film
formula
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PCT/KR2020/001263
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English (en)
Korean (ko)
Inventor
김경환
박찬효
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020190121178A external-priority patent/KR102427759B1/ko
Priority claimed from KR1020190121177A external-priority patent/KR102427758B1/ko
Priority claimed from KR1020190161494A external-priority patent/KR102465430B1/ko
Priority claimed from KR1020190161495A external-priority patent/KR102427760B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/733,816 priority Critical patent/US20210230368A1/en
Priority to JP2020565994A priority patent/JP7414011B2/ja
Priority to CN202080003026.5A priority patent/CN112204085B/zh
Publication of WO2020159183A1 publication Critical patent/WO2020159183A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a polyimide-based resin film, a substrate for a display device using the same, and an optical device capable of securing excellent optical properties even under high temperature heat treatment conditions and stably maintaining optical properties even during additional heat treatment.
  • the display device market is rapidly changing with a focus on flat panel displays (FPDs), which are easy to have a large area and can be thin and light.
  • the flat panel display includes a liquid crystal display (LCD), an organic light emitting display (OLED), or an electrophoretic display (EPD).
  • TFT devices are manufactured by depositing a multilayer inorganic film such as a buffer layer, an active layer, and a gate insulator on a cured polyimide.
  • the emission efficiency may be reduced by a difference between the refractive index of the multi-layered upper layer made of the inorganic film and the refractive index of the polyimide layer as described above.
  • the polyimide material included in the polyimide layer (substrate layer) is cured at a high temperature of 400° C. or higher, a decrease in optical properties may occur due to deterioration of the polyimide.
  • the present invention relates to a polyimide-based resin film capable of securing excellent optical properties even under high temperature heat treatment conditions and stably maintaining optical properties even during additional heat treatment.
  • the present invention is to provide a substrate for a display device using the polyimide-based resin film, and an optical device.
  • the polyimide-based resin containing a polyimide repeating unit represented by the following Chemical Formula 1 is included, and the absolute value of the yellow index change amount ( ⁇ YI) obtained by the following Equation 1 is 4
  • the following is a polyimide-based resin film.
  • X 1 is a tetravalent functional group represented by the following Chemical Formula 2
  • Y 1 is an aromatic divalent functional group having 15 or more carbon atoms with at least one substituted electron withdrawing functional group
  • Ar is a polycyclic aromatic divalent functional group
  • Equation 1 YI f is the final yellow index of the film obtained after heat treatment of the polyimide resin film at a temperature of 400° C. to 450° C. for 130 minutes to 200 minutes, and YI 0 is a polyimide system before the heat treatment. It is the yellow index of the resin film.
  • a substrate for a display device comprising the polyimide-based resin film.
  • optical device comprising the polyimide-based resin film.
  • first component may also be referred to as the second component, and similarly, the second component may be referred to as the first component.
  • the (co)polymer means a polymer or a copolymer
  • the polymer means a homopolymer composed of a single repeating unit
  • the copolymer means a composite polymer containing two or more repeating units.
  • substitution means that other functional groups are bonded in place of the hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and is substituted when two or more are substituted. , 2 or more substituents may be the same or different from each other.
  • substituted or unsubstituted in this specification is deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; Primary amino group; Carboxy group; Sulfonic acid group; Sulfonamide groups; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Alkoxysilylalkyl groups; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted
  • aromatic is a property that satisfies the Huckels Rule (Huckels Rule), it can be defined as a case that satisfies all three conditions according to the Huckel rule.
  • the alkyl group is a monovalent functional group derived from alkane, and may be a straight chain or a branched chain, and the carbon number of the straight chain alkyl group is not particularly limited, but is preferably 1 to 20. Further, the number of carbon atoms in the branched chain alkyl group is 3 to 20.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-non
  • the halo alkyl group means a functional group in which the halogen group is substituted with the aforementioned alkyl group, and examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the haloalkyl group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.
  • a multivalent functional group is a residue in which a plurality of hydrogen atoms bound to an arbitrary compound are removed, for example, a divalent functional group, a trivalent functional group, and a tetravalent functional group.
  • a tetravalent functional group derived from cyclobutane refers to a residue in which any 4 hydrogen atoms attached to cyclobutane are removed.
  • the electron withdrawing group may include one or more selected from the group consisting of haloalkyl groups, halogen groups, cyano groups, nitro groups, sulfonic acid groups, carbonyl groups and sulfonyl groups, preferably It may be a haloalkyl group such as trifluoromethyl group (-CF 3 ).
  • a direct bond or a single bond means that there is no atom or atomic group at the corresponding position, and is connected by a bond line. Specifically, it means that a separate atom is not present in a portion represented by L 1 and L 2 in the chemical formula.
  • the weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by GPC method.
  • detectors and analytical columns such as a commonly known analytical device and a differential index detector, can be used, and the temperature is usually applied.
  • Conditions, solvents and flow rates can be applied.
  • the evaluation temperature is 160°C, and 1,2,4-trichlorobenzene is used as a solvent.
  • the flow rate was 1 mL/min
  • the sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 ⁇ L, and the value of Mw can be obtained by using an assay curve formed using a polystyrene standard.
  • the molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
  • a polyimide containing a polyimide-based resin including a polyimide repeating unit represented by Chemical Formula 1, and having an absolute value of a change in yellow index ( ⁇ YI) obtained by Equation 1 of 4 or less. Based resin film may be provided.
  • the present inventors like the polyimide-based resin film of the above embodiment, the tetravalent functional group derived from the tetracarboxylic acid dianhydride having a specific structure as in Chemical Formula 2 in the polyimide repeating unit structure and the number of carbon atoms substituted with at least one electron withdrawing functional group As the aromatic divalent functional group of 15 or more was contained, the polyimide resin film cured at a high temperature of 400° C. or higher also had excellent optical properties through experiments, and the invention was completed.
  • the polyimide-based resin comprises a reaction product obtained through an imidization reaction of a tetracarboxylic dianhydride containing a structure represented by Formula 2 and an aromatic diamine having 15 or more carbon atoms substituted with at least one electron withdrawing functional group,
  • a trifluoromethyl group capable of imparting an electron withdrawing effect to a diamine monomer compound used in the synthesis of polyimide resin is introduced as a substituent, and CTC (charge of Pi-electrons present in the imide chain) By suppressing the formation of transfer complex), transparency can be secured to realize excellent optical properties.
  • the polyimide-based resin synthesized from an aromatic diamine monomer having 15 or more carbon atoms with at least one electron withdrawing group functionally improves ordering and orientation characteristics between molecules to ensure sufficient heat resistance even in a polyimide film obtained by high temperature curing, thereby making it plastic.
  • the plastic substrate When used as a substrate, when heat-treating the metal layer formed on the plastic substrate, the plastic substrate is prevented from being damaged by heat, and excellent optical properties can be achieved even when heat treatment is performed at an additional high temperature of 400° C. or higher.
  • the polyimide film according to the present invention can increase the refractive index, and is used as a substrate layer in a flexible display device, thereby reducing the difference in refractive index with each layer constituting the device. By reducing the amount of extinguished light, it is possible to effectively increase the emission efficiency of the light (bottom emission).
  • the polyimide-based resin means that polyimide and polyamic acid and polyamic acid ester, which are precursor polymers thereof, are all included. That is, the polyimide-based polymer may include at least one selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit. That is, the polyimide-based polymer may include a polyamic acid repeating unit, one polyamic acid ester repeating unit, one polyimide repeating unit, or a copolymer of two or more repeating units thereof.
  • One or more repeating units selected from the group consisting of the polyamic acid repeating unit, polyamic acid ester repeating unit, and polyimide repeating unit may form a main chain of the polyimide-based polymer.
  • the polyimide-based resin may include a polyimide repeating unit represented by Chemical Formula 1.
  • X 1 is a tetravalent functional group represented by Chemical Formula 2
  • X 1 is a functional group derived from a tetracarboxylic acid dianhydride compound used in the synthesis of polyimide resins.
  • Ar is a polycyclic aromatic divalent functional group.
  • the polycyclic aromatic divalent functional group may be a polycyclic aromatic hydrocarbon compound or a divalent functional group derived from a derivative compound thereof, and may include a fluorenylene group.
  • the derivative compound includes all compounds in which one or more substituents are introduced or carbon atoms are replaced by heteroatoms.
  • the polycyclic aromatic divalent functional group may include a conjugated cyclic divalent functional group containing at least two or more aromatic ring compounds. That is, the polycyclic aromatic divalent functional group may contain at least two or more aromatic ring compounds in the functional group structure, as well as the functional group may have a fused ring structure.
  • the aromatic ring compound may include an arene compound containing at least one benzene ring, or a hetero arene compound in which carbon atoms in the arene compound are replaced by heteroatoms.
  • the aromatic ring compound may contain at least two or more in the polycyclic aromatic divalent functional group, and each of the two or more aromatic ring compounds may form a direct fused ring or a fused ring through a different ring structure.
  • each of the two or more aromatic ring compounds may form a direct fused ring or a fused ring through a different ring structure.
  • two benzene rings are respectively bonded to a cycloalkyl ring structure, it can be defined that two benzene rings each form a cycloalkyl ring.
  • the conjugated cyclic divalent functional group containing at least two or more aromatic cyclic compounds is a divalent functional group derived from a conjugated cyclic compound containing at least two or more aromatic cyclic compounds or a derivative compound thereof, wherein the derivative compound has one or more substituents introduced Or a compound in which the carbon atom has been replaced with a heteroatom.
  • Examples of the polycyclic aromatic divalent functional group are not particularly limited, and examples thereof include a fluorenylene group.
  • the tetravalent functional group represented by Chemical Formula 2 may be a functional group represented by Chemical Formula 2-1.
  • Y 1 is an aromatic divalent functional group having 15 or more carbon atoms substituted with at least one electron withdrawing group, and Y 1 is an action derived from a diamine compound used in the synthesis of polyamic acid, polyamic acid ester, or polyimide. It can be a flag.
  • the aromatic divalent functional group having 15 or more carbon atoms in Y 1 may include three or more aromatic cyclic compounds. As such, as three or more aromatic cyclic compounds are contained, the ordering and orientation characteristics of the polyimide-based resin are improved, and sufficient heat resistance can be secured even in a polyimide film obtained by high temperature curing.
  • the aromatic divalent functional group having 15 or more carbon atoms may include at least one selected from the group consisting of a triphenylene group, a quaterphenylene group, and a pentaphenylene group.
  • the electron withdrawing functional group may include at least one selected from the group consisting of haloalkyl groups, halogen groups, cyano groups, nitro groups, sulfonic acid groups, carbonyl groups and sulfonyl groups.
  • CTC charge transfer complex
  • the aromatic divalent functional group having 15 or more carbon atoms substituted with at least one electron withdrawing functional group of Y 1 may include a functional group represented by the following Chemical Formula 3.
  • T 1 to T 3 are the same or different from each other, each independently an electron withdrawing group, m1 to m3 are the same or different from each other, and at least one of m1 to m3 is an integer of 1 to 4, the rest Is an integer from 0 to 4, and n is an integer from 1 to 10.
  • An aromatic divalent functional group having 15 or more carbon atoms substituted with at least one electron withdrawing functional group of Y 1 may include a functional group represented by the following Chemical Formula 3-1.
  • the polyimide-based resin may include a combination of tetracarboxylic acid dianhydride represented by the following Chemical Formula 4 and aromatic diamine having 15 or more carbon atoms substituted with at least one electron withdrawing functional group.
  • Ar' is a polycyclic aromatic divalent functional group.
  • the polycyclic aromatic divalent functional group is a divalent functional group derived from a polycyclic aromatic hydrocarbon compound, and may include a fluorenylene group as a divalent functional group derived from a fluorenylene group or a derivative compound thereof.
  • the derivative compound includes all compounds in which one or more substituents are introduced or carbon atoms are replaced by heteroatoms.
  • a specific example of the tetracarboxylic acid dianhydride represented by Chemical Formula 4 is 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (9,9-Bis(3,4-dicarboxyphenyl)fluorene Dianhydride, BPAF). Can be lifted.
  • the aromatic diamine having 15 or more carbon atoms in which the electron withdrawing functional group is substituted by at least 1 is a compound in which an amino group (-NH 2 ) is bonded to the sock end of the aromatic di2 having 15 or more carbon atoms in which the electron withdrawing functional group is substituted by at least 1,
  • the description of the aromatic divalent functional group having 15 or more carbon atoms in which the electron withdrawing functional group is substituted by at least one is as described above.
  • aromatic diamine having 15 or more carbon atoms in which the electron withdrawing functional group is substituted with at least one or more include diamine represented by the following formula (a).
  • the polyimide-based resin has a terminal anhydride group (-OC-O-CO-) of tetracarboxylic acid dianhydride represented by Chemical Formula 4 and an aromatic diamine having at least 15 carbon atoms substituted with at least one electron withdrawing group.
  • the reaction between the amino group (-NH 2 ) may form a bond between the nitrogen atom of the amino group and the carbon atom of the anhydride group.
  • the polyimide-based resin may further include a polyimide repeating unit represented by Formula 5 below.
  • X 2 is one of a tetravalent functional group represented by the following Chemical Formula 6, and Y 2 is an aromatic divalent functional group having 15 or more carbon atoms with at least one substituted electron withdrawing functional group,
  • R 1 to R 6 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms
  • L is a single bond, -O-, -CO-, -COO-, -S-, -SO-,- SO 2 -, -CR 7 R 8 -, -(CH 2 ) t -, -O(CH 2 ) t O-, -COO(CH 2 ) t OCO-, -CONH-, phenylene or combinations thereof Any one selected from the group consisting of, wherein R 7 and R 8 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a halo alkyl group having 1 to 10 carbon atoms, and t is an integer of 1 to 10.
  • Functional group represented by Chemical Formula 6 include functional groups represented by Chemical Formula 6-1, functional groups represented by Chemical Formula 6-2, or functional groups represented by Chemical Formula 6-3.
  • the polyimide-based polymer includes: a first repeating unit containing a repeating unit represented by Formula 1, wherein a repeating unit derived from tetracarboxylic acid dianhydride is a functional group represented by Formula 2; And a second repeating unit containing a repeating unit represented by Formula 5, wherein the repeating unit derived from tetracarboxylic dianhydride is a functional group represented by Formula 6 above.
  • the first repeating unit and the second repeating unit are randomly arranged in the polyimide-based polymer to form a random copolymer, or a block between the first repeating unit and a block between the second repeating units to form a block copolymer.
  • the polyimide-based polymer including the repeating unit represented by Chemical Formula 1 and the repeating unit represented by Chemical Formula 5 may be prepared by reacting two or more different tetracarboxylic acid dianhydride compounds with diamine compounds. Tetracarboxylic acid dianhydride may be added simultaneously to synthesize a random copolymer, or sequentially added to synthesize a block copolymer.
  • the polyimide repeating unit represented by Chemical Formula 5 may contain 1 mol% or more and 99 mol% or less of all the repeating units contained in the polyimide resin.
  • the polyimide repeating unit represented by Formula 1 and the polyimide repeating unit represented by Formula 5 are 70 mol% or more, or 80 mol% or more, or 90 mol% or more, compared to the total repeating units contained in the polyimide-based resin, or 70 mol% or more, 100 mol% or less, 80 mol% or more, 100 mol% or less, 70 mol% or more, 90 mol% or less, 70 mol% or more, 99 mol% or less, 80 mol% or more, 99 mol% or less, 90 mol% or more, 99 or more 99 It may contain less than mol%.
  • the polyimide-based resin is composed of only the polyimide repeating unit represented by Formula 1 and the polyimide repeating unit represented by Formula 5, or most of the polyimide repeating unit represented by Formula 1 and Formula 5 It may be made of polyimide repeat units.
  • other diamines other than diamines capable of inducing aromatic divalent functional groups having 15 or more carbon atoms substituted with at least one electron withdrawing functional group are not mixed, or may be mixed in an extremely small amount of less than 1 mol%. have.
  • the polyimide repeating unit represented by Chemical Formula 5 may include one or more repeat units selected from the group consisting of mid repeat units.
  • X 3 is a tetravalent functional group represented by Chemical Formula 6-1
  • Y 3 is an aromatic divalent functional group having 15 or more carbon atoms with at least one substituted electron withdrawing functional group
  • X 4 is a tetravalent functional group represented by Chemical Formula 6-2
  • Y 4 is an aromatic divalent functional group having 15 or more carbon atoms with at least one substituted electron withdrawing functional group
  • X 5 is a tetravalent functional group represented by Chemical Formula 6-3
  • Y 5 is an aromatic divalent functional group having 15 or more carbon atoms with at least one substituted electron withdrawing functional group.
  • the weight average molecular weight (measured by GPC) of the polyimide-based resin is not particularly limited, but may be, for example, 1000 g/mol or more and 200000 g/mol or less, or 10000 g/mol or more and 200000 g/mol or less.
  • the polyimide-based resin according to the present invention can exhibit excellent colorless and transparent characteristics while maintaining characteristics such as heat resistance, mechanical strength, etc. due to a rigid structure, an element substrate, a display substrate for a display, and an optical film , IC (integrated circuit) package, electrodeposition film (adhesive film), multi-layer flexible printed circuit (FRC), tape, touch panel, protective film for optical disk, etc. can be used in various fields, especially suitable for display cover board have.
  • the polyimide-based resin film of the embodiment may include a cured product in which the polyimide-based resin is cured at a temperature of 400° C. or higher.
  • the cured product means a material obtained through a curing process of a resin composition containing the polyimide-based resin, and the curing process is performed at a temperature of 400° C. or higher, or 400° C. or higher and 500° C. or lower, for 50 minutes to 100 minutes. Can proceed.
  • an example of a method for synthesizing the polyimide-based resin film is not particularly limited, and for example, forming a coating film by applying a resin composition containing the polyimide-based resin to a substrate (step 1); Drying the coating film (step 2); A method of manufacturing the film may be used, including the step of curing the dried coating film by heat treatment (step 3).
  • Step 1 is a step of forming a coating film by applying a resin composition containing the above-described polyimide resin to a substrate.
  • the method of applying the resin composition containing the polyimide-based resin to the substrate is not particularly limited, and for example, methods such as screen printing, offset printing, flexo printing, inkjet, and the like can be used.
  • the resin composition containing the polyimide resin may be dissolved or dispersed in an organic solvent.
  • the solution may be the reaction solution itself obtained, and the reaction solution may be diluted with another solvent.
  • a polyimide resin when a polyimide resin is obtained as a powder, it may be dissolved in an organic solvent to form a solution.
  • organic solvent examples include toluene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl Pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3- Ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoa Milk ketone, methyl isopropyl ketone, cyclohexanone,
  • the resin composition containing the polyimide-based resin may contain solid content in an amount to have an appropriate viscosity in consideration of processability such as coatability during the film forming process.
  • the content of the composition may be adjusted such that the total resin content is 5% to 25% by weight, or 5% to 20% by weight, or 5% to 15% by weight. .
  • the resin composition containing the polyimide-based resin may further include other components in addition to the organic solvent.
  • the resin composition containing the polyimide-based resin when applied, it improves the uniformity or surface smoothness of the film thickness, or improves the adhesion to the substrate, or changes the dielectric constant or conductivity.
  • additives that can increase the density may be further included. Examples of such additives include surfactants, silane-based compounds, dielectric or cross-linkable compounds, and the like.
  • the step 2 is a step of drying the coating film formed by applying the resin composition containing the polyimide resin to the substrate.
  • the drying step of the coating film may be performed by heating means such as a hot plate, a hot air circulation path, an infrared furnace, and may be performed at a temperature of 50°C or more and 150°C or less, or 50°C or more and 100°C or less.
  • heating means such as a hot plate, a hot air circulation path, an infrared furnace, and may be performed at a temperature of 50°C or more and 150°C or less, or 50°C or more and 100°C or less.
  • Step 3 is a step of curing the dried coating film by heat treatment.
  • the heat treatment may be performed by heating means such as a hot plate, a hot air circulation path, an infrared furnace, and may be performed at a temperature of 400°C or higher, or 400°C or higher and 500°C or lower.
  • the thickness of the polyimide-based resin film is not particularly limited, for example, it can be freely adjusted within a range of 0.01 ⁇ m or more and 1000 ⁇ m or less. When the thickness of the polyimide-based resin film increases or decreases by a specific value, physical properties measured in the polyimide-based resin film may also change by a certain value.
  • the absolute value of the amount of change in the yellow index obtained by Equation 1 below is 4 or less, or 3.5 or less, or 0.01 or more and 4 or less, or 0.01 or more and 3.5 or less, or 0.05 or more and 4 or less, or 0.05 Or more and 3.5 or less, or 0.1 or more and 4 or less, or 0.1 or more and 3.5 or less.
  • Equation 1 YI f is the final yellow index of the film obtained after heat treatment of the polyimide resin film at a temperature of 400° C. to 450° C. for 130 minutes to 200 minutes, and YI 0 is a polyimide system before the heat treatment. It is the yellow index of the resin film.
  • the change in the actual yellow index according to the additional heat treatment can be compared through the absolute value of the amount of change in yellow index obtained in Equation 1.
  • the yellow index change amount obtained in Equation 1 is a negative number (eg, -1)
  • the absolute value of the yellow index change amount obtained in Equation 1 may be a value with a negative sign removed (eg 1).
  • the yellow index change amount obtained in Equation 1 is a positive number (for example, 1)
  • the absolute value of the yellow index change amount obtained in Equation 1 is a yellow index change amount value (eg, 1) obtained in Equation 1 Is the same as
  • an example of a method of heat-treating the polyimide-based resin film at a temperature of 400°C to 450°C for 130 minutes to 200 minutes is not particularly limited, and the heat treatment may be performed in a single step, or in multiple steps. Can proceed to In the case of the multi-step, an additional heat treatment process of 2 to 10 steps may be performed, and in this case, each step may be performed continuously or discontinuously.
  • each heat treatment step is performed at a temperature of 400°C to 450°C, and the total sum of the times of each heat treatment step satisfies 130 minutes to 200 minutes.
  • the absolute value of the amount of change in the yellow index, which is the optical property of the film is very small to 4 or less, so the polyimide of the above embodiment Based resin film can achieve high heat resistance.
  • the yellow index is a result of analyzing a polyimide-based resin film sample with a color meter (Color-Eye 7000A of GRETAGMACBETH). It can be measured automatically.
  • a pure polyimide-based resin film may be secured through a process of peeling the base film from a laminate including a base film and a polyimide-based resin film coated on the base film.
  • the yellow index may be measured for a sample of a polyimide resin film of one embodiment having a thickness of 5 ⁇ m or more and 30 ⁇ m or less, or 5 ⁇ m or more and 15 ⁇ m or less, or 8 ⁇ m or more and 12 ⁇ m or less.
  • the yellow index of the polyimide resin film before the heat treatment is 15 or less, or 14.5 or less, or 1 or more 15 or less, or 1 or more 14.5 or less, or 5 or more 15 or less, or 5 or more 14.5 or less, or 8.8 or more and 14.1 or less.
  • the polyimide resin film which is a yellow index measurement target of the polyimide resin film before the heat treatment, refers to a material obtained through a curing process of a resin composition containing a polyimide resin as described above, and the curing process is, for example, For example, at a temperature of 400° C. or higher, or 400° C. or higher and 500° C. or lower, the temperature may be 50 minutes or more and 100 minutes or less.
  • the final yellow index of the polyimide-based resin film is 20 or less, or 18 or less, or 5 or more 20 or less, or 5 or more 18 or less, or 8 or more 20 or less, or 8 or more and 18 or less, Or 8.7 or more and 17.6 or less.
  • the final yellow index measurement target polyimide-based resin film means a film obtained after further heat-treating the polyimide-based resin film at a temperature of 400°C to 450°C for 130 minutes to 200 minutes as described above, and the heat treatment Is as described above in Equation (1).
  • a substrate for a display device including the polyimide-based resin film of the other embodiment may be provided.
  • the contents of the polyimide-based resin film may include all of the contents described above in one embodiment.
  • the display device including the substrate is a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display (Flexible Display), or a rollable display device (rollable display or foldable display) ) And the like, but is not limited thereto.
  • LCD liquid crystal display device
  • OLED organic light emitting diode
  • flexible display Flexible Display
  • rollable display device rollable display or foldable display
  • the display device may have various structures depending on the application field and the specific shape, for example, a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (such as an OLED device), and a transparent substrate. have.
  • the polyimide-based resin film of the other embodiments described above may be used for various purposes such as a substrate, an external protective film, or a cover window in these various display devices, and more specifically, may be applied as a substrate.
  • the substrate for a display device may have a structure in which a device protection layer, a transparent electrode layer, a silicon oxide layer, a polyimide resin film, a silicon oxide layer, and a hard coating layer are sequentially stacked.
  • the transparent polyimide substrate may include a silicon oxide layer formed between the transparent polyimide-based resin film and the cured layer in terms of further improving solvent resistance, moisture permeability, and optical properties, and the silicon oxide layer is poly It may be produced by curing silazane.
  • the silicon oxide layer is formed by curing the coated polysilazane after coating and drying a solution containing polysilazane before the step of forming a coating layer on at least one surface of the transparent polyimide resin film.
  • the substrate for a display device can provide a transparent polyimide cover substrate having solvent resistance, optical properties, moisture permeability, and scratch resistance, while having excellent bending properties and impact resistance by including the above-described device protection layer. have.
  • an optical device including the polyimide-based resin film of the other embodiment may be provided.
  • the contents of the polyimide-based resin film may include all of the contents described above in one embodiment.
  • the optical device may include all of various devices using properties realized by light, for example, a display device.
  • a display device include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display, or a rollable display or foldable display And the like, but is not limited thereto.
  • LCD liquid crystal display device
  • OLED organic light emitting diode
  • flexible display or a rollable display or foldable display And the like, but is not limited thereto.
  • the optical device may have various structures according to application fields and specific shapes, and may be, for example, a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (such as an OLED device), and a transparent substrate. have.
  • the polyimide-based resin film of the other embodiments described above may be used in various applications such as a substrate, an external protective film, or a cover window in these various optical devices, and more specifically, may be applied to a substrate.
  • a polyimide-based resin film and a substrate for a display device using the same and a polyimide resin film capable of securing excellent optical properties under high temperature heat treatment conditions and stably maintaining optical properties even during additional heat treatment are provided.
  • the polyimide precursor composition was spin coated on a glass substrate.
  • the glass substrate coated with the polyimide precursor composition was placed in an oven, heated at a rate of 5°C/min, and maintained at 80°C for 20 minutes and at 450°C for 70 minutes to undergo a curing process to perform a polyimide film (thickness: 10 ⁇ m) ) Was prepared.
  • pyromellitic dianhydride (PMDA) was used instead of 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-Biphenyltetracarboxylic dianhydride (BPDA)).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • a polyimide film was manufactured in the same manner as in Example 1, except that.
  • BPDA 4'-biphenyltetracarboxylic dianhydride
  • the polyimide precursor composition was spin coated on a glass substrate.
  • the glass substrate coated with the polyimide precursor composition was placed in an oven, heated at a rate of 5°C/min, and maintained at 80°C for 20 minutes and at 450°C for 70 minutes to undergo a curing process to perform a polyimide film (thickness: 10 ⁇ m) ) Was prepared.
  • the polyimide film having a thickness of 10 ⁇ m obtained in Examples and Comparative Examples was peeled from a glass substrate, and after preparing a sample having a size of 2 cm X 10 cm in width, a color meter (Color-Eye 7000A by GRETAGMACBETH) was used for the sample. Then, the yellow index (YI 0 ) was obtained and is shown in Table 1 below.
  • the polyimide film having a thickness of 10 ⁇ m obtained in Examples and Comparative Examples was further cured at 410° C. for 60 minutes, and then the film further cured at 445° C. for 60 minutes was peeled from the glass substrate, and the size was 2 cm by 10 cm.
  • the final yellow index (YI f ) was measured using a color meter (Color-Eye 7000A manufactured by GRETAGMACBETH), and the amount of change in yellow index ( ⁇ YI) by Equation 1 below was calculated.
  • the heat-resistant yellow index was obtained and is shown in Table 1 below.
  • the polyimide film having a thickness of 10 ⁇ m obtained in Examples and Comparative Examples was further cured at 445° C. for 30 minutes, and then the film cured for an additional 30 minutes at 445° C. was peeled from the glass substrate, and the size was 2 cm X 10 cm
  • the final yellow index (YI f ) was measured using a color meter (Color-Eye 7000A manufactured by GRETAGMACBETH), and the amount of change in yellow index ( ⁇ YI) by Equation 1 below was calculated.
  • the heat-resistant yellow index was obtained and is shown in Table 1 below.
  • Yellow index change amount ( ⁇ YI) (final yellow index obtained in Experimental Example 2 (YI f ))-(yellow index obtained in Experimental Example 1 (YI 0 ))
  • the polyimide resin films of Examples 1 to 3 obtained through a curing process at 450°C for 70 minutes exhibited a yellow index (YI 0 ) of 8.8 or more and 14.1 or less.
  • the polyimide resin films of Comparative Examples 1 to 3 obtained through the curing process at 70 minutes exhibited a yellow index (YI 0 ) of 15.2 or more and 16.8 or less, which is much higher than in Examples.
  • the polyimide system of Examples It was confirmed that the resin film can have excellent optical properties even when curing at a high temperature of 400°C or higher.
  • the polyimide-based resin films of Examples 1 to 3 are heat resistant yellow index ( ⁇ YI) of -0.2 or more and 3.5 or less, or yellow index change amount of 0.1 or more and 3.5 or less ( ⁇ ) YI).
  • the optical properties of the polyimide-based resin film of the embodiment can be stably maintained even at a high temperature heat treatment of 400° C. or higher for the film.

Abstract

La présente invention concerne un film polymère à base de polyimide et un substrat pour un dispositif d'affichage et un dispositif optique, l'utilisant chacun, le film polymère à base de polyimide étant synthétisé par une réaction entre un composé anhydride d'acide structuré spécifiquement et un composé de diamine, et peut ainsi garantir d'excellentes caractéristiques optiques même dans des conditions de traitement thermique à haute température et peut maintenir de manière stable des caractéristiques optiques même lors d'un traitement thermique supplémentaire.
PCT/KR2020/001263 2019-02-01 2020-01-28 Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, l'utilisant chacun WO2020159183A1 (fr)

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US15/733,816 US20210230368A1 (en) 2019-02-01 2020-01-28 Polyimide-based polymer film, substrate for display device, and optical device using the same
JP2020565994A JP7414011B2 (ja) 2019-02-01 2020-01-28 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
CN202080003026.5A CN112204085B (zh) 2019-02-01 2020-01-28 基于聚酰亚胺的聚合物膜、使用其的显示装置用基底和光学装置

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KR10-2019-0013486 2019-02-01
KR20190013486 2019-02-01
KR10-2019-0121178 2019-09-30
KR1020190121178A KR102427759B1 (ko) 2019-09-30 2019-09-30 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
KR10-2019-0121177 2019-09-30
KR20190121176 2019-09-30
KR1020190121177A KR102427758B1 (ko) 2019-09-30 2019-09-30 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
KR10-2019-0121176 2019-09-30
KR1020190161494A KR102465430B1 (ko) 2019-02-01 2019-12-06 폴리이미드 전구체 조성물 및 이로부터 제조된 폴리이미드 필름, 디스플레이 장치용 기판, 및 광학 장치
KR10-2019-0161494 2019-12-06
KR1020190161495A KR102427760B1 (ko) 2019-09-30 2019-12-06 폴리이미드계 수지 필름 및 이를 이용한 디스플레이 장치용 기판, 및 광학 장치
KR10-2019-0161495 2019-12-06

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PCT/KR2020/001263 WO2020159183A1 (fr) 2019-02-01 2020-01-28 Film polymère à base de polyimide et substrat pour dispositif d'affichage et dispositif optique, l'utilisant chacun
PCT/KR2020/001291 WO2020159193A1 (fr) 2019-02-01 2020-01-28 Composition de précurseur de polyimide et film de polyimide, substrat pour dispositif d'affichage, et dispositif optique, chacun fabriqué à partir de celle-ci

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US20230133697A1 (en) 2020-09-08 2023-05-04 Lg Chem, Ltd. Polyimide-based polymer film, substrate for display device, and optical device using the same

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